Curchod Basile F E, Martínez Todd J
Department of Chemistry , Durham University , South Road , Durham DH1 3LE , United Kingdom.
Department of Chemistry and PULSE Institute , Stanford University , Stanford , California 94305 , United States.
Chem Rev. 2018 Apr 11;118(7):3305-3336. doi: 10.1021/acs.chemrev.7b00423. Epub 2018 Feb 21.
The Born-Oppenheimer approximation underlies much of chemical simulation and provides the framework defining the potential energy surfaces that are used for much of our pictorial understanding of chemical phenomena. However, this approximation breaks down when the dynamics of molecules in excited electronic states are considered. Describing dynamics when the Born-Oppenheimer approximation breaks down requires a quantum mechanical description of the nuclei. Chemical reaction dynamics on excited electronic states is critical for many applications in renewable energy, chemical synthesis, and bioimaging. Furthermore, it is necessary in order to connect with many ultrafast pump-probe spectroscopic experiments. In this review, we provide an overview of methods that can describe nonadiabatic dynamics, with emphasis on those that are able to simultaneously address the quantum mechanics of both electrons and nuclei. Such ab initio quantum molecular dynamics methods solve the electronic Schrödinger equation alongside the nuclear dynamics and thereby avoid the need for precalculation of potential energy surfaces and nonadiabatic coupling matrix elements. Two main families of methods are commonly employed to simulate nonadiabatic dynamics in molecules: full quantum dynamics, such as the multiconfigurational time-dependent Hartree method, and classical trajectory-based approaches, such as trajectory surface hopping. In this review, we describe a third class of methods that is intermediate between the two: Gaussian basis set expansions built around trajectories.
玻恩-奥本海默近似是许多化学模拟的基础，并提供了定义势能面的框架，我们对化学现象的许多直观理解都基于这些势能面。然而，当考虑处于激发电子态的分子动力学时，这种近似就不再适用。要描述玻恩-奥本海默近似失效时的动力学，就需要对原子核进行量子力学描述。激发电子态上的化学反应动力学对于可再生能源、化学合成和生物成像等许多应用至关重要。此外，为了与许多超快泵浦-探测光谱实验相联系，这也是必要的。在这篇综述中，我们概述了能够描述非绝热动力学的方法，重点介绍那些能够同时处理电子和原子核量子力学问题的方法。这种从头算量子分子动力学方法在求解核动力学的同时求解电子薛定谔方程，从而避免了预先计算势能面和非绝热耦合矩阵元的需要。通常采用两大类方法来模拟分子中的非绝热动力学：全量子动力学方法，如多组态含时哈特里方法；以及基于经典轨迹的方法，如轨迹表面跳跃法。在这篇综述中，我们描述了介于这两者之间的第三类方法：围绕轨迹构建的高斯基组展开法。
