Density functional theory (DFT) total-energy calculations have been used to investigate the effect of potassium on the adsorption geometry of gold on a TiO(2)(110)- 1 × 1 surface. The gold prefers to sit between the two bridge oxygen atoms above the sixfold titanium atom. The addition of potassium significantly affects the bonding geometry of the gold. Potassium displaces gold from the bridge site and causes its migration to the top of the fivefold titanium atom. Our calculations suggest that potassium is bonded to the bridging oxygen atoms, and to the sixfold titanium atom as well as to gold. This excludes the formation of a K(2)O-like compound at the surface.