Pseudopotential hole–particle formalism for excitations in xenon molecules and clusters. II. The electronic structure of Xe2*

Abstract

The Ω electronic states of the Xe2* excimer dissociating into Xe(5p6, 1S0)+Xe* (5p56s, 5p56p, 5p55d, 5p57s, and 5p57p) are determined using a one-electron hole–particle formalism including spin–orbit coupling. A partially diabatic correlation of the states is achieved. The content of the states in terms of the ionic cores and the Rydberg electron is analyzed theoretically by means of molecular natural orbitals and their overlaps with orbitals of the separated atoms. The spectroscopic molecular constants of all bound states dissociating up to the Xe+Xe*(7s) limit are determined. This theoretical determination of the electronic structure is used to survey and discuss a wide pannel of experimental data characterizing the spectroscopy of the Xe2* excimer and involving both the gerade and ungerade states.