Phase Space Electronic Structure Theory: From Diatomic Lambda-Doubling to Macroscopic Einstein-de Haas

TL;DR

This paper demonstrates that a phase space theory, incorporating both nuclear position and momentum, can accurately describe $ ext{Lambda}$-doubling in diatomic molecules and recover the Einstein-de Haas effect, advancing beyond the Born-Oppenheimer approximation.

Contribution

The authors extend a phase space electronic structure theory to include nuclear momentum, enabling accurate modeling of $ ext{Lambda}$-doubling and angular momentum effects in molecules.

Findings

Phase space potential energy surfaces include electron-rotation coupling.

The method nearly quantitatively reproduces $ ext{Lambda}$-doubling energies.

The approach has computational costs comparable to standard methods.

Abstract

$\Lambda$-doubling of diatomic molecules is a subtle microscopic phenomenon that has long attracted the attention of experimental groups, insofar as rotation of molecular $\textit{nuclei}$ induces small energetic changes in the (degenerate) $\textit{electronic}$ state. A direct description of such a phenomenon clearly requires going beyond the Born-Oppenheimer approximation. Here we show that a phase space theory previously developed to capture electronic momentum and model vibrational circular dichroism -- and which we have postulated should also describe the Einstein-de Haas effect, a macroscopic manifestation of angular momentum conservation -- is also able to recover the $\Lambda$-doubling energy splitting (or $\Lambda$-splitting) of the NO molecule nearly quantitatively. The key observation is that, by parameterizing the electronic Hamiltonian in terms of both nuclear position ($\mathbf{X}$) and nuclear momentum ($\mathbf{P}$), a phase space method yields potential energy surfaces that explicitly include the electron-rotation coupling and correctly conserve angular momentum (which we show is essential to capture $\Lambda-$doubling). The data presented in this manuscript offers another small glimpse into the rich physics that one can learn from investigating phase space potential energy surfaces $E_{PS}(\mathbf{X},\mathbf{P})$ as a function of both nuclear position and momentum, all at a computational cost comparable to standard Born-Oppenheimer electronic structure calculations.