Electronic and nuclear flux analysis on nonadiabatic electron transfer reaction: A view from single‐configuration adiabatic born–huang representation

• Published in: Journal of computational chemistry Vol. 40; no. 1; pp. 148 - 163
• Main Authors: Matsuzaki, Rei, Takatsuka, Kazuo
• Format: Journal Article
• Language: English
• Published: Hoboken, USA John Wiley & Sons, Inc 05-01-2019; Wiley Subscription Services, Inc
• Subjects: Adiabatic flow; electron flux; Electron transfer; Fluctuations; Fluxes; Lithium fluoride; nonadiabatic transition; nuclear flux; Nuclei (nuclear physics); quantum dynamics; Wave functions; nonadiabatic transition; electron transfer; nuclear flux; quantum dynamics; electron flux
• ISSN: 0192-8651; 1096-987X
• 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.
Nonadiabatic electron transfer reaction as in LiF ↔ Li+F‐ is analyzed in terms of the electronic and nuclear fluxes. The resultant electronic flux shows a spatiotemporal oscillatory pattern emerging from instantaneous transitions between ionic and covalent potential curves. We also calculate a correlation function between the nuclear and electronic fluxes, which clearly quantifies the extent of deviation of the actual electronic‐nuclear coupled dynamics from its Born–Oppenheimer adiabatic limit.