Potential energy curves, permanent and transition dipole moments for numerous electronic excited states of CaAr

Abstract

The adiabatic potential energy curves and the permanent and transition dipole moments of the low-lying electronic states of the CaAr molecule dissociating into Ca(4s,3d,4p,5s,4d,5p,4f,6s) + Ar have been investigated. The electronic structure of the Ca-Ar molecule is calculated using [Ca2+] and [Ar] core pseudopotentials complemented by the core polarisation operators with both atoms and full configuration interactions through the CIPSI quantum chemistry methods. The potential energy curves and the spectroscopic constants of all CaAr states dissociating into atomic configurations ranging from the ground state 4s to excited states 6s are determined. The derived spectroscopic constants of the ground state and lower excited states are in good agreement with available experimental and theoretical works. The position of the avoided crossings is used to evaluate the transition dipole moment of the vibrational levels trapped in the excited states for the first time.