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Atomic Clusters (atomic + cluster)
Selected AbstractsAqueous CTAB-Assisted Electrodeposition of Gold Atomic Clusters and Their Oxygen Reduction Electrocatalytic Activity in Acid Solutions,ANGEWANDTE CHEMIE, Issue 16 2010Chinnaiah Jeyabharathi Ein großer Fortschritt: Elektrochemisch synthetisierte, tensidstabilisierte Goldcluster (AuACs; Aun, 5,n,13) katalysieren die elektrochemische Reduktion von Sauerstoff (ORR) in saurer Lösung bei geringen Überpotentialen. Abhängig von der Tensidkonzentration wechselt der Mechanismus der ORR allmählich von einem Vier- zu einem Zweielektronenpfad (siehe Bild; SHE=Standard-Wasserstoffelektrode). Demzufolge verschmelzen die Cluster zu Nanopartikeln. [source] Modeling dioxygen binding to the non-heme iron-containing enzymesINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 10 2006A. V. Nemukhin Abstract The structures and properties of the complexes formed upon binding the oxygen molecule to the iron sites in non-heme 2-oxoglutarate-dependent enzymes are characterized by QM(CASSCF)/MM and density functional theory (DFT) calculations. Molecular models for the calculations are constructed following the crystal structure of hypoxia-inducible factor asparaginyl hydroxylase (FIH-1). DFT calculations for the 37-atomic cluster have been carried out at the B3LYP(LANL2DZdp) level. The flexible effective fragment potential method is used as a combined quantum mechanical,molecular mechanical (QM/MM) technique to characterize the fragment of the enzymatic system, including 1,758 atoms in the MM part and 27 atoms in the QM part. In these calculations, the CASSCF(LANL2DZdp) approach is applied in the QM subsystem, and AMBER force field parameters are used in the MM subsystem. With both approaches, equilibrium geometry configurations have been located for different spin states of the system. In DFT calculations, the order of the states is as follows: septet, triplet (+7.7 kcal/mol), quintet (+10.7 kcal/mol). Geometry configurations correspond to the end-on structures with no evidences of electron transfer from Fe(II) to molecular oxygen. In contrast, QM(CASSCF)/MM calculations predict the quintet state as the lowest one, while the septet structure has slightly (<2 kcal/mol) higher energy, and the triplet state is considerably more energetic. In QM/MM calculations, in both quintet and septet states, the electronic configurations show considerable electron charge transfer from iron to oxygen, and the oxidation state of iron in the metal binding site can be characterized as Fe(III). © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006 [source] Supershells in deformed harmonic oscillators and atomic clustersINTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, Issue 4 2002Dennis Bonatsos Abstract From the mathematical point of view, the appearance of supershells is a general feature of potentials having relatively sharp edges. In physics, supershells have been observed in systems of metal clusters, which are also known to exhibit an underlying shell structure with magic numbers intermediate between the magic numbers of the 3-D isotropic harmonic oscillator and those of the 3-D square well. In the present study, Nilsson's modified harmonic oscillator (without any spin,orbit interaction), as well as the 3-D q -deformed harmonic oscillator with uq(3) , soq(3) symmetry, are considered. The former model has been used for an early schematic description of shell structure in metal clusters, while the latter has been found to successfully reproduce the magic numbers of metal clusters up to 1500 atoms, the expected limit of validity for theories based on the filling of electronic shells. The systematics of the appearance of supershells in the two models will be considered, putting emphasis on the differences between the spectra of the two oscillators. While the validity of Nilsson's modified harmonic oscillator framework is limited to relatively low particle numbers, the 3-D q -deformed harmonic oscillator gives reliable descriptions of the first supershell in metal clusters, which lies within its region of validity. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002 [source] In-situ small-angle scattering study on the formation of a nanocrystalline soft-magnetic alloyJOURNAL OF APPLIED CRYSTALLOGRAPHY, Issue 3-1 2000D. R. Dos Santos A detailed study is presented on the nanocrystallization of the amorphous alloy Fe86Zr7Cu 1B6 (indices indicate at. %). Melt-spun ribbons were rapidly annealed by Joule heating, and the electrical resistance showed strong variations during thermal treatment. X-ray diffraction patterns indicate that these variations are related to the nucleation and growth of ,-Fe nanocrystals, and from peak profile analysis we obtained the average grain size and crystalline volume fraction for different annealing currents. The disorder-order transition was studied by in-situ small-angle X-ray scattering during conventional furnace treatments. SAXS intensity evolution for different temperatures, both below and above the crystallization temperature of the alloy, showed that a fast atomic rearrangement leads to the formation of atomic clusters before crystallization. The evolution of the size distribution function of these clusters as a function of time and temperature was obtained assuming a polydisperse system of spherical particles. [source] Generation and characterization of low-energy structures in atomic clustersJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 7 2010J. M. C. Marques Abstract Factors relevant for controlling the structures determined in the local optimization of argon clusters are investigated. In particular, the role of volume and shape for the box where initial structures are generated is assessed. A thorough characterization of the optimization is also presented, based on a nearest-neighbor analysis, in clusters ranging from 30 to 55 atoms. This includes the assessment of the degree of preservation of aspects of the initial randomly generated structure in the final optimized counterpart, and the correlation between optimized energy and the number of nearest neighbors and average departure from the diatomic reference distance. The usefulness of this analysis to explore the energy landscape of atomic clusters is also highlighted. © 2009 Wiley Periodicals, Inc. J Comput Chem, 2010 [source] Linear augmented Slater-type orbital method for free standing clustersJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 8 2009K. S. Kang Abstract We have developed a Scalable Linear Augmented Slater-Type Orbital (LASTO) method for electronic-structure calculations on free-standing atomic clusters. As with other linear methods we solve the Schrödinger equation using a mixed basis set consisting of numerical functions inside atom-centered spheres and matched onto tail functions outside. The tail functions are Slater-type orbitals, which are localized, exponentially decaying functions. To solve the Poisson equation between spheres, we use a finite difference method replacing the rapidly varying charge density inside the spheres with a smoothed density with the same multipole moments. We use multigrid techniques on the mesh, which yields the Coulomb potential on the spheres and in turn defines the potential inside via a Dirichlet problem. To solve the linear eigen-problem, we use ScaLAPACK, a well-developed package to solve large eigensystems with dense matrices. We have tested the method on small clusters of palladium. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009 [source] On the efficient evaluation of Fourier patterns for nanoparticles and clustersJOURNAL OF COMPUTATIONAL CHEMISTRY, Issue 9 2006Antonio Cervellino Abstract Samples made of an isotropically oriented ensemble of atomic clusters or structures that are not large crystals (i.e. extended less than 10 periods in each direction) are at the frontier of today's material science and chemistry. Examples are nanoparticles, nanotubes, amorphous matter, polymers, and macromolecules in suspension. For such systems the computation of powder diffraction patterns (which may provide an efficient characterization) is to be performed the hard way, by summing contributions from each atom pair. This work deals with performing such computation in the most practical and efficient way. Three main points are developed: how to encode the enormous array of interatomic distances (which increase as the square or higher powers of the cluster diameter) to a much smaller array of equispaced values on a coarse grid (whose size increases linearly with the diameter); how to perform a fast computation of the diffraction pattern from this equispaced grid; how to optimize the grid step to obtain an arbitrarily small error on the computed diffraction pattern. Theory and examples are jointly developed and presented. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 995,1008, 2006 [source] | ||||||||||