Melting phenomena: effect of composition for 55-atom Ag-Pd bimetallic clusters.

PubMed

Cheng, Daojian; Wang, Wenchuan; Huang, Shiping

2008-05-14

Understanding the composition effect on the melting processes of bimetallic clusters is important for their applications. Here, we report the relationship between the melting point and the metal composition for the 55-atom icosahedral Ag-Pd bimetallic clusters by canonical Monte Carlo simulations, using the second-moment approximation of the tight-binding potentials (TB-SMA) for the metal-metal interactions. Abnormal melting phenomena for the systems of interest are found. Our simulation results reveal that the dependence of the melting point on the composition is not a monotonic change, but experiences three different stages. The melting temperatures of the Ag-Pd bimetallic clusters increase monotonically with the concentration of the Ag atoms first. Then, they reach a plateau presenting almost a constant value. Finally, they decrease sharply at a specific composition. The main reason for this change can be explained in terms of the relative stability of the Ag-Pd bimetallic clusters at different compositions. The results suggest that the more stable the cluster, the higher the melting point for the 55-atom icosahedral Ag-Pd bimetallic clusters at different compositions.

Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mannix, A. J.; Zhou, X. -F.; Kiraly, B.

At the atomic-cluster scale, pure boron is markedly similar to carbon, forming simple planar molecules and cage-like fullerenes. Theoretical studies predict that two-dimensional (2D) boron sheets will adopt an atomic configuration similar to that of boron atomic clusters. We synthesized atomically thin, crystalline 2D boron sheets (i.e., borophene) on silver surfaces under ultrahigh-vacuum conditions. Atomic-scale characterization, supported by theoretical calculations, revealed structures reminiscent of fused boron clusters with multiple scales of anisotropic, out-of-plane buckling. Unlike bulk boron allotropes, borophene shows metallic characteristics that are consistent with predictions of a highly anisotropic, 2D metal.

Quantum chemical calculation of the equilibrium structures of small metal atom clusters

NASA Technical Reports Server (NTRS)

Kahn, L. R.

1982-01-01

Metal atom clusters are studied based on the application of ab initio quantum mechanical approaches. Because these large 'molecular' systems pose special practical computational problems in the application of the quantum mechanical methods, there is a special need to find simplifying techniques that do not compromise the reliability of the calculations. Research is therefore directed towards various aspects of the implementation of the effective core potential technique for the removal of the metal atom core electrons from the calculations.

Advanced Electrochemistry of Individual Metal Clusters Electrodeposited Atom by Atom to Nanometer by Nanometer.

PubMed

Kim, Jiyeon; Dick, Jeffrey E; Bard, Allen J

2016-11-15

Metal clusters are very important as building blocks for nanoparticles (NPs) for electrocatalysis and electroanalysis in both fundamental and applied electrochemistry. Attention has been given to understanding of traditional nucleation and growth of metal clusters and to their catalytic activities for various electrochemical applications in energy harvesting as well as analytical sensing. Importantly, understanding the properties of these clusters, primarily the relationship between catalysis and morphology, is required to optimize catalytic function. This has been difficult due to the heterogeneities in the size, shape, and surface properties. Thus, methods that address these issues are necessary to begin understanding the reactivity of individual catalytic centers as opposed to ensemble measurements, where the effect of size and morphology on the catalysis is averaged out in the measurement. This Account introduces our advanced electrochemical approaches to focus on each isolated metal cluster, where we electrochemically fabricated clusters or NPs atom by atom to nanometer by nanometer and explored their electrochemistry for their kinetic and catalytic behavior. Such approaches expand the dimensions of analysis, to include the electrochemistry of (1) a discrete atomic cluster, (2) solely a single NP, or (3) individual NPs in the ensemble sample. Specifically, we studied the electrocatalysis of atomic metal clusters as a nascent electrocatalyst via direct electrodeposition on carbon ultramicroelectrode (C UME) in a femtomolar metal ion precursor. In addition, we developed tunneling ultramicroelectrodes (TUMEs) to study electron transfer (ET) kinetics of a redox probe at a single metal NP electrodeposited on this TUME. Owing to the small dimension of a NP as an active area of a TUME, extremely high mass transfer conditions yielded a remarkably high standard ET rate constant, k 0 , of 36 cm/s for outer-sphere ET reaction. Most recently, we advanced nanoscale scanning electrochemical microscopy (SECM) imaging to resolve the electrocatalytic activity of individual electrodeposited NPs within an ensemble sample yielding consistent high k 0 values of ≥2 cm/s for the hydrogen oxidation reaction (HOR) at different NPs. We envision that our advanced electrochemical approaches will enable us to systematically address structure effects on the catalytic activity, thus providing a quantitative guideline for electrocatalysts in energy-related applications.

Related Structure Characters and Stability of Structural Defects in a Metallic Glass

PubMed Central

Niu, Xiaofeng; Feng, Shidong; Pan, Shaopeng

2018-01-01

Structural defects were investigated by a recently proposed structural parameter, quasi-nearest atom (QNA), in a modeled Zr50Cu50 metallic glass through molecular dynamics simulations. More QNAs around an atom usually means that more defects are located near the atom. Structural analysis reveals that the spatial distribution of the numbers of QNAs displays to be clearly heterogeneous. Furthermore, QNA is closely correlated with cluster connections, especially four-atom cluster connections. Atoms with larger coordination numbers usually have less QNAs. When two atoms have the same coordination number, the atom with larger five-fold symmetry has less QNAs. The number of QNAs around an atom changes rather frequently and the change of QNAs might be correlated with the fast relaxation metallic glasses. PMID:29565298

Understanding and Practical Use of Ligand and Metal Exchange Reactions in Thiolate-Protected Metal Clusters to Synthesize Controlled Metal Clusters.

PubMed

Niihori, Yoshiki; Hossain, Sakiat; Sharma, Sachil; Kumar, Bharat; Kurashige, Wataru; Negishi, Yuichi

2017-05-01

It is now possible to accurately synthesize thiolate (SR)-protected gold clusters (Au n (SR) m ) with various chemical compositions with atomic precision. The geometric structure, electronic structure, physical properties, and functions of these clusters are well known. In contrast, the ligand or metal atom exchange reactions between these clusters and other substances have not been studied extensively until recently, even though these phenomena were observed during early studies. Understanding the mechanisms of these reactions could allow desired functional metal clusters to be produced via exchange reactions. Therefore, we have studied the exchange reactions between Au n (SR) m and analogous clusters and other substances for the past four years. The results have enabled us to gain deep understanding of ligand exchange with respect to preferential exchange sites, acceleration means, effect on electronic structure, and intercluster exchange. We have also synthesized several new metal clusters using ligand and metal exchange reactions. In this account, we summarize our research on ligand and metal exchange reactions. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs.

PubMed

Mannix, Andrew J; Zhou, Xiang-Feng; Kiraly, Brian; Wood, Joshua D; Alducin, Diego; Myers, Benjamin D; Liu, Xiaolong; Fisher, Brandon L; Santiago, Ulises; Guest, Jeffrey R; Yacaman, Miguel Jose; Ponce, Arturo; Oganov, Artem R; Hersam, Mark C; Guisinger, Nathan P

2015-12-18

At the atomic-cluster scale, pure boron is markedly similar to carbon, forming simple planar molecules and cage-like fullerenes. Theoretical studies predict that two-dimensional (2D) boron sheets will adopt an atomic configuration similar to that of boron atomic clusters. We synthesized atomically thin, crystalline 2D boron sheets (i.e., borophene) on silver surfaces under ultrahigh-vacuum conditions. Atomic-scale characterization, supported by theoretical calculations, revealed structures reminiscent of fused boron clusters with multiple scales of anisotropic, out-of-plane buckling. Unlike bulk boron allotropes, borophene shows metallic characteristics that are consistent with predictions of a highly anisotropic, 2D metal. Copyright © 2015, American Association for the Advancement of Science.

Thin Metallic Films From Solvated Metal Atoms

NASA Astrophysics Data System (ADS)

Trivino, Galo C.; Klabunde, Kenneth J.; Dale, Brock

1988-02-01

Metals were evaporated under vacuum and the metal atoms solvated by excess organic solvents at low temperature. Upon warming stable colloidal metal particles were formed by controlled metal atom clustering. The particles were stabilized toward flocculation by solvation and electrostatic effects. Upon solvent removal the colloidal particles grew to form thin films that were metallic in appearance, but showed higher resistivities than pure metallic films. Gold, palladium, platinium, and especially indium are discussed.

Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

PubMed Central

Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Baksi, Ananya; Pradeep, Thalappil

2012-01-01

Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature. PMID:22312454

Dispersed metal cluster catalysts by design. Synthesis, characterization, structure, and performance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Arslan, Ilke; Dixon, David A.; Gates, Bruce C.

2015-09-30

To understand the class of metal cluster catalysts better and to lay a foundation for the prediction of properties leading to improved catalysts, we have synthesized metal catalysts with well-defined structures and varied the cluster structures and compositions systematically—including the ligands bonded to the metals. These ligands include supports and bulky organics that are being tuned to control both the electron transfer to or from the metal and the accessibility of reactants to influence catalytic properties. We have developed novel syntheses to prepare these well-defined catalysts with atomic-scale control the environment by choice and placement of ligands and applied state-of-themore » art spectroscopic, microscopic, and computational methods to determine their structures, reactivities, and catalytic properties. The ligands range from nearly flat MgO surfaces to enveloping zeolites to bulky calixarenes to provide controlled coverages of the metal clusters, while also enforcing unprecedented degrees of coordinative unsaturation at the metal site—thereby facilitating bonding and catalysis events at exposed metal atoms. With this wide range of ligand properties and our arsenal of characterization tools, we worked to achieve a deep, fundamental understanding of how to synthesize robust supported and ligand-modified metal clusters with controlled catalytic properties, thereby bridging the gap between active site structure and function in unsupported and supported metal catalysts. We used methods of organometallic and inorganic chemistry combined with surface chemistry for the precise synthesis of metal clusters and nanoparticles, characterizing them at various stages of preparation and under various conditions (including catalytic reaction conditions) and determining their structures and reactivities and how their catalytic properties depend on their compositions and structures. Key characterization methods included IR, NMR, and EXAFS spectroscopies to identify ligands on the metals and their reactions; EXAFS spectroscopy and high-resolution STEM to determine cluster framework structures and changes resulting from reactant treatment and locations of metal atoms on support surfaces; X-ray diffraction crystallography to determine full structures of cluster-ligand combinations in the absence of a support, and TEM with tomographic methods to observe individual metal atoms and determine three-dimensional structures of catalysts. Electronic structure calculations were used to verify and interpret spectra and extend the understanding of reactivity beyond what is measurable experimentally.« less

Composition formulas of Fe-based transition metals-metalloid bulk metallic glasses derived from dual-cluster model of binary eutectics.

PubMed

Naz, Gul Jabeen; Dong, Dandan; Geng, Yaoxiang; Wang, Yingmin; Dong, Chuang

2017-08-22

It is known that bulk metallic glasses follow simple composition formulas [cluster](glue atom) 1 or 3 with 24 valence electrons within the framework of the cluster-plus-glue-atom model. Though the relevant nearest-neighbor cluster can be readily identified from a devitrification phase, the glue atoms remains poorly defined. The present work is devoted to understanding the composition rule of Fe-(B,P,C) based multi-component bulk metallic glasses, by introducing a cluster-based eutectic liquid model. This model regards a eutectic liquid to be composed of two stable liquids formulated respectively by cluster formulas for ideal metallic glasses from the two eutectic phases. The dual cluster formulas are first established for binary Fe-(B,C,P) eutectics: [Fe-Fe 14 ]B 2 Fe + [B-B 2 Fe 8 ]Fe ≈ Fe 83.3 B 16.7 for eutectic Fe 83 B 17 , [P-Fe 14 ]P + [P-Fe 9 ]P 2 Fe≈Fe 82.8 P 17.2 for Fe 83 P 17 , and [C-Fe 6 ]Fe 3  + [C-Fe 9 ]C 2 Fe ≈ Fe 82.6 C 17.4 for Fe 82.7 C 17.3 . The second formulas in these dual-cluster formulas, being respectively relevant to devitrification phases Fe 2 B, Fe 3 P, and Fe 3 C, well explain the compositions of existing Fe-based transition metals-metalloid bulk metallic glasses. These formulas also satisfy the 24-electron rule. The proposition of the composition formulas for good glass formers, directly from known eutectic points, constitutes a new route towards understanding and eventual designing metallic glasses of high glass forming abilities.

Potential of transition metal atoms embedded in buckled monolayer g-C3N4 as single-atom catalysts.

PubMed

Li, Shu-Long; Yin, Hui; Kan, Xiang; Gan, Li-Yong; Schwingenschlögl, Udo; Zhao, Yong

2017-11-15

We use first-principles calculations to systematically explore the potential of transition metal atoms (Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Ir, Pt, and Au) embedded in buckled monolayer g-C 3 N 4 as single-atom catalysts. We show that clustering of Sc and Ti on g-C 3 N 4 is thermodynamically impeded and that V, Cr, Mn, and Cu are much less susceptible to clustering than the other TM atoms under investigation. Strong bonding of the transition metal atoms in the cavities of g-C 3 N 4 and high diffusion barriers together are responsible for single-atom fixation. Analysis of the CO oxidation process indicates that embedding of Cr and Mn in g-C 3 N 4 gives rise to promising single-atom catalysts at low temperature.

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters

NASA Astrophysics Data System (ADS)

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; Nobusada, Katsuyuki; Jin, Rongchao

2016-03-01

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications. Electronic supplementary information (ESI) available: The pump dependent transient absorption spectra and the corresponding global analysis results. See DOI: 10.1039/c6nr01008c

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, In Soo; Li, Zhanyong; Zheng, Jian

Installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 degrees C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and Xray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novelmore » catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support.« less

Subnanometer to nanometer transition metal CO oxidation catalysts

DOEpatents

Vajda, Stefan; Fortunelli, Alessandro; Yasumatsu, Hisato

2017-12-26

The present invention provides a catalyst defined in part by a conductive substrate; a film overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises between 8 and 11 atoms. Further provided is a catalyst defined in part by a conductive substrate; a layer overlaying a surface of the substrate; and a plurality of metal clusters supported by the layer, wherein each cluster comprises at least two metals.

Formation of fivefold axes in the FCC-metal nanoclusters

NASA Astrophysics Data System (ADS)

Myasnichenko, Vladimir S.; Starostenkov, Mikhail D.

2012-11-01

Formation of atomistic structures of metallic Cu, Au, Ag clusters and bimetallic Cu-Au clusters was studied with the help of molecular dynamics using the many-body tight-binding interatomic potential. The simulation of the crystallization process of clusters with the number of atoms ranging from 300 to 1092 was carried out. The most stable configurations of atoms in the system, corresponding to the minimum of potential energy, was found during super-fast cooling from 1000 K. Atoms corresponding to fcc, hcp, and Ih phases were identified by the method of common neighbor analysis. Incomplete icosahedral core can be discovered at the intersection of one of the Ih axes with the surface of monometallic cluster. The decahedron-shaped structure of bimetallic Cu-Au cluster with seven completed icosahedral cores was obtained. The principles of the construction of small bimetallic clusters with icosahedral symmetry and increased fractal dimensionality were offered.

An intermetallic Au24Ag20 superatom nanocluster stabilized by labile ligands.

PubMed

Wang, Yu; Su, Haifeng; Xu, Chaofa; Li, Gang; Gell, Lars; Lin, Shuichao; Tang, Zichao; Häkkinen, Hannu; Zheng, Nanfeng

2015-04-08

An intermetallic nanocluster containing 44 metal atoms, Au24Ag20(2-SPy)4(PhC≡C)20Cl2, was successfully synthesized and structurally characterized by single-crystal analysis and density funtional theory computations. The 44 metal atoms in the cluster are arranged as a concentric three-shell Au12@Ag20@Au12 Keplerate structure having a high symmetry. For the first time, the co-presence of three different types of anionic ligands (i.e., phenylalkynyl, 2-pyridylthiolate, and chloride) was revealed on the surface of metal nanoclusters. Similar to thiolates, alkynyls bind linearly to surface Au atoms using their σ-bonds, leading to the formation of two types of surface staple units (PhC≡C-Au-L, L = PhC≡C(-) or 2-pyridylthiolate) on the cluster. The co-presence of three different surface ligands allows the site-specific surface and functional modification of the cluster. The lability of PhC≡C(-) ligands on the cluster was demonstrated, making it possible to keep the metal core intact while removing partial surface capping. Moreover, it was found that ligand exchange on the cluster occurs easily to offer various derivatives with the same metal core but different surface functionality and thus different solubility.

Photodissociation Studies of Metal-Containing Clusters and Complexes

NASA Astrophysics Data System (ADS)

Pilgrim, Jeffrey Scott

1995-01-01

There have been two major areas of investigation for researchers working with laser ablation in molecular beams. The first area is the study of weakly-bound complexes. These complexes are bound by electrostatic interactions. In the present study the weakly bound interactions of the rare gases with the magnesium ion are investigated with electronic spectroscopy. The second major area is the study of metal and metal-containing clusters. Examples of previous investigations are the alkali metal clusters and the fullerenes. The present investigation is on metal -carbon clusters. The so-called metallo-carbohedrenes and metal-carbon nanocrystals are studied. Resonance enhanced photodissociation spectroscopy is used to obtain electronic excitation spectra of the Mg^+-rare gas species in the ultraviolet region. This investigation is facilitated by a reflectron time-of-flight mass spectrometer. The interaction of the rare gas with the metal ion is attributed to a "solvation" of the atomic ion transition. Simple bonding arguments predict that the excited state is more bound than the ground state for these complexes. This will result in a shift of the complex vibronic origin to lower energy from the atomic ion transition. This is exactly what is observed in the experiment with progressively larger shifts for the heavier rare gases. The electronic excitation spectra allow the vibrational frequencies and anharmonicities for these complexes to be obtained for the excited state. In turn, the excited state bond dissociation energies can be determined. Finally, conservation of energy allows calculation of the ground state bond dissociation energies. In the metal-carbon systems the stability of the metallo-carbohedrene, met-car, stoichiometry is shown to extend into the transition period at least to the iron group. Photodissociation with a 532 nm laser causes a loss of metal atoms for met-cars formed with first row transition metals and a loss of metal-carbon units for met-cars formed from second-row transition metal atoms. Larger metal-carbon clusters are found to be face-centered-cubic nanocrystals. Photodissociation of these nanocrystals causes fragmentation into smaller nanocrystals. In addition, nanocrystals also dissociatively rearrange into the met -car structure. Two of the metal-carbon nanocrystals ( rm Ti_{14}C_{13 }^+ and rm V_{14 }C_{13}^+) fragment into the met-car with a trapped carbon atom.

Special and general superatoms.

PubMed

Luo, Zhixun; Castleman, A Welford

2014-10-21

Bridging the gap between atoms and macroscopic matter, clusters continue to be a subject of increasing research interest. Among the realm of cluster investigations, an exciting development is the realization that chosen stable clusters can mimic the chemical behavior of an atom or a group of the periodic table of elements. This major finding known as a superatom concept was originated experimentally from the study of aluminum cluster reactivity conducted in 1989 by noting a dramatic size dependence of the reactivity where cluster anions containing a certain number of Al atoms were unreactive toward oxygen while the other species were etched away. This observation was well interpreted by shell closings on the basis of the jellium model, and the related concept (originally termed "unified atom") spawned a wide range of pioneering studies in the 1990s pertaining to the understanding of factors governing the properties of clusters. Under the inspiration of a superatom concept, advances in cluster science in finding stable species not only shed light on magic clusters (i.e., superatomic noble gas) but also enlightened the exploration of stable clusters to mimic the chemical behavior of atoms leading to the discovery of superhalogens, alkaline-earth metals, superalkalis, etc. Among them, certain clusters could enable isovalent isomorphism of precious metals, indicating application potential for inexpensive superatoms for industrial catalysis, while a few superalkalis were found to validate the interesting "harpoon mechanism" involved in the superatomic cluster reactivity; recently also found were the magnetic superatoms of which the cluster-assembled materials could be used in spin electronics. Up to now, extensive studies in cluster science have allowed the stability of superatomic clusters to be understood within a few models, including the jellium model, also aromaticity and Wade-Mingos rules depending on the geometry and metallicity of the cluster. However, the scope of application of the jellium model and modification of the theory to account for nonspherical symmetry and nonmetal-doped metal clusters are still illusive to be further developed. It is still worth mentioning that a superatom concept has also been introduced in ligand-stabilized metal clusters which could also follow the major shell-closing electron count for a spherical, square-well potential. By proposing a new concept named as special and general superatoms, herein we try to summarize all these investigations in series, expecting to provide an overview of this field with a primary focus on the joint undertakings which have given rise to the superatom concept. To be specific, for special superatoms, we limit to clusters under a strict jellium model and simply classify them into groups based on their valence electron counts. While for general superatoms we emphasize on nonmetal-doped metal clusters and ligand-stabilized metal clusters, as well as a few isovalent cluster systems. Hopefully this summary of special and general superatoms benefits the further development of cluster-related theory, and lights up the prospect of using them as building blocks of new materials with tailored properties, such as inexpensive isovalent systems for industrial catalysis, semiconductive superatoms for transistors, and magnetic superatoms for spin electronics.

Infrared Multiple Photon Dissociation Spectroscopy Of Metal Cluster-Adducts

NASA Astrophysics Data System (ADS)

Cox, D. M.; Kaldor, A.; Zakin, M. R.

1987-01-01

Recent development of the laser vaporization technique combined with mass-selective detection has made possible new studies of the fundamental chemical and physical properties of unsupported transition metal clusters as a function of the number of constituent atoms. A variety of experimental techniques have been developed in our laboratory to measure ionization threshold energies, magnetic moments, and gas phase reactivity of clusters. However, studies have so far been unable to determine the cluster structure or the chemical state of chemisorbed species on gas phase clusters. The application of infrared multiple photon dissociation IRMPD to obtain the IR absorption properties of metal cluster-adsorbate species in a molecular beam is described here. Specifically using a high power, pulsed CO2 laser as the infrared source, the IRMPD spectrum for methanol chemisorbed on small iron clusters is measured as a function of the number of both iron atoms and methanols in the complex for different methanol isotopes. Both the feasibility and potential utility of IRMPD for characterizing metal cluster-adsorbate interactions are demonstrated. The method is generally applicable to any cluster or cluster-adsorbate system dependent only upon the availability of appropriate high power infrared sources.

Peptide protected gold clusters: chemical synthesis and biomedical applications

NASA Astrophysics Data System (ADS)

Yuan, Qing; Wang, Yaling; Zhao, Lina; Liu, Ru; Gao, Fuping; Gao, Liang; Gao, Xueyun

2016-06-01

Bridging the gap between atoms and nanoparticles, noble metal clusters with atomic precision continue to attract considerable attention due to their important applications in catalysis, energy transformation, biosensing and biomedicine. Greatly different to common chemical synthesis, a one-step biomimetic synthesis of peptide-conjugated metal clusters has been developed to meet the demand of emerging bioapplications. Under mild conditions, multifunctional peptides containing metal capturing, reactive and targeting groups are rationally designed and elaborately synthesized to fabricate atomically precise peptide protected metal clusters. Among them, peptide-protected Au Cs (peptide-Au Cs) possess a great deal of exceptional advantages such as nanometer dimensions, high photostability, good biocompatibility, accurate chemical formula and specific protein targeting capacity. In this review article, we focus on the recent advances in potential theranostic fields by introducing the rising progress of peptide-Au Cs for biological imaging, biological analysis and therapeutic applications. The interactions between Au Cs and biological systems as well as potential mechanisms are also our concerned theme. We expect that the rapidly growing interest in Au Cs-based theranostic applications will attract broader concerns across various disciplines.

Tailoring oxide properties: An impact on adsorption characteristics of molecules and metals

NASA Astrophysics Data System (ADS)

Honkala, Karoliina

2014-12-01

Both density functional theory calculations and numerous experimental studies demonstrate a variety of unique features in metal supported oxide films and transition metal doped simple oxides, which are markedly different from their unmodified counterparts. This review highlights, from the computational perspective, recent literature on the properties of the above mentioned surfaces and how they adsorb and activate different species, support metal aggregates, and even catalyse reactions. The adsorption of Au atoms and clusters on metal-supported MgO films are reviewed together with the cluster's theoretically predicted ability to activate and dissociate O2 at the Au-MgO(100)/Ag(100) interface, as well as the impact of an interface vacancy to the binding of an Au atom. In contrast to a bulk MgO surface, an Au atom binds strongly on a metal-supported ultra-thin MgO film and becomes negatively charged. Similarly, Au clusters bind strongly on a supported MgO(100) film and are negatively charged favouring 2D planar structures. The adsorption of other metal atoms is briefly considered and compared to that of Au. Existing computational literature of adsorption and reactivity of simple molecules including O2, CO, NO2, and H2O on mainly metal-supported MgO(100) films is discussed. Chemical reactions such as CO oxidation and O2 dissociation are discussed on the bare thin MgO film and on selected Au clusters supported on MgO(100)/metal surfaces. The Au atoms at the perimeter of the cluster are responsible for catalytic activity and calculations predict that they facilitate dissociative adsorption of oxygen even at ambient conditions. The interaction of H2O with a flat and stepped Ag-supported MgO film is summarized and compared to bulk MgO. The computational results highlight spontaneous dissociation on MgO steps. Furthermore, the impact of water coverage on adsorption and dissociation is addressed. The modifications, such as oxygen vacancies and dopants, at the oxide-metal interface and their effect on the adsorption characteristics of water and Au are summarized. Finally, more limited computational literature on transition metal (TM) doped CaO(100) and MgO(100) surfaces is presented. Again, Au is used as a probe species. Similar to metal-supported MgO films, Au binds more strongly than on undoped CaO(100) and becomes negatively charged. The discussion focuses on rationalization of Au adsorption with the help of Born-Haber cycle, which reveals that the so-called redox energy including the electron transfer from the dopant to the Au atom together with the simultaneous structural relaxation of lattice atoms is responsible for enhanced binding. In addition, adsorption energy dependence on the position and type of the dopant is summarized.

