Controlling electronic coherences and the curvature induced by the derivative coupling at a conical intersection: a Quantum Ehrenfest (QuEh) protocol for reaction path following application to "channel 3" benzene photochemistry
Author(s)
Worth, Graham A
Robb, Michael A
Type
Journal Article
Abstract
We report a protocol for the implementation of “reaction path following” from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the “central” Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum. The protocol is applied to the “channel 3” radiationless decay of benzene. We also demonstrate that one can enhance the effect of the derivative coupling and the electronic coherence with an IR pulse.
Date Issued
2024-07-11
Date Acceptance
2024-06-12
Citation
The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory, 2024, 128 (27), pp.5408-5415
ISSN
1089-5639
Publisher
American Chemical Society
Start Page
5408
End Page
5415
Journal / Book Title
The Journal of Physical Chemistry A: Isolated Molecules, Clusters, Radicals, and Ions; Environmental Chemistry, Geochemistry, and Astrochemistry; Theory
Volume
128
Issue
27
Copyright Statement
© 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0 .
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/38917388
Subjects
Chemistry
Chemistry, Physical
MC-SCF
NONADIABATIC DYNAMICS
Physical Sciences
Physics
Physics, Atomic, Molecular & Chemical
Science & Technology
Publication Status
Published
Coverage Spatial
United States
Date Publish Online
2024-06-25