title: Displacement of Cu(II) by Ag(I) in solvated metal sulfides. A DFT and AIM computational study.
abstract: The substitution of Cu2+ by Ag+ in hydrated CuIIS and (CuII)3S3 was modeled computationally by density functional theory quantum theory of atoms in molecules, and solvent field methods. The coordination, first-shell and partly second-shell molecular structures, and thermochemical data for solvated Cu2+, Ag+, CuIIS, (CuII)3S3, AgCu2S3 and their reactions were obtained. The thermochemical data showed that displacement of Cu2+ and Cu+ from CuIIS and (CuII)3S3 by Ag+, while unfavorable in the gas phase, is facilitated in an aqueous environment. Several covalently bonded species were examined as intermediates in the substitution reactions.
authors.affiliation: School of Geography and Earth Sciences, McMaster University, Hamilton, Ontario, Canada L8S 4K1.
authors.forename: James R
authors.initials: JR
authors.lastname: Kramer
authors.forename: Nick H
authors.initials: NH
authors.lastname: Werstiuk
authors.forename: Boris
authors.initials: B
authors.lastname: Ni
mesh_terms: D003198:Computer Simulation; D003300:Copper / Q000737:chemistry*; D008956:Models, Chemical; D011789:Quantum Theory; D012834:Silver / Q000737:chemistry*; D012995:Solubility; D013440:Sulfides / Q000737:chemistry*
chemical_list: D013440:Sulfides; D012834:Silver; D003300:Copper