Premium
Electronic and nuclear flux analysis on nonadiabatic electron transfer reaction: A view from single‐configuration adiabatic born–huang representation
Author(s) -
Matsuzaki Rei,
Takatsuka Kazuo
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25557
Subject(s) - adiabatic process , physics , wave function , electron , electronic correlation , coherence (philosophical gambling strategy) , rabi cycle , oscillation (cell signaling) , atomic physics , born–oppenheimer approximation , quantum , quantum mechanics , chemistry , biochemistry , molecule
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.