Diatomic molecular anions of alkali-metal and alkaline-earth-metal atoms

Abstract

Studies of anions are inherently more challenging than investigations of neutrals and cations because of the diffuse and weakly bound character of an anionic electron. Here, we present a comprehensive computational examination of ground-state diatomic molecular anions composed of alkali-metal (Li, Na, K, Rb, Cs, Fr) and alkaline-earth-metal (Be, Mg, Ca, Sr, Ba, Ra) atoms. We study 21 alkali-metal diatomic anions in the X$^{2}Σ^{+}$ electronic state and 36 alkali-metal--alkaline-earth-metal diatomic anions in the X$^{1}Σ^{+}$ electronic state. The calculations employ a hierarchy of the coupled cluster methods, combined with large Gaussian basis sets and small-core relativistic energy-consistent pseudopotentials for heavier elements. We compute potential energy curves, permanent electric dipole moments, and static polarizabilities, and we assess convergence and uncertainties of our results. Additionally, using the multireference configuration interaction and equation-of-motion electron-attachment coupled cluster methods, we investigate excited electronic states of alkali-metal molecular anions, including valence-bound and dipole-bound states. We predict crossings between ground neutral and excited anionic states, which may enhance resonant electron attachment and subsequent anion dissociation. This finding may be relevant for experiments with mixtures of ultracold ground-state alkali-metal molecules and Rydberg atoms.