Microsolvation of Sr2+ , Ba2+: Structures, energies, bonding, and nuclear magnetic shieldings

An exhaustive exploration using non–relativistic and four–component relativistic formalisms of the potential energy surfaces for the microsolvation of Sr2+, Ba2+ 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 w...

ver descrição completa

Detalhes bibliográficos
Autores: Velásquez, Angie, Chamorro, Yuly, Maldonado, Alejandro Fabián, Aucar, Gustavo Adolfo, Restrepo, Albeiro
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2021
País:Argentina
Recursos:Consejo Nacional de Investigaciones Científicas y Técnicas
Repositorio:CONICET Digital (CONICET)
Idioma:inglés
OAI Identifier:oai:ri.conicet.gov.ar:11336/148688
Acesso em linha:http://hdl.handle.net/11336/148688
Access Level:acceso abierto
Palavra-chave:BONDING INTERACTIONS
MICROSOLVATION
NUCLEAR MAGNETIC SHIELDINGS
RELATIVISTIC EFFECTS
https://purl.org/becyt/ford/1.3
https://purl.org/becyt/ford/1
Descrição
Resumo:An exhaustive exploration using non–relativistic and four–component relativistic formalisms of the potential energy surfaces for the microsolvation of Sr2+, Ba2+ 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 Ba2+ clusters. The nuclei of the central cations are deshielded (around 10% in going from (Formula presented.) to (Formula presented.)) due to microsolvation.