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ACES II Release 2.5.0 User Manual DRAFT COPY

1. 114 A 3 3 IP_EOM IP_CI DIP_EOM DIP_TDA DIP_SSTEOM 114 A 3 4 EA EOM EA_CI DEA_EOM DEA_TDA DEA_STEOM A 35 ACT EA EOM B Standard Basis Sets and ECPs B 1 Basis sets in GENBAS 0 0 000 00 A Q buy TA TRE Q ns TR R ee B 2 ECP sets in ECPDATA 0 20 0000 C Queue Scripts C 1 ACES II script body ee ee aS A A ERE AAA e C 2 LoadLeveler C 3 LSF C 4 GridEngine Index 114 114 115 115 131 132 132 132 132 132 134 1 1 1 Authors Official ACES II citation The users of ACES II must give the following citation The basis set distributed with the ACES II program system is obtained through Pacific Northwest National Laboratory PNNL and any calculation that uses basis sets from this ACES II is a program product of the Quantum Theory Project University of Florida Authors J F Stanton J Gauss S A Perera J D Watts A D Yau M Nooijen N Oliphant P G Szalay W J Lauderdale S R Gwaltney S Beck A Balkov D E Bernholdt K K Baeck P Rozyczko H Sekino C Huber J Pittner W Cencek D Taylor and R J Bartlett Integral packages included are VMOL J Alml f and P R Taylor VPROPS P Taylor ABA CUS T Helgaker H J Aa Jensen P Jorgensen J Olsen and P R Taylor HONDO GAMESS M W Schmidt K K Baldridge J A Boatz S T Elbert M S Gordon J J Jensen S Koseki N Matsunaga K A Nguyen S Su T L Windus M
2. e e We ae Sate 99 11 Troubleshooting 100 TL OOG OST ake ua u a heehee oie h U S aa oe RIE 2 S tl tS 100 11 2 Basic program restrictions lt 4 5 6 6 4 e dob enw ee Ee 101 11 3 Suggestions for reducing resources bag hk ake hak r a sr er ea e 101 12 References 102 12 1 Many body perturbation theory MBPT aaa 102 12 2 Coupled cluster CC theory a EA A rr SN 103 12 3 Analytical gradients for MBPT CC methods 104 12 4 Analytical second derivatives for MBPT CC methods 106 12 5 NMR chemical shift calculations lt 6 08 te we ee wee esa 106 12 6 Methods for calculating excitation energies 106 12 7 Methods for calculating electron attachment energies 107 12 8 Time dependent Hartree Fock methods 107 12 9 HE DET method is Ls aoa a he ee apas a de i Yon at 107 EA lO BASIS A a u e S Mie nae at Mende ce Bee ects 1 107 12 111ntegral Packages a q Bou e pe Dake PE ae Ye eae he S Q 110 A Other Keywords 111 A 1 Experimental obsolete and unused 000000004 111 A 2 Kohn Sham DFT namelists y eee Ge Vials ee Es EE EO ES Eo 112 ARZ AON ha Sta tor A Mine Gal Aho GD ir Siz shite Bs SE se yka s 112 AD INTER 0 Y yas ed Ye ya Pip le als Da TTT 112 Agar MIRGO MaIMelUSis I Y R s G e Y an 6 rt hw kayta AAA Sean digit dt 4 114 A 3 1 mrcc_gen true mrcc Gae ot Wks ee a a a Gn 114 A 3 2 EE EOM THE TDA EE STEOM 60 ca ee
3. ASDF I I 6 6 ISDIG E ez ez I I AE D IZ LI LI I I DE 5 IZ 1 61 1 61 6 6 z DITE I I 6 6 DIZE 61 GT e z GIN I e 2 6 Z IAIN 6 9 G I G IVOS INII 6 9 g I ININ YT E g G I DEOLS 6 6 x g I 59 O18 6 6 g G I DE OLS 6 6 g G I DZOLS DIST a s tw Jon vn an a o Nlola aa H aR H 109 SISeg de sE dz sz ST syu ur sp y3NOIYI ST 107 SV8N3D ur 109 stseq yoo 10 SUOTPOUNJ siseq OY P9ypeIquos jo Joquinu oy 1 ALL 119 9E0 980 S TGT I 81 61 dd 4de 9 4 1 18 9 70 2 08 GT dd Adz OTIE 9 Lg Le 6 6 6 OT ATADO LL LC 0 161 ez e 9 L TI8 9 6 ez ez e O TTE 9 L 16 EJE 61 Sd 9 DTTE9 EEG eld E61 61 C OTTE 9 TZ TZ eT ET DTIS 9 HLL 9 1 oe 9 ET LAE ACE OTE 9 tzez t og 161 161 Z 9 O 12 9 DIST a s tw Jon vn an a o Nfoljajgaa aR n ee dg se dz SZ ST syu ur sp YSNOIY ST 107 SV8N3D ur 109 stseq yoeo 10 SOHO siseq OV poprsjuoo Jo Joquinu oy T AQL 120 68 6 qq 00 ZLAd OO DNV 366 eq 6 ZdAd O0 50V TSG TR 00T ZSADMA DO Of 6ET FOT ZOAOA d 0O 01769 967 ZLAOMd O0 67 U 61 Z AOA d OO st oe e aU Gee Z9IADA DO TR 00T
4. Substitution the string at uname nodename as described by sys utsname h most likely uname n the string returned by getlogin_r or cuserid most likely whoami the session ID of the xgemini process the ID of the xgemini process the ID of the xgemini parent process the MPI process rank in MPI_COMM_WORLD the number of MPI processes in MPI_COMM_WORLD the MPI process rank in MPI_COMM_HOST the number of MPI processes in MPI_COMM_HOST 95 10 3 Examples 10 3 1 Parallel finite differences with MPI automatic The two programs that are of primary concern in this exercise are xgemini and xp_aces2 Assume xgemini creates shared scratch directories WORKDIR gt 1s ZMAT GENBAS WORKDIR gt xgemini i s t local tmp smith GRANK WORKDIR gt ls F ZMAT GENBAS shared 00 shared 10 Before running xp_aces2 the user should determine if output tagging is available for parallel processes Without this the standard output stream of every process will be merged and it will be almost impossible to discern which task did what Furthermore since the operating system buffers I O streams the final lines of output might not contain the final answer IBM s parallel environment can tag each line with the global rank if labelio yes is used or if MP_LABELIO yes is set in the environment HP Compaq computers also have a tagging feature WORKDIR gt xp_aces2 labelio yes gt out WORKDIR gt grep 0 out
5. Using HFSTABILITY ON will perform a stability analysis after the two electron integral transformation and processing Use of HFSTABILITY ON is compatible with continuing on to correlated calculations in the same job Stability analysis is accomplished by forming the orbital rotation hessian and diagonalizing it The eigenvalues of this matrix and their associated eigenvectors indicate the number and type of instabilities present Each negative eigenvalue indicates an instability and their magnitude indicates the sever ity Analysis of the eigenvector corresponding to each instability reveals its nature The direct product of the symmetry irreps of the orbitals involved in the rotation determines the symmetry of the instability Only for instabilities whose direct product is the totally symmetric irrep irrep 1 will the wavefunction maintain the symmetry of the molecular 75 framework Any other result means the instability leads at least initially to a symmetry broken wavefunction In some cases symmetry breaking instabilities arise from the presence of lower energy electronic states different occupations and the rotation specified by the corresponding eigenvector will correspond to changing the occupation to relieve the instabil ity For an RHF wavefunction the UHF orbital rotation hessian is constructed which allows detection of instabilities in which the wavefunction would prefer to be UHF by comparison of the a and 0 spin eigenvect
6. 0 output from task 0 And finally WORKDIR gt xgemini x s WORKDIR gt ls ZMAT GENBAS out The user should not request more process elements than there are finite displacements If this happens then some instances of xjoda will see there are no displacements and bomb The surest way of checking this before submitting the job is by running xjoda on the input file The FD logic will print out a table like the following data from CH fully numerical vibrational frequencies in C4 96 VIBINF I Symmetries species for nuclear motions Irrep Label Total Vibrations Translations Rotations 1 A 15 00 9 00 3 00 3 00 Total number of calculations required 90 Number of single point energy calculations 90 Number of energy gradient calculations 0 For frequency calculations using numerical gradients the reference geometry is added to the set of displacements so the example above can be run with at most 91 process elements CH frequencies in C4 with analytical gradients or geometry optimization with numerical gradients can use at most 18 process elements 10 3 2 Parallel finite differences with scripts manual Running a set of calculations in parallel by hand i e without MPI is certainly doable and because the synchronization is handled through ASCII files the calculations can even be performed on different architectures however it is not pretty to coordinate and if the user is running an optimization with numerical
7. 99 11 Troubleshooting 11 1 Common mistakes The following tips should help users to detect and avoid errors For large calculations it is strongly recommended that users run with trial input files small basis set high convergence tolerances etc before running the actual system e The ACES2 namelist is not terminated properly If it begins with an open parenthesis then it must end with a close parenthesis otherwise it must end with a blank line Even if the namelist is terminated with a close parenthesis there must be a blank line after the namelist and the end of file mark e The BASIS SPECIAL option is used but the order of the basis sets does not corre spond to the order of atoms in the Z matrix The code does not check this and will not crash For example one is allowed to put a C basis set on a CL atom In fact ghost atoms would not be possible without this feature e All atomic symbols should be in upper case For example Cl has to be entered as CL Actually this is not true anymore but older versions of the code would simply give incorrect results If any user finds case sensitivity in the coordinate matrix parsing aces2 qtp ufl edu should be notified with the failing ZMAT e Lower case characters have been used instead of upper case This situation is difficult to pinpoint Most of the ACES2 namelist parsing is case insensitive along with the atomic symbols File directives in the header are st
8. BOFILL are the defaults for minimum energy and transition state searches respectively EVAL_HESS integer 0 Sets the cycle interval for recomputing the Hessian For correlated calculations the Hessian is evaluated only at the SCF level 67 8 1 25 Geometry optimization integral derivatives TRANS INV handle USE Specifies whether or not translational invariance is exploited in derivative calculations USE uses translational invariance while IGNORE does not 8 1 26 Frequencies and other 2 order properties VIBRATION handle NO Specifies the method for calculating vibrational frequencies EXACT SCF only performs normal mode analysis on an analytic force constant matrix and computes rotationally projected frequencies and infrared intensities FINDIF signals ACES II to compute the force constant matrix by finite difference of analytically computed gradients or energies using symmetry adapted mass weighted Cartesian coordinates RAMAN switch OFF Controls raman intensities and depolarization ratios of numerical vibrational frequency calculations VIB FINDIF The Raman intensities are limited to the SCF and CCSD level via EOM CCSD and as a result RAMAN keyword must be used in conjunction with CALC SCF or CALC CCSD We recommend setting EOMPROP QUADRATIC for raman intensities at the CCSD level NOTE This method requires an extra input file named frequency which is described in Section 6 page 2
9. By default all files used by ACES II JOBARC JAINDX 1111 MOINTS etc are kept in the directory in which the xaces2 program is invoked Any file except ZMAT may be relocated with FILE some absolute path to the FILE in which FILE is the name of the particular file For example if a user wants to calculate isotopic shifts after a vibrational frequency calculation it is useful to keep JOBARC and JAINDX in a safe place not in the current directory For water the following input could be used Line 1 Line 2 Line 3 Line 4 Line 5 Line 6 Line 7 Line 8 Line 9 Line 10 Line 11 Line 12 Line 13 Line 14 4 JOBARC u usr safe JOBARC 4 JAINDX u usr safe JAINDX RHF SCF vib freq calc for Water in DZP D 1 R 2R1A R 0 957 A 104 51 ACES2 VIB EXACT BASIS DZP After this job executes the files JOBARC and JAINDX are stored in the directory u usr safe Then the user can simply change to this directory create the appropriate ISOMASS file and run xjoda directly Coarse grain restart capabilities depend on a file named SAVEDIR The path variable is the full name of the directory to use for archiving Y SAVEDIR u home yau RESTART This MUST be unique for all jobs running simultaneously If multiple jobs are using the same save directory then they are clobbering each other s files and the last job to archive 28 its files is the one that wins The default action is to create a directory
10. For calculations involving more than one removal or addition of electrons values are separated by forward slashes and correspond one for one to the QRHF GENERAL value array For example specifying QRHF_GENERAL 2 4 and QRHF_ORBITAL 3 2 means that an electron will be added to the third lowest virtual in symmetry block 2 and another will be removed from the second highest oc cupied orbital in symmetry block 4 Examples in Sections 9 1 4 and pages 71 and further illustrate the QRHF input options QRHF SPIN string of 1D array Specifies the spins of QRHF occupations by overriding the remove from 8 and add to a behavior An element value of 1 means o spin and 2 means spin NOTE This option allows one to construct low spin determinants which generally are unsuitable for single reference coupled cluster calculations An important exception is the open shell singlet coupled cluster method REFERENCE TWODET UNO_REF switch OFF Controls the use of the new UNO reference state The ACES II calculation is initial ized by an open shell SCF calculation specified in the usual way either UHF or RHF The resulting a and 8 density matrices from the SCF calculation are then added into a spatial density matrix and this is diagonalized to yield unrestricted natural orbitals Pulay s UNOs These orbitals are used to create a new reference determinant The UNOs can be used in conjunction with QRHF and NEWVRT keywords to create more c
11. Sets the tolerance for storing transformed integrals Integrals less than 10 are ne glected and not stored on disk NTOP _ TAMP integer 15 Sets the N largest T amplitudes to print for each spin case and excitation level TAMP SUM integer 0 57 Sets how often the largest T amplitudes are printed 0 only prints amplitudes at the beginning and end of the run 1 prints amplitudes after every iteration 2 prints amplitudes after every other iteration etc DENSITY handle RELAXED Specifies whether the relaxed density matrix is computed for correlated wavefunctions RESPONSE skips the orbital relaxation terms that contribute to the density matrix This keyword should only be used by advanced users and ACES II developers who are testing new theories DOHBAR switch OFF Controls what action is taken by the linear response program ON calculates and saves the full effective Hamiltonian OFF solves the lambda linear response equa tions 8 1 15 Excited states general EXCITE handle NONE Specifies the type of excited state calculation to perform Available values are NONE TDA RPA EOMEE CIS CIS D P EOMEE EOM BWPT2 and STEOM This keyword needs a lot of attention ESTATE TOL tol 5 Sets the tolerance used in converging EOM CC excited state calculations The iterative diagonalization continues until the RMS residual falls below 107 ESTATE MAXC integer 20 Sets th
12. Take as a reference a closed shell configuration of the system with one less electron Specify EA SYM to obtain a number of roots of desired symmetry The excitation spectrum is then calculated The following example specifies the input for calculation of the excitation spectrum of MgF The two core orbitals are excluded from the correlation treatment Both CCSD and EA EOMCC 5 roots are found in symmetry block 1 and A symmetries 3 in block 2 II symmetry and one in block 4 80 MgF Excitation Spectrum MG F1R R 1 752 ACES2 REFERENCE RHF CALC CCSD BASIS TZ2P CHARGE 1 MULT 1 SPHERICAL ON DROPMO 1 2 EA_CALC EA_EOMCC EA_SYM 5 3 0 1 The calculation of high spin triplet states for systems with a closed shell ground state Take as a CC reference the high spin doublet ground state of the positive ion and add an extra alpha electron by specifying EA SYM e g EA SSYM 4 3 0 2 0 0 0 0 This yields high spin triplet excited states of the neutral In addition the closed shell ground state can be obtained by adding a beta electron to the proper symmetry block e g EA SYM 4 3 0 2 1 0 0 0 This has the advantage that the proper excitation energies of the system are tabulated by the program We note that singlet and low spin triplet excited state energies can also be obtained by adding a beta electron However such calculations do not yield satisfactory results due to spin contamination of the resulting EA EOMCC states
13. but UHF can do singlets and triplets using the N N N N notation like DEA SYM EE_SEARCH handle LOWEST Specifies the character of the states to calculate If EE SYM is not specified the program attempts to determine all states of the given character otherwise it uses the symmetry constraints imposed by EE SYM The values are LOWEST find the lowest energy roots regardless of character CORE find excitations from core orbitals using guess vectors from a projected TDA matrix LUMO find excitations to the LUMO and HOMO find excitations to the HOMO ESTATE SYM string of 1D array 0 Specifies the number of excited states which are to be determined in each irreducible representation of the computational subgroup The program attempts to find all of the lowest roots but this is not guaranteed since the eigenvalue problem is not solved by direct matrix diagonalization rather by an iterative modified Davidson algorithm For excited state gradient calculations TDA only only one root can be specified so only one non zero entry in the string is allowed and that entry must be set to one The format used for this keyword is identical to that used in the OCCUPATION keyword For example for a computational subgroup having four symmetry species the string 61 ESTATE_SYM 3 1 0 2 specifies that 6 total roots should be searched for three in the first block one in the second block and two in the fourth block This keyword
14. simply runs a harmonic frequency calculation at the desired level of theory and saves the file named FCMINT This formatted file contains the full internal coordinate force constant matrix When xjoda performs a geometry optimization it checks the active working area for the presence of FCMINT no special keywords or commands are needed to do this If the file exists xjoda uses those force constants to initialize the Hessian matrix While the geometry and even the point group symmetry specified by ZMAT in the har monic frequency calculation need not be the same as that used in the first step of the geometry optimization the Z matrix connectivity must be identical If one attempts to use an entirely different Z matrix then the definitions of internal coordinates are no longer the same and chaos may ensue While this point may seem to be unimportant this situation occurs relatively frequently Suppose the equilibrium geometry for a transition state is as sumed to be planar and the user attempts to locate a stationary point However when the harmonic frequencies are calculated two modes are found to have imaginary frequencies an a mode in plane and an a mode with the a mode corresponding approximately to the reaction coordinate of interest As a result the true transition state geometry does not contain a plane of symmetry and another search must be performed in a reduced symmetry To this end it would certainly be useful to use F
15. the orbitals obtained in the reference function calculation without modification and SEMICANONICAL forces a transformation to semicanonical orbitals PERT ORB handle UNKNOWN 48 Specifies whether the gradient formulation assumes that the perturbed orbitals are not those in which the Fock matrix is diagonal STANDARD CANONICAL means that the perturbed orbitals are assumed to be canonical This keyword must be set to CANONICAL in gradient calculations with methods that include triple excitations i e MBPT 4 CCSD T CCSD T and QCISD T 8 1 9 SCF general SCF TYPE handle HF Switches the SCF code between the standard Hartree Fock program HF and the Kohn Sham DFT program KS If SCF_TYPE KS then the KS DFT program gen erates the SCF reference and requires separate namelists viz VSCF and INTGRT FOCK handle PK Specifies the algorithm for constructing the Fock matrix in SCF calculations PK uses the PK supermatrix approach while AO constructs the matrix directly from the AO integrals In general PK is faster but results in considerable use of disk space when out of core algorithms are required CHECK SYM handle OVERRIDE Specifies the action taken when the density matrix does not transform as the totally symmetric irreducible representation of the full molecular point group NORMAL terminates the run if the molecule is nonlinear while OVERRIDE allows the job to continue but prints a warni
16. 108 e T H Dunning Jr and P J Hay in Methods of Electronic Structure Theory edited by H F Schaefer III Plenum New York 1977 6s4p contractions of 11s7p for AlCl Cl basis contains typographical errors see Craven et al Chem Phys Lett 116 119 1985 VDZP basis set for first row elements diffuse and Rydberg functions recom mended polarization exponents from SCF calculations e T H Dunning Jr J Chem Phys 90 1007 1989 PVDZ PVQZ R A Kendall T H Dunning Jr and R J Harrison J Chem Phys 96 6796 1992 diffuse functions for PVDZ to PVQZ D E Woon and T H Dunning Jr J Chem Phys 98 1358 1993 PV5Z and diffuse functions for PV5Z methodology of the correlation consistent sets but does not include the actual sets these must be obtained directly from Dunning via FTP Atomic natural orbital basis sets of Roos and coworkers WMR e P O Widmark P A Malmqvist and B O Roos Theor Chim Acta 77 291 1990 e P O Widmark B J Persson and B O Roos Theor Chim Acta 79 419 1991 Polarized basis sets of Sadlej and coworkers e A J Sadlej Collec Czech Chem Commun 53 1995 1988 e A J Sadlej and M Urban J Mol Struct THEOCHEM 234 147 1991 e A J Sadlej Theor Chim Acta 79 123 1991 e A J Sadlej Theor Chim Acta 81 45 1992 e A J Sadlej Theor Chim Acta 81 339 1992 Basis sets optimized by Ahlrichs and coworkers e A Schafer H Horn and R Ahlrichs J
17. 1st order grid alias loop lastener for numerical gradients 2nd order grid test n 1 amp amp procs 1 procs 1 test procs lt 1 amp amp exit 1 97 alias xj xjoda rank rank procs procs if true Hartree Fock alias scf xvscf alias dint xvdint else DFT alias scf xvscf_ks amp amp xintgrt alias dint xvdint amp amp xvksdint fi function lastener lastgeom 0 while test lastgeom eq 0 do xa2proc rmfiles xj amp amp xvmol amp amp xvmol2ja amp amp scf return 1 xvtran amp amp xintprc amp amp xvcc return 1 lastgeom xa2proc jareq i LASTGEOM 1 tail 1 done function lastgrad lastgeom 0 while test lastgeom eq 0 do xa2proc rmfiles xj amp amp xvmol amp amp xvmol2ja amp amp scf return 1 xvtran amp amp xintprc amp amp xvcc amp amp xlambda return 1 xdens amp amp xanti amp amp xbcktrn return 1 dint return 1 lastgeom xa2proc jareq i LASTGEOM 1 tail 1 done function lastraman lastgeom 0 while test lastgeom eq 0 do xa2proc rmfiles xj amp amp xvmol amp amp xvmol2ja amp amp xvprops amp amp scf return 1 xvtran amp amp xintprc amp amp xvcc amp amp xlambda return 1 xdens amp amp xanti amp amp xbcktrn return 1 dint amp amp xcphf return 1 lastgeom xa2proc jareq i LASTGEOM 1 tail 1 done clear out old FD data rm rf shared fd out rank pro
18. 2 A 1 TO H 3 RHT 13 A 2 T H 4 RHT 14 A 2 T R1 1 207 R 1 05183 RX 0 08546 RHX 1 48313 RHT 0 569 A 90 T 180 T60 60 T12 120 TO 0 TM2 120 TM6 60 ACES2 BASIS DZP CALC 1 OPT_METHOD MANR EVAL_HESS 3 MAX_STEP 750 CONV 5 This ZMAT file specifies a geometry optimization for the D3q isomer of beryllium boro hydride BeB2H3 Compared with the water example above which uses defaults for the optimization keywords this optimization input adds some features The MANR optimiza tion algorithm is used The SCF Hessian will be reevaluated every three cycles and the maximum step length is set to 750 millibohr The convergence criterion CONV is set to 5 which means the optimization will continue until the root mean square force is below 1075 rather than the default of 1074 atomic units An MBPT 2 calculation is specified by the CALC keyword This has been specified using the number corresponding to MBPT 2 al though our recommendation is to use the name The default values for CHARGE MULT REF and OCCUPATION are used The geometry optimization request automatically turns on the necessary gradient options 9 2 3 Full optimization of Cartesian coordinates RIC H2 geom opt H 0 0 O H 0 0 0 5 ACES2 basis DZP geom_opt full This feature is controlled by the GEOM_OPT keyword The RIC analysis includes in formation about atomic radii If the input geometry is far from equilibrium then the bond analy
19. 5 27 4 rmfiles The RMFILES module will delete the five list storage files MOINTS GAMLAM MOABCD DERINT and DERGAM More importantly it will reset the appropriate pointers and counters so the next AME that attempts to initialize the I O subsystem will not crash 5 27 5 parfd The PARFD module is used to export and import finite difference information It was created as a proof of concept program to demonstrate JODA s ability to operate in a parallel finite difference calculation Its main capabilities are incrementing the displacement data parfd update dumping the data to standard output parfd dump and importing data from other calculations parfd load file An example of manual parallel finite differences can be found in Section 10 3 2 page 97 5 27 6 molden and hyperchem These modules create Molden and HyperChem input files respectively that contain geometry wavefunction and vibrational frequency information 5 27 7 jasum and iosum These modules print summary information of the JOBARC records and storage lists re spectively 5 27 8 jarec JAREC and its quiet variant JAREQ will show the formatted contents of a JOBARC record It requires three arguments data type record name case sensitive and dimensions Data types can be i integer d double f float r real ad array of doubles and ai array of integers The first four types are all one dimensional vectors and ad and ai are two dimensional arrays F
20. Chem Phys 86 7041 1987 e G E Scuseria and H F Schaefer Chem Phys Lett 152 382 1988 103 e J D Watts and R J Bartlett J Chem Phys 93 6104 1990 e J D Watts and R J Bartlett Int J Quant Chem Symp 27 51 1993 h ROHF and QRHF CC methods e M Rittby and R J Bartlett J Phys Chem 92 3033 1988 i Brueckner CC methods e R A Chiles and C E Dykstra J Chem Phys 74 4544 1981 e J F Stanton J Gauss and R J Bartlett J Chem Phys 97 5554 1992 j QCISD and QCISD T methods e J A Pople M Head Gordon and K Raghavachari J Chem Phys 87 5968 1987 k UCC methods e J D Watts G W Trucks and R J Bartlett Chem Phys Lett 157 359 1989 1 CCSD TQ CCSD CCSD TQ and QCISD TQ methods e R J Bartlett J D Watts S A Kucharski and J Noga Chem Phys Lett 165 513 1990 e K Raghavachari J A Pople E S Replogle and M Head Gordon J Phys Chem 94 5579 1990 m Two determinant CCSD method e A Balkova and R J Bartlett Chem Phys Lett 193 364 1992 12 3 Analytical gradients for MBPT CC methods Review article e R J Bartlett J F Stanton and J D Watts in Advances in Molecular Vibrations and Collision Dynamics Vol 1 ed J Bowman JAI Press p 139 1991 e J Gauss and D Cremer Adv Quant Chem 23 205 1992 a General MBPT CC gradient theory 104 e E A Salter G W Trucks and R J Bartlett J Chem Phys 90 1752 1989 b Imple
