Direct in situ studies of the surface diffusion of isolated adsorbates at an electrochemical interface by high-speed scanning tunneling microscopy (video STM) are presented for sulfide adsorbates on Cu(100) in HCl solution. As revealed by a quantitative statistical analysis, the adsorbate motion can be described by thermally activated hopping between neighboring adsorption sites with an activation energy that increases linearly with electrode potential by 0.50 eV per V. This can be explained by changes in the adsorbate dipole moment during the hopping process and contributions from coadsorbates.

• Received 19 September 2005

DOI:https://doi.org/10.1103/PhysRevLett.96.026101