Disparate Effects of Cu and V on Structures of Exohedral Transition Metal-Doped Silicon Clusters: A Combined Far-Infrared Spectroscopic and Computational Study.
The growth mechanisms of small cationic silicon clusters containing up to 11 Si atoms, exohedrally doped by V and Cu atoms, are described. We find that as dopants, V and Cu follow two different paths: while V prefers substitution of a silicon atom in a highly coordinated position of the cationic bar...
| Publicado en: | Journal of the American Chemical Society Vol. 132; no. 44; pp. 15589 - 15603 |
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| Autores principales: | , , , , , , |
| Formato: | Artículo |
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American Chemical Society
11/10/2010
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| Materias: | |
| Acceso en línea: | Ver este registro en EBSCOhost |
| fields | @attributes: recordID: 1 pdfLink: plink: https://search.ebscohost.com/login.aspx?direct=true&db=hlh&AN=55353055&site=ehost-live header: @attributes: shortDbName: hlh uiTerm: 55353055 longDbName: Humanities International Complete uiTag: AN controlInfo: bkinfo: jinfo: jid: 00027863 ACS jtl: Journal of the American Chemical Society issn: 00027863 maglogo: N pubinfo: dt: 11/10/2010 vid: 132 iid: 44 pid: 997 pub: American Chemical Society artinfo: ui: 55353055 10.1021/ja105099u ppf: 15589 ppct: 14 formats: tig: atl: Disparate Effects of Cu and V on Structures of Exohedral Transition Metal-Doped Silicon Clusters: A Combined Far-Infrared Spectroscopic and Computational Study. aug: au: Ngan, Vu Thi Gruene, Philipp Claes, Pieterjan Janssens, Ewald Fielicke, André Nguyen, Minh Tho Lievens, Peter affil: Department of Chemistry, Katholieke Universiteit Leuven, B-3001 Leuven, Belgium Institute for Nanoscale Physics and Chemistry (INPAC), Katholieke Universiteit Leuven, B-3001 Leuven, Belgium Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195 Berlin, Germany Laboratory of Solid State Physics and Magnetism, Katholieke Universiteit Leuven, B-3001 Leuven, Belgium su: Transition metals Silicon spectra Spectroscopic imaging Density functionals Infrared spectra sug: subj: Transition metals Silicon spectra Spectroscopic imaging Density functionals Infrared spectra ab: The growth mechanisms of small cationic silicon clusters containing up to 11 Si atoms, exohedrally doped by V and Cu atoms, are described. We find that as dopants, V and Cu follow two different paths: while V prefers substitution of a silicon atom in a highly coordinated position of the cationic bare silicon clusters, Cu favors adsorption to the neutral or cationic bare clusters in a lower coordination site. The different behavior of the two transition metals becomes evident in the structures of SiM (n = 4-11 for M = V, and n = 6-11 for M = Cu), which are investigated by density functional theory and, for several sizes, confirmed by comparison with their experimental vibrational spectra. The spectra are measured on the corresponding SiM·Ar complexes, which can be formed for the exohedrally doped silicon clusters. The comparison between experimental and calculated spectra indicates that the BP86 functional is suitable to predict far-infrared spectra of these clusters. In most cases, the calculated infrared spectrum of the lowest-lying isomer fits well with the experiment, even when various isomers and different electronic states are close in energy. However, in a few cases, namely SiCu, SiCu, and SiV, the experimentally verified isomers are not the lowest in energy according to the density functional theory calculations, but their structures still follow the described growth mechanism. The different growth patterns of the two series of doped Si clusters reflect the role of the transition metal's 3d orbitals in the binding of the dopant atoms. pubtype: Academic Journal doctype: Article src: R language: English refInfo: copyright: @attributes: flag: Y dt: @attributes: year: 2010 holdings: @attributes: islocal: N |
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