Determination of Non-Adiabatic Scattering Wave Functions in a Born-Oppenheimer Model

TL;DR

This paper analyzes non-adiabatic transitions in molecular scattering, deriving precise asymptotic expressions for transition probabilities and momentum shifts near avoided crossings within the Born-Oppenheimer framework.

Contribution

It provides an explicit computation of non-adiabatic transition components and their asymptotic behavior, including exponential smallness and momentum shifts, in a rigorous mathematical setting.

Findings

Transition component is exponentially small in the Born-Oppenheimer parameter squared.

The non-adiabatic component propagates as a free Gaussian with a shifted momentum.

Total transition probability exceeds naive energy conservation estimates.

Abstract

We study non--adiabatic transitions in scattering theory for the time dependent molecular Schroedinger equation in the Born--Oppenheimer limit. We assume the electron Hamiltonian has finitely many levels and consider the propagation of coherent states with high enough total energy. When two of the electronic levels are isolated from the rest of the electron Hamiltonian's spectrum and display an avoided crossing, we compute the component of the nuclear wave function associated with the non--adiabatic transition that is generated by propagation through the avoided crossing. This component is shown to be exponentially small in the square of the Born--Oppenheimer parameter, due to the Landau-Zener mechanism. It propagates asymptotically as a free Gaussian in the nuclear variables, and its momentum is shifted. The total transition probability for this transition and the momentum shift are both larger than what one would expect from a naive approximation and energy conservation.