Gold adatoms modulate sulfur adsorption on gold

Sulfur adsorption on Au(111) at high coverage has been studied by density functional calculations. In this case S species organize into rectangular structures containing 8 S atoms irrespective of the S source, which have been alternatively assigned to adsorbed monomeric S, adsorbed S₂, adsorbed monomeric plus S₂ species, and gold sulfide. We found that monomeric S at the high coverage organizes into S₂ species that are stabilized into the 8-S structures by Au adatoms, forming gold disulfide complexes (Au-(S₂)₄). The Au atoms could be provided by decomposition of more diluted AuS₃ containing phases, as recently proposed, and direct removal from terraces and step edges, both explaining the surface coverage of vacancy islands coexisting with the 8-S structures. The gold-disulfide complexes capture the disorder shown in the experimental STM images, explain the intrigued features of XPS, and also, give a smooth pathway to gold sulfide formation at higher temperatures. More importantly, the gold-disulfide complexes allow a unified picture of the gold-sulfur surface chemistry at high coverage for thiols and adsorbed sulfur species where the surface chemistry remains under discussion.