Electron flux in molecules induced by nuclear motion

Abstract

As a general tool for analysis of chemical reactions from the view point of electron wavepacket dynamics, electron flux within a molecule is numerically realized in terms of physically time-dependent electronic wavefunctions given by the semiclassical Ehrenfest theory. These wavefunctions are synchronized with real time motion of molecular nuclei through the nuclear kinematic coupling (nonadiabatic elements). Since the standard quantum flux gives only a null field for a real-valued electronic eigenfunction, we extend the definition of flux such that the essential information of dynamical flow of electrons can be retrieved even from adiabatic electronic wavefunctions calculated in the scheme of the so-called ab initio molecular dynamics.