21. HF SCF gradient using the GAMESS direct integral derivative package and xp_scfgrd does this in parallel 5 24 cphf xcphf solves the coupled perturbed Hartree Fock equations either for geometric displace ments or for electric or magnetic field components as perturbations 5 25 nmr xnmr calculates the paramagnetic contribution to NMR chemical shifts at correlated levels 18 5 26 asv An ACES State Variable ASV is a runtime variable that controls the calculation and users can affect ASV initialization with keywords in the ACES2 namelist xasv is not a member executable that other AMEs use but rather a tool for the user to examine the validity of keyword value pairs For example if a user wants to check if CALC LCCD is valid then the user would have to create a valid ZMAT file and run xjoda to guarantee it passes keyword parsing Alternatively the user can run xasv CALC LCCD at the shell prompt without the hassle of managing files 5 27 a2proc This program was initially created to reduce the clutter of member executables in the ACES II program system Its two main purposes are to gather many small single use programs and to provide interfaces to external programs like Molden and HyperChem xa2proc help will show the list of available modules and the arguments that each one expects 5 27 1 clrdirty During an optimization or frequency calculation with RESTART ON the default the ACES II file set is tagg
22. LGUESS These files store the coupled cluster T and A amplitudes respectively for restart pur poses 6 10 10 VPOUT This file contains the first order property integrals 6 10 11 GAMESS LOG MP2 LOG DIRGRD LOG All of these files are generated by the GAMESS interface in VSCF DIRMP2 and SCFGRD They are strictly log files and might contain error messages if a program crashes 24 6 10 12 0UT 000 DUMP 000 1ELGRAD 000 All of these files are generated by the GAMESS interface in VSCF DIRMP2 and SCFGRD and are tagged with the MPI rank of each process They are strictly output files and might contain error messages if a program crashes 25 7 File Formats 7 1 ZMAT 7 1 1 File anatomy This specification pertains to a particular version of JODA Older versions might require more rigid input formats but the general structure of ZMAT should never change Every line in ZMAT can be at most 80 characters long The parser does not check the length of each line therefore there are no guarantees that the rules of ZMAT parsing will apply once the line length has been exceeded 1 Header Three types of lines are allowed in the header e blank space consisting of spaces and or tabs e comments first non blank character is a hash mark e file directives first non blank character is a percent sign The header can have an arbitrary number of lines but the first line that does not qualify as one of these three will be rea
23. LMAX 2 d 10 00000000 1 511 9951763 72 55482820 2 93 2801074 12 74502310 2 23 2206669 s d 3 00000000 O 173 1180854 23 83518250 1 185 2419886 473 89304880 2 73 1517847 157 63458230 2 14 6884157 p d 5 00000000 O 100 7191369 6 49909360 1 130 8345665 351 46053950 2 53 8683720 85 50160360 2 14 0989469 CU ECP 18 SK ECP BY STEVENS KRAUSS FOR CU 18 CORE ELECTRONS LMAX 3 NCORE 18 LMAX 3 18 00000000 1 359 2137111 119 92593970 2 67 5347369 29 55328670 2 14 7222923 10 28924330 2 3 9975558 78363630 2 1 1889410 s f 3 00000000 0 19 6202650 20 15792750 1 5 1604389 34 50019060 2 1 2306099 18 98120030 2 1 0850105 p f 5 00000000 0 31 9385762 20 60853280 1 14 9202125 56 00168880 2 15 6835232 57 21701070 2 4 9311614 7 71778780 2 1 0622167 d f 25986160 2 5 1159991 46216800 2 1396784 The first line contains a single star The name of the data group starts with the element symbol followed by the ECP nickname It is useful to give a comment introduced by the 39 hash symbol in the next line to indicate the origin of the ECP The actual ECP data is given in between two lines with a x The first line specifies the number of core electrons described by the ECP NCORE and the maximum angular momentum number of the projector operators LMAX in integers s 0 p 1 d 2 These are followed by the description of the effective core potential which consists of the angular momentum numbe
24. The following input yields triplet excited states for the beryllium atom The SCF calculation is on the closed shell neutral system while the QRHF option is used to create the positive Be ion BE Atom Excitation spectrum QRHF Reference BE ACES2 REFERENCE RHF CALC CCSD BASIS SPECIAL SPHERICAL ON QRHF_G 1 EA_CALC EA_EOMCC EA_SYM 8 4 0 4 0 0 0 0 0 0 0 0 0 0 0 0 BE WMR WARNING In all EOMCC calculations it is highly recommended that the reference state transforms according to a one dimensional representation of the true molecular point group Otherwise the likely outcome is inaccurate results which in addition are very hard to interpret due to a breaking of the symmetry in such a calculation 9 1 13 NMR chemical shifts NMR spectroscopy is a very important analytical tool for the identification and charac terization of molecules However since there is no simple correlation between the measured chemical shifts and structural parameters the interpretation of experimental NMR spectra is not trivial and can be in many cases quite involved The ability to calculate NMR chem ical shifts ab initio is therefore a very important advancement in quantum chemistry The 81 calculation of chemical shifts can provide in many cases the necessary information for the correct interpretation of experimental NMR spectra Therefore methods for the computa tion of NMR chemical shifts at SCF and correlated levels currently limite
25. VEE obo Gl oS asa S ak a dig SUS Oe a ES SR 17 SS 4 2 a Sot S G aed asas SA gh ho oe work we oon a a 17 Del E DENS i heb s kaqa b Se ke ARS dene AAG i ott tle a a aes a 17 0 20 PROP S12 46 8 N a es ged ty uama eet Soca ea kata Me na Aa ay 2 18 DL ANTE t Cela L toe oS te RAT tea AB Se hk GAD eh AA ae ited ed 18 H22 BOKTRN o Ae ae E ae ak aT sig SU eo E E R RTE La 18 5 23 VDINT VKSDINT SCFGRD and PSCFGRD 00 0008 5 18 A L A oy Q A E AE S a A A A A AN oe 2 18 DDO NDR i ee o Mies Rote ce pi at Soe ae Go at ve ae aaa se ed ee oe See e 18 OLOT AS Ves cy tite Sed oy tee he et One re OE ne ee nee 25 ee oh 5 19 D 2 t ADPROO ch OMe S Seat Bo a Nae cy se a S St oe ae Q T Q en eA eo Pad ta 19 Oda JOLRDIRD 2 poets fonts heh So ak Meio Gerke de oe Ges Was areas 19 dile de MEN ITO 19 Iko r ZB RORECOS at di tod A A DO 53 2 Q iY S 5 20 D2 AW IRMBTLES 32 tt sl sa Qn 20 O22 eo PARED n uy s t Ste tee sas le fount hol tien t ut Ate Gt amp 20 5 27 6 MOLDEN and HYPERCHEM 4 422 4 e eee Be ae ee 20 52C JASUM and I SUM o aa a he A Be Be BRS Bnd 20 9 2138 JAREC t u l US et SS ke a Ais AI Sodas A AS 2 aym ud E 20 AS AMAR 21 AT a de A A AS ek BORG SUS O RAS 21 0 29 GEMINIS N a ies a ce oe e hr 21 File Structure 22 Galo ANMAT 2280 O50 E bre ta ted So matt dec ci a A ee a u 22 6 2 GENBAS ZMAT BAS 2 22 09 ECPDATA u a Y Saa kes se Al K Tal A yT a TTT 22 0AF GUESS Sua
26. also includes 6s4p contractions by Dunning and Hay of Huzinaga s 11s7p primitive set for Al Si P S and Cl The published data for Cl are erroneous having at least two typographical errors see W Craven et al Chem Phys Lett 116 119 1985 It is not clear if these are the only errors This the D95 set augmented with a set of polarization exponents of uncertain origin Entries are available for H B F and Al Cl The polarization exponents for the first row elements appear to be those recommended by Dunning and Hay while the source of the second row d exponents is uncertain The exponents are H 1 0 B 0 7 C 0 75 N 0 8 O 0 85 F 0 9 Al 0 25 Si 0 3247 P 0 37 S 0 532 Cl 0 6 TZ2P For first row elements this set comprises Dunning s 5s3p contraction of Huzinaga s 10s6p primitive set augmented with two optimized d p for H functions in a 2 1 contraction of three primitives Entries are available for H B F The F basis is not optimized There is also an entry for Cl under this name This is based on a McLean and Chandler sp set PVDZ Dunning s polarized valence double zeta correlation consistent basis set In terms of contracted functions this set is 3s2pld for second row atoms with one fewer shell of each angular momentum for H and He and one extra shell plus an f function for Na Cl These and the PVTZ and PVQZ sets are hybrids between segmented and generally contracted sets All of these sets ap
27. coordinates 2 ow a oe Bee ee Bo Be eo bk 30 7 1 7 Internal coordinates _ A oe eS EIR SAM 31 7 1 8 Z matrix A Ee a e ee sa ee ee ee os e 33 EOS FACES HRGS a toe a pusa oh a oh wie o a wedded 34 7 1 10 Line item basis ECP definitions 2 0 ed r 37 a GENBAS AMAT BAS os foie bt ors Le tnd eke Sah u A sites ke Sage la 37 Go ECPDATA can a 5 accused A A ho es Sat ht gk a sak ol 39 AS GUESS ei Os a xz An S a eA Il e el e els 40 8 Keywords 42 3 1 SPACES namelist detras wit 2866 2 AA Oe Q NC A y u e ee 42 Sl Systemi genetal es i gras ve RS AA a 43 8 1 2 System molecular control ew eke a 44 Ss Syster debug x u Ar etek Ns ep iP et de Min Pel Oud nd Cn Sua 45 RIA O subsystem uu vat et a a mau mis PR dd ee ee aed 45 81 5 Chemieal system ay ita te te ies a are ait ba ua ght buenas ce beg eked 46 O ASIA ug ua ae ee ete o as A ee Bh ne i od 46 Ber neers cs Sire A Mace s A ee 4 47 Sd Reference ti ngs ua Sub Ae na os aa de ie NE a NY S ee Ge Sr 48 Bal HOOPS general r gas aes ain ee ee ee Sus roel oh als 49 8 1 10 SCR Orbital control 2 2 ar eo a k ss Eo Ee Ye eS 49 8 1 11 SCF iteration control is se Sete ae tee le ph eels 51 8 1 12 SCF reference adjustments 2 24 ew Go eee GS ee Bot dos 52 8 1 13 Post SCF file options cos RE AA 55 8 1 14 Post SCF calculations up yh Gok Agee Geet Akos Se eee ra ey s as 57 8 1 15 Excited states general ais ate ew ude eo a a r Ei 58 8 1 16 Excited states p
28. driver program for other batch based member executables such as xjoda xvscf and xvcc Since xaces2 uses the system function to run these programs the executable path must be set by the user s regular shell environment For example if xaces2 does not appear in the default login environment then running xaces2 directly will likely result in error since the first attempt to run xjoda will fail with xjoda not found The ACES II program system uses many storage files and the developers initially rec ommend running the program in a directory that contains only ZMAT and GENBAS As expe rience with the program increases users will become comfortable with naming files that do not conflict with those used by ACES II gt ls GENBAS gt cat lt lt EOF gt ZMAT H2 H H1R R 0 7356 ACES2 BASIS DZP CALC SCF EOF gt xaces2 gt out The file named out now contains the RHF SCF results of H gt in the DZD basis set provided GENBAS contains the DZP basis set for H Since SCF is the default calculation level the CALC keyword is not necessary The minimum requirements for ZMAT are 1 line title molecular system in internal or Cartesian coordinates blank line ACES2 namelist declaring a basis set to use blank line For more information on ZMAT GENBAS and most of the other files used and created by ACES II Section 6 page 22 describes the overall list of files used by the program and Section 7 page 26 shows the inp
29. g iga The scaling factor is 1024 not 1000 Doubles are not used currently even though we have this capability there are no key words with values of this type Examples would be doublel 1 double2 2 d0 double3 3 5e 6 Version 2 3 introduced environment variable awareness for keyword values It is now possible to enter a value as VARNAME and have xjoda pull the value from the shell environment The most practical application of this would be to loop over variables in a shell script that define various keywords Here is an example 36 gt cat lt lt EOF gt ZMAT envvar test job H H1R R 0 7 ACES2 calc CALC basis BASIS EOF gt for CALC in scf ccsd gt do export CALC for BASIS in DZP TZP TZ2P do export BASIS clean or other cleaning script xaces2 gt CALC BASIS out done N N N N N 7 1 10 Line item basis ECP definitions If the BASIS keyword is set to SPECIAL the default then the basis set specification will be read directly after the ACES2 keyword list One blank line must separate the last line of the keyword list from the beginning of the basis set input section Each entry must be placed on an individual line and the ordering of atoms must follow the Z matrix ordering exactly The names will then be used to find the definitions in the basis set file either GENBAS or ZMAT BAS in the current directory If a basis set is not found ACES II exits with an error cond
30. in the yz plane In this example the y axis in the Ca frame should be the z axis in the C frame so SUBGRPAXIS Z When the true Abelian subgroup is either C2 or D n the orientation is not well defined and it might be necessary to run xjoda twice If SUBGROUP 0 in the first pass then the reference orientation for the true Abelian subgroup can be determined and the appropriate value of SUBGRPAXIS can be selected NOREORI switch OFF Forces the program not to change the internal orientation of the molecule specified by the input Cartesian coordinates To function correctly this keyword also requires turning off symmetry SYMMETRY 0FPF 8 1 3 System debug PRINT integer 0 Controls the amount of printing in all member executables except JODA A value of 1 will produce a modest amount of additional output over the default value which includes some useful information such as SCF eigenvectors JODA PRINT integer 0 Controls the amount of debug printing performed by JODA The higher the value the more information is printed Values of 25 or higher generally do not produce anything of interest to the general user and values greater than 999 will dump the core vector to disk 8 1 4 I O subsystem FILE RECSIZ special 1W Sets the length of the physical records used in direct access file I O This value should always be chosen as a multiple of 512 bytes and is parsed like the MEMORY_SIZE key word The default value 1 de
31. is the same as EE_S YM but EE_SYM is read when PROGRAM ACES3 and ESTATE_SYM is read when PROGRAM ACES2 8 1 19 Excited states ionizations IP_CALC handle NONE Specifies the method for calculating ionization potentials of the closed shell parent state The values are NONE MBPT 2 strict second order perturbation the ory SO_DYSON second order Green s Function iterating the MBPT 2 formula OVGF P_EOMIP partitioned IP EOM the 2h1p 2h1p block is treated as diago nal IP_EOMCC H bar is diagonalized over 1h and 2h1p configurations COMBO and OS_CCSD a state selective multireference CC method in which both orbitals and cluster amplitudes are optimized for the final ionized state of interest This last method requires additional input in the mrcc_gen namelist Analytical gradients are available for IP EOMCC and P EOMIP and require additional input though the mrcc_gen namelist Properties and transition properties of the IP states can be re quested by additional input in MRCC namelists ip_calc section IP SYM string of 1D array 0 Specifies the number of states to calculate by an IP calculation A string e g 4 2 2 0 has to be provided that indicates the number of doublet states in each symmetry block The example string requests 4 doublet states of Al symmetry 2 doublet states in symmetry blocks 2 and 3 and 0 in block 4 The number of IP states to be calculated can also be specified by listing an energ
32. named SAVEDIR in the run directory 7 1 4 Molecular orientation The orientation of the molecule in Cartesian space is related to its point group Two orientations are used extensively in the ACES II program system the standard or com putational orientation which is a standard orientation for the computational point group and a canonical orientation which is the standard orientation for the full point group Note that in some cases the two orientations are identical All calculations are performed in the computational orientation therefore orbital symmetries should be specified according to this Cartesian axis system For the most part the canonical orientation is used internally for tasks such as determining irreducible representations or other properties related to the full point group The standard orientation for each point group follows Cy Rotation axis along z Dy Rotation axes coincident with Cartesian axes and the highest order axis along z C Plane of symmetry is xy Sy Sy axis along z Cno Cy axis along z TZ is dy Cnn Cy axis along z ry is On Dyar Cy axis along z one Cy axis along z Dna Say axis along z one Ca along z T Ca axis along q g q Ta Sa axis along z Ta Ca axis along q q q symmetry planes are xy zz and yz O C axes along x y and z On C4 axes along x y and z I Cs axis along z one C3 lies in the xz plane In Cs axis along z zz is a symmetry
33. of what the program will do Either the keyword controls experimental pathways through the program or the program uses considerable logic to determine the correct default behavior These keywords are listed in ztalics instead of bold Value Conventions Value strings are parsed differently depending on how the corresponding keyword is de fined in JODA Currently there are handles strings integers and reals For clarity this manual also mentions switches and tols tolerances A switch is a handle with only two values ON OFF and a tol is an integer N that corresponds to a value of 10 In ACES II handles are character strings that map onto integers For example the CALC keyword has 41 possible values The code might do one thing if CALC 0 SCF and another if CALC 10 CCSD Keywords of type handle can accept the handle string or the integer as a value so CALC CCSD does the same thing as CALC 10 in the namelist Ultimately the internal integer is irrelevant to the user and could change any time therefore all keywords are described according to their handles only Some keywords only recognize switch like handles TRUE FALSE ON OFF 1 0 etc and are listed as type switch If these keywords appear in the namelist without a value string then they will be set to ON Similarly they can be negated by prefixing them with an exclamation mark For example ACES2 RESTART NONHF will register as RESTART ON 42 and NONHF OFF Keywords
34. parallel run then it is likely that the user would see the following WORKDIR directory listing ZMAT GENBAS compnode0 0 compnodel1 1 compnode2 2 Each compnodeX X is a symbolic link that points to local tmp smithdir and inside each of those local directories are symbolic links back to ZMAT and GENBAS The i flag is what instructs xgemini to create the directories and links It is usually the case that if local directory partitions are available then performing I O on them will yield better performance than reading and writing to a partition over the network The downside is that if a parallel job is stopped and needs to be restarted then the user must tell the parallel job scheduler like LoadLeveler or PBS to run the new job on the same nodes that the previous job ran on simply because those are the nodes with the data 93 10 2 2 Shared scratch directories If a global file system like GPFS or even NFS is used for the scratch directories then a task on any node can get to any other scratch directory Assume user smith can cre ate directories in global tmp Reusing the previous xgemini command line with lo cal changed to global will not work because every parallel task will attempt to create global tmp smithdir One task will succeed but all of the others will fail and crash GEMINI has a rich set of pattern macros for this kind of customization but the simplest command to use for the job would be xgemini i s
35. refer ence for open shell singlet CC calculations is available but the orbitals are obtained from a closed shell state and are not optimum open shell singlet or low spin triplet SCF orbitals The orbital occupancy for subsequent CCSD calculations is specified by the various QRHF keywords NONHE switch OFF Signals the correlation energy code if the reference wavefunction satisfies the Hartree Fock equations Fa 0 Usually there is no need to set this keyword since standard non HF reference functions QRHF and ROHF set this flag internally however if you input a set of orbitals to the correlation energy code directly then it might be necessary to set NONHF ON ORBITALS handle 1 Specifies semicanonical orbitals Fiz Fiz 0 in non HF calculations Semi canonical orbitals are obtained by diagonalizing the occupied occupied 77 and virtual virtual ab blocks of the spin orbital Fock matrix and can be advantageously exploited in certain post SCF calculations This is particularly true for ROHF MBPT and non iterative triple excitation corrections There is no default value for this parameter and considerable logic is used to determine the orbital type in post SCF non HF cal culations if the keyword is not defined It is strongly recommended that this key word not be used by anyone who is not thoroughly familiar with non HF CC MBPT methods since the logic used to set the default value is sound STANDARD uses
36. separated by forward slashes and be positive or parenthesized negative The absolute value of each element specifies the symmetry block involved in the addition or removal of electrons The numerical ordering of the symmetry blocks is consistent with then OCCUPATION keyword the symmetries of the integrals By default the electrons of each irrep are added to the lowest unoccupied o orbital in the symmetry block and removed from the highest occupied orbital Different orbitals and spins can be specified with the QRHF_ORBITAL and QRHF_SPIN keywords 53 NOTE Gradients and property calculations are currently available only for cases in volving addition or removal of electrons Mixed cases involving both processes are not available Gradients and properties are available for open shell singlet CCSD wave functions for the case that the open shell orbitals have different symmetries QRHF_ORBITAL string of 1D array 1 By default in QRHF calculations electrons are removed from the highest occupied 0 orbital in a symmetry block symmetry block HOMO while electrons are added to the lowest unoccupied a orbital within a symmetry block symmetry block LUMO The purpose of the QRHF_ORBITAL keyword is to allow additional flexibility in choosing which orbitals will have their occupation numbers altered The value of this keyword gives the index with respect to the default orbital for the orbital which will be popu lated or depopulated
37. solutions will be considered It is important to understand that following non symmetric eigenvectors lowers the symmetry of the wavefunction and that following RHF UHF stabilities leads to a UHF solution To converge the SCF roots associated with such instabilities one must run the calculation in reduced symmetry and as a closed shell UHF case respectively If not set to 0 the program follows the vector with the N lowest eigenvalue having the proper symmetry totally symmetric and spin RHF RHF or UHF UHF properties BRUECKNER switch OFF Controls whether Brueckner orbitals are to be determined for the specified CC method BRUCK_CONV tol 4 Sets the convergence criterion in Brueckner iterations The calculation is considered converged when the largest single excitation amplitude falls below 1077 QRHF_GENERAL string of 1D array 0 The presence of this keyword turns on QRHF logic and the value of each element specifies which irrep is created positive or annihilated negative In the QRHF scheme an RHF closed shell SCF calculation is performed with the OCCUPATION keyword or the CHARGE and MULTIPLICITY keywords The correlated calculation is then performed on an open shell reference generated from this closed shell state by removing adding or exciting electrons Any number of electrons may be added and all of the electrons may be removed from the SCF reference The array elements associated with this keyword must be
38. t global tmp smithdir GRANK Each task will replace the string AGRANKO will its global rank an integer from 0 to N 1 where N is the number of parallel tasks Creating scratch directories in global allows all nodes in the computer to see all scratch directories but the symbolic links in WORKDIR will still be named compnodeX Y unless the s flag is used If a parallel job is restarted process 0 might be running on compnode2 and it would expect to see compnode2 0 in WORKDIR However if the previous run had process 0 running on compnode0 then it would have created compnode0 0 and the restarted job will crash With s the symbolic links in WORKDIR are named shared rank so it does not matter which actual node created the scratch directory or the link to it If shared links are used then every call to zgemini must use the s flag The downside to remote scratch directories is that performance might decrease with high network traffic although this is highly dependent on the hardware architecture and runtime load Some users might feel more comfortable limiting all activity to WORKDIR In this case the scratch directory pattern can be the same as the symbolic link For example xgemini i s t shared GRANK will create directories instead of symbolic links in WORKDIR The parallel AMEs will not know the difference when they attempt to cd into the scratch directory 10 2 3 Command line flags and pattern macros As previously
39. the behavior if negative eigenvalues are encountered in the totally symmetric Hessian during an NR or MANR search If NEGEVAL ABORT then the job will terminate with an error message If NEGEVAL ABSVAL then the program will just switch the eigenvalue to its absolute value and keep plugging away this is strongly discouraged If NEGEVAL RFA then OPT_METHOD is switched to RFA internally and the optimization is continued 8 1 24 Geometry optimization iteration control CONVERGENCE tol 4 Sets the convergence criterion for geometry optimizations The optimization terminates when the RMS gradient is below 107 Hartree Bohr OPT MAXCYC integer 50 Sets the maximum number of optimization cycles INIT_HESSIAN handle SPECIAL Specifies the initial Hessian for geometry optimizations SPECIAL generates an approximate Hessian internally FCMINT imports an approximate Hessian from the FCMINT file MOPAC generates the FCMINT file by running MOPAC and EXACT uses analytical second derivatives to generate an exact Hessian limited to SCF HESS_UPDATE handle POWELL or BOFILL Specifies the algorithm used to update the Hessian NONE uses the same Hessian throughout the optimization POWELL uses the Powell update BFGS uses the Broyden Fletcher Goldfarb Shanno update MS uses the Murtagh Sargent update BOFILL uses the Bofill mixture of Powell and Murtagh Saregent and PSB uses the Powell symmetric Broyden update POWELL and
