Direct Dynamics with Nuclear–Electronic Orbital Density Functional Theory
Direct Dynamics with Nuclear–Electronic Orbital Density Functional Theory
复制标题
核电子轨道密度泛函理论的直接动力学
DOI：
10.1021/acs.accounts.1c00516
复制
发表时间：
2021
影响因子：
18.3
通讯作者：
Hammes-Schiffer, Sharon
中科院分区：
文献类型：
--
作者：
Tao, Zhen;Yu, Qi;Roy, Saswata;Hammes-Schiffer, Sharon
ConcurrentusDirect动力学模拟的化学反应通常需要选择一种方法来产生的势能面和方法的动态传播的核在这些表面上。核-电子轨道（NEO）框架通过波函数方法或密度泛函理论（DFT）在与电子相同的水平上处理特定的核来避免这种Born-Oppenheimer分离。近地天体方法特别适用于质子、氢化物和质子耦合电子转移反应，其中转移的质子和所有电子都是量子力学处理的。通过这种方式，转移质子的零点能量、密度离域和非谐性本质上有效地包含在能量、优化几何和动力学中，本帐户介绍如何使用各种近地天体方法对电子-质子振动表面进行直接动力学模拟。这些方法的优点和局限性进行了讨论，并提出了说明性的例子。NEO-DFT方法可用于模拟基态振动表面上的化学反应，如C4 H9+中氢化物转移的应用所示。NEO多态DFT（NEO-MSDFT）方法可用于模拟基态反应，其中质子密度在动力学过程中变为双叶，这是氢隧穿的一个特征，如丙二醛中的质子转移所示。NEO含时DFT（NEO-TDDFT）方法产生激发的电子，振动和振动表面。线性响应NEO-TDDFT对H2和H3+以及部分和完全氘代对应物的应用表明，当所有原子核和所有电子都被量子力学处理时，这种方法产生准确的基本振动激发能。此外，当只有指定的原子核量子力学处理，这种方法可以用来优化激发态振动表面上的几何形状，如所示的光诱导的单和双质子转移系统，并进行绝热动力学在这些表面上。实时近地天体TDDFT方法为模拟这类系统的非平衡核电子动力学提供了一种替代方法。这些不同的近地天体方法可以与非绝热动力学方法（如Escherichfest和表面跳跃动力学）相结合，以包括量子和经典子系统之间的非绝热效应。实时NEO-TDDFT Escherichfest动力学模拟的激发态分子内质子转移ino-hydroxybenzaldehyde说明了这种类型的组合方法的力量。多组分量子化学领域还处于早期阶段，本文讨论的方法为广泛的有前途的未来方向提供了基础。一个有吸引力的未来方向是扩展实时NEO-TDDFT方法，以便在同一水平上描述所有原子核和电子的动力学。使用近地天体波函数方法，如运动方程耦合星系团或多构型方法进行直接动力学模拟也是有吸引力的，但计算费用昂贵。近地天体直接动力学方法的进一步发展将使人们能够模拟超出玻恩-奥本海默近似的范围的大量化学和生物过程的核电子动力学。
ConspectusDirect dynamics simulations of chemical reactions typically require the selection of a method for generating the potential energy surfaces and a method for the dynamical propagation of the nuclei on these surfaces. The nuclear–electronic orbital (NEO) framework avoids this Born–Oppenheimer separation by treating specified nuclei on the same level as the electrons with wave function methods or density functional theory (DFT). The NEO approach is particularly applicable to proton, hydride, and proton-coupled electron transfer reactions, where the transferring proton(s) and all electrons are treated quantum mechanically. In this manner, the zero-point energy, density delocalization, and anharmonicity of the transferring protons are inherently and efficiently included in the energies, optimized geometries, and dynamics.This Account describes how various NEO methods can be used for direct dynamics simulations on electron–proton vibronic surfaces. The strengths and limitations of these approaches are discussed, and illustrative examples are presented. The NEO-DFT method can be used to simulate chemical reactions on the ground state vibronic surface, as illustrated by the application to hydride transfer in C4H9+. The NEO multistate DFT (NEO-MSDFT) method is useful for simulating ground state reactions in which the proton density becomes bilobal during the dynamics, a characteristic of hydrogen tunneling, as illustrated by proton transfer in malonaldehyde. The NEO time-dependent DFT (NEO-TDDFT) method produces excited electronic, vibrational, and vibronic surfaces. The application of linear-response NEO-TDDFT to H2and H3+, as well as the partially and fully deuterated counterparts, shows that this approach produces accurate fundamental vibrational excitation energies when all nuclei and all electrons are treated quantum mechanically. Moreover, when only specified nuclei are treated quantum mechanically, this approach can be used to optimize geometries on excited state vibronic surfaces, as illustrated by photoinduced single and double proton transfer systems, and to conduct adiabatic dynamics on these surfaces. The real-time NEO-TDDFT method provides an alternative approach for simulating nonequilibrium nuclear–electronic dynamics of such systems. These various NEO methods can be combined with nonadiabatic dynamics methods such as Ehrenfest and surface hopping dynamics to include the nonadiabatic effects between the quantum and classical subsystems. The real-time NEO-TDDFT Ehrenfest dynamics simulation of excited state intramolecular proton transfer ino-hydroxybenzaldehyde illustrates the power of this type of combined approach. The field of multicomponent quantum chemistry is in the early stages, and the methods discussed herein provide the foundation for a wide range of promising future directions to be explored. An appealing future direction is the expansion of the real-time NEO-TDDFT method to describe the dynamics of all nuclei and electrons on the same level. Direct dynamics simulations using NEO wave function methods such as equation-of-motion coupled cluster or multiconfigurational approaches are also attractive but computationally expensive options. The further development of NEO direct dynamics methods will enable the simulation of the nuclear–electronic dynamics for a vast array of chemical and biological processes that extend beyond the Born–Oppenheimer approximation.