Electron dynamics upon ionization: control of the timescale through chemical substitution and effect of nuclear motion

The Journal of Chemical Physics
Morgane VacherMichael A Robb

Abstract

Photoionization can generate a non-stationary electronic state, which leads to coupled electron-nuclear dynamics in molecules. In this article, we choose benzene cation as a prototype because vertical ionization of the neutral species leads to a Jahn-Teller degeneracy between ground and first excited states of the cation. Starting with equal populations of ground and first excited states, there is no electron dynamics in this case. However, if we add methyl substituents that break symmetry but do not radically alter the electronic structure, we see charge migration: oscillations in the spin density that we can correlate with particular localized electronic structures, with a period depending on the gap between the states initially populated. We have also investigated the effect of nuclear motion on electron dynamics using a complete active space self-consistent field (CASSCF) implementation of the Ehrenfest method, most previous theoretical studies of electron dynamics having been carried out with fixed nuclei. In toluene cation for instance, simulations where the nuclei are allowed to move show significant differences in the electron dynamics after 3 fs, compared to simulations with fixed nuclei.

References

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Citations

Nov 3, 2016·The Journal of Chemical Physics·Andrew J JenkinsMichael A Robb
Nov 13, 2015·Physical Chemistry Chemical Physics : PCCP·C C PapadopoulouC Kosmidis
Oct 11, 2016·Faraday Discussions·Morgane VacherMichael A Robb
Jan 16, 2018·Structural Dynamics·Hans Jakob WörnerOliver Wenger
Feb 25, 2021·Faraday Discussions·Siqi LiJonathan P Marangos
Mar 5, 2021·The Journal of Physical Chemistry. a·Longxing ZhouHaifeng Xu
Apr 10, 2021·The Journal of Chemical Physics·Thomas Schnappinger, Regina de Vivie-Riedle
Nov 18, 2015·Journal of Chemical Theory and Computation·Jan MeisnerMichael A Robb
Dec 16, 2016·The Journal of Physical Chemistry Letters·Jiali GaoPeng Bao
Dec 30, 2016·The Journal of Physical Chemistry. a·Sankhabrata Chandra, Atanu Bhattacharya
Aug 27, 2021·The Journal of Physical Chemistry Letters·Isabella C D MerrittMorgane Vacher

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