40. the known types are handle string long integer and double Handles are strings that map to an integer An example of this is the CALC state variable When the parser reads CALC SCF it scans the CALC lookup table for the case insensitive string that matches SCF Upon finding a match the value of CALC is set to the offset of SCF in the table In this case CALC is set to 0 zero since SCF is 34 the first element Alternatively the namelist could have read CALC 0 and the effect would be the same Some keys take switch values ON and OFF For these cases the keyword may be specified without a value and the parser will assume the value is ON Similarly the negation operator may be used to turn the value to OFF An example is sym ecp meaning SYM 0N ECP 0FF Strings are character arrays that are treated differently depending on the keyword they define There are two types plain text strings and array strings plain text strings are only used by the BASIS keyword currently The exact case sensitive value string is used to find the basis set definition in GENBAS array strings matrices are used by the keywords OCCUPATION IP SYM EA_SYM etc They are loosely defined as irrep by spin This means the parser expects to find spin columns of nirrep rows The row delimiter is a dash and the column delimiter is a forward slash Here are some examples e 4 irreps 2 s
41. the water molecule with the DZP basis set This input is particularly simple since all of the keywords default to the closed shell singlet state of the neutral molecule In other words CHARGE 0 MULTIPLICITY 1 and REFERENCE RHF can all be omitted The OCCUPATION string is not specified which means the program will determine this itself By default all electrons are correlated 9 1 2 UHF CCSD T energy H20 UHF CCSD T energy calculation DZP basis set H D 1 ROH H 2 ROH 1 HOH ROH 0 95 HOH 104 5 ACES2 REF UHF CALC CCSD T OCCUPATION 3 1 1 0 2 1 1 0 H DZ 0 DZP H DZ This illustrates a single point CCSD T energy calculation on the 7A state of the water cation with a special basis set For this system one cannot rely on the defaults that were used in the previous example It is necessary to specify REFERENCE and either OCCU PATION or both CHARGE and MULTIPLICITY Since we want a particular state we use the OCCUPATION keyword The ACES2 namelist is valid even without the initial and final parentheses however if an open parenthesis is used to start the namelist then it must terminate with a close parenthesis 70 9 1 3 ROHF CCSD T energy H20 ROHF CCSD T energy calculation DZP basis set H D 1 ROH H 2 ROH 1 HOH ROH 0 95 HOH 104 5 ACES2 REF ROHF CALC CCSD T BASIS DZP OCCUPATION 3 1 1 0 2 1 1 0 This is essentially identical to the previous example The difference is that the user requests a
42. tives of the energy Except for EOMCC calculations on two electron systems which are exact proper ties obtained by the three approaches will not be equivalent The default value for this keyword is slightly complicated For TDA calculations the default is EXPEC TATION since the evaluation of transition moments involves only a negligible amount of additional computation relative to the evaluation of the excitation energies For EOMCC the default is OFF since evaluation of any transition moments or properties requires approximately twice the computational time ESTATE_PROP RESPONSE is not available for EOMCC calculations Transition moments and dipole strengths are evaluated by default for all values of ESTATE_PROP other than OFF 59 8 1 17 Excited states affinities EA_CALC handle NONE Specifies the method for calculating electron affinities of a closed shell parent state The values are NONE MBPT 2 strict second order perturbation theory SO_DYSON second order Green s Function iterating the MBPT 2 formula OVGF P_EOMEA partitioned EA EOM the 2p1h 2p1h block is treated as diagonal EA EOMCC H bar is diagonalized over 1p and 2p1h configurations COMBO OS_CCSD a state selective multireference CC method in which both orbitals and cluster amplitudes are optimized for the final state of interest This last method requires additional input in the mrcc_gen namelist Analytical gradients are available for EA EOMC
43. 1980 first row elements 107 e M S Gordon J S Binkley J A Pople W J Pietro and W J Hehre J Am Chem Soc 104 2797 1982 second row elements 4 31G e R Ditchfield W J Hehre and J A Pople J Chem Phys 54 724 1971 H C O N and F e W J Hehre and J A Pople J Chem Phys 56 4233 1972 B e W J Hehre and W A Lathan J Chem Phys 56 5255 1972 P S and Cl 6 31G e W J Hehre R Ditchfield and J A Pople J Chem Phys 56 2257 1972 C N O and F e J D Dill and J A Pople J Chem Phys 62 2921 1975 Li Be B e M M Francl W J Pietro W J Hehre J S Binkley M S Gordon D J DeFrees and J A Pople J Chem Phys 77 3654 1982 second row elements 6 31G and 6 31G e P C Hariharan and J A Pople Theor Chim Acta 28 213 1973 first row elements e M M Francl W J Pietro W J Hehre J S Binkley M S Gordon D J DeFrees and J A Pople J Chem Phys 77 3654 1982 second row elements 6 311G e R Krishnan J S Binkley R Seeger and J A Pople J Chem Phys 72 650 1980 first row elements Dunning basis sets e T H Dunning Jr J Chem Phys 53 2823 1970 double zeta and triple zeta valence contractions of 9s5p primitive set for H B F including 4s2p and 4s3p e T H Dunning Jr J Chem Phys 55 716 1971 triple zeta valence and more flex ible contractions of 10s6p primitive set for H B F including 5s3p and 5s4p Also 4s contraction for Li 5s contraction for Be
44. 2 8 1 27 Finite displacements for numerical gradients and Hessians FD STEPSIZE integer 50 Sets the step length in 107 amu Bohr used in generating the force constant matrix by finite difference of Cartesian gradients The default is 0 005 amu Bohr FD IRREPS string of 1D array 0 Lists the symmetry types to be evaluated in a VIBRATION FINDIF calculation The numbers of the irreducible representations for which vibrational analysis is to be per formed are separated by forward slashes For example FD IRREP 1 3 4 computes the frequencies of modes transforming as the first third and fourth irreducible rep resentations If a symmetry is specified for which there are no vibrational modes the program will terminate The labels of the irreducible representations for this keyword 68 are not usually the same as those used in the symmetry adapted integrals Moreover for some point groups like those of linear molecules the two sets of labels refer to different subgroups There is still no straightforward way to determine what they will be without starting a calculation One JODA run will list the relevant irreducible repre sentations If all vibrational frequencies are desired this keyword need not be included The default is to calculate all irreps FD_PROJECT switch ON Controls whether or not rotational degrees of freedom are projected out of symmetry adapted coordinates ON uses rotationally projected
45. 6 e R J Bartlett and I Shavitt Chem Phys Lett 50 190 1977 b Open shell UHF MBPT for molecules e R J Bartlett and G D Purvis III Int J Quantum Chem 14 561 1978 c Open shell ROHF MBPT for molecules e W J Lauderdale J F Stanton J Gauss J D Watts and R J Bartlett Chem Phys Lett 187 21 1991 J Chem Phys 97 6606 1992 102 12 2 Coupled cluster CC theory Review article e R J Bartlett J Phys Chem 93 1697 1989 a CCD method e R J Bartlett and G D Purvis III Int J Quantum Chem 14 561 1978 b CCSD method e G D Purvis III and R J Bartlett J Chem Phys 76 1910 1982 c CCSDT 1 method e Y S Lee S A Kucharski and R J Bartlett J Chem Phys 81 5906 1984 d CCSD T CCSD method e M Urban J Noga S J Cole and R J Bartlett J Chem Phys 83 4041 1985 e CCSD T method adds one HF case or two non HF case small terms to CCSD T CCSD e K Raghavachari G W Trucks J A Pople and M Head Gordon Chem Phys Lett 157 479 1989 e R J Bartlett J D Watts S A Kucharski and J Noga Chem Phys Lett 165 513 1990 e J Gauss W J Lauderdale J F Stanton J D Watts and R J Bartlett Chem Phys Lett 182 207 1991 e J D Watts J Gauss and R J Bartlett J Chem Phys 98 8718 1993 f CCSDT 2 and CCSDT 3 methods e J Noga R J Bartlett and M Urban Chem Phys Lett 134 146 1987 g CCSDT methods e J Noga and R J Bartlett J
46. 69 5 99 E eg dZ LV SOOU mols a S tw low YN an a o N bo a sg nm an H aana de se dz SZ ST syu ur sp y3NOIYI ST 107 SV8N3D ur 109 stseq yoo 10 SOHO siseq OV P9y9e 1quos Jo Joquinu oy T AVL 124 ae ZGAd 00 Lp x DTTE 9 Y xDITE 9 Tp SI z 68 4x1 1679 6 DTE 9 6 DIE9 E 6 DIZE 6z TdT 1 61 1 61 D9 OLS 1 61 1 61 DE OLS DZ7 OLS Ja as sv a9 Ya nz oo IN 00 ga NW wo A H os pales dy PE l syu ur SG YSNOIY PE 107 SVENAD UL Jos stseq 1090 10 SUOTJOUNJ siseq OV P9J981JUO9 Jo Joquinu sy ALL L6OSU LS I 8 8 YT I 8 8 OTHU LS Lid SINTUO 1 N VN aN a Njo a aa n aH H o S F is Tv 5 y E F o l pasei syu ur sp YSNOIY ST 107 SV8N3D ur 109 stseq YOR 10 SOHO siseq OV P9y9e 1quos Jo Joquinu oy T AVL 125 pel Yd OUT Ld Vd dy PE syu ur SG YSNOIY PE 107 SV8N35 UL Jos siseq 0090 10 suomounj siseq OV P9y9e 13u09 Jo qumu AL 9ABL 8 617 Rott OTIST S 6IT TEC T 8611 E HDI LAVA 67T 8 GTT PEPE eer STOTT PEGE OPPs OAZI QTI QTI GADUATALAVd 6 611 6 OTI 8 201 6 0TT 8701 6 0OTI TTDGLLLIVd 79 1Od SHOINTHV ee GG AZL SH
47. 9 1 11 EOM CCSD excitation energy aru doe iP eG ee he e s 79 9 1 12 EOM CCSD electron attachment energy 79 9 1 13 NMR chemical shifts irr wor die aare ge kus are ot ves a kd 81 9 2 Geometry optimizations o a eA ee ed 85 9 21 Full optimization of internal coordinates 85 9 2 2 Partial optimization of internal coordinates 85 9 2 3 Full optimization of Cartesian coordinates 86 9 24 Transition state search ott aa tod Gh oe Pa Oe AA 87 9 2 5 Restarting an optimization or frequency calculation 87 9 2 6 Initializing the Hessian with FCMINT in a geometry search 88 9 3 Frequency calculations a e y 89 9 3 1 Numerical frequencies from analytical gradients 89 9 3 2 Numerical frequencies from energies o 90 9 3 3 Isotopic shite us ue S k A hoe Bete a Ge E o Sr cs 90 10 Parallelization 92 A AA Boe a er SE O es ap ee Ge 92 10 2 Running RO SMINA SS sde E E pu ukap us Bote A Eee re RA Sd 39 ee os 93 10 2 1 Local scratch directories lt a ae Ps A 93 10 2 2 Shared scratch directories ate Woke li Ga Hod hole o 94 10 2 3 Command line flags and pattern macros 94 113 Examples as Ase sua e U Q tes he me A tes be es Due Ader eight i a Quay amp 96 10 3 1 Parallel finite differences with MPI automatic 96 10 3 2 Parallel finite differences with scripts manual 97 10 3 3 SCF geometry optimizations
48. 91 CAD CIILYVd ES Sh Ty r TaD GML 1 9 1 9 TE TOd SHOTNTHV LT I hI g AZL SHOINTHV 2 El T 9 ZLA SHOIWIHV 1 61 OI toj 6 9 g ZGAd SHOIN IHY I L 6 ZdA SHOINTHV YE e 2 NVINdIHO 0 HO s e 9 Z LAd SSANVD TZ I I rt e Z LA SSAINVD se 08T Se gZI se gZI t 07 MO ZEAd 00 2 0 SE Md ZOAd 00 68 sog GT MG ZLAd O0 1 61 E g AT ZGgAd 0O DIST a ls tw Jon vs an a o Nlola aa m an n Soa de se dz SZ ST syu ur sp YSNOIY ST 107 SV8N3D ur 109 stseq uoe 10 SUOTPOUNJ siseq OY p 1owruoo Jo Joquinu oy 1 ALL 123 91 81 91 91 e TANAUO 8 8 8 8 z OLMAS UT 1 81 e 9 AUZATINVT 8 8 6 6 e z ZaZINVT ZA LAVM AVH IN LAVM AVH s1 S stseq do Y CLE OL IOTI E Ez e 9 IFOTSI esa gg gg Ep 09 TH oe 8 or SIO1T0OO0 SHODIIHV yop Yep 9 p er b i dIVOTAOO NOWAG a 68 mas 61 er AONVHOXAZV SSAVDC ay 6 lt 61 Fer INOTNODZV SSAVDA a e 6g eg 61 y TONY HONT TY SR TY Od GF 68 eg 61 y dINOTNOO TV SSAVDG 7 1 61 e 9 dAZI SSNV9A 61 ei rel g dAZq ssnv5q 61 61 ar al z dAZG ssnv5q ii ONV UJHOTTHOSAVA TEL s TL sy e lt SHINV VSVN 5 68 6
49. ACES II Release 2 5 0 User Manual DRAFT COPY Quantum Theory Project P O Box 118435 University of Florida Gainesville FL 32611 January 29 2006 Contents Contents 1 1 Authors 1T Official ACES Ieit tioN lt ec u bud e a Oa Se ose arte lasa 7 1 2 Spec authors A St s a BR Sl s s ea ee Mos S Be ore Pte 7 2 Preface 9 3 Introduction 10 3 1 Overview of capabilities of ACES Il 11 4 Quickstart Guide 14 5 Program Structure 15 Dell AGES2 and PNGB a chess eh asker oo eh ds teen ata bats 15 DD gta OD Ab a A Oa er a SQ thee Meee ishe h SDD ike Si lt Meant Sy Ker T a 2 Ny 82 A 15 Did MOPAG U oS shes Was glk nat goes bees eee a elke Qh oe ee ke Seta eS bh aoe 15 Ds NMOL yo A aaa i A A e Ea do gece AY Sah 15 9 YM IQL O JAA ie o ET Q See a SE ee ee ea A um 16 DO IVBROPS t i d Ano Me is Bete hoo Su Q Sh ee uW ee Gee AE Am um SE T Bz Ht sho 16 Ie NDDOS card TA K R R S ead Eg u 16 5 8 VSCF P_VSCF VSCF_KS INTGRT and INTPACK e oda a 16 59 DIRMP2and PDIRMP2 te al a a Ge 16 DOC VIPRANAD X svete pp dt hie U te e dots Ge fe yta tes een ors e eran 16 eel IST Byes 024 un z Q 32 RN 16 DLUZANTBROS y at nes T TR e doa das mayu Nae hayta hw Aan Dans 17 Blog MOG VCCoT and GORGO s bach od s Sa dig a faba 17 IMAMRCOO a bee X h Uq wU X MUS su S w R O S OO k W s o d Be 17 DO ENO S u L ea TER wA A Beh aca s Sma ae Sa k Saya i TR 17 DIO LAMBDA ao R ene w S a R ee al ee S US N S R Ee aS Q G 17 517 VEA and
50. C and P EOMEA and require additional input though the mrcc_gen namelist Properties and transition properties of the EA states can be requested by additional input in MRCC namelists ea_calc section EA SYM string of 1D array 0 Specifies the number of states to be calculated by the EA CALC calculation A string e g 4 2 2 0 has to be provided that indicates the number of doublet states in each symmetry block The example string requests 4 doublet states of Al symmetry 2 doublet states in symmetry blocks 2 and 3 and 0 in block 4 The number of EA states to be calculated can also be specified by listing an energy range using ea_low and ea_high keywords in the mrcc_gen namelist This can be particularly relevant in vibrational frequency calculations in which the symmetry changes at different geometries DEA_CALC handle NONE Specifies the method for calculating double electron affinities after calculation of the closed shell parent state This type of calculation can be very useful to describe cer tain multireference situations like the C atom or the N20 molecule The values are NONE TDA the analogue of CIS in which a CI calculation is performed over 2 particle states EOMCC STEOM Similarity Transformed Equation of Motion OS CCSD SS_STEOM DEA STEOM is only meaningful if EA CALC EA_ EOMCC OS CCSD and SS STEOM are multireference CC methods which are still in an ex perimental stage Analytical gradients are availa
51. CMINT obtained in the frequency calculation to start the search but one must be careful that the molecular configuration used in the reduced symmetry has exactly the same connectivity scheme as that used in the search for the planar structure 9 3 Frequency calculations 9 3 1 Numerical frequencies from analytical gradients N4 finite difference frequency calculation N 89 ACES2 VIB FINDIF BASIS TZ2P CALC MBPT 2 This ZMAT file directs ACES II to perform a harmonic frequency calculation for N4 and to compute the force constants by numerical differentiation of analytic gradients The TZ2P basis set is selected Note that the TDA parameter is used in the Z matrix Although the specified value in the parameter input section is not the exact tetrahedral angle the program will convert TDA to the correct value 109 4712206 degrees internally Since finite differences are used no symmetry specific keywords can be specified so the orbital symmetry specification is omitted This is because the determination of the force constants requires several gradient calculations at geometries with different symmetries The FINDIF option automatically turns on the requisite gradient and property options Note that no asterisks may appear in the Z matrix in a frequency calculation This is a common error since frequency calculations are usually preceded by geometry optimizations which require the asterisks 9 3 2 Numerical frequencies from energ
52. CSD analytical gradients for open shell singlet states e P G Szalay and R J Bartlett J Chem Phys 101 4936 1994 105 12 4 Analytical second derivatives for MBPT CC methods a MBPT 2 second derivatives for closed shells e N C Handy R D Amos J F Gaw J E Rice E D Simandiras T J Lee R J Harrison W D Laidig G B Fitzgerald and R J Bartlett in Geometrical Derivatives of Energy Surfaces and Molecular Properties edited by P Jorgensen and J Simons Reidel Dordrecht 1986 e N C Handy R D Amos J F Gaw J E Rice E D Simandiras Chem Phys Letters 120 151 1985 e R J Harrison G B Fitzgerald W D Laidig R J Bartlett Chem Phys Lett 124 291 1986 b MBPT 2 second derivatives for open shells UHF and ROHF e J F Stanton J Gauss and R J Bartlett Chem Phys Lett 195 194 1992 e J Gauss J F Stanton and R J Bartlett J Chem Phys 97 7825 1992 12 5 NMR chemical shift calculations a GIAO SCF NMR chemical shift calculations e R Ditchfield Mol Phys 27 789 1974 e K Wolinski J F Hinton and P Pulay J Am Chem Soc 112 8251 1990 e M Haser R Ahlrichs H P Baron P Weis and H Horn Theoret Chim Acta 83 455 1992 b GIAO MBPT 2 NMR chemical shift calculations e J Gauss Chem Phys Lett 191 614 1992 J Chem Phys 99 3629 1993 12 6 Methods for calculating excitation energies a Tamm Dancoff CI singles approximation b Rando
53. Chem Phys 97 2571 1992 These basis sets have been optimized for atoms at the SCF level using analytic gradient techniques and have been supplemented with a suitable choice of polarization functions Input in the ACES II program is in this case always via BASIS SPECIAL The actual basis sets can be obtained via FTP from the authors Some other extended basis sets for second row atoms sp parts e A D McLean and G S Chandler J Chem Phys 72 5639 1980 up to 6s5p sets for second row atoms contracted from up to 12s9p primitive sets 109 Polarization exponents from correlated calculations e L T Redmon G D Purvis III and R J Bartlett J Am Chem Soc 101 2856 1979 recommended polarization exponents for use with DZ basis sets for H B C N and O 12 11 Integral packages The direct integrals are obtained by Rys quadrature 1 using an implementation ex tended to spdfg and L shells taken from GAMESS 2 1 J Rys M Dupuis H F King J Comput Chem 4 154 157 1983 2 M W Schmidt K K Baldridge J A Boatz S T Elbert M S Gordon J J Jensen S Koseki N Matsunaga K A Nguyen 2 Su T L Windus M Dupuis J A Mont gomery J Comput Chem 14 1347 1363 1993 110 A Other Keywords A 1 Experimental obsolete and unused The following keywords in the ACES2 namelist are listed for completeness but they correspond to untested and or experimental code SOLVENT integer 0 Sets the dielec
54. DTYPE AOBASIS This saves disk space for CC methods e SINGLE_STORE ON This saves disk space for correlated methods e DIRECT INTEGRALS GAMESS FOCK AO SYMMETRY OFF This save disk space for all calculations but only applies to SCF and MBPT 2 theories without DROPMO 101 12 References Of the many methods currently implemented in ACES II some are well established while others are new and descriptions have not yet been published It is the purpose of this section to list pertinent literature references which provide more information about the techniques and their implementations and should be cited when results from ACES II calculations are published Some references to basis sets included in the program are also included Guide to Correlated Methods e R J Bartlett and J F Stanton Applications of Post Hartree Fock Methods A Tuto rial in Reviews of Computational Chemistry 5 65 169 edited by K B Lipkowitz and D B Boyd VCH Publishers New York 1994 e R J Bartlett Coupled Cluster Theory An Overview of Recent Developments in Modern Electronic Structure Theory Part I edited by D R Yarkony World Scientific Publishing Co Singapore 1995 12 1 Many body perturbation theory MBPT Review article e R J Bartlett Ann Rev Phys Chem 32 359 1981 a Closed shell RHF MBPT for molecules e R J Bartlett and D M Silver Phys Rev A10 1927 1974 J Chem Phys 62 3258 1975 ibid 64 4578 197
55. Dupuis J A Montgomery catalog must give the following citation in addition to the ACES II citation 1 2 Basis sets were obtained from the Extensible Computational Chemistry Envi ronment Basis Set Database Version 1 0 as developed and distributed by the Molecular Science Computing Facility Environmental and Molecular Sciences Laboratory which is part of the Pacific Northwest Laboratory P O Box 999 Richland Washington 99352 USA and funded by the U S Department of En ergy The Pacific Northwest Laboratory is a multi program laboratory operated by Battelle Memorial Institute for the U S Department Energy under contract DE AC06 76RLO 1830 Contact Karen Schuchardt for further information Specific authors TD CCSD energies P G Szalay and A Balkova TD CCSD analytical derivatives P G Szalay Dropped molecular orbitals in analytical derivative calculations for RHF UHF and ROHF references K K Baeck Equation of motion CCSD calculation of dynamic polarizabilities including parti tioned scheme J F Stanton S A Perera and M Nooijen e Equation of motion CCSD calculation of NMR spin spin coupling constants including partitioned scheme S A Perera and M Nooijen e Partitioned equation of motion CCSD calculations of excitation energies S R Gwalt ney and M Nooijen e Equation of motion CCSD gradient calculations for excited states J F Stanton and J Gauss 2 Preface This manual is maintaine
56. ENSITY 58 DERIV_LEV 44 DIP_CALC 62 DIP_SYM 63 DIRECT 47 DOHBAR 58 DROPMO 52 134 EA_CALC 60 EA SYM 60 ECP 47 EE_SEARCH 61 EE_SYM 61 EIGENVECTOR 66 EOM MAXC 58 EOM PRJCT 59 EOMPROP 64 EOMREF 58 EOMXFIELD 111 EOMYFIELD 111 EOMZFIELD 111 ESTATE_MAXC 58 ESTATE PROP 59 ESTATE SYM 61 ESTATE_TOL 58 EVAL_HESS 67 EXCITE 58 EXTERNAL 69 FD_IRREPS 68 FD_PROJECT 69 FD_STEPSIZE 68 FD USEGROUP 69 FILE_RECSIZ 45 FILE STRIPE 111 FOCK 49 FUNCTIONAL 111 GAMMA ABCD 56 GENBAS_1 46 GENBAS 2 47 GENBAS 3 47 GEOM OPT 66 GLOBAL_MEM 111 GRAD_CALC 44 GUESS 49 HBARABCD 56 HBARABCI 56 HESS_UPDATE 67 HF2_FILE 55 56 HFSTABILITY 52 58 IMEM SIZE 59 INCORE 45 INIT_HESSIAN 67 INSERTF 111 INTEGRALS 47 INTGRL_TOL 47 IP_CALC 62 IP_SEARCH 62 IP_SYM 62 JODA PRINT 45 KS POT 111 KUCHARSKI 111 LINDEP_TOL 46 LOCK ORBOCC 50 LSHF Al 52 LSHF _B1 52 MAKERHF 55 MAX_STEP 66 MEMORY SIZE 43 45 MULTIPLICITY 46 NEGEVAL 67 NEWVRT 50 NONHF 48 NOREORI 45 NT2EOMEE 59 NTOP_TAMP 57 OCCUPATION 50 50 OPT MAXCYC 67 OPT_METHOD 66 ORBITALS 48 ORDER RLE see CC EXPORDER 135 PERT_ORB 48 POINTS 69 POLYRATE 111 PRINT 45 PROGRAM 58 PROPS 64 PRP INTS 65 PSI 111 QRHF_GENERAL 53 QRHF_ORBITAL 54 QRHF SPIN 54 RAMAN 68 RDO 111 REFERENCE 48 RESET FLAGS 111 RESRAMAN 63 RESTART 43 RLE see CC_EXTRAPOL ROT_EVEC 52 RPP see SC
57. F EXTRAP RPP LATEST see SCF EXPSTAR RPP_ORDER see SCF EXPORDER SAVE_INTS 55 SCF_CONV 51 SCF EXPORDER 51 SCF_EXPSTAR 52 SCF_EXTRAP 51 SCF_MAXCYC 51 SCF PRINT 49 SCF_TYPE 49 112 SINGLE STORE 55 SOLVENT 111 SPHERICAL 46 STP SIZ CTL 66 SUBGROUP 44 SUBGRPAXIS 44 SYMMETRY 44 TAMP SUM 57 KS 112 TDHF 64 TRANS INV 68 TREAT PERT 65 TURBOMOLE 111 UNITS 46 UNO_CHARGE 54 UNO MULT 55 UNO REF 54 VIBRATION 68 VTRAN 56 XFIELD 65 XFORM TOL 57 YFIELD 65 ZETA_CONV 63 ZETA MAXCYC 63 ZETA TYPE 63 ZFIELD 65 INTGRT CUTOFF 113 ENEGRID 113 ENETYPE 113 EXACT EX 113 FUNC 113 FUZZYITER 112 KSPOT 113 NUMACC 112 PARTPOLY 112 PARTTYP 112 POTGRID 113 POTRADPTS 112 POTTYPE 113 RADLIMIT 112 RADSCAL 112 RADTYP 112 TDKS 113 VSCF 136
58. II program system is not intended for large scale HF SCF or KS DFT calculations Two important features of the ACES II program system are its effective use of molec ular symmetry particularly in MBPT and CC calculations and the sophisticated gradient methods which are included in the program Even if a few elements of symmetry are present in a molecular system differences in execution times required for calculations with symme try and without can be dramatic The implementation of symmetry currently is limited to D gt and its subgroups and the expected speedup due to symmetry utilization will be on the order of the square of the order of the computational point group for all steps except integral and integral derivative generation and integral sorts in which the speedup can be no greater than the order of the group Gradient techniques are implemented for SCF and the following correlated levels of the ory MBPT 2 MBPT 3 MBPT 4 CCD QCISD CCSD QCISD T and CCSD T for both restricted and unrestricted Hartree Fock RHF and UHF respectively reference func tions In addition for the MBPT 2 MBPT 3 CCSD and CCSD T methods gradients are available for restricted open shell Hartree Fock ROHF reference functions They are also available for certain CCSD calculations based on quasi restricted Hartree Fock QRHF reference functions namely those for high spin doublet cases and two determinant CCSD TD CCSD calculations for open shell
59. K AO DIRECT ON INTEGRALS GAMESS 5 9 dirmp2 and p dirmp2 xdirmp2 calculates the MBPT 2 energy using the GAMESS direct integral package xp_dirmp2 does this in parallel 5 10 vtran xvtran is responsible for the 4 index AO MO integral transformations after the SCF calculation 5 11 tdhf xtdhf performs time dependent Hartree Fock calculations 16 5 12 intpre xintprc sorts the two electron integrals into five basic types OOOO OOOV OOVV OVVV and VVVV in which O and V stand for occupied and virtual orbitals respectively It also calculates the MBPT 2 energy 5 13 vec vec5t and vcc5q These programs calculate the CC energy by solving the T amplitude equations and calculating all non iterative contributions xvcc also calculates finite order perturbation theory energies by manipulating the CC iteration logic 5 14 mrcc The xmrcc program uses a different programming environment than the rest of ACES II This program implements many EOM related excited state theories like IP EOM DIP EOM STEOM etc 5 15 fno xfno rotates the orbitals of the reference wavefunction to frozen natural orbitals for the correlation corrections 5 16 lambda xlambda solves the A equations to determine the response of the CC amplitudes to a given perturbation 5 17 vea and vee xvea calculates electron attachment energies by the EOM CC method xvee calculates excitation energies transition moments and excited state dens
60. NTED or GENERAL NOTE Even for truly segmented basis sets both integral and integral derivative programs run significantly faster in GENERAL mode ECP switch OFF Controls whether effective core potentials a kind of pseudopotential are used ON or not OFF ECP ON requires BASIS SPECIAL and specification of the ECP data sets in a file named ECPDATA 8 1 7 Integrals INTEGRALS handle VMOL Specifies which integral package to use This is not a very robust keyword and should always be set to VMOL unless otherwise directed to change it Other values include SEWARD and GAMESS but these options will not work unless the binaries were linked to the appropriate libraries which require third party license agreements INTGRL_TOL tol 14 Sets the tolerance for storing the two electron integrals such that integrals having an absolute value greater than 107 will be stored on disk 47 DIRECT switch OFF Controls whether two particle AO integrals are calculated on the fly or calculated once and stored in a file This cannot be used with VMOL integrals 8 1 8 Reference REFERENCE handle RHF Specifies the type of SCF reference to use Supported references include spin restricted Hartree Fock RHF spin unrestricted Hartree Fock UHF and spin restricted open shell Hartree Fock ROHF These apply to Kohn Sham DFT references as well e g RHF is spin restricted Kohn Sham REF TWODET two determinant
