: Received: 3 December 2021 / Approved: 7 December 2021 / Online: 7 December 2021 (16:52:33 CET)
: Received: 14 December 2021 / Approved: 16 December 2021 / Online: 16 December 2021 (14:21:43 CET)
Bissesar, S.; Raamsdonk, D.M.E.; Gibbons, D.J.; Williams, R.M. Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline. Molecules2022, 27, 891.
Bissesar, S.; Raamsdonk, D.M.E.; Gibbons, D.J.; Williams, R.M. Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline. Molecules 2022, 27, 891.
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).
photoinduced electron transfer; triplet state formation; charge recombination; charge separation; intersystem crossing; SOCT-ISC; SOCME; electronic coupling
CHEMISTRY, Physical Chemistry
This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.