Direct Nonadiabatic Simulations of the Photoinduced Charge Transfer Dynamics
Direct Nonadiabatic Simulations of the Photoinduced Charge Transfer Dynamics
复制标题
光生电荷转移动力学的直接非绝热模拟
DOI：
10.1021/acs.jpca.0c10151
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发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Huo, Pengfei
中科院分区：
文献类型：
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作者：
Yamijala, Sharma S.;Huo, Pengfei
我们采用直接非绝热动力学模拟研究光诱导电荷转移反应。我们的方法是基于混合量子-经典最少开关表面跳跃（FSSH）方法，通过含时密度泛函理论和经典的核处理转移电子。光诱导激发态被建模为最初占据供体分子/部分的LUMO的转移单电子。这个单粒子电子波函数然后通过在整个系统的瞬时分子轨道（MO）的基础上求解含时薛定谔方程来量子力学地传播。在经典路径近似下，采用FSSH方法模拟了电子态之间的非绝热跃迁。我们应用这种方法来模拟光诱导的电荷转移动力学在几个良好表征的分子系统。我们的结果与实验测量和高水平（但昂贵）的理论结果非常一致。
We apply direct nonadiabatic dynamics simulations to investigate photoinduced charge transfer reactions. Our approach is based on the mixed quantum-classical fewest switches surface hopping (FSSH) method that treats the transferring electron through time-dependent density functional theory and the nuclei classically. The photoinduced excited state is modeled as a transferring single-electron that initially occupies the LUMO of the donor molecule/moiety. This single-particle electronic wave function is then propagated quantum mechanically by solving the time-dependent Schrödinger equation in the basis of the instantaneous molecular orbitals (MOs) of the entire system. The nonadiabatic transitions among electronic states are modeled using the FSSH approach within the classical-path approximation. We apply this approach to simulate the photoinduced charge transfer dynamics in a few well-characterized molecular systems. Our results are in excellent agreement with both the experimental measurements and high-level (yet expensive) theoretical results.