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Lookup NU author(s): Dr Julien EngORCiD, Professor Thomas Penfold
This work is licensed under a Creative Commons Attribution 4.0 International License (CC BY 4.0).
The intersystem crossing (ISC) mechanism of a cyclic (alkyl)(amino) carbene gold (I) complex (CMA1) is studied using quantum dynamics. A model spin-vibronic Hamiltonian is developed, which includes 10 excited states and two important nuclear degrees of freedom. The quantum dynamics reveals that ISC from S1 → T1 occurs on the tens of picosecond time scale, consistent with recent experiments. It is driven by motion along the torsional degree of freedom of the carbazole (Cz) ligand, which causes orthogonality between the donor and acceptor groups closing the gap between the initial (S1) and final (T1) states. The role of higher triplet states through spin-vibronic interactions is also discussed. Although previous calculations, evaluated in the Condon approximation, yield large ISC rates, our present dynamical treatment, taking into account the large amplitude torsional motion, increases the calculated rate by an order of magnitude improving the agreement with experiments. The model spin-vibronic Hamiltonian developed can also be used to understand the properties of related linear metal carbene compounds, facilitating molecular design.
Author(s): Thompson S, Eng J, Penfold TJ
Publication type: Article
Publication status: Published
Journal: Journal of Chemical Physics
Year: 2018
Volume: 149
Print publication date: 01/06/2018
Online publication date: 02/07/2018
Acceptance date: 01/06/2018
Date deposited: 09/07/2018
ISSN (print): 0021-9606
ISSN (electronic): 1089-7690
Publisher: AIP Publishing LLC
URL: https://doi.org/10.1063/1.5032185
DOI: 10.1063/1.5032185
Data Access Statement: http://dx.doi.org/10.17634/162036-1
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