Solvated Nuclear–Electronic Orbital Structure and Dynamics
Solvated Nuclear–Electronic Orbital Structure and Dynamics
复制标题
溶剂化核电子轨道结构和动力学
DOI：
10.1021/acs.jctc.1c01285
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发表时间：
2022
影响因子：
5.5
通讯作者：
Li, Xiaosong
中科院分区：
文献类型：
--
作者：
Wildman, Andrew;Tao, Zhen;Zhao, Luning;Hammes-Schiffer, Sharon;Li, Xiaosong
非绝热动力学过程，如质子耦合电子转移和激发态分子内质子转移已成为许多研究的主题。描述这些过程的一种有希望的理论方法是核电子轨道方法。这一方法本身就考虑到了量子化学计算中的核量子效应，最近随着实时近地天体方法的发展，这一方法已扩展到直接模拟非绝热过程。然而，这些过程也可能显著依赖于周围的化学环境，并且捕获环境的影响对于分析实验相关系统通常是必要的。本工作将NEO密度泛函理论和实时含时密度泛函理论方法通过可极化连续介质模型与溶剂化作用相结合。这种耦合的影响进行了研究的基态性质，溶剂依赖的振动频率，和直接激发态分子内质子转移动力学。
Nonadiabatic dynamical processes such as proton-coupled electron transfer and excited state intramolecular proton transfer have been the subject of much research. One of the promising theoretical methods to describe these processes is the nuclear–electronic orbital (NEO) approach. This approach inherently accounts for nuclear quantum effects within quantum chemistry calculations, and it has recently been extended to directly simulate nonadiabatic processes with the development of real-time NEO methods. These processes can also be significantly dependent on the surrounding chemical environment, however, and capturing the effects of the environment is often necessary for analyzing experimentally relevant systems. This work couples the NEO density functional theory and real-time time-dependent density functional theory approaches with solvation through the polarizable continuum model. The effects of this coupling are investigated for ground state properties, solvent-dependent vibrational frequencies, and direct excited state intramolecular proton transfer dynamics.