Validating potential energy surfaces for classical trajectory calculations

Abstract

Two possible methods for probing flaws in empirical potential energy surfaces are examined, using a simple unimolecular isomerisation as an example. One is a heuristic estimate of the degree of chaos in a vibrating molecule; the other is the energy distribution profiles at the instant of reaction. It is found that deliberate increases in the degree of computational chaos do not alter the ensemble average of intrinsic vibrational chaos in these trajectories.