Ground and excited electronic structure analysis of XM4 (X = N, P and M = Li, Na) and their anions.

Abstract

High-level coupled-cluster, electron propagator, and multi-reference ab initio methods are employed to study the ground and excited electronic states of the XM4 (X = N, P and M = Li, Na) series. All XM4 species bear lower ionization potentials and can be classified as superalkalis. In the ground state each possesses a diffuse electron in the periphery. This expanded electron cloud of tetrahedral NLi4, NNa4, and PNa4 molecules is spherical (similar to an s-orbital) and evenly distributed around the XM4+ core. The outer electron is promoted to higher-angular momentum p-, d-, 2s-type orbitals in excited states. Singly occupied molecular orbitals of excited PLi4 are deformed due to its lower C1 symmetry. The aug-cc-pVQZ basis set was found to describe the excited states of XM4 accurately and efficiently. The bound singlet and triplet electronic states of XM4- that possess two peripheral electrons are also analyzed.