Structure determination of methanethiolate on unreconstructed Cu(111) by scanned-energy mode photoelectron diffraction

2,5-dichlorothiophenol on Cu(111): Initial adsorption site and scanning tunnel microscope-based abstraction of hydrogen at high intramolecular selectivity

“…Measurements of the Woodruff group addressed methanethiol on Cu͑111͒. Upon adsorption at low temperatures they find a nondeprotonated species, 1,2 which is transformed into the thiolate before room temperature is reached. We investigate the adsorption of 2,5-dichlorothiophenol ͑DCTP, Fig.…”

Electronic Origin of Disorder and Diffusion at a Molecule-Metal Interface: Self-Assembled Monolayers OfCH3Son Cu(111)

“…High resolution S 2p photoelectron spectroscopy [10,11] suggests a wide variety of species on the Cu(111) surface with low (LT) and high (HT) temperature CH 3 S=Cu phases (140 and 300 K, respectively) in addition to CH 3 SH and atomic S on the surface. The LT phase has been proposed to consist of a mixture of symmetric hollow sites (65% of hcp and 35% of fcc) or possibly bridge sites, based on x-ray standing waves [10], whereas photoemission diffraction [12] suggests a 71% and 29% population of bridge and fcc sites, respectively. Room temperature STM images [13] revealed three different phases with tentative assignment as the LT and HT phases and a hexagonal full coverage phase.…”

“…Density functional calculations of the CH 3 S=Cu111 SAM were performed using the CPMD and CASTEP codes [19], the Perdew-Burke-Ernzerhof functional, and Vanderbilt ultrasoft pseudopotential with a plane wave cutoff of 25 Ry. The LT phase [10,12] is modeled as a six-layer slab with one and four CH 3 S for the c2 2 and c4 4 cells, respectively, including an 8 Å vacuum layer. This yields a concentration of 3:85 10 ÿ14 cm ÿ2 close to the experimental value of &5 10 ÿ14 cm ÿ2 [10,13].…”

Chemical State‐specific Surface Structure from Photoemission‐monitored X‐ray Standing Waves

“…Figure 4 shows schematically the two low-temperature coadsorbed species: the intact thiol occupies a site with S atop surface Cu atoms, and the thiolate, on the unreconstructed surface, was found to occupy either bridge or mixed hollow sites. More recent work using chemical-state resolved photoelectron diffraction [19] actually indicates that both of these sites are occupied.…”