LAUSR

The initial nucleation of gold clusters Aun (n = 1–5) on TiO2 rutile (110) reduced surface is studied using density functional theory and a full‐potential augmented‐plane‐wave method implemented in the WIEN2k code. The first two gold atoms remained tied to the surface with a bond length similar to those belonging to other well‐known related materials, while the other gold atoms do not spread over the surface; they preferred to form a new layer. The occurrence of relativistic effects produced a preferential triangle geometry for Au3 and a combination of triangular units for Au4 and Au5. The Au–Au average distance increased from n = 2 to n = 5, indicating an expansion with a tendency to the bond distance found in the bulk. We are reporting an early 2D→3D transition of small folding, from Au3→Au4, followed by an Au4→Au5 transition of evident 3D character.