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Issue 43, 2011
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Structures and vibrational spectroscopy of partially reduced gas-phase cerium oxide clusters

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Abstract

This work demonstrates that the most stable structures of even small gas-phase aggregates of cerium oxide with 2–5 cerium atoms show structural motifs reminiscent of the bulk ceria. This is different from main group and transition metal oxide clusters, which often display structural features that are distinctly different from the bulk structure. The structures of Ce2O2+, Ce3O4+, and (CeO2)mCeO+ clusters (m = 0–4) are unambiguously determined by a combination of global structure optimizations at the density functional theory level and infrared vibrational predissociation spectroscopy of the cluster–rare gas atom complexes. The structures of Ce2O2+ and Ce2O3+ exhibit a Ce–O–Ce–O four-membered ring with characteristic absorptions between 430 and 680 cm−1. Larger clusters have common structural features containing fused Ce–O–Ce–O four-membered rings which lead to intense absorption bands at around 500 and 650 cm−1. Clusters containing a terminal Ce[double bond, length as m-dash]O bond show a characteristic absorption band between 800 and 840 cm−1. For some cluster sizes multiple isomers are observed. Their individual infrared signatures are identified by tuning their relative population through the choice of He, Ne or Ar messenger atoms. The present results allow us to benchmark different density functionals which yield different degrees of localization of unpaired electrons in Ce 4f states.

Graphical abstract: Structures and vibrational spectroscopy of partially reduced gas-phase cerium oxide clusters

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Publication details

The article was received on 29 Jun 2011, accepted on 23 Aug 2011 and first published on 04 Oct 2011


Article type: Paper
DOI: 10.1039/C1CP22129A
Citation: Phys. Chem. Chem. Phys., 2011,13, 19393-19400
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    Structures and vibrational spectroscopy of partially reduced gas-phase cerium oxide clusters

    A. M. Burow, T. Wende, M. Sierka, R. Włodarczyk, J. Sauer, P. Claes, L. Jiang, G. Meijer, P. Lievens and K. R. Asmis, Phys. Chem. Chem. Phys., 2011, 13, 19393
    DOI: 10.1039/C1CP22129A

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