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KintechDB User Manual

1. a ne ES m 6 6 R R Stockmayer potential o the length scaling parameter Angstrom It characterizes the effective diameter of the particle in collision process E the energy scaling parameter It is specified divided by the Boltzmann constant e k in K It characterizes the potential well depth max the additional dimensionless parameter to account for the dipole dipole interaction of the molecules 5 4 0 for non polar molecules Stockmayer is the model potential function for polar molecular gases The formula for this potential is a co 1 ao v na 2 z EA Hill Note that Onax F indexes i and j indicate the two colliding molecules F 2cos 6 cos 0 sin 8 sin 8 cos g 9 vector denotes the set of angles to characterize the molecules relative orientation 0 and 0j are the angles of the i th and j th dipoles slope with respect to the line between their centers j j is the angle of the i th dipole turning with respect to the j th dipole in the plane perpendicular to the line between their centers u and uj are the molecules dipole moments The averaged transport collision integrals op for the Stockmayer potential were first calculated and tabulated by Monchick and Mason Monchick L Mason E A J Chem Phys Vol 35 Issue 5 pp 1676 1697 1961 as functions of max and reduced temperature T T e k Buckingham Corner potential Rm the length scaling paramete
2. 3 Processes properties 43 3 1 Contents of the Processes Database seisisssiiicsenansiscssssessanasnaseasiasisecninanutidacsivenemensadedetenentaaaunnna 43 3 1 1 Elementary equilibrium chemical reactions important in Combustion cccceeeeeeeeeeeeeees 43 3 1 2 Elementary equilibrium ion molecule reactions 2 0 ccc eceeeeeeeeeeeeeeeeeaaeeeeeeeeeeeeeeneneeeeees 44 3 1 3 Reactions of neutral molecules under nonequilibrium conditions cece eee e eee eeees 44 3 1 4 Processes of the vibrational energy exchange in COIliSIONS eee eeeeeeeeeeeeeeeeeeeeeeeeeees 44 3 1 5 Electron vibrational translational EVT energy transfer processes n 44 3 1 6 Atomic spontaneous radiation cc ccccccccccecececceeeceeeeeeceeeeeeeceeeeeeeeeeeeeeeeeeeeeceeeeeeeeeeeeeeeeeeeeties 44 3 2 Working with the database xs cssacsinreananatenadueneasancinicatansaeinduieenpsensusanassinardnsudernaneeseinieaanaaetnnonmaaentine 45 3 2 1 Database WINdOW cccccccccceccceeceeeeeee tent eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeneeeeeeeeeeeeeeenetieetiineneess 45 3 2 2 Search and view the processes Filters cccccccecceccceeceecceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeseeteeeeeeeees 46 3 2 3 Addition of a new process to the database ccccccccccccecceecececceeeceeeeeeeeeeeeeeeeeeeeeeeeeeeeenetts 46 3 2 4 Edit the process properties in the database cccccccccecccecececececeeeeeeeeteeeeeeeeeeseeeeeeeteeeeeess 4
3. Database tools for data analysis Mechanism comparison tool e Preferred Gibbs type the type of coefficients to be compared in case of presence of both IVTAN and NASA types of Gibbs approximation e Relative Cp gap the condition of equality of the specific heat e Temperature range gap K the tool ignores the gaps in the temperature range where the Gibbs is defined less than the entered value Rate approximation compare conditions of process rates comparison e Relative error the maximum relative deviation between the values to count them identical e Temperature range e Tmin K minimal temperature of the comparison range e Tmax K maximal temperature of the comparison range e Number of intervals on which the comparison will be made in the said range e Pressure range e Pmin K minimal pressure of the comparison range e Pmax K maximal pressure of the comparison range e Number of intervals on which the comparison will be made in the said range Cross sections compare e Number of intervals on which the comparison will be made The Show menu and toolbar contain the commands the detailed explanation will be given in the next section Button Function e Merge substances is Compare substances Identical substances Different substances First mechanism only substances Second mechanism only substances Wa a OY ihe Identical processes D
4. I Sobelman Introduction to Theory of Atomic Spectra Pergamon Press 1970 pp 1 640 Expressing AC in atomic units 4 in atomic mass 63 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 5 1 3 units 1 66 10 74 g and T in Kelvins Cp could be presented in the following form 3 10 2 5 T gt cm s trad u Broadening of isolated atomic spectral lines due to quadratic Stark effect T Electron temperature K convenient for estimations C 7 54 10 JACH Ws the non adiabatic impact Stark width at density equal to 1016 cm Angstrom 5 relative Stark impact shift dimensionless A relative ion broadening parameter at density equal to 1016 cm dimensionless The broadening due to the quadratic Stark effect of isolated lines of atoms is calculated according with Griem s approximate formulae H R Griem Spectral Line Broadening by Plasmas Academic Press N Y 1974 H R Griem M Baranger A C Kolb G Oertel Phys Rev 125 177 1962 H R Griem Phys Rev 128 515 1962 in Angstroms Ahi 142d 10 om ue i r fw 108m where w 4 are evaluated for N equal to 1016 cm the value of r must be taken from the expression Ry R 2 84 107 w 6 77 Ng is given in cm T in Kelvins Here Ro 4 z N 3 is the mean interparticle distance is the Debye radius N N N is assumed N Ne being the ion a
5. Login User properties E oo 2 Contr atabase role First name g Last name 4 Norm Middle name Title Organization Address City Country Zip Telephone Fax E mail The dialog contains a list of users Login and a table of user parameters User properties Information can be managed using the five buttons on the instrument panel described in the table Button Function R Add a new user Ea Delete a user A Undo the last operation J Accept changes this button must be pressed in order for changes to be saved Close user management dialog Adding a new user To enter a new user push the ag button and enter the name of the user Login in the dialog appeared then press OK t New database user login R The user name appears in the Login list in the Users dialog Highlight the user with the mouse and enter the user s information in the User Properties window To enter parameters in the table click on the necessary line and enter the information in the window which opens After entering the information click 4 Remember that it is not necessary to enter a password for the user the password will be the same as that used for database access Editing user information To change the user s information simply edit the necessary lines in the table by double clicking with the mouse and press 2 Remember that you must have administrative rights in the database in order to edi
6. N low and in cm s T N for addition reactions and Ea low is Arrhenius activation energy in kcal mol M is number density of the bath gas M Py is pressure of M in atm 2 BIMOLECULAR REACTIONS THROUGH THE INTERMEDIATE COMPLEX k T P bal CREAT P T a k ty T lim ok T P A low x TN x exp Ea low RT k wie 2 lim _ M k T P A high x T x exp Ea high RT P00 M 7 33888 x10 ae Rate constant k jow T is low pressure rate constant in cm s Correspondingly A low is preexponential factor in s T N IOW and Ea low is Arrhenius activation energy in kcal mol 50 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 2 3 Rate constant Krhigh T is high pressure rate constant in 1 s Correspondingly A high is preexponential factor in s T N 9 and Ea high is Arrhenius activation energy in kcal mol M is number density of the bath gas M Py is pressure of M in atm Troe interpolation Reaction type drop down list allows to set process type as e unimolecular unimolecular or addition reactions e bimolecular bimolecular reactions through the intermediate complex Alow pre exponential factor in the low pressure limit cm3s T N IW for unimolecular reactions and reactions through the intermediate complex cm s T N for addition reactions Nlow temperature exponent dimensionless Ealow activation energy kcal mol 17 N h
7. 1 Ar 4p 0 5 1 gt Ar 4s 1 5 2 Hv Optical gt Substances Formula Charge Phase Tsomeric form Mod Ar 33 4p 0 5 1 gt Ar 4s 1 5 1 Hv Optical Ar 74p 0 5 1 gt Ar 4s 0 5 0 Hv Optical Ar 4p 0 5 1 gt Ar 4s 0 5 1 Hv Optical Ar Ar 4s 1 5 Ar 4s 1 5 Ar 4s 0 5 Ar 4s 0 5 Ar 4p 0 5 Ar 4p 1 5 1 gt Ar 48 1 5 2 Hv Optical Ar 3 4p 2 5 3 gt Ar 45 1 5 2 Hv Optical Ar 4p 2 5 2 gt Ar 48 1 5 2 Hv Optical WAIN A UV AlLWIN Ar 4p 2 5 2 gt Ar 48 1 5 1 Hv Optical m o Ar 4p 2 5 2 gt Ar 4s 0 5 1 Hv Optical ADDN DWM fFWN me Ar Ar 4p 1 5 1 gt Ar 48 1 5 1 Hv Optical Figure 4 1 68 KintechDB 1 5 User Manual Kintech Lab Mechanisms database Working with database 4 2 4 2 1 4 2 2 4 2 3 The following table describes the window buttons and their functions Button Function hag In the main window adds a new mechanism in the Phase group adds a new phase In the main window deletes a mechanism in the Phase group deletes the selected phase Undo Accept changes changes must be accepted in order to be saved Exit the mechanism editor Show the history of operations with the database Open the substance editor window for the selected mechanism NZILA E Open the reaction editor window for the selected mechanism Working with database Selecting a mechanism
8. The Principal quantum number symbolized as n is the first of a set of quantum numbers which includes the principal quantum number the azimuthal quantum number the magnetic quantum number and the spin quantum number of an atomic orbital The quantum number n labels the energy levels of hydrogenic atoms In the database it means the principal quantum number of outermost external electron The orbital angular momentum quantum number L of electrons in atoms associated with a given quantum state 25 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 2 Total angular momentum quantum number J is a combination of its orbital angular momentum and its spin angular momentum quantum numbers IL S lt J lt L S Diatomic molecules The tab contains data on electronic states and related properties for diatomic molecules Every state is characterized by Type Configuration State energy Stat weight and etc The description of the data is presented below Type Term symbol abbreviated description of the angular momentum quantum numbers and symmetry properties of wave function of a given electronic state of a diatomic molecule Electron configuration standard notation to describe the electron configurations of diatomic molecules State energy To the energy of an electronic state of the diatomic molecule reckoned betw
9. amp Temperature K 1000 61 00 1 760E 32 1 736E 56 Min Max 1000 71 00 1 760E 32 2 020E 56 Step E Pressure atm Min Max Step 1000 100 00 1 760E 32 2 846E 56 Dependency 1000 81 00 1 760E 32 2 305E 56 1000 91 00 1 760E 32 2 589E 56 Generating tables If the list of the functions for the analysis and the boundaries of interval for the independent variables are set than it is possible to generate the table with the numerical data To do this press button amp S The table with the numerical values of the required parameters will be generated If several independent parameters are possible for the data than the data are sorted according to the rule specified in the drop down list Dependency see previous section Generating plots All the data from the table of the numerical values can be plotted for visual analysis which is more convenient in some cases for example when several rate constants for the chemical reaction are compared Za To generate the plot press button of the main toolbar 79 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool Figure 6 6 6 1 2 6 Figure 5 7 amp Reaction analysis TRA IOA KO Reactions amp H 0 M gt HO M T p H 02 M lt gt HO2 M H 02 M lt gt HO2 M IK atm w fcm n s T HAN Arrhenius 200K 300 K onan Lindemann 300 K 300 K 2 089E 33 1 1000 1 0
10. and w is parity which is present for symmetric molecules and ris reflection which is present for states Quantum numbers of term are inserted into the field electronic state attr in the form of a string spectroscopic name JM L r_ wQ where L are Latin analogs of the Greek letters S P II D A F G T An example of the complete description insertion of the excited electronic state of CH3 including configuration 1oy 1my3drq and term B ee is shown in Figure 3 12 Rather often spin orbit coupling is neglected in this case and quantum number Q is omitted Hund coupling case c This coupling case takes place when splitting between the electronic molecular terms due to electrostatic interaction is smaller than that due to spin orbit coupling Here quantum numbers S and A are not defined and the following notation is used in molecular electronic spectroscopy for the term spectroscopic name 2 w is parity which is present for symmetric molecules and ris reflection which is present for the states with Q 0 Quantum numbers of term are inserted into the field electronic state attr in the form of a string spectroscopic name JQr_w An example of the insertion of the l gt excited electronic state B Ta description is shown in Figure 3 13 97 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Figure 7 10 7
11. gt CH Hy C C H C lt gt CH H C C H C lt gt C H H C Arrherdus 290 K 3500 K Ct CO lt gt CO CO C H 0 lt gt H HCO 3 H C lt gt C H H C Ct NO lt gt N CO Arrheruus 290 K 3500 K Substances fel Class Chemical v Select Selection of the functions for the analysis After the selection of the reaction the function for the analysis should be selected The functions available for the analysis are e Thermodynamic functions are calculated on the basis of the information about the reactants and products of the reaction extracted from the Substance and Atomic Molecular properties database 76 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool e AG T Gibbs energy change in the chemical reaction as function of temperature kJ mole e AH T Enthalpy change in the chemical reaction as function of temperature kJ mole e AS T entropy change in the chemical reaction as function of temperature J mole k e AF T reduced Gibbs energy change in the chemical reaction as function of temperature J mole K e ACp T molar specific heat change in the chemical reaction as function of temperature J mole K e Kp T equilibrium constant of the chemical reaction defined through the partial pressures as function of temperature dimensionality of the equilibrium constant depends on the
12. n fs 74 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool 6 1 2 6 1 2 1 6 1 2 1 1 This window contains the following elements Toolbar with buttons x ng 7 reactions selection Lae P numerical table generation ot e graph plot tool 2 e data export to text file Io f exit from the Reaction analysis tool e List of reaction with reaction equation and available rate constant approximation Reactions e List of the functions for the analysis Columns for analysis KF Kr X e Quick function selection toolbar for kinetic analysis and thermodynamic analysis 44 45 AF ACp Kp ke x Setup section for independent parameter interval temperature pressure electron energy Table of the numerical data for thermodynamic functions and rate constants Working with Reaction analysis tool Selection of the reactions for the analysis The Reaction analysis tool allows two strategies for reaction equation input The first one is manual the second one is selection from the Process database If the manual input is performed than only thermodynamic analysis of the reaction will be performed The reaction is loaded from the Process database than thermodynamic analysis as well as rate parameters analysis can be performed Manual reaction input 3 To enter reaction manually press button p of the toolbar Then in the Reacti
13. 26 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties Quadrupole moment electric quadrupole moment Units eA Polarizability Electric dipole polarizability second derivative of the molecular electronic energy with respect to the strength of external uniform electronic field Units A The term symbol is an abbreviated description of the angular momentum quantum numbers and symmetry properties of wave function of a given electronic state of a diatomic molecule It is described by symbols an where S is the total electronic spin momentum A is the projection of the total electronic orbital momentum and Q A 2 is the projection of the total electronic momentum on the internuclear axis 2 S S 1 S is the projection of the spin momentum on the internuclear axis In certain cases Hund s case c the quantum numbers A n lose meaning and the states are characterized only by the values of the quantum number Q which for molecules with an even number of electrons take integer and for molecules with an odd number of electrons take half integer values To simplify input into the database conditional term symbol CTD is introduced There are two types of CTD depending on Hund s case coupling CTD is visualized and printed as conventional term symbol For the detailed information on Input of the CTD please read Appendix B Electron
14. KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification 7 2 2 The particle is in the exited electronic state and vibrational rotational thermally equilibrium state The fields in the wizard specifying electronic state must be filled see the description below and all other fields must be left blank 7 2 3 The particle is a molecule in the ground electronic state with the vibrational modes 1 2 in the definite quantum states specified by the vibrational quantum numbers v1 v2 and other vibrational modes and rotational degrees of freedom are at thermal equilibrium Vibrational quantum numbers v1 v2 are to be inserted into the corresponding fields and all other fields are to be left blank Reaction equation H2045 5 1j 2 lt gt HeOfvl 1iv2 2 4 lt gt lt empty list gt H2O 2 RA Property Value gt state term spectroscopic name spin orbital angular momentum total angular momentum symmetry group symmetry index electronic state attr no vibratonal_state_attr vibr_quant_numb vi 1 C z v3 vibr_rot_quant_numb lt C Show all Figure 7 1 7 2 4 The particle is a molecule in the exited electronic state and with the vibrational modes 1 2 in the definite quantum states specified by the vibrational quantum numbers v1 v2 and other vibrational modes and rotational degrees of freedom are at
15. by the vibrational quantum numbers v1 v2 and other vibrational modes and rotational degrees of freedom are at thermal equilibrium ccccceeccecceeceeeeeeeeeeeeeeeeeeeeteess 87 7 2 5 The particle is an atom in the completely specified ground or excited electronic state 88 7 2 6 The particle is an atom in the artificial excited electronic state cccccceccceceeeceeeeeeeeeeeeees 94 7 2 7 The particle is a linear molecule in the completely specified ground or excited electronic state 20 eee eeeseceeeeeeecaeeeaeeeaeceaeeeaecaeceaeceaeceeccaaeceecceeceaeceecececececeeececeeeeeseeeeeeeeeeeeteeeeeetnees 95 7 2 8 The particle is a linear molecule in the artificial excited electronic state 0 0 e 98 7 2 9 The particle is a nonlinear polyatomic molecule in the completely specified ground or excited electronic State cccecceeeeeeeeeeceeceeeeeeeaeeeaeeaeeaaaeaaaeaaaeaaeeaaecaeeeaeceaeeeeseeeeseeeeess 99 7 2 10 The particle is a polyatomic nonlinear molecule in the artificial excited electronic state 103 5 KintechDB 1 5 User Manual Kintech Lab Installation and configuration General information 1 Installation and configuration 1 1 1 2 1 3 General information KintechDB contains four databases Substances Processes Mechanisms and Tools The Substances database contains the data of the thermodynamic properties of the substances and atomic molecular and electronic
16. database settings dialog invoked by pressing GA button at the mail database dialog window Database connection Use the same settings for all databases Database Server Port Database folder D database E Login type Remember user name and password x Zo Kintech database engine stores the data for substances atoms molecules processes and mechanisms properties separately in several database files or remote databases You can configure connection settings for all databases at one time or separately The checkbox use the same settings for all databases switches between these two regimes of configuration To use local files to store database data one should select Local checkbox and specify the folder with database files in Database folder field KintechDB 1 5 User Manual Kintech Lab Installation and configuration Administration and users management 1 5 1 5 1 1 5 2 1 5 2 1 1 5 2 2 To store the data on the remote server it is necessary to deactivate Local checkbox specify database server name or IP address at Server field database server port at Port field and path to database folder on the remote server at the Database folder field Login type drop down list allows to configure the way how the database GUI stores the user authentication information Administration and users management Administration The d
17. s K N for third order reaction N temperature exponent dimensionless EA activation energy cal mol b1 59 approximation coefficients dimensionless This type of the rate constant approximation is the extension of the original rate constant proposed by Janev Evans Langer and Post for the electron helium and electron hydrogen reactions Janev R K Langer W D Evans J K Post J D E Elementary processes in hydrogen helium plasmas Springer Verlag New York 1987 The expression for the rate constant is E 2 k T AT caf aT b in T k l 60 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 4 11 3 3 4 12 3 3 4 13 3 3 5 3 3 5 1 Arrhenius approximation with temperature series A pre exponential factor cm s K N for second order reaction cm s K N for third order reaction N temperature exponent dimensionless b1 54 approximation coefficients KK k 1 4 This is the extended Arrhenius approximation where a series of the terms is provided for the accurate approximation of the rate constant as function of the electron temperature The expression for the rate constant is MT AT cxf 72 k 1 Dependence on the reduced electric field A pre exponential factor cm s K for second order reaction cm s K N for third order reaction B temperature exponent dimensionless B approximation
