光诱导质子耦合电子转移反应的准绝热动力学研究
Investigating Photoinduced Proton Coupled Electron Transfer Reaction using Quasi Diabatic Dynamics Propagation
摘要：
利用最近发展起来的准非绝热量子动力学传播方法研究了光诱导质子耦合电子转移反应。该方案能够将精确的基于非绝热的量子动力学方法与绝热电子结构计算进行实时模拟。在这里，我们使用QD方案直接传播PI-PCET量子动力学与绝热部分线性化密度矩阵（PLDM）的路径积分方法与瞬时绝热电子-质子振动态。我们的数值计算结果表明，为了获得准确的PI-PCET动力学，质子量子力学处理的重要性，以及溶剂的波动和振动弛豫的质子隧穿在各种反应制度，表现出不同的动力学同位素效应的作用。这项工作打开了可能性，研究具有挑战性的PI-PCET反应，通过准确的非绝热量子动力学方法结合有效的绝热电子结构计算。
英文摘要：
We investigate photoinduced proton-coupled electron transfer (PI-PCET) reaction through a recently devel- oped quasi-diabatic (QD) quantum dynamics propagation scheme. This scheme enables interfacing accurate diabatic-based quantum dynamics approaches with adiabatic electronic structure calculations for on-the-fly simulations. Here, we use the QD scheme to directly propagate PI-PCET quantum dynamics with the di- abatic Partial Linearized Density Matrix (PLDM) path-integral approach with the instantaneous adiabatic electron-proton vibronic states. Our numerical results demonstrate the importance of treating proton quan- tum mechanically in order to obtain accurate PI-PCET dynamics, as well as the role of solvent fluctuation and vibrational relaxation on proton tunneling in various reaction regimes that exhibit different kinetic iso- tope effects. This work opens the possibility to study the challenging PI-PCET reactions through accurate diabatic quantum dynamics approaches combined with efficient adiabatic electronic structure calculations.
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