Jaquet and A. Ipatov and P. Reinhard and F. Fehrer and E. Suraud Spectroscopic properties of Na clusters embedded in a rare-gas matrix Phys. A 71 , Reinhard and and E. A 30 , 65 Suraud Dynamics of metal nanoclusters Nucl. A 2 , Gervais and E. Jacquet and A. Kleinig and D. Dolci Electron infrared quadrupole modes in deformed Na clusters J. Pohl and P. Suraud Angular distribution of electrons emitted from Na clusters Phys.
A 70 , Suraud Exponential Photoelectron spectra in Na clusters J. B 37 , Suraud Crossed beams pump and probe dynamics in metal clusters Phys. Belkacem and M. Bouchenne and P. Suraud Photodynamics of nanoclusters 8 , Giglio and P. Suraud Influence of the dynamical correlations on the ionization of highly irradiated metal clusters Phys. C , Suraud Photoelectron spectra from K and Na clusters Nucl. B 68 , Suraud, Introduction to Cluster Dynamics, Wiley, , Reinhard and E Suraud Metal clusters in strong fields Phys.
A , 41 Andrae and M. Belkacem and T. Dinh and E. Giglio and M. Ma and F. Megi and A. Pohl Analysis of cluster dynamics in: Formation of Correlations - Nonequilibrium at short time scales, editors: K. Morawetz, Springer, Suraud Angular distribution of emitted electrons in sodium clusters: A semi-classical approach Eur. D 67 , Andrae and A. Legrand and M. Ma and E. Bonitz and D. Semkat, World Scientific, Ipatov and E. Suraud and and P. Reinhard A microscopic study of sodium cluster deposition on an insulating surface Encycl. Nesterenko and W. Kleinig and P. Reinhard and N.
Lo Iudice and F. Marinelli Orbital magnetism in axially deformed sodium clusters: From scissors mode to dia-para magnetic anisotropy J. G 27 , 43 Suraud DFT studies of ionic vibrations in Na clusters 21 , Suraud Theoretical exploration of pump and probe in medium size Na clusters Nucl.
B 35 , Reinhard and V. Nesterenko and E. Suraud and S. El Gammal and W. Kleinig Scissors modes in triaxial metal clusters Phys. A 66 , Reinhard Landau fragmentation and deformation effects in dipole response of sodium clusters Eur. D 19 , 57 Berkus and P. Suraud Dynamical effects in the optical response of small carbon chains Int. Legrand and E. Serra and P. Suraud Density functional calculations for shell closures in Mg clusters Eur. D 18 , Kleinig and V.
Reinhard Electric multipole oscillations in deformed sodium clusters Appl. B , 1 Suraud Semi-classical description of ionic and electronic dynamics in metal clusters Ann. Leipzig 11 , Suraud Clusters in intense laser pulses J. B 11 , Suraud and P-G. Reinhard Laser excitation and ionic motion in small clusters Appl. B 14 , Suraud Hybrid ensemble method for the UU collision term J. B 12 , Suraud Dynamics of Na clusters in picosecond laser pulses Phys.
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B 73 , Suraud Influence of intermediate states on photoelectron spectra Nucl. A 34 , Suraud Impact of two-body collisions on explosion dynamics of irradiated clusters Nucl. Reinhard and M. Domps and P. Suraud Semi-classical electron dynamics in metal clusters beyond mean-field Eur. Marinelli and V. Nesterenko and F. Reinhard Twist mode in alcali metal clusters Phys. Ullrich and P. Suraud Simplified implementation of self-interaction correction in sodium clusters Phys.
A 65 , Domps and E. Suraud Semi-classical approach to electron dynamics in metal clusters J. B 33 , L Calvayrac and P. Suraud and C. Ullrich Nonlinear electron dynamics in metal clusters Phys. Suraud Cold versus hot ionization in metal clusters Int. Suraud Towards single particle spectroscopy of small metal clusters Phys. Reinhard Impact of ionic motion on ionization of metal clusters under intense laser pulses Phys. Brack and P.
