TY - JOUR
T1 - Microsolvation of Sr2+, Ba2+
T2 - Structures, energies, bonding, and nuclear magnetic shieldings
AU - Velásquez, Angie
AU - Chamorro, Yuly
AU - Maldonado, Alejandro
AU - Aucar, Gustavo
AU - Restrepo, Albeiro
N1 - Funding Information:
Partial financial support for this project from Universidad de Antioquia via “Estrategia para la sostenibilidad” is acknowledged. A. M. and G. A. acknowledge support from the Argentinian Research Council on Science and Technology, CONICET (Grant PIP 112‐201301‐00361), and from the Argentinian Agency for Promotion of Science and Technology, FONCYT (Grant PICT2016‐2936).
Publisher Copyright:
© 2021 Wiley Periodicals LLC.
PY - 2021/9/15
Y1 - 2021/9/15
N2 - 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.
AB - 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.
KW - bonding interactions
KW - microsolvation
KW - nuclear magnetic shieldings
KW - relativistic effects
UR - http://www.scopus.com/inward/record.url?scp=85108811926&partnerID=8YFLogxK
U2 - 10.1002/qua.26753
DO - 10.1002/qua.26753
M3 - Article
AN - SCOPUS:85108811926
SN - 0020-7608
VL - 121
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 18
M1 - e26753
ER -