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Reaction dynamics on barrierless reaction surfaces: a model for isoergic gas-phase proton-transfer reactions

journal contribution
posted on 1991-06-01, 00:00 authored by Kieran LimKieran Lim, J I Brauman
The kinetics of some gas-phase alcohol/alkoxide proton-transfer reactions is slower than predicted by simple Rice–Ramsberger–Kassel–Marcus (RRKM) rate theory modeling on the near-barrierless reaction surfaces. Reaction dynamics can be investigated in isolation from nonequilibrium and/or thermodynamic considerations through the study of a generic isoergic ion–molecule system X-+X-H. Monte Carlo quasiclassical trajectory simulations on barrierless reaction surfaces show that the slow experimental kinetics is consistent with both (i) locking of the external rotations of the reactants and (ii) passage over the (orbital angular momentum) centrifugal barrier being the rate-determining steps in bimolecular association, rather than only the latter process. In addition, there may be non-RRKM product selectivity.

History

Journal

Journal of chemical physics

Volume

94

Issue

11

Pagination

7164 - 7180

Publisher

AIP Publishing

Location

Melville, N.Y.

ISSN

0021-9606

eISSN

1089-7690

Language

eng

Publication classification

CN.1 Other journal article

Copyright notice

1991, AIP