Danilov, Don;
Jenkins, Andrew J;
Bearpark, Michael J;
Worth, Graham A;
Robb, Michael A;
(2023)
Coherent Mixing of Singlet and Triplet States in Acrolein and Ketene: A Computational Strategy for Simulating the Electron–Nuclear Dynamics of Intersystem Crossing.
The Journal of Physical Chemistry Letters
, 14
(26)
pp. 6127-6134.
10.1021/acs.jpclett.3c01187.
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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.
| Type: | Article |
|---|---|
| Title: | Coherent Mixing of Singlet and Triplet States in Acrolein and Ketene: A Computational Strategy for Simulating the Electron–Nuclear Dynamics of Intersystem Crossing |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acs.jpclett.3c01187 |
| Publisher version: | https://doi.org/10.1021/acs.jpclett.3c01187 |
| Language: | English |
| Additional information: | This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery-pp.ucl.ac.uk/id/eprint/10173120 |
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