Nuclear–Electronic Orbital Quantum Mechanical/Molecular Mechanical Real-Time Dynamics
Nuclear–Electronic Orbital Quantum Mechanical/Molecular Mechanical Real-Time Dynamics
复制标题
核-电子轨道量子力学/分子力学实时动力学
DOI：
10.1021/acs.jpclett.3c02275
复制
发表时间：
2023
期刊：
影响因子：
--
通讯作者：
Hammes-Schiffer, Sharon
中科院分区：
文献类型：
--
作者：
Chow, Mathew;Li, Tao E.;Hammes-Schiffer, Sharon
模拟凝聚相中大规模分子系统的核电子量子动力学是研究质子转移和质子耦合电子转移反应等生物和化学重要过程的关键。在此，实时核电子轨道时间相关密度泛函理论（RT-NEO-TDDFT）方法与混合量子力学/分子力学（QM/MM）策略相结合，能够在溶剂或蛋白质等异质环境中准确描述耦合核电子量子动力学。电子和量子质子的密度实时传播，而其他原子核在瞬时电子-质子振动表面上经典传播。该方法适用于与溶菌酶结合的苯酚、丙二醛中的分子内质子转移以及羟基苯甲醛中的非平衡激发态分子内质子转移。这些例子说明，RT-NEO-TDDFT 框架与环境的原子表示相结合，可以模拟表现出显着核量子效应的凝聚相系统。
Simulating the nuclear–electronic quantum dynamics of large-scale molecular systems in the condensed phase is key for studying biologically and chemically important processes such as proton transfer and proton-coupled electron transfer reactions. Herein, the real-time nuclear–electronic orbital time-dependent density functional theory (RT-NEO-TDDFT) approach is combined with a hybrid quantum mechanical/molecular mechanical (QM/MM) strategy to enable the accurate description of coupled nuclear–electronic quantum dynamics in the presence of heterogeneous environments such as solvent or proteins. The densities of the electrons and quantum protons are propagated in real time, while the other nuclei are propagated classically on the instantaneous electron–proton vibronic surface. This approach is applied to phenol bound to lysozyme, intramolecular proton transfer in malonaldehyde, and nonequilibrium excited-state intramolecular proton transfer ino-hydroxybenzaldehyde. These examples illustrate that the RT-NEO-TDDFT framework, coupled with an atomistic representation of the environment, allows the simulation of condensed-phase systems that exhibit significant nuclear quantum effects.