Long-range interactions between an atom in its ground S state and an open-shell linear molecule

TL;DR

This paper develops a theoretical framework for calculating long-range interactions between ground-state atoms and linear molecules with degenerate electronic states, incorporating multipole polarizabilities and transition moments.

Contribution

It introduces new expressions linking long-range interaction coefficients to all components of static and dynamic multipole polarizability tensors, including non-diagonal terms, for complex atom-molecule systems.

Findings

Derived formulas for long-range coefficients involving multipole polarizabilities.

Demonstrated the theory with numerical results for Rb and Li interacting with specific molecules.

Showed additional terms in induction energy for excited molecular states.

Abstract

Theory of long-range interactions between an atom in its ground S state and a linear molecule in a degenerate state with a non-zero projection of the electronic orbital angular momentum is presented. It is shown how the long-range coefficients can be related to the first and second-order molecular properties. The expressions for the long-range coefficients are written in terms of all components of the static and dynamic multipole polarizability tensor, including the nonadiagonal terms connecting states with the opposite projection of the electronic orbital angular momentum. It is also shown that for the interactions of molecules in excited states that are connected to the ground state by multipolar transition moments additional terms in the long-range induction energy appear. All these theoretical developments are illustrated with the numerical results for systems of interest for the sympathetic cooling experiments: interactions of the ground state Rb($^2$S) atom with CO($^3\Pi$), OH($^2\Pi$), NH($^1\Delta$), and CH($^2\Pi$) and of the ground state Li($^2$S) atom with CH($^2\Pi$).