Готові списки джерел за темами / Nanostructured Transition Metal Clusters

Добірка наукової літератури з теми "Nanostructured Transition Metal Clusters"

Автор: Grafiati
Опубліковано: 7 вересня 2023

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Статті в журналах з теми "Nanostructured Transition Metal Clusters"

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Reetz, Manfred T., and Wolfgang Helbig. "Size-Selective Synthesis of Nanostructured Transition Metal Clusters." Journal of the American Chemical Society 116, no. 16 (August 1994): 7401–2. http://dx.doi.org/10.1021/ja00095a051.

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2

Scharfe, Sandra, and Thomas F. Fässler. "Polyhedral nine-atom clusters of tetrel elements and intermetalloid derivatives." Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences 368, no. 1915 (March 28, 2010): 1265–84. http://dx.doi.org/10.1098/rsta.2009.0270.

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Homoatomic polyanions have the basic capability for a bottom-up synthesis of nanostructured materials. Therefore, the chemistry and the structures of polyhedral nine-atom clusters of tetrel elements [E 9 ] 4− is highlighted. The nine-atom Zintl ions are available in good quantities for E = Si–Pb as binary alkali metal (A) phases of the composition A 4 E 9 or A 12 E 17 . Dissolution or extraction of the neat solids with aprotic solvents and crystallization with alkali metal-sequestering molecules or crown ethers leads to a large variety of structures containing homoatomic clusters with up to 45 E atoms. Cluster growth occurs via oxidative coupling reactions. The clusters can further act as a donor ligand in transition metal complexes, which is a first step to the formation of bimetallic clusters. The structures and some nuclear magnetic resonance spectroscopic properties of these so-called intermetalloid clusters are reviewed, with special emphasis on tetrel clusters that are endohedrally filled with transition metal atoms.
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3

Adams, Brian D., Robert M. Asmussen, Aicheng Chen, and Robert C. Mawhinney. "Interaction of carbon monoxide with small metal clusters: a DFT, electrochemical, and FTIR study." Canadian Journal of Chemistry 89, no. 12 (December 2011): 1445–56. http://dx.doi.org/10.1139/v11-120.

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The adsorption of CO molecules onto small metal clusters was studied using density functional theory (DFT) calculations, and experimental electrochemical and attenuated total reflection-Fourier transform infrared spectroscopic (ATR-FTIR) techniques were used to examine CO adsorbed onto nanostructures of similar composition. The adsorption strengths and CO vibrational stretching frequencies were calculated and analyzed for clusters of the form M–CO for all of the period 4, 5, and 6 d-block transition metals. A direct link between the νCO and the population of d orbitals of the metal was observed. All possible binding sites for CO on clusters of the form Pd4–CO, Pd2Pt2–CO, and Pd2Au2–CO were determined and the corresponding adsorption energies and CO stretching frequencies were examined. Pure Pd and bimetallic PdPt and PdAu nanostructures were fabricated and used as catalysts for the adsorption and electrochemical oxidation of CO. The relative quantities of CO molecules adsorbed to surface of the catalysts decrease in the order of PdPt > Pd > PdAu, consistent with our DFT results. The location of νCO bands of CO adsorbed onto the nanostructured catalysts were determined by means of ATR-FTIR spectroscopy and were found to have values close to that predicted by DFT. This paper shows that DFT calculations on very small metal clusters Mn–CO (n ≤ 4) can be a simple but effective way of screening catalysts for their adsorbing properties.
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4

Bulgakov, Alexander V., Nikolay Y. Bykov, Alexey I. Safonov, Yuri G. Shukhov, and Sergey V. Starinskiy. "Silver Vapor Supersonic Jets: Expansion Dynamics, Cluster Formation, and Film Deposition." Materials 16, no. 13 (July 7, 2023): 4876. http://dx.doi.org/10.3390/ma16134876.

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Supersonic jets of metal vapors with carrier gas are promising for producing nanostructured metal films at relatively low source temperatures and high deposition rates. However, the effects of the carrier gas on the jet composition and expansion dynamics, as well as on film properties, remain virtually unexplored. In this work, the free-jet expansion of a mixture of silver vapor with helium in a rarefied regime at an initial temperature of 1373 K is investigated through mass spectrometry and direct-simulation Monte Carlo methods. Introducing the carrier gas into the source is found to result in a transition from a collisionless to a collision-dominated expansion regime and dramatic changes in the Ag jet, which becomes denser, faster, and more forward-directed. The changes are shown to be favorable for the formation of small Ag clusters and film deposition. At a fairly high helium flow, silver Ag2 dimers are observed in the jet, both in the experiment and the simulations, with a mole fraction reaching 0.1%. The terminal velocities of silver atoms and dimers are nearly identical, indicating that the clusters are likely formed due to the condensation of silver vapor in the expanding jet. A high potential of supersonic Ag-He jets for the deposition of nanostructured silver films is demonstrated. The deposited jet Ag2 dimers appear to serve as nucleation centers and, thus, allow for controlling the size of the produced surface nanostructures.
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Jiang, Ning, Yulong Bai, Bo Yang, Dezhi Wang, and Shifeng Zhao. "Switchable metal–insulator transition in core–shell cluster-assembled nanostructure films." Nanoscale 12, no. 35 (2020): 18144–52. http://dx.doi.org/10.1039/d0nr04681g.

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MELINON, P., V. PAILLARD, V. DUPUIS, A. PEREZ, P. JENSEN, A. HOAREAU, J. P. PEREZ, et al. "FROM FREE CLUSTERS TO CLUSTER-ASSEMBLED MATERIALS." International Journal of Modern Physics B 09, no. 04n05 (February 28, 1995): 339–97. http://dx.doi.org/10.1142/s021797929500015x.

