Coherent mixing of singlet and triplet states in acrolein and ketene: a computational strategy for simulating the electron-nuclear dynamics of intersystem crossing.
File(s)
Published version
Author(s)
Danilov, Don
Jenkins, Andrew J
Bearpark, Michael J
Worth, Graham A
Robb, Michael A
Type
Journal Article
Abstract
We present a theoretical study of intersystem crossing (ISC) in acrolein and ketene with the Ehrenfest method that can describe a superposition of singlet and triplet states. Our simulations illustrate a new mechanistic effect of ISC, namely, that a superposition of singlets and triplets yields nonadiabatic dynamics characteristic of that superposition rather than the constituent state potential energy surfaces. This effect is particularly significant in ketene, where mixing of singlet and triplet states along the approach to a singlet/singlet conical intersection occurs, with the spin-orbit coupling (SOC) remaining small throughout. In both cases, the effects require many recrossings of the singlet/triplet state crossing seam, consistent with the textbook treatment of ISC.
Date Issued
2023-06-26
Date Acceptance
2023-06-23
Citation
Journal of Physical Chemistry Letters, 2023, 14 (26), pp.6127-6134
ISSN
1948-7185
Publisher
American Chemical Society
Start Page
6127
End Page
6134
Journal / Book Title
Journal of Physical Chemistry Letters
Volume
14
Issue
26
Copyright Statement
Copyright © 2023 The Authors. Published by American Chemical Society. This work is published under a CC BY licence.
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/37364275
Publication Status
Published online
Coverage Spatial
United States
Date Publish Online
2023-06-26