A semiclassical model to incorporate （将半古典的模型）.pdfVIP

Volume 205, number 1 CHEMICAL PHYSICS LETfERS 2 April 1993 A semiclassical model to incorporate multidimensional tunneling in classical trajectory simulations using locally conserved actions Shari Keshavamurthy and William H. Miller Department of Chemistry, University of California, Berkeley, C4 94720, USA and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, CA 94720, USA Received 17December 1992 Earlier work, within the context of transition state theory, has shown that tunneling through the saddle point region of a poten- tial energy surface can be characterized by locally conserved action variables associated with the saddle point (transition state). The present Letter shows how this idea can be combined with classical trajectory simulation methods and thus allow tunneling effects to be incorporated into a much wider class of dynamical processes. Application of this approach to a two-dimensional model unimolecular decay potential gives good results over a wide range of system parameters. 1. Introduction from one isomeric form of a molecular system to an- other) - thus the interest in semiclassical extensions This Letter is a contribution towards our goal of of classical mechanics that allow one to describe such developing simpZesemiclassical models and approx- phenomena. imations for incorporating tunneling effects into There already exist “rigorous” semiclassical the- classical trajectory methods for simulating dynami- ories which descri