Theoretical Study of Ground-State Barium-Rare Gas Van der Waals Complexes: Combining Rule Modeling and Ab Initio Calculations.

Abstract

The present study aims to generate the potential energy curves (PECs) and spectroscopic constants for barium alkaline earth (AE) atoms interacting with rare gas (RG) atoms (He, Ne, Ar, Kr, and Xe). The study focuses on investigating the van der Waals bonds that characterize the interactions between alkaline-earth metals and RG atoms, with a specific emphasis on employing the Tang and Toennies (TT) potential model, known to accurately describe such interactions. The TT potential model was employed in conjunction with combining rules to calculate its parameters, which include dispersion coefficients C 2n and Born-Mayer constants A and b. Additionally, we have conducted high-level ab initio calculations at the CCSD(T) level for all Ba-RG ground states. Obtained PECs from both methods have been used to evaluate the spectroscopic properties D e, R e, ωe, B e, and ωeχe. Our findings reveal that the derived spectroscopic constants from the TT model exhibit good agreement with the results obtained from CCSD(T) calculations and with other available theoretical studies. Furthermore, to gain insights into the relative differences among AE-RG species, we calculated the κ parameter for AE-RG and AE+-RG (AE = Sr, Ca, Mg, Ba; RG = He-Xe) complexes. It is found that except for the case of Ba-RG and Ba+-RG, the κ values within the same series, AE-RG and AE+-RG, are remarkably close to each other.