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Microsolvation of Sr 2+ , Ba 2+ : Structures, energies, bonding, and nuclear magnetic shieldings
Author(s) -
Velásquez Angie,
Chamorro Yuly,
Maldonado Alejandro,
Aucar Gustavo,
Restrepo Albeiro
Publication year - 2021
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26753
Subject(s) - chemistry , ionic bonding , dissociation (chemistry) , hydrogen bond , molecule , bond dissociation energy , ion , computational chemistry , atomic physics , chemical physics , crystallography , physics , organic chemistry
An exhaustive exploration using non–relativistic and four–component relativistic formalisms of the potential energy surfaces for the microsolvation of Sr 2+ , Ba 2+ with up to n = 6 water molecules is presented in this work. A multitude of well defined local minima stabilized by cation ⋯ water and by water ⋯ water interactions are found. Cation ⋯ water contacts transcend the electrostatic interactions of simplistic ionic bonding. The formal charge causes a chaotropic effect in the structure of the solvent affecting water to water hydrogen bonds and inducing water dissociation and microsolvation of the resulting H + , OH − ions in extreme cases. Relativistic effects are close to 0.7% or smaller in geometries and electronic energies, but they are around 27% for shieldings of Ba 2+ clusters. The nuclei of the central cations are deshielded (around 10% in going from n = 1 to n = 3 ) due to microsolvation.