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Ultrafast photoinduced dynamics of 1,3-Cyclohexadiene using XMS-CASPT2 surface hopping

Polyak, Iakov ORCID:, Hutton, Lewis, Crespo-Otero, Rachel, Barbatti, Mario and Knowles, Peter J. ORCID: 2019. Ultrafast photoinduced dynamics of 1,3-Cyclohexadiene using XMS-CASPT2 surface hopping. Journal of Chemical Theory and Computation 15 (7) , pp. 3929-3940. 10.1021/acs.jctc.9b00396

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A full-dimensional simulation of the photodissociation of 1,3-cyclohexadiene in the manifold of three electronic states was performed via nonadiabatic surface hopping dynamics using extended multistate complete active space second-order perturbation (XMS-CASPT2) electronic structure theory with fully analytic nonadiabatic couplings. With the 47 ± 8% product quantum yield calculated from the 136 trajectories, generally 400 fs-long, and an estimated excited lifetime of 89 ± 9 fs, our calculations provide a detailed description of the nonadiabatic deactivation mechanism, showing the existence of an extended conical intersection seam along the reaction coordinate. The nature of the preferred reaction pathways on the ground state is discussed and extensive comparison to the previously published full dimensional dynamics calculations is provided.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Advanced Research Computing @ Cardiff (ARCCA)
Publisher: American Chemical Society
ISSN: 1549-9618
Funders: European Regional Development Fund (ERDF) via Welsh Government
Date of First Compliant Deposit: 19 June 2019
Date of Acceptance: 5 June 2019
Last Modified: 09 Nov 2022 10:49

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