Chlorine interaction with defects on the Au(111) surface: A first-principles theoretical investigation

Chlorine is an important element in promoting oxidation on noble metal surfaces. Here, we report a comprehensive theoretical study of chlorine interaction with defects on the Au(111) surface, using density functional theory calculations and periodic slabs to model the surface. We find that chlorine binds preferentially on steps, vacancies, and gold adatoms. The increase in binding energy per chlorine atom, compared to binding on the flat, defect-free surface, is 0.29 eV when the chlorine atom is on top of a gold adatom, 0.38 eV when it is at the edge of a step, and 0.19 eV when it is next to a single surface vacancy. An extensive study of chlorine interaction with different numbers of surface gold vacancies revealed that chlorine interacts the strongest with three vacancies.