Quasistationary states and coherent versus incoherent transitions for crossing diabatic potentials

TL;DR

This paper explores the quantum tunneling behavior in crossing diabatic potentials, revealing how coherent and incoherent transitions occur and identifying a new regime transition influenced by potential shape and energy levels.

Contribution

It introduces a model analyzing tunneling in crossing diabatic potentials with constant coupling, highlighting the transition between coherent and incoherent regimes and their dependence on system parameters.

Findings

Doublet level structure persists under certain conditions.

Oscillating behavior due to resonances in over-barrier energies.

Identification of multiple regime transitions in state evolution.

Abstract

We investigate coherent and incoherent tunneling phenomena in conditions of crossing diabatic potentials. We consider a model of two crossing parabolic diabatic potentials with an independent of coordinates constant adiabatic coupling. As a result of the coupling and level crossing avoiding, we get the asymmetric double-well lower adiabatic potential with a variable shape. We show that the doublet structure of levels (generic for double-well potentials) is remained valid as long as the transition matrix element is smaller than characteristic inter-level spacings (the latter ones in own turn decrease upon increasing of a difference between the diabatic potential minima). In the adiabatic limit the tunneling transitions do not depend on the upper potential. In the over-barrier energy region there is an oscillating behavior due to the resonances between the states in the lower and in the upper adiabatic potentials. A new phenomenom emanated from this oscillating dependence namely, multiple coherent - incoherent regime transitions for the upper adiabatic potential state evolution, is our main concern in this paper. The problem is not only of intellectual interest but also of relevance to various molecular systems undergoing conversion of electronic states or isomerization reactions. Our model exhausts all cases practically relevant for spectroscopy of non-rigid molecules, and can capture many of the features exhibited by experiment.