A Projective Method for the Calculation of Excited-State Electronic Coupling: Isolating Charge Transfer/Recombination Processes in Organic Photovoltaics
A Projective Method for the Calculation of Excited-State Electronic Coupling: Isolating Charge Transfer/Recombination Processes in Organic Photovoltaics
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DOI：
10.1021/acs.jpca.9b10167
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发表时间：
2020-01-23
影响因子：
2.9
通讯作者：
Hodgkiss, Justin M.
中科院分区：
文献类型：
--
作者：
Hume, Paul A.;Hodgkiss, Justin M.
激发态之间的电子耦合是描述光响应有机材料中发生的超快能量和电荷转移过程所需的重要参数。在这样的系统中，短程库仑，交换，重叠和配置相互作用的影响都必须考虑。尽管有许多方法可用，但任意激发态之间的耦合的评估仍然具有挑战性。在这方面的贡献，一个灵活的和可扩展的方法计算激发态之间的短程电子耦合。激发或电荷局域化状态投影到绝热状态的二聚体分子系统使用一个有效的波函数重叠算法。除了正确处理库仑，交换和重叠的贡献，包括多态相互作用是固有的程序。然后，该方法被用来解开激发能量转移，电荷转移，和电荷复合过程中的供体/受体系统相关的有机photoprophics，着眼于材料设计原则的发展。在单激发框架内进行计算，但该计划有可能扩展到多参考/高阶激发量子化学方法。
Electronic coupling between excited states is a vital parameter required to describe ultrafast energy and charge transfer processes that occur in photoresponsive organic materials. In such systems, short-range Coulombic, exchange, overlap, and configuration interaction effects must all be accounted for. Although a number of methods are available, the evaluation of coupling between arbitrary excited states remains challenging. In this contribution, a flexible and scalable method for the calculation of short-range electronic coupling between excited states is developed. Excitation- or charge-localized states are projected onto the adiabatic states of a dimeric molecular system using an efficient wave function overlap algorithm. In addition to correctly treating Coulombic, exchange, and overlap contributions, the inclusion of multistate interactions is inherent in the procedure. The method is then used to disentangle excitation energy transfer, charge transfer, and charge recombination processes in donor/acceptor systems relevant to organic photovoltaics, with a view toward the development of material design principles. Calculations were performed within single-excitation frameworks, but the scheme has the potential to be extended to multireference/higher-order excitation quantum-chemical methods.