R<scp>EACTIONS OF</scp>T<scp>RANSITION</scp>M<scp>ETAL</scp>C<scp>LUSTERS WITH</scp>S<scp>MALL</scp>M<scp>OLECULES</scp>

Knickelbein, Mark B.

doi:10.1146/annurev.physchem.50.1.79

Cited by 273 publications

(193 citation statements)

References 150 publications

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“…1,2 However, structural information on the hydrogen binding sites is relatively scarce. On extended metal surfaces hydrogen is known to have a preference for high coordination sites.…”

Section: Introductionmentioning

confidence: 99%

H₂ Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

et al. 2008

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The adsorption of H 2 on a series of gas-phase transition metal (scandium, vanadium, iron, cobalt, and nickel) clusters containing up to 20 metal atoms is studied using IR-multiple photon dissociation spectroscopy complemented with density functional theory based calculations. Comparison of the experimental and calculated spectra gives information on hydrogen-bonding geometries. The adsorption of H 2 is found to be exclusively dissociative on Sc n O + , V n + , Fe n + , and Co n + , and both atomic and molecularly chemisorbed hydrogen is present in Ni n H m + complexes. It is shown that hydrogen adsorption geometries depend on the elemental composition as well as on the cluster size and that the adsorption sites are different for clusters and extended surfaces. In contrast to what is observed for extended metal surfaces, where hydrogen has a preference for high coordination sites, hydrogen can be both 2-or 3-fold coordinated to cationic metal clusters.

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“…1,2 However, structural information on the hydrogen binding sites is relatively scarce. On extended metal surfaces hydrogen is known to have a preference for high coordination sites.…”

Section: Introductionmentioning

confidence: 99%

H₂ Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

et al. 2008

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Section: Introductionmentioning

confidence: 99%

“…Metallic clusters play a central role in catalysis [3,4,5,6] and nanotechnology [7,8,9]. Cluaters of coinage metals Cu, Ag and Au have been used in a wide range of demonstration [3,4,5,6,7,8,9]. The determination of structural and electronic properties and the growth pattern of coinage metal clusters are of much interest both experimentally [10,11,12,13,14,15,16,17,18] and theoretically [19,20,21,22,23,24].…”

Section: Introductionmentioning

confidence: 99%

Structure and stability of copper clusters: A tight-binding molecular dynamics study

2004

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In this paper we propose a tight-binding molecular dynamics with parameters fitted to firstprinciples calculations on the smaller clusters and with an environment correction, to be a powerful technique for studying large transition/noble metal clusters. In particular, the structure and stability of Cun clusters for n = 3−55 are studied by using this technique. The results for small Cun clusters (n = 3 − 9) show good agreement with ab initio calculations and available experimental results. In the size range 10 ≤ n ≤ 55 most of the clusters adopt icosahedral structure which can be derived from the 13-atom icosahedron, the polyicosahedral 19-, 23-, and 26-atom clusters and the 55-atom icosahedron, by adding or removing atoms. However, a local geometrical change from icosahedral to decahedral structure is observed for n = 40 − 44 and return to the icosahedral growth pattern is found at n = 45 which continues. Electronic "magic numbers" (n = 2, 8, 20, 34, 40) in this regime are correctly reproduced. Due to electron pairing in HOMOs, even-odd alternation is found. A sudden loss of even-odd alternation in second difference of cluster binding energy, HOMO-LUMO gap energy and ionization potential is observed in the region n ∼ 40 due to structural change there. Interplay between electronic and geometrical structure is found.

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“…Aspects of this chemistry have been reviewed by Knickelbein,1 showing that transition metal clusters are amenable to detailed theoretical and experimental investigation, often revealing provocative relationships between physical properties and chemical reactivity. In this paper, the interaction of neutral Nb clusters with ethene in a fast flow gas-phase reactor is reported.…”

Section: Introductionmentioning

confidence: 99%

Cluster Size Selectivity in the Product Distribution of Ethene Dehydrogenation on Niobium Clusters

et al. 2005

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/npsi/ctrl?action=rtdoc&an=12327971&lang=en http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/ctrl?action=rtdoc&an=12327971&lang=fr READ THESE TERMS AND CONDITIONS CAREFULLY BEFORE USING THIS WEBSITE.http://nparc.cisti-icist.nrc-cnrc.gc.ca/npsi/jsp/nparc_cp.jsp?lang=en Vous avez des questions? Nous pouvons vous aider. Pour communiquer directement avec un auteur, consultez la première page de la revue dans laquelle son article a été publié afin de trouver ses coordonnées. Si vous n'arrivez pas à les repérer, communiquez avec nous à PublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. Questions? Contact the NRC Publications Archive team atPublicationsArchive-ArchivesPublications@nrc-cnrc.gc.ca. If you wish to email the authors directly, please see the first page of the publication for their contact information. NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://doi.org/10.1021/jp0506944The Journal of Physical Chemistry A, 109, 32, pp. 7046-7056, 2005-07- Sciences, National Research Council of Canada, 100 Sussex DriVe, Ottawa, Ontario, Canada K1A 0R6 ReceiVed: February 8, 2005; In Final Form: May 13, 2005 Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb 8 and Nb 10 , for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb 10 , yielding either Nb n C 2 H 2 or Nb n C 2 . Over the range Nb-Nb 6 , the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C 2 H 4 ,C 2 H 2 ,o rC 2 . With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb n cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calcu...

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REACTIONS OFTRANSITIONMETALCLUSTERS WITHSMALLMOLECULES

Cited by 273 publications

References 150 publications

H₂ Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

H₂ Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

Structure and stability of copper clusters: A tight-binding molecular dynamics study

Cluster Size Selectivity in the Product Distribution of Ethene Dehydrogenation on Niobium Clusters

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REACTIONS OFTRANSITIONMETALCLUSTERS WITHSMALLMOLECULES

Cited by 273 publications

References 150 publications

H2 Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

H2 Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

Structure and stability of copper clusters: A tight-binding molecular dynamics study

Cluster Size Selectivity in the Product Distribution of Ethene Dehydrogenation on Niobium Clusters

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Product

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H₂ Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study

H₂ Adsorption on 3d Transition Metal Clusters: A Combined Infrared Spectroscopy and Density Functional Study