Effects of single atom doping on the ultrafast electron dynamics of M1Au24(SR)18 (M = Pd, Pt) nanoclusters.

PubMed

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y; Nobusada, Katsuyuki; Jin, Rongchao

2016-04-07

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M1@Au24(SR)18 (M = Pd, Pt; R = CH2CH2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M1Au12 core states; (2) core to shell relaxation in a few picoseconds; and (3) relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au25(SR)18 cluster. The detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.

Effects of single atom doping on the ultrafast electron dynamics of M 1Au 24(SR) 18 (M = Pd, Pt) nanoclusters

DOE PAGES

Zhou, Meng; Qian, Huifeng; Sfeir, Matthew Y.; ...

2016-02-29

Atomically precise, doped metal clusters are receiving wide research interest due to their synergistic properties dependent on the metal composition. To understand the electronic properties of doped clusters, it is highly desirable to probe the excited state behavior. Here, we report the ultrafast relaxation dynamics of doped M 1@Au 24(SR) 18 (M = Pd, Pt; R = CH 2CH 2Ph) clusters using femtosecond visible and near infrared transient absorption spectroscopy. Three relaxation components are identified for both mono-doped clusters: (1) sub-picosecond relaxation within the M 1Au 12 core states; (2) core to shell relaxation in a few picoseconds; and (3)more » relaxation back to the ground state in more than one nanosecond. Despite similar relaxation pathways for the two doped nanoclusters, the coupling between the metal core and surface ligands is accelerated by over 30% in the case of the Pt dopant compared with the Pd dopant. Compared to Pd doping, the case of Pt doping leads to much more drastic changes in the steady state and transient absorption of the clusters, which indicates that the 5d orbitals of the Pt atom are more strongly mixed with Au 5d and 6s orbitals than the 4d orbitals of the Pd dopant. These results demonstrate that a single foreign atom can lead to entirely different excited state spectral features of the whole cluster compared to the parent Au 25(SR) 18 cluster. As a result, the detailed excited state dynamics of atomically precise Pd/Pt doped gold clusters help further understand their properties and benefit the development of energy-related applications.« less

Growth Behavior and Electronic Structure of Noble Metal-Doped Germanium Clusters.

PubMed

Mahtout, Sofiane; Siouani, Chaouki; Rabilloud, Franck

2018-01-18

Structures, energetics, and electronic properties of noble metal-doped germanium (MGe n with M = Cu, Ag, Au; n = 1-19) clusters are systematically investigated by using the density functional theory (DFT) approach. The endohedral structures in which the metal atom is encapsulated inside of a germanium cage appear at n = 10 when the dopant is Cu and n = 12 for M = Ag and Au. While Cu doping enhances the stability of the corresponding germanium frame, the binding energies of AgGe n and AuGe n are always lower than those of pure germanium clusters. Our results highlight the great stability of the CuGe 10 cluster in a D 4d structure and, to a lesser extent, that of AgGe 15 and AuGe 15 , which exhibits a hollow cage-like geometry. The sphere-type geometries obtained for n = 10-15 present a peculiar electronic structure in which the valence electrons of the noble metal and Ge atoms are delocalized and exhibit a shell structure associated with the quasi-spherical geometry. It is found that the coinage metal is able to give both s- and d-type electrons to be reorganized together with the valence electrons of Ge atoms through a pooling of electrons. The cluster size dependence of the stability, the frontier orbital energy gap, the vertical ionization potentials, and electron affinities are given.

Extending DFT-based genetic algorithms by atom-to-place re-assignment via perturbation theory: A systematic and unbiased approach to structures of mixed-metallic clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Weigend, Florian, E-mail: florian.weigend@kit.edu

2014-10-07

Energy surfaces of metal clusters usually show a large variety of local minima. For homo-metallic species the energetically lowest can be found reliably with genetic algorithms, in combination with density functional theory without system-specific parameters. For mixed-metallic clusters this is much more difficult, as for a given arrangement of nuclei one has to find additionally the best of many possibilities of assigning different metal types to the individual positions. In the framework of electronic structure methods this second issue is treatable at comparably low cost at least for elements with similar atomic number by means of first-order perturbation theory, asmore » shown previously [F. Weigend, C. Schrodt, and R. Ahlrichs, J. Chem. Phys. 121, 10380 (2004)]. In the present contribution the extension of a genetic algorithm with the re-assignment of atom types to atom sites is proposed and tested for the search of the global minima of PtHf{sub 12} and [LaPb{sub 7}Bi{sub 7}]{sup 4−}. For both cases the (putative) global minimum is reliably found with the extended technique, which is not the case for the “pure” genetic algorithm.« less

Barrierless growth of precursor-free, ultrafast laser-fragmented noble metal nanoparticles by colloidal atom clusters - A kinetic in situ study.

PubMed

Jendrzej, Sandra; Gökce, Bilal; Amendola, Vincenzo; Barcikowski, Stephan

2016-02-01

Unintended post-synthesis growth of noble metal colloids caused by excess amounts of reactants or highly reactive atom clusters represents a fundamental problem in colloidal chemistry, affecting product stability or purity. Hence, quantified kinetics could allow defining nanoparticle size determination in dependence of the time. Here, we investigate in situ the growth kinetics of ps pulsed laser-fragmented platinum nanoparticles in presence of naked atom clusters in water without any influence of reducing agents or surfactants. The nanoparticle growth is investigated for platinum covering a time scale of minutes to 50days after nanoparticle generation, it is also supplemented by results obtained from gold and palladium. Since a minimum atom cluster concentration is exceeded, a significant growth is determined by time resolved UV/Vis spectroscopy, analytical disc centrifugation, zeta potential measurement and transmission electron microscopy. We suggest a decrease of atom cluster concentration over time, since nanoparticles grow at the expense of atom clusters. The growth mechanism during early phase (<1day) of laser-synthesized colloid is kinetically modeled by rapid barrierless coalescence. The prolonged slow nanoparticle growth is kinetically modeled by a combination of coalescence and Lifshitz-Slyozov-Wagner kinetic for Ostwald ripening, validated experimentally by the temperature dependence of Pt nanoparticle size and growth quenching by Iodide anions. Copyright © 2015. Published by Elsevier Inc.

Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin [Ensemble averaged structure-function relationship for composite nanocrystals: magnetic bcc Fe clusters with catalytically active fcc Pt skin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction,more » respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.« less

Effect of local structures on crystallization in deeply undercooled metallic glass-forming liquids

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, S. Q.; Li, M. Z., E-mail: maozhili@ruc.edu.cn; Wu, Z. W.

2016-04-21

The crystallization mechanism in deeply undercooled ZrCu metallic glass-forming liquids was investigated via molecular dynamics simulations. It was found that the crystallization process is mainly controlled by the growth of crystal nuclei formed by the BCC-like atomic clusters, consistent with experimental speculations. The crystallization rate is found to relate to the number of growing crystal nuclei in the crystallization process. The crystallization rate in systems with more crystal nuclei is significantly hindered by the larger surface fractions of crystal nuclei and their different crystalline orientations. It is further revealed that in the crystallization in deeply undercooled regions, the BCC-like crystalmore » nuclei are formed from the inside of the precursors formed by the FCC-like atomic clusters, and growing at the expense of the precursors. Meanwhile, the precursors are expanding at the expense of the outside atomic clusters. This process is consistent with the so-called Ostwald step rule. The atomic structures of metallic glasses are found to have significant impact on the subsequent crystallization process. In the Zr{sub 85}Cu{sub 15} system, the stronger spatial correlation of Cu atoms could hinder the crystallization processes in deeply undercooled regions.« less

Supersonic Bare Metal Cluster Beams. Final Report

DOE R&D Accomplishments Database

Smalley, R. E.

1997-10-14

A major portion of the project involved elucidating the relation between reactivity and the electronic structure of transition-metal (TM) clusters of 2--200 atoms, which required the construction and continuous development of two principal apparati; the Fourier Transform-Ion Cyclotron Resonance (FT-ICR) apparatus, and Ultraviolet Photoelectron Spectroscopy (UPS). Together, these machines have enabled the most detailed probing of the structure and chemical reactivity of TM clusters. Clusters of all the transition metals were included in these studies. Fundamental aspects in chemisorption, reactivity, and heterogeneous catalysis have also become better understood as a result of these experiments for important classes of systems such as H{sub 2}, CO, and CO{sub 2} adsorbed onto clusters of many of the metals listed above. In particular, a correlation was found between reactivity of H{sub 2} with Fe, Co, and Ni clusters and differences between the cluster IP and EA. As recounted in a previous technical report, the DOE`s role in the initial discovery of fullerenes at Rice was central, and from the start investigations were made into metal atoms trapped in the fullerenes cage. More recently, the authors have discovered that 2--4 atoms of La, Y, or Sc can be produced by laser vaporization of composite graphite/metal-oxide disks. This work was largely motivated by the prospects of using such endohedral TM metals for their catalytic activity without the well-known difficulties of effective support media and lack of control over particle size. Thus, while it will certainly be important to discover ways to efficiently scale up production (e.g., the solar generation method explored with DOE support), the efforts have concentrated more on characterization, purification, and manipulation of doped fullerenes. For the past two years, much of the group`s effort has involved the production, purification, and characterization of carbon nanotubes.

Fundamental Studies and Isolation Strategies for Metal Compound Nanoclusters

DTIC Science & Technology

2009-02-28

probe nanocluster structure, bonding and stability, metal oxide, carbide and silicide clusters with up to 50 atoms were investigated with mass...transition metal compounds (carbides, oxides, silicides ) that are expected to have high stability, an essential property for their isolation...Metal carbide, oxide and silicide nanoclusters are studied in the size range from a few up to about 300 atoms. New infrared laser spectroscopy

Structure of overheated metal clusters: MD simulation study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vorontsov, Alexander

2015-08-17

The structure of overheated metal clusters appeared in condensation process was studied by computer simulation techniques. It was found that clusters with size larger than several tens of atoms have three layers: core part, intermediate dense packing layer and a gas- like shell with low density. The change of the size and structure of these layers with the variation of internal energy and the size of cluster is discussed.

New insights into designing metallacarborane based room temperature hydrogen storage media.

PubMed

Bora, Pankaj Lochan; Singh, Abhishek K

2013-10-28

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of charge transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H2 sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature.

New insights into designing metallacarborane based room temperature hydrogen storage media

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bora, Pankaj Lochan; Singh, Abhishek K.

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of chargemore » transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H{sub 2} sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature.« less

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe 3Mn-Iodosobenzene Adducts

DOE PAGES

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz; ...

2017-03-24

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Accelerated Oxygen Atom Transfer and C-H Bond Oxygenation by Remote Redox Changes in Fe3 Mn-Iodosobenzene Adducts.

PubMed

de Ruiter, Graham; Carsch, Kurtis M; Gul, Sheraz; Chatterjee, Ruchira; Thompson, Niklas B; Takase, Michael K; Yano, Junko; Agapie, Theodor

2017-04-18

We report the synthesis, characterization, and reactivity of [LFe 3 (PhPz) 3 OMn( s PhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57 Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2 Fe II Mn II vs. Fe III 3 Mn II ) influence oxygen atom transfer in tetranuclear Fe 3 Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Water Oxidation Catalysis via Size-Selected Iridium Clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halder, Avik; Liu, Cong; LIU, ZHUN

The detailed mechanism and efficacy of four electron electrochemical water oxidation depend critically upon the detailed atomic structure of each catalytic site, which are numerous and diverse in most metal oxides anodes. In order to limit the diversity of sites, arrays of discrete iridium clusters with identical metal atom number (Ir-2, Ir-4, or Ir-8) were deposited in submonolayer coverage on conductive oxide supports, and the electrochemical properties and activity of each was evaluated. Exceptional electroactivity for the oxygen evolving reaction (OER) was observed for all cluster samples in acidic electrolyte. Reproducible cluster-size-dependent trends in redox behavior were also resolved. First-principlesmore » computational models of the individual discrete-size clusters allow correlation of catalytic-site structure and multiplicity with redox behavior.« less

Generalized vibrating potential model for collective excitations in spherical, deformed and superdeformed systems: (1) Atomic nuclei, (2) Metal clusters

NASA Astrophysics Data System (ADS)

Nesterenko, V. O.; Kleinig, W.

1995-01-01

The self-consistent vibrating potential model (VPM) is extended for description of Eλ collective excitations in atomic nuclei and metal clusters with practically any kind of static deformation. The model is convenient for a qualitative analysis and provides the RPA accuracy of numerical calculations. The VPM is applied to study Eλ giant resonances in spherical metal clusters and deformed and superdeformed nuclei. It is shown that the deformation splitting of superdeformed nuclei results in a very complicated ("jungle-like") structure of the resonances, which makes the experimental observation of E2 and E3 giant resonances in superdeformed nuclei quite problematic. Calculations of E1 giant resonances in spherical sodium clusters Na8, Na20 and Na40 are presented, as a test of the VPM in this field. The results are in qualitative agreement with the experimental data.

Spatial Distributions of Metal Atoms During Carbon SWNTs Formation: Measurements and Modelling

NASA Technical Reports Server (NTRS)

Cau, M.; Dorval, N.; Attal-Tretout, B.; Cochon, J. L.; Loiseau, A.; Farhat, S.; Hinkov, I.; Scott, C. D.

2004-01-01

Experiments and modelling have been undertaken to clarify the role of metal catalysts during single-wall carbon nanotube formation. For instance, we wonder whether the metal catalyst is active as an atom, a cluster, a liquid or solid nanoparticle [1]. A reactor has been developed for synthesis by continuous CO2-laser vaporisation of a carbon-nickel-cobalt target in laminar helium flow. The laser induced fluorescence technique [2] is applied for local probing of gaseous Ni, Co and CZ species throughout the hot carbon flow of the target heated up to 3500 K. A rapid depletion of C2 in contrast to the spatial extent of metal atoms is observed in the plume (Fig. 1). This asserts that C2 condenses earlier than Ni and Co atoms.[3, 4]. The depletion is even faster when catalysts are present. It may indicate that an interaction between metal atoms and carbon dimers takes place in the gas as soon as they are expelled from the target surface. Two methods of modelling are used: a spatially I-D calculation developed originally for the arc process [5], and a zero-D time dependent calculation, solving the chemical kinetics along the streamlines [6]. The latter includes Ni cluster formation. The peak of C2 density is calculated close to the target surface where the temperature is the highest. In the hot region, C; is dominant. As the carbon products move away from the target and mix with the ambient helium, they recombine into larger clusters, as demonstrated by the peak of C5 density around 1 mm. The profile of Ni-atom density compares fairly well with the measured one (Fig. 2). The early increase is due to the drop of temperature, and the final decrease beyond 6 mm results from Ni cluster formation at the eutectic temperature (approx.1600 K).

Computational evaluation of sub-nanometer cluster activity of singly exposed copper atom with various coordinative environment in catalytic CO2 transformation

NASA Astrophysics Data System (ADS)

Shanmugam, Ramasamy; Thamaraichelvan, Arunachalam; Ganesan, Tharumeya Kuppusamy; Viswanathan, Balasubramanian

2017-02-01

Metal cluster, at sub-nanometer level has a unique property in the activation of small molecules, in contrast to that of bulk surface. In the present work, singly exposed active site of copper metal cluster at sub-nanometer level was designed to arrive at the energy minimised configurations, binding energy, electrostatic potential map, frontier molecular orbitals and partial density of states. The ab initio molecular dynamics was carried out to probe the catalytic nature of the cluster. Further, the stability of the metal cluster and its catalytic activity in the electrochemical reduction of CO2 to CO were evaluated by means of computational hydrogen electrode via calculation of the free energy profile using DFT/B3LYP level of theory in vacuum. The activity of the cluster is ascertained from the fact that the copper atom, present in a two coordinative environment, performs a more selective conversion of CO2 to CO at an applied potential of -0.35 V which is comparatively lower than that of higher coordinative sites. The present study helps to design any sub-nano level metal catalyst for electrochemical reduction of CO2 to various value added chemicals.

Investigation of Metal and Metal Oxide Clusters Small Enough to Constitute the Critical Size for Gas Phase Nucleation in Combustion Processes.

DTIC Science & Technology

1980-11-01

Ao-A093 950 NORTHWESTERN UNIV EVANSTON IL DEPT OF M4ECHANICAL ND-ETC F/S 7/4 INVESTIGATION OF 1ETAL AND METAL OXIDE CLUSTERS S1ALL ENOUGH TO--ETC(U...34 " 18. SUPPLEMENTARY NOTES 19. KEY WORDS (Continue on reveroe side if necessary snd Identify by block number) Clusters , Nucleation, Molecular Beam, Free...contract a variety of techniques have been employed to study the properties of small atomic and molecular clusters formed in the gas phase via

Probing the atomic structure of metallic nanoclusters with the tip of a scanning tunneling microscope.

PubMed

Schouteden, Koen; Lauwaet, Koen; Janssens, Ewald; Barcaro, Giovanni; Fortunelli, Alessandro; Van Haesendonck, Chris; Lievens, Peter

2014-02-21

Preformed Co clusters with an average diameter of 2.5 nm are produced in the gas phase and are deposited under controlled ultra-high vacuum conditions onto a thin insulating NaCl film on Au(111). Relying on a combined experimental and theoretical investigation, we demonstrate visualization of the three-dimensional atomic structure of the Co clusters by high-resolution scanning tunneling microscopy (STM) using a Cl functionalized STM tip that can be obtained on the NaCl surface. More generally, use of a functionalized STM tip may allow for systematic atomic structure determination with STM of nanoparticles that are deposited on metal surfaces.

DOE Office of Scientific and Technical Information (OSTI.GOV)

de Ruiter, Graham; Carsch, Kurtis M.; Gul, Sheraz

In this paper, we report the synthesis, characterization, and reactivity of [LFe 3(PhPz) 3OMn( sPhIO)][OTf] x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene–metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, 57Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe III 2Fe IIMn II vs. Fe III 3Mn II) influence oxygen atom transfer in tetranuclear Fe 3Mn clusters. Finally, in particular, a one-electron redox change atmore » a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.« less

Living Colloidal Metal Particles from Solvated Metal Atoms. Clustering of Metal Atoms in Organic Media 15.

DTIC Science & Technology

1986-09-23

alchemists , and over the centuries great medicinal powers were ascribed to gold. And as early as 300 A.D. there are references to the 2 consumption of...gold fluid to prolong life. It is doubtful that this was a colloidal solution of gold since aqua regia 3 was unknown to early Chinese alchemists , and

Ensemble averaged structure–function relationship for nanocrystals: effective superparamagnetic Fe clusters with catalytically active Pt skin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petkov, Valeri; Prasai, Binay; Shastri, Sarvjit

2017-09-12

Practical applications require the production and usage of metallic nanocrystals (NCs) in large ensembles. Besides, due to their cluster-bulk solid duality, metallic NCs exhibit a large degree of structural diversity. This poses the question as to what atomic-scale basis is to be used when the structure–function relationship for metallic NCs is to be quantified precisely. In this paper, we address the question by studying bi-functional Fe core-Pt skin type NCs optimized for practical applications. In particular, the cluster-like Fe core and skin-like Pt surface of the NCs exhibit superparamagnetic properties and a superb catalytic activity for the oxygen reduction reaction,more » respectively. We determine the atomic-scale structure of the NCs by non-traditional resonant high-energy X-ray diffraction coupled to atomic pair distribution function analysis. Using the experimental structure data we explain the observed magnetic and catalytic behavior of the NCs in a quantitative manner. Lastly, we demonstrate that NC ensemble-averaged 3D positions of atoms obtained by advanced X-ray scattering techniques are a very proper basis for not only establishing but also quantifying the structure–function relationship for the increasingly complex metallic NCs explored for practical applications.« less

Effect of Spin Multiplicity in O2 Adsorption and Dissociation on Small Bimetallic AuAg Clusters.

PubMed

García-Cruz, Raúl; Poulain, Enrique; Hernández-Pérez, Isaías; Reyes-Nava, Juan A; González-Torres, Julio C; Rubio-Ponce, A; Olvera-Neria, Oscar

2017-08-17

To dispose of atomic oxygen, it is necessary the O 2 activation; however, an energy barrier must be overcome to break the O-O bond. This work presents theoretical calculations of the O 2 adsorption and dissociation on small pure Au n and Ag m and bimetallic Au n Ag m (n + m ≤ 6) clusters using the density functional theory (DFT) and the zeroth-order regular approximation (ZORA) to explicitly include scalar relativistic effects. The most stable Au n Ag m clusters contain a higher concentration of Au with Ag atoms located in the center of the cluster. The O 2 adsorption energy on pure and bimetallic clusters and the ensuing geometries depend on the spin multiplicity of the system. For a doublet multiplicity, O 2 is adsorbed in a bridge configuration, whereas for a triplet only one O-metal bond is formed. The charge transfer from metal toward O 2 occupies the σ* O-O antibonding natural bond orbital, which weakens the oxygen bond. The Au 3 ( 2 A) cluster presents the lowest activation energy to dissociate O 2 , whereas the opposite applies to the AuAg ( 3 A) system. In the O 2 activation, bimetallic clusters are not as active as pure Au n clusters due to the charge donated by Ag atoms being shared between O 2 and Au atoms.

Composition Formulas of Inorganic Compounds in Terms of Cluster Plus Glue Atom Model.

PubMed

Ma, Yanping; Dong, Dandan; Wu, Aimin; Dong, Chuang

2018-01-16

The present paper attempts to identify the molecule-like structural units in inorganic compounds, by applying the so-called "cluster plus glue atom model". This model, originating from metallic glasses and quasi-crystals, describes any structure in terms of a nearest-neighbor cluster and a few outer-shell glue atoms, expressed in the cluster formula [cluster](glue atoms). Similar to the case for normal molecules where the charge transfer occurs within the molecule to meet the commonly known octet electron rule, the octet state is reached after matching the nearest-neighbor cluster with certain outer-shell glue atoms. These kinds of structural units contain information on local atomic configuration, chemical composition, and electron numbers, just as for normal molecules. It is shown that the formulas of typical inorganic compounds, such as fluorides, oxides, and nitrides, satisfy a similar octet electron rule, with the total number of valence electrons per unit formula being multiples of eight.

Clustered atom-replaced structure in single-crystal-like metal oxide

NASA Astrophysics Data System (ADS)

Araki, Takeshi; Hayashi, Mariko; Ishii, Hirotaka; Yokoe, Daisaku; Yoshida, Ryuji; Kato, Takeharu; Nishijima, Gen; Matsumoto, Akiyoshi

2018-06-01

By means of metal organic deposition using trifluoroacetates (TFA-MOD), we replaced and localized two or more atoms in a single-crystalline structure having almost perfect orientation. Thus, we created a new functional structure, namely, clustered atom-replaced structure (CARS), having single-crystal-like metal oxide. We replaced metals in the oxide with Sm and Lu and localized them. Energy dispersive x-ray spectroscopy results, where the Sm signal increases with the Lu signal in the single-crystalline structure, confirm evidence of CARS. We also form other CARS with three additional metals, including Pr. The valence number of Pr might change from 3+ to approximately 4+, thereby reducing the Pr–Ba distance. We directly observed the structure by a high-angle annular dark-field image, which provided further evidence of CARS. The key to establishing CARS is an equilibrium chemical reaction and a combination of additional larger and smaller unit cells to matrix cells. We made a new functional metal oxide with CARS and expect to realize CARS in other metal oxide structures in the future by using the above-mentioned process.

Self-Learning Off-Lattice Kinetic Monte Carlo method as applied to growth on metal surfaces

NASA Astrophysics Data System (ADS)

Trushin, Oleg; Kara, Abdelkader; Rahman, Talat

2007-03-01

We propose a new development in the Self-Learning Kinetic Monte Carlo (SLKMC) method with the goal of improving the accuracy with which atomic mechanisms controlling diffusive processes on metal surfaces may be identified. This is important for diffusion of small clusters (2 - 20 atoms) in which atoms may occupy Off-Lattice positions. Such a procedure is also necessary for consideration of heteroepitaxial growth. The new technique combines an earlier version of SLKMC [1] with the inclusion of off-lattice occupancy. This allows us to include arbitrary positions of adatoms in the modeling and makes the simulations more realistic and reliable. We have tested this new approach for the case of the diffusion of small 2D Cu clusters diffusion on Cu(111) and found good performance and satisfactory agreement with results obtained from previous version of SLKMC. The new method also helped reveal a novel atomic mechanism contributing to cluster migration. We have also applied this method to study the diffusion of Cu clusters on Ag(111), and find that Cu atoms generally prefer to occupy off-lattice sites. [1] O. Trushin, A. Kara, A. Karim, T.S. Rahman Phys. Rev B 2005

Metal clusters and nanoparticles in dielectric matrices: Formation and optical properties

NASA Astrophysics Data System (ADS)

Gladskikh, I. A.; Vartanyan, T. A.

