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Theoretical calculations of structures, energetics, and kinetics of O ( 3 P) + CH 3 OH reactions
Author(s) -
Alves Marcel M.,
Carvalho Edson F. V.,
Machado Francisco B. C.,
RobertoNeto Orlando
Publication year - 2010
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.22576
Subject(s) - chemistry , extrapolation , basis set , kinetic isotope effect , reaction rate constant , kinetic energy , transition state theory , computational chemistry , kinetics , thermodynamics , atomic physics , density functional theory , physics , deuterium , mathematical analysis , mathematics , quantum mechanics
DFT methods are used in calculations of geometries, energies, and frequencies for O ( 3 P) + CH 3 OH reactions. CCSD(T) single‐point calculations are carried out followed by extrapolation to the complete basis set (CBS) limit and inclusion of core correlation. The best estimate results of the reaction enthalpies (Δ H 0 0 ) for the first (−7.1 kcal/mol), second (2.0 kcal/mol), and the third (25.8 kcal/mol) reactions path are in excellent agreement with the experimental values, i.e., −7.2 ± 0.2, 1.2 ± 1.0, and 26.0 ± 1.2 kcal/mol, respectively. Rate constants and activation energies in the range of 300–2,000 K calculated with the variational transition state theory are in good agreement with previous studies. H/D and 12 C/ 13 C kinetic isotope effects are also calculated in good agreement with available experimental data. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010
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