18. u s gt lt empty list gt H204353 C_2v a1 b1 1 a1 1 C 41B1 C_2v a1 b1 1 b1 1 DA A GZ C2 Lia AA Property Chet phase i phase type charge isomeric form state term spectroscopic name spin orbital angular momentum total angular momentum symmetry group symmetry index electronic state attr vibratonal_state_attr vibr_quant_numb T Show all v value v x TE g 0 no 1 2 Cc 2v gat C 1B1 C_2v a1 b1 1 b1 1 D A1 103 KintechDB 1 5 User Manual Kintech Lab
19. v the average EV E V transition frequency Units cm To obtain the total probability of electronic transition between two molecular states it is necessary to sum over all possible electron vibrational transitions 2 Op Ava 2 aont E OKs Fe DCO 2 81 Neglecting now the influence of vibrational structure on the values of lt q gt gt 1 V 5J V vi o and taking it out of the index of summation one can approximately obtain Ae Pad Ag 256 CDHG 3 c 2 6 D R v P and then 4 EY Cady 3 2 0 Ta D R D R v gt Obviously the value of A j v decreases while v increases due to increasing number of oscillations of nuclear radial functions v R gt between turning points The life time of the particular electronic level i is defined by further summation over all allowed transitions to lower electronic levels 2 Oo hak roti 3 a a alt 2 65 4 D R v Now making the same approximation while deriving 3 one can get e P 2 6 monet Z 3 2 ae Oy J v 2 oa 4 2 saa 7 l lt L Gab O SV De DR v gt 67 KintechDB 1 5 User Manual Kintech Lab Mechanisms database Database window description 4 Mechanisms database 4 1 Database window description The main window of mechanism database contains of a table of mechanisms a table of Phases a table of Reactions and a table
20. 1 A 4 9 2 U J 1 3 Z k 1 if A gt O k 1 if A lt 0 Fo BJ J 1 DJ J 1 and B and D rotational and centrifugal constants for a given vibrational state Diatomic vibrational constants We WeXe WeyYes WeZe Vibrational constant values Units cm 29 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 2 3 2 2 6 2 4 2 2 6 2 5 We error Estimated uncertainty of w value Units cm Vibrational constant values in cm correspond to following expression for energy G v We v 1 2 WeXe V 1 2 2 WeVe Vt1 2 weZ_ vt1 2 It should be noted the series is Oscillating Diatomic rotational constants Be 04 Az Q3 Ay vibrational rotational constant values Units cm Be error Estimated uncertainty of B value Vibrational rotational constant values in cm correspond to following expression for rotational constant B on vibrational quantum number B Be a4 vt1 2 a v 1 2 a3 v 1 2 a4 v 1 2 4 It should be noted the series is oscillating Diatomic centrifugal constants 1 2 3 1 De B1 Bz B3 Ba Vibrational rotational constant values Units cm He V4 V2 V3 V4 Vibrational rotational constant values Units cm Le Aq Ag Ag Ag Vibrational rotational constant values Units cm Vibrational rotational constant value
21. 1 1P 53 G1 4 5 lt gt Ni Gs 3d Ce 4s4p P lt gt lt emptylist gt tf Nif 3 3d B 3F 45 1 4p 1 1P Fs 33 G 15455 _ Property Value Formula Ni alias phase phase type g charge 0 state E term spectroscopic name spin 1 orbital angular momentum 4 total angular momentum FOC B type vibr_type description C Show all Finally it is to be noted that for heavy atoms with the strong spin orbit coupling electronic configuration for the excited states can not be defined and therefore is absent in the field electronic state attr see example below in Figure 3 7 Quantum numbers of term part of electronic state attribute depend on the type of coupling between orbital and spin angular momenta J J coupling This type of coupling may take place in the excited states of heavy atoms with the strong spin orbit coupling Here electronic configuration is not defined and the state is characterized only by the quantum numbers J of the total angular momentum and w of parity Correspondingly the following string is to be inserted into the field electronic state attr J w where w for the odd states and the mark w is omitted for the even states An example for the excited state of Nd with the excitation energy 21184 881 cm 1 is presented in Figure 3 7 90 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equ
22. 2 8 Reaction equation 12 5 8 0 uy33 B 3 0 su lt gt DEO BOU tu lt gt lt empty list gt u 12 j B0 0 _ujj3 B 30 5u Property value formula 12 alias E phase phase type g charge 0 isomeric form no state term LJ spectroscopic name B spin orbital angular momentum total angular momentum 0 reflection paty eT fo E vibratonal state attr v F Show all The particle is a linear molecule in the artificial excited electronic state Considering excitation of a linear molecule by the electron impact it is often suitable to consider several excited electronic states with close energies as one artificial electronic state Name of such an artificial state is inserted in the following way Fields spectroscopic name and total angular momentum are left blank the effective orbital angular momentum is set equal to zero and the quantity Ser g 1 2 is inserted to the field spin Here g 91 9o gn where g is electronic statistical weight of the real state included to the artificial state and N is a number of such states The string which is to be inserted to the field electronic state attr have the form string1 string2 stringN An example of the description of the artificial excited state Iny3og1na Ty tin ae tgw Ay of N3 is shown in Figure 3 14 98 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance n
23. 77 172 38 205 10 rs 898 15 34 36 239 75 27 86 19 18 196 16 208 74 8 998 15 34 88 243 41 31 32 22 64 220 32 212 03 9 1098 15 35 32 246 76 34 83 26 15 244 83 215 04 10 1198 15 35 68 249 85 38 38 29 70 269 66 217 82 11 1298 15 35 99 252 73 41 97 33 29 294 79 220 40 12 1398 15 36 28 255 41 45 58 36 90 320 20 222 81 13 1498 15 36 57 257 93 49 22 40 54 345 87 225 07 14 1598 15 36 81 260 30 52 89 44 21 371 78 227 20 15 1698 15 37 05 262 54 56 59 47 91 397 93 229 22 16 0 1798 15 37 29 264 67 60 30 51 62 424 29 231 13 17 1898 15 37 53 266 69 64 05 55 36 450 85 232 95 18 1998 15 37 77 268 62 67 81 59 13 477 62 234 69 19 2098 15 38 01 270 47 71 60 62 92 aaae ec 72 an 21ne 16 20 ae a4 Approximation interval View interval Tmin 298 15 Eneray Joule Si Tmax 20000 Temperature K v Casve Step 100 Amount Mole a X Close Tmin 298 15 Tmax 20000 The TPIS dialog window contains a table of thermodynamic parameters depending on temperature a group of fields Approximation interval Tmin Tmax a group of fields View interval Tmin Tmax and Step a drop down list Units Energy Temperature Mass and the following buttons 13 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database 2 1 4 3 Figure 2 3 Button Function Opens the graphing window with a graph of the temperature dependence of the selected value See the Working with gra
24. For composite states statistical weight is a sum of constituted states For example P 3 1A 7 Zero point energy ZPE is the lowest possible vibrational rotational level for a given state In harmonic approximation of molecular vibrations for singlet states it is ZPE v d 2 where v and d are frequencies of vibrations and their degeneracy for a given state Multiplicity is the spin degeneracy of a state M 2 S 1 where spin angular momentum quantum number S 0 1 2 1 3 2 2 Group of symmetry is the group of molecules that possess the same symmetry elements These groups of symmetry elements are called point groups The point groups symmetry elements irreducible representation and symmetry numbers are listed below ee Symmetry elements Irreducible representations ae ere e205 Di ip Ar Deere 1 Ugr gr Agr Pg 4 2 Doh P2C 0 125 2C Gece 2 Wa A Dai Sec Cy E A 1 C E op ALA 1 Ca Ei Ag Ay 1 C3 EC A B 2 C3 BCC ye 3 C4 EGGO A B E 4 Co ECOC ac A By Bay Ep 6 S4 ESG Se A 3 E 2 S6 ECO SoSo ar Eo Ar e 3 Con E C2 i Op e Be 2 C3h E C3 C3 op S3 S39 Ar Di Aer ni 3 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties e a 4 Cyn EC C3 Cea S4 Oh Aur Bur Ey P EG GOG a a a a a 6 6h S3 Se S6 S3 Oh Aag Ba Bio Cay E Cy o xz o yz Ay Aj Bi 2 C3 E 2C3 30y Air Ao E 3 Ci B26 C 2626 Poa ae pes 4 Ar AS BT l
25. K a pre exponential factor dimensionless b temperature exponent dimensionless c activation energy K The collision efficiency approximation expresses the fact that not every collision of the two reactive particles results into the successful reaction There is only the probability less than 1 that the reaction could occur The general equation for the probability or efficiency is min 1 aT ex a o 3 The reaction rate constant is given by 82RT M AB k T yN d In this equation 1 1 Pi 1 Ma My My the reduced mass of the particles A and B 55 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 3 3 3 3 1 3 3 4 3 3 4 1 d o u 2 collision diameter Here N4 6 02214179 10 3 mol is Avogadro constant R 8 314472 J mol K Energy exchange processes Landau Teller approximation A pre exponential factor cm3s K N N temperature exponent dimensionless E B C exponent parameters in Landau Teller approximation B in KIB Cin 28 E in kcal mole Rate constants k of the energy exchange processes X i Y gt X N Y m where i j m indicate vibronic states of the particles X and Y depend only on temperature T Generally accepted analytical approximation for such rate constants is the extended Landau Teller formula E B C RT pu 725 k T AT exo a4 Electronical processes Depending
26. Rm the length scaling parameter Angstrom It characterizes the effective diameter of the particle in collision process Rm is the distance between the particles corresponding to the potential minimum U U min at RERm E the energy scaling parameter It is specified divided by the Boltzmann constant e k in K It is equal to the potential well depth U min E Additional parameters A a B Cg Cg C10 D They are dimensionless and provide the accurate fit of the HFD B function to the real interaction potential HFD B potential is sufficiently accurate potential used to describe the interaction of atoms of noble gases The formula is C n 2n U R e Acl ax px F x F x exl 2 1 X lt D x F x 1 x2 D x R R x 5 n 3 The parameters for HFD B potential for noble gases were obtained in particular by R A Aziz with co authors e g Aziz R A Int J Thermophysics Vol 8 No 2 pp 193 203 1987 Aziz R A Slaman M J Molecular Physics Vol 57 p 825 1986 Aziz R A Slaman 41 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties M J ibid Vol 58 p 679 1986 Aziz R A et al ibid Vol 61 p 1487 1987 Aziz R A Slaman M J Chemical Physics Vol 130 p 187 1989 2 2 7 7 Z rotational Zrot Collision number for rotational relaxation or rotational collision number It can be considere
27. Search database aa Search process E C Search in comments Search process Search substance l CT Copy to clipboard l X close To search for properties of substance or process in the database one should specify search criteria at the Search database dialog input filed select Search substance or Search process from pull down list and press the Start button After the search is completed the results will be displayed in the text area bellow 71 KintechDB 1 5 User Manual Kintech Lab Database search Working with database search tool Search database CH4 Search substance Search in comments Substances Found 41 O Substances database Methane CH4 Molecular weight 16 0426 a m u Thermodynamic data 44H 298 15 kJimole C 298 15 JAmole K 298 15 JAmole K H 298 15 H 0 kJimole 4H 0 kJ mole 74 6 35 695 186 26 10 016 66 63 Gibbs polynomial coefficients IVTAN Temperature K F4 F2 Fz Fa Fs Fe F 298 15 2000 154 28 1 9242 0 0036269 0 84573 554 03 701 67 518 33 2000 6000 346 87 95 198 0 19465 8 7721 44 177 9 651 4 2359 Gibbs polynomial coefficients NASA Temperature K a4 az a3 ag ag ag az 298 15 1500 2 9244 0 0025012 8 998e 06 7 154e 09 1 6089e 12 10022 4 654 1500 6000 3 3113 0 007882 2 3565e 06 3 524e 10 1 9605e 14 10908 0 14342 Leeds Methane v1 5 NOx v2 1 SOx v5 1 CH4 Molecular weight 16 043 a m
28. are atomic masses in a m u of isotopic modifications of atoms in a diatomic molecules Number of electronic states total number of electronic states for a given diatomic molecule Electron levels with known constants the number of electron state with known vibration rotational constants in a diatomic molecule First atom mass number Second atom mass number the mass number nearest integer to the isotopic mass of the first atom in a diatomic molecule 23 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 5 3 2 2 6 2 2 6 1 First atom symbol the name of the first atom in a diatomic molecule Second atom symbol the name of the second atom in a diatomic molecule Polyatomic molecules Number of electronic states total number of electronic states for a given molecule Number of different electronic states the number of electronic states with different vibration rotational constants for a given molecule Number of electronic states total number of electronic states for a given atom ion Electronic properties Electronic properties tab is divided onto three areas upper left the list of electronic states with state type and configuration upper right general electronic stat data e down set of tabs describing the peculiar properties of substance electronic state The data of upper
29. be shadowed When you select necessary curve the plot window with two graphs will appear one for each mechanism Using the intuitively understandable graph options and zoom tools you can observe and magnify the interesting area of the plot As well you can print or save the displaying area to a document or graphical file Using the plot window is described with details in the corresponding section of CWB User s guide Procedure of mechanisms comparison We will discuss the mechanism comparison procedure using the toolbar buttons but it can be done equally using the menus 1 Launch the mechanism comparison tool from the Tools menu the button op 2 Load first and second mechanisms from the Database CWB XML or from Chemkin by selecting the required operation from the Pa Load first mechanism and 5 Load second mechanism menus 3 Press Parameters button check the comparison options make adjustments if it is necessary 4 Press op Compare button Wait until the program compare the substances and processes according to the comparison parameters 84 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Mechanism comparison tool At this point the comparison is done scroll through the lists of substances and processes to see the results Further you can 5 Select two substances with the same formula click on them 6 Press tje Compare substances button The comparison r
30. carried out as well To access the Reaction analysis tool click the Tools button of the main database window and select Reaction analysis tool in the drop down list The main window for the reaction analysis will appear Reaction analysis wy ROZ td Reactions C H CH lt gt CH C H Anhenius 290 K 310 K CsHy CH lt gt CH CH Aumhenius 300 K 2500 K CyH C H lt gt C H CH Aumhenius 300 K 2500 K CoH CH lt gt CH CH Arrhenius 300 K 2500 K Columns for analysis MIKT Kr T KF Kr X Property E Temperature K Min Max Step 400 500 600 700 800 300 C2H2 C2H6 lt gt C2H3 C2H5 7 463E 16 5 079E 15 1 605E 14 3 457E 14 5 979E 14 9 018E 14 1 241E 13 1000 1 603E 13 1100 1 976E 13 1200 2 352E 13 1300 2 726E 13 1400 3 094E 13 1500 3 452E 13 1600 3 800E 13 1700 4 135E 13 1800 4 458E 13 47 10NN 4 TERF12 KT cm n js C2H2 C2HS lt gt C2H C2H6 KF T fcm n s 3 642E 30 6 829E 26 2 501E 23 1 280E 21 2 129E 20 1 753E 19 9 035E 19 3 355E 18 9 813E 18 2 400E 17 5 116E 17 9 788E 17 1 717E 16 2 809E 16 4 335E 16 6 376E 16 a nncF IE C2H2 C2H4 lt gt C2H3 C2H3 5 960E 61 1 706E 48 5 082E 41 4 884E 36 1 769E 32 8 263E 30 9 846E 28 4 510E 26 1 031E 24 1 398E 23 1 270E 22 8 415E 22 4 334E 21 1 818E 20 6 446E 20 1 985E 19 E at1F10 KT cm
31. database if a filter has not been set The lower part of the window shows the group of elements Approximations which contains several types Types of the approximations approaches or methods of the description of the rate of the process of the specified class The parameters characterizing the rate of the process are given in the table or several coupled tables The set of elements for managing filters Filter is above of the processes list It consists of a field for entering substances to filter for Substances a field for entering class for process to display Class a drop down list of approximation type used for reaction rate description Approximation type and buttons to choose the reaction class and implement the filter Clicking these buttons opens the Select class window which contains a tree with reaction classes 45 KintechDB 1 5 User Manual Kintech Lab Processes properties Working with the database 3 2 2 3 2 3 A set of buttons which governs the operations on database is placed at the top toolbar of the window The description of the buttons is given in the table Button Function gg In the main window adds a new reaction in the approximation window adds Ee a new set of parameters for the rate approximation In the main window deletes a reaction in the approximation window deletes a set of parameters for the rate approximation Undo Accept changes changes must be accepted in
32. different external parameters of the system overall temperature gas pressure vibrational temperature Correspondingly different analytical approximations of the rate constants as functions of these parameters are used Generally accepted approximations are as follows Arrhenius A pre exponential factor s K N for first order reaction cm s K N for second order reaction cm s K N for third order reaction N temperature exponent dimensionless Ea activation energy kcal mol Arrhenius approximation is applicable for the following classes of reactions 1 EQUILIBRIUM REACTIONS OF NEUTRAL MOLECULES Here it is to be noted that 48 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 2 2 for unimolecular isomerization reactions and unimolecular decomposition of polyatomic molecules this approximation can be used either in the limit of high pressures or in the limit of low pressures for bimolecular reactions through the intermediate complex this approximation can be used only in the limit of low pressures 2 REACTIONS OF NEUTRAL MOLECULES UNDER NONEQUILIBRIUM CONDITIONS Here it is to be noted that for recombination forming electronically exited molecules this approximation can be used either in the limit of high pressures or in the limit of low pressures for bimolecular reactions in two temperature systems and nonequilibrium decomposition of molecules there is
33. electronic shells with kj 2 for 2 0 or k 4 for 2 gt 0 often are not 96 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification 7 2 7 7 1 7 2 7 7 2 shown In molecular electronic spectroscopy values of A for one electron A for all electrons are represented by small capital Greek letters 0 o 1 m II 2 6 A 3 o 4 y T Quantum numbers of configuration are inserted into the field electronic state attr in the form sim k sim 1 k where l are Latin analogs of the Greek letters s o p n d 5 f 6 g y mentioned above letter representation of l are used If k 1 it is also shown An example of the excited electronic configuration isy imdir of CH3 is shown in Figure 3 12 Separation symbol is vertical line Quantum numbers of term include spectroscopic name and quantum numbers which depend on the relation between splitting between the electronic molecular terms due to electrostatic interaction due to spin orbit coupling Hund coupling case a This coupling case takes place when splitting between the electronic molecular terms due to electrostatic interaction is much larger than that due to spin orbit coupling Here the following notation is used in molecular electronic spectroscopy for the term spectroscopic name MA where M 2S 1 letter representation is used for A capital Greek letters
34. in the database an error message will be displayed 15 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database 2 1 6 Editing the information in the database To change the data in any database field except substance name double click on the corresponding fields cells of the tables and edit or enter new data After making changes click v button in the corresponding tab toolbar to save the changes to the database Each database tab contains toolbar with the following buttons Button Function R Adds a new set line of parameters for each table Fa Deletes the selected set line of parameters A Undo changes to the tables J Accept changes in the tables changes must be accepted in order to be saved J Show the history of operations with the corresponding tables You can use these buttons to add a new set of parameters to database or delete the record from database To edit the name of the substance you should enter the new substance to database Deleting the information from the database To delete a substance particle from the database select the substance or substances in the substance list and click ag All the information related with the substance particle will be removed as well To delete only specific property data of the substance particle select this data set line in the corresponding table e g the Gibbs coefficien
35. jth element R 8 314472 J mol k 22 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 5 2 2 5 1 2 2 5 2 lonization potential energy required to remove one electron from the particle Its units in the database is eV electron Volt Electron affinity amount of energy which is released when an electron is detached from the negative ion atom or molecule with the charge 1 In the database it is measured in eV electron Volts Proton affinity amount of energy which is release after attachment of the proton to neutral particle atom molecule or to the anion In the database it is measured in eV electron Volts General properties This tab contains the data on general properties of substance The view of the tab depends on the sort of substance e Atom an electron assumes as an atomic particle e Diatomic e Polyatomic Atom Number of electronic states total number of electronic states for a given atom ion Diatom Number of electronic states total number of electronic states for a given atom ion Symmetry this is rotational symmetry number which is equal 1 for heteronuclear molecules and 2 for homonuclear molecules First atom mass Second atom mass these are atomic weights in a m u of atoms in a diatomic molecules First isotopic mass Second isotopic mass these
