真空和溶液中光生电子转移反应的雷德场传播,Journal of Chemical Theory and Computation

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真空和溶液中光生电子转移反应的雷德场传播
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2022-11-22 , DOI: 10.1021/acs.jctc.2c00538
Jacob Pedersen ₁ , Maria H Rasmussen ₁ , Kurt V Mikkelsen ₁

Affiliation

超快电子转移反应的动力学模拟最受关注。为了允许能量直接耗散到外部周围环境中，已经推导、实施并利用溶剂耦合模型来描述本文模型三元组系统内的光致电子转移动力学。该模型基于雷德菲尔德理论，环境由充满玻色子量子的谐振子表示。为了模仿真实的溶剂，振荡器配备了相应溶剂的频率和极化寿命特征。发现无论介质如何，人口都通过能量最低的电子转移途径转移。观察到凝聚的人口转移动力学高度依赖于溶剂参数。尤其是，溶剂偶联的增加导致人口从最初准备好的非绝热状态转移的滞留和通过其他电子转移途径促进人口转移。已经提供了分别基于 Kohn-Sham Fock 矩阵的对角线和非对角线矩阵元素的两种解释。填充的部分电荷分离状态的寿命随着溶剂极性的增加而延长，这可以用溶剂的偶极矩和碎片电荷之间的吸引相互作用来解释。相关函数中的高频振动精细结构被证明对传递动力学很重要，极性溶剂中相移效应的重要性得到验证并精确到与溶剂的光偏振有关。

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Redfield Propagation of Photoinduced Electron Transfer Reactions in Vacuum and Solution

Dynamical simulations of ultrafast electron transfer reactions are of utmost interest. To allow for energy dissipation directly into an external surrounding environment, a solvent coupling model has been deduced, implemented, and utilized to describe the photoinduced electron transfer dynamics within a model triad system herein. The model is based on Redfield theory, and the environment is represented by harmonic oscillators filled with bosonic quanta. To imitate real solvents, the oscillators have been equipped with frequencies and polarization lifetimes characteristic of the corresponding solvent. The population was found to transfer through the energetically lowest electron transfer route regardless of the medium. The condensed population transfer dynamics were observed to be highly dependent on the solvent parameters. In particular, an increase in the solvent coupling entailed a detainment in the population transfer from the initially prepared diabatic state and a promotion in the population transfer through the other electron transfer route. Two explanations based on the diagonal and off-diagonal matrix elements of the Kohn–Sham Fock matrix, respectively, have been provided. The lifetime of the populated partially charge-separated state was prolonged with increasing solvent polarity, and it was explained in terms of attractive interactions between the solvent’s dipole moments and the fragments’ charges. The high-frequency vibrational fine-structure in the correlation function was demonstrated to be important for the transfer dynamics, and the importance of dephasing effects in polar solvents was verified and precised to concern the optical polarization of the solvents.

更新日期：2022-11-22

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