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In this paper the specific properties of free clusters and the formation of new cluster-assembled materials using the low energy cluster beam deposition (LECBD) technique are discussed. Recent results obtained for free clusters are summarized with special attention to new observed structures. As for the specific structures and properties of cluster-assembled materials, two main aspects are specially emphasized: the memory effect of the free cluster properties leading to the formation of new phases and the effect of the specific nanostructure of the cluster-assembled materials related to the random cluster stacking mechanism characteristic of the LECBD. These effects and the corresponding potential applications are illustrated using some selected examples: new diamond-like carbon films produced by fullerene depositions (memory effect) and grain effect on the magnetic properties of cluster-assembled transition metal films.
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7

Lu, Xizhao, Lei Kang, Binggong Yan, Tingping Lei, Gaofeng Zheng, Haihe Xie, Jingjing Sun, and Kaiyong Jiang. "Evolution of a Superhydrophobic H59 Brass Surface by Using Laser Texturing via Post Thermal Annealing." Micromachines 11, no. 12 (November 29, 2020): 1057. http://dx.doi.org/10.3390/mi11121057.

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To fabricate an industrial and highly efficient super-hydrophobic brass surface, annealed H59 brass samples have here been textured by using a 1064 nm wavelength nanosecond fiber laser. The effects of different laser parameters (such as laser fluence, scanning speed, and repetition frequency), on the translation to super-hydrophobic surfaces, have been of special interest to study. As a result of these studies, hydrophobic properties, with larger water contact angles (WCA), were observed to appear faster than for samples that had not been heat-treated (after an evolution time of 4 days). This wettability transition, as well as the evolution of surface texture and nanograins, were caused by thermal annealing treatments, in combination with laser texturing. At first, the H59 brass samples were annealed in a Muffle furnace at temperatures of 350 °C, 600 °C, and 800 °C. As a result of these treatments, there were rapid formations of coarse surface morphologies, containing particles of both micro/nano-level dimensions, as well as enlarged distances between the laser-induced grooves. A large number of nanograins were formed on the brass metal surfaces, onto which an increased number of exceedingly small nanoparticles were attached. This combination of fine nanoparticles, with a scattered distribution of nanograins, created a hierarchic Lotus leaf-like morphology containing both micro-and nanostructured material (i.e., micro/nanostructured material). Furthermore, the distances between the nano-clusters and the size of nano-grains were observed, analyzed, and strongly coupled to the wettability transition time. Hence, the formation and evolution of functional groups on the brass surfaces were influenced by the micro/nanostructure formations on the surfaces. As a direct consequence, the surface energies became reduced, which affected the speed of the wettability transition—which became enhanced. The micro/nanostructures on the H59 brass surfaces were analyzed by using Field Emission Scanning Electron Microscopy (FESEM). The chemical compositions of these surfaces were characterized by using an Energy Dispersive Analysis System (EDS). In addition to the wettability, the surface energy was thereby analyzed with respect to the different surface micro/nanostructures as well as to the roughness characteristics. This study has provided a facile method (with an experimental proof thereof) by which it is possible to construct textured H59 brass surfaces with tunable wetting behaviors. It is also expected that these results will effectively extend the industrial applications of brass material.
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Soldatov, Mikhail, Kirill Lomachenko, Nikolay Smolentsev, and Alexander Soldatov. "Determination of the local structure in metal-complexes by combining XAS and XES." Acta Crystallographica Section A Foundations and Advances 70, a1 (August 5, 2014): C1521. http://dx.doi.org/10.1107/s2053273314084782.

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Nanoscale local atomic structure determines most of unique properties of novel materials without long range order. To study its fine details one has to use both computer nanodesign and advanced experimental methods for nanodiagnostics. The status of modern theoretical analysis of the experimental x-ray absorption spectra to extract structural parameters is presented. Novel in-situ technique for nanodiagnostics - extracting of 3D structure parameters on the basis of advanced quantitative analysis of X-ray absorption near edge structure (XANES) - has been developed. The possibility to extract information on bond angles and bond-lengths (with accuracy up to 0.002 nm) is demonstrated and it opens new perspectives of quantitative XANES analysis as a 3D local structure probe for any type of materials without long range order in atoms positions (all nanostructured materials and free clusters belong to this class of materials). Even more possibilities are opening by using simultaneously several experimental synchrotron based techniques: XANES and XES and/or RIXS. In the framework of these approaches, the results of recent studies of local atomic structure for several types of nanostructures including nanoclusters with different types of chemical bonding, core-shell nanoneedles and thin films of dilute magnetic semiconductors, 5d-transition metal-organic complexes, Cu1+ and Cu2+ binding sites in amyloid-β peptide, Co aqua complexes in aqueous solution, nanostructured materials for hydrogen storage and nanocatalysts based on zeolites and MOF are reported. Along with the calculations of conventional XANES and XES, we show a possibility to simulate core-to-core and valence-to-core RIXS as well. Molecular orbitals (or DOS) of metal complexes can be directly related to the peaks in XES spectra in RIXS maps. This information is essential for understanding of electronic structure of metal complexes and design of novel materials.
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Miras, Haralampos N., Cole Mathis, Weimin Xuan, De-Liang Long, Robert Pow, and Leroy Cronin. "Spontaneous formation of autocatalytic sets with self-replicating inorganic metal oxide clusters." Proceedings of the National Academy of Sciences 117, no. 20 (May 5, 2020): 10699–705. http://dx.doi.org/10.1073/pnas.1921536117.

