Adsorption of chlorine on Ag(111): No subsurface Cl at low coverage

Abstract

The adsorption of molecular and atomic chlorine on perfect Ag(111) surface has been studied and characterized by means of extensive density-functional-theory calculations. For the molecular adsorption, we find that the dissociation of ${\text{Cl}}_{2}$ proceeds with an almost vanishing barrier. As for the adsorption of atomic Cl, on-surface, subsurface, and substitutional adsorptions are considered as a function of the coverage. At coverage lower than 1/2 ML, the on-surface adsorption displays the most exothermic chemisorption energies, whereas the mixed $\text{on-surface}+\text{subsurface}$ and $\text{on-surface}+\text{substitutional}$ adsorption modes become competitive with pure on-surface adsorption at about 1/2 ML of coverage and at higher coverages even preferred. The analysis of the adsorption free energy as a function of chlorine chemical potential reveals that the on-surface $(\sqrt{3}\ifmmode\times\else\texttimes\fi{}\sqrt{3})R30\ifmmode^\circ\else\textdegree\fi{}$ adsorption phase is thermodynamically the most stable over a very broad range of Cl chemical potential. The mixed adsorption modes become thermodynamically more stable at high coverage for values of the Cl chemical potential that are substantially larger than those needed to form silver chloride. This finding seems to indicate that the formation of mixed adsorption phases, if they would ever occur, cannot be due to thermodynamic equilibrium but can only result from kinetic effects. We also find that the presence of open surface steps does not stabilize the subsurface Cl adsorption at low coverage. However due to the stronger Cl-surface interaction near steps, the mixed $\text{on-surface}+\text{subsurface}$ adsorption on Ag(210) at high coverage becomes thermodynamically the most stable phase at Cl chemical potential close to that needed for the formation of bulk AgCl.