Issue 19, 2014

Adsorbate induced vacancy formation on silver surfaces

Abstract

The energy required to form and remove vacancies on metal surfaces mediates the rate of mass transport during a wide range of processes. These energies are known to be sensitive to environmental conditions. Here, we use electronic structure density functional theory calculations to show that the surface vacancy formation energy of silver changes markedly in the presence of adsorbed and dissolved oxygen. We found that adsorbed atomic oxygen can reduce the surface vacancy formation energy of the Ag(111) surface by more than 30%, whereas surface vacancy formation becomes exothermic in the presence of pure subsurface oxygen. We went on to show that the total directionality of the topologically defined bond paths can be used to understand these changes. The resulting structure–property relationship was used to predict the behavior of silver in different atmospheres. We show that the surface vacancy formation energy decreases when electronegative elements are adsorbed on the surface, but that it can increase when electropositive elements are adsorbed.

Graphical abstract: Adsorbate induced vacancy formation on silver surfaces

Article information

Article type
Paper
Submitted
22 Feb 2014
Accepted
25 Mar 2014
First published
25 Mar 2014
This article is Open Access
Creative Commons BY license

Phys. Chem. Chem. Phys., 2014,16, 9002-9014

Adsorbate induced vacancy formation on silver surfaces

T. E. Jones, T. C. R. Rocha, A. Knop-Gericke, C. Stampfl, R. Schlögl and S. Piccinin, Phys. Chem. Chem. Phys., 2014, 16, 9002 DOI: 10.1039/C4CP00778F

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