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Here we show how a simple inorganic salt can spontaneously form autocatalytic sets of replicating inorganic molecules that work via molecular recognition based on the {PMo12} ≡ [PMo12O40]3– Keggin ion, and {Mo36} ≡ [H3Mo57M6(NO)6O183(H2O)18]22– cluster. These small clusters are able to catalyze their own formation via an autocatalytic network, which subsequently template the assembly of gigantic molybdenum-blue wheel {Mo154} ≡ [Mo154O462H14(H2O)70]14–, {Mo132} ≡ [MoVI72MoV60O372(CH3COO)30(H2O)72]42– ball-shaped species containing 154 and 132 molybdenum atoms, and a {PMo12}⊂{Mo124Ce4} ≡ [H16MoVI100MoV24Ce4O376(H2O)56 (PMoVI10MoV2O40)(C6H12N2O4S2)4]5– nanostructure. Kinetic investigations revealed key traits of autocatalytic systems including molecular recognition and kinetic saturation. A stochastic model confirms the presence of an autocatalytic network involving molecular recognition and assembly processes, where the larger clusters are the only products stabilized by the cycle, isolated due to a critical transition in the network.
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10

Dupuis, V., J. P. Perez, J. Tuaillon, V. Paillard, P. Mélinon, A. Perez, B. Barbara, L. Thomas, S. Fayeulle, and J. M. Gay. "Magnetic properties of nanostructured thin films of transition metal obtained by low energy cluster beam deposition." Journal of Applied Physics 76, no. 10 (November 15, 1994): 6676–78. http://dx.doi.org/10.1063/1.358165.

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Дисертації з теми "Nanostructured Transition Metal Clusters"

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Borghi, F. M. "ENGINEERING THE STRUCTURAL AND FUNCTIONAL PROPERTIES OF TRANSITION METAL OXIDE INTERFACES BY CLUSTER ASSEMBLING." Doctoral thesis, Università degli Studi di Milano, 2015. http://hdl.handle.net/2434/278394.

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Nanostructured materials are defined as systems composed of single or multiple phases such that at least one of them has characteristic dimensions in the nanometer range (1-100 nm). The strategic importance of nanostructured materials rely on the fact that their structural, electronic, magnetic, catalytic, and optical properties can be tuned and controlled by a careful choice and assembling of their nanoscale elemental building blocks. Clusters, aggregations of a few atoms to a few thousands of atoms, are the building blocks used to synthetize nanostructured materials. Low-Energy Cluster Beam Deposition (LECBD) is a technique of choice for the fabrication of nanostructured systems, since it allows the deposition on a substrate of neutral particles produced in the gas phase and maintaining their properties even after deposition. This has been proven to be a powerful bottom-up approach for the engineering of nanostructured thin films with tailored properties, since it allows in principle the control of the physical and chemical characteristics of the building blocks. Among different approaches to LECBD, supersonic cluster beam deposition (SCBD) present several advantages in terms of deposition rate, lateral resolution compatible with planar microfabrication technologies and neutral particle mass selection by exploiting aerodynamic focusing effects. All these features make SCBD a superior tool to synthesize nanostructured films and their integration on microfabricated platforms. The morphology of cluster-assembled materials is characterized by a hierarchical arrangements of small units in larger and larger features up to a certain critical length-scale, in general determined by the duration of the deposition process. The cluster-assembled film morphology is characterized by high specific area and porosity at the nano and sub-nanometer scale, extending in the bulk of the film. Surface pores and surface specific area, as well as rms roughness, depend on film thickness, and increase with it. All these morphological properties is of great relevance for the use of cluster-assembled film in devices as gas sensor, (photo) catalysis, solar energy conversion and as biocompatible substrates.Recently it has been recognized that nanoscale surface morphology and nanopores play an important role in processes involving the interaction of biological entities (protein, viruses, enzymes) with nanostructured surfaces, via the modulation of electric interfacial properties. In particular, when the nanostructured material is used to produce electrodes and substrates for operation in liquid electrolytes, with given pH and ionic strength, double layer phenomena take place. An important parameter to describe these electrostatic phenomena is the IsoElectric Point (IEP), which corresponds to the pH value at which the net charge of the compact layer is zero. When two interacting surfaces approach to a distance comparable or smaller than the typical screening length of the electrolytic solution (the Debye length, determined by the ionic strength of the solution), the overlap of the charged layers determines complex regulation phenomena that are difficult to describe theoretically. While significant insights have been obtained on the properties of the electric double layers formed between flat smooth surfaces, the case of rough surfaces still represents a severe challenge, hampering analytical, yet approximate, solutions of the double layer equations to be reliably obtained. Anyway, these phenomena have been recently shown to be strongly influenced by the morphological properties of the surface. The quantitative characterization of all these interfacial properties requires imaging and force spectroscopy techniques with a resolution in and beyond the nanometer-scale. Atomic Force Spectroscopy (AFM) is an excellent candidate, since it couples the possibility of scanning with a z-resolution lower than fraction of nanometer and x-y resolution of 1 nm and also of performing very accurate force spectroscopy measurements. The first aim of my PhD work is to characterize by AFM the evolution of morphological properties of transition-metal oxides cluster-assembled materials (in particular nanostructured Titania (ns-TiOx) and nanostructured Zirconia (ns-ZrOx), starting from sub-monolayer regime to thin film, and especially to describe the influence of the building-blocks dimensions on the growth mechanisms and on the final surface morphology and topography. With this information, I have explored the influence of nanoscale morphology on double layer interactions which takes place on these nanostructured interfaces and on the wettability behaviour. The results have been used to highlight the role of morphological and structural surface properties as biophysical signal mediators for protein adsorption processes and cellular adhesion.
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2

Zosiak, Lukasz. "Simulations of atomic and electronic structure of realistic Co and Pt based nanoalloy clusters." Thesis, Strasbourg, 2013. http://www.theses.fr/2013STRAE038/document.

