Quantum theory of enhanced unimolecular reaction rates below the ergodicity threshold

被引：21

作者：

Leitner, David M.

Wolynes, Peter G.

机构：

[1] Univ Nevada, Dept Chem, Reno, NV 89557 USA

[2] Univ Nevada, Chem Phys Program, Reno, NV 89557 USA

[3] Univ Calif San Diego, Dept Chem & Biochem, La Jolla, CA 92093 USA

[4] Univ Calif San Diego, Dept Phys, La Jolla, CA 92093 USA

来源：

CHEMICAL PHYSICS | 2006年 / 329卷 / 1-3期

关键词：

quantum energy flow; unimolecular reaction kinetics;

D O I：

10.1016/j.chemphys.2006.05.013

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：

A variety of unimolecular reactions exhibit measured rates that exceed Rice-Ramsperger-Kassel-Marcus (RRKM) predictions. We show using the local random matrix theory (LRMT) of vibrational energy flow how the quantum localization of the vibrational states of a molecule, by violating the ergodicity assumption, can give rise to such an enhancement of the apparent reaction rate. We present an illustrative calculation using LRMT for a model 12-vibrational mode organic molecule to show that below the ergodicity threshold the reaction rate may exceed many times the RRKM prediction due to quantum localization of vibrational states. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：163 / 167

页数：5

共 44 条

[1] Influence of vibrational energy flow on isomerization of flexible molecules: Incorporating non-Rice-Ramsperger-Kassel-Marcus kinetics in the simulation of dipeptide isomerization [J].