2016-12-01

The optical properties of thin dielectric films with metal inclusions and their dependence on thermal and laser annealing are studied experimentally. Metal clusters (Ag, Au, and Cu) in dielectric materials (Al2O3 and SiO2) are obtained by simultaneous vacuum deposition of metal and dielectric on the surface of a corresponding dielectric substrate (sapphire and quartz). It is shown that, depending on the deposited dielectric material, on the weight ratio of deposited metal and dielectric, and on the subsequent thermal treatment, one can obtain different metal structures, from clusters with a small number of atoms to complex dendritic plasmonic structures.

Al7CX (X=Li-Cs) clusters: Stability and the prospect for cluster materials

NASA Astrophysics Data System (ADS)

Ashman, C.; Khanna, S. N.; Pederson, M. R.; Kortus, J.

2000-12-01

Al7C clusters, recently found to have a high-electron affinity and exceptional stability, are shown to form ionic molecules when combined with alkali-metal atoms. Our studies, based on an ab initio gradient-corrected density-functional scheme, show that Al7CX (X=Li-Cs) clusters have a very low-electron affinity and a high-ionization potential. When combined, the two- and four-atom composite clusters of Al7CLi units leave the Al7C clusters almost intact. Preliminary studies indicate that Al7CLi may be suitable to form cluster-based materials.

Electronic levels and charge distribution near the interface of nickel

NASA Technical Reports Server (NTRS)

Waber, J. T.

1982-01-01

The energy levels in clusters of nickel atoms were investigated by means of a series of cluster calculations using both the multiple scattering and computational techniques (designated SSO) which avoids the muffin-tin approximation. The point group symmetry of the cluster has significant effect on the energy of levels nominally not occupied. This influences the electron transfer process during chemisorption. The SSO technique permits the approaching atom or molecule plus a small number of nickel atoms to be treated as a cluster. Specifically, molecular levels become more negative in the O atom, as well as in a CO molecule, as the metal atoms are approached. Thus, electron transfer from the nickel and bond formation is facilitated. This result is of importance in understanding chemisorption and catalytic processes.

A Density Functional Theory Investigation of Nin , Pdn , and Ptn Clusters (n=1-4) Adsorbed on Buckminsterfullerene.

PubMed

Pham, Nguyet N T; Le, Hung M

2017-05-19

In this study, we examine the adsorptions of Ni, Pd, and Pt clusters on C 60 by using a computational approach. Our calculation results show that the base structure of C 60 can host Ni n /Pd n /Pt n (n=1-4) clusters with good adsorption stability and the complexes establish either two or no unpaired electrons. The binding energy of Pd and Pt clusters increases as the number of metal atoms increases, implying that the coverage of C 60 with Pd or Pt preferentially establishes a large-size metal cluster. A single metal atom favorably occupies the C-C bridge site. For dimer clusters, the three metals of interest share a similar binding fashion, in which two metal atoms establish direct interactions with the C-C bridge sites. For trimer adsorptions, the formation of linear and triangular structures is observed. Both Pt 3 and Ni 3 preferably constitute isosceles triangles on C 60 , whilst Pd 3 favorably establishes a linear shape. Finally, for each of the Ni 4 and Pd 4 adsorption cases, we observed three stable binding configurations: rhombus, tetrahedron, and Y-form. Whereas Ni 4 establishes a tetrahedral form, Pd 4 attains the most stable form with the Y-shape geometry on C 60 . Overall, we observe that the trend of Pd binding to C 60 tends to go beyond the fashion of Ni and Pt. In terms of magnetic alignment, the Pd n -C 60 systems seem to be non-magnetic in most cases, unlike the Ni and Pt cases, the structures of which possess magnetic moments of 2 μB in their most stable forms. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and theoretical study on activation of the C-H bond in pyridine by [M(m)]- (M = Cu, Ag, Au, m = 1-3).

PubMed

Liu, Xiao-Jing; Hamilton, I P; Han, Ke-Li; Tang, Zi-Chao

2010-09-21

Activation of the C-H bond of pyridine by [M(m)](-) (M = Cu, Ag, Au, m = 1-3) is investigated by experiment and theory. Complexes of coinage metal clusters and the pyridyl group, [M(m)-C(5)H(4)N](-), are produced from reactions between metal clusters formed by laser ablation of coinage metal samples and pyridine molecules seeded in argon carrier gas. We examine the structure and formation mechanism of these pyridyl-coinage metal complexes. Our study shows that C(5)H(4)N bonds to the metal clusters through a M-C sigma bond and [M(m)-C(5)H(4)N](-) is produced via a stepwise mechanism. The first step is a direct insertion reaction between [M(m)](-) and C(5)H(5)N with activation of the C-H bond to yield the intermediate [HM(m)-C(5)H(4)N](-). The second step is H atom abstraction by a neutral metal atom to yield [M(m)-C(5)H(4)N](-).

Electrophobic interaction induced impurity clustering in metals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Hong-Bo; Wang, Jin-Long; Jiang, W.

2016-10-01

We introduce the concept of electrophobic interaction, analogous to hydrophobic interaction, for describing the behavior of impurity atoms in a metal, a 'solvent of electrons'. We demonstrate that there exists a form of electrophobic interaction between impurities with closed electron shell structure, which governs their dissolution behavior in a metal. Using He, Be and Ar as examples, we predict by first-principles calculations that the electrophobic interaction drives He, Be or Ar to form a close-packed cluster with a clustering energy that follows a universal power-law scaling with the number of atoms (N) dissolved in a free electron gas, as wellmore » as W or Al lattice, as Ec is proportional to (N2/3-N). This new concept unifies the explanation for a series of experimental observations of close-packed inert-gas bubble formation in metals, and significantly advances our fundamental understanding and capacity to predict the solute behavior of impurities in metals, a useful contribution to be considered in future material design of metals for nuclear, metallurgical, and energy applications.« less

Composition-dependent metallic glass alloys correlate atomic mobility with collective glass surface dynamics.

PubMed

Nguyen, Duc; Zhu, Zhi-Guang; Pringle, Brian; Lyding, Joseph; Wang, Wei-Hua; Gruebele, Martin

2016-06-22

Glassy metallic alloys are richly tunable model systems for surface glassy dynamics. Here we study the correlation between atomic mobility, and the hopping rate of surface regions (clusters) that rearrange collectively on a minute to hour time scale. Increasing the proportion of low-mobility copper atoms in La-Ni-Al-Cu alloys reduces the cluster hopping rate, thus establishing a microscopic connection between atomic mobility and dynamics of collective rearrangements at a glass surface made from freshly exposed bulk glass. One composition, La60Ni15Al15Cu10, has a surface resistant to re-crystallization after three heating cycles. When thermally cycled, surface clusters grow in size from about 5 glass-forming units to about 8 glass-forming units, evidence of surface aging without crystal formation, although its bulk clearly forms larger crystalline domains. Such kinetically stable glass surfaces may be of use in applications where glassy coatings stable against heating are needed.

The Electronic Structure of Transition Metal Coated Fullerenes

NASA Astrophysics Data System (ADS)

Patton, David C.; Pederson, Mark R.; Kaxiras, Efthimios

1998-03-01

Clusters composed of fullerene molecules with an outer shell of transition metal atoms in the composition C_60M_62 (M being a transition metal) have been produced with laser vaporisation techniques(F. Tast, N. Malinowski, S. Frank, M. Heinebrodt, I.M.L. Billas, and T. P. Martin, Z. Phys D 40), 351 (1997).. We have studied several of these very large systems with a parallel version of the all-electron NRLMOL cluster code. Optimized geometries of the metal encased fullerenes C_60Ti_62 and C_60V_62 are presented along with their HOMO-LUMO gaps, electron affinities, ionization energies, and cohesive energies. We compare the stability of these clusters to relaxed met-car structures (e.g. Ti_8C_12) and to relaxed rocksalt metal-carbide fragments (TiC)n with n=8 and 32. In addition to metal-coated fullerenes we consider the possibility of a trilayered structure consisting of a small shell of metal atoms enclosed by a metal coated fullerene. The nature of bonding in these systems is analyzed by studying the electronic charge distributions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Jun; Ma, Evan; Asta, Mark

Using molecular dynamics simulations, we have studied the atomic correlations characterizing the second peak in the radial distribution function (RDF) of metallic glasses and liquids. The analysis was conducted from the perspective of different connection schemes of atomic packing motifs, based on the number of shared atoms between two linked coordination polyhedra. The results demonstrate that the cluster connections by face-sharing, specifically with three common atoms, are most favored when transitioning from the liquid to glassy state, and exhibit the stiffest elastic response during shear deformation. These properties of the connections and the resultant atomic correlations are generally the samemore » for different types of packing motifs in different alloys. Splitting of the second RDF peak was observed for the inherent structure of the equilibrium liquid, originating solely from cluster connections; this trait can then be inherited in the metallic glass formed via subsequent quenching of the parent liquid through the glass transition, in the absence of any additional type of local structural order. In conclusion, increasing ordering and cluster connection during cooling, however, may tune the position and intensity of the split peaks.« less

Density functional study of structural and electronic properties of bimetallic silver-gold clusters: Comparison with pure gold and silver clusters

NASA Astrophysics Data System (ADS)

Bonacic-Koutecky, Vlasta; Burda, Jaroslav; Mitric, Roland; Ge, Maofa; Zampella, Giuseppe; Fantucci, Piercarlo

2002-08-01

Bimetallic silver-gold clusters offer an excellent opportunity to study changes in metallic versus "ionic" properties involving charge transfer as a function of the size and the composition, particularly when compared to pure silver and gold clusters. We have determined structures, ionization potentials, and vertical detachment energies for neutral and charged bimetallic AgmAun 3[less-than-or-equal](m+n)[less-than-or-equal]5 clusters. Calculated VDE values compare well with available experimental data. In the stable structures of these clusters Au atoms assume positions which favor the charge transfer from Ag atoms. Heteronuclear bonding is usually preferred to homonuclear bonding in clusters with equal numbers of hetero atoms. In fact, stable structures of neutral Ag2Au2, Ag3Au3, and Ag4Au4 clusters are characterized by the maximum number of hetero bonds and peripheral positions of Au atoms. Bimetallic tetramer as well as hexamer are planar and have common structural properties with corresponding one-component systems, while Ag4Au4 and Ag8 have 3D forms in contrast to Au8 which assumes planar structure. At the density functional level of theory we have shown that this is due to participation of d electrons in bonding of pure Aun clusters while s electrons dominate bonding in pure Agm as well as in bimetallic clusters. In fact, Aun clusters remain planar for larger sizes than Agm and AgnAun clusters. Segregation between two components in bimetallic systems is not favorable, as shown in the example of Ag5Au5 cluster. We have found that the structures of bimetallic clusters with 20 atoms Ag10Au10 and Ag12Au8 are characterized by negatively charged Au subunits embedded in Ag environment. In the latter case, the shape of Au8 is related to a pentagonal bipyramid capped by one atom and contains three exposed negatively charged Au atoms. They might be suitable for activating reactions relevant to catalysis. According to our findings the charge transfer in bimetallic clusters is responsible for formation of negatively charged gold subunits which are expected to be reactive, a situation similar to that of gold clusters supported on metal oxides.

MicroED Structure of Au146(p-MBA)57 at Subatomic Resolution Reveals a Twinned FCC Cluster.

PubMed

Vergara, Sandra; Lukes, Dylan A; Martynowycz, Michael W; Santiago, Ulises; Plascencia-Villa, Germán; Weiss, Simon C; de la Cruz, M Jason; Black, David M; Alvarez, Marcos M; López-Lozano, Xochitl; Barnes, Christopher O; Lin, Guowu; Weissker, Hans-Christian; Whetten, Robert L; Gonen, Tamir; Yacaman, Miguel Jose; Calero, Guillermo

2017-11-16

Solving the atomic structure of metallic clusters is fundamental to understanding their optical, electronic, and chemical properties. Herein we present the structure of the largest aqueous gold cluster, Au 146 (p-MBA) 57 (p-MBA: para-mercaptobenzoic acid), solved by electron micro-diffraction (MicroED) to subatomic resolution (0.85 Å) and by X-ray diffraction at atomic resolution (1.3 Å). The 146 gold atoms may be decomposed into two constituent sets consisting of 119 core and 27 peripheral atoms. The core atoms are organized in a twinned FCC structure, whereas the surface gold atoms follow a C 2 rotational symmetry about an axis bisecting the twinning plane. The protective layer of 57 p-MBAs fully encloses the cluster and comprises bridging, monomeric, and dimeric staple motifs. Au 146 (p-MBA) 57 is the largest cluster observed exhibiting a bulk-like FCC structure as well as the smallest gold particle exhibiting a stacking fault.

MicroED structure of Au146(p-MBA)57 at subatomic resolution reveals a twinned FCC cluster

PubMed Central

Vergara, Sandra; Lukes, Dylan A.; Martynowycz, Michael W.; Santiago, Ulises; Plascencia-Villa, German; Weiss, Simon C.; de la Cruz, M. Jason; Black, David M.; Alvarez, Marcos M.; Lopez-Lozano, Xochitl; Barnes, Christopher O.; Lin, Guowu; Weissker, Hans-Christian; Whetten, Robert L.; Gonen, Tamir; Jose-Yacaman, Miguel; Calero, Guillermo

2018-01-01

Solving the atomic structure of metallic clusters is fundamental to understanding their optical, electronic, and chemical properties. Herein we present the structure of the largest aqueous gold cluster, Au146(p-MBA)57 (p-MBA: para-mercaptobenzoic acid), solved by electron diffraction (MicroED) to subatomic resolution (0.85 Å) and by X-ray diffraction at atomic resolution (1.3 Å). The 146 gold atoms may be decomposed into two constituent sets consisting of 119 core and 27 peripheral atoms. The core atoms are organized in a twinned FCC structure whereas the surface gold atoms follow a C2 rotational symmetry about an axis bisecting the twinning plane. The protective layer of 57 p-MBAs fully encloses the cluster and comprises bridging, monomeric, and dimeric staple motifs. Au146(p-MBA)57 is the largest cluster observed exhibiting a bulk-like FCC structure as well as the smallest gold particle exhibiting a stacking fault. PMID:29072840

Probing C-O bond activation on gas-phase transition metal clusters: Infrared multiple photon dissociation spectroscopy of Fe, Ru, Re, and W cluster CO complexes

NASA Astrophysics Data System (ADS)

Lyon, Jonathan T.; Gruene, Philipp; Fielicke, André; Meijer, Gerard; Rayner, David M.

2009-11-01

The binding of carbon monoxide to iron, ruthenium, rhenium, and tungsten clusters is studied by means of infrared multiple photon dissociation spectroscopy. The CO stretching mode is used to probe the interaction of the CO molecule with the metal clusters and thereby the activation of the C-O bond. CO is found to adsorb molecularly to atop positions on iron clusters. On ruthenium and rhenium clusters it also binds molecularly. In the case of ruthenium, binding is predominantly to atop sites, however higher coordinated CO binding is also observed for both metals and becomes prevalent for rhenium clusters containing more than nine atoms. Tungsten clusters exhibit a clear size dependence for molecular versus dissociative CO binding. This behavior denotes the crossover to the purely dissociative CO binding on the earlier transition metals such as tantalum.

New mechanisms of cluster diffusion on metal fcc(100) surfaces

NASA Astrophysics Data System (ADS)

Trushin, Oleg; Salo, Petri; Alatalo, Matti; Ala-Nissila, Tapio

2001-03-01

We have studied atomic mechanisms of the diffusion of small clusters on the fcc(100) metal surfaces using semi-empirical and ab-initio molecular static calculations. Primary goal of these studies was to investigate possible many-body mechanisms of cluster motion which can contribute to low temperature crystal growth. We used embedded atom and Glue potentials in semi-empirical simulations of Cu and Al. Combination of the Nudged Elastic Band and Eigenvector Following methods allowed us to find all the possible transition paths for cluster movements on flat terrace. In case of Cu(001) we have found several new mechanisms for diffusion of clusters, including mechanisms called row-shearing and dimer-rotating in which a whole row inside an island moves according to a concerted jump and a dimer rotates at the periphery of an island, respectively. In some cases these mechanisms yield a lower energy barrier than the standard mechanisms.

Interaction of size-selected gold nanoclusters with dopamine

NASA Astrophysics Data System (ADS)

Montone, Georgia R.; Hermann, Eric; Kandalam, Anil K.

2016-12-01

We present density functional theory based results on the interaction of size-selected gold nanoclusters, Au10 and Au20, with dopamine molecule. The gold clusters interact strongly with the nitrogen site of dopamine, thereby forming stable gold-dopamine complexes. Our calculations further show that there is no site specificity on the planar Au10 cluster with all the edge gold atoms equally preferred. On the other hand, in the pyramidal Au20 cluster, the vertex metal atom is the most active site. As the size increased from Au10 to Au20, the interaction strength has shown a declining trend. The effect of aqueous environment on the interaction strengths were also studied by solvation model. It is found that the presence of solvent water stabilizes the interaction between the metal cluster and dopamine molecule, even though for Au10 cluster the energy ordering of the isomers changed from that of the gas-phase.

Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

DOE PAGES

Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

2018-04-24

In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-Molecular Dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients; we use this approach to examine atomic condensation onto 6-56 atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity ( v) between atom and cluster andmore » the initial impact parameter ( b). In all cases there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms, and for 14 atom and 28 atom Mg clusters, as cluster equilibration temperature increases the condensation rate coefficient drops to values below the hard sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (> 1000 m s -1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). In conclusion, the presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.« less

Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-Molecular Dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients; we use this approach to examine atomic condensation onto 6-56 atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity ( v) between atom and cluster andmore » the initial impact parameter ( b). In all cases there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms, and for 14 atom and 28 atom Mg clusters, as cluster equilibration temperature increases the condensation rate coefficient drops to values below the hard sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (> 1000 m s -1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). In conclusion, the presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.« less

Evolution and stabilization of subnanometric metal species in confined space by in situ TEM

DOE PAGES

Liu, Lichen; Zakharov, Dmitri N.; Arenal, Raul; ...

2018-02-08

Understanding the behavior and dynamic structural transformation of subnanometric metal species under reaction conditions will be helpful for understanding catalytic phenomena and for developing more efficient and stable catalysts based on single atoms and clusters.In this work,the evolution and stabilization of subnanometric Pt species confined in MCM-22 zeolite has been studied by in situ transmission electron microscopy (TEM). By correlating the results from in situ TEM studies and the results obtained in a continuous fix-bed reactor,it has been possible to delimitate the factors that control the dynamic agglomeration and redispersion behavior of metal species under reaction conditions. Here, the dynamicmore » reversible transformation between atomically dispersed Pt species and clusters/nanoparticles during CO oxidation at different temperatures has been elucidated.Ithas also been confirmed that subnanometric Pt clusters can be stabilized in MCM-22 crystallites during NO reduction with CO and H 2.« less

Evolution and stabilization of subnanometric metal species in confined space by in situ TEM

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Lichen; Zakharov, Dmitri N.; Arenal, Raul

Understanding the behavior and dynamic structural transformation of subnanometric metal species under reaction conditions will be helpful for understanding catalytic phenomena and for developing more efficient and stable catalysts based on single atoms and clusters.In this work,the evolution and stabilization of subnanometric Pt species confined in MCM-22 zeolite has been studied by in situ transmission electron microscopy (TEM). By correlating the results from in situ TEM studies and the results obtained in a continuous fix-bed reactor,it has been possible to delimitate the factors that control the dynamic agglomeration and redispersion behavior of metal species under reaction conditions. Here, the dynamicmore » reversible transformation between atomically dispersed Pt species and clusters/nanoparticles during CO oxidation at different temperatures has been elucidated.Ithas also been confirmed that subnanometric Pt clusters can be stabilized in MCM-22 crystallites during NO reduction with CO and H 2.« less

Equilibrium structure and atomic vibrations of Nin clusters

NASA Astrophysics Data System (ADS)

Borisova, Svetlana D.; Rusina, Galina G.

2017-12-01

The equilibrium bond lengths and binding energy, second differences in energy and vibrational frequencies of free clusters Nin (2 ≤ n ≤ 20) were calculated with the use of the interaction potential obtained in the tight-binding approximation (TBA). The results show that the minimum vibration frequency plays a significant role in the evaluation of the dynamic stability of the clusters. A nonmonotonic dependence of the minimum vibration frequency of clusters on their size and the extreme values for the number of atoms in a cluster n = 4, 6, 13, and 19 are demonstrated. This result agrees with the theoretical and experimental data on stable structures of small metallic clusters.

Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations.

PubMed

Yang, Huan; Goudeli, Eirini; Hogan, Christopher J

2018-04-28

In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard-sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-molecular dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients. We use this approach to examine atomic condensation onto 6-56-atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity (v) between atom and cluster and the initial impact parameter (b). In all cases, there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard-sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms and for 14- and 28-atom Mg clusters, as cluster equilibration temperature increases, the condensation rate coefficient drops to values below the hard-sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (>1000 m s -1 ) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). The presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.

Condensation and dissociation rates for gas phase metal clusters from molecular dynamics trajectory calculations

NASA Astrophysics Data System (ADS)

Yang, Huan; Goudeli, Eirini; Hogan, Christopher J.

2018-04-01

In gas phase synthesis systems, clusters form and grow via condensation, in which a monomer binds to an existing cluster. While a hard-sphere equation is frequently used to predict the condensation rate coefficient, this equation neglects the influences of potential interactions and cluster internal energy on the condensation process. Here, we present a collision rate theory-molecular dynamics simulation approach to calculate condensation probabilities and condensation rate coefficients. We use this approach to examine atomic condensation onto 6-56-atom Au and Mg clusters. The probability of condensation depends upon the initial relative velocity (v) between atom and cluster and the initial impact parameter (b). In all cases, there is a well-defined region of b-v space where condensation is highly probable, and outside of which the condensation probability drops to zero. For Au clusters with more than 10 atoms, we find that at gas temperatures in the 300-1200 K range, the condensation rate coefficient exceeds the hard-sphere rate coefficient by a factor of 1.5-2.0. Conversely, for Au clusters with 10 or fewer atoms and for 14- and 28-atom Mg clusters, as cluster equilibration temperature increases, the condensation rate coefficient drops to values below the hard-sphere rate coefficient. Calculations also yield the self-dissociation rate coefficient, which is found to vary considerably with gas temperature. Finally, calculations results reveal that grazing (high b) atom-cluster collisions at elevated velocity (>1000 m s-1) can result in the colliding atom rebounding (bounce) from the cluster surface or binding while another atom dissociates (replacement). The presented method can be applied in developing rate equations to predict material formation and growth rates in vapor phase systems.

Composition formulas of binary eutectics

PubMed Central

Ma, Y. P.; Dong, D. D.; Dong, C.; Luo, L. J.; Wang, Q.; Qiang, J. B.; Wang, Y. M.

2015-01-01

The present paper addresses the long-standing composition puzzle of eutectic points by introducing a new structural tool for the description of short-range-order structural unit, the cluster-plus-glue-atom model. In this model, any structure is dissociated into a 1st-neighbor cluster and a few glue atoms between the clusters, expressed by a cluster formula [cluster]gluex. This model is applied here to establish the structural model for eutectic liquids, assuming that a eutectic liquid consist of two subunits issued from the relevant eutectic phases, each being expressed by the cluster formula for ideal metallic glasses, i.e., [cluster](glue atom)1 or 3. A structural unit is then composed of two clusters from the relevant eutectic phases plus 2, 4, or 6 glue atoms. Such a dual cluster formulism is well validated in all boron-containing (except those located by the extreme phase diagram ends) and in some commonly-encountered binary eutectics, within accuracies below 1 at.%. The dual cluster formulas vary extensively and are rarely identical even for eutectics of close compositions. They are generally formed with two distinctly different cluster types, with special cluster matching rules such as cuboctahedron plus capped trigonal prism and rhombidodecahedron plus octahedral antiprism. PMID:26658618

Geometric, electronic, and bonding properties of AuNM (N = 1-7, M = Ni, Pd, Pt) clusters.

PubMed

Yuan, D W; Wang, Yang; Zeng, Zhi

2005-03-15

Employing first-principles methods, based on density functional theory, we report the ground state geometric and electronic structures of gold clusters doped with platinum group atoms, Au(N)M (N = 1-7, M = Ni, Pd, Pt). The stability and electronic properties of Ni-doped gold clusters are similar to that of pure gold clusters with an enhancement of bond strength. Due to the strong d-d or s-d interplay between impurities and gold atoms originating in the relativistic effects and unique properties of dopant delocalized s-electrons in Pd- and Pt-doped gold clusters, the dopant atoms markedly change the geometric and electronic properties of gold clusters, and stronger bond energies are found in Pt-doped clusters. The Mulliken populations analysis of impurities and detailed decompositions of bond energies as well as a variety of density of states of the most stable dopant gold clusters are given to understand the different effects of individual dopant atom on bonding and electronic properties of dopant gold clusters. From the electronic properties of dopant gold clusters, the different chemical reactivity toward O(2), CO, or NO molecule is predicted in transition metal-doped gold clusters compared to pure gold clusters.

Nanosized (mu12-Pt)Pd164-xPtx(CO)72(PPh3)20 (x approximately 7) containing Pt-centered four-shell 165-atom Pd-Pt core with unprecedented intershell bridging carbonyl ligands: comparative analysis of icosahedral shell-growth patterns with geometrically related Pd145(CO)x(PEt3)30 (x approximately 60) containing capped three-shell Pd145 core.