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Cette thèse présente une étude théorique de la structure électronique et de la tendance à l'ordre dans les nanoalliages de métaux de transition en se référant au cas des systèmes à base de cobalt-platine (CoPt) qui présentent un intérêt particulier dans les domaines du magnétisme et de la catalyse. Il est ainsi important de décrire au mieux l'évolution de la structure électronique en lien avec la structure atomique ou l'arrangement chimique en fonction de la taille de tels nanoalliages en vue de prédire des propriétés potentielles pouvant différer fortement de celles du matériau massif correspondant. Dans ce contexte, des calculs systématiques de DFT ont été mis en œuvre sur des systèmes modèles simples, alliages massifs, surfaces et nanoparticules, qui ont permis de montrer qu'une règle de neutralité de charge locale, par site espèce et orbitale, s'applique au système CoPt massif et s'étend aux nanoalliages. Sur cette base, des calculs auto cohérents de liaisons fortes ont été développés et ont permis de proposer un moyen précis de prédire les caractéristiques de nanoalliages réalistes, en termes de redistribution des états électroniques et de tendance à l'ordre. Les grandeurs caractéristiques déduites de ces calculs, telles que le désordre diagonal et non diagonal, peuvent être en effet être déterminées à partir de lois simples linéaires de variations des centres et des largeurs de bandes sur les sites Co et Pt. Les valeurs issues de ces lois peuvent être placées sur des cartographies de domaines de tendance à l'ordre et l'ensemble de la méthodologie devrait être étendue facilement à d'autres systèmes binaires
The interest in alloys of late transition metals arises from their potential applications in high-density magnetic storage devices where they can be used as supported magnetic nanoparticle arrays and as stable, efficient and selective catalysts. The preparation of materials with optimal properties faces a number of technological and physical restrictions and requires an in-depth knowledge of the interplay between structural features on the atomic level and the desired macroscopic properties. In the thesis, after extensive discussion of Density Functional Theory and Tight Binding approaches the work focused on DFT calculations of bulk systems, surfaces and small clusters. The results allow to conclude on general validity of the method and especially to justify the local neutrality assumption in the case of low-coordinated sites in nanoparticles. Basic structural, magnetic and energetic properties were also studied and compared with the experimental data. Subsequently TB calculations were performed and verified with DFT results. The scope of the calculations was then extended for the case of nanoclusters of realistic sizes, unavailable in DFT. Local Densities of State on sites with different chemical environment and coordination numbers were analyzed. The observations prove that basic features of LDOS (d-band centre and d-band width) can be predicted by simple laws on the basis of two terms: a structural term represented by the linear function of the site coordination and a chemical term as a rigid shift which opens a new way to predict the ordering tendency (mapping of the ordering domains) for any transition metal nanoalloy as a function of its size
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3

Taylor, Stephanie Merac. "Calixarene supported transition metal clusters." Thesis, University of Edinburgh, 2013. http://hdl.handle.net/1842/7770.

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This thesis describes a series of calix[n]arene polynuclear transition metal and lanthanide complexes. Calix[4]arenes possess lower-rim polyphenolic pockets that are ideal for the complexation of various transition metal and lanthanide centres. Surprisingly however, with only a few exceptions, the coordination chemistry of p-tBucalix[ 4]arene (TBC[4]), p-tBu-calix[8]arene (TBC[8]) and p-tBuhomotrioxacalix[ 3]arene (TBOC[3]) with paramagnetic transition metal ions for the purpose of making and studying magnetically interesting molecules is unknown. Chapter two describes the reaction of TBC[4] with manganese salts in the presence of an appropriate base (and in some cases co-ligand) resulting in the formation of a family of calixarene-supported [MnIII 2MnII 2] clusters (1-7) that behave as Single-Molecule Magnets (SMMs). These are: [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)6]·2MeOH (1), [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)4(H2O)2]·4MeOH·2DMF (2), [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)6]·2.8MeOH (3), [MnIII 2MnII 2(OH)2(TBC[4])2(DMF)4(EtOH)(H2O)] (4), [MnIII 2MnII 2(OH)2(TBC[4])2(DMSO)6]·2MeOH·2DMSO (5) , [MnIII 2MnII 2(OH)2(TBC[4])2(DMSO)6] (6) and [MnIII 2MnII 2(OH)2(C[4])2(MeOH)6]·4MeOH (7). Variation in the alkyl groups present at the upper-rim of the cone allows for the expression of a degree of control over the self-assembly of these SMM building blocks, whilst retaining the general magnetic properties. The presence of various different ligands around the periphery of the magnetic core has some effect over the extended self-assembly of these SMMs. Chapter three describes how the combination of complementary cluster ligands; sodium phenylphosphinate and the N,O-chelate 2-(hydroxy-methyl)pyridine (hmpH) with TBC[4] results in the formation of two new calixarene-supported clusters. This being an unusual [MnIIIMnII]2 dimer of dimers [MnIIIMnII(O2P(H)Ph)(DMF)2(MeOH)2]2 (8) and a ferromagnetic [Mn5] cage that displays the characteristic bonding modes of each support [MnIII 3MnII 2(OH)2(TBC[4])2(hmp)2(DMF)6](TBC[4]-H)·xDMF ·xH2O (9). Chapter four details how using oxacalix[3]arenes can tune the nature of the metal binding site, by introduction of ≥ 1 ethereal bridge. This results in Mn(II) rather than Mn(III) bonding in the phenolic pocket, and that these components self-assemble with additional Mn(II) and Mn(III) ions to form a [Mn10] supertetrahedron with an unusual oxidation state distribution, [MnII 6MnIII 4O4(TBOC[3])4(Cl)4(DMF)3]∙3.3H2O ∙ 1.5DMF (10). Chapter five introduces a family of lanthanide complexes formed using TBC[8]. Variation in the experimental conditions employed in the reaction of TBC[8] with lanthanide salts (LnX3) provides access to Ln1, Ln2, Ln4, Ln5, Ln6, Ln7 and Ln8 complexes, [Gd(TBC[8]-2H)Cl(DMSO)4]·MeCN·H2O·(DMSO)2·hex (11), [CeIV 4(TBC[8]-6H)2(μ3- O)2(DMF)4]·(DMF)5·hex·MeCN (12), [TbIII 5(TBC[8]-5H)(μ4-O)(μ3- OH)4Cl(DMSO)8(H2O)3]Cl3·(DMSO)2(hex)2 (13), [CeIV 6(TBC[8]-6H)2(μ4-O)2(μ2-OMe)4(μ2- O)2(DMF)4]·(DMF)6·hex (14), [Dy7(TBC[8]-7H)(TBC[8]-6H)(μ4-O)2(μ3-OH)2(μ2- OH)2(DMF)9]·(DMF)3 (15) and [Gd8(TBC[8]-7H)2(μ4-CO3)2(μ5-CO3)2(μ2-HCO2)2(DMF)8] (16), with all polymetallic clusters containing the common bi-nuclear lanthanide fragment. Closer inspection of the structures of the polymetallic clusters reveals that all but one (Ln8) are in fact based on metal octahedra or the building blocks of octahedra.
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4

