Abstract
The adsorption structure of 3-chlorothiophene on Cu(111) has been investigated using a combination of normal incidence X-ray standing wavefield absorption (NIXSW) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. For coverages up to saturation of the chemisorbed layer, the 3-chlorothiophene bonds through the S atom. The S atom adsorbs in an atop site with a Cu–S distance identical, within experimental error, to that observed for thiophene on the same substrate. From a combination of NEXAFS and NIXSW, thiophene was found to adsorb with the aromatic ring flat lying. From NIXSW measurements the S–Cl axis was found to be inclined by 12±2° from the surface. Whilst NEXAFS data suggested an orientation of 23±8° for the aromatic ring of 3-chlorothiophene. The Cl atom interacted only weakly with the substrate, with a Cl–surface distance longer than the Cu–Cl van der Waal separation.
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