36. no generally accepted approximation for the rate constant and user defined approximation is to be used 3 ION MOLECULE REACTIONS Here it is to be noted that Bimolecular ion molecule reaction and charge transfer can proceed through the intermediate complex and in these cases Arrhenius approximation can be used only in the limit of low pressures Arrhenius approximation for the rate constant k T Ea k T AT exp T r Here Ea is Arrhenius activation energy is taken in kcal mol R 1 9859 cal is xmol universal gas constant T is absolute temperature in K and A is preexponential factor in s T for the first order reactions unimolecular reactions in the high pressure limit in cm s T N for the second order reactions unimolecular reactions in the low pressure limit addition and combination reactions in the high pressure limit direct bimolecular reactions bimolecular reactions through the intermediate complex in the limit of low pressures in cm s T for the third order reactions addition and combination reactions in the low pressure limit termolecular reactions The quantities T min T max define temperature range in which approximation is applicable For pressure dependent rate constants interpolation expressions between high and low pressures are used Lindemann Hinshelwood interpolation Reaction type drop down list allows to set process type as e unimolecular unimolecular or addition react
37. on the type of the electronical process its cross sections may depend on different external parameters of the processes energy threshold of process various fitting parameters which provide essential energy dependence Correspondingly different analytical approximations of the rate constants as functions of these cross sections are used Generally accepted approximations are as follows JILA cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that oj 0 Scale Energies N set of energy points eV CrossSections N set of corresponding cross section JILA cross section table form is applicable for the following classes of reactions 1 ELASTIC ELECTRON ATOM AND ELECTRON MOLECULE COLLISIONS 2 ELECTRON IMPACT EXCITATION OF ATOM 3 ELECTRON IMPACT EXCITATION OF MOLECULE 56 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 4 2 3 3 4 3 3 3 4 4 4 ELECTRON IMPACT DISSOCIATION OF MOLECULE 5 IONIZATION 6 RECOMBINATION OF CHARGED PARTICLES 7 ATTACHMENT AND DETACHMENT Ar allow cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that oj 0 Scale Fo oscillator st
38. on this inequality e Symmetric tops or symmetric rotors Ig lt I oblate symmetric tops saucer or disc shaped 4 lt Ig Ic prolate symmetric tops rugby football or cigar shaped e Spherical tops or spherical rotors l4 Ip Ic e Asymmetric tops the case when all three moments of inertia are different Symmetry number o is the number of unique orientations of the rigid molecule that only interchange identical atoms The number depends on point group of a molecule and is presented in table below Group o Group o Group o Group o Cy Ci Cy Cov Dich 2 TT ly 12 Oh 24 Cp Chv Cah n Dp Dnb Daa 2n Sn n 2 Ih 60 Number of vibrational frequencies is the number of normal vibrations in molecule with their degeneracy Total number of vibrations for linear molecules is 3N 5 and for nonlinear molecules is 3N 6 where N is number of atoms in a molecule The properties related with the selected electronic state of the polyatomic molecule are presented on several subtabs These properties include vibrational and rotational parameters and are described below 36 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 3 1 2 2 6 3 2 2 2 6 3 3 Vibrational states polyatomic molecule Symmetry type symbol of irreducible representation Every normal vibration mode belon
39. order to be saved Exit the reaction database editor Show the history of operations with the database Open the reaction editor Choose a filter by reaction class Deactivate a filter by reaction class REELS Activate the filter by substances Search and view the processes Filters To view information select the desired reaction in the table of reactions and the type of rate approximation for the given reaction The approximation parameters are entered in the table If there is no data for the desired type of approximation another approximation type can be used A desired reaction in the table of reactions can be located using filters Reactions can be filtered by class sub class and substances participating in the reaction To add a filter select one or several filter criteria in the filter field In the Substances field you can enter substances participating in a reaction delimited by commas The Approximation type list allows the user to choose a class for the reaction To choose a class for the reaction click a and choose a class from the tree This class will be show in the field Class To remove the filter by reaction class click After entering information for the filter click w to add matching reactions to the table Addition of a new process to the database To add the new process and related data into the database click the El button of the main window The Reaction equation wizard
40. populated But although the rotational quantum B or B is much less even at the room translational temperatures of heavy particles in the discharge usually the rotational sublevels could not be considered as degenerate ones So each J sublevel is occupied with some probability that is much less than unity while the summation over all sublevels would give obviously unity That is why in this last case the value from equation could be considered as integral probability of the electron vibrational band if to substitute in to equation some mean value of a i v J j v J ON the other hand the 2J 1 sublevels of the level with fixed J are usually degenerate and that is why the statistical weight neglecting L doubling is equal to 2J 1 This consideration shows that the expression in the equation is the key quantity in the description of the intensity distribution of the molecular spectra Molecular E E Upper term the upper electronic term i Lower term the lower electronic term j v vibrational number of the upper electron vibrational level A Einstein coefficient of quantum transition i v gt j v A projection of the electronic angular momentum L on the internuclear axis N projection of the electronic angular momentum L on the internuclear axis 66 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties
41. properties of the species The Processes database contains information on rates of the elementary processes Mechanisms database contains a collection of the compiled and validated kinetic mechanisms which contain consistent information on the properties of the species and processes The database is tightly integrated with the KHIMERA and Chemical Workbench and can export import data to from these products of the Kintech Lab Ltd Installation To install the database run the setup exe file of the KintechDB distributive The installation wizard will install the KintechDB to the windows Program Files Kintech directory If necessary the user can specify another location The local copy of the database files will be stored the data subfolder e g C Program Files Kintech Database data for the launching the database on the local computer Launching the database GUI Database GUI can be evoked through Windows Start menu Start gt Programs gt Kintech gt Database Editor Main window of the database interface is shown in the figure KintechDB 1 5 User Manual Kintech Lab Installation and configuration Database connection settings Figure 1 1 1 4 1 4 1 Figure 1 2 Tools sy Database connection settings Database settings dialog Database user interface engine is capable to work with database files located on the local computer or with remote database server Connection settings can be configured through
42. right and down part of the tab depend on the electronic state selected in the upper left part of the tab The data and fields in Electronic properties tab depends on the sort of substance and described below Atom The tab contains the data on electronic energy levels and their related properties Every level is characterized by Electron configuration standard notation to describe the electron configurations of atoms It is a string of characters Term symbol abbreviated description of the angular momentum quantum numbers in a multi electron atom It is a string of characters State energy The energy of an electronic state of the atom reckoned from the ground state Units are cm Stat weight the number of degenerate substates contained in the state dimensionless State nature Spin multiplicity denotes the number of possible quantum states of a system with given spin quantum number S Principal quantum number principal quantum number of the electronic state Total orbital momentum the orbital angular momentum quantum number L of electrons in atoms associated with a given quantum state 24 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties Total angular momentum the total angular momentum quantum number J Number of valence electrons number of the electrons at the outermost external el
43. small Latin letter g or u Quantum numbers of term are inserted into the field electronic state attr in the form of a string spectroscopic name MSyms An example of the complete description insertion of the excited electronic state of H2O including symmetry group Czy configuration a4 b4a4 and term 1B4 is shown in Figure 3 17 102 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification 7 2 10 Figure 7 15 The particle is a polyatomic nonlinear molecule in the artificial excited electronic state Considering excitation of a nonlinear molecule atom by the electron impact it is often suitable to consider several excited electronic states with close energies as one artificial electronic state Name of such an artificial state is inserted in the following way Fields spectroscopic name and symmetry and index are left blank and the quantity So g 1 2 is inserted to the field spin Here g gj Qot gyy where g is electronic statistical weight of the real state included to the artificial state and N is a number of such states The string which is to be inserted to the field electronic state attr have the form string stringo string An example of the description of the artificial excited state Co a4b a 1B Co a 2b b D A is shown in Figure 3 18 Reaction equation HOCl C al aDOM aN WaN ONIDA
44. substances only in the specified phase state gas liquid condensed crystal amorphous glass surface View of the substance particle information To view the data available in database highlight the formula of the substance particle in the list at the left part of the window The data available for this substance are displayed on the right part of the window To look at the information on the specific properties of the substance particle navigate through the Tabs Visualization of the substance thermodynamic properties Working with the TPIS and JANAFF tables for calculating temperature dependences of thermodynamic functions The database of thermodynamic properties allows the user to output data on various thermodynamic parameters in the form of a table with temperature dependences These tables are analogous to the tables in the TPIS reference books Thermodynamic Properties of Individual Substances and JANAFF The tables can be opened with the res and 2 buttons on the Thermodynamics tab of the Substance database window Working with the TPIS dialog Cp T S T H T H O H T G T F T 3 mole k 3 mole k kJ mole kJ mole kJ mole 3 mole K 1 298 15 129 38 205 04 8 68 0 00 61 13 175 92 2 390 15 el 30 09 213 62 11 65 2 97 82 08 184 36 3 498 15 31 09 220 47 14 71 6 03 103 80 190 95 4 598 15 32 08 226 25 17 87 9 19 126 14 196 38 5 698 15 32 96 231 27 21 12 12 44 149 02 201 02 6 798 15 33 72 235 74 24 45 15
45. the state Dipole moment electric dipole moment first derivative of the molecular electronic energy with respect to the strength of external uniform electronic field directed along the intermolecular axis Units Debay Quadrupole moment electric quadrupole moment Units eA Polarizability Electric dipole polarizability second derivative of the molecular electronic energy with respect to the strengh of external uniform electronic field Units A Zero point energy ZPE the lowest possible vibrational rotational level for a given state Level type Level identification the type of the electronic state ground excited resonance Absolute energy energy of the electronic state obtained from quantum chemical calculation Units are 1 cm 32 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties Multiplicity spin degeneracy of a state Group of symmetry the group of molecules that possess the same symmetry elements These groups of symmetry elements are called point groups Top type there are three types of tops depending on the inequality las lgs Ic where I Bc momentum of inertia of the top Symmetry number 0 the number of unique orientations of the rigid molecule that only interchange identical atoms Number of vibrational frequencies the number of normal vibrations in molecule with their
46. u Gibbs polynomial coefficients NASA Temperature K a4 az a3 a4 as ag az 200 1000 5 1499 0 013671 4 918e 05 4 8474e 08 1 6669e 11 10247 4 6413 1000 6000 1 6354 0 010084 3 3692e 06 5 3497e 10 3 1553e 14 10006 9 9937 C1 C3 San Diego Mechanism 2005 12 01 CH4 L8 88 Molecular weight 16 043 a m u v l CH copy to clipboard X Close Figure 6 2 5 2 1 Searching for substance properties To search for substance properties in the database one should specify a valid substance name as search criteria and select Search substance from pull down list If Search in comments checkbox is selected the search criteria can be an arbitrary text string 5 2 2 Searching for process properties To search for process properties in the database one can specify on of the following search criteria e List of process reagents or products divided by space All of the reagents or products should have valid substance names e Valid process equation e Arbitrary text string for search in comments 72 KintechDB 1 5 User Manual Kintech Lab Database search Working with database search tool 5 2 3 Working with search results After the search is completed the search results will be displayed in the text area of the search window The results are grouped by the databases and mechanisms where the data were found in the case of the results from mechanism database by mechanism wher
47. 0 1 760E 32 saa 1 3 i oe a Pr pe 1 00 atm Columns for analysis H i j m H O2 M lt gt HO2 M VI KF T i f l i f i KFCT ne kr T cm n js P 1 00 atm i i i i A i H 02 M lt gt HO2 M l t KFCT DANI KF kr X icm n s Property amp Temperature K Min Max Step Pressure atm Min Max Step lt f i f 0 0003 0 0004 0 0005 0 0006 0 0007 0 0008 0 0009 0 001 Saving data The numerical data from the table can be transferred to another program as formatted text including tabs or saved into text file as formatted text as well Stored data can be plotted with another suitable program To transfer the data to another program or text file press button ol The drop down list will appear with two options e Copy table to clipboard e Save table to file amp Reaction analysis H PR WhO Save table to file Reactions H 0 M lt gt HO MI KFET cm n Arrhenius 200 K 300 K ub z 1 1000 1 00 1 760E 32 Lindemann 300 K 300 K 2 1100 1 00 1 600E 32 If the first option is selected the data are stored into clipboard and can be inserted into another program for further analysis e g Microsoft Notepad or Microsoft Excel If the second option is selected the program will prompt to enter the path and file name for the data to be stored 80 KintechDB 1 5 User Manual K
48. 1098 15 35 32 246 76 222 95 26 15 1198 15 35 68 249 85 225 06 29 70 1298 15 35 99 252 73 227 09 33 29 1398 15 36 28 255 41 229 02 36 90 1498 15 36 57 257 93 230 86 40 54 1598 15 36 81 260 30 232 63 44 21 1698 15 37 05 262 54 234 33 47 91 1798 15 37 29 264 67 235 96 51 62 1898 15 37 53 266 69 237 52 55 36 1998 15 37 77 268 62 239 03 59 13 2098 15 38 01 270 47 240 49 62 92 an _21ne 16 2020 279 98 241 on 622 Approximation interval Tmin 298 15 Tmax 20000 View interval Tmin 298 15 Tmax 20000 Step 100 Units Energy Temperature K Amount Joue v v Mole 2 Plot lH Save X Close 14 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database The dialog window contains a table of thermodynamic function of the substance depending on temperature a group of fields Approximation interval Tmin Tmax a group of fields View interval Tmin Tmax and Step a drop down list Units Energy Temperature Mass and the following buttons Button Function Opens the graphing window with a graph of the temperature dependence of the selected value See Working with graphs below save Saves the table to a text file X chose Closes the JANAF table The tables below show the description of the columns of the JANAF table Column Function T Temperature Cp 7 Heat capacity at co
49. 13 21 1 2n S 42 3 2 3dC 1 LALLY 2 G4 Mica Exe Property Value Elec formula Ne v alias phase v Ok a phase type g charge 0 state term spectroscopic name spin orbital angular momentum total angular momentum 4 CEES ce E2 E2212 222 type vibr_type description T Show all Figure 7 8 7 2 7 The particle is a linear molecule in the completely specified ground or excited electronic state The characteristics of the state are inserted into the fields of the menu term of the Particle name wizard 7 2 7 1 Spectroscopic name In the case of the molecular electronic states spectroscopic name is usually present spectroscopic name is small or capital Latin letter may be with prime or with tilde see example in Figure 3 12 Reaction equation CH2 3551 s _u 2 1 ph_u 1 3d ph_g 1 B 3 S _u0 5 B 1 0 0 ju lt gt CH Ey udo lw 3da BE yo tu lt gt lt empty list gt u CH2 14s u 2 1p _u 1 3dip l1 B 3454 _u0 B 1 0 0 u Property Value Chet state S term s i spectroscopic name B spin 1 orbital angular momentum total angular momentum 0 reflection parity u B symmetry group symmetry index electronic state attr 1 s _u 2 1 p _u 1sdip _o 1 IB 3 s _uol B vibratonal_state_attr vibr_quant_numb vi v2 v C Show all Figure 7 9 95 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substan
50. 2 2 2072E 001 8 0699E 000 1 7254E 000 6000 20000 2 8835E 002 7 8938E 001 2 6793E 000 2 6722E 001 1 7676E 001 1 7197E 001 1 7688E 001 CAT Fe FX 2F X GFX 12F X H T Fo 2F sf FX Fax 2F X SFX S T F F2 Folog X Faf X 2FX SFX 4FX O T F Filog X Fax FX FX FX FX Here X T K 0 0001 C T in 3 mole K H T in J mole S T in Jj mole K p 1 atm 16Q u 7 9975 onstants of Dia i This report can be saved as HTML file or printed Interactive help system The interactive help system is associated with the every element of the window which is currently active Pressing F1 key at the keyboard lunches the interactive help explorer and shows the theory related with the data presented in the active table the table which elements are marked or selected with the mouse For example if the user views thermodynamic properties of the substance namely the Gibbs coefficients for the IVTAN approximation he she can press F1 key on the keyboard to start the window with the description of the meanings of the coefficients and general formulas for the calculation of the thermodynamic functions Review of the history of the revisions in the database The database engine allows the user to view the history of operations with the database The database changes history is available only for users with administrative rights To view the h
51. 7 3 2 5 Exiting the editor WIDOW x21 stiorssce czeintesasieeer Eesaraaudonautsenbedendesiacetepbadtansvansistes Eedecbauayeedeedrenens 48 3 3 Guide to Process properties nas cssicesesecsssscisesceensedsvevaseysadsusdecensevevtadssnvscndbocsvesdenesssensedsssaescencesenses 48 3 3 1 General classification of the processes ccccccceccecceeeceeeceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeteeenennes 48 3 3 2 Chemical Processes srsiceacivncecsaswssnevostedoaubinedsbnonstadeeancedadadecasbensnuddeaaadoadvebeuWediuaeevabudeaduencaaniuiied s 48 3 3 3 Energy exchange processes aissicct viicesreccanddeasaccesnntnad steve tiuvantavadasknosteten sar eansedchotexsbucucnenttcantecans 56 3 3 4 Electronical processes cccccccccccccccecceecceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeetenenitneas 56 3 39 5 Optical PrOCESSES ee 61 4 Mechanisms database 6 sccis a aaa 8 4 1 Database window description ccccceeceeeeeeeeeeeee eee eeeeeeee eee eeeeeeeeeeeeeeeeeeeeeeeeeeseeeneseeeeeneeneeeneseeees 68 4 2 Working with database isisicassrsenssscacexnnceansansiniiviaaneananavidecnisaabise bs vas eaieiacnctdasnudiinnnsunanedanedintanaeninn 69 4 2 1 Selecting a mechanism and view its phases substances processes cccccceceeeeeeeeeees 69 4 2 2 Creating a new mechanism ascgcusesccvteseluncneve nate virasiadiesbecaligtiastdeniouseseuecnesdcniuwtenenevianeta ides 69 4 2 3 Addition and deletion of the new phases substances and re
52. 75 X46 F6 X 12 F7 X X Molar entropy S T F1 F2 F2 mX 23 2 F5 X 3 F6 X 4 F7 X Molar enthalpy change with respect to 0 K H T H 0 T Faa 3 4 4 5 4 42 F6 X243 FT X X X Total molar enthalpy H T DHf 298 15 H T H 0 H 298 15 H 0 Molar Gibbs free energy G T H T T S T Molar reduced Gibbs free energy F r s r 0 Note that for the calculation thermodynamic functions in addition to polynomial coefficients F1 F7 the molar enthalpy of formation at standard conditions should be known NASA polynomial approximations Tmin low temperature boundary of the approximation interval K Tmax upper temperature boundary of the approximation interval K a1 a7 set of the Gibbs coefficients On the basis of the coefficients a1 a7 the main thermodynamic functions of the species can be calculated over the temperature interval Tmin lt T lt Tmax Molar specific heat C 2 3 4 a a T tal ta a T Molar total enthalpy H RT Enthalpy at 0 K a6 ah e e e ie 21 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 3 2 2 4 H 0 a R Molar entropy S alisar Sr 4S Sr oa R 2 3 4 Molar Gibbs free energy G T H T T S T Molar reduced Gibbs free energy Substance properties The following information for the substance is available in database Molecula
