Structures of Butylthiolate Self-Assembled Monolayers on Au(111) with Gold Adatoms

A density functional theory method with the local basis set was employed to perform slab calculations to study thiolate-induced surface reconstruction structures of butylthiolates (ButS) with c(4 x 2) superlattice of the Au(111) surface. The slab calculations indicate that the most stable adsorption structure is the ButS-Au (adatom)-SBut complex form, which is in good agreement with the reported experiments and theoretical results for thiolates with shorter alkyl chains. The cis form of ButS-Au (adatom)-SBut motifs is preferred by 0.11 eV with respect to the trans form, and by 0.15 eV over the mixed cis-trans configurations due to the steric hindrance between adjacent butyl groups. It appears that the motif of Au adatom on the Au(111) surface is favored even for butylthiolate.