First-principles study of chlorine atom diffusion on Si(1 1 1)-5 × 5 reconstructed surfaces

► Cl diffusion on Si(1 1 1) surface is investigated by first-principles calculations. ► Cl atom diffuses on the surface in a SiCl complex form. ► The activation energy and the diffusion path are very similar to the F case. ► The complex diffusion corresponds to the Si diffusion with carrying a halogen atom.