61. OIMTHV ge TV ZLA SHOIYTIHV qe 9 ZCAd SHOINTHV C66 AGE ZCA SHOIMNTHV 9 0PT MU ZSAd D N MG ZOAd O0O 67 MG ZLAd OO 67 Md ZqAd 00 92061 ZG amp Ad 00 DNV 9 6TT ZOAd O0 DNV 069 ZLAd OO DNV 68 ZdAd O00 50n0V 9 0FT ZSAdOO M8 ZOAd O0O Tp ZLAd OO Ja as sv ao vo nz oo IN oo ga Nw Yo a H OS mee 126 pe pe DIMAS 1 21 JAZZ INV 8 0 TE ZACINVI TE ZCA LOVM AVH TE TT INTLAVM AVH sos sIiseq dow 99 YUT T 96 06 96 EINOTAOO SHOITHV K soq ANO TNOD NONAA sag AONVHOXAZV SSAVDC E INOTAODGV SSAVDA 99 Ee T NVHOXTIV SSNV A KC KC gINO 1nOO Iv SSnv5q 6 dAZq ssnv5q 62 9 JAZO SSAVDA S 601 ONV UHHOTTHOSNVA 069 e G6OI 069 e SHINV VSWN 611 dZLV SOOU 01 cg IZAV SOOY 1 09 AFSUALHOVM p ZLAd ti IqvS 1 61 1 9 SLM Ja ae alas vo nz oo in oo aa NNT wo a 11 os eit r PE syu ur SG YSNOIY PE 107 SV8N35 UL Jos SIseq 0090 10 suomounj sIseq OV P9y9e 13uo9 Jo qumu oy 9ABL 127 6e 9 6F 6OSYULS f S 6 OTH LS E SUNTUO TOE 919 TANTAD Ja jas sv ao vo nz no IN loo ga Nw Yo A H OS or dy PE syu ur SG YSNOIY PE 107 SV8N35 UL 109 siseq YORe 101 suom
62. RST First derivatives to be calculated SECOND Second derivatives to be calculated This is automatically set 8 1 2 System molecular control SYMMETRY handle ON Specifies which subgroup computational point group of the full point group is to be used in the energy and or gradient calculation OFF forces a no symmetry run in C1 ON runs the calculation in the largest self adjoint subgroup D gt and its subgroups and FULL uses the full point group Currently ACES II does not support groups with degenerate representations so the FULL option has no value unless JODA is used to make input files for another program package SUBGROUP handle DEFAULT Specifies a lower computational point group symmetry to use provided it is a subgroup of the full group Acceptable values are DEFAULT C1 C2 CS CI C2V C2H D2 and D2H SUBGROUP C1 is equivalent to SYMMETRY OFF The DEFAULT option uses the highest order Abelian subgroup including the full group SUBGRPAXIS handle X This is a somewhat complicated keyword to use The value can be X Y or Z The use of the keyword is best described by example Suppose one is running a calculation on water and wishes to run it in the C point group with the special plane being the one that bisects the H O H bond angle SUBGRPAXIS specifies which Cartesian direction in the C2 frame becomes the special direction in the C frame Normally 44 JODA will orient water
63. VEDIR but will not delete that top level directory This behavior might change in that if xjoda created SAVEDIR then it will delete it as well 9 2 6 Initializing the Hessian with FCMINT in a geometry search All of the geometry optimization algorithms incorporated into ACES II are based on the Newton Raphson method in which step directions and sizes are related to the first and second derivatives of the molecular potential energy However in almost all practical calcu lations the exact second derivative matrix is not evaluated but rather approximated As the calculation progresses well established numerical methods are used to estimate the elements of the Hessian matrix based on all previous optimization steps After a large number of steps have been taken one may safely assume that the totally symmetric Hessian used to form the step is a reasonable approximation to the correct Hessian However in the early stages of the optimization there is not a sufficient amount of available information to accurately estimate the Hessian and problems may ensue By default ACES II geometry optimizations begin with a very crude estimate of the Hessian in which all force constants for bonded interac tions as specified by the Z matrix connectivity are set to 1 hartree bohr all bending force constants corresponding to bond angles in the Z matrix are set to 0 25 hartree bohr and all torsional force constants are set to 0 10 hartree bohr While this initia
64. ZMAT ZMAT is the primary user interface to ACES II and it must exist in the run directory 6 2 GENBAS ZMAT BAS The files named GENBAS and ZMAT BAS contain the basis set definitions that the program can use In practice GENBAS is a large file and xjoda can spend most of its time scanning the file for the basis set definitions ZMAT BAS is created by xjoda to cache the relevant basis sets from GENBAS in other words if xjoda sees ZMAT BAS then it will try to read the basis information from there If a definition is missing from ZMAT BAS then xjoda will crash just as if GENBAS was missing the definition Appendix B 1 page 115 lists the contents of the standard GENBAS file 6 3 ECPDATA This file contains the data for effective core potentials Standard sets can be found in Appendix B 2 page 131 6 4 GUESS The GUESS file is used to control the placement of electrons in the SCF initial guess and can be used only with GUESS READ SO_MOS i e initial orbitals are read from OLDMOS 6 5 NEWMOS OLDMOS These files contain the MOs in the symmetry adapted AO basis of the SCF wavefunc tion NEWMOS is created by the SCF program after the last iteration and the user can copy this file to OLDMOS to initialize the MOs of a later calculation on the same molecule and basis set The example in Section 9 1 6 page 72 illustrates this capability 6 6 AOBASMOS OLDAOMOS These files contain the MOs in the AO basis before symmetry ada
65. ZqAOd D0O 08681 Ty 0C 1 TOT OI ZDADADO 01769 01769 967 e 6 ZLAOd 0O 67 67 61 61 ZGA0d 00 TL Z Cota EOC Z9Ad OO OGL DEl 00 a 502 ZqAd OO S P UL oO aan POC ZOAd OO0 368 206 70 ef ZLAd D0O U 61 U 61 91 eT q ZqAd 0O tpg Or 97 q Aza cI ea q dAS TL q T ZL T OT OT Z Za 6 6 Z AS m s a is ow YN an a o N ola sg n aH H ee de se dz SZ ST syu ur sp YSNOIY ST 107 SV8N3D ur 109 stseq uoe 10 SUOTPOUNJ siseq OY p 1owruoo Jo Joquinu oy 1 ALL 121 02192 ZGA0d 00 DNV OF PLT 08681 ZOANd O0 DNV vI 68 01 69 ZLAOd OO DAV E 6g 6 ZCA0d 00 DNV 06 047 06 997 32 ZST Z9Ad O0 NV 88 98 aa q0l ZgAd 00 90V 2601 36 q01 0768 ZOAd O0 DNV r s a jis ty fowl vn an a o njola aa m aH H anes de se dz SZ sI syu ur sp YSNOIY ST 107 SV8N3D5 ur Jos stseq YOR 10 SOHO siseq OV poprsjyuoo Jo Joquinu oy T AQL 122 6 6 teg a 6 IZAV SOOY AFSUALHOVM TE TE amp 97 TUE e 6 ZLAALATAVS 6 9 g L SLM V IDATULUVA 29 98 19 SI CTT IY 1g a 6h
66. alculations for open shell singlet state e Equation of motion CCSD calculation of dynamic polarizabilities including parti tioned scheme e Equation of motion CCSD calculation of NMR spin spin coupling constants including partitioned scheme e Partitioned equation of motion CCSD calculations of excitation energies e Kohn Sham DFT methods combined with a wide selection of density functionals Analytical gradients e Independent particle models include RHF UHF and ROHF e Correlation methods utilizing RHF and UHF reference determinants include MBPT 2 MBPT 3 SDQ MBPT 4 MBPT 4 CCD CCSD CCSD T CCSD CCSD T CCSDT 1 CCSDT 2 CCSDT 3 QCISD QCISD T UCC 4 UCCSD 4 CID and CISD e Correlation methods that can also utilize ROHF reference determinants include MBPT 2 CCSD and CCSD T e Correlation methods that can also utilize QRHF reference determinants include CCSD e Two determinant CCSD calculations for open shell singlet state based on QRHF or bitals 12 e EOM CCSD analytical gradients for excited states e TD CCSD analytical derivatives e Dropped core and or virtual orbitals in analytical derivative calculations for RHF UHE and ROHF references Analytical Hessians e Independent particle models include RHF UHF and ROHF 13 4 Quickstart Guide At the bare minimum the user must provide an input file named ZMAT and a basis set file named GENBAS The main executable xaces2 is a
67. ane TMS has been chosen as standard and the corresponding c values are 198 944 dzp dz 193 103 tzp dz 193 419 tzp dzp at GIAO SCF level and 205 720 dzp dz 83 198 890 tzp dz and 197 191 tzp dzp at GIAO MBPT 2 level The MBPT 2 6 31G optimized geometry has been used in all the GIAO calculations for TMS With respect to basis sets the following recommendations can be made In case of B and C nuclei which have been extensively studied the dzp dz basis set dzp for C and dz for H is in most cases sufficient for relative shifts though the use of the tzp dz basis tzp for C and dz for H is recommended Larger basis sets i e tzp tzp2 or even qz2p are in most cases not needed for the accurate prediction of chemical shifts On the other side N YO and TYE NMR chemical shift calculations require larger basis sets of at least triple zeta plus polarization quality Though qualitatively good results are obtained in many cases with the tzp basis even larger basis sets such as tz2p or qz2p are recommended for more reliable calculations For other nuclei not very much can be said at the moment and the user is strongly urged to check carefully the basis set dependence to ensure reliable theoretical results However limited experience suggests that for second row elements quite large basis sets are needed for accurate calculations Note NMR chemical shift calculations can currently only be performed with Cartesian basis fun
68. atch directories from a central location Each MPI task of xgemini or the parallel AMEs must start in this directory which means it must be globally visible on distributed computers Henceforth this directory will be called WORKDIR Depending on the machine architecture the two choices the user must make are 1 where will the private scratch directories be created and 2 how will the AMEs get to them These decisions will affect performance if local disks are available on each node and will determine how a parallel job should be restarted When the user runs a parallel member executable usually xp_aces2 each parallel task must start in WORKDIR which usually contains ZMAT and GENBAS Before reading any files each task attempts to cd into a directory called nodename rank The tasks on a machine named crunch would look for crunch 0 crunch 1 etc If they cannot find these directories then they try to cd into directories called shared rank shared 0 shared 1 etc If those are not found either then the tasks start running in the current directory 10 2 1 Local scratch directories For the following example assume that the parallel computer has compute nodes called compnode0 compnodel etc and that the user named smith is allowed to create directories in local tmp The following command will create a directory called smithdir on every node xgemini i t local tmp smithdir Assuming all compute nodes took part in the
69. ber of checks These include determination of whether coordinates given the same name are actually equivalent or coordinates having different names are equivalent whether a non zero gradient is possible with respect to modes which are not being optimized etc In addition it determines the number of degrees of freedom within the totally symmetric subspaces of nuclear configurations and compares this value with the number of independent coordinates which are being optimized If they are not equal a warning message is printed out For most Z matrices with poorly defined internal coordinates the analyzer prints out a number of warning messages but does not halt the ACES II execution sequence However for Z matrices which are particularly bad it will terminate the job All users are encouraged to carefully inspect the output of the analyzer and to check that the full molecular point group printed out below the output from the analyzer is the one intended If warning messages are printed or if the symmetry is not what the user expects then reconstruct as necessary A rule of thumb for Z matrix construction is that each internal coordinate included in the Z matrix must be accompanied by all others which are equivalent to it by the symmetry of the molecule For example in water it is best to specify the molecular geometry by the two O H distances and the H O H bond angle rather than by the O H distance the H H distance and the H H O angle Although
70. bitals are to be replaced by a set determined from an N 1 potential This is an orthogonal transformation within the virtual space As long as appropriate fi and fab are included the energies of standard single reference methods are unchanged However for TD CC methods this keyword mixes one of the occupied orbitals with the virtual space and the results are changed It is anticipated that TD CCSD calculations will be improved by the use of this keyword but this has yet to be demonstrated NEWVRT is useful for interpreting results of EOM EE calculations since excitations tend to be more easily identified as involving one occupied and one virtual orbital OFF does not rotate the virtual space and ON rotates the virtual space 8 1 11 SCF iteration control SCF_CONV tol 7 Sets the convergence criterion for the SCF equations Equations are considered con verged when the maximum change in density matrix elements is less than 107 SCF_MAXCYC integer 150 Sets the maximum number of SCF iterations DAMP_TYP handle NONE Specifies what type of damping is used during the SCF iterations The value can be NONE no damping DAVIDSON Davidson s empirical dynamical damping scheme and STATIC a fixed damping parameter Note that RPP convergence extrapolation is not turned on until the damp factor has gone below DAMP_TOL and the energy change is below 0 05 a u DAMP_TYP DAVIDSON is recommended even though NONE is the de
71. ble for TDA and STEOM and require additional input though the mrcc_gen namelist Properties and transition properties of the DEA states can be requested by additional input in MRCC namelists dea_calc section DEA SYM string of 1D array 0 60 Specifies the number of states to be calculated by a DEA calculation A string e g 4 2 2 0 2 1 1 1 has to be provided that indicates the number of singlet states in each symmetry block followed by the number of triplet states in each symmetry block The example string requests 4 singlet states of Al symmetry 2 singlet states in symmetry blocks 2 and 3 and 0 in block 4 In addition 2 triplet states will be calculated in block 1 and 1 triplet in blocks 2 3 and 4 each The triplet vector and the forward slash are optional 8 1 18 Excited states electronic absorption EE_SYM string of 1D array 0 Specifies the number of states to be calculated by an EE calculation A string e g 4 2 2 0 has to be provided that indicates the number of singlet states in each sym metry block The example string requests 4 singlet states of Al symmetry 2 states in symmetry blocks 2 and 3 and 0 in block 4 The number of EE states to calculate can also be specified by listing an energy range using ee_low and ee high keywords in the mrcc_gen namelist This can be particularly relevant in vibrational frequency calculations in which the symmetry changes at different geometries RHF is limited to singlets
72. c irrep Likewise instabilities which take RHF wavefunctions into UHF ones must be followed using a UHF calculation Following instabilities often leads to solutions which are lower in energy but lack the symmetry of the molecular framework are heavily spin contaminated in the UHF case or are otherwise non physical Instabilities in Hartree Fock wavefunctions are a very complex problem and must be treated with great care in order to obtain any meaningful information Experience has shown that in general molecules with instabilities will have more than one and that solutions obtained by following an instability may have further instabilities It is impossible to predict exactly what will be uncovered by a stability analysis and the current drivers for ACES II are configured to handle only the simplest cases Examining a tree of instabilities or other specialized procedures will require the user to create an appropriate driver of their own which is usually specialized to the system under study A suprising number of molecules will exhibit instabilities under various conditions If you encounter one don t panic Take a deep breath go for a walk get a cup of coffee Not all instabilities indicate pathological cases or intractable problems 9 1 10 Time dependent Hartree Fock In order to provide properties such as frequency dependent polarizabilities ACES II provides time depenent Hartree Fock TDHF calculations The TDHF code can solv
73. cate Most member executables will not allocate more than the amount specified but some will attempt to allocate extra bits on the order of a few megabytes that are of little consequence compared to the main memory heap There is special parsing logic for the corresponding value string The tail of the string is checked for case insensitive units and optional prefixes Units can be W integer words or B bytes and prefixes can be K M or G kilo mega and giga respectively The number part is read with the atof C function NOTE The prefixes scale the units by 219 1024 not 1000 and the default unit is integer words 4 bytes for 32 bit binaries and 8 bytes for 64 bit binaries RESTART switch ON 43 Controls the creation updating and reading of a checkpoint directory Currently only coarse grain restarts are available which means geometry optimizations and finite difference calculations can be restarted from the last checkpoint Fine grain restarts are not available yet but will also checkpoint SCF T and Lambda iterations GRAD_CALC handle AUTO Specifies whether to calculate a gradient analytically or numerically This should be used only to override analytical gradients since the program will attempt to use them whenever possible DERIV_LEV handle 1 Specifies whether or not derivatives of the energy are to be calculated and if so then whether first or second NONE Derivatives not calculated FI
74. ce though more efficient with respect to CPU timings The current limits for GIAO MBPT 2 calculations depend on the available hardware resources However as a rough guide the limits for a IBM RS6000 350 work station with 80 Mbyte memory and 3 5 Gbyte scratch space are given Within this environment calculations with about 250 basis functions in D gt symmetry about 200 basis functions in C2 Con and D symmetry about 170 basis functions in Ca G and C symmetry and about 130 basis functions in cases without symmetry are feasible From these estimates it is seen that the limits strongly depend on the molecular symmetry Thus users are urged to use symmetry whenever possible It should be also noted that the computational requirements depend somewhat on the ratio n N and that the costs increases with the number of occupied orbitals As the final result the corresponding chemical shielding tensors of all nuclei in the molecule are obtained in a GIAO SCF and or GIAO MBPT 2 calculation The output produced by the module xjoda gives the absolute isotropic shielding one third of the trace of the shielding tensor as well as the anisotropic shielding which is usually of less interest In order to compare with experimental results the absolute shielding must be converted to the relative shifts 6 This is easily accomplished via Oref 0 1 with o ez as the absolute shielding of the chosen reference compounds For C tetram ethylsil
75. ces a GIAO MBPT 2 calcula 82 tions requires the storage of the AO two electron integrals files III HJJ IJIJ and IJKL depending on symmetry and with a total size of approximately 1 5 N 8h eight byte words note that the CRAY version requires 2 x N 8h words the storage of the MO integrals file MOINTS the largest portion is here given by the integrals ab ci with a total size nN h eight byte words the storage of the GIAO integrals files IIX IIJJX IJIJX IJKLX in case of a symmetric perturbation B or IIJX IJIKX IJKLX for a non symmetric perturbation B The files for the perturbations B and B are named using the same convention with Y or Z instead of X The total size of these files is for each perturbation approximately given by 1 5 Vf 4h CRAY version 2x NW 4h and the storage of the derivative MO integrals and amplitudes files DERGAM and DERINT with the largest portion given by the perturbed ab ci integrals size nN h eight byte words To keep the disk space requirements at a minimum it is strongly recommended to use the keyword TREAT_PERTURBATION SEQUENTIAL as this forces the program to treat each mag netic field component separately and thus requires only the storage of one type of GIAO integrals at one time TREAT_PERTURBATION SIMULTANEOUS which is currently the default requires the simultaneous storage of all GIAO integrals and is therefore much more demanding in terms of disk spa
76. coordinates while OFF re tains the rotational degrees of freedom At a stationary point on the potential surface both options will give equivalent harmonic force fields but OFF should be used at non stationary points FD_USEGROUP handle FULL Specifies the point group to be used in generating the symmetry adapted vibrational coordinates FULL specifies the full molecular point group COMP specifies the Abelian subgroup used in the electronic structure calculation POINTS handle DOUBLE Specifies either single SINGLE or double sided DOUBLE numerical differen tiation in the finite difference evaluation of the Hessian Two sided numerical differ entiation is considerably more accurate than the single sided method and its use is strongly recommended for production work 8 1 28 External interfaces EXTERNAL handle NONE Specifies what type of external file interface for third party programs to create Current interfaces include HYPERCHEM and MOLDEN A2PROC help This is not a keyword per se but is used by ACES II to generate the external interfaces and it can be used to generate such interfaces after a calculation has finished 69 9 Examples 9 1 Single point calculations 9 1 1 RHF CCSD T energy H20 CCSD T energy calculation DZP basis set H O 1 ROH H 2 ROH 1 HOH ROH 0 95 HOH 104 5 ACES2 CALC CCSD T BASIS DZP This illustrates a single point CCSD T energy calculation on
77. cs 1 while test frank ge 0 do this is the xgemini portion mkdir shared rank cd shared rank ln s ZMAT ln s GENBAS this is the meat of the routine loop gt rank out exit 1 xa2proc parfd updump gt gt fd out update and print the FD data reset and cycle to the next process 98 cd let rank 1 done cd shared 0 xa2proc parfd load fd out load the FD data from the other procs xjoda procs procs run the final xjoda cd For geometry optimizations every process will have to load the FD data and the entire procedure will have to loop over coordinates until convergence when the integer record JODADONE is 1 Needless to say this is not an exercise for even intermediate users of ACES II but the capability exists should the need arise 10 3 3 SCF geometry optimizations In Script 3 from the Overview section page 92 the core of the commands are contained in another shell script parscfopt sh That script contains the loop logic to iterate until xjoda has found the minimum energy geometry bin sh parscfopt sh test d shared 0 amp amp s s s rootdir ls d 0 PRUN xgemini s xjoda cd rootdir jodadone xa2proc jareq i JODADONE 1 tail 1 cd while test jodadone eq 0 do PRUN xgemini s xvmol amp amp xvmol2ja PRUN xp_vscf PRUN xp_scfgrd PRUN xgemini s xjoda cd rootdir jodadone xa2proc jareq i JODADONE 1 tail 1 cd done
78. ctions SPHERICAL ON may not be specified GIAO MBPT 2 NMR chemical shift calculations for the benzonium cation 000000 0 000000 1 393615 000000 0 000000 1 413386 000000 1 250334 0 632255 000000 1 250334 0 632255 000000 1 237545 0 742530 000000 1 237545 0 742530 853412 0 000000 2 102274 853412 0 000000 2 102274 000000 2 189398 1 180688 000000 2 189398 1 180688 000000 2 161755 1 310996 000000 2 161755 1 310996 000000 0 000000 2 502007 GD D GD DD D r Q O O O O I Se GO GOGO OOO OO O ACES2 CALC MBPT 2 PROP NMR CHARGE 1 COORD CARTESIAN TREAT_PERTURBATION SEQUENTIAL MEMORY 24000000 DZP DZP DZP DZP DZP DZP DZ DZ DZ DZ DZ DZ DZ GP DD DD DD O O OQ OO O This example features a calculation of the NMR chemical shifts at the MBPT 2 level 84 using gauge including atomic orbitals GIAOs NMR shifts are requested by the keyword PROP NMR The input of the coordinates in this example is via Cartesian coordinates in Angstroms and the basis set is specified via the non standard input which allows the use of different basis sets for different atoms in this case DZP for C and DZ for H To reduce disk space requirements the keyword TREAT_PERTUBATION SEQUENTIAL is specified which forces the program to treat each magnetic field perturbation separately thus storing only GIAO integrals of one particular type at one time The memory requirement in this example is
79. culation is to be performed IDCOR specifies if a DC electric field induced OR calculation is to be performed IIDRI specifies if am intensity dependent refractive index calculation is to be performed IDCSHG specifies if DC electric field SHG calculation is to be performed ITHG specifies if third harmonic generation calculation is to be performed The method of solution of the TDHF equations is controlled by the parameter NITER default value is 20 If NITER is 0 an iterative method of solution is used if it is 1 a non iterative method of solution is used if it is greater than 1 the reduced linear equation method will be used When NITER 1 more than one frequency can be solved for For the other methods of solution only one frequency can be considered in a single calculation The number of 78 nonzero frequencies is specified by NFREQ The NFREQ frequencies are listed one per line following the INPUTP namelist Static calculations are also performed along with the dynamic calculations To obtain only static results all parameters should be set to 0 The following is an example of a TDHF calculation on Na N2 TDHF TEST Sadlej basis set N N1R R 2 07434 ACES2 UNITS BOHR BASIS SPECIAL TDHF 0N N PBS N PBS INPUTP IOPU 0 IOPFE 0 IOPEV 0 IOPPR 0 NITER 1 NFREQ 4 IDCSHG 1 I0KE 1 IDCOR 1 IIDRI 1 ITHG 1 IWRPA 1 SEND 0 072 0 0886 0 0934 0 0995 WARNING There does not seem to be a portable format for Fortran namel
80. d STEOM methods The programs collectively known as ACES II began development in early 1990 and the first version of the code was written by J F Stanton J Gauss J D Watts W J Lauderdale and R J Bartlett Program development is continuing and the capabilities as well as the contributors to the development of the ACES II program system are continually increas ing At present there are more than 30 member executables each of which performs a well defined function and communicates with the rest of ACES II through stored files The ACES II program system has been interfaced with external programs such as MOLCAS and GAMESS The primary function of the MOLCAS and GAMESS interfaces is to provide in tegral and integral derivative programs that are more efficient and have direct capabilities to complement the functionalities of the locally modified version of VMOL VPROPS and VDINT programs A complete replacement of these member executables is not yet feasible since the specialized integrals such as Gauge origin independent GIAO integrals and NMR spin spin coupling operator integrals are only available in VMOL VPROPS and VDINT ACES II can also generate interfaces to graphical programs such as MOLDEN and gOpenMol wave func tion analysis codes such as Natural Bond Orbital NBO and semi emperical programs such as HyperChem NDDO and MOPAC The ACES II distribution comes with these capabil ities however ACES II developers are not responsible
