Ultrafast photodissociation dynamics of dichloromethane on three-dimensional potential energy surfaces and its Coulomb explosion signature

TL;DR

This study uses advanced molecular dynamics simulations to explore the ultrafast photodissociation of dichloromethane and its Coulomb explosion signatures, providing insights into reaction pathways and imaging techniques.

Contribution

It introduces a reliable simulation approach combining potential energy surfaces and Coulomb explosion modeling to analyze photodissociation dynamics.

Findings

Intra-molecular photoisomerization of dichloromethane is unlikely.

Discrepancy of 5-8 eV in kinetic energy release estimates.

Coulomb explosion imaging effectively maps structural changes.

Abstract

We present efficient and reliable molecular dynamics simulations of the photodissociation of dichloromethane followed by Coulomb explosion. These simulations are performed by calculating trajectories on accurate potential energy surfaces of the low-lying excited states of the neutral dichloromethane molecule. The subsequent time-resolved Coulomb explosions are simulated on the triply charged ionic state, assuming Coulomb interactions between ionic fragments. Both the neutral state trajectories and the simulated Coulomb explosion observables indicate that intra-molecular photoisomerization of dichloromethane is unlikely to occur. Estimating the kinetic energy release using \textit{ab initio} ionic potential reveals a discrepancy of approximately 5-8 eV compared to our simulated values using Coulomb potential. The molecular structural changes during photodissociation are clearly mapped to the ionic-fragment coincidence signals, demonstrating the Coulomb explosion imaging technique as a powerful tool to probe the time-resolved reaction dynamics.