A structural study of the interaction of methanethiol with Pt(1 1 1) using X-ray standing waves

In combination with surface characterisation by synchrotron radiation X-ray photoelectron spectroscopy, the normal incidence X-ray standing wave (NIXSW) technique has been applied to a determination of the structure of surface phases formed on Pt(1 1 1) by reaction with methanethiol. On surfaces heated to ⩾ ≈500 K, producing only coadsorbed atomic S and C, the S atoms are found to occupy fcc hollow sites (directly above Pt atoms in the third layer) in a geometry essentially identical to that of simple ordered S overlayer phases on Pt(1 1 1) with a S–Pt layer spacing of 1.67 Å, but with possible fractional co-occupation of a complex S phase. On a surface annealed to ≈223 K only a surface methanethiolate (CH3S–) species is believed to be present, the favoured model involves a tilted off-atop bonding such that the S atoms are located offset from the fcc hollow sites, with frustrated rotational vibrations of large amplitude, although an alternative model based on co-occupation of atop and fcc hollow sites is also consistent with the NIXSW data.