81. d as a set of BTFX documents under CVS control along with the ACES II source code Every version of the code has an accompanying manual and while the user interface is relatively stable it is not guaranteed that the manual of one version is compatible with binary executables of a different version Any errors in the manual should be reported to aces2 qtp ufl edu The goal of this manual is to provide beginners and experts alike with enough information to run any calculation that the software allows A reference section is provided for further reading on the theories and algorithms implemented in the program 3 Introduction ACES II is a set of programs that performs ab initio quantum chemistry calculations The package has a high degree of flexibility and supports many kinds of calculations at a number of levels of theory The major strength of the program system is using many body methods to treat electron correlation These approaches broadly categorized as many body perturbation theory MBPT and the coupled cluster CC approximation offer a reliable treatment of correlation and have the attractive property of size extensivity which means the energies scale properly with the size of the system As a result of this property MBPT and CC methods are ideally suited for the study of chemical reactions While ACES II can perform Hartree Fock Self Consistent Field HF SCF and Kohn Sham Density Functional Theory KS DFT calculations the ACES
82. d as the job title 2 Job title The first non blank non comment non directive line is the job title It may consist of any character and may be at most 80 characters long 3 Molecular system The coordinate matrices must immediately follow the job title Every line must describe one atom dummy or otherwise The first blank or comment line terminates the coordinate matrix Atom descriptions may have hash delimited comments and the coordinate strings may be separated with spaces or tabs There are two types of coordinate matrices internal Z matrix and Cartesian Internal coordinate matrices have two parts separated by a blank line the Z matrix and the parameter definitions Cartesian coordinate matrices are the standard X Y Z format with no blank lines For LST and QST geometry search algorithms multiple XYZ and Z matrix parameter matrices can be supplied in the following order INITIAL TRANSITION FINAL The transition geometry is only used for QST Supplying a transition geometry for 26 LST will yield incorrect results since the parser will read the second set of coordinates as the final geometry 4 Namelists Any number of blank lines may pad the namelists In general a namelist is delimited by an asterisk immediately followed by the case sensitive name of the namelist ACES2 INTGRT Only the ACES2 namelist is required for every calculation Some programs or features recognize other namelists b
83. d to MBPT 2 have been added in the last years to the functionalities of the ACES II program system However before discussing the details of the calculation of NMR chemical shifts a few general remarks are required The main problem in all calculations of magnetic properties i e NMR chemical shifts and magnetizabilities using finite basis sets as they are usually employed in quantum chemical calculations is the gauge invariance problem This simply means that the results of such a calculation depend on the chosen gauge origin and are not invariant with respect to gauge transformations as required by exact theory A trivial solution to the gauge invariance problem would be the use of very large basis sets in order to minimize the gauge error but this approach due to large computational costs is limited to small molecules More satisfying solutions are offered by approaches which introduce local gauge origins to define the vector potential such as the IGLO method of Kutzelnigg and Schindler the LORG method of Hansen and Bouman and the GIAO approach of Ditchfield The latter originates in London s work on molecular diamagnetism in the thirties and was first used by Hameka during the sixties to calculate magnetizabilities and chemical shieldings ACES Il incorporates the GIAO SCF and GIAO MBPT 2 method for calculating chemical shifts since in our opinion the GIAO approach is the most elegant solution to the gauge invariance problem and in con
84. demonstrated xgemini can create the runtime environment with i can use shared node names with s and can create private scratch directories with almost any name the user requires with t and macro substitution In addition it can use arbitrary input and basis files with z and b can run serial commands in each directory all arguments that are not flags and can clean up after a parallel run with x The command line structure is as follows 94 xgemini h s i z file b file t pattern x exec Flag z file b file t pattern exec Description print usage text use shared scratch directories useful for restarts initialize make scratch directories and symlinks link file to ZMAT default is ZMAT link file to GENBAS default is GENBAS pattern defines scratch directory paths clean remove scratch directories and symlinks terminate xgemini flag parsing pass exec arguments to a system command in each scratch directory The pattern that defines the scratch directories can be an absolute or relative path with respect to WORKDIR Another example of directory patterns is usr var tmp LOGNAME scr GRANK which would become usr var tmp smith scr 0 for the root task of user smith The following table shows the complete list of macros and their substituted values Macro NODENAME CLOGNAMEO SIDO PID PPID GRANK GPROCS CHRANKO CHPROCSO
85. e OFF Specifies whether properties other than the energy geometry and vibrational frequen cies are calculated Acceptable values are OFF no properties are calculated FIRST_ORDER dipole moment quadrupole moment electrical field gradients spin densities etc and the approximate perturbative relativistic correction to the energy by Cowan Griffin SECOND_ORDER frequency independent polarizabilities commonly known as the CPHF polarizabilities provided CALC SCF EOM_NLO both frequency dependent and independent polarizabilities at the CCSD level using EOM CC see EOMPROP J_SO paramagnetic and diamagnetic spin orbit contributions to the NMR spin coupling constant J_SD spin dipole contribution to the NMR spin coupling constant J_FC Fermi contact contribution to the NMR spin coupling constant JSC ALL all four contributions NMR NMR chemical shifts limited to SCF and MBPT 2 with SPHERICAL OFF Note that options J SO J SD J FC and JSC_ALL require CALC CCSD and that options J SO J_FC and JSC_ALL require REF UHF see EOMPROP EOMPROP handle CILIKE Specifies the method of calculating EOM CCSD second order properties polarizabil ities and spin spin coupling constants CILIKE uses a Cl like formula which is not rigorously size extensive LINEAR removes unlinked diagrams from the Cl like formula QUADRATIC uses a size extensive quadratic formula and COMBO com putes a
86. e chemically bonded Only for gt 1 PARNAM 3 1 2 A character variable name corresponding to the distance between atom NCON 3 1 2 and atom I NCON 3 1 1 The third member of the triangle formed by atoms I and NCON 3 I 2 Only for I gt 2 PARNAM 3 1 1 A character variable corresponding to the associated angle NCON 3 I The fourth member of the dihedral angle formed by atoms I NCON 3 1 2 and NCON 3 I 1 Only for gt 3 PARNAM 3 1 A character variable name corresponding to a dihedral angle determined as follows In the plane perpendicular to the NCON 3 1 2 gt NCON 3 L1 axis the angle is that needed to rotate the projection of the I NCON 3 I 2 vector into the projection of the NCON 3 I NCON 3 L 1 vector Clockwise is taken to be positive Values must be restricted from 180 to 180 All variable names PARNAM array are limited to five characters An asterisk x immediately after the variable name implies an optimization No numbers are allowed inside the Z matriz all internal coordinates must be given a symbol even if the value is not going to be optimized Z matrix Parameters After a blank line following the Z matrix the values of all unique internal coordinates those with different names are specified as follows PNM Value where PNM is one of the unique members of the PARNAM array see above and Value is the value assigned to that coordinate The first non blank string after the equal sign is
87. e maximum number of iterative diagonalization steps for each root in excited state calculations EOM MAXCYC integer 50 Sets the number of iterations in EOM excited state calculations If it has the value N and NROOT roots have been requested for a given symmetry then the program will allow up to N N ROOT iterations to find all of the requested roots for that symmetry This keyword is only used by the iterative solution of the HF Stability analysis and has nothing to do with EO M PROGRAM handle DEFAULT 58 EOMREF handle NONE IMEM_SIZE special 3000000W EOM_PRJCT handle NONE NT3EOMEE handle NONE ACC_SYM handle NONE 8 1 16 Excited states properties ESTATE_PROP handle OFF Specifies whether any excited state one electron properties are to be calculated but it only applies to EOM CC calculations Proper use of this keyword might require some fairly advanced knowledge of quantum chemistry and the available options are discussed here The values are OFF no properties or transition moments are calculated EXPECTATION transition moments and dipole strengths are calculated along with selected one electron properties which are evaluated as expectation values UNRELAXED gt selected one electron properties are calculated in an approximation that neglects relaxation of molecular orbitals RESPONSE selected one electron properties are calculated as analytic first deriva
88. e the general order TDHF problem for closed shell RHF wavefunctions The TDHF keyword must be set to ON and additional parameters controlling the TDHF calculation are included in a namelist which is located at the end of the ZMAT file The variables in the namelist are as follows Printing options e IOPDA controls density matrix printing 0 means no printing default and 1 means print the matrix e IOPEV controls MO coefficient printing 0 means no printing default and 1 means print the matrix TT e IOPU controls U matrix printing 0 means no printing default and 1 means print the matrix e IOPFE controls Fock matrix printing 0 means no printing default and 1 means print the matrix e IOPPR controls property integral printing 0 means no printing default and 1 means print the matrix For subsequent options 0 means do not do this type of calculation otherwise do it The default is to do the calculation so if a parameter is not specified the program will perform that calculation For the polarizability a e IDALPH specifies if o is to be calculated For the first hyperpolarizability 0 e IOR specifies if optical rectification calculation is to be performed e IEOPE specifies if electro optical Pockels effects calculation is to be performed e ISHG specifies if second harmonic generation calculation is to be performed For the second hyperpolarizability y e IOKE specifies if an optical Kerr effect cal
89. each atom in coordinate order must be specified after the ACES2 namelist SPHERICAL switch OFF Controls whether 0N spherical harmonic 5d 7f 9g or OFF Cartesian 6d 10f 15g basis functions are used LINDEP_TOL tol 5 Sets the tolerance for linear dependencies in the basis set The basis set is considered linearly dependent and eigenvectors of the overlap matrix are neglected if the associated eigenvalues are less than 107 46 GENBAS 1 integer 0 This keyword applies to first row elements H and HE and specifies the number of contracted Gaussian functions per shell There is usually no need to use this keyword but it can be useful for using a subset of the functions in a particular entry in the GENBAS file particularly for generally contracted basis sets For example if entry H BASIS in the GENBAS file contains 7 contracted s functions 4 p functions and one d function then setting GENBAS_1 730 would eliminate the last p function and the d function The default for this keyword is to use the unaltered entry in GENBAS GENBAS 2 integer 0 This keyword performs the same function as GENBAS_1 but applies only to second row atoms GENBAS_3 integer 0 This keyword performs the same function as GENBAS_1 and GENBAS_2 but applies only to third row atoms CONTRACTION handle GENERAL Specifies the contraction scheme used by the integral and integral derivative programs This can be set to SEGME
90. ed with a dirty flag Immediately before a call to xjoda xaces2 will clear the dirty flag thus signaling xjoda to backup the files If the dirty flag is not clear then xjoda will assume the calculation has crashed and restore the previous file set instead of saving the current set Users must clear the dirty flag manually with xa2proc clrdirty if they are running each AME separately otherwise ACES II will loop over the same geometry forever it will not even increment the step counter and stop after a certain number of steps 5 27 2 mem A user can alter the MEMORY_SIZE state variable of a STATIC ACES II file set with the MEM module If no AMEs are using the JOBARC and JAINDX files then xa2proc mem amount will change the value that each AME uses to allocate memory This change will remain in effect until the next run of xjoda which will reset it to whatever value is in the ZMAT file amount is a double precision number optionally followed by a unit Valid case insensitive units are B KB MB GB W KW MW and GW The number and units must be one string no spaces 19 For example a user might be nursing a large calculation by running each executable by hand and backing up the files between them If he or she discovers ACES needs more memory then the user changes the MEMSIZE value in ZMAT and runs xa2proc mem on the backup files 5 27 3 zerorec This module flushes records in the JOBARC file with zeroes
91. f there are no orbitals of a particular symmetry type then a zero must be entered If the reference wavefunction is for an open shell system then two strings of NIRREP occupation numbers separated by a forward slash define the a and 7 sets of orbitals An example of the use of the OCCUPATION keyword for the water molecule would be OCCUPATION 3 1 1 0 For the 7A water cation an open shell system the keyword would be specified by OCCUPATION 3 1 1 0 2 1 1 0 It should be noted that the VMOL integral program orders the irreducible representa tions in a strange way which most users do not perceive to be a logical order Hence it is advised to run a single point SCF calculation to determine the initial number and ordering of the irreducible representations The occupation keyword may be omit ted in which case an initial orbital occupancy is determined by diagonalizing the core Hamiltonian In many cases SCF calculations that use the core Hamiltonian guess will converge to the lowest energy SCF solution but this is not guaranteed LOCK ORBOCC switch OFF Controls orbital occupancies among symmetry blocks in the SCF iterations ON locks the occupation to the OCCUPATION value array or the initial guess if OCCUPATION is undefined OFF permits the occupation to change NOTE If the OCCUPATION keyword is defined then LOCK_ORBOCC is switched on automatically NEWVRT switch OFF 50 Signals if the SCF virtual or
92. f symmetry 1 A4 As in the ROHF example the program automatically turns on the NON HF option so that the appropriate non Hartree Fock terms are included in the coupled cluster equations 71 9 1 5 Effective core potentials CRF6 SINGLE POINT ENERGY CALCULATION USING AN ECP FOR CR CR RMC RMC 2 W1 RMC 3 W1 2 T1 RMC 4 W1 3 T2 RMC 5 W1 4 T1 RMC 6 W1 5 T2 tr yyy yy KA KA KK KA KA ps RMC 1 676125 W1 90 T1 90 T2 270 ACES2 BASIS SPECIAL ECP ON CALCLEVEL SCF OCC 10 6 6 2 6 2 2 0 SPHERICAL 0N CR SBKJC F DZP F DZP F DZP F DZP F DZP The use of effective core potentials is specified in the ZMAT file by the keyword ECP 0N The keyword BASIS must be set to BASIS SPECIAL The ecp nicknames are listed below the last basis set separated by a blank line using the same format as the non standard basis set specification XX ECPNAM As for the GENBAS file the ECPDATA file may be searched for XX where XX is the atomic symbol to show what ECPs are available for that atom Atoms included in the ZMAT file without an ecp parameter set are marked by the nickname NONE 9 1 6 Initial guessing with OLDMOS Suppose the user wishes to run an ROHF calculation but the default ROHF procedure does not converge or converges to the wrong electronic state The user could try to start the ROHF calculation from a converged set of UHF orbitals First run a UHF calculation xvscf writes the UHF orbitals to a small formatted f
93. fault DAMP_TOL integer 10 If DAMP_TYP DAVIDSON then the cutoff is defined to be N x 0 01 so the default cutoff is 0 1 DAMPSCF integer 20 If DAMP_TYP STATIC then the static damping factor used in the SCF iterations is N x 0 01 so the default damping factor is 0 2 SCF_EXTRAP previously RPP switch ON Controls whether or not the reduced partitioning procedure is to be used to accelerate convergence of the SCF equations 51 SCF_EXPORDER previously RPP_ORDER integer 6 Sets the number of density matrices to be used in the RPP convergence acceleration procedure SCF_EXPSTAR previously RPP_LATEST integer 8 Sets the latest iteration for initiation of the RPP convergence acceleration procedure RPP is switched on when the error falls below a certain threshold but in difficult cases in which the iterations are oscillatory it is necessary to force it on when the error is still large In these cases the RPP will begin on the iteration number specified by this parameter LSHF _A1 integer 0 Sets the doubles singles level shifting parameter a in which a Nx0 01 This keyword is currently only meaningful in ROHF calculations LSHF B1 integer 0 Sets the singles virtuals level shifting parameter 0 in which 0 N 0 01 This keyword is currently only meaningful in ROHF calculations 8 1 12 SCF reference adjustments DROPMO string of 1D array 0 Lists which molecular orbita
94. for H Ne It has been claimed in the literature that this basis set is not really of triple zeta valence quality 6 31G 6 31G supplemented with d polarization functions p functions for H and He It should be used with the SPHERICAL OFF option 6d functions since this is how the set was defined and developed Entries are available for H Cl The 6 31G basis set excludes p functions from H and He while retaining d functions on other atoms Polarization exponents are as follows H He 1 1 Li 0 2 Be 0 4 B 0 6 C Ne 0 8 Na Mg 0 175 Al 0 325 Si 0 45 P 0 55 S 0 65 Cl 0 75 6 311G 6 311G supplemented with polarization functions This should be used with the SPHERICAL ON option 5d functions Entries are available for H Ne Polarization 115 DZ DZP D95 D95 exponents are H He 0 75 Li 0 2 Be 0 401 C 0 626 N 0 913 O 1 292 F 1 75 Ne 2 304 This basis set was developed for correlated calculations This is the well known Dunning double zeta contraction of Huzinaga s 9s5p primitive gaussian basis set for first row atoms Entries are available for H B F This is the DZ set augmented with the polarization functions recommended by Red mon Purvis and Bartlett which were determined from correlated calculations Entries are available for H B F The polarization exponents are H 0 7 B 0 386 C 0 654 N 0 902 O 1 211 F 1 580 This is the same as DZ for H B F but
95. for distributing or maintaining the external programs Having independent licenses for external programs along with ACES II will allow users to take full advantage of this functionality Since ACES Il is the product of academic research group and not a software company we are unable to guarantee that all results obtained with it are correct Although we have made great progress in removing serious errors from the codes problems may still occur and should be reported to aces2 qtp ufl edu Any suggestions for improving the input or output wish lists for features or other comments may also be sent to this address 3 1 Overview of capabilities of ACES II The general capabilities of ACES II to determine single point energies analytical gra dients and analytical hessians are as follows 11 Single point energy calculations e Independent particle models include RHF UHF and ROHF e Correlation methods utilizing RHF and UHF reference determinants include MBPT 2 MBPT 3 SDQ MBPT 4 MBPT 4 CCD CCSD CCSD T CCSD TQ CCSD CCSD TQ CCSDT 1 CCSDT 2 CCSDT 3 QCISD QCISD T QCISD TQ UCCS 4 UCCSD 4 CID and CISD e Correlation methods that can use ROHF reference determinants include MBPT 2 CCSD CCSDT CCSD T CCSDT 1 CCSDT 2 and CCSDT 3 e Correlation methods that can use QRHF or Brueckner orbital reference determinants include CCSD CCSDT CCSD T CCSDT 1 CCSDT 2 and CCSDT 3 e Two determinant CCSD c
96. genvalue 0 2166464610 Instability classification RHF gt RHF with broken symmetry There are 2 instabilities within irrep 7 Eigenvalue 0 3586792381 Instability classification RHF gt UHF with broken symmetry Eigenvalue 0 2166464610 Instability classification RHF gt RHF with broken symmetry There are 0 instabilities within irrep 8 It is sometimes desirable to obtain solutions corresponding to following instabilities to lower energy stationary points in the orbital rotation space The keywords HFSTABIL ITY FOLLOW and ROT_EVEC are provided to assist with this When HFSTABILITY FOLLOW is set the stability analysis is performed as for HF STABILITY ON then the orbital rotation corresponding to the chosen instability is applied 76 to the SCF eigenvectors and the SCF calculation is repeated with these rotated vectors as a starting guess This is not strictly eigenvector following nor direct minimization SCF but in practice the procedure is quite effective By default the lowest eigenvalue of the totally symmetric irrep is followed Others can be followed by explicitly specifying them with the ROT_EVEC parameter Because instabilities in other than the totally symmetric irrep reduce the symmetry of the wavefunction only those in irrep 1 can be followed Following other instabilities requires performing the calculation in reduced symmetry Note that in C symmetry all instabilities will be in the totally symmetri
97. gradients then he or she should expect a lot of intervention before the coordinates converge In addition to complicated shell scripting the user must also know the exact order of ACES member executables that are required for each single point calculation The serial xjoda binary can accept two command line flags procs and rank that instruct it to set up single point calculations on a subset of the displacements Once the last displacement is complete but before the final xjoda the user must update each local file set with the data from all of the other file sets For vibrational frequencies this can be done on a single file set but for geometry optimizations each file set must be updated before taking the next step The two programs that are of primary concern are xjoda and xa2proc Every time xjoda is called the number of processes and the rank must be supplied on the command line xa2proc contains a module that will update print and load the data needed from each file set The following Korn shell script will run through every AME for every virtual process and collate the results of a vibrational frequency calculation This example does the same thing as the serial caces2 program on one CPU and is shown for demonstration purposes only bin ksh echo Do not run this script as is amp amp exit 1 pick a function alias loop lastraman for analytical gradients w raman intensities alias loop lastgrad for analytical gradients
98. has a number of options In RHF closed shell and UHF open shell calculations difficult cases will often converge with the use of a dynamical damping algo rithm due to E R Davidson This is achieved through the option DAMP_TYP DAVIDSON Damping serves to prevent excessively large oscillations in the early iterations Once the SCF convergence appears to be sufficiently smooth the damp factor is smaller than DAMP_TOL and the energy difference is sufficiently small the program reverts to repeated diagonal ization and DIIS extrapolation For ROHF calculations one can also use the damping algorithm but in addition the level shifting technique M F Guest and V R Saunders Mol Phys 28 819 1974 is particularly useful In this scheme one adds a positive number a to all diagonal elements of the singly occupied orbital block of the Fock matrix and a positive number a 0 to the diagonal elements of the virtual orbital block of the MO basis Fock matrix and 0 are set by the LSHF_Al and LSHF_B1 keywords If one wishes to use a value 0 2 a u for the level shifters LSHF_A1 and LSHF_B1 should be set to 20 This is a reasonable value for most systems Larger values of level shifters are sometimes necessary for transition metal systems especially when the singly occupied orbitals lie below some of the double occupied orbitals An example is provided by the following FeCl input excitation energies of this system were studied by N Oliphant and R J Bar
99. hat this is a somewhat simplified description that would work for a tetra atomic molecule such as hydrogen peroxide but would not be satisfactory for acetylene The latter requires dummy atoms These and several other tips for forming Z matrices are discussed below A more formal description of a line in the Z matrix input is as follows Each line may have as many as seven entries We consider the I line The contents are the 1 element of the ZSYM array the 3x I 3 x I 1 and 3 I 2 elements of the NCON and PARNAM arrays The ZSYM array is of length N where N is the number of lines in the Z matrix this includes those for any dummy and ghost atoms and contains the chemical symbols of all the atoms in the Z matrix The NCON and PARNAM arrays are of length 3 N NCON contains the numbers of atoms relative to which each atom is specified The PARNAM array contains the names of the lengths angles and dihedral angles contained in 31 the Z matrix Positions 3 J 2 are for lengths 3 J 1 for angles and 3 are for dihedral angles I 1 2 N It should be clear that elements 1 2 3 and 5 6 and 9 of NCON and PARNAM are not defined The I line I 1 2 N then has the general form ZSYM The atomic symbol of the atom dummy atom is X ghost is GH NCON 3 1 2 The number of the atomic center to which the atom is formally linked Note that this need only be a formal link the two atoms need not b
