A measure for adiabatic contributions to quantum transitions

TL;DR

This paper introduces a new measure to quantify the adiabatic contribution to quantum transitions, applicable in complex systems with partial adiabaticity and multiple eigenstates, aiding in understanding charge and energy transfer.

Contribution

The paper develops a novel measure for adiabatic contributions in quantum transitions that works in arbitrary bases and complex dynamics, enhancing analysis in molecular simulations.

Findings

The measure distinguishes between adiabatic and non-adiabatic transitions.

Application to density functional theory simulations quantifies adiabaticity effects.

Facilitates analysis of charge and energy transfer processes.

Abstract

We construct a measure for the adiabatic contribution to quantum transitions in an arbitrary basis, tackling the generic complex case where dynamics is only partially adiabatic, simultaneously populates several eigenstates and transitions between non-eigenstates are of key interest. Our measure is designed to distinguish transitions between basis states that occur due to the adiabatic change of the underlying populated eigenstates from transitions that occur due to beating between several such eigenstates. We demonstrate that the measure can be applied to material or molecular simulations using time-dependent density functional theory, allowing to quantify the relative importance of adiabaticity and thus nuclear motion, for example, in charge or energy transfer.