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Title: Direct dynamics for free radical kinetics in solution: Solvent effect on the rate constant for the reaction of methanol with atomic hydrogen

Abstract

Recent years have seen great progress in modeling solvation effects on chemical reactions, especially ionic reactions and polar rearrangements. Radical chain reactions, in which a radical abstracts an atom from a molecule which is thereby converted to a radical, are an important class of reactions that has been less well studied. Such bimolecular radical substitution (S{sub R}2) reactions typically have smaller solvent effects than ionic reactions, and thus they provide a sensitive test of theory. The authors calculate the rate constant for the reaction {sup {sm_bullet}}H + CH{sub 3}OH {yields} H{sub 2} + {sup {sm_bullet}}CH{sub 2}OH both in the gas phase and in aqueous solution at 298 K. To accomplish this, they apply two different methods to estimate the electronic energies along the reaction path.

Authors:
; ; ; ;  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Sponsoring Org.:
USDOE, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
OSTI Identifier:
682167
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 25; Other Information: PBD: 24 Jun 1999
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; CHEMICAL REACTION KINETICS; METHANOL; HYDROGEN; SOLVATION; METHYL RADICALS

Citation Formats

Chuang, Y Y, Radhakrishnan, M L, Fast, P L, Cramer, C J, and Truhlar, D G. Direct dynamics for free radical kinetics in solution: Solvent effect on the rate constant for the reaction of methanol with atomic hydrogen. United States: N. p., 1999. Web. doi:10.1021/jp990969d.
Chuang, Y Y, Radhakrishnan, M L, Fast, P L, Cramer, C J, & Truhlar, D G. Direct dynamics for free radical kinetics in solution: Solvent effect on the rate constant for the reaction of methanol with atomic hydrogen. United States. https://doi.org/10.1021/jp990969d
Chuang, Y Y, Radhakrishnan, M L, Fast, P L, Cramer, C J, and Truhlar, D G. 1999. "Direct dynamics for free radical kinetics in solution: Solvent effect on the rate constant for the reaction of methanol with atomic hydrogen". United States. https://doi.org/10.1021/jp990969d.
@article{osti_682167,
title = {Direct dynamics for free radical kinetics in solution: Solvent effect on the rate constant for the reaction of methanol with atomic hydrogen},
author = {Chuang, Y Y and Radhakrishnan, M L and Fast, P L and Cramer, C J and Truhlar, D G},
abstractNote = {Recent years have seen great progress in modeling solvation effects on chemical reactions, especially ionic reactions and polar rearrangements. Radical chain reactions, in which a radical abstracts an atom from a molecule which is thereby converted to a radical, are an important class of reactions that has been less well studied. Such bimolecular radical substitution (S{sub R}2) reactions typically have smaller solvent effects than ionic reactions, and thus they provide a sensitive test of theory. The authors calculate the rate constant for the reaction {sup {sm_bullet}}H + CH{sub 3}OH {yields} H{sub 2} + {sup {sm_bullet}}CH{sub 2}OH both in the gas phase and in aqueous solution at 298 K. To accomplish this, they apply two different methods to estimate the electronic energies along the reaction path.},
doi = {10.1021/jp990969d},
url = {https://www.osti.gov/biblio/682167}, journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
number = 25,
volume = 103,
place = {United States},
year = {Thu Jun 24 00:00:00 EDT 1999},
month = {Thu Jun 24 00:00:00 EDT 1999}
}