Underpotential deposition of metals: Structural and thermodynamic considerations

The dependence of underpotential deposition (UPD) shift on work function differences, lattice coordination numbers, solvent desorption energies, and surface coverages is analyzed. The transport processes that govern monolayer formation and bulk deposition are incorporated. The parameteric dependence of the UPD shift on different thermodynamic quantities and adsorbate charge densities is reported. The validity of the formalism is demonstrated by comparison with the experimental data.