Semiclassical Calculation of Chemical Reaction Dynamics via Wavepacket Correlation Functions

Abstract

Calculation of chemical reaction dynamics is central to theoretical chemistry. The majority of calculations use either classical mechanics, which is computationally inexpensive but misses quantum effects, such as tunneling and interference, or quantum mechanics, which is computationally expensive and often conceptually opaque. An appealing middle ground is the use of semiclassical mechanics. Indeed, since the early 1970s there has been great interest in using semiclassical methods to calculate reaction probabilities. However, despite the elegance of classical S-matrix theory, numerical results on even the simplest reactive systems remained out of reach. Recently, with advances both in correlation function formulations of reactive scattering as well as in semiclassical methods, it has become possible for the first time to calculate reaction probabilities semiclassically. The correlation function methods are contrasted with recent flux-based methods, which, although providing somewhat more compact expressions for the cumulative reactive probability, are less compatible with semiclassical implementation.