100. ies CCSD TQf NUMERICAL VIBRATION CALCULATION FOR N2 N 1R R 1 116 ACES2 CALC CCSD TQf BASIS DZP VIB FINDIF GRAD_CALC NUMERICAL This example specifies a finite difference frequency calculation for Ny using energy points from the CCSD TQf method This method of calculating frequencies is applicable to all types of energy calculations not just CCSD TQf 9 3 3 Isotopic shift ACES II provides a straightforward way to calculate changes in harmonic vibrational frequencies and infrared intensities due to isotopic substitutions This is accomplished with a free format file called ISOMASS which contains the desired atomic masses in their ZMAT order excluding dummy atoms For example if a user wants to calculate the 0 180 isotopic shift for the vibrational frequencies of water then the following ZMAT and ISOMASS files may be used 90 ZMAT Water frequency calculation ACES2 CALC SCF BASIS DZP VIB EXACT ISOMASS 18 0 1 00797 1 00797 91 10 Parallelization 10 1 Overview ACES II can perform the following calculations in parallel 1 HF SCF and MBPT 2 single point energies 2 HF SCF analytical geometry optimizations and 3 all finite displacement methods numerical geometry optimizations and vibrational fre quency calculations The SCF and MBPT 2 energy programs xp vscf and xp dirmp2 use direct integrals and communicate over the Message Passing Interface MPI The SCF gradients in xp_scfgrd use d
101. ile called NEWMOS These are expressed in terms of the symmetry adapted AO basis functions 72 and are printed by spin and symmetry block To run an ROHF calculation starting from these UHF orbitals 1 copy NEWMOS to OLDMOS in a new directory 2 copy in ZMAT and change REF UHF to REF ROHF 3 add GUESS READ_ SO MOS to the ACES2 namelist 4 copy in ZMAT BAS or GENBAS 5 run xaces2 The UHF job cd usr var tmp yau scr rm cp yau nh2 uhf zmt ZMAT cp yau GENBAS GENBAS xaces2 gt yau nh2 uhf out cp NEWMOS yau nh2 uhf mos The ROHF job cd usr var tmp yau scr rm cp yau nh2 rohf zmt ZMAT cp yau nh2 uhf mos OLDMOS cp yau GENBAS GENBAS xaces2 gt yau nh2 rohf out cp NEWMOS yau nh2 rohf mos 9 1 7 Initial guessing with OLDAOMOS The main use of this option is in finite difference vibrational frequency calculations In these calculations it is not possible to use the OCCUPATION keyword since the symmetry can change at various displacements Therefore the SCF program is not always able to converge to the correct electronic state at each geometry and sometimes the frequency calculation cannot be completed The GUESS READ_AO_MOS option is intended to solve this problem Users begin by performing a single point SCF calculation at the geometry at which vibrational frequencies are to be calculated In this calculation the occupation can be set to obtain the correct electronic state After the SCF xvscf creates a fo
102. ill case sensitive as are basis set names e The OCCUPATION keyword takes precedent over CHARGE and MULTIPLICITY This can lead to confusion in open shell SCF calculations Here are some usage tips 1 If OCCUPATION has been specified then the CHARGE and MULTIPLICITY keywords are ignored It is however good practice to make these consistent with OCCUPATION 2 If the REFERENCE keyword is absent from an open shell calculation or is erro neously set to RHF then unpredictable things might happen ACES II does not have a default type of open shell SCF 3 The occupation specified in the GUESS file takes precedent over all keywords Again it is sensible to make them the same to avoid confusion 100 4 In older binaries specifying only the a occupation with OCCUPATION dropped all electrons This is trapped in the current version e An input file contains text beyond the 80th column e There is no title line and the first line of the Z matrix has been entered as the title e There were files from a previous ACES II calculation in the workspace In general one should clear the workspace of all previous ACES II files prior to copying in the new files 11 2 Basic program restrictions e ZMAT should not change during a running calculation There might be some hacks that involve changing convergence tolerances mid stream but these are not documented supported or advised 11 3 Suggestions for reducing resources e ABC
103. ing the HF2 files created by VTRAN multiple times note that this option requires more CPU processing time and the setting of HF2_FILE SAVE AOBASIS uses an AO based algorithm to evaluate all terms involving the VVVV MO integrals Again use of this option results in considerably longer CPU times but significantly reduces the amount of disk storage more so for UHF and ROHF references than RHF AO LADDERS handle SINGLEPASS Specifies the algorithm used by ACES II when ABCDTYPE AOBASIS MUL TIPASS uses an approach where the AO integral file is read a number of times to maximize vectorization and is usually the optimal strategy on vector supercomputers SINGLEPASS determines the contributions with only a single pass through the AO integral files at the cost of significantly reduced vectorization 59 SAVE INTS switch OFF Controls deletion of the AO integrals file s after the AO to MO integral transformation If SAVE_INTS ON then these files are not deleted Any method that requires AO integrals during a post SCF calculation will automatically switch on this keyword VTRAN handle FULL PARTIAL Specifies what type of integral transformation is to be performed in the transforma tion program VTRAN FULL PARTIAL allows the program to choose the appro priate type of transformation while FULL forces a full integral transformation and PARTIAL skips the VVVV integrals This keyword is set automatically based on other re
104. irect integral derivatives in the same fashion The parallel finite displacement algorithm is handled by the main driver program xp_aces2 and distributes displacements to each MPI task All of these programs require each MPI task to have its own set of files which can be managed before and after the parallel run by xgemini ACES III the fully parallel successor to ACES II will be able to compute HF SCF MBPT 2 and CCSD energies and gradients using a message passing protocol either MPI or shmem Despite the new internal architecture it will be compatible with the current input files ZMAT and GENBAS but it will not require separate file sets for each task The following scripts illustrate each parallel capability The sections that follow describe in further detail how some of these capabilities work bin sh Script 1 parallel SCF and MBPT 2 energies mpirun np N xgemini i s t shared GRANK xjoda amp amp xvmol amp amp xvmol2ja mpirun np N xp_vscf mpirun np N xp_dirmp2 OMIT THIS LINE FOR SCF ENERGIES ONLY mpirun np N xgemini x s bin sh Script 2 parallel finite differences mpirun np N xgemini i s t shared GRANK mpirun np N xp_aces2 mpirun np N xgemini x s bin sh Script 3 parallel SCF geometry optimizations mpirun np N xgemini i s t shared GRANK PRUN mpirun np N parscfopt sh mpirun np N xgemini x s 92 10 2 Running xgemini xgemini is a tool for managing private scr
105. ists The code that parses ZMAT contains an error handler that shows the expected format in the event a read error occurs For TDHF calculations in particular the developers suggest running a small test calculation to verify the proper formats are used 9 1 11 EOM CCSD excitation energy EOM CCSD excitation energies and transition moments for water 01R H2R1A ACES2 BASIS TZ2P CALC CCSD EXCITE EOMEE ESTATE_SYM 1 1 1 1 ESTATE_PROP EXPECTATION This example specifies an equation of motion coupled cluster excitation energy calculation for the water molecule using the TZ2P basis set The program will attempt to find the lowest root in each of the four symmetry species of the Cy point group and oscillator strengths will be evaluated for all excited states 9 1 12 EOM CCSD electron attachment energy EOM CC electron attachment calculations yield energy differences between an N electron reference state and one or more electronic states of the N 1 electron system obtained by 79 adding an electron The keywords such as REFERENCE CHARGE MULTIPLICITY and OCCUPATION define the electronic state of the N electron system If EA CALC is set to EA EOMCC then energies of N 1 electron states are calculated The states are specified by the EA SYM keyword as a string of NIRREP REFERENCE RHF or 2 NIRREP REFERENCE UHF or ROHF integers where NIRREP is the number of irreducible representations in the computational point group The st
106. ition ACES II does not check to make sure that the atom to which the basis set belongs corresponds to the atomic designation in the corresponding row of the Z matrix No entries are made for dummy atoms The format of the basis set names in GENBAS is XX BASNAM where XX is the atomic symbol of the atom in capital letters and BASNAM is the name of the basis For new users it is probably best to search GENBAS for XX XX being the atomic symbol since this will show all of the available basis sets for that atom A description of the format of GENBAS and its contents are given in the next section 7 2 GENBAS ZMAT BAS The following fixed format is used to store basis sets in the GENBAS file Note that lines 5 7 and 8 define numbers of shells NS contractions NC and exponents NE 37 Fortran format A80 A80 A80 A80 13 NS 15 NS 15 NS I5 A80 NE F14 7 A80 NC F10 7 1X A80 Description blank line name of the basis set comment line blank line the number of shells in the basis set NS angular momentum for each shell L number of contracted basis functions for each shell NC number of exponents for that shell NE blank line exponents for the first shell blank line contraction coefficients for the first shell blank line It is necessary that the shells are grouped by angular momentum with the s shell s first followed by p shell s etc otherwise the input file written for the VMOL in
107. ity matrices for TDA EOM CC methods Unlike MRCC they both use the standard ACES II programming environment 5 18 vcceh xvcceh calculates EOM CCSD polarizability and NMR spin spin coupling constants 5 19 dens xdens calculates the one and two particle correlated density matrices in the MO basis 17 5 20 props xprops computes all of the first order properties dipole moments electric field gradients electric quadrupole moments electrostatic potentials spin densities for open shell molecules etc It also computes the scalar relativistic corrections and the Mulliken population anal ysis 5 21 anti xanti sorts and de antisymmetrizes the two particle density matrix 5 22 bcktrn xbcktrn performs the MO AO transformation of the density matrices for direct con traction with the integral derivatives in the AO basis 5 23 vdint vksdint scfgrd and p_scfgrd VDINT is a heavily modified version of the integral derivative program ABACUS written by T Helgaker P Jorgensen H Aa Jensen and P R Taylor suitable for CC MBPT gradi ent calculations In addition to integral derivatives with respect to geometrical perturbations it calculates one and two electron integrals required for chemical shift calculations within the GIAO scheme For the most part xvdint calculates the gradient in ACES II For KS reference wavefunctions xvksdint calculates the contribution from the functional deriva tive xscfgrd calculates the
108. levant keywords HF2 FILE handle USE Specifies whether the HF2 file series including HF2AA HF2BB and HF2AB is deleted after the first stage of integral processing The default is to delete these files however when ABCDTYPE MULTIPASS these files must not be deleted and the program sets HF2_FILE SAVE ABCDFULL handle UNKNOWN This is a debug aid and is concerned with the storage of VVVV integrals and effective Hamiltonian elements It is only relevant to RHF calculations and it should never be necessary for users to set this keyword Possible values are UNKNOWN the program will choose an appropriate value ON full storage and OFF reduced storage HBARABCD handle UNKNOWN Controls the formation and storage of the VVVV block of the effective Hamiltonian It should never be necessary for users to set this keyword Possible values are UN KNOWN the program will choose an appropriate value ON full storage and OFF reduced storage HBARABCI handle UNKNOWN Controls the formation and storage of the VVVO block of the effective Hamiltonian It should never be necessary for users to set this keyword Possible values are UN KNOWN the program will choose an appropriate value ON full storage and OFF reduced storage GAMMA_ABCD handle DISK 56 Controls the evaluation of the two particle density elements when all four indices cor respond to virtual orbitals This works in conjuncti
109. lization and the subsequent numerical updates work satisfactorily for most small molecules there can be oc casional problems In these cases one might wish to use an alternative initial force constant matrix particularly one obtained by ACES II at the same or another level of theory There are a number of ways in which one might do this First the EVAL_HESS keyword can be used If nonzero the value associated with this keyword directs ACES II to calculate the 88 SCF Hessian matrix prior to the first optimization step and then every N steps thereafter where N is the value of EVAL_HESS By setting N to a sufficiently large value larger than OPT MAXCYC then the Hessian will never be recalculated and the optimization will begin with the SCF Hessian However the strategy based on EVAL_HESS is not sufficient for all purposes For ex ample one might wish to use a Hessian which is evaluated at the correlated level This is not possible with EVAL_HESS since it will direct ACES II to calculate only the SCF Hessian regardless of the calculation type Alternatively one might adopt the economi cal strategy of using a Hessian which is evaluated at a low level of theory such as SCF with the STO 3G basis set This is the recommended approach for transition state searches and all optimizations for which the default Hessian is inadequate In any event it is quite straightforward to use another set of force constants to begin an optimization First one
110. ll approximations This keyword only has meaning when PROP EOM_NLO J_SO J_FC J_SD or JSC_ALL 64 TDHF switch OFF Controls whether a time dependent Hartree Fock calculation of nonlinear optical prop erties is to be performed This keyword can only be used for closed shell SCF calcula tions with no dropped MOs The nonlinear properties which are to be calculated are specified by a namelist which is put at the end of the ZMAT file A description of this namelist and an example can be found in Section 9 1 10 page 77 CPHF_CONVER tol 12 Sets the convergence criterion for the iterative solution of the CPHF and Z vector equations The solutions are considered to be converged when the error falls below 10 CPHF_MAXCYC integer 64 Sets the maximum number of cycles allowed for the solution of the CPHF and Z vector equations TREAT PERT handle SIMULTANEOUS This keyword is used for certain types of correlated second derivative calculations presently only GIAO NMR shift calculations and directs ACES II to either treat all perturbations at once or treat them sequentially The latter approach results in less demand for physical disk space at the cost of increased cpu time Available options are SIMULTANEOUS and SEQUENTIAL XFIELD integer 0 Sets the X component of an external electric field The value must be specified as an integer and the field used by the program will be N x 1076 This allows field strengths IE g
111. ls will be dropped from the post SCF calculation The orbitals are ordered by eigenvalue from the most stable negative energy to the most unstable largest positive energy regardless of irrep The delimiter is a forward slash that separates single orbitals and orbital ranges x y inclusive For example the string 1 5 55 62 64 will cause VTRAN to drop orbitals 1 2 3 4 5 55 62 63 and 64 For UHF calculations the appropriate orbitals are deleted from both spin cases HFSTABILITY handle OFF Checks the stability of RHF and UHF wavefunctions and optionally rotates the orbitals to a lower SCF solution There are three possible options for this keyword OFF does nothing and ON performs a stability check and returns the number of negative eigenvalues in the orbital rotation Hessian FOLLOW performs the stability check and then proceeds to rotate the SCF orbitals in the direction of a particular negative eigenvalue of the orbital rotation Hessian see the explanation of the ROT_EVEC keyword below after which the SCF is rerun 52 ROT_EVEC integer 0 Defines which eigenvector of the orbital rotation Hessian will be used to rotate the original SCF orbitals By default it will use the eigenvector with the lowest eigenvalue of irrep 1 the totally symmetric part of the block factored Hessian This choice often leads to the lowest energy SCF solution For RHF stability checks only those instabilities which correspond to RHF
112. ly included as a reminder of the options The input is as follows NIRREP is the order of the computational point group or 4 in the present case and NSPIN is the number of spins 1 for RHF 2 for UHF and ROHF 40 Line 1 A80 A title Next NSPIN NIRREP 13 The alpha beta occupation vector Next NIRREP NSPIN 4 13 Pairs of orbitals to be swapped in each spatial symmetry block for each spin sym metry Two numbers are needed to specify each pair therefore no more than two interchanges may be made for a given symmetry block and spin Next NSPIN NIRREP 13 Symmetry block occupation lock flags Orbital occupation proceeds in the direction of minimum change by monitoring C3 p C Zero is unlocked a positive integer is locked Next NSPIN NIRREP 13 Print flags for alpha beta initial guess A positive integer prints the guess for that symmetry block while a zero does not Next 1 2 13 Stopping parameters Set the first value to a positive integer to stop the SCF after computing the initial guess Next 1 13 I O parameter If set to a positive integer then the initial guess MOS are read from OLDMOS Next 1 13 UHF creation parameter which copies the alpha MOs to the beta MOs This is only meaningful if the guess is read from OLDMOS This allows a user for example to start a UHF calculation with an RHF closed shell set of orbitals A positive integer reads only the alpha orbitals and a zero read
113. m Phase approximation RPA c Equation of Motion Coupled Cluster EOM CC methods e J F Stanton and R J Bartlett J Chem Phys 98 7029 1993 106 12 7 Methods for calculating electron attachment energies The electron affinity equation of motion coupled cluster method e M Nooijen and R J Bartlett J Chem Phys 102 3629 1995 12 8 Time dependent Hartree Fock methods e H Sekino and R J Bartlett J Chem Phys 85 976 1986 e H Sekino and R J Bartlett Int J Quantum Chem 43 119 1992 12 9 HF DFT method e P M W Gill B G Johnson and J A Pople Int J Quantum Chem Symp 26 319 1992 e G E Scuseria J Chem Phys 97 7528 1992 e N Oliphant and R J Bartlett J Chem Phys 100 6550 1994 12 10 Basis sets STO 3G e W J Hehre R F Stewart and J A Pople J Chem Phys 51 2657 1969 first row elements e W J Hehre R Ditchfield R F Stewart and J A Pople J Chem Phys 52 2769 1970 second row elements and improved scale factors for Li and Be e W J Pietro B A Levi W J Hehre and R F Stewart Inorg Chem 19 2225 1980 third row elements e W J Pietro E S Blurock R F Hout Jr W J Hehre D J DeFrees and R F Stewart In org Chem 20 3650 1981 fourth row elements e W J Pietro and W J Hehre J Comput Chem 4 241 1983 first and second row transition metal elements 3 21G e J S Binkley J A Pople and W J Hehre J Am Chem Soc 102 939
114. mal basis set developed by Pople and coworkers in the early 1970s entries are in the GENBAS file for all atoms from H to Cl STO 3G basis sets are available in the literature for the third and fourth row main group elements as well as some transition metal elements The STO 3G basis is now largely obsolete except for some calculations on large molecules Its use is not recommended for other than testing and rough preliminary investigations 3 21G This is a small split valence basis set developed by Pople and coworkers It uses a minimal basis or single zeta description for the core orbitals and a double zeta description for the valence orbitals Entries are in the GENBAS file for H Cl 3 21G sets are available in the literature for heavier elements This and other sets of this type such as 4 31G and 6 31G are often termed double zeta valence This is not strictly accurate since the s and p exponents are constrained to be equal which they are not in a true double zeta set although the two sets give results of similar quality 4 31G This is similar to the 3 21G set but with more primitive gaussian functions Entries are available for H Cl 6 31G This is yet another split valence set employing still more primitive gaussians Entries are available for H Cl 6 311G This is a split valence set with a triple zeta description of the valence orbitals and a minimal basis set description of the core orbitals Entries are available
115. mentation for closed and open shell CCSD e J Gauss J F Stanton and R J Bartlett J Chem Phys 95 2623 1991 c QRHF CCSD gradients e J Gauss J F Stanton and R J Bartlett J Chem Phys 95 2639 1991 d ROHF CCSD gradients e J Gauss W J Lauderdale J F Stanton J D Watts and R J Bartlett Chem Phys Lett 182 207 1991 e QCISD gradients e J Gauss and D Cremer Chem Phys Lett 150 280 1988 e J Gauss J F Stanton and R J Bartlett J Chem Phys 95 2623 1991 f MBPT 4 gradients for closed and open shells e J Gauss and D Cremer Chem Phys Lett 138 131 1987 153 303 1988 e G W Trucks J D Watts E A Salter and R J Bartlett Chem Phys Lett 153 490 1988 e J D Watts G W Trucks and R J Bartlett Chem Phys Lett 164 502 1989 e J D Watts J Gauss and R J Bartlett Chem Phys Lett 200 1 1992 g CCSD T CCSD CCSD T gradients for closed and open shells e J D Watts J Gauss and R J Bartlett Chem Phys Lett 200 1 1992 e J D Watts J Gauss and R J Bartlett J Chem Phys 98 8718 1993 h QCISD T gradients e J Gauss and D Cremer Chem Phys Lett 163 549 1990 e J D Watts J Gauss and R J Bartlett Chem Phys Lett 200 1 1992 i UCC 4 gradients for closed and open shells e J D Watts G W Trucks and R J Bartlett Chem Phys Lett 157 359 1989 e J D Watts G W Trucks and R J Bartlett Chem Phys Lett 164 502 1989 j Two determinant CCSD TD C
116. most users would definitely use the first Z matrix the idea of using just chemical bonds as internuclear distances can be dangerous 33 For example in a regular hexagonal ring a little reflection will show that one cannot include all six inter vertex distances in the Z matrix If only five are specified such as in the Z matrix below the 1 6 distance is missing the internal coordinate gradient cannot have the full symmetry of the molecule and the first step of a geometry optimization will break the molecular symmetry This results in extremely slow convergence and significantly increased CPU time due to the reduced molecular symmetry A poor Z matrix for hexagonal C6 C C 1 R C 2 R 1 C3R2A1T C4R3 A2T C5R4A3T R 1 33 A 120 T 0 In these situations it is always best to use dummy atoms which are merely mechanisms to reference a point in space for other coordinates One or more dummy atoms are needed in essentially all Z matrices for molecules with high symmetry As an example of their use a good Z matrix for the Ce ring is shown below Don t be afraid to use dummy atoms A better Z matrix for hexagonal C6 X X 1 RX C2R1A C2R1A3T C2R1A4T C2R1A5T C2R1A6T C 2 Rl AT T RX 1 0 R 1 33 A 90 T 60 7 1 9 ACES2 namelist The ACES2 namelist is a keyword value pair listing with a few tweaks Every keyword has an internally declared type which controls what form the value word s may take Currently
117. nents are those of Redmon et al for H B F while estimates of 0 2 0 3 and 1 9 are used for Li Be and F 117 svp dzp tzp tzplarge qz2p These are the new basis sets from Schafer Horn and Ahlrichs which have been optimized for atoms and supplemented by suitable polarization func tions Note that these basis sets are denoted in the GENBAS file by lower case letters They are recommended in particular for chemical shift calculations and should in the long run replace the old and not completely optimized Dunning Huzinaga basis sets denoted by DZP and TZ2P in the GENBAS file Basis sets are in principle available for all atoms If a needed basis set is not included in the GENBAS file it can be obtained via FTP The tables on the following pages list the numbers of generally contracted AO basis functions for each element in each set The negative subscript shows the number of redundant Cartesian AOs For example oxygen in the CC PVQZ basis set listed as 70 15 has 70 Cartesian AOs but only 55 if spherical harmonics are used with SPHERICAL ON in the ACES2 namelist 118 2 ez 61 61 PE OFFTE9 LI LI eT I G D I8 9 S g 61 61 S 0T TEH 61 61 S S g noia 61 61 aor E DIE 9 I I 6 6 S 518 9 I 6 6 OTE I I 6 6
118. ng Entries are available for H Ne PBS These are double zeta plus diffuse basis sets developed by Sadlej for the calculation of electrical properties They seem to do a good job of predicting dipole moments and polarizabilities and are also useful in excited state calculations where the first member of a Rydberg series is usually recovered TZP This is a triple zeta valence plus polarization basis set Entries are currently available for H B Ne Na and Mg For H it comprises Dunning s 3s contraction of Huzinaga s 5s primitive set augmented with the p exponent of Redmon Purvis and Bartlett 0 7 For B F it comprises Dunning s 5s3p contraction of Huzinaga s 10s6p primitive set augmented with the polarization exponents of Redmon Purvis and Bartlett see entry DZP above For Ne the basis set is the Dunning 5s3p set augmented with a polarization exponent of 1 9 an estimate based on the values of Redmon et al For Na and Mg the basis set is 6s5p1d with the sp part coming from McLean and Chandler and d exponents of 0 1 and 0 2 reasonable estimates 5s4pld As TZP but the sp part Dunning s 5s4p contraction of Huzinaga s 10s6p primitive Entries are available for B Ne VDZP This is a valence double zeta plus polarization basis set for all first row atoms except He taken from Dunning and Hay It has the advantage that sets for Li and Be exist in contrast to the DZP set However it has not been well tested The polarization expo
119. ng message Nonsymmetric density matrices result from calculations on electronically degenerate states or from broken symmetry SCF solu tions Often such calculations do not give meaningful results and inexperienced users are encouraged to use CHECK_SYM NORMAL in their calculations on nonlinear molecules For IT A states of linear molecules however meaningful calculations can still be performed even though the density matrix is not symmetric SCF_PRINT integer 0 This keyword is currently not used but exists for future compatibility 8 1 10 SCF orbital control GUESS handle MOREAD Specifies where the initial SCF eigenvectors are read from The HF SCF executable checks multiple places for pre existing orbitals but this keyword can override that logic 49 MOREAD JOBARC file CORE core Hamiltonian READ SO MOS gt OLDMOS file from NEWMOS READ_AO_MOS OLDAOMOS file from AOBASMOS Other options include NDDO WALT_PRJDEN MIN_BASIS and HUCKEL although some of these are still experimental and not fully supported OCCUPATION string of irrep by spin array Specifies the orbital occupancy of the reference wavefunction in terms of the occupation numbers per irrep per spin The occupancy is specified by NIRREP or 2 NIRREP integers that define the number of occupied orbitals of each symmetry type NIRREP is the number of irreducible representations in the computational point group I
