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Adsorption Geometry of CO versus Coverage on TiO2(110) from s- and p-Polarized Infrared Spectroscopy.

Authors
  • Petrik, Nikolay G1
  • Kimmel, Greg A1
  • 1 Chemical and Materials Sciences Division, Pacific Northwest National Laboratory, MSIN K8-88, P.O. Box 999, Richland, Washington 99352, United States. , (United States)
Type
Published Article
Journal
The Journal of Physical Chemistry Letters
Publisher
American Chemical Society
Publication Date
Dec 06, 2012
Volume
3
Issue
23
Pages
3425–3430
Identifiers
DOI: 10.1021/jz301413v
PMID: 26290967
Source
Medline
Keywords
Language
English
License
Unknown

Abstract

The adsorption of CO on reduced, rutile TiO2(110) is investigated using IR reflection-absorption spectroscopy and temperature-programmed desorption. Experiments using s- and p-polarized IR light incident along the [001] and [11̅0] azimuths give detailed information on the adsorption geometry of the CO as a function of the CO coverage, θCO. The results indicate that for θCO ≤ 1 ML, CO adsorbs oriented perpendicular to the surface at Ti5c sites. For 1 < θCO ≤ 1.5 ML, the bonding geometry of the CO adsorbed at Ti5c sites is unchanged, whereas the additional CO molecules adsorb at Ob sites parallel to the surface and parallel to the [11̅0] azimuth. The results do not support previous suggestions that CO at Ti5c sites tilt ∼20° from normal at high coverages. The results demonstrate the utility of polarization-resolved infrared reflection-absorption spectroscopy for elucidating adsorption geometries on dielectric substrates.

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