Foster, D. F. "Stabilised transition metal carbonyl clusters." Thesis, University of Liverpool, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.354541.

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5

Hay, C. M. "Structural investigations of transition metal clusters." Thesis, University of Cambridge, 1987. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.234979.

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The work described in this dissertation is concerned with structural aspects of the chemistry of transition metal cluster compounds, in particular with carbonyl clusters of the second and third transition series. The structures of a range of these complexes have been investigated, in the solid state, by single-crystal X-ray diffraction techniques, and in the solid and in solution, to a limited extent, by EXAFS spectroscopy. In Chapter One the basics of the single-crystal X-ray diffraction technique for determining the crystal and molecular structure of compounds in the solid state is described. The various steps of sample preparation, data collection, structure solution and refinement are discussed. Chapter Two is a review of the known structural chemistry of heterometallic cluster complexes which contain gold, or gold - phosphine units coordinated to the rest of the metal framework. The majority of complexes discussed in subsequent chapters are of this type. Simple 'electron counting' schemes which have been used to rationalise the structures of this class of compound are discussed critically. Chapter Three is divided up into five sections, each of which is concerned with a different class of heterometallic cluster containing an AuPR3 unit as a ligand. In section 1, the structure of [Os3(CO)10(AuPPh3)Cl], in which the Au atom bridges an Os-Os edge of the Os3 triangle, is described. In section 2, the structures of [HOs3Co(CO)13], [Os3Co(CO)13(AuPPh3)], and [HOs3Ru(CO)13(AuPEt3)] are described, and comment is made on the structural changes which occur when a bridging hydride ligand is replaced by a bridging AuPR3 group. In section 3 the structures of [Os4(CO)13(AuPEt3)], [Os4(CO)12(AuPPh2Me)2], and [Os4(CO)12(AuAsPPh3)2] are described, and a change in geometry is noted when a CO ligand is removed from the former complex and the level of unsaturation formally increased. In section 4 the structures of [Ru5C(CO)14(AuPEt3)2] and [Os6(CO)18P(AuPPh3)] are discussed. Both these clusters contain an interstitial atom which modifies the structural chemistry. Section 5 contains a description of the structures of [Os6(CO)16 lbraceP(OMe)3 rbrace (AuPEt4)2] and [Os6C(CO)20(OMe)Au]. The Os atom framework in these clusters is contrasted with a number of hexaosmium systems which do not contain gold. The structures of two hexaosmium 'raft' clusters, [Os6O(CO)18(PPh3)] and [H2Os6(CO)18(PPh)] are described in Chapter Four. The effect of the introduction of the capping O atom and the PPh group on to the previously planar metal system is discussed, and is related to molecular orbital calculations on the systems. In Chapter Five the introduction of heavy, main group metal atoms into a transition metal cluster system is discussed, with reference to the structures of [H3BiRu3(CO)9], [Bi2Os3(CO)9], and [Bi2Ru4(CO)12]. Both steric and electronic effects are shown to be of importance. Finally, in Chapter Six, the technique of EXAFS spectroscopy is described. The limitations of the technique when applied to transition metal cluster systems are discussed with reference to data obtained from two pentaosmium cluster complexes.
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Wang, John S. "Pseudocapacitive effects in nanostructured transition metal oxide materials." Diss., Restricted to subscribing institutions, 2008. http://proquest.umi.com/pqdweb?did=1680034181&sid=11&Fmt=2&clientId=1564&RQT=309&VName=PQD.

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7

Harding, Daniel James. "Structure and reactivity of transition metal clusters." Thesis, University of Warwick, 2008. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.527439.

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Hermes, A. C. "Structure and reactivity of transition metal clusters." Thesis, University of Oxford, 2013. http://ora.ox.ac.uk/objects/uuid:91e9449f-8c1e-4955-8c08-d9f24e5bbe6a.

