Optimization of a distributed Gaussian basis set using simulated annealing: Application to the adiabatic dynamics of the solvated electron

Abstract

A molecular dynamics technique is introduced for the simulation of the adiabatic dynamics of an excess electron coupled to a classical many-body system. The instantaneous ground state wave function of the electron is represented by a superposition of distributed Gaussian basis functions, each with equal amplitude. We present generalized equations of motion for the coupled system, which optimize the positions and widths of the Gaussians by simulated annealing. The condition of equal amplitude ensures the aggregation of the Gaussians in regions of finite electron probability density and hence yields a particularly efficient representation of localized ground states. The method is applied to an electron solvated in liquid ammonia and results for equilibrium properties are compared to quantum path integral calculations. New results for the dynamics are discussed in the light of mobility measurements.