Matsuzaki Rei, Takatsuka Kazuo
Fukui Institute for Fundamental Chemistry, Kyoto University, Sakyou-ku, Kyoto, Japan.
J Comput Chem. 2019 Jan 5;40(1):148-163. doi: 10.1002/jcc.25557.
A detailed flux analysis on nonadiabatically coupled electronic and nuclear dynamics in the intramolecular electron transfer of LiF is presented. Full quantum dynamics both of electrons and nuclei within two-state model has uncovered interesting features of the individual fluxes (current of probability density) and correlation between them. In particular, a spatiotemporal oscillatory pattern of electronic flux has been revealed, which reflects the coherence coming from spatiotemporal differential overlap between nuclear wavepackets running on covalent and ionic potential curves. In this regard, a theoretical analogy between the nonadiabatic transitions and the Rabi oscillation is surveyed. We also present a flux-flux correlation between the nuclear and electronic motions, which quantifies the extent of deviation of the actual electronic and nuclear coupled dynamics from the Born-Oppenheimer adiabatic limit, which is composed only of a single product of the adiabatic electronic and nuclear wavefunctions. © 2018 Wiley Periodicals, Inc.
本文对LiF分子内电子转移过程中非绝热耦合的电子与核动力学进行了详细的通量分析。在两态模型中对电子和核的完全量子动力学研究揭示了各个通量（概率密度流）的有趣特征以及它们之间的相关性。特别地，揭示了电子通量的时空振荡模式，这反映了在共价和离子势曲线上运行的核波包之间时空微分重叠产生的相干性。在此方面，研究了非绝热跃迁与拉比振荡之间的理论类比。我们还给出了核运动与电子运动之间的通量 - 通量相关性，它量化了实际电子与核耦合动力学偏离仅由绝热电子波函数与核波函数的单一乘积组成的玻恩 - 奥本海默绝热极限的程度。© 2018威利期刊公司。
