Investigation of Adsorption Behavior of Mercury on Au(111) from First Principles

ABSTRACT: The structural and electronic properties of Hg, SO2, HgS, and HgO adsorption on Au(111) surfaces have been determined using density functional theory with the generalized gradient approximation. The adsorption strength of Hg on Au(111) increases by a factor of 1.3 (from −9.7 to −12.6 kcal/mol) when the number of surface vacancies increases from 0 to 3; however, the adsorption energy decreases with more than three vacancies. In the case of SO2 adsorption on Au(111), the Au surface atoms are better able to stabilize the SO2 molecule when they are highly undercoordinated. The SO2 adsorption stability is enhanced from −0.8 to −9.3 kcal/mol by increasing the number of vacancies from 0 to 14, with the lowest adsorption energy of −10.2 kcal/mol at 8 Au vacancies. Atomic sulfur and oxygen precovered-Au(111) surfaces lower the Hg stability when Hg adsorbs on the top of S and O atoms. However, a cooperative effect between adjacent Hg atoms is observed as the number of S and Hg atoms increases on the perfect Au(111) surface, resulting in an increase in the magnitude of Hg adsorption. Details of the electronic structure properties of the Hg−Au systems are also discussed. 1