53. 930077 1 725360036 no filter 3 6000 20000 288 3450012 78 93810272_ 2 679280043 26 72220039 17 67560005 0 1719740033 0 176880002 All no filter Figure 2 1 On the figure above the editor window for the substances atomic molecular properties database is shown The window contains a list of particles substances with search and 11 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database filter functions a table of properties Substance name properties and tables of properties of substances atoms molecules with a set of tabs for opening the necessary table Tables contains parameters characterizing the substance Formula and six tabs Thermodynamics Substance properties Molecular properties General Properties Electronic properties Interaction potentials The filter functions consist of drop down lists View Atom Charge and Phase as well as the Search field Substance name properties contains the common names of substance properties Phase state Isomeric Form Modification International name Local name CAS index and Comment Functions of the buttons of the top of the Substances window are described in the table Button Function big Add a new substance Fa Delete a substance A Undo changes in any of the tables until the Commit but
54. Cp 298 standard state molar specific heat at constant pressure J mol K 298 standard state molar entropy J mol K H 298 H 0 molar enthalpy increase from 0 K to 298 K DHf 0 molar enthalpy of formation kJs mol Table Thermodynamic functions contains the thermodynamic properties of the substance in the standard state The standard state conditions temperature 298 15 K and pressure 1 atmosphere 2 2 2 2 Gibbs coefficients The thermodynamic functions of the individual substances depend on temperature To account this dependence in the applications the thermodynamic functions are represented as polynomial functions of the temperature Every polynomial approximation is accurate only through the limited temperature interval To calculate the thermodynamic functions over the wide temperature ranges usually several intervals are required 2 2 2 2 1 IVTAN polynomial approximations Tmin low temperature boundary of the approximation interval K Tmax upper temperature boundary of the approximation interval K F1 F7 set of the Gibbs coefficients 20 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 2 2 2 On the basis of the Gibbs coefficients F1 F7 the main thermodynamic functions of the species can be calculated over the temperature interval Tmin lt T lt Tmax Molar specific heat C T F24 2 73 42
55. IONS THROUGH THE INTERMEDIATE COMPLEX k T P k a P T M ko T F Sixe ee i S4 x T P T P 1 krign T T lim _ k T P A low x T x exp Ea low RT M k T P A high x T x high RT 1 1 InP T P k low K nig T lim P02 m 7 33888 x10 u 7 Rate constant k jow T is low pressure rate constant in cm s Correspondingly A low is preexponential factor in s T N low and Ea low is Arrhenius activation energy in kcal mol Rate constant Krhigh T is high pressure rate constant in 1 s Correspondingly A high is preexponential factor in s T N 9 and Ea high is Arrhenius activation energy in kcal mol M is number density of the bath gas M Py is pressure of M in atm Parameters S1 S5 are dimensionless parameters S2 S3 are in K and parameter S4 is in K S5 Chebyshev polynomial interpolation Tmin low temperature boundary of the interpolation interval K Tmax upper temperature boundary of the interpolation interval K Pmin low pressure boundary of the interpolation interval atm Pmax upper pressure boundary of the interpolation interval atm n Chebyshev polynomial number on temperature dimensionless 53 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 2 6 m Chebyshev polynomial number on pressure dimensionless Anm interpolation coefficient dimensionless The Chebyshev interpolatio
56. KintechDB 1 5 User Manual Technical Support Kintech Lab provides an allotment of technical support to its customers free of charge To request technical support please include your license number along with your Khimera project and any error messages pertaining to your question or problem Requests may be directed by e mail support kintechlab com Additional technical support hours may also be purchased Please contact Kintech Lab for more details Copyright Copyright 2008 Kintech Lab All rights reserved No part of this manual may be reproduced in any form or by any means without express written permission from Kintech Lab Trademark Khimera is registered trademark of Kintech Lab and Freescale inc Chemical Workbench is registered trademark of Kintech Lab All other trademarks are the property of their respective holders Limitation of Warranty The software is provided as is without warranty of any kind including without limitation any warranty against infringement of third party property rights fitness or merchantability or fitness for a particular purpose even if Kintech Lab has been informed of such purpose Furthermore Kintech Lab does not warrant guarantee or make any representations regarding the use or the results of the use of the software or documentation in terms of correctness accuracy reliability or otherwise No agent of Kintech Lab is authorized to alter or exceed the warranty obligation
57. Molecular properties database is described 18 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 1 2 2 2 The information is presented in the following way Property tab Name gt Figure amp List Description of the parameters gt Description Substance Name properties The Substance Name properties section of the database contains information about the substance which is directly displayed in the window and list of substances particles This information differs one substance from another and determines is uniqueness in the database Formula text string which contains the list of chemical elements and their amount in the substance It should be according standard chemical rules and should contain only the elements from periodic table Alias user defined text strung which helps to identify the substance For example the n octane and iso octane have the same formulas and the user can specify in the alias field n octane for the n octane and i octane for the iso octane Charge charge of the substance particle Should be integer Phase state specifies the state for the substance aggregate state which determines the thermodynamic properties of the substance The following types are available gas liquid condensed crystal amorphous glass surface Isomeric form left handed or right handed type of the opti
58. Vol 22 No 6 P 1469 1993 Though almost all the rate constants are given at 298 K due to very week temperature dependence of exothermic ion molecule reactions with measurable rate constants rate constants present in the KintechDB can in fact be used in the wide range of temperatures This large amount of kinetic information can be of great help developing or upgrading plasma chemical mechanisms Reactions of neutral molecules under nonequilibrium conditions Here rate constants of about 60 processes under conditions with different forms of departure from thermal equilibrium are presented In particular rate constants of about 30 direct bimolecular reactions with participation of electronically excited atoms and diatomic molecules under conditions of vibrational rotational translational equilibrium are given in the narrow temperature range near 300 K The data were taken from two trustful sources S P Sander et al Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies JPL Publication 06 2 NASA Panel for Data Evaluation 2006 T Herron Evaluated Chemical Kinetics Data for Reactions of N 2D N P and N A z in the Gas Phase J Phys Chem Ref Data Vol 28 N 5 P 1453 1999 Processes of the vibrational energy exchange in collisions As examples rate constants of about 20 vibrational energy exchange processes are given in the wide temperature range from hundreds to several thousands K The data is taken from t
59. actions cccccccceeeeeeereees 69 424 EXiting the editor iiia resia bdanep leek taemstueuesdates ucdedtdenbtadeel A tssdadan deter AEEA aeai 70 5 Database SCID a gcesaticceccseensessxecearicnsnsivececeiamannincertiaascniaveianoeosanssieparccesasieseiacereasten 71 5 1 Description sisser aaaeeeaa aeaaaee aaan a NNa eaaa aaiae aa 71 5 2 Working with database search tool ccccccesssseeeeeeeeeeeeseeseneeeeeeeeeeeeesseneeeeeeesssneneeeeeeeeeeeeeeeeeens 71 5 2 1 Searching for substance properties ccccccccccecccecceeccececeeceeeeeeeceeeeeeeeeeseeceeeeeeeeeeeeeeeeeeeetess 72 5 2 2 Searching for process properties ccccccccceccecccececeeceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeseeeeeeeeeeeeess 72 5 2 3 Working with search results vcisc20t ccceresceasicees hecatapcisnguaaeonedenaeasiee tee cactasuvessdaseiMboudianceduenuaseas 73 6 Database tools for data analysis eeeoeeosseessesosssesssossesssecsssessecosecssseosesssseese 74 6 1 Reaction analysis tool ccssienidccusmnisteansencineerendrnatnateamcainmidenmcunmusubntneieankadieaennamiiauvenniacaviemeneaatas 74 6 1 1 General description 2 22 ccc c cece eee e cnet eee e cette ence ee eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeetitnneiees 74 6 1 2 Working with Reaction analysis tool sites wictesntce secs cuctatsisenctadencdgotetecesuedeaviaceundcciudaceenluanaes 75 4 KintechDB 1 5 User Manual Kintech Lab 6 2 Mechanism comparison tool cc
60. active help system s 20 c20 sesacucteeec acuese tesen acatnastlacearedeMelasastats ateags Seasuelbacs uae nedensieeatteadhs 17 2 1 11 Review of the history of the revisions in the database 00 0 0 eee eeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeenaaes 17 2 1 12 Exiting the Substance and atomic Molecular properties database c ccecceteeeeeeeees 18 2 2 Guide to Substance and Atomic Molecular properties ccccccceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeees 18 2 2 1 Substance Name properties cccsseccecccececnecceceaeceeeceecececceeeeeeeececeeeeeeeeeeeeeeeeeeseeseeeeseeeeeens 19 2 2 2 GRIMY MEIGS caces hela selel luce ya aatstcnecing old aa sahara a nA Aeae S EE REE Oira neal DORE AE ANASA NEE DRESE 19 2 2 3 Substance properties cc ceeeeesscceeeceseeceeceaeeaaecaeecaeceeeceecceaeceeeeeeeeeeceeeeeeeeeeeeeeeseeeeeeseeeeenetnees 22 2 2 4 Molecular properties ccccsecsscccecccaccaaecaaeeaaecaeccaeceeeceeccaaeceeeececececeeeeeeeeeeeeeeeeeeeeeeeeeeeenetness 22 2 2 5 General properties ccc ceccseesecccseencecaneaaeeaaneaeeaaeeaanaaeeaaaeeaeaeaeaeaeeaecaaeceaecaaeceaeeaaeaseseeeeneeees 23 2 2 6 Electronic properties ccccccsccscccsccceeccececeeceeeceeccnecceecceeceescceeeeeseeeeeeeseeeeeeeeeeeeseeseeeeeesetsininas 24 2 2 7 Interaction potentials ccccccsccsseceecceecaeceaeceeeccaeceeeceeceeeceeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeeteeeenetiess 39 3 KintechDB 1 5 User Manual Kintech Lab
61. ame specification Reaction equation N2 533 1 p _u 4 3 s _q 1 1 p _q 1 a 1 P _g 1 p _u 3 3 s _q 2 1 p _a 1 w 1 D _u 33 G 3 2 0 lt gt NeCSi 1 p _u 4 3aq 1ag lalT P g 1 p _u 3 3aq 119 wAn Hu lt gt lt empty list gt u 51 pl_u 4 3 s _q 1 1 p _g 1 la 1 P _g 1 p _u 3 3 st_g 2 1 pt_ot1 lwE 1 D _u 5 3 G 3 2 0 Property Value s alias amp phase phase type g charge 0 isomeric Form no B state term spectroscopic name spin 3 2 _ orbital angular momentum 0 total angular momentum reflection a parity electronic state attr LPi _g 14p u 3 3is1 o2 aC lw 1D u vibratonal_state_attr vibr_quant_numb v C Show all Figure 7 11 7 2 9 The particle is a nonlinear polyatomic molecule in the completely specified ground or excited electronic state The characteristics of the state are inserted into the fields of the menu term of the Substance name wizard 7 2 9 1 Spectroscopic name In the case of the molecular electronic states spectroscopic name is usually present Spectroscopic name is small or capital Latin letter may be with prime or with tilde see example in Figure 3 15 7 2 9 2 Spin Spin is the quantum number S of the total spin of the molecular electronic state which can assume nonnegative integer or half integer values see example in Figure 3 15 99 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substa
62. and view its phases substances processes To view a mechanism select it in the list A mechanism can contain several phases which can be selected in the table and a list of substances and reactions can be viewed in the table of the editor Choose the phase then view the substances and reactions in the corresponding table To edit substances or processes in selected mechanism click or button respectively A window similar to the windows for the substance and reaction databases will open Any further operations are similar to that described in the previous sections Creating a new mechanism To create a new mechanism click bg in the main window and in the next window enter the properties of the new mechanism and its name Select the newly created mechanism bag in the phase window and create a new phase Enter the properties of the and click newly created phase and click J to save Create a list of reactions and a list of substances for the new mechanism see below Enter transport coefficients if necessary Addition and deletion of the new phases substances and reactions To add a new phase click hag in the phase table and fill in the cells in the table To delete a phase click Click VA to save changes 69 KintechDB 1 5 User Manual Kintech Lab Mechanisms database Working with database 4 2 4 To create or edit a list of substances select a phase in the list of phases and click to enter i
63. atabase requires configuration of the connection to the server or of the path to local file as well as management of access and user rights Users management The database supports a multi user access and personalization of the information Database access rights A database user can has various privileges for viewing and editing the information in the database User rights are managed by adding users to one or another group The database has four user groups with various rights Normal Contributor Expert and Administrator The rights of each group are the following Normal Has rights only to view information in the database Contributor Can add information to the database and edit including delete information entered by the same user earlier but cannot edit or delete information entered by other users Expert Can add edit and delete information in the database but cannot delete or edit users or change the system settings Administrator Can perform any operation with the database Only the administrator can view the history of operations with the database User management dialog Figure below shows the database user management dialog This dialog allows to add edit and delete users and their information and to set user rights assignments KintechDB 1 5 User Manual Kintech Lab Installation and configuration Administration and users management Figure 1 3 1 5 2 3 Figure 1 4 1 5 2 4 a ke AS
64. ate constants Kf and Kr in the Columns for analysis pick the function s for the analysis Repeat the same operation for every reaction and rate constant approximation to be analyzed If the same thermodynamic function s should be analyzed for all reactions then the corresponding button on the Quick function selection toolbar KF Kt X should be pressed This action automatically picks the desired function through the whole list of the reactions rate approximations 77 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool Figure 6 4 6 1 2 3 amp Reaction analysis C H C H lt gt C H C H C H C H lt C H C H Arrhenius 300 K 2500 K C H C H lt gt C H CH Avrheruus 300 K 2500 K C H C H lt gt C H C H Arrhenius 300 K 2500 K Columns for analysis IKT L kr T ardo lt Setting up the limits for the independent variables The thermodynamic functions are the functions of the temperature The rate constants of the elementary chemical reactions are functions of the temperature and pressure for pressure dependent reactions Other elementary processes are the functions of another parameters e g the cross section of the ionization elementary process depends on electron energy Therefore for the analysis of the numerical values of the reaction rate characteristics the boundaries of the intervals for the i
65. ate universal expression of the half width at the half maximum of intensity HWHM AA s gt was obtained in W Furssow A Wlassow Physik Z Sowjetunion 10 378 1936 W Furssow A Wlassow J Phys U S S R 1 335 1939 Using upper index r to designate resonance line below its expression in the wavelength scale modified according to Griem s derivation that differ by a factor of 2 from the conventional result 4 5 since it is related only to the impact region I I Sobelman Introduction to Theory of Atomic Spectra Pergamon Press 1970 pp 1 640 A W Ali H R Griem Phys Rev 140 1044 1965 errata ibid 144 366 1966 is presented Ayr a A 2 2J 1 o4 22N ny 24 27 41 c t or in the numerical form 62 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 5 1 2 2J 1 A Anestroms 5 39 10 A7 nlng l V7 1 a04 A Ni where g 2J 1 2 7 2J 1 20 is given in Angstroms N is given in cm Van der Waals broadening by buffer gases in adiabatic approximation Buffer gas symbol of the buffer gas Atom which interacts with the radiator string ACs difference of Van der Waals coefficients related to the interaction of given radiator in the given upper i gas atom measured in Atomic units and lower levels j with the given buffer C 5000 K adiabatic impact Van der Waals broadening coefficient at
66. ation Nd 544 35 Gi lt gt n Nd 4 0 4 lt gt lt empty list gt tu IN tt Git 7 Property value chet formula Nd alias phase phase type g charge 0 state S term spectroscopic name spin orbital angular momentum total angular momentum 4 electronic state at RG type vibr_type description C Show all Figure 7 4 7 2 5 5 2 LS coupling In this case the following notation is used in spectroscopy for the term a Od where M 2S 1 letter representation is used for L capital Latin letters and w is parity For the odd states w o and for the even states the mark w is omitted Quantum numbers of term are inserted into the field electronic state attr in the form ML J w where w for the odd states and the mark w is omitted for the even states An example of the complete description of the excited electronic state of Ni including configuration 3d8 F 4s3p P and term G is shown in Figure 3 8 91 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equation HNH 30 8 SF 4s 1 4p 1 HIPHSGSY G L45 lt gt Ni Gs3d EJs4p P Gs tu lt gt lt empty list gt u Ni 3d BSF 4861 4p HIPH3GSY 5 50G 145 Property Value Formula Ni alias phase phase type g charge 0 B state E term spectroscopic name spin 1 orbital angular momentum 4 t
67. c linear molecule such as O C O H C H or homonuclear diatomic molecule with respect to the inversion in the center of symmetry parity can assume the values g Ag states or u A States which are to be inserted to the field see example in Figure 3 12 Electronic state attr Molecular electronic states can not be specified completely by the quantum numbers S A Q reflection and parity The complete specification needs additional information which is provided by filling the field electronic state attr The field electronic state attr includes a complete set of the quantum numbers characterizing molecular electronic state These quantum numbers include electronic configuration and term Correspondingly the contents of the field has the form electronic configuration separation symbol term Sometimes electronic configuration is not shown and in this case separation symbol is not inserted before the string describing the term In molecular spectroscopy general form of the electronic configuration is as follows g knas k gt A A sim sim d Here 2 is an absolute value of the projection of the electron orbital angular momentum on the molecular axis sim may be a number or a number small Latin letter and discriminates one electron state among other one electron states with the same values of A k is a number of electrons on the sim 4 electronic shell If some k it is not shown Closed
68. cal isomer enantiomer Modification user defined description of the substance specific properties e g electronic state structural isomer name etc Thermodynamics This tab Thermodynamics contains the data on thermodynamics functions of the individual substances and their dependence on temperature 19 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties lt gt Substances wiAS amp YAS O 4 Substance name properties Formula Al f i F _ Property Value o Formula 02 Alias 3 ot Charge o 4 Phase state gas p 5 o Isomeric form x Modification F 6 0 5 si oy Thermodynamics Substance properties Molecular properties General properties Electronic properties Interaction potentials 8 O a 1 k Fue Hyg A JS mis une 4 Thermodynamics functions 10 H DHF 298 kJ mole Cp 298 J mole K 5 298 J mole k H 298 H 0 kJ mole DHF O kJ mole Comment Default Recommended 11 H 10 29 378 205 038 8 68 o v v 12 H 13 H 14 H 15 OH 116 OH jaz oF 18 H Eo al LS lon H Om y Gibbs coefficients 7 oo oee e ee pe o a e ee ro ter 3 8500 20000 Sa aap Sie SAS E PET aan v Phase jal Figure 2 6 lt zl 2 2 2 1 Thermodynamic functions DHf 298 standard state molar enthalpy of formation kJ mol
69. ccceeeee cece cece eee e eee eeee ee eeee eee eee ee nena eee eee ee eeeeeeeeseeeeeeenene 81 6 2 1 General description 2 22 cece ccc ce cece cent cee e eee e eee e eee ttrt eeeeeeeeeeeeeeeeeeeeeeeeseeeeeeeeeeeeeeeeeeetiinneienes 81 6 2 2 Procedure of MECHANISMS COMPALISON cccccecccecceeeccececeeeeecceecceeeeeeeeeeceeeeeeeeeeetetereeeeeess 84 7 Specifying substance name using Substance name wizard csccceeeees 86 CA aiioe lU eado p MEE EEEa E EEE EE geile devencvcdeeeetoaedigiesaued E EE 86 7 2 Rules for substance name specification with the use of the Substance name wizard 86 7 2 1 The particle is in the ground electronic state and vibrational rotational thermally equilibrium state eect cette eter eeeeeeeeeeeeeeeeeeeaaeeeeeeeeneeeaa 86 7 2 2 The particle is in the exited electronic state and vibrational rotational thermally equilibrium State eee ceneeee eee e eee eeeeeeeeeeeeeeeeeeeeeaaeeeeeeeeeeeeea 87 7 2 3 The particle is a molecule in the ground electronic state with the vibrational modes 1 2 in the definite quantum states specified by the vibrational quantum numbers v1 v2 and other vibrational modes and rotational degrees of freedom are at thermal equilibrium ee ee ccecccecceeeceeeceeeeeeeeeeeeeeeeeteeteeeneenees 87 7 2 4 The particle is a molecule in the exited electronic state and with the vibrational modes 1 2 in the definite quantum states specified
