Bonding mechanism and atomic geometry of an ordered hydroxyl overlayer on Pt(111)

Exposing water to a (2 x 2)-O precovered Pt(111) surface at 100 K and subse quently annealing at 155 K led to the formation of a well-ordered (root3 x root3)R30 degrees overlayer. The structure of this overlayer is determined by DFT and full dynamical LEED calculations. There are two O containing gro ups per (root3 x root3)R30 degrees unit cell and both occupy near on-top po sitions with a Pt-O bond length of (2.11 +/- 0.04) Angstrom. DFT calculatio ns determined the hydrogen positions of the OH species and clearly indicate hydrogen bonds between the neighboring adsorbed OH groups whose interactio n is mainly of electrostatic nature. A theoretical comparison with H2O show s the hybridization of OH on Pt(111) to be sp(3).