Solvation effects and stabilization of multicharged ions: a case study of ArmBeOq+ complexes

Abstract

Using first-principle methods, we characterized Ar_mBeO^q+ (0 ≤ m ≤ 3 and 0 ≤ q ≤ 2) and BeO^q+ (3 ≤ q ≤ 5) multicharged ions (MCIs). This includes their structural parameters, relative stabilities and vibrational wavenumbers. Our calculations confirm the existence of the ArBeO complex. In addition, we found (meta-)stable neutral and ionic complexes such as ArBeO⁺, ArBeO²⁺, Ar₂BeO, Ar₂BeO⁺, Ar₂BeO²⁺, Ar₃BeO, Ar₃BeO⁺ and Ar₃BeO²⁺. The analysis of the structural parameters and of the electron density differences shows that a strong perturbation in the electronic structure of the BeO^q+ (q = 1,2) moiety occurs upon complexation, resulting in a major increase in covalency of these multicharged ions (MCIs). The consequences of solvation of MCIs in argon matrices are pointed out. More generally, the effects on the spectroscopy of MCIs trapped on cold matrices are discussed.