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Rate constants for the CH 3 O + NO → CH 3 ONO reaction by classical trajectory and canonical variational transition state theory calculations
Author(s) -
MartínezNúñez Emilio,
Borges Itamar,
Vázquez S. A.
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.460
Subject(s) - chemistry , reaction rate constant , potential energy surface , transition state theory , dissociation (chemistry) , thermodynamics , work (physics) , transition state , recombination , computational chemistry , quantum mechanics , kinetics , physics , molecule , catalysis , organic chemistry , biochemistry , gene
Classical trajectory and canonical variational transition state theory (CVTST) calculations were performed on the CH 3 O + NO → CH 3 ONO recombination reaction for the temperature range 300–1000 K to study theoretically this reaction for the first time. The dynamics calculations employ our previously reported potential energy surface for the dissociation and elimination reactions of methyl nitrite (Martínez‐Núñez E, Vázquez SA. J. Chem. Phys . 1998; 109 : 8907). In the present work this surface was conveniently modified to reproduce more accurately the experimental CH 3 ONO dissociation energy and to obtain more reliable rate constants for both the dissociation and the recombination reactions. The recombination rate constants calculated with this modified version of the original potential energy surface agree better with the experimental results than do the rates obtained with the original one. Copyright © 2001 John Wiley & Sons, Ltd.