Cadmium underpotential deposition on Cu(111) In situ scanning tunneling microscopy

Abstract

Atomically resolved in situ STM images are presented for an underpotentially deposited (upd) cadmium layer on a Cu(111) electrode from a 10⁻⁴ M CdCl₂/10⁻² M HCl solution. The observed moiré-like structure seen in the images is analysed by means of an algebraic model for this long-range superstructure. A structure model for the upd layer is developed which reflects all features of the observed moiré pattern. Furthermore the height modulation was simulated by a hard-sphere model for the Cd overlayer and shows remarkable agreement with the detailed tunneling current density distribution of the measured STM images. The existence of translational and rotational domains is demonstrated. The results are also compared and shown to be fully consistent with previous (ex situ) low-energy electron diffraction (LEED) observations of this system. The mechanism of Cd upd involves a dynamic site exchange between preadsorbed Cl⁻ anions and adsorbing Cd²⁺ cations as previously concluded from ex situ X-ray photoelectron (XPS) and low-energy ion scattering (LEIS) measurements.