Not so loosely bound rare gas atoms: finite-temperature vibrational fingerprints of neutral gold-cluster complexes
| dc.contributor.author | Ghiringhelli, Luca M. | |
| dc.contributor.author | Gruene, Philipp | |
| dc.contributor.author | Lyon, Jonathan T. | |
| dc.contributor.author | Rayner, David M. | |
| dc.contributor.author | Meijer, Gerard | |
| dc.contributor.author | Fielicke, André | |
| dc.contributor.author | Scheffler, Matthias | |
| dc.date.accessioned | 2022-02-15T16:09:03Z | |
| dc.date.available | 2022-02-15T16:09:03Z | |
| dc.date.issued | 2013-08-01 | |
| dc.date.updated | 2022-02-10T11:17:16Z | |
| dc.description.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. | en |
| dc.description.sponsorship | DFG, 390540038, EXC 2008: Unifying Systems in Catalysis "UniSysCat" | en |
| dc.identifier.eissn | 1367-2630 | |
| dc.identifier.uri | https://depositonce.tu-berlin.de/handle/11303/16393 | |
| dc.identifier.uri | http://dx.doi.org/10.14279/depositonce-15169 | |
| dc.language.iso | en | en |
| dc.rights.uri | https://creativecommons.org/licenses/by/3.0/ | en |
| dc.subject.ddc | 530 Physik | de |
| dc.subject.other | rare gas atoms | en |
| dc.subject.other | neutral gold-cluster complexes | en |
| dc.subject.other | multiple photon dissociation | en |
| dc.subject.other | neutral gold clusters | en |
| dc.subject.other | krypton atoms | en |
| dc.title | Not so loosely bound rare gas atoms: finite-temperature vibrational fingerprints of neutral gold-cluster complexes | en |
| dc.type | Article | en |
| dc.type.version | publishedVersion | en |
| dcterms.bibliographicCitation.articlenumber | 083003 | en |
| dcterms.bibliographicCitation.doi | 10.1088/1367-2630/15/8/083003 | en |
| dcterms.bibliographicCitation.issue | 8 | en |
| dcterms.bibliographicCitation.journaltitle | New Journal of Physics | en |
| dcterms.bibliographicCitation.originalpublishername | IOP | en |
| dcterms.bibliographicCitation.originalpublisherplace | Bristol | en |
| dcterms.bibliographicCitation.volume | 15 | en |
| tub.accessrights.dnb | free | en |
| tub.affiliation | Verbundforschung::Exzellenzcluster (EXC)::UniSysCat | de |
| tub.affiliation.faculty | Verbundforschung | de |
| tub.affiliation.group | UniSysCat | de |
| tub.affiliation.institute | Exzellenzcluster (EXC) | de |
| tub.publisher.universityorinstitution | Technische Universität Berlin | en |