PubMed

Mednikov, Evgueni G; Jewell, Matthew C; Dahl, Lawrence F

2007-09-19

Presented herein are the preparation and crystallographic/microanalytical/magnetic/spectroscopic characterization of the Pt-centered four-shell 165-atom Pd-Pt cluster, (mu(12)-Pt)Pd(164-x)Pt(x)(CO)(72)(PPh(3))(20) (x approximately 7), 1, that replaces the geometrically related capped three-shell icosahedral Pd(145) cluster, Pd(145)(CO)(x)(PEt(3))(30) (x approximately 60), 2, as the largest crystallographically determined discrete transition metal cluster with direct metal-metal bonding. A detailed comparison of their shell-growth patterns gives rise to important stereochemical implications concerning completely unexpected structural dissimilarities as well as similarities and provides new insight concerning possible synthetic approaches for generation of multi-shell metal clusters. 1 was reproducibly prepared in small yields (<10%) from the reaction of Pd(10)(CO)(12)(PPh(3))(6) with Pt(CO)(2)(PPh(3))(2). Its 165-atom metal-core geometry and 20 PPh(3) and 72 CO ligands were established from a low-temperature (100 K) CCD X-ray diffraction study. The well-determined crystal structure is attributed largely to 1 possessing cubic T(h) (2/m3) site symmetry, which is the highest crystallographic subgroup of the noncrystallographic pseudo-icosahedral I(h) (2/m35) symmetry. The "full" four-shell Pd-Pt anatomy of 1 consists of: (a) shell 1 with the centered (mu(12)-Pt) atom encapsulated by the 12-atom icosahedral Pt(x)Pd(12-x) cage, x = 1.2(3); (b) shell 2 with the 42-atom nu(2) icosahedral Pt(x)Pd(42-x) cage, x = 3.5(5); (c) shell 3 with the anti-Mackay 60-atom semi-regular rhombicosidodecahedral Pt(x)Pd(60-x) cage, x = 2.2(6); (d) shell 4 with the 50-atom nu(2) pentagonal dodecahedral Pd(50) cage. The total number of crystallographically estimated Pt atoms, 8 +/- 3, which was obtained from least-squares (Pt(x)/Pd(1-x))-occupancy analysis of the X-ray data that conclusively revealed the central atom to be pure Pt (occupancy factor, x = 1.00(3)), is fortuitously in agreement with that of 7.6(7) found from an X-ray Pt/Pd microanalysis (WDS spectrometer) on three crystals of 1. Our utilization of this site-occupancy (Pt(x)Pd(1-x))-analysis for shells 1-3 originated from the microanalytical results; otherwise, the presumed metal-core composition would have been (mu(12)-Pt)Pd(164). [Alternatively, the (mu(12)-Pt)M(164) core-geometry of 1 may be viewed as a pseudo-Ih Pt-centered six-shell successive nu(1) polyhedral system, each with radially equivalent vertex atoms: Pt@M(12)(icosahedron)@M(30)(icosidodecahedron)@M(12)(icosahedron)@M(60)(rhombicosidodecahedron)@M(30)(icosidodecahedron)@M(20)(pentagonal dodecahedron)]. Completely surprising structural dissimilarities between 1 and 2 are: (1) to date 1 is only reproducibly isolated as a heterometallic Pd-Pt cluster with a central Pt instead of Pd atom; (2) the 50 atoms comprising the outer fourth nu(2) pentagonal dodecahedral shell in 1 are less than the 60 atoms of the inner third shell in 1, in contradistinction to shell-by-shell growth processes in all other known shell-based structures; (3) the 10 fewer PR3 ligands in 1 necessitate larger bulky PPh(3) ligands to protect the Pd-Pt core-geometry; (4) the 72 CO ligands consist of six bridging COs within each of the 12 pentagons in shell 4 that are coordinated to intershell metal atoms. SQUID magnetometry measurements showed a single-crystal sample of 1 to be diamagnetic over the entire temperature range of 10-300 K.

Improvements in Ionized Cluster-Beam Deposition

NASA Technical Reports Server (NTRS)

Fitzgerald, D. J.; Compton, L. E.; Pawlik, E. V.

1986-01-01

Lower temperatures result in higher purity and fewer equipment problems. In cluster-beam deposition, clusters of atoms formed by adiabatic expansion nozzle and with proper nozzle design, expanding vapor cools sufficiently to become supersaturated and form clusters of material deposited. Clusters are ionized and accelerated in electric field and then impacted on substrate where films form. Improved cluster-beam technique useful for deposition of refractory metals.

The Design, Synthesis, and Characterization of Open Sites on Metal Clusters

NASA Astrophysics Data System (ADS)

Nigra, Michael Mark

Coordinatively unsaturated corner and edge atoms have been hypothesized to have the highest activity of sites responsible for many catalytic reactions on a metal surface. Recent studies have validated this hypothesis in varied reaction systems. However, quantification of different types of coordinatively unsaturated sites, and elucidation of their individual catalytic rates has remained a largely unresolved challenge when understanding catalysis on metal surfaces. Yet such structure-function knowledge would be invaluable to the design of more active and selective metal-surface catalysts in the future. I investigated the catalytic contributions of undercoordinated sites such as corner and edge atoms are investigated in a model reaction system using organic ligands bound to the gold nanoparticle surface. The catalyst consisted of 4 nm gold nanoparticles on a metal oxide support, using resazurin to resorufin as a model reaction system. My results demonstrate that in this system, corner atom sites are the most undercoordinated sites, and are over an order of magnitude more active when compared to undercoordinated edge atom sites, while terrace sites remain catalytically inactive for the reduction reaction of resazurin to resorufin. Catalytic activity has been also demonstrated for calixarene-bound gold nanoparticles using the reduction of 4-nitrophenol. With the 4-nitrophenol reduction reaction, a comparative study was undertaken to compare calixarene phosphine and calixarene thiol bound 4 nm gold particles. The results of the study suggested that a leached site was responsible for catalysis and not sites on the original gold nanoparticles. Future experiments with calixarene bound gold clusters could investigate ligand effects in reactions where the active site is not a leached or aggregated gold species, possibly in oxidation reactions, where electron-rich gold is hypothesized to be a good catalyst. The results that emphasize the enhanced catalytic activity of undercoordinated sites led me to synthesize small gold clusters consisting of a high fraction of coordinatively unsaturated open sites. This was enabled through an approach that utilized bulky calix[4]arene ligands that are bound to a gold core. Since the size of the calix[4]arene ligand is commensurate with the size of the gold cluster core, the calix[4]arene ligand does not pack closely together on the gold cluster surface. This in turn results in areas of accessible gold atom sites between ligands. Additionally, these calix[4]arene ligands prevent cluster aggregation and electronically tune the gold core in a manner conceptually similar to enzymes affecting reactivity through organic side-chains acting as ligands. I quantified the number of open sites that result from this packing problem on the gold cluster surface, using fluorescence probe chemisorption experiments. The results of these chemisorption measurements support the mechanical model of accessibility whereby accessibility is not dependent on the identity of the functional group, whether it be calixarene phosphines or N-heterocyclic carbenes, bound to the gold surface, but rather to the relative radii of curvature of bound ligands and the gold cluster core. Additional materials characterization was completed with transmission electron microscopy in both bright-field imaging of zeolites, in MCM-22 and delaminated ITQ-2 and UCB-1 materials, and in dark field imaging of glucan coatings on oxide particles. These materials could prove to be interesting materials as to use as supports for the calixarene-bound metal clusters described above or for other metal clusters.

Adsorption behavior of Fe atoms on a naphthalocyanine monolayer on Ag(111) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan, Ling -Hao; Wu, Rong -Ting; Bao, De -Liang

2015-05-29

Adsorption behavior of Fe atoms on a metal-free naphthalocyanine (H 2Nc) monolayer on Ag(111) surface at room temperature has been investigated using scanning tunneling microscopy combined with density functional theory (DFT) based calculations. We found that the Fe atoms adsorbed at the centers of H 2Nc molecules and formed Fe-H 2Nc complexes at low coverage. DFT calculations show that the configuration of Fe at the center of a molecule is the most stable site, in good agreement with the experimental observations. After an Fe-H 2Nc complex monolayer was formed, the extra Fe atoms self-assembled to Fe clusters of uniform sizemore » and adsorbed dispersively at the interstitial positions of Fe-H 2Nc complex monolayer. Furthermore, the H 2Nc monolayer grown on Ag(111) could be a good template to grow dispersed magnetic metal atoms and clusters at room temperature for further investigation of their magnetism-related properties.« less

Icosahedral quasicrystals as twins of cubic crystals containing large icosahedral clusters of atoms: The 1012-atom primitive cubic structure of Al(6)CuLi(3), the C-phase Al(37)Cu(3)Li(21)Mg(3), and GaMg(2)Zn(3).

PubMed

Pauling, L

1988-06-01

Single-grain precession x-ray diffraction photographs of Al(6)CuLi(3) have been successfully indexed on the basis of icosahedral twinning of cubic crystals with a 1012-atom primitive cubic unit with edge 25.70 A, giving support to the proposal that the so-called icosahedral quasicrystals are twins of crystals containing eight large icosahedral clusters in the beta-W arrangement. In this compound two of the clusters consist of 104 atoms and six consist of 136 atoms, with 24 atoms shared. The same structure is assigned to the C-phase, Al(37)Cu(3)Li(21)Mg(3), and to GaMg(2)Zn(3). A theory of icosahedral quasicrystals and amorphous metals is described.

Icosahedral quasicrystals as twins of cubic crystals containing large icosahedral clusters of atoms: The 1012-atom primitive cubic structure of Al6CuLi3, the C-phase Al37Cu3Li21Mg3, and GaMg2Zn3

PubMed Central

Pauling, Linus

1988-01-01

Single-grain precession x-ray diffraction photographs of Al6CuLi3 have been successfully indexed on the basis of icosahedral twinning of cubic crystals with a 1012-atom primitive cubic unit with edge 25.70 Å, giving support to the proposal that the so-called icosahedral quasicrystals are twins of crystals containing eight large icosahedral clusters in the β-W arrangement. In this compound two of the clusters consist of 104 atoms and six consist of 136 atoms, with 24 atoms shared. The same structure is assigned to the C-phase, Al37Cu3Li21Mg3, and to GaMg2Zn3. A theory of icosahedral quasicrystals and amorphous metals is described. PMID:16593929

Generation of subnanometric platinum with high stability during transformation of a 2D zeolite into 3D.

PubMed

Liu, Lichen; Díaz, Urbano; Arenal, Raul; Agostini, Giovanni; Concepción, Patricia; Corma, Avelino

2017-01-01

Single metal atoms and metal clusters have attracted much attention thanks to their advantageous capabilities as heterogeneous catalysts. However, the generation of stable single atoms and clusters on a solid support is still challenging. Herein, we report a new strategy for the generation of single Pt atoms and Pt clusters with exceptionally high thermal stability, formed within purely siliceous MCM-22 during the growth of a two-dimensional zeolite into three dimensions. These subnanometric Pt species are stabilized by MCM-22, even after treatment in air up to 540 °C. Furthermore, these stable Pt species confined within internal framework cavities show size-selective catalysis for the hydrogenation of alkenes. High-temperature oxidation-reduction treatments result in the growth of encapsulated Pt species to small nanoparticles in the approximate size range of 1 to 2 nm. The stability and catalytic activity of encapsulated Pt species is also reflected in the dehydrogenation of propane to propylene.

Cooling rate dependence of simulated Cu{sub 64.5}Zr{sub 35.5} metallic glass structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryltsev, R. E.; Ural Federal University, 19 Mira Str., 620002 Ekaterinburg; L.D. Landau Institute for Theoretical Physics, Russian Academy of Sciences, 2 Kosygina Str., 119334 Moscow

Using molecular dynamics simulations with embedded atom model potential, we study structural evolution of Cu{sub 64.5}Zr{sub 35.5} alloy during the cooling in a wide range of cooling rates γ ∈ (1.5 ⋅ 10{sup 9}, 10{sup 13}) K/s. Investigating short- and medium-range orders, we show that the structure of Cu{sub 64.5}Zr{sub 35.5} metallic glass essentially depends on cooling rate. In particular, a decrease of the cooling rate leads to an increase of abundances of both the icosahedral-like clusters and Frank-Kasper Z16 polyhedra. The amounts of these clusters in the glassy state drastically increase at the γ{sub min} = 1.5 ⋅ 10{supmore » 9} K/s. Analysing the structure of the glass at γ{sub min}, we observe the formation of nano-sized crystalline grain of Cu{sub 2}Zr intermetallic compound with the structure of Cu{sub 2}Mg Laves phase. The structure of this compound is isomorphous with that for Cu{sub 5}Zr intermetallic compound. Both crystal lattices consist of two types of clusters: Cu-centered 13-atom icosahedral-like cluster and Zr-centered 17-atom Frank-Kasper polyhedron Z16. That suggests the same structural motifs for the metallic glass and intermetallic compounds of Cu–Zr system and explains the drastic increase of the abundances of these clusters observed at γ{sub min}.« less

Small Au clusters on a defective MgO(1 0 0) surface

NASA Astrophysics Data System (ADS)

Barcaro, Giovanni; Fortunelli, Alessandro

2008-05-01

The lowest energy structures of small T]>rndm where rndm is a random number (Metropolis criterion), the new configuration is accepted, otherwise the old configuration is kept, and the process is iterated. For each size we performed 3-5 BH runs, each one composed of 20-25 Monte Carlo steps, using a value of 0.5 eV as kT in the Metropolis criterion. Previous experience [13-15] shows that this is sufficient to single out the global minimum for adsorbed clusters of this size, and that the BH approach is more efficient as a global optimization algorithm than other techniques such as simulated annealing [18]. The MgO support was described via an (Mg 12O 12) cluster embedded in an array of ±2.0 a.u. point charges and repulsive pseudopotentials on the positive charges in direct contact with the cluster (see Ref. [15] for more details on the method). The atoms of the oxide cluster and the point charges were located at the lattice positions of the MgO rock-salt bulk structure using the experimental lattice constant of 4.208 Å. At variance with the ), evaluated by subtracting the energy of the oxide surface and of the metal cluster, both frozen in their interacting configuration, from the value of the total energy of the system, and by taking the absolute value; (ii) the binding energy of the metal cluster (E), evaluated by subtracting the energy of the isolated metal atoms from the total energy of the metal cluster in its interacting configuration, and by taking the absolute value; (iii) the metal cluster distortion energy (E), which corresponds to the difference between the energy of the metal cluster in the configuration interacting with the surface minus the energy of the cluster in its lowest-energy gas-phase configuration (a positive quantity); (iv) the oxide distortion energy (ΔE), evaluated subtracting the energy of the relaxed isolated defected oxide from the energy of the isolated defected oxide in the interacting configuration; and (v) the total binding energy (E), which is the sum of the binding energy of the metal cluster, the adhesion energy and the oxide distortion energy (E=E+E-ΔE). Note that the total binding energy of gas-phase clusters in their global minima can be obtained by summing E+E.

Density functional study of hypophosphite adsorption on Ni (1 1 1) and Cu (1 1 1) surfaces

NASA Astrophysics Data System (ADS)

Zeng, Yue; Liu, Shubin; Ou, Lihui; Yi, Jianlong; Yu, Shanci; Wang, Huixian; Xiao, Xiaoming

2006-02-01

Surface structures and electronic properties of hypophosphite, H 2PO 2-, molecularly adsorbed on Ni(1 1 1) and Cu(1 1 1) surfaces are investigated in this work by density functional theory at B3LYP/6-31++g(d, p) level. We employ a four-metal-atom cluster as the simplified model for the surface and have fully optimized the geometry and orientation of H 2PO 2- on the metal cluster. Six stable orientations have been discovered on both Ni (1 1 1) and Cu (1 1 1) surfaces. The most stable orientation of H 2PO 2- was found to have its two oxygen atoms interact the surface with two P sbnd O bonds pointing downward. Results of the Mulliken population analysis showed that the back donation from 3d orbitals of the transition metal substrate to the unfilled 3d orbital of the phosphorus atom in H 2PO 2- and 4s orbital's acceptance of electron donation from one lone pair of the oxygen atom in H 2PO 2- play very important roles in the H 2PO 2- adsorption on the transition metals. The averaged electron configuration of Ni in Ni 4 cluster is 4s 0.634p 0.023d 9.35 and that of Cu in Cu 4 cluster is 4s 1.004p 0.033d 9.97. Because of this subtle difference of electron configuration, the adsorption energy is larger on the Ni surface than on the Cu surface. The amount of charge transfers due to above two donations is larger from H 2PO 2- to the Ni surface than to the Cu surface, leading to a more positively charged P atom in Ni nH 2PO 2- than in Cu nH 2PO 2-. These results indicate that the phosphorus atom in Ni nH 2PO 2- complex is easier to be attacked by a nucleophile such as OH - and subsequent oxidation of H 2PO 2- can take place more favorably on Ni substrate than on Cu substrate.

Atomic and electronic structure of the silicon and silicon-metal Si{sub 20}, Si{sub 20}{sup -}, NaSi{sub 20}, KSi{sub 20} nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Borshch, N. A., E-mail: ssd18@phys.vsu.ru; Pereslavtseva, N. S.; Kurganskii, S. I.

The results of atomic-structure optimization and calculation of the electronic structure of the Si{sub 20}, Si{sub 20}{sup -}, NaSi{sub 20}, and KSi{sub 20} clusters are reported. The PM3 and AM1 semiempirical methods were used in the calculations. It is shown that the Na and K atoms stabilize the fullerene-like silicon structure. The effect of configuration of the clusters on their electronic structure is analyzed.

Effects of carbonyl bond, metal cluster dissociation, and evaporation rates on predictions of nanotube production in high-pressure carbon monoxide

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Smalley, Richard E.

2003-01-01

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNTs) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the conformation of CO2. It is shown that the production of CO2 is significantly greater for FeCO because of its lower bond energy as compared with that of NiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Effects of Carbonyl Bond and Metal Cluster Dissociation and Evaporation Rates on Predictions of Nanotube Production in HiPco

NASA Technical Reports Server (NTRS)

Scott, Carl D.; Smalley, Richard E.

2002-01-01

The high-pressure carbon monoxide (HiPco) process for producing single-wall carbon nanotubes (SWNT) uses iron pentacarbonyl as the source of iron for catalyzing the Boudouard reaction. Attempts using nickel tetracarbonyl led to no production of SWNTs. This paper discusses simulations at a constant condition of 1300 K and 30 atm in which the chemical rate equations are solved for different reaction schemes. A lumped cluster model is developed to limit the number of species in the models, yet it includes fairly large clusters. Reaction rate coefficients in these schemes are based on bond energies of iron and nickel species and on estimates of chemical rates for formation of SWNTs. SWNT growth is measured by the co-formation of CO2. It is shown that the production of CO2 is significantly greater for FeCO due to its lower bond energy as compared with that ofNiCO. It is also shown that the dissociation and evaporation rates of atoms from small metal clusters have a significant effect on CO2 production. A high rate of evaporation leads to a smaller number of metal clusters available to catalyze the Boudouard reaction. This suggests that if CO reacts with metal clusters and removes atoms from them by forming MeCO, this has the effect of enhancing the evaporation rate and reducing SWNT production. The study also investigates some other reactions in the model that have a less dramatic influence.

Cryochemistry of Metal Nanoparticles

NASA Astrophysics Data System (ADS)

Sergeev, Gleb B.

2003-12-01

The interaction of metal atoms, clusters and nanoparticles with different organic and inorganic substances were studied at low temperature (10-40K). Combination of matrix isolation technique and preparative cryochemistry was applied for the investigation of activity and selectivity of metal particles of different size. Encapsulation of metal nanoparticles in polymers was studied. The metal-polymer films thus obtained exhibited satisfactory sensitivity to ammonia.

Atomically Precise Metal Nanoclusters for Catalytic Application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jin, Rongchao

2016-11-18

The central goal of this project is to explore the catalytic application of atomically precise gold nanoclusters. By solving the total structures of ligand-protected nanoclusters, we aim to correlate the catalytic properties of metal nanoclusters with their atomic/electronic structures. Such correlation unravel some fundamental aspects of nanocatalysis, such as the nature of particle size effect, origin of catalytic selectivity, particle-support interactions, the identification of catalytically active centers, etc. The well-defined nanocluster catalysts mediate the knowledge gap between single crystal model catalysts and real-world conventional nanocatalysts. These nanoclusters also hold great promise in catalyzing certain types of reactions with extraordinarily highmore » selectivity. These aims are in line with the overall goals of the catalytic science and technology of DOE and advance the BES mission “to support fundamental research to understand, predict, and ultimately control matter and energy at the level of electrons, atoms, and molecules”. Our group has successfully prepared different sized, robust gold nanoclusters protected by thiolates, such as Au 25(SR) 18, Au 28(SR) 20, Au 38(SR) 24, Au 99(SR) 42, Au 144(SR) 60, etc. Some of these nanoclusters have been crystallographically characterized through X-ray crystallography. These ultrasmall nanoclusters (< 2 nm diameter) exhibit discrete electronic structures due to quantum size effect, as opposed to quasicontinuous band structure of conventional metal nanoparticles or bulk metals. The available atomic structures (metal core plus surface ligands) of nanoclusters serve as the basis for structure-property correlations. We have investigated the unique catalytic properties of nanoclusters (i.e. not observed in conventional nanogold catalysts) and revealed the structure-selectivity relationships. Highlights of our works include: i) Effects of ligand, cluster charge state, and size on the catalytic reactivity in CO oxidation, semihydrogenation of alkynes; ii) Size-controlled synthesis of Au-n clusters and structural elucidation; iii) Catalytic mechanisms and correlation with structures of cluster catalyst; iv) Catalytic properties of Au nanorods in chemoselective hydrogenation of nitrobenzaldehyde and visible light driven photocatalytic reactions.« less

Density functional investigation of mercury and arsenic adsorption on nitrogen doped graphene decorated with palladium clusters: A promising heavy metal sensing material in farmland

NASA Astrophysics Data System (ADS)

Zhao, Chunjiang; Wu, Huarui

2017-03-01

Density functional theory calculations are carried out to study the adsorption of mercury and arsenic on Pdn (n = 1-6) supported on pyridine-like nitrogen doped graphene (PNG). Owing to the promising sensitivity in trace amounts of atoms or molecules, PNG can be acted as micro-sensor for sensing heavy metals in agriculture soils. Through the analyses of structural and electronic properties of pristine PNG and Pd atom decorated PNG, we find that the most favorable adsorption site for Pd atom is the vacancy site. The analyses of structural and electronic properties reveal that the Pd atom or clusters can enhance the reactivity for Hg and AsH3 adsorption on PNG. The adsorption ability of Hg on Pdn decorated PNG is found to be related to the d-band center (εd) of the Pdn, in which the closer εd of Pdn to the Fermi level, the higher adsorption strength for Hg on Pdn decorated PNG. Moreover, the charge transfer between Pdn and arsenic may constitute arsenic adsorption on Pdn decorated PNG. Further design of highly efficient carbon based sorbents for heavy metals removal should be focused on tailoring εd of adsorbed metals.

Structure of fluorescent metal clusters on a DNA template.

NASA Astrophysics Data System (ADS)

Vdovichev, A. A.; Sych, T. S.; Reveguk, Z. V.; Smirnova, A. A.; Maksimov, D. A.; Ramazanov, R. R.; Kononov, A. I.

2016-08-01

Luminescent metal clusters are a subject of growing interest in recent years due to their bright emission from visible to near infrared range. Detailed structure of the fluorescent complexes of Ag and other metal clusters with ligands still remains a challenging task. In this joint experimental and theoretical study we synthesized Ag-DNA complexes on a DNA oligonucleotide emitting in violet- green spectral range. The structure of DNA template was determined by means of various spectral measurements (CD, MS, XPS). Comparison of the experimental fluorescent excitation spectra and calculated absorption spectra for different QM/MM optimized structures allowed us to determine the detailed structure of the green cluster containing three silver atoms in the stem of the DNA hairpin structure stabilized by cytosine-Ag+-cytosine bonds.

