Ab-Initio Surface Hopping and Multiphoton Ionisation Study of the Photodissociation Dynamics of CS$_2$

TL;DR

This study combines ab-initio surface hopping simulations with experimental multiphoton ionisation spectroscopy to investigate the early-time photodissociation dynamics of CS₂, emphasizing the role of triplet states.

Contribution

It introduces new computational simulations including spin-orbit coupling and correlates them with experimental data to elucidate the dissociation process of CS₂.

Findings

Triplet states significantly influence early dissociation dynamics.

Simulations successfully reproduce experimental spectral signatures.

Electronic and nuclear degrees of freedom are linked to observed spectral changes.

Abstract

New ab-initio surface hopping simulations of the excited state dynamics of CS$_2$ including spin-orbit coupling are compared to new experimental measurements using a multiphoton ionisation probe in a photoelectron spectroscopy experiment. The calculations highlight the importance of the triplet states even in the very early time dynamics of the dissociation process and allow us to unravel the signatures in the experimental spectrum, linking the observed changes to both electronic and nuclear degrees of freedom within the molecule.