We investigated the adsorption of 2,5-di-chloro-thio-phenol (DCTP) on Cu(111) at 15 K and the formation of the thiolate upon electronic and thermal excitation. Initially, the sulfur atom of DCTP adsorbs at an on-top site and the molecule is able to rotate through six almost identical surface orientations. Attachment or removal of electrons from anywhere within the molecule at several hundred mV bias leads to the abstraction of the hydrogen atom from the thiol group in a nonthermal one-electron process with perfect selectivity. The resultant thiolate is locked into position on the surface. (C) 2003 American Institute of Physics.