{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,14]],"date-time":"2025-10-14T00:26:46Z","timestamp":1760401606720,"version":"build-2065373602"},"reference-count":39,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2005,6,21]],"date-time":"2005-06-21T00:00:00Z","timestamp":1119312000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["ChemPhysChem"],"published-print":{"date-parts":[[2005,7,11]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p><jats:italic>The influence of oxygen precoverage on the bonding geometry of methoxide on Ru(001) was studied using the isotopically labeled molecule CHD<jats:sub>2<\/jats:sub>OH by reflection\u2013absorption infrared spectroscopy (RAIRS). This molecule is an excellent model because the vibrational spectra of CHD<jats:sub>2<\/jats:sub>O<\/jats:italic><jats:sup><jats:italic>\u2212<\/jats:italic><\/jats:sup> <jats:italic>may be unambiguously correlated with the adsorption configuration. For Ru(001)\uf8ffO layers with an effective oxygen coverage (<\/jats:italic>\u03b8<jats:sub><jats:italic>0<\/jats:italic><\/jats:sub><jats:italic>) 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 [D<jats:sub>2<\/jats:sub>]methanol (0.01 L; L=Langmuir, 1 L=10<\/jats:italic><jats:sup><jats:italic>\u22126<\/jats:italic><\/jats:sup> <jats:italic>torr\u2009s), at 90 K, no oxygen\u2010coverage effects were detected on the geometry of [D<jats:sub>2<\/jats:sub>]methoxide: it adsorbs in an upright orientation (pseudo\u2010<\/jats:italic>C<jats:sub><jats:italic>3<\/jats:italic>v<\/jats:sub> <jats:italic>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<\/jats:italic> \u03b8<jats:sub><jats:italic>O<\/jats:italic><\/jats:sub><jats:italic>=0.25 ML,<\/jats:italic> C<jats:sub>s<\/jats:sub><jats:italic>\/<\/jats:italic>C<jats:sub><jats:italic>1<\/jats:italic><\/jats:sub> <jats:italic>and intrinsic<\/jats:italic> C<jats:sub><jats:italic>1<\/jats:italic><\/jats:sub> <jats:italic>configurations are present on the surface, whereas for<\/jats:italic> \u03b8<jats:sub><jats:italic>O<\/jats:italic><\/jats:sub><jats:italic>\u22650.5 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 (<\/jats:italic>\u03b8<jats:sub><jats:italic>O<\/jats:italic><\/jats:sub><jats:italic>=0.6 ML), formate. The influence of the oxygen precoverage becomes determinant when annealing a [D<jats:sub>2<\/jats:sub>]methanol multilayer to 105 K: for<\/jats:italic> \u03b8<jats:sub><jats:italic>O<\/jats:italic><\/jats:sub><jats:italic>=0.25 ML, the RAIR spectrum correlates with a disordered layer of tilted methoxide and formaldehyde, whereas for<\/jats:italic> \u03b8<jats:sub><jats:italic>O<\/jats:italic><\/jats:sub><jats:italic>=0.6 ML upright methoxide, formate, and carbon monoxide were identified. On clean Ru(001), for methanol exposures \u22650.1 L, the<\/jats:italic> C<jats:sub><jats:italic>3<\/jats:italic>v<\/jats:sub> <jats:italic>methoxide configuration was never attained upon thermal activation.<\/jats:italic><\/jats:p>","DOI":"10.1002\/cphc.200400546","type":"journal-article","created":{"date-parts":[[2005,6,21]],"date-time":"2005-06-21T05:24:28Z","timestamp":1119331468000},"page":"1299-1306","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":8,"title":["Adsorption of [D<sub>2<\/sub>]Methanol on Ru(001)\uf8ffO Surfaces: The Influence of Preadsorbed Oxygen on the Methoxide Geometry"],"prefix":"10.1002","volume":"6","author":[{"given":"Ricardo B.","family":"Barros","sequence":"first","affiliation":[]},{"given":"Ana Rosa","family":"Garcia","sequence":"additional","affiliation":[]},{"given":"Laura 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