Dynamics of metal-induced crystallization of ultrathin Ge films by rapid thermal annealing

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Yuanxun; Huang, Shujuan; Shrestha, Santosh

2015-12-07

Though Ge crystallization has been widely studied, few works investigate metal-induced crystallization of ultrathin Ge films. For 2 nm Ge films in oxide matrix, crystallization becomes challenging due to easy oxidation and low mobility of Ge atoms. Introducing metal atoms may alleviate these problems, but the functions and the behaviours of metal atoms need to be clarified. This paper investigates the crystallization dynamics of a multilayer structure 1.9 nm Ge/0.5 nm Al/1.5 nm Al{sub 2}O{sub 3} under rapid thermal annealing (RTA). The functions of metal atoms, like effective anti-oxidation, downshifting Raman peaks, and incapability to decrease crystallization temperature, are found and explained. The metalmore » behaviours, such as inter-diffusion and defect generation, are supported with direct evidences, Al-Ge nanobicrystals, and Al cluster in Ge atoms. With these understandings, a two-step RTA process achieves high-quality 2 nm nanocrystal Ge films with Raman peak at 298 cm{sup −1} of FWHM 10.3 cm{sup −1} and atomic smooth interfaces.« less

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

PubMed

Manzoor, Dar; Pal, Sourav

2015-06-18

Metal clusters of silver have attracted recent interest of researchers as a result of their potential in different catalytic applications and low cost. However, due to the completely filled d orbital and very high first ionization potential of the silver atom, the silver-based catalysts interact very weakly with the reacting molecules. In the current work, density functional theory calculations were carried out to investigate the effect of hydrogen atom chemisorption on the reactivity and catalytic properties of inert silver clusters. Our results affirm that the hydrogen atom chemisorption leads to enhancement in the binding energy of the adsorbed O2 molecule on the inert silver clusters. The increase in the binding energy is also characterized by the decrease in the Ag-O and increase in the O-O bond lengths in the case of the AgnH silver clusters. Pertinent to the increase in the O-O bond length, a significant red shift in the O-O stretching frequency is also noted in the case of the AgnH silver clusters. Moreover, the hydrogen atom chemisorbed silver clusters show low reaction barriers and high heat of formation of the final products for the environmentally important CO oxidation reaction as compared to the parent catalytically inactive clusters. The obtained results were compared with those of the corresponding gold and hydrogen atom chemisorbed gold clusters obtained at the same level of theory. It is expected the current computational study will provide key insights for future advances in the design of efficient nanosilver-based catalysts through the adsorption of a small atom or a ligand.

Catalytic dehydrogenation of alcohol over solid-state molybdenum sulfide clusters with an octahedral metal framework

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kamiguchi, Satoshi, E-mail: kamigu@riken.jp; Organometallic Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako City, Saitama 351-0198; Okumura, Kazu

Graphical abstract: - Highlights: • Solid-state molybdenum sulfide clusters catalyzed the dehydrogenation of alcohol. • The dehydrogenation proceeded without the addition of any oxidants. • The catalytic activity developed when the cluster was activated at 300–500 °C in H{sub 2}. • The Lewis-acidic molybdenum atom and basic sulfur ligand were catalytically active. • The clusters function as bifunctional acid–base catalysts. - Abstract: Solid-state molybdenum sulfide clusters with an octahedral metal framework, the superconducting Chevrel phases, are applied to catalysis. A copper salt of a nonstoichiometric sulfur-deficient cluster, Cu{sub x}Mo{sub 6}S{sub 8–δ} (x = 2.94 and δ ≈ 0.3), is storedmore » in air for more than 90 days. When the oxygenated cluster is thermally activated in a hydrogen stream above 300 °C, catalytic activity for the dehydrogenation of primary alcohols to aldehydes and secondary alcohols to ketones develops. The addition of pyridine or benzoic acid decreases the dehydrogenation activity, indicating that both a Lewis-acidic coordinatively unsaturated molybdenum atom and a basic sulfur ligand synergistically act as the catalytic active sites.« less

A comparative study for Hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lu, Jinlian; Guo, Yanhua; Zhang, Yun

A comparative study for hydrogen storage in metal decorated graphyne nanotubes and graphyne monolayers has been investigated within the framework of first-principle calculations. Our results show that the binding energies of Li, Ca, Sc, Ti on graphyne nanotubes are stronger than that on graphyne monolayers. Such strong binding would prevent the formation of metal clusters on graphyne nanotubes. From the charge transfer and partial density of states, it is found that the curvature effect of nanotubes plays an important role for the strong binding strength of metal on graphyne nanotubes. And the hydrogen storage capacity is 4.82 wt%, 5.08 wt%,more » 4.88 wt%, 4.76 wt% for Li, Ca, Sc, Ti decorated graphyne nanotubes that promise a potential material for storing hydrogen. - Graphical abstract: Metal atoms (Li, Ca, Sc and Ti) can strongly bind to graphyne nanotubes to avoid the formation of metal clusters, and a capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015. Twenty-four hydrogen molecules absorb to Ti-decorated graphyne nanotube. - Highlights: • The binding strength for metal on graphyne nanotubes is much stronger than that on γ-graphyne monolayer. • Metal atoms can strongly bind to the curving triangle acetylenes rings to avoid the formation of metal clusters. • A capacity of Ca@graphyne nanotube is 5.08 wt% which is close to the requirement of DOE in 2015.« less

Metastability and structural polymorphism in noble metals: the role of composition and metal atom coordination in mono- and bimetallic nanoclusters.

PubMed

Sanchez, Sergio I; Small, Matthew W; Bozin, Emil S; Wen, Jian-Guo; Zuo, Jian-Min; Nuzzo, Ralph G

2013-02-26

This study examines structural variations found in the atomic ordering of different transition metal nanoparticles synthesized via a common, kinetically controlled protocol: reduction of an aqueous solution of metal precursor salt(s) with NaBH₄ at 273 K in the presence of a capping polymer ligand. These noble metal nanoparticles were characterized at the atomic scale using spherical aberration-corrected scanning transmission electron microscopy (C(s)-STEM). It was found for monometallic samples that the third row, face-centered-cubic (fcc), transition metal [(3M)-Ir, Pt, and Au] particles exhibited more coherently ordered geometries than their second row, fcc, transition metal [(2M)-Rh, Pd, and Ag] analogues. The former exhibit growth habits favoring crystalline phases with specific facet structures while the latter samples are dominated by more disordered atomic arrangements that include complex systems of facets and twinning. Atomic pair distribution function (PDF) measurements further confirmed these observations, establishing that the 3M clusters exhibit longer ranged ordering than their 2M counterparts. The assembly of intracolumn bimetallic nanoparticles (Au-Ag, Pt-Pd, and Ir-Rh) using the same experimental conditions showed a strong tendency for the 3M atoms to template long-ranged, crystalline growth of 2M metal atoms extending up to over 8 nm beyond the 3M core.

Keeping the ball rolling: fullerene-like molecular clusters.

PubMed

Kong, Xiang-Jian; Long, La-Sheng; Zheng, Zhiping; Huang, Rong-Bin; Zheng, Lan-Sun

2010-02-16

The discovery of fullerenes in 1985 opened a new chapter in the chemistry of highly symmetric molecules. Fullerene-like metal clusters, characterized by (multi)shell-like structures, are one rapidly developing class of molecules that share this shape. In addition to creating aesthetically pleasing molecular structures, the ordered arrangement of metal atoms within such frameworks provides the opportunity to develop materials with properties not readily achieved in corresponding mononuclear or lower-nuclearity complexes. In this Account, we survey the great variety of fullerene-like metal-containing clusters with an emphasis on their synthetic and structural chemistry, a first step in the discussion of this fascinating field of cluster chemistry. We group the compounds of interest into three categories based on the atomic composition of the cluster core: those with formal metal-metal bonding, those characterized by ligand participation, and those supported by polyoxometalate building blocks. The number of clusters in the first group, containing metal-metal bonds, is relatively small. However, because of the unique and complex bonding scenarios observed for some of these species, these metalloid clusters present a number of research questions with significant ramifications. Because these cores contain molecular clusters of precious metals at the nanoscale, they offer an opportunity to study chemical properties at size ranges from the molecular to nanoscale and to gain insights into the electronic structures and properties of nanomaterials of similar chemical compositions. Clusters of the second type, whose core structures are facilitated by ligand participation, could aid in the development of functional materials. Of particular interest are the magnetic clusters containing both transition and lanthanide elements. A series of such heterometallic clusters that we prepared demonstrates diverse magnetic properties including antiferromagnetism, ferrimagnetism, and ferromagnetism. Considering the diversity of their composition, their distinct electronic structures, and the disparate coordination behaviors of the different metal elements, these materials suggest abundant opportunities for designing multifunctional materials with varied structures. The third type of clusters that we discuss are based on polyoxometalates, in particular those containing pentagonal units. However, unlike in fullerene chemistry, which does not allow the use of discrete pentagonal building blocks, the metal oxide-based pentagonal units can be used as fundamental building blocks for constructing various Keplerate structures. These structures also have a variety of functions, including intriguing magnetic properties in some cases. Coupled with different linking groups, such pentagonal units can be used for the assembly of a large number of spherical molecules whose properties can be tuned and optimized. Although this Account focuses on the topological aspects of fullerene-like metal clusters, we hope that this topical review will stimulate more efforts in the exploratory synthesis of new fullerene-like clusters. More importantly, we hope that further study of the bonding interactions and properties of these molecules will lead to the development of new functional materials.

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100-x Al x Metallic Glasses

NASA Astrophysics Data System (ADS)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-03-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated <0, 0, 12, 0> and 13-coordinated <0, 1, 10, 2>) and by playing a main role in the structure stability of the Ti-Al MGs.

Atomic Scale Investigation of Structural Properties and Glass Forming Ability of Ti100- x Al x Metallic Glasses

NASA Astrophysics Data System (ADS)

Tahiri, M.; Hasnaoui, A.; Sbiaai, K.

2018-06-01

In this work, we employed molecular dynamics (MD) simulations to study Ti-Al metallic glasses (MGs) using the embedded atom method (EAM) potential to model the atomic interaction with different compositions. The results showed evidence of the metallic glass formation induced by the split occurring in the second peak of the radial distribution function (RDF) curves implying both Ti and Al atoms. The common neighbor analysis (CNA) method confirmed the presence of the icosahedral clusters with a maximum amount observed for an alloy with 75 pct of Al. Analysis of coordination numbers (CNs) indicated that the total CNs are nearly unchanged in these systems. Finally, Voronoi tessellation analyses (VTA) showed a higher value of the number of icosahedral units at Ti25Al75 composition. This specific composition represents a nearby peritectic point localized at a low melting point in the Ti-Al binary phase diagram. The glass forming ability (GFA) becomes important when the fraction of Al increases by forming and connecting "icosahedral-like" clusters (12-coordinated <0, 0, 12, 0> and 13-coordinated <0, 1, 10, 2>) and by playing a main role in the structure stability of the Ti-Al MGs.

Atomic and electronic structure of Pd40Ni40P20 bulk metallic glass from ab initio simulations

NASA Astrophysics Data System (ADS)

Kumar, Vijay; Fujita, T.; Konno, K.; Matsuura, M.; Chen, M. W.; Inoue, A.; Kawazoe, Y.

2011-10-01

The atomic structure of Pd40Ni40P20 bulk metallic glass has been simulated using an ab initio molecular dynamics method with projector-augmented wave pseudopotentials for electron-ion interaction and generalized gradient approximation for exchange-correlation energy. The calculated extended x-ray absorption fine structure (EXAFS) spectra of Pd-K and Ni-K edges, the mass density, and the electronic structure agree remarkably well with the available experimental data and the EXAFS spectra measured at the SPring-8 synchrotron radiation facility. Our results show that the atomic structure can be described in terms of P-centered polyhedra. There are no two P atoms that are nearest neighbors at this composition, and this could be a reason for the observed optimal P concentration of about 20 at.%. The neighboring polyhedra share metal (M) atoms and form a polar covalently bonded random network of P-M-P favoring certain angles. The remaining M atoms act as metallic glue with a tendency of nanoscale clustering of Pd-Pd and Ni-Ni atoms.

How can we make stable linear monoatomic chains? Gold-cesium binary subnanowires as an example of a charge-transfer-driven approach to alloying.

PubMed

Choi, Young Cheol; Lee, Han Myoung; Kim, Woo Youn; Kwon, S K; Nautiyal, Tashi; Cheng, Da-Yong; Vishwanathan, K; Kim, Kwang S

2007-02-16

On the basis of first-principles calculations of clusters and one dimensional infinitely long subnanowires of the binary systems, we find that alkali-noble metal alloy wires show better linearity and stability than either pure alkali metal or noble metal wires. The enhanced alternating charge buildup on atoms by charge transfer helps the atoms line up straight. The cesium doped gold wires showing significant charge transfer from cesium to gold can be stabilized as linear or circular monoatomic chains.

On the question of fractal packing structure in metallic glasses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Jun; Asta, Mark; Ritchie, Robert O.

2017-07-25

This work addresses the long-standing debate over fractal models of packing structure in metallic glasses (MGs). Through detailed fractal and percolation analyses of MG structures, derived from simulations spanning a range of compositions and quenching rates, we conclude that there is no fractal atomic-level structure associated with the packing of all atoms or solute-centered clusters. The results are in contradiction with conclusions derived from previous studies based on analyses of shifts in radial distribution function and structure factor peaks associated with volume changes induced by pressure and compositional variations. Here in this paper, the interpretation of such shifts is shownmore » to be challenged by the heterogeneous nature of MG structure and deformation at the atomic scale. Moreover, our analysis in the present work illustrates clearly the percolation theory applied to MGs, for example, the percolation threshold and characteristics of percolation clusters formed by subsets of atoms, which can have important consequences for structure–property relationships in these amorphous materials.« less

Significant Transient Mobility of Platinum Clusters via a Hot Precursor State on the Alumina Surface.

PubMed

Beniya, Atsushi; Hirata, Hirohito; Watanabe, Yoshihide

2016-11-17

Relaxation dynamics of hot metal clusters on oxide surfaces play a crucial role in a variety of physical and chemical processes. However, their transient mobility has not been investigated as much as other systems such as atoms and molecules on metal surfaces due to experimental difficulties. To study the role of the transient mobility of clusters on the oxide surface, we investigated the initial adsorption process of size-selected Pt clusters on a thin Al 2 O 3 film. Soft-landing the size-selected clusters while suppressing the thermal migration resulted in the transient migration controlling the initial adsorption states as an isolated and aggregated cluster, as revealed using scanning tunneling microscopy. We demonstrate that transient migration significantly contributes to the initial cluster adsorption process; the cross section for aggregation is seven times larger than the expected value from geometrical considerations, indicating that metal clusters are highly mobile during a energy dissipation process on the oxide surface.

Kinetic Monte Carlo Simulation of the Growth of Various Nanostructures through Atomic and Cluster Deposition: Application to Gold Nanostructure Growth on Graphite

NASA Astrophysics Data System (ADS)

Claassens, C. H.; Hoffman, M. J. H.; Terblans, J. J.; Swart, H. C.

2006-01-01

A Kinetic Monte Carlo (KMC) method is presented to describe the growth of metallic nanostructures through atomic and cluster deposition in the mono -and multilayer regime. The model makes provision for homo- and heteroepitaxial systems with small lattice mismatch. The accuracy of the model is tested with simulations of the growth of gold nanostructures on HOPG and comparisons are made with existing experimental data.

Aluminum Cluster-Based Materials for Propulsion and Other Applications

DTIC Science & Technology

2012-04-04

CuMg8- and AuMg8- . It was shown that aromaticity, traditionally used to understand stability of organic systems , can also stabilize metallic...of arsenic and K atoms. Extensions of these to other systems is currently under study. Since 2009, 12 group publications (GP) have resulted with...CuAl22- using DFT. 9 B. Stable Aromatic Aluminum-Based Metal Clusters: Aromaticity has historically been applied to organic systems that are

Correlation study of sodium-atom chemisorption on the GaAs(110) surface

NASA Astrophysics Data System (ADS)

Song, K. M.; Khan, D. C.; Ray, A. K.

1994-01-01

Different possible adsorption sites of sodium atoms on a gallium arsenide surface have been investigated using ab initio self-consistent unrestricted Hartree-Fock total-energy cluster calculations with Hay-Wadt effective core potentials. The effects of electron correlation have been included by invoking the concepts of many-body perturbation theory and are found to be highly significant. We find that the Na-atom adsorption at a site modeled with an NaGa5As4H12 cluster is most favored energetically followed by Na adsorption at the site modeled with the NaGa4As5H12 cluster. The effects of charge transfer from Na to the GaAs surface as also possibilities of metallization are also analyzed and discussed.

Ion mobility studies of PdC{sub n}{sup +} clusters: Where are the fullerenes?

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shelimov, K.B.; Jarrold, M.F.

1995-12-14

Gas-phase ion mobility measurements have been used to study the structures and isomerization of PdC{sub n}{sup +} (n = 10-60) clusters. Non-fullerene isomers of PdC{sub n}{sup +} clusters are similar to those of C{sub n}{sup +} and MC{sub n}{sup +} (M = La and Nb) clusters, and include metal-containing mono- and bicyclic rings and graphite sheets. Neither endohedral nor nonendohedral PdC{sub n} {sup +} fullerene isomers are detected. When collisionally heated, PdC{sub n}{sup +} clusters efficiently convert into fullerenes, but the exothermicity of this process results in the loss of the Pd atom and the formation of a pure carbonmore » cluster cation. PdC{sub n}{sup +} bicyclic rings with an odd number of carbon atoms efficiently isomerize into monocyclic rings, while no evidence is found for this isomerization process for bicyclic rings with an even number of carbon atoms. 18 refs., 4 figs.« less

Structural, energetic, and electronic trends in low-dimensional late-transition-metal systems

NASA Astrophysics Data System (ADS)

Hu, C. H.; Chizallet, C.; Toulhoat, H.; Raybaud, P.

2009-05-01

Using first-principles calculations, we present a comprehensive investigation of the structural trends of low dimensionality late 4d (from Tc to Ag) and 5d (from Re to Au) transition-metal systems including 13-atom clusters. Energetically favorable clusters not being reported previously are discovered by molecular-dynamics simulation based on the simulated annealing method. They allow a better agreement between experiments and theory for their magnetic properties. The structural periodic trend exhibits a nonmonotonic variation of the ratio of square to triangular facets for the two rows, with a maximum for Rh13 and Ir13 . By a comparative analysis of the relevant energetic and electronic properties performed on other metallic systems with reduced dimensionalities such as four-atom planar clusters, one-dimensional (1D) scales, double scales, 1D cylinders, monatomic films, two and seven layer slabs, we highlight that this periodic trend can be generalized. Hence, it appears that 1D-metallic nanocylinders or 1D-double nanoscales (with similar binding energies as TM13 ) also favor square facets for Rh and Ir. We finally propose an interpretation based on the evolution of the width of the valence band and of the Coulombic repulsions of the bonding basins.

Bridging Zirconia Nodes within a Metal-Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires.

PubMed

Platero-Prats, Ana E; League, Aaron B; Bernales, Varinia; Ye, Jingyun; Gallington, Leighanne C; Vjunov, Aleksei; Schweitzer, Neil M; Li, Zhanyong; Zheng, Jian; Mehdi, B Layla; Stevens, Andrew J; Dohnalkova, Alice; Balasubramanian, Mahalingam; Farha, Omar K; Hupp, Joseph T; Browning, Nigel D; Fulton, John L; Camaioni, Donald M; Lercher, Johannes A; Truhlar, Donald G; Gagliardi, Laura; Cramer, Christopher J; Chapman, Karena W

2017-08-02

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis, and difference envelope density analysis, with electron microscopy imaging and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO x H y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield heterobimetallic metal-oxo nanowires. This bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering resistance of these clusters during the hydrogenation of light olefins.

Controlled Expansion of a Strong-Field Iron Nitride Cluster: Multi-Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity.

PubMed

Drance, Myles J; Mokhtarzadeh, Charles C; Melaimi, Mohand; Agnew, Douglas W; Moore, Curtis E; Rheingold, Arnold L; Figueroa, Joshua S

2018-05-02

Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ 4 -nitrido cluster [Fe 4 (μ 4 -N)(CO) 12 ] - , this analogy is limited owing to the electron-withdrawing effect of carbonyl ligands on the iron nitride core. Described here is the synthesis and reactivity of [Fe 4 (μ 4 -N)(CO) 8 (CNAr Mes2 ) 4 ] - , an electron-rich analogue of [Fe 4 (μ 4 -N)(CO) 12 ] - , where the interstitial nitride displays significant nucleophilicity. This characteristic enables rational expansion with main-group and transition-metal centers to yield unsaturated sites. The resulting clusters display surface-like reactivity through coordination-sphere-dependent atom rearrangement and metal-metal cooperativity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ab initio molecular dynamics simulations of short-range order in Zr 50Cu 45Al 5 and Cu 50Zr 45Al 5 metallic glasses

DOE PAGES

Huang, Yuxiang; Huang, Li; Wang, C. Z.; ...

2016-02-01

Comparative analysis between Zr-rich Zr 50Cu 45Al 5 and Cu-rich Cu 50Zr 45Al 5 metallic glasses (MGs) is extensively performed to locate the key structural motifs accounting for their difference of glass forming ability. Here we adopt ab initio molecular dynamics simulations to investigate the local atomic structures of Zr 50Cu 45Al 5 and Cu 50Zr 45Al 5 MGs. A high content of icosahedral-related (full and distorted) orders was found in both samples, while in the Zr-rich MG full icosahedrons < 0,0,12,0 > is dominant, and in the Cu-rich one the distorted icosahedral orders, especially < 0,2,8,2 > and , are prominent. And the < 0,2,8,2 > polyhedra in Cu 50Zr 45Al 5 MG mainly originate from Al-centered clusters, while the < 0,0,12,0 > in Zr 50Cu 45Al 5 derives from both Cu-centered clusters and Al-centered clusters. These difference may be ascribed to the atomic size difference and chemical property between Cu and Zr atoms. Lastly, the relatively large size of Zr and large negative heat of mixing between Zr and Al atoms, enhancing the packing density and stability of metallic glass system, may be responsible for the higher glass forming ability of Zr 50Cu 45Al 5.« less

Ab initio molecular dynamics simulations of short-range order in Zr50Cu45Al5 and Cu50Zr45Al5 metallic glasses

NASA Astrophysics Data System (ADS)

Huang, Yuxiang; Huang, Li; Wang, C. Z.; Kramer, M. J.; Ho, K. M.

2016-03-01

Comparative analysis between Zr-rich Zr50Cu45Al5 and Cu-rich Cu50Zr45Al5 metallic glasses (MGs) is extensively performed to locate the key structural motifs accounting for their difference of glass forming ability. Here we adopt ab initio molecular dynamics simulations to investigate the local atomic structures of Zr50Cu45Al5 and Cu50Zr45Al5 MGs. A high content of icosahedral-related (full and distorted) orders was found in both samples, while in the Zr-rich MG full icosahedrons < 0,0,12,0> is dominant, and in the Cu-rich one the distorted icosahedral orders, especially < 0,2,8,2> and < 0,2,8,1> , are prominent. And the < 0,2,8,2> polyhedra in Cu50Zr45Al5 MG mainly originate from Al-centered clusters, while the < 0,0,12,0> in Zr50Cu45Al5 derives from both Cu-centered clusters and Al-centered clusters. These difference may be ascribed to the atomic size difference and chemical property between Cu and Zr atoms. The relatively large size of Zr and large negative heat of mixing between Zr and Al atoms, enhancing the packing density and stability of metallic glass system, may be responsible for the higher glass forming ability of Zr50Cu45Al5.

Atomic-scale dynamics of a model glass-forming metallic liquid: Dynamical crossover, dynamical decoupling, and dynamical clustering

DOE PAGES

Jaiswal, Abhishek; Egami, Takeshi; Zhang, Yang

2015-04-01

The phase behavior of multi-component metallic liquids is exceedingly complex because of the convoluted many-body and many-elemental interactions. Herein, we present systematic studies of the dynamic aspects of such a model ternary metallic liquid Cu 40Zr 51Al 9 using molecular dynamics simulation with embedded atom method. We observed a dynamical crossover from Arrhenius to super-Arrhenius behavior in the transport properties (diffusion coefficient, relaxation times, and shear viscosity) bordered at T x ~1300K. Unlike in many molecular and macromolecular liquids, this crossover phenomenon occurs in the equilibrium liquid state well above the melting temperature of the system (T m ~ 900K),more » and the crossover temperature is roughly twice of the glass-transition temperature (T g). Below T x, we found the elemental dynamics decoupled and the Stokes-Einstein relation broke down, indicating the onset of heterogeneous spatially correlated dynamics in the system mediated by dynamic communications among local configurational excitations. To directly characterize and visualize the correlated dynamics, we employed a non-parametric, unsupervised machine learning technique and identified dynamical clusters of atoms with similar atomic mobility. The revealed average dynamical cluster size shows an accelerated increase below T x and mimics the trend observed in other ensemble averaged quantities that are commonly used to quantify the spatially heterogeneous dynamics such as the non-Gaussian parameter and the four-point correlation function.« less

Calcium-decorated carbyne networks as hydrogen storage media.

PubMed

Sorokin, Pavel B; Lee, Hoonkyung; Antipina, Lyubov Yu; Singh, Abhishek K; Yakobson, Boris I

2011-07-13

Among the carbon allotropes, carbyne chains appear outstandingly accessible for sorption and very light. Hydrogen adsorption on calcium-decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H(2) molecules per Ca atom with a binding energy of ∼0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed ∼8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H(2) molecules on the Ca atom was also investigated using equilibrium grand partition function.

A DFT investigation on geometry and chemical bonding of isoelectronic Si8N6V-, Si8N6Cr, and Si8N6Mn+ clusters

NASA Astrophysics Data System (ADS)

Tam, Nguyen Minh; Pham, Hung Tan; Cuong, Ngo Tuan; Tung, Nguyen Thanh

2017-10-01

The geometric feature and chemical bonding of isoelectronic systems Si8N6Mq (M = V, Cr, Mn and q = -1, 0, 1, respectively) are investigated by means of density-functional-theory calculations. The encapsulated form is found for all ground-state structures, where the metal atom locates at the central site of the hollow Si8N6 cage. The Si8N6 cage is established by adding two Si atoms to a distorted Si6N6 prism, which is a combination of Si4N2 and Si2N4 strings. Chemical bonding of Si8N6Mq systems is explored by using the electron localization indicator and theory of atom in molecule, revealing the vital role of metal center in stabilizing the clusters.

