Theoretical study on low-lying electronic states of Kr2+, Xe2+, and Rn2+

Abstract

In this work, the equation-of-motion coupled-cluster approach with spin-orbit coupling (SOC) for ionization potentials (IP) at the singles and doubles level (EOMIP-CCSD) is employed to calculate spectroscopic constants of low-lying states of rare gas dimer ions Kr 2 + , Xe 2 + , and Rn 2 + . Two approaches are proposed to include contributions of triples: (1) energies of these states are calculated by adding the IPs from EOMIP-CCSD and the CCSD(T) energy of the rare gas dimers and (2) CCSD(T) energies without SOC for Rg 2 + are first calculated and energies of these states with SOC are determined subsequently using the SOC matrix between these states. The first approach can provide accurate results for the three most stable states, while overestimates bond lengths for the other states. The second approach has been adopted previously and the SOC matrix element between 2 1/2 + and 2 1/2 states was set to be 1/ √ 2 times that of the SOC constant. In our work, the SOC matrix elements are determined from the calculated IPs and reasonable results for these states can be achieved with this approach, which could be useful for experimental works.

Ab initio study of rare gas halides

“…+ ions Diatomic rare gas ions have been the subject of many studies, both theoretical and experimental (Mastalerz et al (2012), Liang et al (2013) and references cited therein). The present ab initio calculations were performed with the aim of comparing (i) the equilibrium Rg-Rg distance in the free Rg 2 + ion and in electronic states of Rg 2 X, (ii) dissociation energies of Rg 2 + and Rg 2 + X − (along the Rg + RgX(B,C) coordinate).…”