A model for the effect of ion pairing on an outer sphere electron transfer. Issue 25 (16th June 2020)

• Record Type: Journal Article
• Authors: Nazmutdinov, Renat; Quaino, Paola; Colombo, Estefania; Santos, Elizabeth; Schmickler, Wolfgang
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 25(2020)
• Page Start: 13923
• Page End: 13929
• Publication Date: 2020-06-16
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp01915a
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Our theory for the effect of ion pairing on electron transfer explains why the chloride ion catalyses copper deposition. Abstract : Ion pairing can strongly affect the rates of electron transfer reactions. To explain this effect, we propose a model Hamiltonian that describes the interactions between the pairing ion and the reactant, solvent and inner sphere reorganization, and bond breaking. Explicit expressions for the energies of the initial and final states, and for the energy of activation are derived in the weak adiabatic limit. The model is applied to the reduction of Cu(ii ) in the presence of chloride ions. For this purpose, the pertinent system parameters are obtained from density functional theory. Our model explains why the chloride ion enhances the rate of the first electron transfer in copper deposition.