, Volume 9, Issue 3, pp 370–379 | Cite as

Chemisorbed Oxygen at Pt(111): a DFT Study of Structural and Electronic Surface Properties

Original Research


Simulations based on density functional theory are used to study the electronic and electrostatic properties of a Pt(111) surface covered by a layer of chemisorbed atomic oxygen. The impact of the oxygen surface coverage and orientationally ordered interfacial water layers is explored. The oxygen adsorption energy decreases as a function of oxygen coverage due to the lateral adsorbate repulsion. The surficial dipole moment density induced by the layer of chemisorbed oxygen causes a positive shift of the work function. In simulations with interfacial water layers, ordering and orientation of water molecules strongly affect the work function. It is found that the surficial dipole moment density and charge density are roughly linearly dependent on the oxygen surface coverage. Moreover, we found that water layers exert only a small impact on the surface charging behavior of the surface.

Graphical Abstract

Plane-averaged line charge density at the Pt(111)–Oad surface in the presence of one monolayer of water.


Pt electrocatalysis Surface charge density Work function change Dipole moment Electrostatic properties 



A. Malek and M. Eikerling gratefully acknowledge the financial support towards this project from the NSERC APC network CaRPE-FC. The DFT calculations were performed by the support provided by WestGrid (www.westgrid.ca) and Compute Canada (www.computecanada.ca).


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Authors and Affiliations

  1. 1.Department of ChemistrySimon Fraser UniversityBurnabyCanada

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