Theoretical investigation of RbXe and CsXe excimers including the spin–orbit interaction

Abstract

The potential energy curves and spectroscopic constants of ground and many excited states of the RbXe and CsXe van der Waals systems have been determined using a one-electron pseudopotential approach. This has reduced the number of active electrons of the RbXe and CsXe van der Waals systems to only one electron, the valence electron; and has led to the use of large basis sets for Rb, Cs and Xe atoms. In this context, the potential energy curves of the ground and many excited states are calculated at the SCF level, and the spin–orbit interaction is considered. The core–core interactions for Rb+Xe and Cs+Xe were included using the CCSD(T) accurate potential energy curves of Hickling et al (2004 Phys. Chem. Chem. Phys. 6 4233–4239). The spectroscopic constants of these states are derived and compared with the available theoretical and experimental results. Such comparisons show very good agreement for the ground and the first excited states. Moreover, the transition dipole function has been determined for a large and dense grid of internuclear distances, including the spin–orbit effect.