Metallic-covalent bonding conversion and thermoelectric properties of Al-based icosahedral quasicrystals and approximants.

PubMed

Takagiwa, Yoshiki; Kimura, Kaoru

2014-08-01

In this article, we review the characteristic features of icosahedral cluster solids, metallic-covalent bonding conversion (MCBC), and the thermoelectric properties of Al-based icosahedral quasicrystals and approximants. MCBC is clearly distinguishable from and closely related to the well-known metal-insulator transition. This unique bonding conversion has been experimentally verified in 1/1-AlReSi and 1/0-Al 12 Re approximants by the maximum entropy method and Rietveld refinement for powder x-ray diffraction data, and is caused by a central atom inside the icosahedral clusters. This helps to understand pseudogap formation in the vicinity of the Fermi energy and establish a guiding principle for tuning the thermoelectric properties. From the electron density distribution analysis, rigid heavy clusters weakly bonded with glue atoms are observed in the 1/1-AlReSi approximant crystal, whose physical properties are close to icosahedral Al-Pd-TM (TM: Re, Mn) quasicrystals. They are considered to be an intermediate state among the three typical solids: metals, covalently bonded networks (semiconductor), and molecular solids. Using the above picture and detailed effective mass analysis, we propose a guiding principle of weakly bonded rigid heavy clusters to increase the thermoelectric figure of merit ( ZT ) by optimizing the bond strengths of intra- and inter-icosahedral clusters. Through element substitutions that mainly weaken the inter-cluster bonds, a dramatic increase of ZT from less than 0.01 to 0.26 was achieved. To further increase ZT , materials should form a real gap to obtain a higher Seebeck coefficient.

Metastable States Arising from the Ablation of Solid Copper

NASA Astrophysics Data System (ADS)

Andrejeva, Anna; Harris, Joe; Wright, Tim

2014-06-01

Laser ablation is a popular method for generating metal atoms so that metal clusters, complexes, and molecules may be investigated in gas phase spectroscopic studies. However, the initial production of a highly energetic metal plasma from the surface of a solid metal target can produce atoms which are not in their ground electronic state, and consequently atomic spectra can become quite complicated due to transitions arising from metastable atomic excited states which remain populated on the experimental timescale. Presented herein are details of the laser vaporisation source in use by our group. Spectra of atomic copper are presented, recorded via (1+1') and (2+1) resonance enhanced multiphoton ionisation (REMPI) spectroscopy. The energetic regions examined are expected to correspond to the (4s24p) 2P ← 2S and the (4s2nd) 2D ← 2S Rydberg series respectively, but the observed spectra also exhibit many additional contributions which are found to arise from electronically excited states, and these will be discussed.

Force Field Development and Molecular Dynamics of [NiFe] Hydrogenase

DOE Office of Scientific and Technical Information (OSTI.GOV)

Smith, Dayle MA; Xiong, Yijia; Straatsma, TP

2012-05-09

Classical molecular force-field parameters describing the structure and motion of metal clusters in [NiFe] hydrogenase enzymes can be used to compare the dynamics and thermodynamics of [NiFe] under different oxidation, protonation, and ligation circumstances. Using density functional theory (DFT) calculations of small model clusters representative of the active site and the proximal, medial, and distal Fe/S metal centers and their attached protein side chains, we have calculated classical force-field parameters for [NiFe] in reduced and oxidized states, including internal coordinates, force constants, and atom-centered charges. Derived force constants revealed that cysteinate ligands bound to the metal ions are more flexiblemore » in the Ni-B active site, which has a bridging hydroxide ligand, than in the Ni-C active site, which has a bridging hydride. Ten nanosecond all-atom, explicit-solvent MD simulations of [NiFe] hydrogenase in oxidized and reduced catalytic states established the stability of the derived force-field parameters in terms of C{alpha} and metal cluster fluctuations. Average active site structures from the protein MD simulations are consistent with [NiFe] structures from the Protein Data Bank, suggesting that the derived force-field parameters are transferrable to other hydrogenases beyond the structure used for testing. A comparison of experimental H{sub 2}-production rates demonstrated a relationship between cysteinate side chain rotation and activity, justifying the use of a fully dynamic model of [NiFe] metal cluster motion.« less

Fullerene-like boron clusters stabilized by an endohedrally doped iron atom: B(n)Fe with n = 14, 16, 18 and 20.

PubMed

Tam, Nguyen Minh; Pham, Hung Tan; Duong, Long Van; Pham-Ho, My Phuong; Nguyen, Minh Tho

2015-02-07

Stabilized fullerene and tubular forms can be produced in boron clusters Bn in small sizes from n∼ 14 to 20 upon doping by transition metal atoms. B14Fe and B16Fe are stable tubes whereas B18Fe and B20Fe are stable fullerenes. Their formation and stability suggest the use of dopants to induce different growth paths leading to larger cages, fullerenes and tubes of boron.

Porphyrins as Templates for Site-Selective Atomic Layer Deposition: Vapor Metalation and in Situ Monitoring of Island Growth

DOE Office of Scientific and Technical Information (OSTI.GOV)

Avila, Jason R.; Emery, Jonathan D.; Pellin, Michael J.

Examinations of enzymatic catalysts suggest one key to efficient catalytic activity is discrete size metallo clusters. Mimicking enzymatic cluster systems is synthetically challenging because conventional solution methods are prone to aggregation or require capping of the cluster, thereby limiting its catalytic activity. We introduce site-selective atomic layer deposition (ALD) on porphyrins as an alternative approach to grow isolated metal oxide islands that are spatially separated. Surface-bound tetra-acid free base porphyrins (H2TCPP) may be metalated with Mn using conventional ALD precursor exposure to induce homogeneous hydroxide synthetic handles which acts as a nucleation point for subsequent ALD MnO island growth. Analyticalmore » fitting of in situ QCM mass uptake reveals island growth to be hemispherical with a convergence radius of 1.74 nm. This growth mode is confirmed with synchrotron grazing-incidence small-angle X-ray scattering (GISAXS) measurements. Finally, we extend this approach to other ALD chemistries to demonstrate the generality of this route to discrete metallo island materials.« less

Probing Metal Cluster and Metal Oxide Cluster Interactions with Organo-Sulfur and Organo-Phosphorous Molecules using Mass Spectrometry and Anion PES

DTIC Science & Technology

2002-10-30

atomic anions and methanol: Anion photoelectron spectroscopy and density functional theory calculations on HNiCO-, PdCO - and PtCO-,” Bappaditya...HNiC2H, Ni(C2H)2, PdCO , PdCN, PdC2H, PtCO, PtCN, PtC2H), they are not included in this report, but can be found in the papers cited above. PE

(Tl, Au)/Si(1 1 1){\\sqrt7 \\times \\sqrt7} 2D compound: an ordered array of identical Au clusters embedded in Tl matrix

NASA Astrophysics Data System (ADS)

Mihalyuk, A. N.; Hsing, C. R.; Wei, C. M.; Eremeev, S. V.; Bondarenko, L. V.; Tupchaya, A. Y.; Gruznev, D. V.; Zotov, A. V.; Saranin, A. A.

2018-01-01

Formation of the highly-ordered \\sqrt7 × \\sqrt7 -periodicity 2D compound has been detected in the (Tl, Au)/Si(1 1 1) system as a result of Au deposition onto the Tl/Si(1 1 1) surface, its composition, structure and electronic properties have been characterized using scanning tunneling microscopy, angle-resolved photoelectron spectroscopy and density-functional-theory calculations. On the basis of these data, the structural model of the Tl-Au compound has been proposed, which adopts 12 Tl atoms and 10 Au atoms (in total, 22 atoms) per \\sqrt7 × \\sqrt7 unit cell, i.e.  ˜1.71 ML of Tl and  ˜1.43 ML of Au (in total, ˜3.14 ML). Qualitatively, the model can be visualized as consisting of truncated-pyramid-like Au clusters with a Tl atom on top, while the other Tl atoms form a double layer around the Au clusters. The (Tl, Au)/Si(1 1 1)\\sqrt7 × \\sqrt7 compound has been found to exhibit pronounced metallic properties at least down to temperatures as low as  ˜25 K, which makes it a promising object for studying electrical transport phenomena in the 2D metallic systems.

Structure determination in 55-atom Li-Na and Na-K nanoalloys.

PubMed

Aguado, Andrés; López, José M

2010-09-07

The structure of 55-atom Li-Na and Na-K nanoalloys is determined through combined empirical potential (EP) and density functional theory (DFT) calculations. The potential energy surface generated by the EP model is extensively sampled by using the basin hopping technique, and a wide diversity of structural motifs is reoptimized at the DFT level. A composition comparison technique is applied at the DFT level in order to make a final refinement of the global minimum structures. For dilute concentrations of one of the alkali atoms, the structure of the pure metal cluster, namely, a perfect Mackay icosahedron, remains stable, with the minority component atoms entering the host cluster as substitutional impurities. At intermediate concentrations, the nanoalloys adopt instead a core-shell polyicosahedral (p-Ih) packing, where the element with smaller atomic size and larger cohesive energy segregates to the cluster core. The p-Ih structures show a marked prolate deformation, in agreement with the predictions of jelliumlike models. The electronic preference for a prolate cluster shape, which is frustrated in the 55-atom pure clusters due to the icosahedral geometrical shell closing, is therefore realized only in the 55-atom nanoalloys. An analysis of the electronic densities of states suggests that photoelectron spectroscopy would be a sufficiently sensitive technique to assess the structures of nanoalloys with fixed size and varying compositions.

Atomic structure and glass forming ability of Cu46Zr46Al8 bulk metallic glass

NASA Astrophysics Data System (ADS)

Wang, X. D.; Jiang, Q. K.; Cao, Q. P.; Bednarcik, J.; Franz, H.; Jiang, J. Z.

2008-11-01

By using a combination of state-of-the-art experimental and computational methods, the high glass forming ability (GFA) of Cu46Zr46Al8 alloy is studied from the view of its atomic packing. Three-dimensional atomic configuration is well established. It is found that Al atoms almost homogeneously distribute around Cu and Zr atoms without segregation, causing the local environment around Cu and Zr atoms in Cu46Zr46Al8 bulk metallic glass different from that of the major competing phase of Cu10Zr7. Furthermore, the addition of Al not only increases the amount of icosahedronlike clusters but also makes them more homogeneous distribution, which can enhance the GFA by increasing the structural incompatibility with the competing crystalline phases.

Small angle neutron and X-ray studies of carbon structures with metal atoms

NASA Astrophysics Data System (ADS)

Lebedev, V. T.; Szhogina, A. A.; Bairamukov, V. Yu

2017-05-01

Encapsulation of metal atoms inside carbon single-wall cages or within multi-layer cells has been realized using molecular precursors and high temperature processes transforming them into desirable structures. Endohedral fullerenols Fe@C60(OH)X with 3d-metal (iron) have been studied by SANS in aqueous solutions where they form stable globular clusters with radii R C ∼ 10-12 nm and aggregation numbers N C ∼ 104. This self-assembly is a crucial feature of paramagnetic fullerenols as perspective contrast agents for Magneto-Resonance Imaging in medicine. Cellular carbon-metal structures have been created by the pyrolysis of diphthalocyanines of lanthanides and actinides. It was established that these ultra porous matrices consist of globular cells of molecular precursor size (∼ 1 nm) which are aggregated into superstructures. This provides retain of metal atoms inside matrices which may serve for safety storage of spent fuel of nuclear power plants.

Planar CoB18- Cluster: a New Motif for - and Metallo-Borophenes

NASA Astrophysics Data System (ADS)

Chen, Teng-Teng; Jian, Tian; Lopez, Gary; Li, Wan-Lu; Chen, Xin; Li, Jun; Wang, Lai-Sheng

2016-06-01

Combined Photoelectron Spectroscopy (PES) and theoretical calculations have found that anion boron clusters (Bn-) are planar and quasi-planar up to B25-. Recent works show that anion pure boron clusters continued to be planar at B27-,B30-,B35- and B36-. B35- and B36- provide the first experimental evidence for the viability of the two-dimensional (2D) boron sheets (Borophene). The 2D to three-dimensional (3D) transitions are shown to happen at B40-,B39- and B28-, which possess cage-like structures. These fullerene-like boron cage clusters are named as Borospherene. Recently, borophenes or similar structures are claimed to be synthesized by several groups. Following an electronic design principle, a series of transition-metal-doped boron clusters (M©Bn-, n=8-10) are found to possess the monocyclic wheel structures. Meanwhile, CoB12- and RhB12- are revealed to adopt half-sandwich-type structures with the quasi-planar B12 moiety similar to the B12- cluster. Very lately, we show that the CoB16- cluster possesses a highly symmetric Cobalt-centered drum-like structure, with a new record of coordination number at 16. Here we report the CoB18- cluster to possess a unique planar structure, in which the Co atom is doped into the network of a planar boron cluster. PES reveals that the CoB18- cluster is a highly stable electronic system with the first adiabatic detachment energy (ADE) at 4.0 eV. Global minimum searches along with high-level quantum calculations show the global minimum for CoB18- is perfectly planar and closed shell (1A1) with C2v symmetry. The Co atom is bonded with 7 boron atoms in the closest coordination shell and the other 11 boron atoms in the outer coordination shell. The calculated vertical detachment energy (VDE) values match quite well with our experimental results. Chemical bonding analysis by the Adaptive Natural Density Partitioning (AdNDP) method shows the CoB18- cluster is π-aromatic with four 4-centered-2-electron (4c-2e) π bonds and one 19-centered-2-electron (19c-2e) π bond, 10 π electrons in total. This perfectly planar structure reveals the viability of creating a new class of hetero-borophenes and metallo-borophenes by doping metal atoms into the plane of monolayer boron atoms. This gives a new approach to design perspective hetero-borophenes and metallo-borophenes materials with tunable chemical, magnetic and optical properties.

Effects of Al addition on atomic structure of Cu-Zr metallic glass

NASA Astrophysics Data System (ADS)

Li, Feng; Zhang, Huajian; Liu, Xiongjun; Dong, Yuecheng; Yu, Chunyan; Lu, Zhaoping

2018-02-01

The atomic structures of Cu52Zr48 and Cu45Zr48Al7 metallic glasses (MGs) have been studied by molecular dynamic simulations. The results reveal that the molar volume of the Cu45Zr48Al7 MG is smaller than that of the Cu52Zr48 MG, although the size of the Al atom is larger than that of the Cu atom, implying an enhanced atomic packing density achieved by introducing Al into the ternary MG. Bond shortening in unlike atomic pairs Zr-Al and Cu-Al is observed in the Cu45Zr48Al7 MG, which is attributed to strong interactions between Al and (Zr, Cu) atoms. Meanwhile, the atomic packing efficiency is enhanced by the minor addition of Al. Compared with the Cu52Zr48 binary MG, the potential energy of the ternary MG decreases and the glass transition temperature increases. Structural analyses indicate that more Cu- and Al-centered full icosahedral clusters emerge in the Cu45Zr48Al7 MG as some Cu atoms are substituted by Al. Furthermore, the addition of Al leads to more icosahedral medium-range orders in the ternary MG. The increase of full icosahedral clusters and the enhancement of the packing density are responsible for the improved glass-forming ability of Cu45Zr48Al7.

Barrier-free subsurface incorporation of 3 d metal atoms into Bi(111) films

DOE PAGES

Klein, C.; Vollmers, N. J.; Gerstmann, U.; ...

2015-05-27

By combining scanning tunneling microscopy with density functional theory it is shown that the Bi(111) surface provides a well-defined incorporation site in the first bilayer that traps highly coordinating atoms such as transition metals (TMs) or noble metals. All deposited atoms assume exactly the same specific sevenfold coordinated subsurface interstitial site while the surface topography remains nearly unchanged. Notably, 3 d TMs show a barrier-free incorporation. The observed surface modification by barrier-free subsorption helps to suppress aggregation in clusters. Thus, it allows a tuning of the electronic properties not only for the pure Bi(111) surface, but may also be observedmore » for topological insulators formed by substrate-stabilized Bi bilayers.« less

Ab initio investigation on hydrogen adsorption capability in Zn and Cu-based metal organic frameworks

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanuwijaya, V. V., E-mail: viny.veronika@gmail.com; Hidayat, N. N., E-mail: avantgarde.vee@gmail.com; Agusta, M. K., E-mail: kemal@fti.itb.ac.id

2015-09-30

One of the biggest challenge in material technology for hydrogen storage application is to increase hydrogen uptake in room temperature and pressure. As a class of highly porous material, Metal-Organic Frameworks (MOF) holds great potential with its tunable structure. However, little is known about the effect of metal cluster to its hydrogen storage capability. Investigation on this matter has been carried out carefully on small cluster of Zn and Cu-based MOF using first principles method. The calculation of two distinct building units of MOFs, namely octahedral and paddle-wheel models, have been done with B3LYP density functional method using 6-31G(d,p) andmore » LANL2DZ basis sets. From geometry optimization of Zn-based MOF linked by benzene-dicarboxylate (MOF-5), it is found that hydrogen tends to keep distance from metal cluster group and stays above benzene ring. In the other hand, hydrogen molecule prefers to stay atop of the exposed Cu atom in Cu-based MOF system linked by the same linker group (Cu-bdc). Calculated hydrogen binding enthalpies for Zn and Cu octahedral cages at ZnO{sub 3} sites are 1.64kJ/mol and 2.73kJ/mol respectively, while hydrogen binding enthalpies for Zn and Cu paddle-wheel cages calculated on top of metal atoms are found to be at 6.05kJ/mol and 6.10kJ/mol respectively. Major difference between Zn-MOF-5 and Cu-bdc hydrogen uptake performance might be caused by unsaturated metal sites present in Cu-bdc system and the influence of their geometric structures, although a small difference on binding energy in the type of transition metal used is also observed. The comparison between Zn and Cu-based MOF may contribute to a comprehensive understanding of metal clusters and the importance of selecting best transition metal for design and synthesis of metal-organic frameworks.« less

Atomic-Level Properties of Thermal Barrier Coatings: Characterization of Metal-Ceramic Interfaces

DTIC Science & Technology

2001-01-01

these cases metal - metal bonds were stronger than metal - substrate bonds, thus predicting a 3D (cluster) growth mode as opposed to layer-by-layer...coat layer must be deposited. The top coat serves as the insulator and the bond coat mediates contact between the top coat and metal alloy substrate ...in thermomechanical properties between a YSZ top coat and a metal -alloy substrate is enough to require the introduction of an intermediate layer. This

Photochemical cleavage of metal--carbon nanocrystals and their reconstruction into met--cars clusters

NASA Astrophysics Data System (ADS)

Pilgrim, J. S.; Duncan, M. A.

1994-10-01

Titanium and zirconium metal--carbon clusters are produced by laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. In addition to the now-familiar "met-cars" stoichiometry (M8C12), larger magic number clusters are produced with near 1:1 metal--carbon ratios. The special stoichiometries observed correspond to face-centered cubic crystal fragments, with a strong preference for fragments with symmetrical x,y,z dimensions. Mass-selected photodissociation experiments are used to investigate the structural patterns and stabilities of these systems. Photodissociation of the larger "nanocrystal" clusters leads to cleavage along crystal planes, producing smaller crystals also having highly symmetric dimensions. Photoexcitation of all these crystallites, in particular the 3 × 3 × 3 species, also leads to surface reconstruction, forming the M8C12 met-cars cluster and/or the M8C13 cluster, the latter of which is assigned to a met--cars cage with an endohedral carbon atom.

Anion photoelectron spectroscopy of germanium and tin clusters containing a transition- or lanthanide-metal atom; MGe(n)- (n = 8-20) and MSn(n)- (n = 15-17) (M = Sc-V, Y-Nb, and Lu-Ta).

PubMed

Atobe, Junko; Koyasu, Kiichirou; Furuse, Shunsuke; Nakajima, Atsushi

2012-07-14

The electronic properties of germanium and tin clusters containing a transition- or lanthanide-metal atom from group 3, 4, or 5, MGe(n) (M = Sc, Ti, V, Y, Zr, Nb, Lu, Hf, and Ta) and MSn(n) (M = Sc, Ti, Y. Zr, and Hf), were investigated by anion photoelectron spectroscopy at 213 nm. In the case of the group 3 elements Sc, Y, and Lu, the threshold energy of electron detachment of MGe(n)(-) exhibits local maxima at n = 10 and 16, while in the case of the group 4 elements Ti, Zr, and Hf, it exhibits a local minimum only at n = 16, associated with the presence of a small bump in the spectrum. A similar behavior is observed for MSn(n)(-) around n = 16, and these electronic characteristics of MGe(n) and MSn(n) are closely related to those of MSi(n). Compared to MSi(n), however, the larger cavity size of a Ge(n) cage allows metal atom encapsulation at a smaller size n. A cooperative effect between the electronic and geometric structures of clusters with a large cavity of Ge(16) or Sn(16) is discussed together with the results of experiments that probe their geometric stability via their reactivity to H(2)O adsorption.

Nanoclusters as a new family of high temperature superconductors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Halder, Avik; Kresin, Vitaly V.

2017-03-01

Electrons in metal clusters organize into quantum shells, akin to atomic shells in the periodic table. Such nanoparticles are referred to as "superatoms". The electronic shell levels are highly degenerate giving rise to sharp peaks in the density of states, which can enable exceptionally strong electron pairing in certain clusters containing tens to hundreds of atoms. A spectroscopic investigation of size - resolved aluminum nanoclusters has revealed a sharp rise in the density of states near the Fermi level as the temperature decreases towards 100 K. The effect is especially prominent in the closed-shell "magic" cluster Al66 [1, 2]. The characteristics of this behavior are fully consistent with a pairing transition, implying a high temperature superconducting state with Tc < 100K. This value exceeds that of bulk aluminum by two orders of magnitude. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks. ---------- 1. Halder, A., Liang, A., Kresin, V. V. A novel feature in aluminum cluster photoionization spectra and possibility of electron pairing at T 100K. Nano Lett 15, 1410 - 1413 (2015) 2. Halder, A., Kresin, V. V. A transition in the density of states of metal "superatom" nanoclusters and evidence for superconducting pairing at T 100K. Phys. Rev. B 92, 214506 (2015).

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lara-Castells, María Pilar de, E-mail: Pilar.deLara.Castells@csic.es; Fernández-Perea, Ricardo; Madzharova, Fani

2016-06-28

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet thismore » challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He–Mg pair potentials is also presented, as an improvement of the approximation using isolated He–Mg pairs.« less

Post-Hartree-Fock studies of the He/Mg(0001) interaction: Anti-corrugation, screening, and pairwise additivity

NASA Astrophysics Data System (ADS)

de Lara-Castells, María Pilar; Fernández-Perea, Ricardo; Madzharova, Fani; Voloshina, Elena

2016-06-01

The adsorption of noble gases on metallic surfaces represents a paradigmatic case of van-der-Waals (vdW) interaction due to the role of screening effects on the corrugation of the interaction potential [J. L. F. Da Silva et al., Phys. Rev. Lett. 90, 066104 (2003)]. The extremely small adsorption energy of He atoms on the Mg(0001) surface (below 3 meV) and the delocalized nature and mobility of the surface electrons make the He/Mg(0001) system particularly challenging, even for state-of-the-art vdW-corrected density functional-based (vdW-DFT) approaches [M. P. de Lara-Castells et al., J. Chem. Phys. 143, 194701 (2015)]. In this work, we meet this challenge by applying two different procedures. First, the dispersion-corrected second-order Möller-Plesset perturbation theory (MP2C) approach is adopted, using bare metal clusters of increasing size. Second, the method of increments [H. Stoll, J. Chem. Phys. 97, 8449 (1992)] is applied at coupled cluster singles and doubles and perturbative triples level, using embedded cluster models of the metal surface. Both approaches provide clear evidences of the anti-corrugation of the interaction potential: the He atom prefers on-top sites, instead of the expected hollow sites. This is interpreted as a signature of the screening of the He atom by the metal for the on-top configuration. The strong screening in the metal is clearly reflected in the relative contribution of successively deeper surface layers to the main dispersion contribution. Aimed to assist future dynamical simulations, a pairwise potential model for the He/surface interaction as a sum of effective He-Mg pair potentials is also presented, as an improvement of the approximation using isolated He-Mg pairs.

Metal-metal bond lengths in complexes of transition metals.

PubMed

Pauling, L

1976-12-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths.

Impurity-doped Si10 cluster: Understanding the structural and electronic properties from first-principles calculations

NASA Astrophysics Data System (ADS)

Majumder, Chiranjib; Kulshreshtha, S. K.

2004-12-01

Structural and electronic properties of metal-doped silicon clusters ( MSi10 , M=Li , Be, B, C, Na, Mg, Al, and Si) have been investigated via ab initio molecular dynamics simulation under the formalism of the density functional theory. The exchange-correlation energy has been calculated using the generalized gradient approximation method. Several stable isomers of MSi10 clusters have been identified based on different initial configurations and their relative stabilities have been analyzed. From the results it is revealed that the location of the impurity atom depends on the nature of interaction between the impurity atom and the host cluster and the size of the impurty atom. Whereas Be and B atoms form stable isomers, the impurity atom being placed at the center of the bicapped tetragonal antiprism structure of the Si10 cluster, all other elements diffuse outside the cage of Si10 cluster. Further, to understand the stability and the chemical bonding, the LCAO-MO based all electron calculations have been carried out for the lowest energy isomers using the hybrid B3LYP energy functional. Based on the interaction energy of the M atoms with Si10 clusters it is found that p-p interaction dominates over the s-p interaction and smaller size atoms interact more strongly. Based on the binding energy, the relative stability of MSi10 clusters is found to follow the order of CSi10>BSi10>BeSi10>Si11>AlSi10>LiSi10>NaSi10>MgSi10 , leading one to infer that while the substitution of C, B and Be enhances the stability of the Si11 cluster, others have an opposite effect. The extra stability of the BeSi10 clusters is due to its encapsulated close packed structure and large energy gap between the HOMO and LUMO energy levels.

