Quantum-classical Dynamics of Vibration-Induced Autoionization in Molecules

TL;DR

This paper introduces a new quantum-classical simulation method for vibration-induced autoionization in molecules, providing detailed insights into the dynamics, electron distributions, and structural changes during autoionization.

Contribution

The paper develops a novel quantum-classical surface hopping approach with a discretization scheme for continuum states, enabling detailed autoionization simulations.

Findings

Autoionization occurs on specific time scales.

Electron ejection shows characteristic energetic and angular distributions.

Autoionization influences molecular geometry and promotes isomerization.

Abstract

We present a novel method for the simulation of the vibration-induced autoionization dynamics in molecular anions in the framework of the quantum-classical surface hopping approach. Classical trajectories starting from quantum initial conditions are propagated on a quantum-mechanical potential energy surface while allowing for autoionization through transitions into discretized continuum states. These transitions are induced by the couplings between the electronic states of the bound anionic system and the electron-detached system composed of the neutral molecule and the free electron. A discretization scheme for the detached system is introduced and a set of formulae is derived which enables the approximate calculation of couplings between the bound and free-electron states. We demonstrate our method on the example of the anion of vinylidene, a high-energy isomer of acetylene, for which detailed experimental data is available. Our results provide information on the time scale of the autoionization process and give an insight into the energetic and angular distribution of the ejected electrons as well as into the associated changes of the molecular geometry. We identify the formation of structures with reduced C-C bond lengths and T-like conformations through bending of the CH$_2$ group with respect to the C-C axis and point out the role of autoionization as a driving process for the isomerization to acetylene.