Long range interactions between like homonuclear alkali metal diatoms

TL;DR

This paper calculates long-range electrostatic and van der Waals interactions for homonuclear alkali metal diatoms using ab initio and DFT methods, providing new data and validating interaction potentials.

Contribution

It systematically evaluates long-range coefficients and electric moments for alkali diatoms, including new results for Rb2 and Cs2, and compares different computational approaches.

Findings

Good agreement with existing data for Li2 and K2

New results for Rb2 and Cs2

Interaction potentials match high-level ab initio calculations

Abstract

Long range electrostatic and van der Waals coefficients up to terms of order R-8 have been evaluated by the sum over states method using ab initio and time dependent density functional theory. We employ several widely used density functionals and systematically investigate the convergence of the calculated results with basis set size. Static electric moments and polarizabilities up to octopole order are also calculated. We present values for Li2 through K2 which are in good agreement with existing values, in addition to new results for Rb2 and Cs2. Interaction potential curves calculated from these results are shown to agree well with high level it ab initio theory.