Quantum–classical dynamics of vibration-induced autoionization in molecules

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 formulas is derived that enable 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 are available. Our results provide information on the time scale of the autoionization process and give insight into the energetic and angular distribution of the ejected electrons, as well as the associated changes in the molecular geometry. We identify the formation of structures with reduced C–C bond lengths and T-like conformations through bending of the CH2 group with respect to the C–C axis and point out the role of autoionization as a driving process for the isomerization to acetylene.