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.
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页码：9605 / 9610
页数：6
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