Surface hopping molecular dynamics simulation of ultrafast methyl iodide photodissociation mapped by Coulomb explosion imaging

Fuente: arXiv
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Autores principales: Ding, Yijue, Greenman, Loren, Rolles, Daniel
Formato: Preprint
Publicado: 2024
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author Ding, Yijue
Greenman, Loren
Rolles, Daniel
author_facet Ding, Yijue
Greenman, Loren
Rolles, Daniel
contents We present a highly efficient method to directly simulate the photodissociation followed by Coulomb explosion of methyl iodide. In order to achieve statistical reliability, more than 40,000 trajectories are calculated on accurate potential energy surfaces of both the neutral molecule and the doubly charged cation. Non-adiabatic effects during photodissociation are treated using a Landau-Zener surface hopping algorithm. The simulation is performed analogous to a recent pump-probe experiment using coincident ion momentum imaging [Ziaee \textit{et al., Phys. Chem. Chem. Phys.} 2023, \textbf{25}, 9999]. At large pump-probe delays, the simulated delay-dependent kinetic energy release signals show overall good agreement with the experiment, with two major dissociation channels leading to $\text{I}(^2\text{P}_{3/2})$ and $\text{I}^*(^2\text{P}_{1/2})$ products. At short pump-probe delays, the simulated kinetic energy release shows a clear bifurcation near 12 fs, owing to non-adiabatic transitions through a conical intersection. The developed method is particularly suitable and efficient in simulating processes that highly rely on statistics or for identifying rare reaction channels.
format Preprint
id arxiv_https___arxiv_org_abs_2403_11592
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Surface hopping molecular dynamics simulation of ultrafast methyl iodide photodissociation mapped by Coulomb explosion imaging
Ding, Yijue
Greenman, Loren
Rolles, Daniel
Chemical Physics
We present a highly efficient method to directly simulate the photodissociation followed by Coulomb explosion of methyl iodide. In order to achieve statistical reliability, more than 40,000 trajectories are calculated on accurate potential energy surfaces of both the neutral molecule and the doubly charged cation. Non-adiabatic effects during photodissociation are treated using a Landau-Zener surface hopping algorithm. The simulation is performed analogous to a recent pump-probe experiment using coincident ion momentum imaging [Ziaee \textit{et al., Phys. Chem. Chem. Phys.} 2023, \textbf{25}, 9999]. At large pump-probe delays, the simulated delay-dependent kinetic energy release signals show overall good agreement with the experiment, with two major dissociation channels leading to $\text{I}(^2\text{P}_{3/2})$ and $\text{I}^*(^2\text{P}_{1/2})$ products. At short pump-probe delays, the simulated kinetic energy release shows a clear bifurcation near 12 fs, owing to non-adiabatic transitions through a conical intersection. The developed method is particularly suitable and efficient in simulating processes that highly rely on statistics or for identifying rare reaction channels.
title Surface hopping molecular dynamics simulation of ultrafast methyl iodide photodissociation mapped by Coulomb explosion imaging
topic Chemical Physics
url https://arxiv.org/abs/2403.11592