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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

Journal Article · · Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
DOI:https://doi.org/10.1021/jp990969d· OSTI ID:682167
; ; ; ;  [1]
  1. Univ. of Minnesota, Minneapolis, MN (United States)

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.

Sponsoring Organization:
USDOE, Washington, DC (United States); National Science Foundation, Washington, DC (United States)
OSTI ID:
682167
Journal Information:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 103, Issue 25; Other Information: PBD: 24 Jun 1999
Country of Publication:
United States
Language:
English