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A range of computational and experimental techniques have been applied to the study of four metal cluster systems. Decorated rhodium clusters Rh n O m (N 2 O) + ( n = 4 − 8, m = 0 − 2) have been investigated both experimentally by IR-MPD and computationally using DFT. The effect of cluster size as well as oxygen coverage on the spectroscopy of the N 2 O bend are analyzed. The infrared-induced decomposition of N 2 O on Rh n O + m is observed on all cluster sizes, with marked differences as a function of size and oxygen coverage, particularly in the case of Rh 5 (N 2 O) + . The oxidation of CO was studied on the surface of small platinum cluster cations Pt n O + m ( n = 3 − 7, m = 2 , 4) by IR-MPD at 400 – 2100cm −1 . Spectroscopically, oxygen is found to be bound both dissociatively and molecularly on the cluster surface, while the CO band is found to red shift in cluster size, and blue shift with oxygen coverage. Oxidation of CO proceeds on all cluster sizes, with a constant branching ratio of 40% : 60% . DFT calculations identified key stationary points and barriers on the Pt 4 O 2 CO + reaction pathway. The one-colour Ta 2 photodissociation is studied by photoionization and VMI in the range 23500 – 24000cm −1 , finding clear evidence of a fragmentation process producing Ta , which is interpreted as fragmentation of cationic Ta + 2 at the two photon level. A majority of the observed channels produce either atomic ( Ta( 4 F 3/2 ) ) or cationic ( Ta + ( 5 F 1 ) ) ground state. An improved value for the dissociation energy D 0 ( Ta + 2 ) is obtained, in agreement with computational predictions. The anisotropies observed show weak evidence of a perpendicular transition being involved in the photodissociation process. Finally, the photodissociation dynamics of Cu 2 are studied by spectroscopy in the range 36000 – 38200cm −1 as well as VMI. Clear evidence for resonant photolysis of Cu 2 is obtained, as a result of both direct dissociation of the Cu + 2 2 Π ion state as well as dissociation of doubly excited Cu 2 states, which leads to a determination of dimer dissociation energies. Finally, the production of Cu + 2 is interpreted as evidence of photolysis of Cu 3 , from which a Cu 3 dissociation energy is derived.
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9

Parry, Imogen Sophie. "Collisional and photoexcitation of transition metal clusters." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:b1f2fc37-97ff-4500-ab34-ceb7e515b9d2.

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The properties of transition metal clusters differ from those of both atomic and bulk size regimes. Such clusters are incompletely understood and potentially useful, making them attractive targets for further study. The very smallest clusters studied in this thesis (CuO, Cu2 and Cu3) have been investigated with velocity map imaging. 1+1' photodissociation of CuO X 2Π3/2 was observed, via the C, D, E, F and H states of CuO. CuO* was photodissociated to form Cu(2D3/2) + O(1D2). D0(CuO) was determined to be 3.041±0.030 cm-1. Non-resonant three-photon Cu2 photodissociation occurred throughout the energy range studied to produce one ground-state and one highly-excited copper atom,Cu*. Cu* was ionised by a single additional visible photon. Nearly all Cu* atoms with internal energies between 41000 and 53000 cm-1 were observed. D0(Cu2) has been calculated to be 1.992±0.037 eV. Features arising from photodissociation of Cu3 were observed in the Cu+ and Cu2+ ion yield spectra and images. Their structure was ill-resolved due to uncertainties in the internal energy of both parent Cu3 and product Cu2. These features correspond to single-photon dissociation of Cu3 to produce metastable D-states of the copper atom and vibrationally excited Cu2. One series of features implies a previously-unobserved state of either Cu2 or Cu3. RhnN2O+ and RhnON2O+ (n=5, 6) were collisionally activated in collision-induced dissociation (CID) experiments with Ar and 13CO. These experiments were carried out in a Fourier Transform Ion Cyclotron Resonance(FT-ICR)spectrometer. Argon collisions induced both N2O desorption and N2O reduction. The branching ratios observed reproduced those seen in prior IR-MPD experiments. 13CO was observed to chemisorb to the cluster upon collision, activating not only N2O desorption and reduction but also CO oxidation. Formation of CO2 was noted to be particularly rapid on the n=5 cluster compared to the n=6 cluster. Reactions of RhnN2O+ (n=4-6) clusters were also activated by black body radiation. This technique is known as BIRD - black-body induced infrared radiative dissociation. These studies revealed that the N2O desorption barrier exceeds the N2O reduction barrier on all clusters studied, but that the entropic favourability of desorption increases its rate relative to reduction with increasing cluster internal energy. The BIRD rate was much reduced upon cooling the ICR cell to 100 K. A further test of the BIRD mechanism increased the number of N2O ligands and hence the absorption rate. An approximately linear increase in the dissociation rate of Rhn(N2O)m+ was observed with index m. Deviations from linearity were caused by variations in the N2O desorption rate. In the case of Rh5(N2O)m+, desorption rates corresponded closely to N2O binding energies calculated by density functional theory. The system was modelled using a master equation approach.
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Gu, Yanjuan, and 谷艳娟. "Nanostructure of transition metal and metal oxide forelectrocatalysis." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 2006. http://hub.hku.hk/bib/B37774396.

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Книги з теми "Nanostructured Transition Metal Clusters"

1

International, Workshop on Clusters and Nanostructured Materials (1st 1996 Puri India). Clusters and nanostructured materials. Commack, N.Y: Nova Science Publishers, 1996.

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2

1947-, Kawazoe Y., Ohno K. 1955-, and Kondow Tamotsu 1936-, eds. Clusters and nanomaterials. Berlin: Springer, 2002.

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3

H, Chisholm Malcolm, ed. Early transition metal clusters with [pi]-donor ligands. New York: VCH, 1995.

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4

Y, Kawazoe, Ohno K, and Kondow Tamotsu, eds. Clusters and nanomaterials: Theory and experiment. New York: Springer, 2002.

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5

Kawazoe, Y. Clusters and nanomaterials: Theory and experiment. Berlin: Springer, 2001.

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6

Halet, Jean-François, ed. Ligated Transition Metal Clusters in Solid-state Chemistry. Cham: Springer International Publishing, 2019. http://dx.doi.org/10.1007/978-3-030-25124-6.

