Time-dependent generalized-active-space configuration-interaction approach to photoionization dynamics of atoms and molecules

TL;DR

This paper introduces a wave-function based time-dependent CI method with generalized-active-space restrictions to efficiently simulate strong-field ionization in atoms and molecules, revealing correlation effects on photoelectron emission.

Contribution

The paper develops a novel TD-GASCI approach combining CI with GAS restrictions, enabling controllable electron correlation modeling in strong-field dynamics.

Findings

Uncovered correlation-induced shift in photoelectron emission direction.

Demonstrated convergence of the method with respect to active space size.

Applied the method successfully to polar diatomic molecules.

Abstract

We present a wave-function based method to solve the time-dependent many-electron Schr\"odinger equation (TDSE) with special emphasis on strong-field ionization phenomena. The theory builds on the configuration-interaction (CI) approach supplemented by the generalized-active-space (GAS) concept from quantum chemistry. The latter allows for a controllable reduction in the number of configurations in the CI expansion by imposing restrictions on the active orbital space. The method is similar to the recently formulated time-dependent restricted-active-space (TD-RAS) CI method [D. Hochstuhl, and M. Bonitz, Phys. Rev. A 86, 053424 (2012)]. We present details of our implementation and address convergence properties with respect to the active spaces and the associated account of electron correlation in both ground state and excitation scenarios. We apply the TD-GASCI theory to strong-field ionization of polar diatomic molecules and illustrate how the method allows us to uncover a strong correlation-induced shift of the preferred direction of emission of photoelectrons.