TY - JOUR
T1 - Microsolvation of heavy halides
AU - Chamorro, Yuly
AU - Flórez, Edison
AU - Maldonado, Alejandro
AU - Aucar, Gustavo
AU - Restrepo, Albeiro
N1 - Funding Information:
The work in Colombia was partially supported by Colciencias, Project 111571249844, and by University of Antioquia via ?Estrategia para la sostenibilidad.? Yuly Chamorro thanks University of Antioquia for her graduate scholarship. The work in Argentina was supported by Argentinian Research Council on Science and Technology, CONICET (Grant PIP112-201301-00361), and by the Argentinian Agency for Promotion of Science and Technology, FONCYT (Grant PICT2016-2936).
Publisher Copyright:
© 2020 Wiley Periodicals LLC
PY - 2021/4/5
Y1 - 2021/4/5
N2 - The fundamental question of how intermolecular interactions lead to the stabilization of heavy halides (Br−, I−, At−) microsolvated with up to six explicit water molecules is addressed here. An exhaustive exploration of the potential energy surfaces using a random search algorithm followed by optimization of molecular geometries using pseudopotentials and at the full four component relativistic levels of theory, affords a good number of structures with high probabilities of occurrence, highlighting the important role of local minima to reproduce experimentally measured properties. Sequential hydration enthalpies for astatide are reported here for the first time in the scientific literature. Closed shell (ionic, long range) as well as intermediate character interactions (contributions from closed shell and covalent) are at play stabilizing the clusters. The ability of water molecules to either donate or to accept electron density dictates the nature and strength of the corresponding hydrogen bonds in solvation shells. Binding energies and molecular geometries are shown to be more sensitive to electron correlation than to relativistic effects.
AB - The fundamental question of how intermolecular interactions lead to the stabilization of heavy halides (Br−, I−, At−) microsolvated with up to six explicit water molecules is addressed here. An exhaustive exploration of the potential energy surfaces using a random search algorithm followed by optimization of molecular geometries using pseudopotentials and at the full four component relativistic levels of theory, affords a good number of structures with high probabilities of occurrence, highlighting the important role of local minima to reproduce experimentally measured properties. Sequential hydration enthalpies for astatide are reported here for the first time in the scientific literature. Closed shell (ionic, long range) as well as intermediate character interactions (contributions from closed shell and covalent) are at play stabilizing the clusters. The ability of water molecules to either donate or to accept electron density dictates the nature and strength of the corresponding hydrogen bonds in solvation shells. Binding energies and molecular geometries are shown to be more sensitive to electron correlation than to relativistic effects.
KW - heavy halides
KW - intermolecular interactions
KW - microsolvation
KW - potential energy surfaces
KW - relativistic effects
UR - http://www.scopus.com/inward/record.url?scp=85097413493&partnerID=8YFLogxK
U2 - 10.1002/qua.26571
DO - 10.1002/qua.26571
M3 - Article
AN - SCOPUS:85097413493
SN - 0020-7608
VL - 121
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 7
M1 - e26571
ER -