Non-adiabatic transitions through tilted avoided crossings

TL;DR

This paper derives an explicit formula for quantum wave-packet transitions at tilted avoided crossings, validated by high-precision calculations, advancing understanding of non-adiabatic molecular dynamics.

Contribution

It introduces a new analytical approach using superadiabatic representations to accurately describe non-adiabatic transitions in tilted avoided crossings.

Findings

Explicit transition wavefunction formula derived

Excellent agreement with ab-initio calculations

Enhanced understanding of non-adiabatic dynamics

Abstract

We investigate the transition of a quantum wave-packet through a one-dimensional avoided crossing of molecular energy levels when the energy levels at the crossing point are tilted. Using superadiabatic representations, and an approximation of the dynamics near the crossing region, we obtain an explicit formula for the transition wavefunction. Our results agree extremely well with high precision ab-initio calculations.