70. ce name wizard Rules for substance name specification 7 2 7 2 7 2 7 3 7 2 7 4 7 2 7 5 7 2 7 6 7 2 7 7 spin Spin is the quantum number S of the total spin of the molecular electronic state which can assume nonnegative integer or half integer values see example in Figure 3 12 Orbital angular momentum Orbital angular momentum is the quantum number A of the absolute value of the projection of the electronic orbital angular momentum on the molecular axis which can assume nonnegative integer values see example in Figure 3 12 It is to be noted that molecular electronic states exist for which S and A are not defined and the corresponding fields are to be left blank Total angular momentum Total angular momentum is the quantum number Q of the of the absolute value of the projection of the total electronic angular momentum on the molecular axis which can assume nonnegative integer or half integer values see example in Figure 3 12 If both S and A are defined quantum number Q is often omitted and corresponding field is left blank Reflection Reflection is the character of the electronic wave function with respect to the reflection in the plane containing molecular reflection can assume the values X states or states which are to be inserted to the field see example in Figure 3 12 Parity Parity is the character of the electronic wave function of the symmetric polyatomi
71. change of the moles in the chemical reaction Kc T equilibrium constant of the chemical reaction defined through the molar concentrations as function of temperature dimensionality of the equilibrium constant depends on the change of the moles in the chemical reaction e Rate constant of the reaction or process calculated on the basis of the reaction process rate parameters loaded from the Process database e kf T forward reaction rate constant as function of temperature cm s where n is the reaction order kf T reverse reaction rate constant as function of temperature cem 1 s where n is the reaction order To analyze the desired thermodynamic function pick the necessary reaction in the list Reactions In the list of the thermodynamic functions Columns for analysis pick the function s for the analysis Repeat the same operation for every reaction to be analyzed If the same thermodynamic function s should be analyzed for all reactions then the corresponding button on the Quick function selection toolbar AG AH AS AF ACp Kp Kci X should be pressed This action automatically picks the desired function through the whole list of the reactions To analyze the rate constants or process rate parameter of a single or several reaction it is necessary to do the following steps First pick the necessary rate constant approximation title of the desired reaction in the list Reactions In the list of the r
72. chanism compare parameters window Clear removes the loaded mechanisms from the comparison tool X W amp 81 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Mechanism comparison tool Compare performs the mechanisms comparison Compare process list performs the processes comparison Exit exit from the comparison tool The Parameters button opens the Mechanism compare parameters window ry p ae Mechanisms compare parameters Mechanisms compare parameters Substance TD compare Relative error o 5 Number of intervals 100 Preferred Gibbs type Relative Cp gap o 0 01 Temperature range gap K 10 Rate approximation compare Relative error 5 Temperature range Tmin K 8e 02 Tmax K Number of intervals Pressure range Pmin atm Pmax atm Number of intervals Cross sections compare Number of intervals 100 Figure 6 9 This window contain options to compare two mechanisms based on which the program will judge about identity of properties of substances and processes The list of option is this 1 Substance TD compare the thermodynamic properties comparison parameters e Relative error the maximum relative deviation between the values to count them identical e Number of intervals on which the comparison will be made 82 KintechDB 1 5 User Manual Kintech Lab
73. coefficient Td This is the Arrhenius like approximation which defines the rate constant of the process between particle and electron as function of the reduced electric field E N where E is the electric field intensity N is particle number density The expression for the rate constant is k E N A E N exp B E N Dependence on the electron temperature A pre exponential factor cm s K N for second order reaction cm s K N for third order reaction B temperature exponent dimensionless Ea approximation coefficient kcal mol This is the Arrhenius approximation which defines the rate constant of the process between particle and electron as function of the electrons temperature The expression for the rate constant is k T A T exp E RT Optical processes Atomic Optical radiator the symbol of the atom which spectral line broadening is calculated it is given by string Ao the nominal unperturbed wavelength of transition Angstrom 61 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 5 1 1 Aij Einstein coefficient of quantum transition from i to j st The Atomic section of the Optical processes class provides information required for the calculation of the broadening parameters of the discrete spectrum of atoms The discrete spectrum itself is characterized by nominal unperturbed wavelength 2 and Einstein coefficient of
74. configuration is a standard notation to describe the electron configurations of diatomic molecules The notation consists of a string of molecular orbital labels e g o 115 with the number of electrons assigned to each molecular orbital placed as a superscript To simplify input into the database conditional configuration CCD is introduced CCD is transformed into usual form of electron configuration presentation at visualization printing For the detailed information on Input of the CCD please read Appendix B Stat Weight is the statistical weight P is the true or assumed for composite terms degeneracy If values S and A are known P 2 S 1 2 if A gt 0 P 2 S 1 ifA 0 If value Q is known P 2 ifQ gt 0 orQ lt 0 P 1 ifQ 0 For example P 2A 4 P 04 2 27 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 2 1 P fZ 4 For composite states statistical weight is a sum of constituted states For example P N 7 The spin angular momentum quantum number S 0 1 2 1 3 2 2 It is related with multiplicity M 2S 1 Diatom state At diss limit A and At diss limit B atom ion and term symbols of atomic products correlating with a given molecular state A B for homonuclear molecules Re equilibrium internuclear distance or internuclear distance at the minimum of the elec
75. ctor in the high pressure limit s reactions and reactions through the intermediate complex em s 1T for addition reactions Nhigh temperature exponent dimensionless Eahigh activation energy kcal mol 1 S2 S3 S4 S5 interpolation parameters S1 and S5 dimensionless S2 and S3 in K S4 in KS 1 UNIMOLECULAR AND ADDITION REACTIONS 52 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 2 5 k T P r a P T M ko T p Sixe em S4xT P T P 1 Krign T K vie T A high x T x exp Ea high RT amp 1 A lowxT x exp Ea low RT 1 P M 7 33888x10 1 InP T P T Rate constant khign T is high pressure rate constant in 1 s for unimolecular reactions and in cm s for addition reactions Correspondingly A high is preexponential factor in I gt high N high and in cm s T for addition reactions and Ea high is Arrhenius activation energy in kcal mol Rate constant kjoy T is low pressure rate constant in cm s for unimolecular reactions and in cm s for addition reactions Correspondingly A low is preexponential factor in cm s 1T N low and in cm s 1T N for addition reactions and Ea low is Arrhenius activation energy in kcal mol M is number density of the bath gas M P yis pressure of M in atm Parameters S1 S5 are dimensionless parameters S2 S3 are in K and parameter S4 is in K 85 2 BIMOLECULAR REACT
76. d as the number of the collisions necessary for an effective rotational translational energy transfer or as the average number of the collisions required to transfer one rotational energy quantum into the translational mode 42 KintechDB 1 5 User Manual Kintech Lab Processes properties Contents of the Processes Database 3 Processes properties 3 1 3 1 1 Contents of the Processes Database The main idea underlying the filling of the processes database was to consider predominantly direct experimental data on the rate characteristics of the elementary chemical energy transfer and radiative processes and processes with participation of electrons It is to be emphasized that such characteristics may often differ from those entering kinetic mechanisms many of such schemes can be found in the KintechDB Mechanisms This is due to the fact that the latter characteristics are often adjusted to reproduce experimental macroscopic kinetics in the framework of the included to the mechanism sets of substances and processes At present stage KintechDB contains information on elementary processes important in combustion and plasma chemistry taken mainly from the most competent recent compilations in the fields presented below Elementary equilibrium chemical reactions important in combustion Rate constants of about 2200 reactions are included into the database About 1600 of them are taken from the original experimental and theoretical pape
77. degeneracy The Term symbol is an abbreviated description of irreducible representation of point group of symmetry the angular momentum quantum numbers and symmetry properties of wave function of a given electronic state of a polyatomic molecule For linear molecules term symbol is described just as for diatomic molecules by symbols 2StI Ao where S is the total electronic spin momentum A is the projection of the total electronic orbital momentum and Q A is the projection of the total electronic momentum on the internuclear axis 2 S S 1 S is the projection of the spin momentum on the internuclear axis For certain cases Hund s case c the quantum numbers A n lose meaning and the states are characterized only by the values of the quantum number Q which for molecules with an even number of electrons take integer and for molecules with an odd number of electrons take half integer values To simplify input into the database conditional term symbol CTP is introduced see Appendix C for detailed description For nonlinear molecules term symbol is described as irreducible representation of point group of symmetry and additional alphanumeric information about spectroscopic properties and multiplicity CTP consists of group of the characters designating spectroscopic notation of the state upright slash multiplicities integer and irreducible representation name The spectroscopic name of a state often containing letters with wa
78. dimensionless Allow cross section is applicable for the following classes of reactions 1 EXCITATION OF ATOM INTO OPTICALLY ALLOWED STATE 2 ELECTRONIC EXCITATION OF MOLECULE Cross section of excitation of atom into optically allowed state 6 E 2 Ht AE E AE o E za AE aC bog eee 7 ik ik where a the Bohr radius 0 529177 A AE threshold value eV Fg oscillator strength Ht 27 2 eV Forbid cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that o 0 Scale Q0 fitting parameter in equation dimensionless Forbid cross section is applicable for the following classes of reactions 1 EXCITATION OF ATOM INTO OPTICALLY FORBIDDEN STATE 2 ELECTRONIC EXCITATION OF MOLECULES Cross section of excitation of atom into optically forbidden state o E AE ik AE ik E where ao the Bohr radius 0 529177 A AE threshold value eV Qo parameters in equation o E 4ra Q 1 1 gt AST allow cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that o 0 Scale Max energy Maximum energy limit eV Fo oscillator strength dimensionless AST allow cross section is applicab
79. e description C Show all Figure 7 6 7 2 5 5 4_j L coupling In this case the following notation is used in spectroscopy for the term Mij Here j is the total angular momentum which arises from the coupling of the total angular momentum of one group of electrons with the total orbital angular momentum of another group of electrons M is multiplicity of the latter group of electrons J is the total angular momentum of all the electrons and w is parity It is to be noted that quantum numbers S and L can not be defined in this case The quantity j can assume integer or half integer values For the odd states w o and for the even states the mark w is omitted Quantum numbers of term are inserted into the field electronic state attr in the form of a string M j J w where w for the odd states and the mark w is omitted for the even states An example of the complete description of the excited state of Ne including configuration 2p P3 3d and term 2 3 2 4 is shown in Figure 3 10 93 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equation Ne i 2p Psj93d 3 211 ta lt gt lt empty list gt u Nets 2ptsH2P s2yrsdl2 a2 y s G DN _ Property value Chei formula Ne alias phase phase type g charge 0 state term spectroscopic name spin orbital angular momentum total angular momentum 1 e
80. e the data was found The found substances are displaying with the available thermodynamic data the found precesses with the available reaction rate approximation data Names of the found substances and processes are displaying as html links Click on this link opens the substances processes or mechanism database with the found object selected It is possible to copy the found results to clipboard and then to paste it into Chemical Workbench process or mechanism databases To select the data to copy check the corresponding checkbox to the left of the found data It is possible to select a single processes rate approximation the all data available for particular process all data found from particular mechanism or process database etc For the substance data it is possible to select the data available in the substance database or mechanism database 73 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool 6 Database for data ana 6 1 6 1 1 Figure 6 Reaction analysis tool General description tools lysis KintechDB includes specially designed Reaction analysis tool for the reaction elementary process analysis It is possible to carry out the thermodynamic analysis of the given chemical reaction or to calculate and plot the rate constants cross sections of the processes Besides comparison of the parameters for the different reactions or rate approximations can be
81. ectron shell Orbital momentum of valence electrons the momentum quantum number for the electrons on the outermost external electron shell Quadrupole momentum the quadrupole momentum of atom in given electronic state units eA Polarizability polarizability of the atom in given electronic state units A The notation for the Electron configuration consists of a string of atomic orbital labels e g 1s 3d 4f with the number of electrons assigned to each orbital placed as a superscript The detailed description of the rules how to enter the electron configuration into the database so called Conditional Configuration or CC is given in Appendix A The Term symbol is an abbreviated description of the angular momentum quantum numbers in a multi electron atom To simplify input into the database conditional term symbol CT is introduced and described in Appendix A Stat Weight is the number P of degenerate substates contained in the state and is given by P 2 J 1 in all cases when J is known P 2 S 1 2 Z 1 in the case of LS coupling and when J is unknown P 2 2 K 1 in the case of j coupling and when J is unknown For composite states statistical weight is a sum of constituted states For example P 3D 3F 9G D F G 84 P Fsj F 3 2 10 State nature Spin multiplicity M denotes the number of possible quantum states of a system with given spin quantum number S It is given by M 2S 1
82. eeeeeeseeeeeegs 8 1 5 2 Users management sxeccssccnctdeiensannancucraucival auishddecthe nies cterca mii didecumuauhaentsces tk eanastebadaceneeumnanvaanteecaeys 8 2 Substances and Atomic Molecular properties csccscesceecsecsscsecscceceeees 11 2 1 Working with the database cccccescesscisatcacanssavnenetnnassncanispenncnadnnsecndesentanduninsncssavnanadnancaaeieatenanasions 11 2 1 1 Description of the main WINdOW ccccccssecceeceeeceaeceececaeeaaecaeccaeceaeceaeccaeceeceeeceaaeseeeeaeeeaeees 11 2 1 2 Search in the database Filters 2 0 00 ccesssssseceseeceeeaeeaeeeaeeeaeeaecceeceaecceceeeceeeeeeeceeeeeeeeeeeeeeeess 12 2 1 3 View of the substance particle information cccccccccccecceccececececeeeeeeeceeeeeeeeeeeeeeeeeeeeeeteess 13 2 1 4 Visualization of the substance thermodynamic properties cccccececceeeeeeeeeeeeeeeeeeeeeeeees 13 2 1 5 Addition of the new substance particle to the database cccccccccecceeceeeceeeeeeeeeeeeteeeteess 15 2 1 6 Editing the information in the database ccccsssccsceeeeeeeeesseeeeeeneeeeseeeeeneeeneeeeeeenseseeneees 16 2 1 7 Deleting the information from the database o oo cece ee eee eeeneeeeeeeeeeeeteneneeeeeeeeeeeeeeeenaaes 16 2 1 8 Import and export data issii e i eaea r e a Ee E Ere eia aa EErEE IE PAESE 16 2 1 9 Review of the substance particle properties and printing a report ssssssssseerrrerrrrnrrerreene 16 2 1 10 Inter
83. een zero point vibrational levels of a given and the ground state Units cm State energy Te energy of an electronic state of the diatomic molecule reckoned between potential function minima of a given and the ground state Units cm Number number is automatic numbering of electronic states as 0 1 2 etc Energy error estimated uncertainty of state energy Units cm Stat Weight Statistical weight P is the true or assumed for composite terms degeneracy Dissociation limit energy difference between energy of atomic states correlating with a given molecular state and zero point vibrational energy of the state Units cm Dissociation limit error The quantity is estimated uncertainty of energy difference between energy of atomic products correlating with a given molecular state and zero point vibrational energy of the state Units cm Orbital momentum projection lambda orbital angular momentum quantum number A 2 0 P 1 A 2 3 Full momentum projection omega the total spin plus orbital electronic angular momentum quantum number Q 0 1 2 1 3 2 2 Spin momentum the spin angular momentum quantum number S 0 1 2 1 3 2 2 Dipole moment electric dipole moment first derivative of the molecular electronic energy with respect to the strength of external uniform electronic field directed along the intermolecular axis Units Debay
84. ensionless lon cross section is applicable for the following classes of reactions 1 DIRECT COLLISION ELECTRON IMPACT IONIZATION OF AN ATOM 2 DIRECT COLLISION IONIZATION OF MOLECULES Cross section of direct collision electron impact ionization of an atom o E 59 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 4 9 3 3 4 10 o E 0 28x ioan 82 f x E T O x 1 where f x ee Eletskii Smirnov similarity function ionization potential eV N TH X X fitting parameter Ry Rydberg 1 09737 10 cm AST ion cross section Threshold value ionization potential eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that o 0 Scale Max energy Maxim energy limit eV A1 A2 A3 A4 As Ag B Fitting parameters in equation dimensionless Ast ion cross section is applicable for the following classes of reactions 1 DIRECT COLLISION ELECTRON IMPACT IONIZATION OF AN ATOM 2 DIRECT COLLISION IONIZATION OF MOLECULES Cross section of direct collision electron impact ionization of an atom o E Ht lt Iy E E 10 A l1 Bln SNE 6 2 ae 5 where ionization potential eV A 1 6 and B fitting parameter Ht 27 2 eV Janev approximation A pre exponential factor cm s K N for second order reaction cm
85. eport will appear in a message window 7 If you find identical substances in the different lines select them and press Merge substances button Substances will be marked as identical and will be moved to the same line As an example see the substances SCH2 and CH2 S at the Mechanism compare window picture above 8 Press Dn Compare process list button Process list will be compared again taking into account new pair of identical substances 9 Also you can control the displaying of the substances and processes by pressing the last eight buttons or the Show toolbar to select the identical different or unpaired items 85 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Introduction 7 Specifying substance name using Substance name wizard 7 1 7 2 7 2 1 Introduction Substance name wizard allows to specify and edit different substance name parameters It becomes important while editing reaction equation involving particles at electronic or vibrational excited state Next sections is described how to specify electronic and vibrational state characteristics for different states and syntax of Substance name wizard input fields Rules for substance name specification with the use of the Substance name wizard The particle is in the ground electronic state and vibrational rotational thermally equilibrium state All the fields in the wizard must be left blank 86
86. es the Electronic properties tab contains the data on electronic energy levels and their related properties Every level is characterized by Type Configuration State energy Stat weight and etc First of all linearity property is defined Other properties critically depend on the definition The description of the data is presented below Linearity property which defines the geometrical configuration of the polyatomic molecule Linear for linear molecules in a given state NonLinear for nonlinear molecules in a given state Type Term symbol term symbol is an abbreviated description of irreducible representation of point group of symmetry the angular momentum quantum numbers and symmetry properties of wave function of a given electronic state of a polyatomic molecule Its representation depends on whether the molecule linear or not Electron configuration standard notation to describe the electron configurations of polyatomic molecules It is a string of characters and its representation depend whether the molecule is linear or nonlinear Number number is automatic numbering of electronic states as 0 1 2 etc Energy energy of an electronic state of the molecule in cm reckoned between potential surface minima of a given and the ground state Energy error It is estimated uncertainty of state energy in cm Stat Weight statistical weight P is the number of degenerate substates contained in
