Structure determination of PF3 adsorption on Cu(100) using X-ray standing waves

The local structure of the Cu(100)c(4×2)–PF3 adsorption phase has been investigated through the use of normal-incidence X-ray standing waves (NIXSW), monitored by P 1s and F 1s photoemission, together with P K-edge near-edge X-ray absorption fine structure (NEXAFS). NEXAFS shows the molecule to be oriented with its C3v symmetry axis essentially perpendicular to the surface, while the P NIXSW data show the molecule to be adsorbed in atop sites 2.37±0.04Å above the surface, this distance corresponding to the Cu–P nearest-neighbour distance in the absence of any surface relaxation. F NIXSW indicates a surprisingly small height difference of the P and F atoms above the surface 0.44±0.06Å, compared with the value expected for an undistorted gas-phase geometry of 0.77Å, implying significant increases in the F–P–F bond angles. In addition, however, the F NIXSW data indicate that the molecules have a well-defined azimuthal orientation with a molecular mirror plane aligned in a 〈011〉 substrate mirror plane, and with a small (5–10°) tilt of the molecule in this plane such that the two symmetrically-equivalent F atoms in each molecule are tilted down towards the surface.