Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies
Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies
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多组分时变密度泛函理论：质子和电子激发能
DOI：
10.1021/acs.jpclett.8b00547
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Hammes-Schiffer, Sharon
中科院分区：
文献类型：
--
作者：
Yang, Yang;Culpitt, Tanner;Hammes-Schiffer, Sharon
在计算激发态性质时，电子和质子的量子力学处理对于描述非绝热过程（如光致质子耦合电子转移）至关重要。多组分密度泛函理论能够对一种以上的粒子进行一致的量子力学处理，并且以前已经在核电子轨道（NEO）框架内研究基态分子性质，其中所有电子和特定质子都被量子力学处理。为了研究激发态分子的性质，本文推导了线性响应多组分含时密度泛函理论（TDDFT），并在近地天体框架内实现。FHF-和HCN的初步应用表明，NEO-TDDFT提供准确的质子和电子激发能在一个单一的计算。由于其计算成本与传统的电子TDDFT相似，NEO-TDDFT方法有望用于各种应用，特别是非绝热质子转移反应，这可能会表现出混合的电子-质子振动激发。
The quantum mechanical treatment of both electrons and protons in the calculation of excited state properties is critical for describing nonadiabatic processes such as photoinduced proton-coupled electron transfer. Multicomponent density functional theory enables the consistent quantum mechanical treatment of more than one type of particle and has been implemented previously for studying ground state molecular properties within the nuclear–electronic orbital (NEO) framework, where all electrons and specified protons are treated quantum mechanically. To enable the study of excited state molecular properties, herein the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. Initial applications to FHF–and HCN illustrate that NEO-TDDFT provides accurate proton and electron excitation energies within a single calculation. As its computational cost is similar to that of conventional electronic TDDFT, the NEO-TDDFT approach is promising for diverse applications, particularly nonadiabatic proton transfer reactions, which may exhibit mixed electron–proton vibronic excitations.