87. ey ET 6 ce E2226 C2026 ga 2 D EC C C A By B2 B3 4 D E 2C3 3C7 Ai Ao E 6 A Ao Bi Bo 8 D4 E E a sie 2 Ai Ao Bir Bor 12 De E 2C 2C3 C3 3Cy 3C 2 Aor B B B 4 r i a dB ey 2h o xy 6 xz o yz Ae ie Eo AG A E 6 D3h E 2C3 3C3 Oh 2S3 30 AY A gt BY Agr Agr Bigr Bogr 8 ECGs E Ege Pan 284 op 20 204 X Aiur Azur Biur Bour Eu n a e a a zal 5h 285 50y ALIT A 92 E Be Abe Bie Doy 12 7 B 20 20 30 36 Pone 6h 3 i 3S3 286 Oh 304 30 ee een eee Eius Epu Dog E 284 Cy 2C 2Cy 204 Air Aor Bir Bo 4 Aigr Agr Egr 6 D34 E 2C3 3C i 2S6 304 Alur Azur Ey 35 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 5 E 2Sg 2C4 28g Cy 4C gt Ary Az By Bor E 8 ec Ey E3 Aror Adar Eig E A PE a a a 5d 2S10 304 Alu Adu Eiu Epu T ECC Aye 12 Ne eae ee f E 3C 4Cy 4Cy2 30 gree ge i h oe Aur Eur Fy Tq E 8C3 3C 6S4 664 Ai Aor E Fi Eb 12 R A E leg o 1 5 E 8C 6C 6C4 3C i i 6S4 8S6 36 604 Aiur Azur Eyr Fis Fou Pile 100 206 0 97 2a a7 60 Ih 15C i 128j9 12849 2056 150 Aur Fius Pour Gur Hy Top type In general for any nonlinear molecule there are three moments of inertia 14 IB and I about three mutually orthogonal axes The general convention is to define the axes such that the axis A has the smallest moment of inertia such that lt Ig lt Ic There are three types of tops depending
88. f Diatomic Molecules Van Nostrand Reinhold Company N Y 1979 L Kuznetsova et al Probabilities of Optical Transitions of Diatomic Molecules Nauka Moscow 1980 in Russian 319 p in Russian Kovacs Rotational Structure in the Spectra of Diatomic Molecules Akademiai Kiado Budapest 1969 320 p to be exact the case a of Hund rules is assumed A _4 e Q One se v v D iv jav 3 he 2 Sya O v jav e ij where R is the internuclear distance between the atoms forming the particular electronic term De j R is the reduced matrix element of the electronic dipole operator due to the transition between the electron states labeled by the set of quantum numbers of the electron potential curves of the upper i and lower j terms the vibrational quantum 2 65 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 5 3 numbers v v 7 is the unit vector along the direction of the total electronic dipole moment A A are projections of the electronic angular momentum L L of the upper and lower electronic terms correspondingly on the internuclear axis the factor 2 do being due to A doubling The A doubling factor is the same for all sublevels belonging to the same electron state potential term All quantities entering these equation are expressed in atomic units The equation is obtained by the direct summation over the all possible rotationa
89. gs some of irreducible representations of a molecule point group of symmetry Symmetry type is symbol of such irreducible representation Frequency the frequency of the periodic motion of atoms in molecule described using normal coordinates is known as a normal vibration frequency Units cm Frequency error the frequency error i e estimated uncertainty of the frequency Units cm Vibration frequency degeneracy dimension of irreducible representation to which the frequency belongs Vibrational momentum projection of the momentum of deformation vibration of the linear molecule onto its axis of symmetry Units dimensionless units of Planck constant h Rotational constants linear polyatomic molecule Moment of inertia lg in 10 g cm of a molecule in a given state Moment of inertia error the estimated uncertainty in the moment of inertia p Units 10739 g cm Rotation constant B rotational spectra of linear molecule are characterized by the constant B where B h 8117 5 h is Planck constant g molecule momentum of inertia Units in the database cm Rotation constant D centrifugal constant in cm in rotational energy expression for linear molecule F J B J J 1 D J2 J 1 where J rotational quantum number Rotational constants nonlinear polyatomic molecule Number of internal rotation tops number of tops for which vibration modes are exchanged by internal ro
90. he compilation V K Ablekov Yu N Denisov F N Lyubchenko Reference book on gas dynamic lasers Moscow Mashinostroenie 1982 in Russian and article A Lifshitz Correlation of Vibrational De excitation Rate Constants ko lt 1 of Diatomic Molecules J Chem Phys Vol 61 P 2478 1974 Electron vibrational translational EVT energy transfer processes As examples rate constants of about 100 EVT energy transfer processes taken from the original experimental papers are included to the database Atomic spontaneous radiation Wave lengths and experimental Einstein coefficients of spontaneous radiation for atoms from the first five periods of the Mendeleev table are given about 600 radiation lines This data covers practically all the needs of combustion and plasma chemical modeling Information was taken from the trustful recent compilation J E Sansonettia W C Martin 44 KintechDB 1 5 User Manual Kintech Lab Processes properties Working with the database 3 2 3 2 1 Figure 3 1 Handbook of Basic Atomic Spectroscopic Data J Phys Chem Ref Data Vol 34 No 4 P 1559 2005 Working with the database Database window Processes we amp Filter w Class E E Approximation type Chemical 7 Substances Reaction Approximation type Class C H 0O gt CH CO Chemical C H 0 lt CO HCO Chemical C H 0 lt HCCO 0 Chemical Direct bimolecular reaction C H OH lt CH CO Chemical Di
91. ide to Process properties 3 3 2 4 2 BIMOLECULAR REACTIONS THROUGH THE INTERMEDIATE COMPLEX 1 IE E E p T m ET nowi P T P 1 i keg T n d In P c k T lim ok T P A low x T x exp Ea low RT k rig T limp o M k T P A high x T x exp Ea high RT c 0 4 0 67In F n 0 75 1 27In F d 0 14 T T T4 F 1 Tl e Tle eT IM 7 33888 x10 u Rate constant k joy T is low pressure rate constant in cm s Correspondingly A low is preexponential factor in s T and Ea low is Arrhenius activation energy in kcal mol Rate constant k pigh T is high pressure rate constant in 1 s Correspondingly A high is 17 N high preexponential factor in s and Ea high is Arrhenius activation energy in kcal mol M is number density of the bath gas M Py is pressure of M in atm Parameter T1 is dimensionless and parameters T2 T3 T4 are in K SRI interpolation Reaction type drop down list allows to set process type as e unimolecular unimolecular or addition reactions e bimolecular bimolecular reactions through the intermediate complex Alow pre exponential factor in the low pressure limit cm3s T N IW for unimolecular reactions and reactions through the intermediate complex cm s T N for addition reactions Nlow temperature exponent dimensionless Ealow activation energy kcal mol 17 N high for unimolecular N high Ahigh pre exponential fa
92. ifferent processes H 83 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Mechanism comparison tool 6 2 2 First mechanism only processes 2 Second mechanism only processes n the working area of the tool there are two tabbed pages Substances and Processes They contain the tables of the mechanisms substances and processes and have the next columns 1 st column Counter 2 nd column Status designates the presence of the item in the mechanisms and shows if it is described identically or not 3 rd column First name shows the name of the item in the first mechanism 4 th column Second name shows the name of the item in the second5 mechanism 5 th column Plot button allows to plot various characteristics of the item which present in both mechanisms 6 th column Message shows if the item is identical in both mechanisms or not If it is different then holding the mouse pointer on the Message cell will show a pop up bubble with the list of conditions which do not meet the comparison parameters The Plot button shows the available data to plot the graph For substances the list will contain Cp T S T H T HO T G T F T For processes it will be the list of direct and reverse reaction rates and cross section K T K P Krev T Krev P S E The available options if the corresponding data exist in the mechanism will be highlighted overwise it will
93. igh for unimolecular 17 N high Ahigh pre exponential factor in the high pressure limit s reactions and reactions through the intermediate complex cms for addition reactions Nhigh temperature exponent dimensionless Eahigh activation energy kcal mol T1 T2 T3 T4 interpolation parameters T1 dimensionless T2 T4 in K 1 UNIMOLECULAR AND ADDITION REACTIONS P T 1 Krign T n d In P c e k yig T A high x T x exp Ea high RT k T A low x T x exp Ea low RT c 0 4 0 67In F n 0 75 1 27ln F d 0 14 He gD 1 EE Orfa ny Fe J me T T T4 P F 1 T1 e Tle e T M 7 33888 x10 Rate constant kpigh T is high pressure rate constant in 1 s for unimolecular reactions and in cm s for addition reactions Correspondingly A high is preexponential factor in Tt high and in cm s tT N high energy in kcal mol for addition reactions and Ea high is Arrhenius activation Rate constant kjoy T is low pressure rate constant in cm s for unimolecular reactions and in cm s for addition reactions Correspondingly A low is preexponential factor in cm s T N low and in cm s 1T N for addition reactions and Ea low is Arrhenius activation energy in kcal mol M is number density of the bath gas M Py is pressure of M in atm Parameter T1 is dimensionless and parameters T2 T3 T4 are in K 51 KintechDB 1 5 User Manual Kintech Lab Processes properties Gu
94. intech Lab Database tools for data analysis Mechanism comparison tool 6 1 2 7 6 2 6 2 1 Figure 6 8 Closing the Reaction analysis tool To close the Reaction analysis tool press button of the main toolbar Mechanism comparison tool General description Mechanism comparison tool allows detailed comparison of two kinetic mechanisms including comparison of substance thermodynamic properties and reaction rate constant values Comparison is performing in the lists of substances the properties of substances the lists of processes and in the properties of processes The Mechanisms compare window with loaded mechanisms looks like following Mechanisms compare OX File Show 2e 5x DSO 2 e K z sels Substances Processes Status Firstname Secondname Plot Message 1 CH CH 2 Identical 2 SCH2 3 CH2 S The window has two menus File and Show and two toolbars with the same commands as in the menus The File menu is responsible for preparing and running the comparison and the Show menu controls the displaying options Below the toolbars there are two pages with tabs Substances and Processes The File menu and toolbar contain the commands Button Function Load first mechanism a menu with commands Load from DB Load CWB Ee XML and Import from Chemkin Load second mechanism it is a menu with the same options as in the first mechanism Parameters opens the Me
95. ions 49 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties e bimolecular bimolecular reactions through the intermediate complex Alow pre exponential factor in the low pressure limit cm3s T N IOW for unimolecular reactions and reactions through the intermediate complex cm s T N for addition reactions Nlow temperature exponent dimensionless Ealow activation energy kcal mol 17 N high for unimolecular 17 N high Ahigh pre exponential factor in the high pressure limit s reactions and reactions through the intermediate complex cms for addition reactions Nhigh temperature exponent dimensionless Eahigh activation energy kcal mol 1 UNIMOLECULAR AND ADDITION REACTIONS P T M k T p t w iy k T P k T TP k sil erat keg T k tie T A high x T x exp Ea high RT k 7 A low x TN x exp Ea low RT M 7 33888x 10 a Rate constant khign T is high pressure rate constant in 1 s for unimolecular reactions and in cm s for addition reactions Correspondingly A high is preexponential factor in ea la high and in cm s tT Nhigh energy in kcal mol for addition reactions and Ea high is Arrhenius activation Rate constant kj T is low pressure rate constant in cm s for unimolecular reactions and in cm s for addition reactions Correspondingly A low is preexponential factor in cm s T
96. istory of operations for selected table click the y button located on the table toolbar A history dialog will open The dialog contains a table with a list of operations and a History record table 17 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties A O Molecular property OH Date Op User History record EEE 2 15 10 2008 14 35 U ADMIN 3 15 10 2008 14 35 U ADMIN Figure 2 5 The dialog contains the following buttons Button Function Fa Delete an operation record A Undo changes v Accept changes changes must be accepted to be saved Exit the dialog The table of operations has the following columns Date Op User The date of the follows operation The code of the operation as U update of information D deleted information I added information The login name of the user who conducted the operation The History record shows the values which were changed or deleted 2 1 12 Exiting the Substance and atomic Molecular properties database When finished working with the database don t forget to click v to save your changes after which click button or close the window 2 2 Guide to Substance and Atomic Molecular properties In this section the description of the data which can be stored in the Substance and Atomic
97. l b1 1 a1 1 C1815 5 Cm 05 5550 20 of L Property Yalue Chei phase E phase type g charge 0 isomeric Form no state term spectroscopic name Cw eae SS Pare orbital angular momentum total angular momentum symmetry group symmetry E index 2v electronic state attr C_2v fal b1 1fa1j1 C 1B1 vibratonal_state_attr vibr_quant_numb lt Show all Figure 7 14 Separation symbol is vertical line In molecular electronic spectroscopy general form of the electronic configuration is as follows Jet Jet Here let is a small Latin letter subscript s is a number or 1 2 small Latin letter g or u k is a number of electrons on the et electronic shell Zet is the notation of the irreducible representation of the molecular symmetry group If some k 1 it is not shown Quantum numbers of configuration are inserted into the field electronic state attr in the form let s k let s k If k 2 it is not shown An example of insertion of the excited electronic configuration a 7b4a of CH3 is shown in Figure 3 17 Separation symbol is vertical line Quantum numbers of term include spectroscopic name and after the separation symbol specification of the spin S of the state and irreducible representation of the molecular symmetry group in the form Msym where M 2S 1 is multiplicity Sym is a capital Latin letter May be with one or two primes and s is a number or
98. l transitions and neglecting the influence of rotational structure on os v j v The value of A wv j v is the total probability of the electron vibrational rotational transitions from the j v J level while J j v and i v being fixed does not depend on J J is the total momentum of the upper state Now one can remember that the v v band is formed by at least 3 branches of electron vibrational rotational transitions with fixed v v P Q R depending on the value of AJ J J during the transition So all realizable J values belonging to the lower electron vibrational state may contribute to the total probability of the electron vibrational band And now the notion of the electron vibrational band probability would depend on whether the J sublevels of the electron vibrational state could be considered degenerate or not If the first statement would be true then the total probability of the electron vibrational transition would be formed by the value from equation multiplied by the number of realizable J states of the upper lower in the case of absorption electron vibrational level with the accuracy due to the weak dependence of equation on the difference between the energies of various rotational states with respect to the difference of the vibrational energy and even less with respect to the difference of the electron energy In this case it would be supposed that all those states are equally
99. lar properties Guide to Substance and Atomic Molecular properties 2 2 6 2 2 the number of vibrational levels from which rotational constants B Dy and related vibrational rotational constants were derived for a given vibronic state Spin rotation coupling constant y in cm is valid for 2X states and is a coefficient in rotational energy as a function of rotational quantum number J F4 Bu J 1 DJ J 1 0 5yJ Fo BJ J 1 DJ J 1 0 5 y J 1 where B and D rotational and centrifugal constants for a given vibrational state Spin rotation coupling constants A and in cm are valid for 9X states and are coefficients in rotational energy as a function of rotational quantum number J F Fo B 2u 3 A p J 1 B 2J 3 2 A B A7 F2 Fo F3 Fo B 2U 1 A p J B2 2u 1 2 2 A B A2 2 where Fo Bu J 1 Du J 1 and B and D rotational and centrifugal constants for a given vibrational state The spin orbit coupling constant A in cm is coefficient in rotational energy for 2A states F4 Fo 0 5 B 4 J 0 5 A B A B 4 A912 J A 1 2 1 2 3 F Fo 0 5 B 4 J 0 5 A B A B 4 AZ J A 1 2 1 2 3 and 3A states F1 Fo k Z4 Z2 J A 1 41 42 3 2x F2 Fo 2 Z2 J A 1 2 3 F3 Fo k Z4 Z2 J A 1 1 2 3 where Z4 B A B A B 4 A2 4 3 4 J J 1 Z 2 B A B A B
100. le for the following classes of reactions 58 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 4 7 3 3 4 8 1 EXCITATION OF ATOM INTO OPTICALLY ALLOWED STATE 2 ELECTRONIC EXCITATION OF MOLECULES Cross section of excitation of atom into optically allowed state o E a In 1 0 5 E AE 1 o B 028 24 fo TRAE 3 ik where AE threshold value eV Fo oscillator strength Ht 27 2 eV AST forbid cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that o 0 Scale Max energy Maxim energy limit eV a b c fitting parameters in equation dimensionless AST forbid cross section is applicable for the following classes of reactions 1 EXCITATION OF ATOM INTO OPTICALLY FORBIDDEN STATE 2 ELECTRONIC EXCITATION OF MOLECULES Cross section of excitation of atom into optically forbidden state 6 E Oo E c VE AE l b 2 a EJAE where AE threshold value eV a b c fitting parameters in equation lon cross section Threshold value ionization potential eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that oj oj Scale Max energy Maxim energy limit eV N fitting parameter in equation dim
101. lectronic state attr ESCHESPVENI FEF type vibr_type description C Show all Figure 7 7 7 2 6 The particle is an atom in the artificial excited electronic state Considering excitation of an atom by the electron impact it is often suitable to consider several excited electronic states with close energies as one artificial electronic state Name of such an artificial state is inserted in the following way Fields spectroscopic name spin and orbital angular momentum are left blank The effective total angular momentum Jeg is evaluated using the formula Jeg g 1 2 where g g1t Qot gn 9F2J1 J is the total angular momentum of the real state included to the artificial state and Nis a number of such states The string which is to be inserted to the field electronic state attr have the form string stringo string An example of the description of the artificial excited state 2p 2P 4 5 3d 7 3 2 2p 7P3 5 3d 7 3 2 2p 7P3 5 3d 7 1 2 of Ne is shown in Figure 3 11 94 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equation Nefs3s 2p S 2P 12 3d 1 213 21 1 2p S 2P 3 2 9aC1 2T3 ZIAY 2p SH2PCH NISACA IATL ZAPF Gaia lt gt a Ne 4 2p Py 23d 3 211 2p P3 2 3d 3 2 1 20 Paj2 ad FILLOS Ha lt gt lt empty list gt u ___3d 1 1213 21 1 2p 5 2P 3 2 3d 1 12
102. molecule and is defined from point group of the fragment Number of potential function minima the number n in the simple form of internal rotational potential function 38 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 7 2 2 7 1 2 2 7 2 Vg V 2 1 cos n is internal rotation coordinate and V is barrier to internal rotation Top multiplicity the number of identical internal rotors in a molecule vo the quantity Vo is a coefficient in general form of potential function of internal rotation Vlo Vo 1 2 V 1 cos kg Dy V 1 sin k FO the quantity Fp is a coefficient in general form of kinematical parameter of internal rotation F g Fo Zya1 Fy cos kg Ly F sin k 9 Interaction potentials The Interaction Potentials tab contains in data of various intermolecular potentials for the substance For all model potentials Lennard Jones 12 6 Lennard Jones m 6 Stockmayer Buckingham Corner Born Mayer HFD B the data fields consist of the specific potential parameters One also can indicate the default potential to be loaded from the DB The description of the model potentials and their parameters is presented below Lennard Jones 12 6 potential o the length scaling parameter Angstrom It characterizes the effective diameter of the particle in collision proce
103. n of the pressure dependent reaction rates is suited for the cases when the Lindemann Hinshelwood or Troe an SRI interpolations are not applicable In that case the temperature and pressure range Tmin lt T lt Tmax Pmin lt P lt Pmax of the interpolation should be specified with the set of the corresponding interpolation coefficients Anm The Chebyshev polynomial interpolation is the bi variate polynomial interpolation which is defined by the equation logk 7 2 gt n l m Anm 7 P Me Il ji where x cos n 1 cos a cos x arccos x is the n th order Chebyshev polynomial The temperature and pressure are mapped onto interval 1 lt x lt 1 where the Chebyshev polynomials are defined by the transformations 2 1 1 f T Tmin T max 7 1 1 Tmin Tmax p 2log P log P min log P max log P max log P min To define the rate constant interpolation user should secifiy the following set of data indices n and m which define the Chebyshev polynomial order in the interpolation series and corresponding coefficient Anm Note that as the log k is interpolated the Anm is dimensionless The default values for Tmin is 300 K for Tmax is 2500 K for Pmin is 0 001 atm for Pmax is 100 atm Log P interpolation Tmin low temperature boundary of the interpolation interval K Tmax upper temperature boundary of the interpolation interval K P pressure value at which the c
104. nce name wizard Rules for substance name specification Figure 7 12 7 2 9 3 Reaction equation HeO E 0 lt gt lt empty list gt u H20 5535550 Coj 0 Property Value N formula H2O alias B phase phase type g charge 0 isomeric form no state term 5 spectroscopic name C spin 0 orbital angular momentum total angular momentum B symmetry group as FI index electronic state attr is C show all 0 Symmetry group Symmetry group characterizes the symmetry of the equilibrium configuration of the molecule in the electronic state under consideration Specification of the symmetry group is achieved by inserting from the drop down menu capital Latin letter to the field symmetry and subscript including one or two symbols from the drop down menu to the field index An example for HzO in the excited singlet electronic state C with the symmetry C gt is shown in Figures 3 15 and 3 16 100 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equation PIII 2 HeO Cay C 0 lt gt lt empty list gt Property value Chei formula H20 alias phase phase type g charge 0 isomeric Form no state term spectroscopic name Ce spin 0 orbital angular momentum total angular momentum symmetry group symmetry index electronic state att
