Microsolvation of Sr ²⁺ , Ba ²⁺ : Structures, energies, bonding, and nuclear magnetic shieldings

An exhaustive exploration using non–relativistic and four–component relativistic formalisms of the potential energy surfaces for microsolvation Sr2+, Ba2+ with up to n = 6 water molecules is presented in this work. A multitude well defined local minima stabilized by cation ? interactions are found. Cation contacts transcend electrostatic simplistic ionic bonding. The formal charge causes a chaotropic effect structure solvent affecting hydrogen bonds inducing dissociation resulting H+, OH? ions extreme cases. Relativistic effects close 0.7% or smaller geometries electronic energies, but they around 27% shieldings clusters. nuclei central cations deshielded (around 10% going from ) due microsolvation.