Experimental vibrational spectra of gas-phase tantalum cluster cations

Gruene, Philipp; Fielicke, André; Meijer, Gerard

doi:10.1063/1.2806177

Cited by 27 publications

(42 citation statements)

References 48 publications

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“…The reduced complex formation at the critical size of n = 11 is attributed to the encapsulation of the dopant atom from this size onwards, in line with the observations for other dopants (Ti, V, Cr, Co, and Cu). 25 Surprisingly, the propensity of Ar and Xe complex formation for Si 7 Mn + is exceptionally low, an effect that has not been observed for any of the other TM dopants studied before. In order to understand why the fraction of Si 7 Mn + ÁRG complexes is so much lower than those of other Si n Mn + (n r 10) clusters, we set out a theoretical study of the chemical bonding of Ar and Xe atoms with two series of clusters: Si n Mn + (n = 6-10) and Si 7 TM + (TM = Cr, Mn, Cu, and Zn).…”

Section: Mass Spectrometric Observationsmentioning

confidence: 81%

“…For Si 7 Mn + much smaller BDE are found. The stationary structure Com-A of Si 7 Mn + ÁAr even has negative BDE after correction for ZPEs, meaning that such a complex will only be metastable.…”

Section: Mass Spectrometric Observationsmentioning

confidence: 91%

“…Com-A of Si 7 Mn + ÁXe has an exceptionally low BDE of only 0.03 eV. The BDE of Com-B is 0.02 eV for Si 7 Mn + ÁAr and 0.14 eV for Si 7 Mn + ÁXe. Complexes with a BDE larger than B0.15 eV (such as for Si n Mn + ÁRG with n = 6, 8-10 and RG = Ar, Xe) are observed in the mass spectra with higher abundances.…”

Section: Mass Spectrometric Observationsmentioning

confidence: 96%

“…Structurally, only the exact binding position of the rare gas atom is unsure, as the available IR spectrum was not very sensitive to this. We therefore have searched different isomers of the rare gas complexes and found only two isomers for Si 7 Mn + ÁRG and one stable isomer for other Si n Mn + ÁRG. Due to the weak interaction, the rare gas attachment does not lead to changes in the electronic/spin state of the clusters.…”

Section: Mass Spectrometric Observationsmentioning

confidence: 99%

“…3. For Si 7 Mn + ÁRG, two stable structural isomers, Com-A and Com-B, have been identified. The RG directly binds to the Mn dopant atom along an axis connecting the Mn atom with the center of the cluster (principal axis).…”

Section: Mass Spectrometric Observationsmentioning

confidence: 99%

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Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

Ngân

Janssens

Claes

et al. 2015

Phys. Chem. Chem. Phys.

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Mass spectrometry experiments show an exceptionally weak bonding between Si 7 Mn + and rare gas atoms as compared to other exohedrally transition metal (TM) doped silicon clusters and other Si n Mn + (n = 5-10) sizes. The Si 7 Mn + cluster does not form Ar complexes and the observed fraction of Xe complexes is low. The interaction of two cluster series, Si n Mn + (n = 6-10) and Si 7 TM + (TM = Cr, Mn, Cu, and Zn), with Ar and Xe is investigated by density functional theory calculations. The cluster-rare gas binding is for all clusters, except Si 7 Mn + and Si 7 Zn + , predominantly driven by short-range interaction between the TM dopant and the rare gas atoms. A high s-character electron density on the metal atoms in Si 7 Mn + and Si 7 Zn + shields the polarization toward the rare gas atoms and thereby hinders formation of short-range complexes.Overall, both Ar and Xe complexes are similar except that the larger polarizability of Xe leads to larger binding energies.Atomic clusters emerge as interesting materials in the size regime between single atoms and nanoparticles, whose properties are strongly influenced by confinement effects. Understanding of their size and composition dependent structures and properties is primordial for further usage. The interactions between clusters and rare gas (RG) atoms are of crucial importance in many experimental techniques. For example, RG complexes are used for action spectroscopy in cluster science due to the inherent weak interaction, 1 Ar titration and tagging have been used to obtain isomer-specific photoelectron spectra for 2D and 3D gold clusters 2,3 and isomer selective infrared (IR) spectra of niobium clusters. 4 In most experimental studies, it has been assumed that the RG atoms do not significantly influence the intrinsic structure and properties of the bare clusters, and are therefore called messenger or spectator atoms. A negligible influence of the RG atoms is inferred from their low adsorption energies and from insignificant differences in measured IR spectra of elemental clusters and their Ar-complexes, such as for V n + , 5 Nb n + , 6 Ta n + (n = 6-20), 7 Si n + (n = 6-21), 8 as well as for binary Si n V + and Si n Cu + (n = 6-11) clusters. 9 Nevertheless, such an assumption is not always applicable. Stronger cluster-RG interactions, which cause discernible changes in the IR spectra of the bare clusters, were observed for some Co n + , Au n , and doped Au n Y clusters. 10-12 Moreover, the RG tagging of some oxide clusters changes the energetic ordering of the isomers, in which case a low-energetic structural isomer, and thus not the ground state structure of the bare cluster, is probed in the experiment. 13 A simple electrostatic picture was put forward to explain the stronger influence of the RG atom, analogous to models often used to interpret the interaction of RG atoms with metal surfaces 14 or metal complexes. 15 Much effort has been devoted to reveal the nature of interaction between RG and metal surfaces 12,16 or metal-atom complexes. 14,17 There are a...

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Section: Mass Spectrometric Observationsmentioning

confidence: 81%

Section: Mass Spectrometric Observationsmentioning

confidence: 91%

Section: Mass Spectrometric Observationsmentioning

confidence: 96%

Section: Mass Spectrometric Observationsmentioning

confidence: 99%

Section: Mass Spectrometric Observationsmentioning

confidence: 99%

See 3 more Smart Citations

Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

Ngân

Janssens

Claes

et al. 2015

Phys. Chem. Chem. Phys.

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New Tools for Structure Elucidation in the Gas Phase: IR Spectroscopy of Bare and Doped Silicon Nanoparticles

Gruene

Meijer

Lievens

et al. 2010

Ideas in Chemistry and Molecular Sciences

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Die CO‐Oxidation als Modellreaktion für heterogene Prozesse

et al. 2011

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Die CO‐Oxidation, obwohl eine scheinbar einfache chemische Reaktion, dient als ein Modell, welches die Vielfalt und Attraktivität der heterogenen Katalyse offenbart. Das Fritz‐Haber‐Institut ist ein Ort, an dem ein multidisziplinärer Forschungsansatz zum Studium einer solchen heterogenen Reaktion innerhalb eines Instituts entwickelt und umgesetzt werden kann. Dabei ist die Forschung am Institut primär durch Neugier getrieben, was sich auch in den fünf Abschnitten dieses Aufsatzes widerspiegelt. Wir nutzen dabei mikroskopische Konzepte, um die Wechselwirkung einfacher Moleküle mit wohldefinierten Materialien wie Clustern in der Gasphase oder festen Oberflächen zu untersuchen. Dieser Ansatz erfordert nicht selten die Entwicklung von neuen Methoden, Werkzeugen und Materialien zur Verifizierung dieser Konzepte, und dies ermöglicht eine methodologisch solide, breit aufgestellte Herangehensweise als ein Markenzeichen des Instituts.

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Experimental vibrational spectra of gas-phase tantalum cluster cations

Cited by 27 publications

References 48 publications

Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

New Tools for Structure Elucidation in the Gas Phase: IR Spectroscopy of Bare and Doped Silicon Nanoparticles

Die CO‐Oxidation als Modellreaktion für heterogene Prozesse

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