Anion⋯Anion (MX3−)2 Dimers (M = Zn, Cd, Hg; X = Cl, Br, I) in Different Environments
Document Type
Article
Author ORCID Identifier
Rafał Wysokiński https://orcid.org/0000-0002-1133-3535
Wiktor Zierkiewicz https://orcid.org/0000-0002-4038-5959
Mariusz Michalczyk https://orcid.org/0000-0002-6495-6963
Steve Scheiner https://orcid.org/0000-0003-0793-0369
Journal/Book Title
Physical Chemistry Chemical Physics
Publication Date
6-16-2021
Publisher
Royal Society of Chemistry
Award Number
NSF, Division of Chemistry (CHE) 1954310
Funder
NSF, Division of Chemistry (CHE)
Volume
23
Issue
25
First Page
13853
Last Page
13861
Abstract
The possibility that MX3− anions can interact with one another is assessed via ab initio calculations in gas phase as well as in aqueous and ethanol solution. A pair of such anions can engage in two different dimer types. In the bridged configuration, two X atoms engage with two M atoms in a rhomboid structure with four equal M–X bond lengths. The two monomers retain their identity in the stacked geometry which contains a pair of noncovalent M⋯X interactions. The relative stabilities of these two structures depend on the nature of the central M atom, the halogen substituent, and the presence of solvent. The interaction and binding energies are fairly small, generally no more than 10 kcal mol−1. The large electrostatic repulsion is balanced by a strong attractive polarization energy.
Recommended Citation
Wysokiński, Rafał, et al. “Anion⋯anion (MX 3 − ) 2 Dimers (M = Zn, Cd, Hg; X = Cl, Br, I) in Different Environments.” Physical Chemistry Chemical Physics, vol. 23, no. 25, 2021, pp. 13853–61. DOI.org (Crossref), https://doi.org/10.1039/D1CP01502H.