Paris 62 , Kohl and E. Reinhard Second Harmonic Generation in deposited clusters Eur. D 11 , Suraud On violent excitations in metal clusters: a semi-classical approach Comp. Science 17 , Kohl and S. El-Gammal and F. Calvayrac and E. Reinhard Towards spectral pattern of spin polarized sodium clusters: the example of Na 12 Eur.
Suraud Excitation of metal clusters by intense lasers Phys.
B , Suraud Resonance dynamics in metal clusters and nuclei in: Cluster Physics, editors: W. Ekardt, Wiley, Suraud On electron dynamics in violent cluster excitations Bull. Suraud Dynamics of sodium clusters in a diabatic electron-ion model Eur. D 9 , Calvayrac and C. Ullrich and M. Although few metal carbonyl clusters are catalytically useful, naturally occurring Iron-sulfur proteins catalyse a variety of transformations, such as the stereo-specific isomerization of citrate to isocitrate via cis - aconitate , as required by the tricarboxylic acid cycle. Nitrogen is reduced to ammonia at an Fe-Mo-S cluster at the heart of the enzyme nitrogenase.
Hydrogenases rely on Fe 2 and NiFe clusters. Metal carbonyl cluster compounds have been evaluated as catalysts for a wide range of reactions, especially for conversions of carbon monoxide. The clusters Ru 3 CO 12 and Ir 4 CO 12 catalyze the Water gas shift reaction , also catalyzed by iron oxide , and Rh 6 CO 16 catalyzes the conversion of carbon monoxide into hydrocarbons, reminiscent of the Fischer-Tropsch process , also catalyzed by simple iron compounds.
Some define cluster catalysis to include clusters that have only one active site on one metal atom. The definition can be further relaxed to include clusters that remain intact during at least one reaction step, and can be fragmented in all others. Metal carbonyl clusters have several properties that suggest that they may prove as useful catalysts. The absence of large bulk phases leads to a high surface-to-volume ratio, which is advantageous in any catalyst application as this maximizes the reaction rate per unit amount of catalyst material, which also minimizes cost.
In general, as the number of atoms in a metal particle decrease, their coordination number decreases, and significantly so in particles having less than atoms. Metal clusters are sometimes characterized by a high degree of fluxionality of surface ligands and adsorbates associated with a low energy barrier to rearrangement of these species on the surface. Interconversion ligands between terminal, double-, and triply bridging sites is often facile. It has further been found that metal atoms themselves can easily migrate in or break their bonds with the cluster structure.
Although not used for any commercial process, metal carbonyl clusters have been subjected to many studies aimed at demonstrating their reactivity. Some of these examples include the following:. Species that are typical ligands for a metal cluster represent obvious reactant-catalyst combinations. It has been proposed that coordination of CO to multiple metal sites weakens the triple-bond enough to allow hydrogenation. The selectivity is heavily influenced by the particular cluster used. Steric effects are the most important consideration in many cases, however electronic effects dominate in hydrogenation reactions where one adsorbate hydrogen is relatively small.
In some cases, a metal cluster must be "activated" for catalysis by substitution of one or more ligands, such as acetonitrile. An example of the former is empirical packing energy calculations, where only interactions between adjacent atoms are considered. The packing potential energy can be expressed as follows:. DFT has been used more recently to study a wide variety of properties of metal clusters. However the fundamental form of the energy functional is only approximately known, and unlike other methods there is no hierarchy of approximations which allow a systematic optimization of results.
Tight bonding molecular dynamics has been used to study bond lengths, bond energies, and magnetic properties of metal clusters, however this method is less effective for clusters with less than metal atoms due to a larger influence of approximation errors for small clusters. From Wikipedia, the free encyclopedia. Main article: Metal carbonyl cluster. Introduction to cluster chemistry. Englewood Cliffs, N. J: Prentice Hall.
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