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Ab initio calculations and absolute rate theory. Critical test for a series of elementary gas‐phase reactions
Author(s) -
Čársky P.,
Zahradník R.
Publication year - 1979
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560160205
Subject(s) - chemistry , isomerization , ab initio , computational chemistry , basis set , series (stratigraphy) , ab initio quantum chemistry methods , reaction rate constant , absolute deviation , gaussian orbital , thermodynamics , molecule , density functional theory , physics , kinetics , organic chemistry , quantum mechanics , paleontology , biology , catalysis , statistics , mathematics
Absolute rate theory ( ART ) was applied to a series of reactions of the type A+BC → AB+C containing H, F, HF, H 2 , and F 2 , trans – cis isomerization of dideuteroethylene, and processes H + CH 4 → H 2 + CH 3 and H′+CH 4 → H′CH 3 + H. Geometries and energies of activated complexes were taken from the best ab initio studies reported in the literature in which at least a DZ + P basis set was used and a large portion of the correlation energy was included. Vibrational frequencies needed for the zero‐point energies and vibrational partition functions were estimated from the reported potential surfaces (HHF and HFF) or evaluated from SCF 4‐31G calculations (HFH, FHF, twisted C 2 H 4 , and CH 5 complexes). Compatability of calculated rate constants with the experimental data was examined.