Quantum soldering of individual quantum dots.

PubMed

Roy, Xavier; Schenck, Christine L; Ahn, Seokhoon; Lalancette, Roger A; Venkataraman, Latha; Nuckolls, Colin; Steigerwald, Michael L

2012-12-07

Making contact to a quantum dot: Single quantum-dot electronic circuits are fabricated by wiring atomically precise metal chalcogenide clusters with conjugated molecular connectors. These wired clusters can couple electronically to nanoscale electrodes and be tuned to control the charge-transfer characteristics (see picture). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

DOE PAGES

Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia; ...

2017-07-11

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. Notably, atomic layer deposition (ALD) in MOFs has recently emerged as a versatile approach to functionalize MOF surfaces with a wide variety of catalytic metal-oxo species. Understanding the structure of newly deposited species and how they are tethered within the MOF is critical to understanding how these components couple to govern the active material properties. By combining local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and differencemore » envelope density analysis, with electron microscopy imag-ing and computational modeling, we resolve the precise atomic structure of metal-oxo species deposited in the MOF NU-1000 through ALD. These analyses demonstrate that deposition of NiO xH y clusters occurs selectively within the smallest pores of NU-1000, between the zirconia nodes, serving to connect these nodes along the c-direction to yield hetero-bimetallic metal-oxo nanowires. Finally, this bridging motif perturbs the NU-1000 framework structure, drawing the zirconia nodes closer together, and also underlies the sintering-resistance of these clusters during the hydrogenation of light olefins.« less

Methane Oxidation to Methanol Catalyzed by Cu-Oxo Clusters Stabilized in NU-1000 Metal-Organic Framework.

PubMed

Ikuno, Takaaki; Zheng, Jian; Vjunov, Aleksei; Sanchez-Sanchez, Maricruz; Ortuño, Manuel A; Pahls, Dale R; Fulton, John L; Camaioni, Donald M; Li, Zhanyong; Ray, Debmalya; Mehdi, B Layla; Browning, Nigel D; Farha, Omar K; Hupp, Joseph T; Cramer, Christopher J; Gagliardi, Laura; Lercher, Johannes A

2017-08-02

Copper oxide clusters synthesized via atomic layer deposition on the nodes of the metal-organic framework (MOF) NU-1000 are active for oxidation of methane to methanol under mild reaction conditions. Analysis of chemical reactivity, in situ X-ray absorption spectroscopy, and density functional theory calculations are used to determine structure/activity relations in the Cu-NU-1000 catalytic system. The Cu-loaded MOF contained Cu-oxo clusters of a few Cu atoms. The Cu was present under ambient conditions as a mixture of ∼15% Cu + and ∼85% Cu 2+ . The oxidation of methane on Cu-NU-1000 was accompanied by the reduction of 9% of the Cu in the catalyst from Cu 2+ to Cu + . The products, methanol, dimethyl ether, and CO 2 , were desorbed with the passage of 10% water/He at 135 °C, giving a carbon selectivity for methane to methanol of 45-60%. Cu oxo clusters stabilized in NU-1000 provide an active, first generation MOF-based, selective methane oxidation catalyst.

First principles study of vibrational dynamics of ceria-titania hybrid clusters

NASA Astrophysics Data System (ADS)

Majid, Abdul; Bibi, Maryam

2017-04-01

Density functional theory based calculations were performed to study vibrational properties of ceria, titania, and ceria-titania hybrid clusters. The findings revealed the dominance of vibrations related to oxygen when compared to those of metallic atoms in the clusters. In case of hybrid cluster, the softening of normal modes related to exterior oxygen atoms in ceria and softening/hardening of high/low frequency modes related to titania dimmers are observed. The results calculated for monomers conform to symmetry predictions according to which three IR and three Raman active modes were detected for TiO2, whereas two IR active and one Raman active modes were observed for CeO2. The comparative analysis indicates that the hybrid cluster CeTiO4 contains simultaneous vibrational fingerprints of the component dimmers. The symmetry, nature of vibrations, IR and Raman activity, intensities, and atomic involvement in different modes of the clusters are described in detail. The study points to engineering of CeTiO4 to tailor its properties for technological visible region applications in photocatalytic and electrochemical devices.

Helium cluster isolation spectroscopy

NASA Astrophysics Data System (ADS)

Higgins, John Paul

Clusters of helium, each containing ~103- 104 atoms, are produced in a molecular beam and are doped with alkali metal atoms (Li, Na, and K) and large organic molecules. Electronic spectroscopy in the visible and UV regions of the spectrum is carried out on the dopant species. Since large helium clusters are liquid and attain an equilibrium internal temperature of 0.4 K, they interact weakly with atoms or molecules absorbed on their surface or resident inside the cluster. The spectra that are obtained are characterized by small frequency shifts from the positions of the gas phase transitions, narrow lines, and cold vibrational temperatures. Alkali atoms aggregate on the helium cluster surface to form dimers and trimers. The spectra of singlet alkali dimers exhibit the presence of elementary excitations in the superfluid helium cluster matrix. It is found that preparation of the alkali molecules on the surface of helium clusters leads to the preferential formation of high-spin, van der Waals bound, triplet dimers and quartet trimers. Four bound-bound and two bound-free transitions are observed in the triplet manifold of the alkali dimers. The quartet trimers serve as an ideal system for the study of a simple unimolecular reaction in the cold helium cluster environment. Analysis of the lowest quartet state provides valuable insight into three-body forces in a van der Waals trimer. The wide range of atomic and molecular systems studied in this thesis constitutes a preliminary step in the development of helium cluster isolation spectroscopy, a hybrid technique combining the advantages of high resolution spectroscopy with the synthetic, low temperature environment of matrices.

DFT Studies of Adsorption of Cu7-atom Nanoclusters on TiO2 Surfaces and Application to Methanol Steam Reforming Reactions

NASA Astrophysics Data System (ADS)

Taft, Michael J., Sr.

Alcohol conversion to hydrogen, via steam reforming, is an alternative energy process that is promising for the future of clean energy economies. With advancements in fuel cell technologies, on-board hydrogen reforming could leverage already existing automotive designs and fuel infrastructure. The design of catalytic materials with tunable properties requires a level of insight that has yet to be achieved experimentally. The central objective of this project is to develop a working model of metal-oxide surface mediated copper clusters, since such catalytic beds have a wide-range of applications. More specifically, we investigate the catalytic framework of this process with theoretical models of the active metal (Cu) and metal­oxide support (TiO2). We employ a Density Functional Theory (DFT)-Generalized Gradient Approximation (GGA) approach for the quantum level electronic structure calculations of Cu, TiO2 and CH3OH. Additionally, we have generated anatase (A(001), A(101)) and rutile (R(100), R(110)) surface morphologies and 7­atom copper cluster complexes with those planes. To examine the possible influence of TiO2 on the adsorption properties of our active metal, Cu7, we have carried out adsorption studies with CH3OH. Our final data and observations predict that the Cu7 cluster adopts a symmetric pentagonal bipyramidal geometry with D5h symmetry. We find that the anatase morphology has a greater overall stability than rutile. The adsorption strength of the Cu7 cluster has been predicted in this study to be according to the following order: A(001) > A(101)> R(110). Indeed, the R(100) surface appears to be an unfavorable surface for metal cluster binding. Our data indicates that copper cluster stabilization on the metal-oxide surface depends on the nature of the crystal face. Again, we studied the adsorption properties of methanol on nascent Cu7 cluster, Cu7-TiO 2 complex and on pure TiO2-surface in A(001) polymorphic form. The calculations revealed that methanol adsorbs more efficiently on TiO2-bound copper clusters than either the copper cluster alone or the surface of TiO2. Additionally, we find that the metal-oxide support plays a significant role in stabilizing the catalytic reactions of CH3OH adsorption. Here, we have shown that TiO2 clearly enhances the catalytic properties of copper clusters.

Bimetallic cages

NASA Astrophysics Data System (ADS)

Fournier, René; Afzal-Hussain, Sabeen

2013-02-01

We report the results of density functional theory for 39 clusters AxBy (x + y = 10 or 12) where A and B are metals from group 1, 2, 11, 12, 13, or 14 of the periodic table. The chemical compositions were chosen to satisfy an electronic shell closing criterion. We performed an unbiased search for the global minimum (GM) by taboo search in descriptor space in each case. Eight of the 39 putative GM are cages even though none of the clusters contains gold, a metal with a well known propensity to form cages. These cages are large enough to accommodate a dopant atom with an atomic radius varying between 0.7 Å and 1.2 Å. The chemical compositions most likely to produce cages have an element of group 11 alloyed with an element of group 2, 12, or 13.

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. We here demonstrate the saturating reaction of trimethylindium (InMe3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOF node to generatemore » a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. We further demonstrate tunable metal loading through controlled number density of the reactive handles (-OH and -OH2) achieved through node dehydration at elevated temperatures.« less

Thermal O-H Bond Activation of Water as Mediated by Heteronuclear [Al2Mg2O5]•+: Evidence for Oxygen-Atom Scrambling.

PubMed

Geng, Caiyun; Li, Jilai; Weiske, Thomas; Schwarz, Helmut

2018-06-25

Mechanistic insight into the thermal O-H bond activation of water by the cubane-like, prototypical heteronuclear oxide cluster [Al 2 Mg 2 O 5 ] •+ has been derived from a combined experimental/computational study. Experiments in the highly diluted gas phase using Fourier transform ion-cyclotron resonance mass spectrometry show that hydrogen-atom abstraction from water by the cluster cation [Al 2 Mg 2 O 5 ] •+ occurs at ambient conditions accompanied by the liberation of an OH • radical. Due to a complete randomization of all oxygen atoms prior to fragmentation about 83% of the oxygen atoms of the hydroxyl radical released originate from the oxide cluster itself. The experimental findings are supported by detailed high-level quantum chemical calculations. The theoretical analysis reveals that the transfer of a formal hydrogen atom from water to the metal-oxide cation can proceed mechanistically via proton- or hydrogen-atom transfer exploiting different active sites of the cluster oxide. In addition to the unprecedented oxygen-atom scrambling, one of the more general and quite unexpected findings concerns the role of spin density at the hydrogen-acceptor oxide atom. While this feature is so crucial for [M-O] + /CH 4 couples, it is much less important in the O-H bond activation of water.

Theoretical investigations on the d-p hybridized aromaticity, photoelectron spectroscopy and neutral salts of the LaX2- (X=Al, Ga, In) clusters.

PubMed

Chen, Jing; Yang, Huan; Wang, Jing; Cheng, Shi-Bo

2018-05-30

We present an extensive density functional theory (DFT) calculations on the geometrical and electronic structures of the triatomic LaX 2 - (X=Al, Ga, In) clusters. Various trail structures and spin states have been attempted to determine the lowest-energy geometries of these La-doped metal clusters. The ground states of all three clusters are calculated to possess the trigonal structures with the singlet multiplicities. The calculations on molecular orbitals (MOs) and nucleus-independent chemical shift (NICS) values have been performed to examine the aromatic characteristics of the LaX 2 - (X=Al, Ga, In) clusters. The present calculations disclose that all these metal clusters are doubly aromatic, namely d-p hybridized σ and π aromaticity resulting from the effective overlap between the 5d atomic orbital of the La atom and the p orbitals of the IIIA group elements. Theoretical vertical detachment energies (VDEs) were also calculated to simulate the photoelectron spectra (PES) of the clusters. In addition, by adding the alkali cations (Li + and Na + ) into the LaX 2 - (X=Al, Ga, In) clusters, the geometries and electronic structures of the corresponding neutral salts have also been investigated to gain more insights in the potential of using these aromatic anions as building blocks. Copyright © 2018 Elsevier B.V. All rights reserved.

Partial Ionic Character beyond the Pauling Paradigm: Metal Nanoparticles

DOE PAGES

Duanmu, Kaining; Truhlar, Donald G.

2014-11-12

A canonical perspective on the chemical bond is the Pauling paradigm: a bond in a molecule containing only identical atoms has no ionic character. However, we show that homonuclear silver clusters have very uneven charge distributions (for example, the C 2v structure of Ag 4 has a larger dipole moment than formaldehyde or acetone), and we show how to predict the charge distribution from coordination numbers and Hirshfeld charges. The new charge model is validated against Kohn–Sham calculations of dipole moments with four approximations for the exchange–correlation functional. We report Kohn–Sham studies of the binding energies of CO on silvermore » monomer and silver clusters containing 2–18 atoms. We also find that an accurate charge model is essential for understanding the site dependence of binding. In particular we find that atoms with more positive charges tend to have higher binding energies, which can be used for guidance in catalyst modeling and design. Furthermore, the nonuniform charge distribution of silver clusters predisposes the site preference of binding of carbon monoxide, and we conclude that nonuniform charge distributions are an important property for understanding binding of metal nanoparticles in general.« less

Iron-Rhodium and Iron-Iridium Mixed-Metal Nitrido-Carbonyl Clusters. Synthesis, Characterization, Redox Properties, and Solid-State Structure of the Octahedral Clusters [Fe(5)RhN(CO)(15)](2)(-), [Fe(5)IrN(CO)(15)](2)(-), and [Fe(4)Rh(2)N(CO)(15)](-). Infrared and Nuclear Magnetic Resonance Spectroscopic Studies on the Interstitial Nitride.

PubMed

Della Pergola, Roberto; Cinquantini, Arnaldo; Diana, Eliano; Garlaschelli, Luigi; Laschi, Franco; Luzzini, Paola; Manassero, Mario; Repossi, Andrea; Sansoni, Mirella; Stanghellini, Pier Luigi; Zanello, Piero

1997-08-13

The cluster [Fe(5)RhN(CO)(15)](2)(-) was synthesized in 40% yield from [Fe(4)N(CO)(12)](-) and [Rh(CO)(4)](-) in refluxing tetrahydrofuran, whereas the analogous anion [Fe(5)IrN(CO)(15)](2)(-) was prepared in CH(3)CN at room temperature from [Fe(6)N(CO)(15)](3)(-) and [Ir(C(8)H(14))(2)Cl](2); the yields are higher than 60%. The monoanion [Fe(4)Rh(2)N(CO)(15)](-) was obtained in 70% yield from [Fe(5)RhN(CO)(15)](2)(-) and hydrated RhCl(3). The solid-state structures of the three anions were determined on their [PPh(4)](+) salts: the six metal atoms are arranged in octahedral cages and are coordinated to 3 edge-bridging and 12 terminal carbonyl ligands and to a &mgr;(6)-N ligand. The Rh and Ir atoms have less terminal COs than Fe, in order to equalize the excess electrons at the d(9) metal centers. The two rhodium atoms in [Fe(4)Rh(2)N(CO)(15)](-) are directly bound. The (15)N NMR spectra of the three compounds have been recorded; the signals of the nitride ligands were found at delta = 514 ppm for the dianions and 470 ppm for [Fe(4)Rh(2)N(CO)(15)](-); any group 9 atom shifts the resonance of nitrogen to higher fields. The coupling constants J((15)N-(103)Rh) are 8-9 Hz. The vibrational patterns of the metal cores have been interpreted on the basis of an idealized M(6) octahedral arrangement, subsequently modified by the perturbations given by different atomic masses and M-M stretching force constants. The motions of the nitrogen are related to the idealized symmetry of the cage; the M-N force constant values depend on the type of metal and on the charge of the anion. The dianions [Fe(5)MN(CO)(15)](2)(-) can be electrochemically oxidized at -20 degrees C to their short-lived monoanions, which can be characterized by EPR spectroscopy. In contrast, the cluster [Fe(4)Rh(2)N(CO)(15)](-) undergoes a single-step 2-electron reduction to the partially stable trianion [Fe(4)Rh(2)N(CO)(15)](3)(-), which was also characterized by EPR spectroscopy. The Fe-Rh nitride clusters are active catalysts for the hydroformylation of 1-pentene, but display low selectivity (35-65%) in n-hexanal and are demolished under catalytic conditions.

Absorption spectroscopy of heavy alkaline earth metals Ba and Sr in rare gas matrices—CCSD(T) calculations and atomic site occupancies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Davis, Barry M.; McCaffrey, John G., E-mail: john.mccaffrey@nuim.ie

2016-01-28

Isolation of the heavier alkaline earth metals Ba and Sr in the solid rare gases (RGs) Ar, Kr, and Xe is analysed with absorption spectroscopy and interpreted partly with the assistance of ab initio calculations of the diatomic M ⋅ RG ground state interaction potentials. The y{sup 1}P←a{sup 1}S resonance transitions in the visible spectral region are used to compare the isolation conditions of these two metal atom systems and calcium. Complex absorption bands were recorded in all three metal atom systems even after extensive sample annealing. Coupled cluster calculations conducted on the ground states of the nine M ⋅more » RG diatomics (M = Ca, Sr, and Ba; RG = Ar, Kr, and Xe) at the coupled cluster single, double, and non-iterative triple level of theory revealed long bond lengths (>5 Å) and shallow bound regions (<130 cm{sup −1}). All of the M ⋅ RG diatomics have bond lengths considerably longer than those of the rare gas dimers, with the consequence that isolation of these metal atoms in a single substitutional site of the solid rare gas is unlikely, with the possible exception of Ca/Xe. The luminescence of metal dimer bands has been recorded for Ba and Sr revealing very different behaviours. Resonance fluorescence with a lifetime of 15 ns is observed for the lowest energy transition of Sr{sub 2} while this transition is quenched in Ba{sub 2}. This behaviour is consistent with the absence of vibrational structure on the dimer absorption band in Ba{sub 2} indicating lifetime broadening arising from efficient relaxation to low-lying molecular states. More extensive 2D excitation-emission data recorded for the complex site structures present on the absorption bands of the atomic Ba and Sr systems will be presented in future publications.« less

Making sense of the conflicting magic numbers in WSi{sub n} clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Abreu, Marissa Baddick; Reber, Arthur C.; Khanna, Shiv N.

2015-08-21

First principles studies on the geometric structure, stability, and electronic structure of WSi{sub n} clusters, n = 6-16, have been carried out to show that the observed differing “magic sizes” for WSi{sub n} clusters are associated with the nature of the growth processes. The WSi{sub 12} cluster, observed as a magic species in experiments reacting transition metal ions with silane, is not stable due to a filled shell of 18 electrons, as previously proposed, but due to its atomic structure that arrests further growth because of an endohedral transition metal site. In fact, it is found that all of thesemore » clusters, n = 6-16, have filled 5d shells except for WSi{sub 12}, which has a 5d{sup 8} configuration that is caused by crystal field splitting. The stability of WSi{sub 15}{sup +}, observed as highly stable in clusters generated by vaporizing silicon and metal carbonyls, is shown to be associated with a combination of geometric and electronic features. The findings are compared with previous results on CrSi{sub n} clusters.« less

Temperature-programmed reduction of Pt-Ir/. gamma. -Al/sub 2/O/sub 3/ catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.; Prins, R.

1979-10-15

An intriguing feature of the evidence for the existence of Pt-Re clusters in the reduced state of the catalyst, Pt-Re/..gamma..-Al/sub 2/O/sub 3/ was the segregation of Pt and Re oxides observed after oxidation of the bimetallic clusters at temperatures above about 200/sup 0/C. Evidently, the oxide moieties are immiscible on the scale of the small clusters (up to 10 to 15 atoms) in the case of these metals. The present results for Pt-Ir/..gamma..-Al/sub 2/O/sub 3/ represent an example of a supported, highly dispersed system in which the intimacy of the metals remains intact even after fairly severe oxidation treatments. Studymore » of other bimetallic system on alumina by TPR should yield further valuable information on this interesting aspect of metal cluster behavior. 1 figure.« less

Trends in hydrogen chemisorption on transition metals

NASA Astrophysics Data System (ADS)

Muscat, J. P.

1981-10-01

A systematic study of H adsorption on the close-packed surfaces of the transition metals in the 3d and 4d series is presented. The effect of the TM d band on the chemisorption bond is investigated, by embedding a cluster of TM muffin tins at the surface of an effective jellium-like medium. It is found that the broad and incomplete H/jellium resonance is narrowed, shifted down and made to contain more electrons as a result of hybridization with the TM d states. These effects are larger in the case of the 4d metals, thus indicating a greater participation in the chemisorption bond of the d electrons for these metals than for the 3d metals. Calculation of one-electron energy differences on going from the H on jellium system to that of H on the TM cluster are presented. Trends for the one-electron energy differences are compared to trends in experimental chemisorption energy. H adsorption in the three-fold hollow site with no secondlayer TM atom below the H site is favoured for the hcp metals, while no discernible preference between the two hollow sites is recorded for the fcc metals, with the exception of Rh where the site with no second-layer TM atom below is preferred.

Tuning the Emission and Quantum Yield of Gold and Silver Nanoclusters Through Ligand Design and Doping

NASA Astrophysics Data System (ADS)

Mishra, Dinesh

Nanoparticles have been extensively studied in the past few decades due to the possibilities they offer in applications ranging from medicine to energy generation. A new class of ultra-small noble metal nanoparticles consisting of tens to hundreds of atoms, commonly known as clusters or nanoclusters, have drawn interest of the research community recently due to their unique optical, electronic and structural properties. Over the past few years, advances have been made in the synthesis of atomically precise noble metal clusters (for example, silver and gold) with distinct optical properties. Their ultra-small size distinguishes them from conventional plasmonic nanoparticles and the properties are very sensitive to the slight variation in the compositon of the cluster, i.e. the number of the metal atoms and/or the nature of the ligands. These clusters are interesting because of their potential applications in field such as sensing, imaging, catalysis, clean energy, photonics, etc. as well as they provide fundamental insight into the evolution of the optical and electronic properties of these clusters. In this project, we explored the strategies to synthesize luminescent metallic clusters of gold and silver and to promote their solubility and stability in aqueous and biological medium. We focused particularly on the thiolate protected clusters due to the higher affinity of gold and silver to sulfur. Lipoic acid (Thioctic acid) is a bio-molecule with a cyclic disulfide ring, which also acts as a chelating ligand. Due to the higher binding affinity of the cyclic disulfide ring to nanocrystal surface, lipoic acid and chemically modified lipoic acid molecules have been widely reported for the synthesis and functionalization of inorganic nanocrystals. Here, we describe the use of bidentate lipoic acid ligands in the one phase growth of luminescent gold and silver nanoclusters. In addition, we have synthesized a new set of monothiol ligands containing PEG and zwitterion for the functionalization of fluorescent clusters. Chapter 1 introduces the fundamental properties of metallic clusters and the origin of these properties from electronic and structural point of view. The optical properties of ultra-small nanocrystals (<2 nm) in comparison to the plasmonic particles is described. In addition, the variation of optical and structural properties from one metal to another as well as one ligand to another is also compared. Chapter 2 describes the synthesis of ultra-small size gold clusters with different optical emission (ranging from blue to red) using photo-activated LA-PEG ligands. The influence of various factors on the growth of the clusters is also studied. Optical properties of the clusters were studied by UV-visible absorption, PL emission and excitation and time resolved fluorescence spectroscopy. XPS and DOSY NMR were used to characterize the oxidation states and sizes of these clusters. The photo-chemical transformation of LA-PEG ligands to thiols and the effect of various experimental parameters such as solvent, oxygen, ligand functional group and effect of acid are described in chapter 3. Thiol yield percentage was quantified using ellman assay. Chapter 4 describes the one phase aqueous synthesis of Ag29 clusters capped with bidentate dihydrolipoic acid (DHLA). We also describe the drastic enhancement of the PL intensity upon gold doping of the Ag29 clusters. Optical properties along with the size characterization by electrospray ionization mass spectrometry is also described. We further describe the growth of these clusters using DHLA-PEG molecules. Chapter 5 describes the synthesis of highly fluorescent Au25-xAgx clusters stabilized with two types of ligands (triphenylphosphine and thiols). We designed a set of monothiolate ligands appended with PEG and zwitterionic moieties. This approach allows to prepare water soluble and stable metallic clusters with enhanced photoluminescence and well defined optical properties. Chapter 6 is the overall summary of our findings and prospects and outlook.

Dynamical, structural and chemical heterogeneities in a binary metallic glass-forming liquid

NASA Astrophysics Data System (ADS)

Puosi, F.; Jakse, N.; Pasturel, A.

2018-04-01

As it approaches the glass transition, particle motion in liquids becomes highly heterogeneous and regions with virtually no mobility coexist with liquid-like domains. This complex dynamic is believed to be responsible for different phenomena including non-exponential relaxation and the breakdown of the Stokes-Einstein relation. Understanding the relationships between dynamical heterogeneities and local structure in metallic liquids and glasses is a major scientific challenge. Here we use classical molecular dynamics simulations to study the atomic dynamics and microscopic structure of Cu50Zr50 alloy in the supercooling regime. Dynamical heterogeneities are identified via an isoconfigurational analysis. We demonstrate the transition from isolated to clustering low mobility with decreasing temperature. These slow clusters, whose sizes grow upon cooling, are also associated with concentration fluctuations, characterized by a Zr-enriched phase, with a composition CuZr2 . In addition, a structural analysis of slow clusters based on Voronoi tessellation evidences an increase with respect of the bulk system of the fraction of Cu atoms having a local icosahedral order. These results are in agreement with the consolidated scenario of the relevant role played by icosahedral order in the dynamic slowing-down in supercooled metal alloys.

