The adsorption of multivalent thiols on gold (111) surface was investigated using density functional theory applying the Perdew-Burke-Ernzerhof functional. Through the comparison of differences in energetics, structure and charge density distribution of a set of monodentate and polydentate thiols, we have described in detail the factors affecting the adsorption energy and the role played by the multivalence, which causes a decreasing of adsorption energy because of both electronic and steric hindrance effects. Finally, the comparison between the adsorption of 1,2- and 1,3-disulfides revealed how the chain length may affect the cleavage of the S-S bond when they adsorb on Au(111) surface.
Keywords: Au (111); ab initio; adsorption; density functional theory; multivalence; thiols.
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