Electronic energy levels with the help of trajectory-guided random grid of coupled wave packets. I. Six-dimensional simulation of H2

Abstract

As a preliminary to future work on the behavior of atoms and molecules in strong time-dependent fields, we apply the coupled coherent-states (CCS) technique of multidimensional phase-space quantum dynamics to obtain Born-Oppenheimer energy levels of electrons in molecules. Unlike traditional approaches based on atomic and molecular-orbital basis sets and time-independent Schrodinger equation the CCS method exploits the solution of the time-dependent Schrodinger equation in the basis of Monte Carlo-selected trajectory-guided coherent states, which treat classical electron correlations exactly. In addition the CCS trajectories move over averaged potentials, which remove the Coulombic singularities.