title: On the coupling of solvent characteristics to the electronic structure of solute molecules.
abstract: We present the results of a theoretical investigation focusing on the solvent structure surrounding the -1, 0 and +1 charged species of F, Cl, Br and I halogen atoms and F2, Cl2, Br2 and I2 di-halogen molecules in a methanol solvent and its influence on the electronic structure of the solute molecules. Our results show a large stabilizing effect arising from the solute-solvent interactions. Well-formed first solvation shells are observed for all species, the structure of which is strongly influenced by the charge of the solute species. Detailed analysis reveals that coordination number, CN, solvent orientation, θ, and solute-solvent distance, d, are important structural characteristics which are coupled to changes in the electronic structure of the solute. We propose that the fundamental chemistry of any solute species is generally regulated by these solvent degrees of freedom.
authors.affiliation: Eenheid Algemene Chemie, Vrije Universiteit Brussel (VUB), Faculteit Wetenschappen, Pleinlaan 2, 1050 Brussels, Belgium. sbogatko@vub.ac.be.
authors.forename: Stuart
authors.initials: S
authors.lastname: Bogatko
authors.forename: Emilie
authors.initials: E
authors.lastname: Cauët
authors.forename: Paul
authors.initials: P
authors.lastname: Geerlings
authors.forename: Frank
authors.initials: F
authors.lastname: De Proft