Determination of the step dipole moment and the step line tension on Ag(0 0 1) electrodes

Abstract

Using impedance spectroscopy, we determined the step dipole moment and the potential dependence of the step line tension of silver electrodes in contact with an electrolyte: (0 0 1) and vicinal surfaces (1 1 n) with n = 5, 7, 11 in 10 mM ClO 4 −-solutions were investigated. The step dipole moment is determined from the shift of the potential of zero charge ( pzc) as a function of the surface step density. The dipole moment per step atom was found to be 3.5 ± 0.5 × 10 −3 e Å. From the pzc and the potential dependence of the capacitance curves, the potential dependence of the surface tension of the vicinal surfaces is determined. The line tension of the steps is then calculated from the difference between the surface tensions of stepped (1 1 n) and the nominally step-free (0 0 1) surfaces. The results are compared to a previous study on Au(1 1 n) surfaces. For gold, the step line tension decreases roughly linear with potential, whereas a parabolic shape is observed for silver.