Displacement of Cu(II) by Ag(I) in solvated metal sulfides. A DFT and AIM computational study
James R Kramer1, Nick H Werstiuk, Boris Ni
1School of Geography and Earth Sciences, McMaster University, Hamilton, Ontario, Canada L8S 4K1.
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.
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