A novel approach to measure the step line tension and the step dipole moment on vicinal Au(001) electrodes

Abstract In this paper we introduce a new experimental approach to determine the potential dependence of the step line tension on metal electrodes in contact with an electrolyte: (0 0 1) and (1 1  n ) surfaces of single crystal gold electrodes were investigated by impedance spectroscopy in solutions containing weakly adsorbing anions, such as ClO 4 - , F − and SO 4 2 - . Within the limits of error the shift in the potential of zero charge is proportional to the step density of the vicinal surfaces indicative of a well-defined dipole moment per step length. The dipole moments per step atom are 6.8 ± 0.8, 5.2 ± 0.4, 5.8 ± 0.5 × 10 −3  eA for SO 4 2 - , ClO 4 - , and F − containing electrolytes, respectively. Using the values for 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 tension of the stepped and the step free surface. Our results represent the first experimental confirmation of a recent theoretical model proposing that in absence of specifically adsorbed ions the step line tension should decrease (roughly linear) with potential.