1. Theoretical calculations of structures, energetics, and kinetics of O (3P) + CH3OH reactions.
- Author
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Alves, Marcel M., Carvalho, Edson F. V., Machado, Francisco B. C., and Roberto‐Neto, Orlando
- Subjects
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ISOTOPES , *EXTRAPOLATION , *ENTHALPY , *APPROXIMATION theory , *NUCLIDES - Abstract
DFT methods are used in calculations of geometries, energies, and frequencies for O (3P) + CH3OH 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 (ΔH
00 ) 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 12C/13C kinetic isotope effects are also calculated in good agreement with available experimental data. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 [ABSTRACT FROM AUTHOR]- Published
- 2010
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