REACTION DYNAMICS ON BARRIERLESS REACTION SURFACES - A MODEL FOR ISOERGIC GAS-PHASE PROTON-TRANSFER REACTIONS

被引：42

作者：

LIM, KF ^{[1
]}

BRAUMAN, JI ^{[1
]}

机构：

[1] STANFORD UNIV, DEPT CHEM, STANFORD, CA 94305 USA

来源：

JOURNAL OF CHEMICAL PHYSICS | 1991年 / 94卷 / 11期

关键词：

D O I：

10.1063/1.460724

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

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.

引用

页码：7164 / 7180

页数：17

共 94 条

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