Theoretical study of ethynylbenzene adsorption on Au(111) and implications for a new class of self-assembled monolayer

Density functional calculations of the adsorption of ethynylbenzene on the Au(I 11) surface show that, after cleavage of the C-H bond, the terminal carbon makes a strong covalent bond to the surface. The bond energy is shown to be about 70 kcal(.)mol(-1) with the fee hollow site being most stable and the molecule oriented perpendicular to the surface. Adsorption without elimination of hydrogen is also possible via a hydrogen 1.2 shift to form a vinylidene surface-bound species, or opening of the C-C triple bond and adsorption through the two carbon atoms in a flat conformation. The reaction energy for formation of the surface-bound vinylidene is estimated to be 5 kcal(.)mol(-1) exothermic relative to the isolated ethynylbenzene and gold substrate.