Thompson Lee M, Kempfer-Robertson Emily M, Saha Saptarshi, Parmar Saurav, Kozlowski Pawel M
Department of Chemistry, University of Louisville, Louisville, Kentucky 40929, United States.
J Chem Theory Comput. 2023 Nov 14;19(21):7685-7694. doi: 10.1021/acs.jctc.3c00898. Epub 2023 Oct 20.
In this study, the use of self-consistent field quasi-diabats is investigated for calculation of triplet energy transfer diabatic coupling elements. It is proposed that self-consistent field quasi-diabats are particularly useful for studying energy transfer (EnT) processes because orbital relaxation in response to changes in electron configuration is implicitly built into the model. The conceptual model that is developed allows for the simultaneous evaluation of direct and charge-transfer mechanisms to establish the importance of the different possible EnT mechanisms. The method's performance is evaluated using two model systems: the ethylene dimer and ethylene with the methaniminium cation. While states that mediate the charge-transfer mechanism were found to be higher in energy than the states involved in the direct mechanism, the coupling elements that control the kinetics were found to be significantly larger in the charge-transfer mechanism. Subsequently, we discuss the advantage of the approach in the context of practical difficulties with the use of established approaches.
在本研究中，对使用自洽场准绝热态来计算三重态能量转移非绝热耦合元素进行了研究。有人提出，自洽场准绝热态对于研究能量转移（EnT）过程特别有用，因为该模型隐含地考虑了电子构型变化所引起的轨道弛豫。所建立的概念模型允许同时评估直接机制和电荷转移机制，以确定不同可能的EnT机制的重要性。使用两个模型系统对该方法的性能进行了评估：乙烯二聚体和带有甲亚胺阳离子的乙烯。虽然发现介导电荷转移机制的态能量高于直接机制所涉及的态，但发现控制动力学的耦合元素在电荷转移机制中要大得多。随后，我们在使用既定方法存在实际困难的背景下讨论了该方法的优势。
