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:
-
- 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}
}