Thermodynamic Cyclic Voltammograms Based on Ab Initio Calculations: Ag(111) in Halide-Containing Solutions.

ABSTRACT: Cyclic voltammograms (CVs) are a central experimental tool for assessing the structure and activity of electrochemical interfaces. Based on a mean-field ansatz for the interface energetics under applied potential conditions, we here derive an ab initio thermodynamics approach to efficiently simulate thermodynamic CVs. All unknown parameters are determined from density functional theory (DFT) calculations coupled to an implicit solvent model. For the showcased CVs of Ag(111) electrodes in halide-anion-containing solutions, these simulations demonstrate the relevance of double-layer contributions to explain experimentally observed differences in peak shapes over the halide series. Only the appropriate account of interfacial charging allows us to capture the differences in equilibrium

SUBMITTER: Hormann NG 

PROVIDER: S-EPMC8023662 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature