Methanethiolate adsorption site on Au(111): a combined STM/DFT study at the single-molecule level

The chemisorptive bonding of methanethiolate (CH(3)S) on the Au(111) surface has been investigated at a single-molecule level using low-temperature scanning tunneling microscopy (LT-STM) and density functional theory (DFT). The CH(3)S species were produced by STM-tip-induced dissociation of methanethiol (CH(3)SH) or dimethyl disulfide (CH(3)SSCH(3)) at 5 K. The adsorption site of an isolated CH(3)S species was assigned by comparing the experimental and calculated STM images. We conclude that the S-headgroup of chemisorbed CH(3)S adsorbs on the 2-fold coordinated bridge site between two Au atoms, consistent with theoretical predictions for CH(3)S on the nondefective Au(111) surface. Our assignment is also supported by the freezing of the tip-induced rotational dynamics of a single CH(3)SH molecule upon conversion to CH(3)S via deprotonation.