Strong-Field Molecular Ionization Beyond The Single Active Electron Approximation

TL;DR

This study investigates the limits of the Single-Active Electron approximation in strong-field ionization of dihydrogen, using a multi-configuration approach to reveal complex ionization behaviors influenced by electron interactions and molecular elongation.

Contribution

It introduces a time-dependent multi-configuration method to analyze multi-electron effects beyond SAE in strong-field molecular ionization.

Findings

Ionization probability shows non-monotonous behavior at intermediate elongations.

Enhanced ionization and quenching phenomena are observed.

Resonance-Enhanced-Multiphoton Ionization explains the interference effects.

Abstract

The present work explores quantitative limits to the Single-Active Electron (SAE) approximation, often used to deal with strong-field ionization and subsequent attosecond dynamics. Using a time-dependent multi\-configuration approach, specifically a Time-Dependent Configuration Interaction (TDCI) method, we solve the time-dependent Schr{\"o}dinger equation (TDSE) for the two-electron dihydrogen molecule, with the possibility of tuning at will the electron-electron interaction by an adiabatic switch-on/switch-off function. We focus on signals of the single ionization of $H_2$ under a strong near-infrared (NIR) four-cycle, linearly-polarized laser pulse of varying intensity, and within a vibrationally frozen molecule model. The observables we address are post-pulse total ionization probability profiles as a function of the laser peak intensity. Three values of the internuclear distance R taken as a parameter are considered, R = R$_{eq}$ = 1.4 a.u, the equilibrium geometry of the molecule, R = 5.0 a.u for an elongated molecule and R = 10.2 a.u for a dissociating molecule. The most striking observation is the non-monotonous behavior of the ionization probability profiles at intermediate elongation distances with an instance of enhanced ionization and one of partial ionization quenching. We give an interpretation of this in terms of a Resonance-Enhanced-Multiphoton Ionization (REMPI) mechanism with interfering overlapping resonances resulting from excited electronic states.