Semiclassical initial value representation for the Boltzmann operator in thermal rate constants

被引：37

作者：

Zhao, Y ^{[1
]}

Miller, WH

机构：

[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA

[2] Univ Calif Berkeley, Kenneth S Pitzer Ctr Theoret Chem, Berkeley, CA 94720 USA

[3] Lawrence Berkeley Lab, Div Chem Sci, Berkeley, CA 94720 USA

来源：

JOURNAL OF CHEMICAL PHYSICS | 2002年 / 117卷 / 21期

关键词：

D O I：

10.1063/1.1517044

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 thermal rate constant for a chemical reaction, k(T), can be expressed as the long time limit of the flux-side correlation C-fs(t)=tr[e(-beta(H) over cap /2)(F) over cape(-beta(H) over cap /2)e-(i (H) over capt/(h) over bar)(h) over cape(-i (H) over capt/(h) over bar)]. Previous work has focused on semiclassical (SC) approximations [implemented via an initial value representation (IVR)] for the time evolution operators exp(+/-i (H) over capt/(h) over bar) in the correlation function, and this paper shows how an SC-IVR can also be used to approximate the Boltzmann operators exp(-beta(H) over cap /2). Test calculations show that over a wide temperature range little error is introduced in the rate constant by this SC approximation for the Boltzmann operator. (C) 2002 American Institute of Physics.

引用

页码：9605 / 9610

页数：6

共 39 条

[1] CLASSICAL TRAJECTORY APPROACH TO PHOTO-DISSOCIATION - THE WIGNER METHOD [J].