Adsorption of [D2]methanol on Ru(001)--O surfaces: the influence of preadsorbed oxygen on the methoxide geometry.

The influence of oxygen precoverage on the bonding geometry of methoxide on Ru(001) was studied using the isotopically labeled molecule CHD2OH by reflection-absorption infrared spectroscopy (RAIRS). This molecule is an excellent model because the vibrational spectra of CHD2O- may be unambiguously correlated with the adsorption configuration. For Ru(001)--O layers with an effective oxygen coverage (theta0) between 0.25 and 0.6 ML (ML=monolayer), the influence of the oxygen precoverage was shown to vary with the initial methanol exposure. For an extremely low dose of [D2]methanol (0.01 L; L=Langmuir, 1 L=10(-6) torr s), at 90 K, no oxygen-coverage effects were detected on the geometry of [D2]methoxide: it adsorbs in an upright orientation (pseudo-C(3v) local symmetry), just as on clean Ru(001). An increase in the methanol exposure to 0.1 L, at the same temperature, results in the formation of a disordered layer of tilted methoxide: for theta(O)=0.25 ML, C(s)/C1 and intrinsic C1 configurations are present on the surface, whereas for theta(O)> or =0.5 ML, only the former species were identified. The thermal activation of these tilted layers to 105 K results in a lower coverage of upright methoxide for any oxygen precoverage, coadsorbed with decomposition products, as confirmed by the detection of adsorbed formaldehyde and, on the denser oxygen layer (theta(O)=0.6 ML), formate. The influence of the oxygen precoverage becomes determinant when annealing a [D2]methanol multilayer to 105 K: for theta(O)=0.25 ML, the RAIR spectrum correlates with a disordered layer of tilted methoxide and formaldehyde, whereas for theta(O)=0.6 ML upright methoxide, formate, and carbon monoxide were identified. On clean Ru(001), for methanol exposures > or =0.1 L, the C(3v) methoxide configuration was never attained upon thermal activation.