Real-Time Time-Dependent Nuclear−Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation
Real-Time Time-Dependent Nuclear−Electronic Orbital Approach: Dynamics beyond the Born–Oppenheimer Approximation
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实时瞬态核电子轨道方法：超越玻恩奥本海默近似的动力学
DOI：
10.1021/acs.jpclett.0c00701
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发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Li, Xiaosong
中科院分区：
文献类型：
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作者：
Zhao, Luning;Tao, Zhen;Pavošević, Fabijan;Wildman, Andrew;Hammes-Schiffer, Sharon;Li, Xiaosong
电子和原子核的量子力学处理在非绝热动力学过程如质子耦合电子转移中是至关重要的。核电子轨道（NEO）方法提供了一个优雅的框架，可以将核量子效应包括在玻恩-奥本海默近似之外。为了使非平衡性质的研究，我们推导和实施实时近地天体（RT-NEO）的方法的基础上，随时间变化的哈特里-福克或密度泛函理论，其中电子和核的自由度传播随时间变化的框架。利用RT-NEO方法计算出的随时间变化的偶极矩可以分辨出核和电子光谱特征。测试结果表明，量子核和电子之间的动力学相互作用，通过振动耦合。此外，在RT-NEO方法中的振动激发是通过施加共振驱动场来证明的，电子激发是通过模拟激发态分子内质子转移来证明的。这项工作表明，RT-NEO方法是一种很有前途的工具，可用于研究电子和核耦合自由度随时间变化描述中的非绝热量子动力学过程。
The quantum mechanical treatment of both electrons and nuclei is crucial in nonadiabatic dynamical processes such as proton-coupled electron transfer. The nuclear−electronic orbital (NEO) method provides an elegant framework for including nuclear quantum effects beyond the Born–Oppenheimer approximation. To enable the study of nonequilibrium properties, we derive and implement a real-time NEO (RT-NEO) approach based on time-dependent Hatree-Fock or density functional theory, in which the electronic and nuclear degrees of freedom are propagated in a time-dependent variational framework. Nuclear and electronic spectral features can be resolved from the time-dependent dipole moment computed using the RT-NEO method. The test cases show the dynamical interplay between the quantum nuclei and the electrons through vibronic coupling. Moreover, vibrational excitation in the RT-NEO approach is demonstrated by applying a resonant driving field, and electronic excitation is demonstrated by simulating excited state intramolecular proton transfer. This work shows that the RT-NEO approach is a promising tool to study nonadiabatic quantum dynamical processes within a time-dependent variational description for the coupled electronic and nuclear degrees of freedom.