Underpotential deposition (UPD) of manganese on gold and lead was studied by density functional calculation and cyclic voltammetry. The theoretical calculation is on the hypothesis of formation of a condensed two-dimensional (2D) phase of the UPD metal on the substrate metal (S). Underpotential shifts ∆fE2DMe for manganese UPD on gold and lead were calculated by using DMol3 that is based on the density functional theory. The results show that Mn/Au is a UPD system but Mn/Pb is not a UPD system. By contraries, cyclic voltammograms (CV) show that no phenomenon of manganese UPD occurs on gold since evaluation of hydrogen easily occurs on gold, while manganese UPD occurs on lead from ammonium-chloride solution. This difference between theoretical calculation and CV experiments is likely to be due to solvent effects and/or anion adsorption which were not included in the model of the theoretical calculation.

Key words: manganese, underpotential deposition, density functional calculation, cyclic voltammetry