Adsorption site determination of a large π-conjugated molecule by normal incidence x-ray standing waves: End-capped quaterthiophene on Ag(111)

Abstract

Using normal incidence x-ray standing waves, we determined the geometric structure of the adsorption site of a large \ensuremath{\pi}-conjugated molecule with six rings, end-capped quaterthiophene (EC4T), on the Ag(111) surface in the commensurate monolayer. The S $1s$ absorption profiles were measured for the (111) and $(1\ifmmode\bar\else\textasciimacron\fi{}11)$ Bragg reflections. The vertical coherent position ${D}_{\mathrm{co}}^{(111)},$ i.e., the average distance between molecules and Ag surface, was determined to $3.15\ifmmode\pm\else\textpm\fi{}0.05\AA{}.$ This is less than expected for van der Waals bonding and more than known for a local S-Ag bond, thus revealing that the surface bonding involves the entire conjugated \ensuremath{\pi} system, in agreement with earlier photoemission results. The lateral position of the EC4T molecule was obtained from a simulation of the experimental coherent position in $[1\ifmmode\bar\else\textasciimacron\fi{}11]$ direction $(1.02\ifmmode\pm\else\textpm\fi{}0.1\AA{}).$ This results in the first complete determination of the adsorption geometry of a large flat-lying organic molecule on an inorganic surface.