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7

1946-, Salahub Dennis R., Russo Nino 1947-, North Atlantic Treaty Organization. Scientific Affairs Division., and NATO Advanced Study Institute on Metal-Ligand Interactions: from Atoms, to Clusters, to Surfaces (1991 : Cetraro, Italy), eds. Metal-ligand interactions: From atoms, to clusters, to surfaces. Dordrecht: Kluwer Academic, 1992.

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8

George, Maroulis, ed. Structures and properties of clusters: From a few atoms to nanoparticles. Leiden, The Netherlands: Brill Academic, 2006.

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9

Mariscal, Marcelo Mario. Metal Clusters and Nanoalloys: From Modeling to Applications. New York, NY: Springer New York, 2013.

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10

Toshihiro, Arai, ed. Mesoscopic materials and clusters: Their physical and chemical properties. [Tokyo]: Kodansha, 1999.

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Частини книг з теми "Nanostructured Transition Metal Clusters"

1

Pruchnik, Florian P., and Stan A. Duraj. "Metal-Metal Bonds and Clusters." In Organometallic Chemistry of the Transition Elements, 129–98. Boston, MA: Springer US, 1990. http://dx.doi.org/10.1007/978-1-4899-2076-8_3.

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2

Chandra Sekhar, S., Bhimanaboina Ramulu, and Jae Su Yu. "Transition Metal Oxides for Supercapacitors." In Nanostructured Materials for Supercapacitors, 267–92. Cham: Springer International Publishing, 2022. http://dx.doi.org/10.1007/978-3-030-99302-3_13.

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3

Tast, F., N. Malinowski, S. Frank, M. Heinebrodt, I. M. L. Billas, and T. P. Martin. "Transition metal coated fullerenes." In Small Particles and Inorganic Clusters, 351–54. Berlin, Heidelberg: Springer Berlin Heidelberg, 1997. http://dx.doi.org/10.1007/978-3-642-60854-4_83.

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4

Sawada, S., and S. Sugano. "Dynamics of transition-metal clusters." In Small Particles and Inorganic Clusters, 189–91. Berlin, Heidelberg: Springer Berlin Heidelberg, 1989. http://dx.doi.org/10.1007/978-3-642-74913-1_43.

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5

Sawada, S. "Dynamics of Transition-Metal Clusters." In Springer Series in Materials Science, 211–17. Berlin, Heidelberg: Springer Berlin Heidelberg, 1987. http://dx.doi.org/10.1007/978-3-642-83064-8_27.

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6

Saito, Naoaki, Kazuyoshi Koyama, and Mitsumori Tanimoto. "Stability of Multiply Charged Transition Metal Clusters." In Clusters and Nanomaterials, 89–96. Berlin, Heidelberg: Springer Berlin Heidelberg, 2002. http://dx.doi.org/10.1007/978-3-662-04812-2_3.

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7

Fujima, Nobuhisa, and Tsuyoshi Yamaguchi. "Electronic States of Transition Metal Clusters." In Mesoscopic Materials and Clusters, 249–58. Berlin, Heidelberg: Springer Berlin Heidelberg, 1999. http://dx.doi.org/10.1007/978-3-662-08674-2_24.

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8

Paz Borbón, Lauro Oliver. "38-Atom Binary Clusters." In Computational Studies of Transition Metal Nanoalloys, 55–76. Berlin, Heidelberg: Springer Berlin Heidelberg, 2011. http://dx.doi.org/10.1007/978-3-642-18012-5_5.

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9

Angelici, R. J. "Binding and Reactivity of Thiophene-Type Ligands in Transition Metal Complexes and Clusters." In Transition Metal Sulphides, 89–127. Dordrecht: Springer Netherlands, 1998. http://dx.doi.org/10.1007/978-94-017-3577-3_4.

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10

Riley, S. J. "The Chemistry of Transition Metal Clusters." In Metal-Ligand Interactions: From Atoms, to Clusters, to Surfaces, 17–36. Dordrecht: Springer Netherlands, 1992. http://dx.doi.org/10.1007/978-94-011-2822-3_2.

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Тези доповідей конференцій з теми "Nanostructured Transition Metal Clusters"

1

Merchan-Merchan, W., A. V. Saveliev, and Aaron Taylor. "Flame Synthesis of Nanostructured Transition Metal Oxides." In ASME 2008 International Mechanical Engineering Congress and Exposition. ASMEDC, 2008. http://dx.doi.org/10.1115/imece2008-68987.

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Various transition metal oxide nanostructures are synthesized using a novel probe-flame interaction method. An opposed flow flame of methane and oxygen enriched air provides a high-temperature reacting environment forming various metal oxide structures directly on the surface of pure metal probes. The unique thermal profile and chemical composition of the generated flame tends to convert almost pure bulk (99.9%) metallic materials into 1-D and 3-D structures of different chemical compositions and unique morphologies. The synthesized molybdenum, tungsten, and iron oxide structures exhibit unique morphological characteristics. The application of Mo probes results in the formation of micron size hollow and non-hollow Mo-oxide channels and elongated structures with cylindrical shapes. The use of W probes results in the synthesis of 1-D carbon-oxide nanowires, 3-D structures with rectangular shapes, and thin oxide plates with large surface areas. The formation of elongated iron-oxide nanorods is observed on iron probes. The iron nanorods’ diameters range from ten nanometers to one hundred nanometers with lengths of a few micrometers. Flame position, probe diameter, and flame exposure time tend to play an important role for material shape and selectivity.
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2

Riley, Stephen J., Eric K. Parks, and Kopin Liu. "The Chemistry Of Isolated Transition Metal Clusters." In 1986 Quebec Symposium, edited by D. K. Evans. SPIE, 1986. http://dx.doi.org/10.1117/12.938944.

