Not so loosely bound rare gas atoms : finite-temperature vibrational fingerprints of neutral gold-cluster complexes

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DOIResolve DOI: http://doi.org/10.1088/1367-2630/15/8/083003
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TypeArticle
Journal titleNew Journal of Physics
ISSN1367-2630
Volume15
Issue8
Pages123; # of pages: 23
AbstractWe present an experimental and theoretical study of the structure of small, neutral gold clusters—Au3, Au4 and Au7—'tagged' by krypton atoms. Infrared (IR) spectra of AuNcenterdotKrM complexes formed at 100 K are obtained via far-IR multiple photon dissociation in a molecular beam. The theoretical study is based on a statistical (canonical) sampling of the AuNcenterdotKrM complexes through ab initio molecular dynamics using density-functional theory in the generalized gradient approximation, explicitly corrected for long-range van-der-Waals (vdW) interactions. The choice of the functional is validated against higher-level first-principle methods. Thereby finite-temperature theoretical vibrational spectra are obtained that are compared with the experimental spectra. This enables us to identify which structures are present in the experimental molecular beam for a given cluster size. For Au2, Au3 and Au4, the predicted vibrational spectra of the Kr-complexed and pristine species differ. For Au7, the presence of Kr influences the vibrational spectra only marginally. This behavior is explained in terms of the formation of a weak chemical bond between Kr and small gold clusters that localizes the Kr atom at a defined adsorption site, whereas for bigger clusters the vdW interactions prevail and the Kr adatom is delocalized and orbits the gold cluster. In all cases, at temperatures as low as T = 100 K, vibrational spectra already display a notable anharmonicity and show, in comparison with harmonic spectra, different position of the peaks, different intensities and broadenings, and even the appearance of new peaks.
Publication date
LanguageEnglish
AffiliationSecurity and Disruptive Technologies; National Research Council Canada
Peer reviewedYes
NPARC number21270335
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Record identifier6af4f89c-71d2-4f85-8161-d1384b4d1dca
Record created2014-01-30
Record modified2017-03-23
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