Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline

Version 1 : Received: 3 December 2021 / Approved: 7 December 2021 / Online: 7 December 2021 (16:52:33 CET)
Version 2 : Received: 14 December 2021 / Approved: 16 December 2021 / Online: 16 December 2021 (14:21:43 CET)

How to cite: Bissesar, S.; Raamsdonk, D.M.E.V.; Gibbons, D.J.; Williams, R.M. Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline. Preprints 2021, 2021120109 (doi: 10.20944/preprints202112.0109.v1). Bissesar, S.; Raamsdonk, D.M.E.V.; Gibbons, D.J.; Williams, R.M. Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline. Preprints 2021, 2021120109 (doi: 10.20944/preprints202112.0109.v1).

Abstract

The conformational dependence of the matrix element for spin-orbit coupling and of the electronic coupling for charge separation are determined for an electron donor-acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the (Semi-Classical) Marcus Theory for electron transfer. The spin-orbit coupling, which plays a significant role in charge recombination to the triplet state can be probed by (TD-)DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin-orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

Keywords

photoinduced electron transfer; triplet state formation; charge recombination; charge separation; intersystem crossing; SOCT-ISC; SOCME; electronic coupling

Subject

CHEMISTRY, Physical Chemistry

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