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3

KOOI, S. E., B. D. LESKIW, and A. W. CASTLEMAN. "IONIZATION DYNAMICS OF TRANSITION METAL - CARBON CLUSTERS." In Proceedings of the International Symposium. WORLD SCIENTIFIC, 2000. http://dx.doi.org/10.1142/9789812793805_0066.

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4

Lee, Keeyung. "Magnetic properties of 4d transition metal clusters." In Similarities and differences between atomic nuclei and clusters. AIP, 1997. http://dx.doi.org/10.1063/1.54550.

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5

Andersson, Mats T., H. Gronbeck, L. Holmgren, and Arne Rosen. "Reactivity of small transition-metal clusters with CO." In SPIE's 1995 International Symposium on Optical Science, Engineering, and Instrumentation, edited by John W. Hepburn. SPIE, 1995. http://dx.doi.org/10.1117/12.220843.

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6

REDDY, B. V. "MAGNETISM OF TRANSITION METAL CLUSTERS AND THEIR COMPOUNDS." In Proceedings of the International Symposium. WORLD SCIENTIFIC, 2000. http://dx.doi.org/10.1142/9789812793805_0017.

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7

Russon, Larry M., Scott A. Heidecke, Michelle K. Birke, J. Conceicao, P. B. Armentrout, and Michael D. Morse. "Bond Energies of Small Transition Metal Cation Clusters." In High Resolution Spectroscopy. Washington, D.C.: Optica Publishing Group, 1993. http://dx.doi.org/10.1364/hrs.1993.pd2.

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A new experimental apparatus has been constructed for photodissociation spectroscopy of transition metal-containing cations. redissociation thresholds for Co 2 + , Co 3 + , and Ti 2 + have been observed and values of 2.765 ± 0.001 eV, 2.086 ± 0.002 eV, and 2.435 ± 0.002 eV, respectively, have been determined for the bond energies for these species. These are in good agreement with results obtained by collision-induced dissociation (CID) experiments. Comparison of bond strengths obtained from the observation of predissociation thresholds with those obtained by non-optical methods, such as collision-induced dissociation and Knudsen cell mass spectrometry, have allowed criteria for the interpretation of a pre-dissociation threshold as a bond strength to be developed.
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Frisenda, Riccardo, Andres Castellanos-Gomez, David Perez de Lara, Robert Schmidt, Steffen Michaelis de Vasconcellos, and Rudolf Bratschitsch. "Biaxial strain in atomically thin transition metal dichalcogenides." In Optical Sensing, Imaging, and Photon Counting: Nanostructured Devices and Applications 2017, edited by Oleg Mitrofanov, Chee Hing Tan, Manijeh Razeghi, and José Luis Pau Vizcaíno. SPIE, 2017. http://dx.doi.org/10.1117/12.2274756.

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Uchida, N., H. Kintou, Y. Matsushita, T. Tada, K. Kirihara, H. Oyanagi, and T. Kanayama. "Synthesis and Characterization of Clusters Assembled Films Composed of Transition-Metal Encapsulating Si Clusters." In 2008 International Conference on Solid State Devices and Materials. The Japan Society of Applied Physics, 2008. http://dx.doi.org/10.7567/ssdm.2008.p-8-13l.

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10

Kokkin, Damian, and Timothy Steimle. "APPLICATION OF TWO DIMENSIONAL FLOURESCENCE SPECTROSCOPY TO TRANSITION METAL CLUSTERS." In 69th International Symposium on Molecular Spectroscopy. Urbana, Illinois: University of Illinois at Urbana-Champaign, 2014. http://dx.doi.org/10.15278/isms.2014.tk12.

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Звіти організацій з теми "Nanostructured Transition Metal Clusters"

1

Ogut, Serdar. Excited State Phenomena in Correlated Nanostructures: Transition Metal Oxide Clusters and Nanocrystals. Office of Scientific and Technical Information (OSTI), September 2017. http://dx.doi.org/10.2172/1864865.

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2

Gallaway, J. Clusters of Transition Metal Atoms. Fort Belvoir, VA: Defense Technical Information Center, January 1988. http://dx.doi.org/10.21236/ada191265.

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3

Callaway, J. Clusters of Transition Metal Atoms. Fort Belvoir, VA: Defense Technical Information Center, January 1985. http://dx.doi.org/10.21236/ada153126.

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4

Armentrout, P. Thermochemistry of transition metal clusters. Technical progress report. Office of Scientific and Technical Information (OSTI), January 1993. http://dx.doi.org/10.2172/6395690.

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5

Armentrout, P. Thermochemistry of transition metal clusters. Technical progress report. Office of Scientific and Technical Information (OSTI), January 1992. http://dx.doi.org/10.2172/7281505.

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Knickelbein, M. B. Particle-like absorption spectra in small transition metal clusters. Office of Scientific and Technical Information (OSTI), February 1995. http://dx.doi.org/10.2172/10120654.

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Talu, Orhan, and Surendra N. Tewari. Sub-Nanostructured Non Transition Metal Complex Grids for Hydrogen Storage. Office of Scientific and Technical Information (OSTI), October 2007. http://dx.doi.org/10.2172/918886.

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8

Ogut, Serdar. Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks. Office of Scientific and Technical Information (OSTI), September 2017. http://dx.doi.org/10.2172/1389151.

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9

Armentrout, Peter. THERMOCHEMISTRY AND REACTIVITY OF TRANSITION METAL CLUSTERS AND THEIR OXIDES. Office of Scientific and Technical Information (OSTI), June 2014. http://dx.doi.org/10.2172/1135682.

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10

Dunkerton, L., C. Hinckley, J. Tyrrell, and P. Robinson. Interactions of sulfur-containing compounds with transition metal clusters and metal surfaces III. Office of Scientific and Technical Information (OSTI), January 1989. http://dx.doi.org/10.2172/7019171.

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