Tracking the Ultraviolet Photochemistry of Thiophenone During and Beyond the Initial Ultrafast Ring Opening

TL;DR

This study combines advanced spectroscopy and theoretical calculations to elucidate the ultrafast electronic and nuclear dynamics of thiophenone's ring-opening reaction, revealing detailed mechanisms and subsequent isomerization and fragmentation processes.

Contribution

It provides the first detailed experimental and theoretical insights into the femtosecond-scale ring opening and subsequent dynamics of thiophenone molecules.

Findings

Ring opening complete within 350 fs

Visualization of isomer formation and interconversion

Observation of long-timescale fragmentation (CO loss)

Abstract

Photoinduced isomerization reactions, including ring-opening reactions, lie at the heart of many processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics unfolding on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free electron laser to trace the ultrafast ring opening of gas phase thiophenone molecules following photoexcitation at 265 nm. When combined with cutting edge ab initio electronic structure and molecular dynamics calculations of both the excited and ground state molecules, the results provide unprecedented insights into both electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state is shown to be driven by ballistic SC bond extension and to be complete within 350 femtoseconds. Theory and experiment also allow clear visualization of the rich ground-state dynamics involving formation of, and interconversion between, several ring opened isomers and the reformed cyclic structure, and fragmentation (CO loss) over much longer timescales.