Non-adiabatic quantum molecular dynamics: Ionization of many electron systems

Abstract We propose a novel method to describe realistically ionization processes with absorbing boundary conditions in basis expansion within the formalism of the so-called Non-Adiabatic Quantum Molecular Dynamics. This theory couples self-consistently a classical description of the nuclei with a quantum mechanical treatment of the electrons in atomic many-body systems. In this paper we extend the formalism by introducing absorbing boundary conditions via an imaginary potential. It is shown how this potential can be constructed in time-dependent density functional theory in basis expansion. The approach is first tested on the hydrogen atom and the pre-aligned hydrogen molecular ion H+2 in intense laser fields where reference calculations are available. It is then applied to study the ionization of non-aligned H+2 and H2. Striking differences in the orientation dependence between both molecules are found. Surprisingly, enhanced ionization is predicted for perpendicularly aligned molecules.