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Alkanethiol self-assembled monolayers (SAMs) have been attracted considerately attentions during last two decades due to its easy preparation and highly ordered 2D structure.Despite its simplicity and accessibility in most laboratories,many aspects of the SAM/Au(111) system remain controversial[1-3],such as the adsorption moiety at the SAM/Au(111) interface.Its shown that dimethyl sulfide (DMDS) will dissociate into methanethiolate (C1) and two of them will be bonded by one Au adatom to form RS-Au-RS configuration on Au(111) at low temperature[3].