Wilhelm, Florian; Schmickler, Wolfgang; Nazmutdinov, Renat R.; Spohr, Eckhard:
Modeling proton transfer to charged silver electrodes
2011
In: Electrochimica acta : the journal of the International Society of Electrochemistry., Jg. 56 (2011), Heft 28, S. 10632 - 10644
Artikel/Aufsatz in Zeitschrift2011Chemie
Fakultät für Chemie
Titel:
Modeling proton transfer to charged silver electrodes
Autor(in):
Wilhelm, Florian; Schmickler, Wolfgang; Nazmutdinov, Renat R.; Spohr, EckhardLSF
Erscheinungsjahr
2011

Abstract:

Density functional theory (DFT) and molecular dynamics (MD) techniques are used to study proton transfer from an aqueous solution to an Ag(1 1 1) surface. DFT is applied to study Ag–water and Ag–hydronium interactions as well as proton transfer for small systems based on the cluster model. The data gained are then used to adjust an empirical Ag–water interaction potential and to reparametrize an empirical valence-bond (EVB) model, which has been successfully applied for the study of proton transfer to a Pt(1 1 1) surface before. Employing these force fields in MD simulations enables dynamic modeling of the electrolyte–metal interface on a scale large enough to give realistic results. Results from a MD trajectory study on Ag(1 1 1) are reported and compared to the analogous study for platinum. Low discharge rates on Ag(1 1 1) are observed, and the potential range for hydrogen evolution can be estimated. The different behavior relative to Pt(1 1 1) can be traced to features of the respective potential energy surfaces and to the different structural properties of the aqueous/metallic interfaces.