105. nd electron density accordingly The factor r corresponds to approximate corrections due to Debye screening of plasma ions microfield by electrons and accounting for ion ion correlations in microfield distribution function In fact the value of this factor conventionally designated by the letter a serves as the universal plasma parameter labeling the microfield distribution functions Then the Stark broadening shift may be written as H R Griem Phys Rev 128 515 1962 for plasma ions and Rp s ova 10 cm send 1 2 N 10 cm gt In the formulae presented above it is assumed that ion 7 and electron 7 temperatures are equal to each other so called LTE Local Thermodynamic Equilibrium approximation 64 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 5 2 However in the limits while ions could be considered as static the values of 9 11 would be predominantly determined by the electron temperature although ion and electron temperature were not equal The approximation presented above is valid while 0 05 lt A lt 0 5 H R Griem Spectral Line Broadening by Plasmas Academic Press N Y 1974 These impact Stark widths and reduced shifts values are represented according to H R Griem Spectral Line Broadening by Plasmas Academic Press N Y 1974 as tables of parameters ws in Angstroms d and A for a given atom given at
106. ndependent variables should be specified The specification of the boundaries for the independent variables can be performed after the selection of the function for the analysis As it is shown on the figure below the following parameters should be provided for every independent variable e lower boundary of the interval which is denoted as Min upper boundary of the interval which is denoted as Max step of the increment for the independent variable for the numerical table generation which is denoted as Step e If several independent variables are possible e g temperature and pressure for pressure dependent chemical reactions than the Dependency drop down list should be settled This parameter defines the order of the independent variables according to which the calculated data will be ordered 78 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool Figure 6 5 6 1 2 4 6 1 2 5 Reaction analysis mw ROZ hO Reactions f i p H OZ M lt gt HO2 M_ H 02 M lt gt HO2 M 6 H 0 M lt gt HO M KF T KFT k atm em n js fcm n s Arbenius 200 K 300 K 1000 1 00 1 760E 32 2 846E 58 Lindemann 300 K 300 K 1000 11 00 1 760E 32 3 130E 57 Columns for analysis l KFET 1000 21 00 1 760E 32 5 976E 57 OKT 1000 31 00 1 760E 32 8 821E 57 1000 41 00 1 760E 32 1 167E 56 KF kr X 1000 51 00 1 760E 32 1 451E 56 Property
107. nformation in the new window which is analogous to the substance database editor described in the section 2 Substances are added to the mechanism list in the same way as to the substance database Enter the thermodynamic parameters of the substances when adding them to a mechanism In comparison with the Substance database editor Substance list window in Mechanism database has one additional button EB This button opens window for editing electronic properties of substances used in plasma type mechanisms To create or edit a reaction list click z and enter information in the window which is analogous to the window for editing the reaction database Reactions are added to a mechanism in the same way as to the reaction database Exiting the editor When finished working with the database don t forget to click VA to accept changes then click to exit or simply close the window 70 KintechDB 1 5 User Manual Kintech Lab Database search Description 5 Database search 5 1 5 2 Figure 6 1 Description Database search tool is designed for searching in the Kintech DB database for particular data The peculiarity of this tool is that search is automatically performed in all databases Substances Processes and MEchanism database Working with database search tool To open the database search tool click on the search button Qe at the main database window and the Database search window will appear
108. nstant pressure S T Entropy A T H 298 Change in enthalpy from the standard state H 298 G T T To build a table in the necessary interval enter the minimum and maximum temperature values in the fields Tmin View interval and Tmax View interval respectively as well as Step View interval Choose the desired units of measurement from the drop down list Units Energy Temperature Mass The table will be populated base on the data entered To build a graph click Plot and in the next window choose the function to plot To save the table to a file click Save button select the location and enter the file name The information will be saved in text format Addition of the new substance particle to the database Click the ig button to add a new substance particle to the database A window will be opened allowing the user to enter a new substance particle name parameters The dialog has the field Formula for entering the formula of the substance and Charge for entering its charge Also one can include Phase state Isomeric form and Modification data as well as OK and Cancel buttons To add a substance enter its formula and charge and click OK By default the Phase state is gas and the Charge is zero 0 Highlight the added substance in the substance list at the left side of the main database window and enter its properties in the corresponding tables as described in the following section If the substance already exists
109. of Substances see figure bellow The database contains supplemental windows with a list of substances and reactions and their properties Mechanisms HRAS ev O Mechanism name MType Description Plasma Excitation kinetics in Ar H2O system compiled by A Knizhnik AICI3 Plasma Excitation kinetics in AIClk system compiled by M Deminsky Xe Cl Plasma Excitation kinetics in Xe Cl2 system compiled by M Deminsky Kr CO Plasma Excitation kinetics in Kr CO system compiled by I Kochetov Hg Ar Plasma Excitation kinetics in Hg Ar system CN Plasma Excitation kinetics in CN system H25 dissociation Thermal gas Compiled at Kintech H25 02 dissociation Thermal gas Compiled at Kintech H2 air Connaire Westbrook Thermal gas Connaire M O Curran H J Simmie J M Pitz W J and Westbrook C K A Comprehen 10 Methane Leeds 1 5 Thermal gas Leeds methane combustion mechanism http www chem leeds ac uk Combustion Combu oon nun wn 11 SanDiego Thermal gas Chemical Kinetic Mechanisms for Combustion Applications http maeweb ucsd edu com 12 H2 air Marinov Thermal gas Marinov N Westbrook C K and Pitz W J Detailed and Global Chemical Kinetics Model for L13 GRI MECH 3 0 _ Thermal aas ___GRI MECH 3 0 httn www me berkelev edu ari_mech Phases Reactions Kg Fa A 2 3 Reaction Class Ar 48 1 5 1 gt Ar Hv 100 Optical Name Description Ar 33 48 0 5 1 gt Ar Hv 100 Optical
110. omic transition with the mean value of the wavelength of the multiplet in Angstroms for the several fixed values of plasma temperature values at plasma density equal to 1016 cm The latter fact is taken into account while writing above equations for adjusting to aforementioned tables In these tables the values of parameters depend on contributions from many atomic levels and could not be reproduced via simple calculations In particular in H R Griem Spectral Line Broadening by Plasmas Academic Press N Y 1974 one can find additionally the percentage of adiabatic contributions Molecular EV E V Upper term the upper electronic term i Lower term the lower electronic term j v vibrational number of the upper electron vibrational level v the vibrational number of the lower electron vibrational level A Einstein coefficient of quantum transition i v gt j v A projection of the electronic angular momentum L on the internuclear axis A projection of the electronic angular momentum L on the internuclear axis v the average EV E V transition frequency Units cm The electron vibrational molecular line has complicated internal structure due to the complex electron vibrational energy spectrum of molecules The Einstein coefficients of emission transitions may be expressed in the form K P Huber G Herzberg Molecular Spectra and Molecular Structure Part IV Constants o
111. onnegative integer or half integer values see example in Figure 3 5 7 2 5 3 orbital angular momentum Orbital angular momentum is the quantum number L of the orbital angular momentum of the atomic state which can assume nonnegative integer values It is to be noted that atomic states exist for which S and L are not defined and the corresponding fields are to be left blank see example in Figure 3 5 7 2 5 4 Total angular momentum Total angular momentum is the quantum number J of the total angular momentum of the atomic state which can assume nonnegative integer or half integer values 88 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification 7 2 5 5 Electronic state attribute Atomic states can not be specified completely by the quantum numbers S L and J The complete specification needs additional information which is provided by filling the field electronic state attr The field electronic state attr includes a complete set of the quantum numbers characterizing atomic electronic state These quantum numbers include electronic configuration and term The contents of the field has the form electronic configuration separation symbol term Sometimes electronic configuration is not shown and in this case separation symbol is not inserted before the string describing the term Separation symbol is a vertical line In atomic spectroscopy gene
112. ons list the blank input field will appear and the mouse cursor will blink Enter the reaction equation and press Enter key button 75 KintechDB 1 5 User Manual Kintech Lab Database tools for data analysis Reaction analysis tool Figure 6 2 amp Reaction analysis Hy 0 2H 0 H2 cl2 6 1 2 1 2 Input of the reaction from the Process database Figure 6 3 6 1 2 2 To load reactions from the Process database press button iv of the toolbar New window with the reactions list will appear In this window all the reactions from the Process database are listed It is possible to filter some reactions according to substance Substances field and button for filter activation and reaction class supported by the database Class drop down list To select reaction mark it by mouse click and press Select button at the bottom of the window To select several reactions hold the Ctrl button on the key pad and mark reactions by mouse click Than press Select button The reactions will be loaded into the Reaction analysis tool with their rate constant approximations or cross sections as it is shown on the figure amp Select reaction amp Reaction analysis Select reactions for analysis Reaction hag Ei y D a al C H C lt gt C H H C Reactions CGH H C lt gt GH C 2 a C H C lt gt C H H C CH O C lt CH CO C Sry Pee eG TT Arrhenius 290 K 3500 K Cally C lt
113. orresponding Arrhenius parameters A N EA are defined atm A pre exponential factor defined at pressure P s T for first order reactions cm s T N for second order reaction cm s T N for third order reaction N temperature exponent dimensionless EA activation energy cal mol 54 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 2 7 The general Log P interpolation provides the possibility to calculate the pressure dependent reaction rates on the basis of reaction rate constants evaluated at a several pressures defined as set of pressures P The linear logarithmic interpolation used for the calculation of the rate constant at the desired pressure Pi lt P lt Pit 1 log P log Pi log k logk logk NE ies Pela los where the Pi is the user specified pressure at which the reaction rate constant ki is evaluated according to Arrhenius law k AiT exp 24 RT and Ai Ni EAi are Arrhnius parameters corresponding to the pressure Pi R is universal gas constant see in Arrhenius approximation theory The units of the pre exponential factor Ai s T N for first order reactions cm s T for second order reaction cm s T N for third order reaction The activation energy units are cal mol Collision efficiency Tmin low temperature boundary of the interpolation interval K Tmax upper temperature boundary of the interpolation interval
114. otal angular momentum 5 electronic statea EOE type vibr_type description C Show all Figure 7 5 7 2 5 5 3 J j coupling In this case the following notation is used in spectroscopy for the term j jo Here j4 and j2 are total angular momenta of two groups of electrons which can assume integer or half integer values J is the total angular momentum of all the electrons and w is parity It is to be noted that quantum numbers S and L can not be defined in this case For the odd states w o and for the even states the mark w is omitted Quantum numbers of term are inserted into the field electronic state attr in the form j j2 J where w for the odd states and the mark w is omitted for the even states An example of the complete description of the excited state of Hg including configuration 6s 7S 2 6d 7D 3 9 and term 1 2 3 2 is shown in Figure 3 9 92 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equation Haj 3365 1425 1 2 6d 1 2D 3 2 H 41 2 3 21 1 533 G lt gt Hg Ci6s S1 Dodds 1 2 3 2 1 ta lt gt lt empty list gt u Haj 3365 1125 1 2 6d 1 H2D 3 2IHL1 2 3 2H Us G DN i J Property Value Opti formula Hg EER alias phase phase type g charge 0 state E term spectroscopic name spin orbital angular momentum ua oa momentum COE 342K S type d vibr _typ
115. phs section for details Plot X close Closes the TPIS window izl Save Saves the table in a text file The tables below shows the description of the table columns Column Function T Temperature C T Specific heat at constant pressure S T Entropy A T H 0 Enthalpy change A T Total enthalpy G T Gibbs free energy F T Reduced Gibbs energy To build a table for the desired temperature interval enter the values of the minimum and maximum temperature in the fields Tmin View interval and Tmax View interval respectively as well as Step View interval Choose the desired units of measurement by selecting from the drop down list Units Energy Temperature Mass Press lt Enter gt key at the keyboard The table will be populated based on the data entered To build a graph click Plot and in the next window select the function to plot The data collected in the table can be exported to the text file To do this lick Save select the location and enter a file name The information will be saved in text format Working with the JANAF tables vi Cp T S T H 298 G T T H T H 298 3 mole k 3 mole k 3i mole k kJ mole 15 29 38 205 04 205 04 0 00 30 09 213 62 206 17 2 97 31 09 220 47 208 37 6 03 32 08 226 25 210 89 9 19 32 96 231 27 213 46 12 44 33 72 235 74 215 97 15 77 34 36 239 75 218 40 19 18 34 88 243 41 220 73 22 64
116. quantum transition Aj If it is supposed that the impact approximation is valid for all broadening mechanisms then it is easy to show that the resulting line contour also is the Lorentz function with the half width equal to the sum of impact widths due to each broadening mechanisms l I Sobelman Introduction to Theory of Atomic Spectra Pergamon Press 1970 pp 1 640 H R Griem Spectral Line Broadening by Plasmas Academic Press N Y 1974 H R Griem Principles of Plasma Spectroscopy Cambridge University Press 2005 pp 1 366 The normalized to unity collisional line contour is given by the following expression AA m A Ay T A42 T A Aki Ani Ahi SAGs J where A ia S contribution to the contour half width due to Stark broadening by plasma electrons and ions A is contribution to the half width due to the resonance self broadening by radiators themselves and AA is contribution to the half width due to adiabatic broadening by buffer gas atom of species j The total line contour A is a result of convolution of 2 with Doppler profile giving in the output the Voigt function As it follows from equations four broadening mechanisms are operating independently from each other Resonance broadening gr the statistical weight of the upper level dimensionless g the statistical weight of the lower level dimensionless For the resonance broadening mechanism the approxim
117. r Show all Figure 7 13 7 2 9 4 Electronic state attr Molecular electronic states can not be specified completely by spectroscopic name and_ spin S The complete specification needs additional information which is provided by filling the field electronic state attr The field electronic state attr includes symmetry group and a complete set of the quantum numbers characterizing molecular electronic state These quantum numbers include electronic configuration and term Correspondingly the contents of the field has the form symmetry group separation symbol electronic configuration separation symbol term Rather often electronic configuration is not shown Symmetry group is specified in the form Syming where Sym is a capital Latin letter which is already introduced to the field symmetry and ind is one or two symbols coinciding with those which are already inserted into the field index Symmetry group is inserted into the field electronic state attr in the form Sym_ind For the example presented in Figures 3 15 3 16 symmetry group Cy Insertion of symmetry group to the field electronic state attr is illustrated in Figure 3 17 101 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Reaction equation HeO CayiC 0 Coyal biat B1 lt gt lt empty list gt u H20 53 C_2v a
118. r Angstrom It characterizes the effective diameter of the particle in collision process R is the distance between the particles corresponding to the potential minimum U U min at RERm E the energy scaling parameter It is specified divided by the Boltzmann constant e k in K It is equal to the potential well depth U j a the additional dimensionless parameter to vary the slope of the potential curve 40 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 7 5 2 2 7 6 Buckingham Corner is the general purpose potential It is more accurate than the common Lennard Jones 12 6 due to the third adjustable parameter a The formula for this potential U R 6 RY Sent att eiR 2 4 s l F R eo a S R lt Rp S R 1 R gt R m Born Mayer potential a the inverse length scaling parameter 1 Angstrom That is the parameter p 1 a characterizes the particle effective diameter in collision process A the energy scaling parameter eV Born Mayer potential is often used in high temperature calculations in particular for atom atom and atom molecule interactions This potential is monotonous one it describes only the repulsion between the particles at a small distance R corresponding to the high energy temperature interactions The formula is U R A exp a R HFD B potential
119. r weight molecular weight of the substance particle accounting for the its abundance in the nature It is measured in atomic mass units a m u Critical temperature pressure molar volume the group of these parameters is usually called as critical state and specifies the conditions at which the difference between liquid and gas vapour phases ceases to exist These parameters are used to write the equations of state of substances in non dimensional form in which these equations of state becomes similar The critical temperature should be specified in Kelvins K pressure in Mega Pascal MPa and molar critical volume in m mol Molar refractivity measure of the total polarizability of a mole of a substance Molecular properties This tab describes the specific properties of molecules Is radical the molecular substance is radical or not It is boolean value and can be True or False Is polar the molecular substance is radical or not It is boolean value and can be True or False Entropy nuclear spin contrib Practical thermodynamic functions published in literature differ from total thermodynamic functions in the magnitude of nuclear spin contribution The nuclear spin contribution to the entropy is calculated by the relation Spuer RY pn podali Xpo where nj is the number of atoms of element j in the molecule of a given substance Xj and ik are the molar fraction and nuclear spin of the kth isotope of the
120. ral form of the electronic configuration is as follows nl Lis Jah Ly sis where M 2S 1 is multiplicity Here n is a principle quantum number of the electron is an orbital quantum number of the electron k is a number of electrons on the n electronic shell S L J are spin orbital angular momentum and total angular momentum of the n electronic shell If some k 1 it is not shown In the case of the closed shell or shell with only one electron corresponding SIT are not shown In some cases a Bag may refer to several shells Closed electronic shells with k 2 2 1 often are not shown The values of J often are not shown In atomic spectroscopy values of the orbital angular momentum of one electron total orbital angular momentum L of k electrons are represented by small capital Latin letters 0 s S 1 p P 2 d D 3 f F 4 g G Quantum numbers of configuration are inserted into the field electronic state attr in the form of a string nl k M L J nh k M L J gt where mentioned above letter representation of l and L are used If k 1 it is also shown An example of the excited electronic configuration 3d8 3F 4s3p P of Ni is shown in Figure 3 6 89 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification Figure 7 3 7 2 5 5 1 Reaction equation Nis 534 8 3F 45 1 4p
121. rect bimolecular reaction C H Are C 2H Ar Chemical C H C lt C 2H C Chemical C H C H lt gt C H H Chemical 2 C H lt gt C H C H Chemical CH C H lt 2 C H Chemical CH C H lt gt C H C H Chemical CH C H lt gt C3H C H Chemical C H CH lt gt C H Chemical C H CH lt gt C H H Chemical C H CH lt gt C H CH Chemical CH CHy lt gt C 2 H CH Chemical CH CO lt C 2H CO Chemical CH CO lt gt C H HCO Chemical Approximations Contributor All Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction oon on es oO NM amp Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction Direct bimolecular reaction m HRAJI YA Arrhenius Tmin K Tmax K 4 Ea kcal mole Error tedium identificatior Lindemann Troe interpolation i out 2500 Aa g SRI interpolation Chebyshev Collision efficiency Logarithm interpolation Comment Tsang W Hampson R F J Phys Chem Ref Data 15 1087 1986 User defined The processes database editor see figure above contains a list of processes which match the filter criteria or all processes in the
