Soliton model of electron transfer in mixed-valence dimers and trimers

Abstract

The soliton approximation is examined for mixed-valence dimers and trimers with one migrating electron. The calculations use Hamilton's canonical equations and a time-dependent wave function of the soliton type. In the two limiting cases (strong and weak vibronic coupling), the soliton approximation correlates well with the exact analytical solution. As in the adiabatic approximation at g2/v=1, the delocalized limit (quasifree electron) is transformed to the localized one (electron locked on the center). For molecular trimers, the soliton approximation allows us to reveal the cases where the transfer of an electron from the first to the third center is accompanied by electron density concentration on the intermediate center.