Computing expectation values for molecular quantum dynamics

摘要

We compute expectation values for the solution of the nuclear Schr?dinger equation. The proposed particle method consists of three steps: sampling of the initial Wigner function, classical transport of the sampling points, and weighted phase space summation for the final computation of the expectation values. The Egorov theorem guarantees that the algorithm is second order accurate with respect to the semiclassical parameter. We present numerical experiments for a two-dimensional torsional potential with three different sets of initial data and for a six-dimensional Henon-Heiles potential. By construction, the computing times scale linearly with the number of initial sampling points and range between three seconds and one hour.