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

Ghiringhelli LM, Gruene P, Lyon JT, Rayner DM, Meijer G, Fielicke A, Scheffler M (2013)

Publication Type: Journal article

Publication year: 2013

Journal

New Journal of Physics Institute of Physics: Open Access Journals / Institute of Physics (IoP) and Deutsche Physikalische Gesellschaft

Book Volume: 15

Article Number: 083003

DOI: 10.1088/1367-2630/15/8/083003

Abstract

We 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 AuN· KrM 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 AuN·KrM 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. © IOP Publishing and Deutsche Physikalische Gesellschaft.

Authors with CRIS profile

Luca Ghiringhelli

Involved external institutions

Fritz-Haber-Institut der Max-Planck-Gesellschaft (FHI)

Germany (DE) National Research Council / Conseil national de recherches Canada

Canada (CA)

How to cite

APA:

Ghiringhelli, L.M., Gruene, P., Lyon, J.T., Rayner, D.M., Meijer, G., Fielicke, A., & Scheffler, M. (2013). Not so loosely bound rare gas atoms: Finite-temperature vibrational fingerprints of neutral gold-cluster complexes. New Journal of Physics, 15. https://doi.org/10.1088/1367-2630/15/8/083003

MLA:

Ghiringhelli, Luca M., et al. "Not so loosely bound rare gas atoms: Finite-temperature vibrational fingerprints of neutral gold-cluster complexes." New Journal of Physics 15 (2013).

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