Bissesar Shivan, van Raamsdonk Davita M E, Gibbons Dáire J, Williams René M
Molecular Photonics Group, van 't Hoff Institute for Molecular Sciences (HIMS), Universiteit van Amsterdam, Science Park 904, 1098 XH Amsterdam, The Netherlands.
Molecules. 2022 Jan 28;27(3):891. doi: 10.3390/molecules27030891.
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 Classical Marcus Theory of 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).
对于一个包含芘受体和二甲基苯胺供体的电子供体-受体体系，确定了自旋-轨道耦合的矩阵元以及电荷分离的电子耦合的构象依赖性。讨论了在自旋-轨道电荷转移系间窜越（SOCT-ISC）机制中起作用的不同动力学和能量方面。这包括使用经典的马库斯电子转移理论与初始电荷分离和电荷复合途径相关的参数。在向三重态的电荷复合中起重要作用的自旋-轨道耦合，可以通过（TD）-DFT进行探测，将后者用作理解和预测SOCT-ISC机制的工具。丙酮和4-硫代胸腺嘧啶的自旋-轨道耦合矩阵元用于基准测试。使用量子化学程序阿姆斯特丹密度泛函（ADF）进行（含时）密度泛函理论（DFT和TD-DFT）计算。
