Journal Article
The Journal of Chemical Physics, vol. 98, iss. 5, pp. 4120-4127, 1993
Authors
Michael Messina, Gregory K. Schenter, Bruce C. Garrett
Abstract
We review several approximate methods for evaluating quantum mechanical partition functions with the goal of obtaining a method that is easy to implement for multidimensional systems but accurately incorporates quantum mechanical corrections to classical partition functions. A particularly promising method is one based upon an approximation to the path integral expression of the partition function. In this method, the partition-function expression has the ease of evaluation of a classical partition function, and quantum mechanical effects are included by a weight function. Anharmonicity is included exactly in the classical Boltzmann average and local quadratic expansions around the centroid of the quantum paths yield a simple analytic form for the quantum weight function. We discuss the relationship between this expression and previous approximate methods and present numerical comparisons for model one-dimensional potentials and for accurate three-dimensional vibrational force fields for H2O and SO2.