122. rength dimensionless Ar allow cross section is applicable for the following classes of reactions 1 EXCITATION OF ATOM INTO OPTICALLY ALLOWED STATE Cross section of excitation of Ar atom into optically allowed state o E 2 Ht F E Og E z E AE log AE ik ik where ay the Bohr radius 0 529177 A AE threshold value eV Fg oscillator strength Ht 27 2 eV Ar forbid cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that o 0 Scale alpha a beta 8 gamma y B fitting parameters in equation dimensionless Ar forbid cross section is applicable for the following classes of reactions 1 EXITATION OF ATOM INTO OPTICALLY FORBIDDEN STATE Cross section of excitation of Ar atom into optically forbidden state o E a E 2aai 2 a 1 a8 1 2E where ay the Bohr radius 0 529177 A AE threshold value eV a B y B parameters in equation Hf 27 2 eV Allow cross section Threshold value cross section threshold value eV Scale scale factor for cross section dimensionless default value 1 Scale parameter gives cross section scale factor so that oj 0 Scale 57 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 3 4 5 3 3 4 6 Fo oscillator strength
123. rs Rate constants of about 600 reactions are taken from the most trustworthy compilation by D L Baulch C T Bowman C J Cobos et al Evaluated Kinetic Data for Combustion Modeling Supplement Il J Phys Chem Ref Data Vol 34 No 3 P 757 2005 These are direct bimolecular reactions bimolecular reactions through the intermediate complex decomposition addition and combination reactions Rate constants for practically all the reactions are given in wide temperature range Parameters characterizing pressure dependence of the rate constants are given for the pressure dependent reactions This comprehensive amount of data can be a good starting point for developing and upgrading of the combustion mechanisms 43 KintechDB 1 5 User Manual Kintech Lab Processes properties Contents of the Processes Database 3 1 2 Elementary equilibrium ion molecule reactions Rate constants of about 2500 ion molecule reactions are included to the base This set comprises direct bimolecular reactions charge transfer and clusterization with participation of positive and negative ions About 1000 of them are taken from the original experimental and theoretical papers About 1500 reactions with participation of positive ions are taken from the compilation V G Anicich Evaluated Bimolecular lon Molecule Gas Phase Kinetics of Positive lons for Use in Modeling Planetary Atmospheres Cometary Comae and Interstellar Clouds J Phys Chem Ref Data
124. s in cm correspond to following expressions for rotational constant D and others on vibrational quantum number Dy De By v 1 2 Bo vt1 2 Ba v 1 2 3 By v 1 2 4 Hy He V4 v 1 2 Vo v 1 2 va vt1 2 9 Ly Le Uy vt1 2 Uo vt1 2 Us v 1 2 3 It should be noted the series are oscillating Morse Wx We potential parameter Units Wexe potential parameter Re equilibrium separation distance A Three parameter Morse potential form for the potential energy function U r D exp c r Re 1 Te is assumed Dissociation energy D is determined by the vibrational frequency e and unharmonicity eXe D 0 25We7 Wexe the exponential parameter is expressed in terms of the entities above as 30 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 2 6 2 2 6 2 7 2 2 6 2 8 2 2 6 2 9 a 2mWexe 2 m standing for the reduced mass Enter three parameters We cm Wexe cm and equilibrium separation Re A u is defined by the chemical formula Morse D De dissociation energy Units eV Re equilibrium internuclear distance Units A a potential parameter Three parameter Morse potential form for the potential energy function U r De exp a r Re 1 7 To is assumed RKR potential V vibrational quantum number R1 R2 internuclear distance trning poi
125. s of Kintech Lab as set forth herein Any liability of Kintech Lab its officers agents or employees with respect to the software or the performance thereof under any warranty contract negligence strict liability vicarious liability or other theory will be limited exclusively to product replacement or if replacement is inadequate as a remedy or in Kintech Lab s opinion impractical to a credit of amounts paid to Kintech Lab for the license of the software 2 KintechDB 1 5 User Manual Kintech Lab Table of Contents 1 installation Gnd configuration sescenti aeia aE 6 1 1 GOMEFALINTOFMATUON sseni ennie Dipende aaiae aera aieiaiei aaia eiaeia ainda 6 1 2 Installation sscsssciesscssscctecctesssdesadestesessececeensececscececdeenccebeeasedessceseccueasceeleectipesscnstcesrecasdessansnacartesacsensas 6 1 3 Launching the database GUI ciisisssscsssicevedendsteussteccaantastanendestncviaunstunnssiaenvedansadenssiesecarensienuacereanaeen 6 1 4 Database connection settings siisciiicsscsscccsscscsesscnsecenssennssssersscresecsersewersercnnyscervessesveeennvertsedsceuseres 7 1 4 1 Database settings dialog 22 02 00 cccccssccseccneecaaeeaeceaeeeaecaeceaeceaeccaeccaeceeeeeeceeeeeeceeeeceeeseeseeeneesetigs 7 1 5 Administration and users management cccceeceeeeeeeeee eee eeeeeeeeeeneneeseeeeeeesseeeneeeeeeeeasneeeeneneeeeenes 8 1 5 1 Administration 2 0 0 0 cccceeeceseeeeceeeeeeeeeeeaeeaaeeaaeeaaeaaaeaaecaaeeaaecaecaaeceaeceaeceaeceaeceeeeeeeeeee
126. select the process in the list and enter or edit rate constants by choosing the type of approximation and entering its parameters in the corresponding tables A new set of parameters for the approximation can be entered by 47 KintechDB 1 5 User Manual Kintech Lab Processes properties Guide to Process properties 3 2 5 3 3 3 3 1 3 3 2 3 3 2 1 clicking ag button while table cells can be edited by double clicking the cell and entering the information To delete an interval click Fa Changes must be saved by clicking A Exiting the editor window When user finished working with the database don t forget to click v to accept and save all changes after which click to exit or simply close the window Guide to Process properties General classification of the processes All the reactions in the database are divided into the following classes Chemical processes which allows to calculate the rate constants of the chemical reactions between particles at thermodynamic equilibrium conditions i e equilibrium distribution of the particles in energy levels Energy exchange processes which describe the energy exchange between particles in different vibrational states e Electronical processes which describes the rate parameters of the processes between particles neutral in ground state and excited ions Chemical Processes Depending on the type of the chemical process its rate constants may depend on
127. ss It is equal to the potential root value U 0 at R o E the energy scaling parameter It is specified divided by the Boltzmann constant e k in K It is equal to the potential well depth i e is the absolute value of the potential minimum U min E Lennard Jones 12 6 is the general purpose potential It is not accurate but is commonly used in calculations at T 300 4000 K Khimera database provides the parameters of this potential for more than 700 pure gases The formula for Lennard Jones 12 6 is o 12 g 6 vel 3 R R Lennard Jones m 6 potential o the length scaling parameter Angstrom It characterizes the effective diameter of the particle in collision process It is equal to the potential root value U 0 at R o E the energy scaling parameter It is specified divided by the Boltzmann constant e k in K It is equal to the potential well depth i e is the absolute value of the potential minimum U min m the additional dimensionless parameter to vary the slope of the potential curve 39 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 7 3 2 2 7 4 Lennard Jones m 6 is the general purpose potential It is more accurate than the common Lennard Jones 12 6 due to the third adjustable parameter m The formula for Lennard Jones m 6 is m m 6 m 6 o m 6 U R 6e
128. t user information KintechDB 1 5 User Manual Kintech Lab Installation and configuration Administration and users management 1 5 2 5 Deleting a user To delete a user highlight the user with the mouse and click Eag Next to the user name the symbol will appear instead of the line number Press v to save the change Remember that you must have administrative rights in order to delete users 10 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database 2 Substances and Atomic Molecular properties 2 1 Working with the database 2 1 1 Description of the main window Substances BRAY 4A a DER Phase state Jsomeric form _ Modification _ Local name Thermodynamics Substance properties Molecular properties General properties Electronic properties Intermolecular potentials eA SJ 3 Thermodynamics functions DHf 298 kJ mole Cp 298 3 mole K S 298 J mole K H 298 H 0 kJ mole DHf 0 kJ mole Comment Recommended Default __ 29 38027954 205 0403137 _8 680753708 o i v v MEEA AN mee Gibbs coefficients O TMn K TMax K Fie re e u Lc F7 __ Recomm 1 298 1499939 1500 249 2230072 20 15410042 0 00103128 0 22640900 1403650055 295 2170105 347 5079956 2 1500 6000 279 4299927 30 38850021 0 00664923 0 01485630 22 07150078 8 069
129. tation Product of moments of inertia the product of principal moments of inertia lalglc of molecule in a given state Units in the database 107117 g3cm IAIBIC error the estimated uncertainty in the product of principal moments of inertia glc Units in the database 107117 g3cm Rotation constant A rotational spectra are characterized by the constants A B and C where A h 81r7 and likewise for B and C here h is Planck constant IA B C molecule momentum of inertia Units in the database cm Rotation constant B rotational spectra are characterized by the constants A B and C where B h 8117 5 and likewise for A and C Units in the database are cm 37 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 3 4 Rotation constant C rotational spectra are characterized by the constants A B and C where C h 8117 c and likewise for A and B Units in the database in cm Average momentum projection Internal rotations Rotational barrier barrier to internal rotation of an internal rotor in a molecule Units in the database in cm Rotational barrier error the estimated uncertainty of the barrier to internal rotation in cm of an internal rotor in a molecule Reduced moment of inertia the reduced moment of inertia in 10798 g cm is a kinematical parameter of an in
130. temperature of relative atomic motion equal to 5000 K cm rad s For the Van der Waals buffer gas adiabatic impact broadening the half width at half maximum HWHM of the Lorentz profile is defined as see Sobelman Introduction to Theory of Atomic Spectra Pergamon Press 1970 pp 1 640 _ Ag Ahi pam he or in numerical form A Angstroms 1 49 10 A C N 3 where Np is the buffer gas concentration in cm Ag in Angstroms Cp in cm s rad The coefficient Cp is proportional to the difference of Cg Van der Waals coefficients describing the interaction of radiator in the upper and lower levels with the buffer gas atom W Furssow A Wlassow J Phys U S S R 1 335 1939 In the adiabatic approximation the constant Ch could be expressed in the form 3 10 imp C 3 9504 ace 2 5 3 10 C 5000K T 5000 mu Here k is the Boltzmann constant T is the temperature of relative motion of buffer gas atom and radiator x is the reduced mass of a pair radiating atom and atom of buffer gas perturbing particles AC is the difference of Van der Waals interaction constants in the impact region that are given in atomic units There is slight difference in numerical coefficient in the equation for Cp 3 9504 instead of conventional 4 04 This difference is due to the performed actual average over Maxwellian distribution of velocities instead of simple substitution of v by lt v gt
131. ternal rotor in a molecule General approach to the calculation of the parameter was developed by Pitzer and Gwinn K S Pitzer and W G Gwinn J Chem Phys Vol 10 p 428 1942 For a symmetric rotor such as a methyl group is the reduced moment of inertia for the internal rotation and is given by equation L hop lop 0H B It 71 Ic where hop is the moment of inertia of the rotating fragment about the axis of internal rotation and is expressed as hop ymyr7 where the m are atomic masses r is the distance of atom i from the axis of internal rotation and the sum runs over all atoms in the rotating fragment The quantities a B y are the cosines of the angles formed between the internal rotation axis and the principal axes of the overall molecule that correspond to l4 Ig and Ic respectively Reduced moment of inertia error the estimated uncertainty in the reduced moment of inertia of the internal rotor Units in the database in cm Rotation constant B rotational spectra of linear molecule are characterized by the constant B where B h 81r7 5 h is Planck constant Ig is momentum of inertia Units in the database cm Rotation constant D centrifugal constant in rotational energy expression for linear molecule F J B J J 1 D P JDP where J rotational quantum number Units in the database cm Symmetry number of internal rotor rotational symmetry number of rotating fragment of a
132. thermal equilibrium The fields in the wizard specifying electronic state must be filled see the description below and vibrational quantum numbers v1 v2 are to be inserted into the corresponding fields and all other fields are to be left blank 87 KintechDB 1 5 User Manual Kintech Lab Specifying substance name using Substance name wizard Rules for substance name specification 7 2 5 The particle is an atom in the completely specified ground or excited electronic state The characteristics of the state are inserted into the term tree node of the Substance name wizard 7 2 5 1 Spectroscopic name In the case of the atomic states spectroscopic name usually is not used because other quantum numbers practically always specify atomic states completely Nevertheless sometimes spectroscopic name which is small or capital Latin letter see example in Figure 3 5 is to be inserted Reaction equation Bly Dsjaids S 4d Dsja hu gt AIC Pa 2 38 S 9p P3 20 bie tu AUS i38 241S 4d 112065 2 5 My 2 2 5 2 oF Spoj Property Value Optil formula Al alias phase phase type g charge 0 state term spectroscopic name y spin 1 2 orbital angular momentum 2 total angular momentum 5 2 electronic state attr 3s 23415 4d 1 2D 5 2 gt type vibr_type description C Show all Figure 7 2 7 2 5 2 Spin Spin is the quantum number S of the total spin of the atomic state which can assume n
133. ton is pressed J Accept changes in any of the tables changes must be accepted in order to be saved Open summary report of the selected substance properties in HTML format Show the history of changes of the database Search the substances in the database elja Close substance properties window Search in the database Filters To view or edit information on a certain substance you can choose it from the list of substances or find it by using a filter or search function To search substance in the database enter the name or part of the name of a substance in the Search field and press Q button or lt Enter gt key The first substance satisfying the search criteria will be highlighted in the table Subsequently clicking the button or lt Enter gt key will find further matches for the name in the search field For the search according the specific criterion the filters should be used The following filters are available e View shows the substances particles according to the type of the specified particle type monatomic diatomic polyatomic Atom shows the substances particles which contain the specified atom as a part of the formula e Charge shows the substance particle with the required charge or charge range 12 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database 2 1 4 2 1 4 1 2 1 4 2 Figure 2 2 e Phase shows the
134. tronic or potential energy curve for a given state Units A Hund hund s case of angular momentum coupling It can be c or any other letter which will be interpreted as not c case Parity symmetry of the wave function of a given state with respect to the inversion valid for homonuclear molecules only It can be g symmetricat or u anti symmetric Plane reflection the reflection symmetry with respect to an arbitrary plane containing the inter nuclear axis is designated by or Fine structure constant gamma spin rotation coupling constant y is valid for 25 states and is a coefficient in rotational energy as a function of rotational quantum number J Units cm Fine structure constants lam and mu spin rotation coupling constants A and are valid for 3z states and are coefficients in rotational energy as a function of rotational quantum number J Units cm Spin orbit coupling constant A the spin orbit coupling constant A is coefficient in rotational energy for 2A states and 3A states Units cm1 Spin orbit coupling constant error the uncertainty estimated for spin orbit coupling constant A Units cm Number of known vibrational levels the number of levels from which vibrational constants were derived for a given state Number of known rotational levels 28 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecu
135. ts Units A U potential energy Units cm Potential energy curve U r of a bound state is defined pointwise by a set of vibrational energy values E where v is the vibrational quantum number and internuclear distance values r v U r v Ey turning points Normally obtained by processing of experimental spectra and applicable to simple single minima curves so that there are two turning points r1 v left and r2 v right where the horizontal line U E crosses the potential curve U r U potential energy Atomic units R internuclear distance Atomic units Potential energy curve defined by a set of points U r i e its values for certain internuclear distances usually obtained by electronic structure calculations For each point two numbers should be provided U r and r both in atomic units Repulsive term RO potential parameter Units A E0 potential parameter Units eV Te potential parameter Units eV Simple exponential approximation for repulsive potential energy function U r Eo exp r ro Te 31 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties 2 2 6 3 Enter three parameters E eV ro A and T eV the latter quantity is the difference between ground state equilibrium energy and the dissociation limit of the repulsive state in Polyatomic molecules For the polyatomic molecul
136. ts for the specific temperature interval and press the same button Click the button to accept the deletion Import and export data You can export the data from database to XML file by clicking the R button in the main database window toolbar To import data from XML file or IVTAN text file format use ay button on the main database dialog toolbar Review of the substance particle properties and printing a report To review print and export as HTML file all the data in the database related with the substance click mj button The HTML viewer will be opened with the report containing the database data summary for selected substance 16 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Working with the database Figure 2 4 2 1 10 2 1 11 ll amp Dioxygen 02 Molecular weight 31 9988 a m u Atomic mass a m u Isotope mass a m u o 15 9994 15 99492 Thermodynamic data Thermodynamic function Yalue it AH 298 15 kJ mole o AHO kJ mole 0 H 298 15 H 0 ka mole 8 6808 5298 15 3 mole k 205 0403 298 15 J mole K 29 3803 Gibbs polynomial coefficients I Temperature K Fi F2 Fa Fa Fs Fe F 298 15 1500 2 4922E 002 2 0154E 001 1 0313E 003 2 2641E 001 1 4037E 002 2 9522E 002 3 4751E 002 1500 6000 2 7943E 002 3 0389E 001 6 6492E 003 1 4856E 00
137. vy feature For the description of the Electron configuration there is a standard notation It depends on the type of the molecule linear or nonlinear For linear molecules the notation is the same as for diatomic molecules and consists of a string of molecular orbital labels e g o 1175 with the number of electrons assigned to each molecular orbital placed as a superscript To simplify input into the database conditional configuration CCP is introduced see detailed description in Appendix C CCP is transformed into usual form of electron configuration presentation at visualization printing For nonlinear molecules CCP is entered as sequence of groups of variables each of which consists of several figures names of irreducible representations of a symmetry group of a molecule in round brackets see detailed description in Appendix C Stat weight P is the number of degenerate substates contained in the state For linear molecules 33 KintechDB 1 5 User Manual Kintech Lab Substances and Atomic Molecular properties Guide to Substance and Atomic Molecular properties If values S and A are known then P 2 S 1 2 if A gt 0 P 2 S 1 if 4 0 If value Q is known then P 2 ifQ gt 0 orQ lt 0 P 1 ifQ 0 For example P 2A 4 P 311 4 2 P 42 4 For nonlinear molecules P 2 S 1 D where D is degeneration of irreducible representation D 1 for A and B D 2 for E D 3 for F D 4 for G D 5 for H
138. window will open see figure bellow The window contains input filed for reaction equation wizard line with html representation of the reaction equation and drop down lists for selection of the reaction class and approximation type 46 KintechDB 1 5 User Manual Kintech Lab Processes properties Working with the database Reaction equation lt empty list gt lt gt empty list gt Chemistry of heavy particles Chemical Figure 3 2 Clicking on the reagent or product name opens Substance name wizard which allows to specify reagent or products state characteristics vibrational and electronic state parameters in table form without using complex text representation see figure bellow Please see Appendix for guidance of using Substance name wizard Se cee symmetry group symmetry ndex abiri Saa atr X vibretonal_state_sttr G vie Quant nun vi 1 CS ir i qart und O Stow at Figure 3 3 Reaction class and corresponding approximation type will be determined automatically but user has the possibility to change it After the reaction has been entered select it in the list of reactions and enter rate constants see next section for details 3 2 4 Edit the process properties in the database To edit reaction equations press A to open the reaction equation wizard describe in the section Addition of a new process to the database on page 46 To change the data on the rate of a process

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