The Quantum-Ehrenfest method with the inclusion of an IR pulse: Application to electron dynamics of the allene radical cation
File(s)JCP20-CM-02077.pdf (1.8 MB)
Accepted version
Author(s)
Tran, thierry
Jenkins, andrew
Worth, Graham A
Robb, Michael
Type
Journal Article
Abstract
We describe the implementation of a laser control pulse in the Quantum-Ehrenfest method, a molecular quantum dynamics method that solves the time-dependent Schrödinger equation for both electrons and nuclei. The oscillating electric fielddipole interaction is incorporated directly in the one-electron Hamiltonian of the electronic structure part of the algorithm. We then use the coupled electron-nuclear dynamics of the π-system in allene radical cation (•CH2=C=CH2)+ as a simple model of a pump-control experiment. We start (pump) with a two-state superposition of two cationic states. The resulting electron dynamics corresponds to the rapid oscillation of the unpaired electron between the two terminal methlylenes. This electron dynamics is in turn coupled to the torsional motion of the terminal methylenes. There is a conical intersection at 90° twist where the electron dynamics collapses because the adiabatic states become degenerate. After passing the conical intersection the electron dynamics revives. The IR pulse (control) in our simulations is timed to have its maximum at the conical intersection. Our simulations show that the effect of the (control) pulse is to change the electron dynamics at the conical intersection and, as a consequence, the concomitant nuclear dynamics which is dominated by change of the torsional angle.
Date Issued
2020-07-21
Date Acceptance
2020-06-25
Citation
Journal of Chemical Physics, 2020, 153 (3)
ISSN
0021-9606
Publisher
AIP Publishing
Journal / Book Title
Journal of Chemical Physics
Volume
153
Issue
3
Copyright Statement
© 2020 Author(s). Published under license by AIP Publishing. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in J. Chem. Phys. 153, 031102 (2020); and may be found at https://doi.org/10.1063/5.0015937
Sponsor
Engineering & Physical Science Research Council (EPSRC)
Grant Number
EP/T006943/1
Subjects
Chemical Physics
02 Physical Sciences
03 Chemical Sciences
09 Engineering
Publication Status
Published
Article Number
031102
Date Publish Online
2020-07-15