120. of type string are self explanatory however they are used to read in fixed format arrays until we define a general expression for array notation Hopefully the formats of keywords that accept arrays are clearly described in the manual Integers are also self explanatory and can be used in place of handles for those keywords of such type As mentioned before a tol type is an integer that corresponds to the negative power of 10 Some keywords are defined with unusual units and these are appropriately identified in the manual Currently reals apply only to memory related keywords These are identified as type special because the parser will scale the real by units suffixed to the value string 8 1 1 System general CALCLEVEL handle SCF Specifies the general level of theory to be used throughout the program Acceptable values are SCF MBPT 2 MBPT 3 SDQ MBPT 4 MBPT 4 LCCD LCCSD UCCSD 4 CCD UCC 4 CCSD CCSD T CCSD TQ CCSDT 1 CCSDT 1b CCSDT 2 CCSDT 3 CCSDT 4 CCSDT LCCSDT CCD ST CCD QCISD T CCSD T QCISD CID CISD QCISD TQ CCSD TQ CCSD TQ CCSDT Q CCSDT Q CC5SD T CCSD T CC3 CCSDT T1T2 CCSDTQ 1 CCSDTQF 1 CCSDTQ 2 CCSDTQ 3 CCSDTQ ACCSD and HFDFT Emphasized calculation levels in italics are not implemented currently but are planned for future versions of the program CALC HFDFT has been obsoleted by SCF_TYPE KS MEMORY SIZE special 15000000W Sets the maximum memory to allo
121. omplicated vacuum states for post Hartree Fock calculations NOTE The UNO keywords together with MAKERHF can be used to create a refer ence determinant that is used primarily in connection to certain types of multireference calculations run in MRCC 54 UNO_CHARGE integer 0 Sets the charge of the final reference state UNO_MULT integer 1 Sets the spin multiplicity of the final reference state The orbitals are occupied in order of their natural occupation number Often this keyword is used to create a closed shell reference vital if the MRCC module is used In this case the program can proceed as an RHF calculation MAKERHF switch OFF MAKERHF ON instructs the post SCF logic to proceed as an RHF calculation and must be specified in an MRCC calculation 8 1 13 Post SCF file options SINGLE STORE switch OFF Controls storing permutations of commonly resorted two particle quantities like MO integrals and T amplitudes If a calculation is running out of disk space then setting SINGLE_STORE ON might allow the calculation to finish ABCDTYPE handle STANDARD Specifies the way that VVVV molecular orbital integrals having four virtual MOs are handled in post SCF calculations STANDARD uses a technique that mini mizes CPU time but makes liberal use of disk storage particularly during the integral processing program INTPRC MULTIPASS avoids creating intermediate sort files during INTPRC by read
122. on with the ABCDTYPE key word When ABCDTYPE AOBASIS the ABCD integrals are not stored on disk and GAMMA_ABCD is set to DIRECT When ABCD integrals are stored to disk GAMMA_ABCD must be set to DISK 8 1 14 Post SCF calculations CC_CONV tol 7 Sets the convergence criterion for the CC and Lambda equations Equations are con sidered converged when the maximum change in amplitudes is less than 107 CC_MAXCYC integer 50 Sets the maximum number of CC or Lambda iterations CC_EXTRAPOL previously RLE handle DIIS Specifies the type of convergence acceleration used during the CC iterations STAN DARD uses the RLE method of Bartlett and Purvis with periodic extrapolation of the solution vector DIIS uses the DHS approach of Pulay NOJACOBI uses the RLE method with continuous extrapolation and OFF uses no convergence acceleration In general DIIS works well for a wide range of molecular systems while RLE can be better for certain cases NOJACOBI might offer advantages in cases where the reduced subspace becomes singular too rapidly NOJACOBI requires some additional disk stor age which might be disadvantageous for very large calculations OFF is generally a bad idea for CC calculations but might be preferred by some CI calculations CC_EXPORDER previously ORDER_RLE integer 5 Sets the maximum number of iterates to include in the R matrix used by RLE and DIIS The maximum value allowed is 25 XFORM TOL tol 11
123. or the arrays the dimension string can be of the form R C RxC 20 and RXC in which R is the number of rows and C is the number of columns The following results were taken after an H202 DZP SCF geometry optimization gt xa2proc jareq i NATOMS 1 4 gt xa2proc jareq d TOTENERG 1 0 150816196754E 03 gt xa2proc jareq ad GRADIENT 3x4 0 000079292458 0 000079292458 O 000034723378 0 000034723378 O 000006762679 0 000006762679 O 000088780697 0 000088780697 O 000000000000 O 000000000000 O 000000000000 O 000000000000 5 27 9 xyz This module prints the Cartesian coordinates of the current geometry This could be used in a script that automatically runs a vibrational frequency calculation after a geometry optimization 5 27 10 test The TEST module is used by the automated regression test suite Its use is beyond the scope of this manual but interested users are encouraged to examine the files in the ACES II test directory 5 28 gemini xgemini is used to manage scratch directories in parallel calculations Parallel AMEs xp aces2 finite differences xp_vscf xp_scfgrd SCF energies and gradients and xp_dirmp2 MBPT 2 energies all operate under the premise that each MPI task has its own ACES II file set to modify To prevent the tasks from clobbering each other s files xgemini can create destroy and manipulate private scratch directories for each task 21 6 File Structure 6 1
124. ors Zero eigenvalues will occur for degenerate electronic states and merely indicate the equiv alence of occupations within the computational point group Small numerical inaccuracies frequently result in nominally zero eigenvalues having small non zero values The sign of such eigenvalues will determine whether or not they are reported as instabilities Thus the program might not show the expected number of zero small eigenvalues Other instabilities such as the wavefunction becoming complex are not tested since complex wavefunctions are not presently supported in ACES II In the program output stability analysis is headed by the label RHFSTAB or UHF STAB The number of instabilities in each irrep is given along with their eigenvalue and classification For example RHFSTAB Performing stability analysis of RHF wavefunction Orbital rotation parameters will be evaluated for each symmetry block There are 0 instabilities within irrep 1 There are 1 instabilities within irrep 2 Eigenvalue 0 1411211526 Instability classification RHF gt UHF with broken symmetry There are 1 instabilities within irrep 3 Eigenvalue 0 1411211526 Instability classification RHF gt UHF with broken symmetry There are 0 instabilities within irrep 4 There are 0 instabilities within irrep 5 There are 2 instabilities within irrep 6 Eigenvalue 0 3586792381 Instability classification RHF gt UHF with broken symmetry Ei
125. ounj stiseq OV P9y9e 13u09 Jo qumu AL 9ABL 128 THE TT TANAYO pe pg Oras ET JOZATINVT 8 0 YT ZAZINVI YT ZCA LAVM AVH YT INTLAVM AVH S S SISeq dow ep gg Sg t 99 16r 16 9 46 83 16 ot 93 16 96 9 46 96 06 awoiNn0o SHOraTHV E E diVOTNOO NOWAG aog aag HONVHOXA TV SSAVDA agg E INOTNODTV SSAVIDA 6 68 dAZG ssnv5q 1 46 ZLAdLATAVS 6 9 97 9 SILM 2719 xO 11679 S5779 e KO LIS 9 v 19 e DITE 9 ee E DIE 0 GIN IGN 6 6 DE OLS 1 az as NS nt ao ov aa wa ou on ow an Juz a en dg PY syuatua e SQ YSNOIT Pp 107 SYANAD ut 109 stseq YORe 10 suomo unj siseq OV popriyuo Jo Joquinu oy ARI 129 x E 6 LOOSU LS F OTH LS S oT SANduo AL as ns N ao ov aa mu ow OL ow an uz A pos de py syuatua e SQ YSNOIT Pp 107 SV8N3D5 ut Jos stseq YORe 10 SOHO siseq OV pojovsyuod Jo Joquinu AL IABL 130 B 2 ECP sets in ECPDATA 131 C Queue Scripts While nothing prevents ACES II programs from running interactively or in the back ground many computing facilities require large batch jobs to be executed by automated queueing systems Documenting every scheduler that use
126. passed to a number parser so trailing text like a comment is ignored Angles must be entered in degrees and bond angles as distinct from dihedral angles of 0 and 180 are not allowed since these lead to a singularity in the transformation between 32 Cartesian and internal coordinates and do not allow dihedral angles to be defined This of course does not mean that ACES II is unable to handle linear molecules such as carbon dioxide Rather for linear molecules dummy atoms must be used in the Z matrix to avoid problematic bond angles To facilitate construction of Z matrices for highly symmetric molecules certain variable names have been reserved for specific values To use these parameters which are listed below the user must specify a value in the parameter input section but it need not be correct since it will be converted to the exact value internally TDA Specifies the tetrahedral angle Cos 3 L e 109 4712 IHA Specifies the icosahedral angle Cos v3 i e 63 4349 7 1 8 Z matrix analyzer A unique feature of ACES II is the Z matrix analyzer which is capable of detecting subtle and obvious deficiencies in the definition of internal coordinates This is particularly important for geometry optimizations in which the construction of the Z matrix and the choice of parameters to be optimized are of vital importance The analyzer inspects the internal coordinates and carries out a num
127. pear to be best used with the SPHERICAL ON option Indeed whether SPHERICAL is ON or OFF has a significant effect on the results Entries are available for H He B Ne and Al Ar We do not recommend the PVDZ set For little extra cost one may use the DZP basis set and obtain significantly improved results PVTZ Dunning s polarized valence triple zeta correlation consistent basis 4s3p2d1f for second row atoms Entries are available for H He B Ne Al Ar 116 PVQZ Dunning s polarized quadruple zeta valence correlation consistent basis set 5s4p3d2 f 1g for second row atoms Entries are available for H He B Ne and Al Ar PV5Z Dunning s polarized pentuple zeta valence correlation consistent basis set 6s5p4d3 f2g1h for second row atoms Entries are available for H B F Al Ar WMR Generally contracted basis functions developed by Widmark Malmqvist and Roos for the study of molecular and atomic properties These are rather large basis sets 6s4p3d for H 7s4p3d for He 7s6p4d3f for second row atoms and can be reduced to normal size through use of the GENBAS_X keywords A limited amount of experience with these basis sets suggests that valence double zeta and valence triple zeta contractions 3s2pld and 4s3p2d1f for first row atoms 2s1p for H and He work reasonably well For a given level of contraction these basis sets appear to provide superior molecular structures and properties to the correlation consistent sets of Dunni
128. pins occ 1 1 2 2 1 1 2 2 e 2 irreps 1 spin ip sym 1 0 e 8 irreps 3 spin pairs ee sym 1 1 1 1 0 0 0 0 1 1 1 1 0 0 0 0 1 1 1 1 0 0 0 0 Sets are merely one dimensional arrays of values The set delimiters are the same as the matrix ones except that the dash specifies a range of values and the forward slash separates single values Currently the only keywords that accept this type of string are DROPMO FD_IRREPS ESTATE_SYM QRHF_GEN QRHF_ORB and QRHF_SPIN Here are some examples e drop orbitals 1 2 3 10 11 and 12 dropmo 1 3 10 12 e compute frequencies of modes that transform as irreps 1 3 and 4 fd irreps 1 3 4 e add an electron to the third lowest virtual of irrep 2 and remove an elec tron from the highest occupied of irrep 4 qrhf_gen 2 4 qrhf_orb 3 1 NOTE This syntax is very different from previous versions Some value strings may be allowed by any version but might mean entirely different things For example DROPMO 1 31 used to mean dropping orbitals 1 35 and 31 from the correlated calculation If that string was parsed by the new xjoda VTRAN would attempt to remove every orbital from 1 to 31 long Integers are parsed in a fairly straightforward manner For example print 1 and charge 1 There is one special state variable that recognizes units appended to the value and that is MEMORY Recognized units are b ytes and w ords with SI prefixes k ilo m ega and
129. plane 29 For groups with ambiguities D gt D n C2 there is no standard orientation at present and users might want to run xjoda once to show which orientation is used before assigning orbital symmetries For example water belongs to the C2 point group and the symme try plane containing the hydrogen atoms might be assigned to either the xz or yz planes leading to an ambiguity between the b and ba irreducible representations Eventually some criterion could be established that can define a standard orientation for these groups thereby alleviating this issue 7 1 5 Dummy and ghost atoms Dummy atoms represented with X are only useful for internal coordinates and define points in space They do not have basis functions and do not affect the symmetry of the molecule They are necessary to break angles of 180 and are used to define highly symmetric molecules with no atom at the center of mass Ghost atoms which are specified by the symbol GH have zero nuclear charge However while dummy atoms are invisible to the program outside the coordinate generator ghost atoms serve as a center for basis functions This feature is particularly useful for calculations that determine the basis set superposition error BSSE and has several other applications such as describing lone pair electrons of a molecule by functions that are not centered at any of the molecular nuclei Symmetry can be used in such calculations bu
130. ptation AOBASMOS and OLDAOMOS work the same as NEWMOS and OLDMOS except that OLDAOMOS can be used to initialize SCF orbitals in vibrational frequency calculations in which the point group symmetry could change for each displacement 22 6 7 FCMINT FCM FCMSCR and FCMFINAL FCMINT contains the full internal coordinate force constant matrix The other files FCM FCMSCR and FCMFINAL correspond to the symmetrized mass weighted and analytical force constant matrices respectively The example in Section 9 2 6 page 88 shows how FCMINT can be used to initialize the Hessian matrix in a geometry search 6 8 frequency This file is a simple ASCII free format file that specifies the frequency or frequencies at which dynamic polarizabilities are computed 6 9 ISOMASS Vibrational frequencies can be calculated with standard atomic masses or user supplied masses usually of isotopes If a file named ISOMASS is found then the vibrational frequency logic in JODA replaces the atomic masses with those found in the file The content is free format ASCII and the order of the masses must match the non dummy centers in ZMAT 6 10 System files 6 10 1 JOBARC JAINDX The JOBARC file stores records named arrays for the ACES II program system The accompanying file JAINDX stores metadata about the records 6 10 2 MOINTS GAMLAM MOABCD DERINT DERGAM These files store lists of double precision arrays used by all of the post SCF member exec
131. rch RFA uses the Rational Function Approx imation minimum energy search and can be used when the initial structure is in a region where the number of negative Hessian eigenvalues is nonzero MANR uses a Morse adjusted Newton Raphson minimum energy search and is very efficient if the Hessian is available EVFTS uses Cerjan Miller eigenvector following for finding a transition state can be started in a region where the Hessian index the number of negative Hessian eigenvalues is not equal to one MAEVFTS uses a Morse adjusted eigenvector following for finding a transition state MAX STEP integer 300 Sets the largest step size in millibohr STP_SIZ_CTL handle TRUST_RADIUS Controls how the step size is scaled TRUST_RADIUS uses the dynamic scaling by Fletcher NORM uses the absolute step length and MAXIMUM uses the largest individual step in the internal coordinate space EIGENVECTOR integer 1 Sets which eigenvector of the totally symmetric part of the block factored Hessian is to be followed uphill in a transition state search Eigenvectors are indexed by their 66 eigenvalues the lowest eigenvalue is 1 the next lowest is 2 etc The default should always be used if you are not looking for a specific transition state which you know corresponds to motion along a different mode The value of EIGENVECTOR has no meaning if OPT_METHOD is not set to EVFTS or MAEVFTS NEGEVAL handle RFA Specifies
132. restricted open shell Hartree Fock reference The program automatically turns on the NON HF option so the appropriate non Hartree Fock terms are included in the coupled cluster equations It also automatically sets ORBITAL SEMICANONICAL which is needed to evaluate triple excitations non iteratively as in the CCSD T method 9 1 4 QRHF CCSD T energy H20 QRHF CCSD T energy calculation DZP basis set H D 1 ROH H 2 ROH 1 HOH ROH 0 95 HOH 104 5 ACES2 REF RHF CALC CCSD T BASIS DZP QRHF_GENERAL 1 ORBITAL SEMICANONICAL OCCUPATION 3 1 1 0 3 1 1 0 This is another way in which one can calculate the energy of an open shell molecule Here the energy of the 7A state of the water cation is being calculated by the QRHF CCSD T method The orbitals however are not from an SCF calculation on H20 Rather they are orbitals from the neutral molecule In general QRHF means orbitals are taken from a convenient closed shell system and are then used in an open shell system An important difference between this example and the previous examples is that the CHARGE MULT REF and OCCUPATION keywords do not refer to the system being studied HOF but instead refer to the system from which the orbitals are obtained H20 QRHF_GENERAL 1 along with the default values for QRHF_ORBITAL and QRHF SPIN means the reference function for the correlated calculation is to be formed by removing a P spin electron from the highest occupied orbital o
133. ring of numbers specifies the numbers of N 1 electron states of a given symmetry and the spin of the additional electron in each N 1 electron state For closed shell systems only the alpha roots have to be specified EA SYM 3 2 0 2 for example For open shell systems one can either attach an electron of alpha spin or one of beta spin leading to different states of the N 1 electron system The different spin blocks are separated by a slash as in EA SYM 3 2 0 2 0 1 0 4 This keyword does not have to be specified in an EA EOMCC calculation If EA SYM is not specified but EA CALC EA_EOMCC the program tries to find the ground state of the N 1 electron system internally We can recommend three types of applications of the EA EOMCC program 1 The calculation of electron affinities Only EA CALC EA_EOMCC needs to be spec ified If it is known what the symmetry of the ground state is for the N 1 electron system specify also EA SYM The following input yields the electron affinity of the sodium atom NA atom NA ACES2 REFERENCE UHF CALC CCSD BASIS DZP MULTIPLICITY 2 SPHERICAL ON EA_CALC EA_EOMCC The keyword EA_SYM 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 might have been specified such that only the closed shell 3s state of the sodium anion is calculated and no other possibilities are considered for the symmetry of the anion ground state 2 The calculation of excitation spectra for systems with an odd number of electrons
134. rmatted file called AOBASMOS Before the frequency calculation the OCCUPATION keyword must be removed from ACES2 the option GUESS READ_AO_MOS must be set and the AOBASMOS file must be renamed OLDAOMOS At each point in the frequency calculation the MOs are read from 73 OLDAOMOS and transformed to the current symmetry The occupation is determined in the current point group and since the displacements from the reference geometry are small the initial guess is usually very good It is also possible to use the final AOBASMOS file from a geometry optimization or transition state search as the OLDAOMOS file in a frequency calculation The GUESS READ_AO_MOS option can be used in other situations but it might not work well when the geometry changes significantly The reason for this is that a transformation matrix relating the different geometries must be calculated and this is only approximated well by a rotation if the geometries are close 9 1 8 Improving SCF convergence VSCF contains a number of options for accelerating and controlling the SCF convergence By default the first few iterations proceed by repeated diagonalization of appropriate Fock matrices Once either a certain number of iterations have been performed specified by RPP_LATEST or an initial convergence criterion has been met the DHS convergence ex trapolation procedure of Pulay begins If convergence difficulties are experienced with the default scheme the user
135. rocedure Like all optimizations transition states searches use analytical gradients by default If these are not available then the user must use GRAD_CALC NUMERICAL 9 2 5 Restarting an optimization or frequency calculation savedir SAVEDIR restartable H2 geom opt H H 1 R R 1 0 ACES2 basis DZP restart 87 This example reinforces the default restart behavior If restarting the calculation is not necessary then use RESTART OFF or RESTART in the ACES2 namelist All of the restart capability is built into xjoda and is controlled by two values the SAVEDIR directive and the RESTART flag The SAVEDIR directive is case insensitive and the path may be absolute or relative Each time xjoda is called it copies the optimization history files to SAVEDIR If xjoda is called and the files are contaminated meaning the previous job was interrupted or the dirty flag was not cleared then it will restore the history files from SAVEDIR and continue on as if nothing had happened This applies to both geometry optimizations and VIB FINDIF frequency calculations WARNING Restarts are only implemented for coarse grain checkpointing If other ACES II files are in the directory interesting things might happen For the best results calculations should be restarted from a clean directory i e only the original user input files should be present When the optimization is finished xjoda will delete the CURRENT and OLD directories within SA
136. roperties et EL e Sere A 59 8 1 17 Excited states affinities ete les wt oad Se al eked ee Ee a aes 60 8 1 18 Excited states electronic absorption 61 8 1 19 Excited states ionizations 0 00080 0 eee 62 8 1 20 Excited states gradients __ _ _ eo ad eh r 63 al VP TOP CRUIES e ia g u ipu SE he thnk YE S k Ae hee Gace AE Sri G Stk Tong sp St Sos 64 8 1 22 Geometry optimization general 0 2 2 0 00 eae 66 8 1 23 Geometry optimization stepping algorithm 66 8 1 24 Geometry optimization iteration control 67 8 1 25 Geometry optimization integral derivatives 68 8 1 26 Frequencies and other 2 4 order properties o o a 68 8 1 27 Finite displacements dle duc i Ants ne ete Gh wien a A ee 68 8 1 28 External interfaces aoaaa aa 69 9 Examples 7O 9 1 Single point calculations 2 keene de ke ola ek IE ia gt e bd 70 9 1 1 RHE CGSD0UCI energy Dec eee da aid 70 9 1 2 UHE CCSD T energy ds A alae aed E Va 70 91 37 ROME CCSD T energy si ia ind 71 9 1 4 QRHF CCSD T energy a he eo 71 9 1 5 Effective core potentials 2 0 0 eee ee 72 9 1 6 Initial guessing with OLDMOS 0 72 9 1 7 Initial guessing with OLDADMOS 0 73 9 1 8 Improving SCF convergence 00 00 eee 74 9 1 9 Hartree Fock stability analysis 2 26 eee e 4 75 9 1 10 Time dependent Hartree Fock 0 0 000000 4 TT
137. rs and by the analytical representation of the operator The latter includes the coefficient cm the exponent Nm of r and the exponent am of the gaussian U r Ye em Nm For a detailed description see L R Kahn P Baybutt and D G Truhlar J Chem Phys 65 3826 1976 7 4 GUESS The GUESS file is used to control the placement of electrons in the SCF initial guess and can be used only with GUESS READ_SO_MOS orbitals come from OLDMOS All options in the GUESS file must be specified there are no defaults The following is an example of the GUESS file for a state of the water cation Line 1 H20 TEST Line 2 3 1 1 0 alpha occ Line 3 3 0 1 O beta occ Line 4 O 0 0 O alpha pairs to be swapped irrep 1 Line 5 0 0 0 0 alpha irrep 2 Line 6 0 0 0 0 alpha irrep 3 Line 7 0 0 0 0 alpha irrep 4 Line 8 O 0 O O beta pairs to be swapped irrep 1 Line 9 0 0 0 O beta irrep 2 Line 10 0 0 0 O beta irrep 3 Line 11 0 0 0 O beta irrep 4 Line 12 0 0 0 O alpha locking within each irrep Line 13 0 0 0 0 beta locking within each irrep Line 14 O 0 0 O alpha printing of initial guess Line 15 0 0 0 0 beta printing of initial guess Line 16 0 0 stopping parameters Line 17 1 read from OLDMOS Line 18 1 beta orbitals are copied from alpha orbitals Line 19 0 reuse GUESS for every SCF calculation This is a formatted file The trailing text on each line is not parsed as input as long as each line is at most 80 characters but it is usual
138. rs might encounter is far beyond the scope of this manual but the following sections list the most common options that the developers have used C 1 ACES II script body bin sh zmt ZMAT_FILE out 0UT_FILE genbas GENBAS_FILE workdir WORK_DIRECTORY test d workdir amp amp rmwd 0 rmwd 1 test rmwd eq 1 amp amp mkdir p workdir cd workdir cp zmt ZMAT cp genbas GENBAS xaces2 gt out cd test rmwd ne O amp amp rm rf workdir C 2 LoadLeveler output STDOUT_FILE error STDERR_FILE class CLASS job_type JOB_TYPE node_usage USAGE_TYPE node NNODES total_tasks NTASKS network MPI css0 shared us Requirements OPT1 VALUE1 amp amp OPT2 VALUE2 wall_clock_limit HH MM SS C 3 LSF BSUB P ACCOUNT BSUB J JOBNAME BSUB o STDOUT_FILE BSUB e STDERR_FILE BSUB q QUEUE W TIME BSUB n NPES C 4 GridEngine S SHELL N JOBNAME o STDOUT_FILE 132 e STDERR_FILE 1 COMPLEX pe PE_ENV NPES 133 Index ACES2 ABCDFULL 56 ABCDTYPE 55 56 57 ACC_SYM 59 AO_LADDERS 55 BASIS 46 BRUCK_CONV 53 BRUECKNER 53 CACHE_RECS 45 CALCLEVEL 43 CC_CONV 57 CC_EXPORDER 57 CC_EXTRAPOL 57 CC_MAXCYC 57 CCR12 111 CHARGE 46 CHECK SYM 49 CONTRACTION 47 CONVERGENCE 67 COORDINATES 46 CPHF_CONVER 65 CPHF_MAXCYC 65 CURVILINEAR 66 DAMP TOL 51 DAMP TYP 51 DAMPSCF 51 DEA_CALC 60 DEA SYM 60 D
