Hu Zhubin, Sun Xiang
Division of Arts and Sciences, New York University Shanghai, 1555 Century Avenue, Shanghai 200122, China.
NYU-ECNU Center for Computational Chemistry, New York University Shanghai, 3663 Zhongshan Road North, Shanghai 200062, China.
J Chem Theory Comput. 2022 Oct 11;18(10):5819-5836. doi: 10.1021/acs.jctc.2c00631. Epub 2022 Sep 8.
Direct all-atom simulation of nonadiabatic dynamics in disordered condensed phases like liquid solutions and amorphous solids has been challenging. The first all-atom simulation of the photoinduced charge-transfer dynamics of a prototypical organic photovoltaic carotenoid-porphyrin-C molecular triad in explicit tetrahydrofuran is presented. Based on the Meyer-Miller mapping Hamiltonian, various semiclassical and mixed quantum-classical dynamics are employed, including the linearized semiclassical, symmetrical quasiclassical, mean-field Ehrenfest, classical mapping model, and spin-mapping model approaches. The all-atom nonadiabatic dynamics were compared to multi-state harmonic models with a globally shared bath, and the models built using the ensemble averages on the initial electronic state could reproduce the all-atom results. The solvent effect was found to be critical for the photoinduced charge transfer, and the time-dependent solute-solvent radial distribution functions revealed that only the nonadiabatic dynamics started with the effective forces on the initial electronic state could capture the correct nuclear dynamics. The proposed strategy for modeling condensed-phase nonadiabatic dynamics with atomistic details is readily applied to complex condensed-phase systems.
对诸如液体溶液和非晶态固体等无序凝聚相中的非绝热动力学进行直接全原子模拟一直具有挑战性。本文展示了在显式四氢呋喃中对典型有机光伏类胡萝卜素 - 卟啉 - C分子三联体的光诱导电荷转移动力学进行的首次全原子模拟。基于迈耶 - 米勒映射哈密顿量，采用了各种半经典和混合量子 - 经典动力学方法，包括线性化半经典、对称准经典、平均场埃伦费斯特、经典映射模型和自旋映射模型方法。将全原子非绝热动力学与具有全局共享浴的多态谐波模型进行了比较，并且使用初始电子态上的系综平均值构建的模型能够重现全原子结果。发现溶剂效应对于光诱导电荷转移至关重要，并且随时间变化的溶质 - 溶剂径向分布函数表明，只有以初始电子态上的有效力开始的非绝热动力学才能捕捉到正确的核动力学。所提出的用于对具有原子细节的凝聚相非绝热动力学进行建模的策略可轻松应用于复杂的凝聚相系统。
