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CASPT2 investigation of ethane dissociation and methyl recombination using canonical variational transition state theory
Author(s) -
Li Hua,
Chen BoZhen,
Huang MingBao
Publication year - 2008
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.20299
Subject(s) - chemistry , dissociation (chemistry) , recombination , reaction rate constant , thermodynamics , transition state , transition state theory , computational chemistry , kinetics , quantum mechanics , physics , catalysis , organic chemistry , gene , biochemistry
Ethane dissociation and the reverse recombination reactions were investigated based on CASPT2 and CASSCF calculations. The CASPT2 (partial) geometry optimization calculations and the CASSCF frequency calculations provided geometrical parameters, potential energies, and vibrational frequencies along the reaction pathway. For determining dissociation and recombination rate constants at a temperature range from 200 to 2000 K, two models (models 1 and 2) were used on the basis of the canonical variational transition state theory. The different methods for accounting for the five transitional modes were proposed in the two models. Dissociation activation parameters evaluated using the two models are in good agreement with the data available in the literature. Model 1 predicts reasonable rate constant values for methyl recombination at high temperature, and model 2 predicts reasonable values in both high‐ and low‐temperature ranges. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 161–173, 2008