Metal Clusters and Metal Surfaces

Muetterties, E. L.; Wexler, R.M.

doi:10.1016/b978-0-12-610510-0.50008-0

Cited by 33 publications

(9 citation statements)

References 206 publications

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“…Many gas−surface interactions have analogues in organometallic and coordination chemistry. This analogy was first proposed by Muetterties , and he and others then developed this idea in more recent work. − The most important idea to come out of this analogy was the use of vibrational frequencies from carbonyl and nitrosyl compounds to provide the basis for the assignment of CO and NO vibrational modes on surfaces to adsorption at a site with a particular geometry. In particular, NO was classified into adsorption in 3-fold, 2-fold bridging, atop or bent configurations, and each of these gave rise to different vibrational frequencies.…”

Section: Introductionmentioning

confidence: 99%

NO Chemisorption and Reactions on Metal Surfaces: A New Perspective

2000

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NO adsorption on metal surfaces has been studied extensively due to its important role in many catalytic processes. In the past, it was recognized that the tendency for a metal surface to dissociate NO depends on its position in the periodic table, but little was understood about the dissociation process itself. Recent experimental and theoretical studies have shown that this view is oversimplified. In addition to the distinction between molecular and dissociative adsorption on surfaces, the structure of NO on metal surfaces has also been the subject of detailed study and debate. It is therefore timely to update our ideas about NO adsorption and reactivity. Here we examine the structure of NO on surfaces, in particular the break-down of vibrational assignments and we look at how these assignments can be improved. The NO dissociation process is also discussed along with the formation, and reactions, of the NO dimer, (NO) 2 , on some metal surfaces.

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Section: Introductionmentioning

confidence: 99%

NO Chemisorption and Reactions on Metal Surfaces: A New Perspective

2000

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“…The electronic and geometric structures of vanadium oxide gas phase clusters can correspond to condensed phase surface and/or defect structures, and thus, such clusters can have properties and behavior that relate or correspond to condensed phase chemical and physical phenomena. This local approach to condensed phase modeling was first articulated by Mutterties and has since been explored by a number of other research groups …”

Section: Introductionmentioning

confidence: 99%

Identification, Structure, and Spectroscopy of Neutral Vanadium Oxide Clusters

Matsuda

Bernstein

2005

J. Phys. Chem. A

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Neutral vanadium oxide clusters are studied by photoionization time-of-flight (TOF) mass spectroscopy, electronic spectroscopy, and density functional theory (DFT) calculations. Mass spectra of vanadium oxide clusters are observed by photoionization with lasers of three different wavelengths: 118, 193, and 355 nm. Mechanisms of 118 nm single photon ionization and 193 and 355 nm multiphoton ionization/fragmentation of vanadium oxide clusters are discussed on the basis of observed mass spectral patterns and line widths of the mass spectral features. Only the 118 nm laser light can ionize vanadium oxide neutral species by single photon ionization without fragmentation. The stable vanadium oxide neutral clusters under saturated oxygen growth conditions are found to be of the form (VO 2 ) x (V 2 O 5 ) y . Structures of the first few members of this series of clusters are determined through high level DFT calculations. Fragmentation of this series of clusters through 355 and 193 nm multiphoton ionization processes is discussed in light of these calculated structures. The B ˜2B 2 r X ˜2A 1 transition is observed for the VO 2 neutral species, and ν 1 and ν 2 vibrations are assigned for both electronic states. From this spectrum, the VO 2 rotational and vibrational temperatures are found to be ∼50 and ∼700 K, respectively.

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“…The ligand coordination to large metal cores of clusters may model ligand coordination on metal surfaces. 2 High-nuclearity metal clusters may also produce facile multicenter transformations of small molecules and thereby function in an analogous fashion to homogeneous and heterogeneous metal catalysts. 3 Heterometallic carbonyl clusters are especially useful as precursors for obtaining decarbonylated support-attached species for heteronuclear interactions and bifunctional catalysis.…”

Section: Introductionmentioning

confidence: 99%