139. s both sets Next 1 13 A flag that forces xvscf to read GUESS every time an SCF calculation is performed This applies only to calculations that run multiple SCF calculations geometry opti mizations HF stability analyses etc Set to 0 for just the first time otherwise set to a positive integer If it is set to 0 GUESS is deleted after it has been read 41 8 Keywords 8 1 ACES2 namelist The user can control the behavior of an ACES II job through the use of keywords in the ACES2 namelist In some cases the value for a keyword can be specified by an integer or by a character string In our opinion the latter is preferable as it makes the input file more readable All possible keywords in the ACES2 namelist are discussed below As there are a lot of keywords we have grouped them according to the general flow of a calculation Keyword Conventions Keywords in the ACES2 namelist are matched to an initial substring of the actual keyword in xjoda For example the full keyword is CALCLEVEL but the unique substring is CALC so CALC CALCULATION and CALCLEVEL may all be used to set the calculation level The underlined substring in the following keyword definitions is what is used to match the keyword As another example the memory keyword is defined as MEMORY_SIZE but any keyword in the ACES2 namelist starting with MEM will be used to set the memory size Some keywords should not be set by the user without careful consideration
140. set to 24000000 integer words 91 5MB on 32 bit builds and 183 1MB on 64 bit builds 9 2 Geometry optimizations 9 2 1 Full optimization of internal coordinates H20 CCSD optimization H D 1 ROH H 2 ROH 1 HOH ROH 0 95 HOH 104 5 ACES2 CALC CCSD BASIS DZP This specifies a geometry optimization of the water molecule with the CCSD method and the DZP basis set The input is exactly the same as the RHF single point energy example except that an asterisk x is placed after each variable to be optimized both bond lengths and the bond angle Since all of the parameters are being optimized it is also sufficient to use GEOM_OPT FULL and leave the asterisks out of the Z matrix Defaults for all of the optimization keywords e g METHOD and CONVERGENCE are used The presence of the asterisks promotes the GEOM_OPT keyword from NONE to PARTIAL which turns on all appropriate derivative keywords Geometry optimizations by default are performed using analytical gradients If analytical gradients are not available one can do geometry optimizations from energies using GRAD_CALC NUMERICAL 9 2 2 Partial optimization of internal coordinates Beryllium borohydride D3d structure geometry optimization BE 1 R1 2 R 2 R 2 RX 2 RX 5 RHX 5 RHX O gt lt gt lt LU J NNRRRE gt gt gt gt Ka S OQ O HAHAH 85 H 5 RHX 2 A 1 TM6 H 6 RHX 2 A 1 T12 H 6 RHX 2 A 1 TM2 H 6 RHX 2 A 1 TO X 3R1 2 A 1 TO X 4R1
141. singlet states in which the open shell orbitals have different symmetries Efficient algorithms for geometry optimization and transition state searching have also been included and may be used at all levels of theory The analytical gradients employed during geometry optimizations and vibrational frequency calculations depend on their avail ability When analytical gradients are not available automated finite differencing proce dures can be used to compute the derivatives Analytic second derivatives have been imple mented for SCF using RHF UHF and ROHF reference functions In addition analytically evaluated NMR chemical shift tensors are available at the SCF and MBPT 2 levels using 10 gauge including atomic orbitals GIAOs to ensure exact gauge invariance Other features include the direct calculation of electronic excitation energies using the Tamm Dancoff or configuration interaction singles model CIS the random phase approximation RPA the equation of motion coupled cluster approach EOM CC and similarity transform equation of motion STEOM and molecular ionization potentials and electron affinities with EOM STEOM and Fock space coupled cluster methods Transition moments between ground and excited states can be calculated for all of the methods as well as selected excited state properties The excited state geometry optimization and frequency calculations employ the analytical gradients capabilities available for the EOM an
142. sis may not be accurate and the calculation will become unstable but it might not crash 86 9 2 4 Transition state search CH20 gt H2 CO transition state search DZP basis 0 C 1 R H 2 R2x 1 Ax H 3 RHH 2 A 1 T R 1 254 R2 1 08 RHH 1 01 A 133 5 T 0 ACES2 OPT_METHOD EVFTS MAX_STEP 150 BASIS DZP CALCLEVEL MBPT 2 OCCUPATION 7 1 As implied by the job title this ZMAT file specifies an initial geometry and basis set for a transition state search In the Z matrix the parameters designated R R2 RHH and A will be optimized while parameter T will be fixed at 0 degrees This obviously constrains the structure to be planar The ACES2 namelist parameters tell ACES II that 1 this is a transition state search using the Cerjan Miller eigenvector following method 2 the maximum allowed step length is 150 millibohr this corresponds to the absolute step length 1 norm since the default value of SCALE_ON has not been overridden 3 the DZP basis set is to be used 4 the calculation type is MBPT 2 and 5 the occupation appropriate for the C point group is 7 1 The value EVFTS automatically turns on the necessary gradient options In transition searches it is necessary to provide an initial estimate of the hessian This is usually done by saving the FCMINT file from a frequency calculation and copying this to the workspace at the beginning of a transition state search Another example details this p
143. ss s alba AA Ae aiik us ee E DS a ett 0 ds 22 6 5 NEWMOS OLDMOS _ _ _ _ 0 00000 00 0 en 22 6 6 AOBASMOS OLDAOMOS 7 0 6 ace ak AAA a ae we ee 22 6 7 FCMINT FCM FCMSCR and FCMFINAL 0 0 23 DR EGITEN es weg Sey oh a Khe R Ae ee ee we a Ee hh 23 6 9 TSOMASS wc Sree tei ad ek oe oe eh a A 23 BAN System las Sanss a a el ek ae 23 6 10 1 JOBARC JAINDX I rerai ae n ke cs 23 6 10 2 MOINTS GAMLAM MOABCD DERINT DERGAM 23 6 10 3 MOL IIII IIJJ IJIJ IJKL 23 6 10 4 OPTARC OPTARCBK 000000 ee 24 6 10 5 DIPOL DIPDER POLAR POLDER 24 GDE HLR 15 R ay tikes oh uka S oh S ar eee aot h San SY SL QS Ta NW sz 24 6 10 7 HF2 HF2AA HF2AB HF2BB 000 24 610 8 UIE YZ uriy E a Ate hod PS ae sb S SD che Ane te Al eho en eee vines 16 Ge AY is 24 6 10 9 TGUESS LGUESS 0 0 00 00 000000004 24 GAOTOVPOUT ario gua sp s RL Hag ki O ET rke a Gu Sur a S5 Tue sb asus 24 6 10 11GAMESS LOG MP2 LOG DIRGRD LOG 24 6 10 12 0UT 000 DUMP 000 1ELGRAD 000 1 25 7 File Formats 26 sl SZMATS G z obs do oe Sasa t dts a tt te a yta Sue Sette ye San et RA EK 26 TEL Fileanatomny ire ereen et as Dl a tee 26 Pole ESCAPES e a Z RE Slds alga AS AO 1 27 TLS lr AAA 28 7 1 4 Molecular orientation dt e ds eds A a Be HOS 29 7 1 5 Dummy and ghost atoms Sa tad 2 erated 2 SA eee eo 30 7 1 6 Cartesian
144. ssentials of Z matrix construction can be illustrated by considering a Z matrix for a system of four atoms ABCD not linked in any particular order Arbitrary ABCD molecule A B C 2 CAB D 2 DCB 1 TAU BiaA C1A D 3 C The first line in the Z matrix contains the atomic symbol of one of the atoms say A The second line specifies the position of a second atom say B relative to the first atom Suppose that B is a distance AB from A The second line then contains the atomic symbol B followed by the number 1 A is atom number 1 and a parameter label AB B 1 AB For the specification of the third atom a distance and an angle are needed We may use the distance between atoms A and C and the angle CAB or we may use the distance between atoms B and C and the angle CBA In the first case the third line would have the form C 1 AC 2 CAB while in the second case it would have the form C 2 BC 1 CBA Finally there is a line specifying the position of D relative to the other atoms This line must contain a distance a bond angle and a dihedral angle and could have the form D 3 CD 2 DCB 1 TAU with TAU being the angle between the BCD and ABC planes For a system with more than four atoms the fifth and subsequent lines follow the same pattern as the fourth line of the example given above i e they also contain a length angle and dihedral angle and the numbers of three previously specified centers It should be emphasized t
145. t 1078 to be used YFIELD integer 0 Sets the Y component of an external electric field See above ZFIELD integer 0 Sets the Z component of an external electric field See above PRP_INTS handle PARTIAL Specifies the types of property integrals that are computed Setting this to FULL or PARTIAL computes the full set or sub set respectively This works in conjunction with the PROPS keyword and the defaults are set automatically 65 8 1 22 Geometry optimization general GEOM_OPT handle NONE Specifies the scope of coordinate optimizations This keyword is automatically set to PARTIAL if a geometry optimization is implied with asterisks in the internal coordi nate Z matrix Setting GEOM_OPT FULL will optimize all coordinates regardless of asterisks in the Z matrix COORD INTERNAL and will optimize a Cartesian input geometry using Redundant Internal Coordinates RICs CURVILINEAR handle OFF Specifies whether or not the Hessian matrix is transformed nonlinearly to curvilinear internal coordinates OFF turns the transformation off if analytical force constants are not available while it is always performed if CURVILINEAR ON NO uncondi tionally turns the transformation off This keyword is set automatically 8 1 23 Geometry optimization stepping algorithm OPT METHOD handle AUTO Specifies the geometry optimization strategy AUTO NR uses a straightforward Newton Raphson minimum energy sea
146. t is restricted to the symmetry of the supermolecule comprised of the real and ghost atoms The additional basis functions do not necessarily form a complete set of symmetry adapted functions within the point group of the supermolecule This is different from the use of dummy atoms which do not affect the symmetry of the calculation Currently only single point energy calculations are possible with ghost atoms In ad dition the basis set must be supplied explicitly with BASIS SPECIAL and the line item basis set definitions after the ACES2 namelist 7 1 6 Cartesian coordinates The format is straightforward Each line defines one atom with the atomic symbol and the values of the x y and z coordinates in free format The coordinates may be given in either atomic units or Angstroms Older versions of xjoda require COORDINATE CARTESIAN for this to work but any version after 2 5 0 attempts to figure it out automatically since the first line of a Z matrix has only one word If the Cartesian coordinates are specified in atomic units then the keyword UNITS BOHR must be used 30 7 1 7 Internal coordinates The specification by internal coordinates is known as the Z matrix Centers of the nuclei are expressed relative to previously defined centers by means of distances and angles The specification includes a length a bond angle and a dihedral angle The number associated with each atom is governed by its position in the Z matrix The e
147. tal stage Analytical gradients are available for TDA and STEOM and require additional input though the mrcc_gen namelist Properties and transition properties of the DIP states can be requested by additional input in MRCC namelists dip_calc section DIP_SYM string of 1D array 0 Specifies the number of states to be calculated by a DIP calculation A string e g 4 2 2 0 2 1 1 1 has to be provided that indicates the number of singlet states in each symmetry block followed by the number of triplet states in each symmetry block The example string requests 4 singlet states of Al symmetry 2 singlet states in symmetry blocks 2 and 3 and 0 in block 4 In addition 2 triplet states will be calculated in block 1 and 1 in blocks 2 3 and 4 each The triplet vector and the forward slash are optional 8 1 20 Excited states gradients ZETA_TYPE handle DIS Specifies the algorithm used to solve linear equations zeta equations in excited state gradient theory POPLE uses Pople s orthogonal subspace approach and DIIS uses Pulay s DUS approach ZETA_CONV tol 12 Sets the convergence criterion for the iterative solution of the Zeta equations and Z vector equations The solutions are considered to be converged when the error falls below 1071 ZETA_MAXCYC integer 50 Sets the maximum number of cycles allowed for the solution of the Zeta equations RESRAMAN switch OFF 63 8 1 21 Properties PROPS handl
148. te differences and restart capabilities are all handled by this program 5 3 mopac ACES II has a modified version of MOPAC version 5 that can generate an initial guess Hessian for geometry optimizations 5 4 vmol xvmol calculates the one and two electron AO integrals over Gaussian basis functions VMOL was written by J Aml f and P R Taylor and was modified to include an option for effective core potentials 15 5 5 vmol2ja xvmol2ja creates most of the transformation matrices needed to switch between internal VMOL and external ZMAT ordering of atoms and atomic orbitals It also creates the Cartesian Spherical orbital transformations 5 6 vprops xvprops evaluates one electron integrals needed for the calculation of various first order properties such as dipole moment quadrupole moment electrical field gradients or spin densities It originates from POLYATOM and was interfaced to the VMOL integral program by P R Taylor 5 7 nddo xnddo calculates the NDDO density which can be used as an initial guess for the SCF algorithm 5 8 vscf p vscf vscf ks intgrt and intpack These programs are responsible for generating the Hartree Fock xvscf and Kohn Sham xvscf_ks SCF reference wavefunctions For KS SCF the numerical integrator xintgrt is used to calculate the functional energy and xintpack is used for OEP calculations The parallel HF SCF program xp_vscf should be used for GAMESS direct integrals FOC
149. tegral program will be incorrect Lines 10 through 13 repeat NS number of times An example of the boron PVTZ basis set entry is included below B PVTZ JFS DUNNING CORRELATION CONSISTENT BASIS FROM FTP 4 0 1 4 3 10 5 5473 000 5 999 0005550 0042910 0219490 0844410 2385570 4350720 3419550 0368560 0095450 0023680 0000000000 12 050 0131180 0798960 2772750 5042700 3536800 G GO GO O 0 661 1 0000000 0 0000000 2 3 2 1 2 1 0000 820 9000000 0000 2 2080000 0 0001120 0 0008680 0 0044840 0 0176830 0 0536390 0 1190050 0 1658240 0 1201070 0 5959810 0 4110210 0000000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 O GO K GO OO OOO O 0000 2 6130000 0 0000000 0 0000000 0 0000000 1 0000000 0 0000000 0 0000000 0 0000000 0 0000000 0 0000000 1 0000000 0000 0 1990000 0 0000000 1 0000000 186 8000000 52 8300000 17 0800000 0 5879000 0 2415000 0 0861000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 0000000 K O GO GO GO OOO O O 0 7475000 0 2385000 0 0769800 38 0 4900000 1 0000000 7 3 ECPDATA The parameters of the effective core potentials are specified in a format similar to GENBAS For example the entry for copper is given below CU ECP 10 SK ECP BY STEVENS KRAUSS FOR CU 10 CORE ELECTRONS LMAX 2 NCORE 10
150. termines a size based on the value of MEMORY SIZE CACHE RECS integer 1 Sets the number of physical records of length FILE_RECSIZE held in the I O cache The maximum number of records is 128 and the default value 1 determines a number based on the value of MEMORY SIZE INCORE handle NONE 45 This keyword can be used to reduce disk I O usually by a significant amount Ac ceptable values are NONE NOABCD NOABCI NOABIJ ALL and T NONE and ALL load no and all lists into core memory respectively NOABCD NOABCI and NOABIJ load all lists that are at most the size of Ab C7 Ab Ij and Ij Ka molecular integral lists respectively These options are implemented in VCC LAMBDA DENS ANTI BCKTRN and VEE The T option only applies to VCC which will load T and T amplitudes into memory All of the other executables will treat T as NONE including LAMBDA although this should change soon 8 1 5 Chemical system COORDINATES handle AUTO Specifies whether the molecular system is defined in INTERNAL Z matrix or CARTE SIAN xyz coordinates UNITS handle ANGSTROM Specifies the units used for molecular geometries The value can be ANGSTROM or BOHR CHARGE integer 0 Sets the molecular charge MULTIPLICTY integer 1 Sets the spin multiplicity 25 1 8 1 6 Basis set BASIS string SPECIAL Defines the name of the basis set to use for all atoms in the molecule If BA SIS SPECIAL then
151. tiple types of strings The regular expression is exch coeff corr coeff This means one exchange or two exchange and correlation functionals can be used to evaluate the total SCF energy and each can have an optional coefficient default is 1 0 To use B3LYP the format must be func b3lyp with no coefficients or additional correlation functionals The following exchange and hybrid functionals are available lda LDA Slater Xalpha exchange becke Becke exchange hf Exact Nonlocal Exchange exchange pbeex Perdew Burke Ernzerhof exchange pw9lex Perdew Wang 91 exchange b3lyp Becke III LYP hybrid The following correlation functionals are available vwn Vosko Wilk Nusair lyp Lee Yang Parr pbe_cor Perdew Burke Ernzerhof pw91_cor Perdew Wang 91 wl Wilson Levy wi Wilson Ivanov KSPOT string hf The KSPOT value string takes the same format as FUNC The available exchange potentials are Ilda becke and hf The available correlation potentials are vwn and lyp CUTOFF tol 12 113 A 3 mrcc namelists A 3 1 mrcc gen true_mrcc cse A 3 2 EE_EOM EE_TDA EE_STEOM A 3 3 IP_EOM IP CI DIP_EOM DIP_TDA DIP_STEOM A 3 4 EA_EOM EA CI DEA_EOM DEA TDA DEA STEOM A 3 5 ACT EA EOM 114 B Standard Basis Sets and ECPs B 1 Basis sets in GENBAS The following is a listing of the basis sets currently included in the standard GENBAS file STO 3G This is the well known mini
152. tlett J Am Chem Soc 116 4091 1994 FeC14 sextet FE 0 0000 0 0000 0 0000 CL 0 0000 3 4826 2 2358 CL 0 0000 3 4826 2 2358 74 CL 3 4826 0 0000 2 2358 CL 3 4826 0 0000 2 2358 ACES2 REF ROHF PRINT 1 CALC SCF MULT 6 CHARGE 1 BASIS SPECIAL UNITS BOHR COORDINATES CARTESIAN SPHERICAL ON ECP 0N DAMP_TYP DAVIDSON DAMP_TOL 5 LSHF_A1 50 LSHF_B1 50 OCCUPATION 7 6 6 6 5 5 5 5 FE SBKJC CL SBKJC CL SBKJC CL SBKJC CL SBKJC FE SBKJC CL SBKJC CL SBKJC CL SBKJC CL SBKJC Another tip for ROHF convergence which the developers strongly recommend is starting the SCF from UHF orbitals from a closely related closed shell system UHF is necessary since ROHF reads both o and 7 orbitals 9 1 9 Hartree Fock stability analysis The Hartree Fock procedure at convergence guarantees the resulting wavefunction is a stationary point in the space of orbital rotations mixing of occupied and virtual orbitals Though in the majority of cases this stationary point is also a minimum all orbital rotations increase the energy it may not always be so In some cases the second derivative of the energy with respect to one or more orbital rotations may be zero or negative indicating rota tions which will leave the energy unchanged or lower it The ACES II program system has the ability to test RHF and UHF wavefunctions for some of the most common instabilities controlled by the HFSTABILITY and ROT_EVEC keywords
153. trast to the IGLO method is easily extended to correlated approaches as for example in the GIAO MBPT 2 method The calculation of NMR chemical shifts are invoked via the keyword PROP NMR to gether with the appropriate specification of the quantum chemical method CALC SCF gives then GIAO SCF CALC MBPT 2 gives GIAO MBPT 2 In principle no other op tion is required to run calculations of NMR chemical shifts However to ensure the success of GIAO MBPT 2 calculations and in particular large scale calculations with the GIAO MBPT 2 method the computational requirements of such calculations should be kept in mind While CPU requirements are of less interest a GIAO MBPT 2 calculation is in terms of the CPU usually less expensive than the corresponding MBPT 2 geometry optimization memory and disk space requirements are of special concern The memory requirements are for the xnmr module approximately 2 n N h eight byte words with n denoting the num ber of occupied orbitals N denoting the number of virtual orbitals and h specifying the order of the molecular point group However the current memory bottleneck is the integral sorting in the module xintpre which requires roughly 2 n N h eight byte words and which therefore is more demanding The disk space requirement of a GIAO MBPT 2 calculation is for most parts determined by the fact that the current version depends on the storage of the GIAO integrals To summarize the necessary resour
154. tric constant used to determine the orbitals A cavity size may be specified as well by creating a file named radius which is read by the SCF code This contains the cavity radius in A If the file is not present the program uses a value calculated from 0 5 A plus half of the longest internuclear distance TURBOMOLE switch OFF POLYRATE switch OFF CCR12 switch OFF KUCHARSKI switch OFF KS_POT Obsoleted by the VSCF namelist FUNCTIONAL Obsoleted by the INTGRT namelist EOMXFIELD EOMYFIELD EOMZFIELD RDO FILE STRIPE RESET FLAGS PSI INSERTF GLOBAL_MEM 111 A 2 Kohn Sham DFT namelists A 2 1 VSCF KS switch ON Controls the type of SCF KS ON performs a Kohn Sham DFT calculation with nu merical integration and KS OFF performs the standard analytical Hartree Fock SCF with the KS SCF program xvscf_ks The ACES2 keyword SCF_TYPE must be set to KS in addition to this switch which defaults to ON A 2 2 INTGRT POTRADPTS integer 50 RADTYP handle Handy Handy Gauss Legendre PARTPOLY handle bsrad equal bsrad dynamic RADSCAL handle Slater none Slater PARTTYP handle fuzzy rigid fuzzy FUZZYITER integer 4 RADLIMIT real 3 0 112 N UM ACC switch ON EXACT EX switch OFF TDKS switch OFF ENEGRID integer 4 POTGRID integer 4 ENETYPE handle lebedev POTTYPE handle lebedev FUNC string none This keyword can accept mul
155. ut formats for certain user files 14 5 Program Structure The ACES II program system is a collection of programs that work together to perform the user s calculation An ACES Member Executable AME is referenced by the name of its source code e g JODA and the name of its binary executable e g xjoda Most users will only interact with the driver program xaces2 but it is strongly recommended that users familiarize themselves with xjoda since that program reads the input file and initializes the ACES II file set 5 1 aces2 and p_aces2 xaces2 is the main program that drives the ACES II program system After an initial call to xjoda it determines the proper calling sequence of programs based on the calculation level and various other keywords In principle this program is not necessary if the user knows the exact calling sequence of member executables and the calculation does not involve dropped MO gradients xp_aces2 is a parallel version of xaces2 that should be used ONLY for calculations that perform numerical finite differences geometry optimizations with GRAD_CALC NUMER ICAL or vibrational frequencies with VIB FINDIF See the examples of parallel calcula tions in Section 10 3 page 96 for more information 5 2 joda Along with parsing ZMAT building the keyword environment and initializing the ACES II file set JODA is responsible for everything between single point calculations Geometry optimizations numerical fini
156. ut the rules for parsing the strings are specific for each list Rules for parsing the ACES2 namelist can be found further down 5 Line item basis set and ECP data assignments If either BASIS SPECIAL the default or ECP ON off by default then there must be one blank line between the ACES2 namelist and the assignment block If both blocks are required then there must be one blank line between the ACES2 namelist and the basis set block followed by another blank line and the ECP block 6 Footer Any unrecognized text non namelist following the internal coordinate definitions is ignored If there is no footer then ZMAT must terminate with a blank line 7 1 2 Examples Line 1 RHF CCSD property calc of C6 in DZP Line 2 Line 3 Line 4 Line 5 Line 6 Line 7 Line 8 Line 9 Line 10 Line 11 Line 12 Line 13 Line 14 Line 15 Line 16 ACES2 CALC CCSD PROPS FIRST_ORDER BASIS DZP Line 17 Q OQ OQ OO O O gt gt N N N N N N S RE H s KA KA KK KK KA KA gt gt gt gt gt gt NOOB W HAHAHAHA Ps II dl 1 33 90 60 H gt I o 2d Line 1 Line 2 Line 3 Line 4 Line 5 Line 6 Line 7 Line 8 RHF MBPT 2 property calc of Formaldehyde in DZP 0 0 0 0 0 1 22 C 0 0 0 0 0 0 H 0 0 0 873489539 0 545816842 H 0 0 0 873489539 0 545816842 ACES2 CALC MBPT 2 PROPS FIRST_ORDER BASIS DZP 7 1 3 File directives Users can control the locations of files with file directives in the header
157. utables They will be VERY large for big molecules and basis sets 6 10 3 MOL IIII IIJJ IJIJ IJKL The MOL file is created by xjoda and stores the molecular system and basis set information used by xvmol and any AME that uses GAMESS integrals The IIII file stores the one electron integrals and all totally symmetric two electron integrals in the AO basis This file will be very large for big basis sets The other three files IIJJ IJIJ and IJKL store two electron AO integrals that are not totally symmetric 23 6 10 4 OPTARC OPTARCBK The iteration history of geometry optimizations is stored in OPTARC OPTARCBK is a backup of the true OPTARC file which gets clobbered during geometry optimizations with numerical gradients 6 10 5 DIPOL DIPDER POLAR POLDER DIPOL and POLAR contain the dipole moments and polarizabilities respectively and DIPDER and POLDER contain their derivatives 6 10 6 GRD This file was intended for programs to extract gradients from ACES II With the func tionality in the ACESCORE library and xa2proc this file interface is obsolete 6 10 7 HF2 HF2AA HF2AB HF2BB These files are created by xvtran and store partially transformed two electron integrals for use in xintprc Usually they are deleted by xintprc unless a particular post SCF option requires them such as ABCDTYPE MULTIPASS 6 10 8 IUHF This file contains the RHF UHF flag Its use is limited and it should disappear in a future release 6 10 9 TGUESS
158. y range using ip_low and ip_high keywords in the mrcc_gen namelist This can be particularly relevant in vibrational frequency calculations in which the symmetry changes at different geometries IP_SEARCH handle VALENCE Specifies the character of the IP states to zoom in on If IP_SYM is not specified the program attempts to determine all IP s of the given character otherwise it uses the symmetry constraints imposed by IP SYM The values are VALENCE all valence IP s LOWEST only the ground state of the cation COREIP only the core ion ization potentials IPs larger than about 100 eV SHAKEUP shake up states and KOOPMANS all principle IP s having predominantly 1h character KOOPMANS type can be very difficult for inner valence ionization potentials and SHAKEUP is not implemented yet 62 DID C ALC handle NONE Specifies the method for calculating double IP states of the closed shell parent state This type of calculation can be very useful to describe certain multireference situations like biradicals The values are NONE TDA the analogue of CIS in which a CI calculation is performed over 2 hole states EOMCC H bar is diagonalized over 2h and 3hlp calculations STEOM Similarity Transformed Equation of Motion OS_CCSD and SS_STEOM To run a meaningful DIP STEOM calculation one must also set IP CALC IP EOMCC OS CCSD and SS STEOM are multireference CC methods which are still in an experimen

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