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Dissociative Water Adsorption on Gas-Phase Titanium Dioxide Cluster Anions Probed with Infrared Photodissociation Spectroscopy

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http://pubman.mpdl.mpg.de/cone/persons/resource/persons192335

Debnath,  Sreekanta
Molecular Physics, Fritz Haber Institute, Max Planck Society;
Wilhelm-Ostwald-Institut für Physikalische und Theoretische Chemie, Universität Leipzig;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons21548

Gewinner,  Sandy
Molecular Physics, Fritz Haber Institute, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons22079

Schöllkopf,  Wieland
Molecular Physics, Fritz Haber Institute, Max Planck Society;

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Citation

Weichman, M. L., Debnath, S., Kelly, J. T., Gewinner, S., Schöllkopf, W., Neumark, D. M., et al. (2018). Dissociative Water Adsorption on Gas-Phase Titanium Dioxide Cluster Anions Probed with Infrared Photodissociation Spectroscopy. Topics in Catalysis, 61(1-2), 92-105. doi:10.1007/s11244-017-0863-4.


Cite as: http://hdl.handle.net/21.11116/0000-0000-7475-A
Abstract
Gas-phase complexes of water on small titanium oxide clusters are model systems to examine the molecular-level mechanism of dissociative water adsorption at defect sites on bulk titania surfaces. Here, we report infrared photodissociation (IRPD) spectra for [(TiO2)n(D2Om)]- clusters with n = 2–4 and m = 1–3; the clusters are tagged with weakly-bound D2 so that only single photon absorption is required for photodissociation. Vibrational features are reported in the spectral windows of 400–1200 and 2600–3000 cm-1, capturing both fingerprint cluster modes and O–D stretching modes. The IRPD spectra are interpreted with the aid of ωB97X-D/aug-cc-pVDZ density functional theory calculations. We conclusively assign the IRPD spectra of the n = 2, m = 1,2 and n = 3, m = 1–3 clusters to global minimum-energy structures containing dissociatively adsorbed water. We also provide insight into the more complicated spectroscopy of the n = 4 clusters, which show possible contributions from a kinetically trapped reactive intermediate in addition to the global minimum-energy isomer. From this work, we can draw conclusions about the size dependence and site-specificity of (TiO2)n- cluster reactivity.