論文

査読有り
2006年2月

Path-integral virial estimator for reaction-rate calculation based on the quantum instanton approximation

JOURNAL OF CHEMICAL PHYSICS
  • S Yang
  • ,
  • T Yamamoto
  • ,
  • WH Miller

124
8
記述言語
英語
掲載種別
研究論文(学術雑誌)
DOI
10.1063/1.2171693
出版者・発行元
AMER INST PHYSICS

The quantum instanton approximation is a type of quantum transition-state theory that calculates the chemical reaction rate using the reactive flux correlation function and its low-order derivatives at time zero. Here we present several path-integral estimators for the latter quantities, which characterize the initial decay profile of the flux correlation function. As with the internal energy or heat-capacity calculation, different estimators yield different variances (and therefore different convergence properties) in a Monte Carlo calculation. Here we obtain a virial (-type) estimator by using a coordinate scaling procedure rather than integration by parts, which allows more computational benefits. We also consider two different methods for treating the flux operator, i.e., local-path and global-path approaches, in which the latter achieves a smaller variance at the cost of using second-order potential derivatives. Numerical tests are performed for a one-dimensional Eckart barrier and a model proton transfer reaction in a polar solvent, which illustrates the reduced variance of the virial estimator over the corresponding thermodynamic estimator.

リンク情報
DOI
https://doi.org/10.1063/1.2171693
Web of Science
https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=JSTA_CEL&SrcApp=J_Gate_JST&DestLinkType=FullRecord&KeyUT=WOS:000235663300009&DestApp=WOS_CPL
ID情報
  • DOI : 10.1063/1.2171693
  • ISSN : 0021-9606
  • eISSN : 1089-7690
  • Web of Science ID : WOS:000235663300009

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