Curved-line search algorithm for ab initio atomic structure relaxation

NASA Astrophysics Data System (ADS)

Chen, Zhanghui; Li, Jingbo; Li, Shushen; Wang, Lin-Wang

2017-09-01

Ab initio atomic relaxations often take large numbers of steps and long times to converge, especially when the initial atomic configurations are far from the local minimum or there are curved and narrow valleys in the multidimensional potentials. An atomic relaxation method based on on-the-flight force learning and a corresponding curved-line search algorithm is presented to accelerate this process. Results demonstrate the superior performance of this method for metal and magnetic clusters when compared with the conventional conjugate-gradient method.

Titanium Insertion into CO Bonds in Anionic Ti-CO2 Complexes.

PubMed

Dodson, Leah G; Thompson, Michael C; Weber, J Mathias

2018-03-22

We explore the structures of [Ti(CO 2 ) y ] - cluster anions using infrared photodissociation spectroscopy and quantum chemistry calculations. The existence of spectral signatures of metal carbonyl CO stretching modes shows that insertion of titanium atoms into C-O bonds represents an important reaction during the formation of these clusters. In addition to carbonyl groups, the infrared spectra show that the titanium center is coordinated to oxalato, carbonato, and oxo ligands, which form along with the metal carbonyls. The presence of a metal oxalato ligand promotes C-O bond insertion in these systems. These results highlight the affinity of titanium for C-O bond insertion processes.

A density functional global optimisation study of neutral 8-atom Cu-Ag and Cu-Au clusters

NASA Astrophysics Data System (ADS)

Heard, Christopher J.; Johnston, Roy L.

2013-02-01

The effect of doping on the energetics and dimensionality of eight atom coinage metal subnanometre particles is fully resolved using a genetic algorithm in tandem with on the fly density functional theory calculations to determine the global minima (GM) for Cu n Ag(8- n) and Cu n Au(8- n) clusters. Comparisons are made to previous ab initio work on mono- and bimetallic clusters, with excellent agreement found. Charge transfer and geometric arguments are considered to rationalise the stability of the particular permutational isomers found. An interesting transition between three dimensional and two dimensional GM structures is observed for copper-gold clusters, which is sharper and appears earlier in the doping series than is known for gold-silver particles.

Dynamic stabilities of icosahedral-like clusters and their ability to form quasicrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liang, Xiaogang; Hamid, Ilyar; Duan, Haiming, E-mail: dhm@xju.edu.cn

2016-06-15

The dynamic stabilities of the icosahedral-like clusters containing up to 2200 atoms are investigated for 15 metal elements. The clusters originate from five different initial structures (icosahedron, truncated decahedron, octahedron, closed-shell fragment of an HCP structure, and non-closed-shell fragment of an HCP structure). The obtained order of the dynamic stabilities of the icosahedral-like clusters can be assigned to three groups, from stronger to weaker, according to the size ranges involved: (Zr, Al, Ti) > (Cu, Fe, Co, Ni, Mg, Ag) > (Pb, Au, Pd, Pt, Rh, Ir), which correspond to the predicted formation ability of the quasicrystals. The differences ofmore » the sequences can be explained by analyzing the parameters of the Gupta-type many-body inter-atomic potentials.« less

Metal-metal bond lengths in complexes of transition metals*

PubMed Central

Pauling, Linus

1976-01-01

In complexes of the transition metals containing clusters of metal atoms the cobalt-cobalt bond lengths are almost always within 1 pm of the single-bond value 246 pm given by the enneacovalent radius of cobalt, whereas most of the observed iron-iron bond lengths are significantly larger than the single-bond value 248 pm, the mean being 264 pm, which corresponds to a half-bond. A simple discussion of the structures of these complexes based on spd hybrid orbitals, the electroneutrality principle, and the partial ionic character of bonds between unlike atoms leads to the conclusion that resonance between single bonds and no-bonds would occur for iron and its congeners but not for cobalt and its congeners, explaining the difference in the bond lengths. PMID:16592368

Electronic Effects on Room-Temperature, Gas-Phase C-H Bond Activations by Cluster Oxides and Metal Carbides: The Methane Challenge.

PubMed

Schwarz, Helmut; Shaik, Sason; Li, Jilai

2017-12-06

This Perspective discusses a story of one molecule (methane), a few metal-oxide cationic clusters (MOCCs), dopants, metal-carbide cations, oriented-electric fields (OEFs), and a dizzying mechanistic landscape of methane activation! One mechanism is hydrogen atom transfer (HAT), which occurs whenever the MOCC possesses a localized oxyl radical (M-O • ). Whenever the radical is delocalized, e.g., in [MgO] n •+ the HAT barrier increases due to the penalty of radical localization. Adding a dopant (Ga 2 O 3 ) to [MgO] 2 •+ localizes the radical and HAT transpires. Whenever the radical is located on the metal centers as in [Al 2 O 2 ] •+ the mechanism crosses over to proton-coupled electron transfer (PCET), wherein the positive Al center acts as a Lewis acid that coordinates the methane molecule, while one of the bridging oxygen atoms abstracts a proton, and the negatively charged CH 3 moiety relocates to the metal fragment. We provide a diagnostic plot of barriers vs reactants' distortion energies, which allows the chemist to distinguish HAT from PCET. Thus, doping of [MgO] 2 •+ by Al 2 O 3 enables HAT and PCET to compete. Similarly, [ZnO] •+ activates methane by PCET generating many products. Adding a CH 3 CN ligand to form [(CH 3 CN)ZnO] •+ leads to a single HAT product. The CH 3 CN dipole acts as an OEF that switches off PCET. [MC] + cations (M = Au, Cu) act by different mechanisms, dictated by the M + -C bond covalence. For example, Cu + , which bonds the carbon atom mostly electrostatically, performs coupling of C to methane to yield ethylene, in a single almost barrier-free step, with an unprecedented atomic choreography catalyzed by the OEF of Cu + .

Theoretical study of negatively charged Fe(-)-(H2O)(n ≤ 6) clusters.

PubMed

Castro, Miguel

2012-06-14

Interactions of a singly negatively charged iron atom with water molecules, Fe(-)-(H(2)O)(n≤6), in the gas phase were studied by means of density functional theory. All-electron calculations were performed using the B3LYP functional and the 6-311++G(2d,2p) basis set for the Fe, O, and H atoms. In the lowest total energy states of Fe(-)-(H(2)O)(n), the metal-hydrogen bonding is stronger than the metal-oxygen one, producing low-symmetry structures because the water molecules are directly attached to the metal by basically one of their hydrogen atoms, whereas the other ones are involved in a network of hydrogen bonds, which together with the Fe(δ-)-H(δ+) bonding accounts for the nascent hydration of the Fe(-) anion. For Fe(-)-(H(2)O)(3≤n), three-, four-, five-, and six-membered rings of water molecules are bonded to the metal, which is located at the surface of the cluster in such a way as to reduce the repulsion with the oxygen atoms. Nevertheless, internal isomers appear also, lying less than 3 or 5 kcal/mol for n = 2-3 or n = 4-6. These results are in contrast with those of classical TM(+)-(H(2)O)(n) complexes, where the direct TM(+)-O bonding usually produces high symmetry structures with the metal defining the center of the complex. They show also that the Fe(-) anions, as the TM(+) ions, have great capability for the adsorption of water molecules, forming Fe(-)-(H(2)O)(n) structures stabilized by Fe(δ-)-H(δ+) and H-bond interactions.

Atomically manufactured nickel-silicon quantum dots displaying robust resonant tunneling and negative differential resistance

NASA Astrophysics Data System (ADS)

Cheng, Jian-Yih; Fisher, Brandon L.; Guisinger, Nathan P.; Lilley, Carmen M.

2017-12-01

Providing a spin-free host material in the development of quantum information technology has made silicon a very interesting and desirable material for qubit design. Much of the work and experimental progress has focused on isolated phosphorous atoms. In this article, we report on the exploration of Ni-Si clusters that are atomically manufactured via self-assembly from the bottom-up and behave as isolated quantum dots. These small quantum dot structures are probed at the atomic-scale with scanning tunneling microscopy and spectroscopy, revealing robust resonance through discrete quantized energy levels within the Ni-Si clusters. The resonance energy is reproducible and the peak spacing of the quantum dot structures increases as the number of atoms in the cluster decrease. Probing these quantum dot structures on degenerately doped silicon results in the observation of negative differential resistance in both I-V and dI/dV spectra. At higher surface coverage of nickel, a well-known √19 surface modification is observed and is essentially a tightly packed array of the clusters. Spatial conductance maps reveal variations in the local density of states that suggest the clusters are influencing the electronic properties of their neighbors. All of these results are extremely encouraging towards the utilization of metal modified silicon surfaces to advance or complement existing quantum information technology.

Atomically manufactured nickel–silicon quantum dots displaying robust resonant tunneling and negative differential resistance

DOE PAGES

Cheng, Jian -Yih; Fisher, Brandon L.; Guisinger, Nathan P.; ...

2017-05-22

Providing a spin-free host material in the development of quantum information technology has made silicon a very interesting and desirable material for qubit design. Much of the work and experimental progress has focused on isolated phosphorous atoms. In this article, we report on the exploration of Ni–Si clusters that are atomically manufactured via self-assembly from the bottom-up and behave as isolated quantum dots. These small quantum dot structures are probed at the atomic-scale with scanning tunneling microscopy and spectroscopy, revealing robust resonance through discrete quantized energy levels within the Ni–Si clusters. The resonance energy is reproducible and the peak spacingmore » of the quantum dot structures increases as the number of atoms in the cluster decrease. Probing these quantum dot structures on degenerately doped silicon results in the observation of negative differential resistance in both I–V and dI/dV spectra. At higher surface coverage of nickel, a well-known √19 surface modification is observed and is essentially a tightly packed array of the clusters. Spatial conductance maps reveal variations in the local density of states that suggest the clusters are influencing the electronic properties of their neighbors. Furthermore, all of these results are extremely encouraging towards the utilization of metal modified silicon surfaces to advance or complement existing quantum information technology.« less

Atomically manufactured nickel–silicon quantum dots displaying robust resonant tunneling and negative differential resistance

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Jian -Yih; Fisher, Brandon L.; Guisinger, Nathan P.

Providing a spin-free host material in the development of quantum information technology has made silicon a very interesting and desirable material for qubit design. Much of the work and experimental progress has focused on isolated phosphorous atoms. In this article, we report on the exploration of Ni–Si clusters that are atomically manufactured via self-assembly from the bottom-up and behave as isolated quantum dots. These small quantum dot structures are probed at the atomic-scale with scanning tunneling microscopy and spectroscopy, revealing robust resonance through discrete quantized energy levels within the Ni–Si clusters. The resonance energy is reproducible and the peak spacingmore » of the quantum dot structures increases as the number of atoms in the cluster decrease. Probing these quantum dot structures on degenerately doped silicon results in the observation of negative differential resistance in both I–V and dI/dV spectra. At higher surface coverage of nickel, a well-known √19 surface modification is observed and is essentially a tightly packed array of the clusters. Spatial conductance maps reveal variations in the local density of states that suggest the clusters are influencing the electronic properties of their neighbors. Furthermore, all of these results are extremely encouraging towards the utilization of metal modified silicon surfaces to advance or complement existing quantum information technology.« less

DNA-Templated Molecular Silver Fluorophores

PubMed Central

Petty, Jeffrey T.; Story, Sandra P.; Hsiang, Jung-Cheng; Dickson, Robert M.

2013-01-01

Conductive and plasmon-supporting noble metals exhibit an especially wide range of size-dependent properties, with discrete electronic levels, strong optical absorption, and efficient radiative relaxation dominating optical behavior at the ~10-atom cluster scale. In this Perspective, we describe the formation and stabilization of silver clusters using DNA templates and highlight the distinct spectroscopic and photophysical properties of the resulting hybrid fluorophores. Strong visible to near-IR emission from DNA-encapsulated silver clusters ranging in size from 5–11 atoms has been produced and characterized. Importantly, this strong Ag cluster fluorescence can be directly modulated and selectively recovered by optically controlling the dark state residence, even when faced with an overwhelming background. The strength and sequence sensitivity of the oligonucleotide-Ag interaction suggests strategies for fine tuning and stabilizing cluster-based emitters in a host of sensing and biolabeling applications that would benefit from brighter, more photostable, and quantifiable emitters in high background environments. PMID:23745165

Nanoscale decomposition of Nb-Ru-O

NASA Astrophysics Data System (ADS)

Music, Denis; Geyer, Richard W.; Chen, Yen-Ting

2016-11-01

A correlative theoretical and experimental methodology has been employed to explore the decomposition of amorphous Nb-Ru-O at elevated temperatures. Density functional theory based molecular dynamics simulations reveal that amorphous Nb-Ru-O is structurally modified within 10 ps at 800 K giving rise to an increase in the planar metal - oxygen and metal - metal population and hence formation of large clusters, which signifies atomic segregation. The driving force for this atomic segregation process is 0.5 eV/atom. This is validated by diffraction experiments and transmission electron microscopy of sputter-synthesized Nb-Ru-O thin films. Room temperature samples are amorphous, while at 800 K nanoscale rutile RuO2 grains, self-organized in an amorphous Nb-O matrix, are observed, which is consistent with our theoretical predictions. This amorphous/crystalline interplay may be of importance for next generation of thermoelectric devices.

Studies of Copper, Silver, and Gold Cluster Anions: Evidence of Electronic Shell Structure.

NASA Astrophysics Data System (ADS)

Pettiette, Claire Lynn

A new Ultraviolet Magnetic Time-of-Flight Photoelectron Spectrometer (MTOFPES) has been developed for the study of the electronic structure of clusters produced in a pulsed supersonic molecular beam. This is the first technique which has been successful in probing the valence electronic states of metal clusters. The ultraviolet photoelectron spectra of negative cluster ions of the noble metals have been taken at several different photon energies. These are presented along with the electron affinity and HOMO-LUMO gap measurements for Cu_6^- to Cu_ {41}^-, using 4.66 eV and 6.42 eV detachment energies; Ag_3^- to Ag_{21}^-, using 6.42 eV detachment energy; and Au_3^ - to Au_{21}^-, using 6.42 eV and 7.89 eV detachment energies. The spectra provide the first detailed probes of the s valence electrons of the noble metal clusters. In addition, the 6.42 eV and 7.89 eV spectra probe the first one to two electron volts of the molecular orbitals of the d valence electrons of copper and gold clusters. The electron affinity and HOMO-LUMO gap measurements of the noble metal clusters agree with the predictions of the ellipsoidal shell model for mono-valent metal clusters. In particular, cluster numbers 8, 20, and 40--which correspond to the spherical shell closings of this model--have low electron affinities and large HOMO-LUMO gaps. The spectra of the gold cluster ions indicate that the molecular orbital energies of the cluster valence electrons are more widely spaced for gold than for copper or silver. This is to be expected for the heavy atom clusters when relativistic effects are taken into account.

Understanding boron through size-selected clusters: structure, chemical bonding, and fluxionality.

PubMed

Sergeeva, Alina P; Popov, Ivan A; Piazza, Zachary A; Li, Wei-Li; Romanescu, Constantin; Wang, Lai-Sheng; Boldyrev, Alexander I

2014-04-15

Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center-two-electron (2c-2e) σ bonds on the periphery and delocalized multicenter-two-electron (nc-2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron's electron deficiency and leads to fluxional behavior, which has been observed in B13(+) and B19(-). A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiation has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B(-), formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B(-)/C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors' laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.

Understanding Boron through Size-Selected Clusters: Structure, Chemical Bonding, and Fluxionality

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sergeeva, Alina P.; Popov, Ivan A.; Piazza, Zachary A.

Conspectus Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters are found to have planar or quasi-planar structures, stabilized by localized two-center–two-electron (2c–2e) σ bonds on the periphery and delocalized multicenter–two-electron (nc–2e) bonds in both σ and π frameworks. Electron delocalization is a result of boron’s electron deficiency and leads to fluxional behavior, which has been observed in B13+ and B19–. A unique capability of the in-plane rotation of the inner atoms against the periphery of the cluster in a chosen direction by employing circularly polarized infrared radiationmore » has been suggested. Such fluxional behaviors in boron clusters are interesting and have been proposed as molecular Wankel motors. The concepts of aromaticity and antiaromaticity have been extended beyond organic chemistry to planar boron clusters. The validity of these concepts in understanding the electronic structures of boron clusters is evident in the striking similarities of the π-systems of planar boron clusters to those of polycyclic aromatic hydrocarbons, such as benzene, naphthalene, coronene, anthracene, or phenanthrene. Chemical bonding models developed for boron clusters not only allowed the rationalization of the stability of boron clusters but also lead to the design of novel metal-centered boron wheels with a record-setting planar coordination number of 10. The unprecedented highly coordinated borometallic molecular wheels provide insights into the interactions between transition metals and boron and expand the frontier of boron chemistry. Another interesting feature discovered through cluster studies is boron transmutation. Even though it is well-known that B–, formed by adding one electron to boron, is isoelectronic to carbon, cluster studies have considerably expanded the possibilities of new structures and new materials using the B–/C analogy. It is believed that the electronic transmutation concept will be effective and valuable in aiding the design of new boride materials with predictable properties. The study of boron clusters with intermediate properties between those of individual atoms and bulk solids has given rise to a unique opportunity to broaden the frontier of boron chemistry. Understanding boron clusters has spurred experimentalists and theoreticians to find new boron-based nanomaterials, such as boron fullerenes, nanotubes, two-dimensional boron, and new compounds containing boron clusters as building blocks. Here, a brief and timely overview is presented addressing the recent progress made on boron clusters and the approaches used in the authors’ laboratories to determine the structure, stability, and chemical bonding of size-selected boron clusters by joint photoelectron spectroscopy and theoretical studies. Specifically, key findings on all-boron hydrocarbon analogues, metal-centered boron wheels, and electronic transmutation in boron clusters are summarized.« less

Atomic switch: atom/ion movement controlled devices for beyond von-neumann computers.

PubMed

Hasegawa, Tsuyoshi; Terabe, Kazuya; Tsuruoka, Tohru; Aono, Masakazu

2012-01-10

An atomic switch is a nanoionic device that controls the diffusion of metal ions/atoms and their reduction/oxidation processes in the switching operation to form/annihilate a conductive path. Since metal atoms can provide a highly conductive channel even if their cluster size is in the nanometer scale, atomic switches may enable downscaling to smaller than the 11 nm technology node, which is a great challenge for semiconductor devices. Atomic switches also possess novel characteristics, such as high on/off ratios, very low power consumption and non-volatility. The unique operating mechanisms of these devices have enabled the development of various types of atomic switch, such as gap-type and gapless-type two-terminal atomic switches and three-terminal atomic switches. Novel functions, such as selective volatile/nonvolatile, synaptic, memristive, and photo-assisted operations have been demonstrated. Such atomic switch characteristics can not only improve the performance of present-day electronic systems, but also enable development of new types of electronic systems, such as beyond von- Neumann computers. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Energy of Supported Metal Catalysts: From Single Atoms to Large Metal Nanoparticles

DOE PAGES

James, Trevor E.; Hemmingson, Stephanie L.; Campbell, Charles T.

2015-08-14

It is known that many catalysts consist of late transition metal nanoparticles dispersed across oxide supports. The chemical potential of the metal atoms in these particles correlate with their catalytic activity and long-term thermal stability. This chemical potential versus particle size across the full size range between the single isolated atom and bulklike limits is reported here for the first time for any metal on any oxide. The chemical potential of Cu atoms on CeO 2(111) surfaces, determined by single crystal adsorption calorimetry of gaseous Cu atoms onto slightly reduced CeO 2(111) at 100 and 300 K is shown tomore » decrease dramatically with increasing Cu cluster size. The Cu chemical potential is ~110 kJ/mol higher for isolated Cu adatoms on stoichometric terrace sites than for Cu in nanoparticles exceeding 2.5 nm diameter, where it reaches the bulk Cu(solid) limit. In Cu dimers, Cu’s chemical potential is ~57 kJ/mol lower at step edges than on stoichiometric terrace sites. Since Cu avoids oxygen vacancies, these monomer and dimer results are not strongly influenced by the 2.5% oxygen vacancies present on this CeO 2 surface and are thus considered representative of stoichiometric CeO 2(111) surfaces.« less

UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}: A ribbon structure containing a heterobimetallic 5d-5f M{sub 3} cluster

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wells, Daniel M.; Chan, George H.; Ellis, Donald E.

2010-02-15

A new solid-state compound containing a heterobimetallic cluster of U and Ta, UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6}, has been synthesized and its structure has been characterized by single-crystal X-ray diffraction methods. UTa{sub 2}O(S{sub 2}){sub 3}Cl{sub 6} was synthesized from UCl{sub 4} and Ta{sub 1.2}S{sub 2} at 883 K. The O is believed to have originated in the Ta{sub 1.2}S{sub 2} reactant. The compound crystallizes in the space group P1-bar of the triclinic system. The structure comprises a UTa{sub 2} unit bridged by mu{sub 2}-S{sub 2} and mu{sub 3}-O groups. Each Ta atom bonds to two mu{sub 2}-S{sub 2}, the mu{submore » 3}-O, and two terminal Cl atoms. Each U atom bonds to two mu{sub 2}-S{sub 2}, the mu{sub 3}-O, and four Cl atoms. The Cl atoms bridge in pairs to neighboring U atoms to form a ribbon structure. The bond distances are normal and are consistent with formal oxidation states of +IV/+V/-II/-I/-I for U/Ta/O/S/Cl, respectively. The optical absorbance spectrum displays characteristic transition peaks near the absorption edge. Density functional theory was used to assign these peaks to transitions between S{sup 1-} valence-band states and empty U 5f-6d hybrid bands. Density-of-states analysis shows overlap between Ta 5d and U bands, consistent with metal-metal interactions. - The UTa2O(S2)3Cl6 cluster with completed coordination sphere around uranium« less

Composite Reinforcement using Boron Nitride Nanotubes

DTIC Science & Technology

2014-05-09

while retaining the nanotube structure. This project involves the use of computational quantum chemistry to study interactions of aluminium (Al...small clusters of 1–4 metal atoms. The effect of varying the radius of the nanotubes and the size of aluminium and titanium clusters was considered...15. SUBJECT TERMS Boron Nitride Nanotubes, composite materials, Aluminum Alloys , Titanium Alloy , Theoretical Chemistry 16. SECURITY

Density-functional theory study of ionic inhomogeneity in metal clusters using SC-ISJM

NASA Astrophysics Data System (ADS)

Payami, Mahmoud; Mahmoodi, Tahereh

2017-12-01

In this work we have applied the recently formulated self-compressed inhomogeneous stabilized jellium model [51] to describe the equilibrium electronic and geometric properties of atomic-closed-shell simple metal clusters of AlN (N = 13, 19, 43, 55, 79, 87, 135, 141), NaN, and CsN (N = 9, 15, 27, 51, 59, 65, 89, 113). To validate the results, we have also performed first-principles pseudo-potential calculations and used them as our reference. In the model, we have considered two regions consisting of ;surface; and ;inner; ones, the border separating them being sharp. This generalization makes possible to decouple the relaxations of different parts of the system. The results show that the present model correctly predicts the size reductions seen in most of the clusters. It also predicts increase in size of some clusters, as observed from first-principles results. Moreover, the changes in inter-layer distances, being as contractions or expansions, are in good agreement with the atomic simulation results. For a more realistic description of the properties, it is possible to improve the method of choosing the surface thicknesses or generalize the model to include more regions than just two.

Metallothionein-like multinuclear clusters of mercury(II) and sulfur in peat

USGS Publications Warehouse

Nagy, K.L.; Manceau, A.; Gasper, J.D.; Ryan, J.N.; Aiken, G.R.

2011-01-01

Strong mercury(II)-sulfur (Hg-SR) bonds in natural organic matter, which influence mercury bioavailability, are difficult to characterize. We report evidence for two new Hg-SR structures using X-ray absorption spectroscopy in peats from the Florida Everglades with added Hg. The first, observed at a mole ratio of organic reduced S to Hg (Sred/Hg) between 220 and 1140, is a Hg4Sx type of cluster with each Hg atom bonded to two S atoms at 2.34 ?? and one S at 2.53 ??, and all Hg atoms 4.12 ?? apart. This model structure matches those of metal-thiolate clusters in metallothioneins, but not those of HgS minerals. The second, with one S atom at 2.34 ?? and about six C atoms at 2.97 to 3.28 ??, occurred at S red/Hg between 0.80 and 4.3 and suggests Hg binding to a thiolated aromatic unit. The multinuclear Hg cluster indicates a strong binding environment to cysteinyl sulfur that might impede methylation. Along with a linear Hg(SR)2 unit with Hg - S bond lengths of 2.34 ?? at Sred/Hg of about 10 to 20, the new structures support a continuum in Hg-SR binding strength in natural organic matter. ?? 2011 American Chemical Society.

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE PAGES

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.; ...

2015-07-02

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOFmore » node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.« less

Targeted Single-Site MOF Node Modification: Trivalent Metal Loading via Atomic Layer Deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, In Soo; Borycz, Joshua; Platero-Prats, Ana E.

Postsynthetic functionalization of metal organic frameworks (MOFs) enables the controlled, high-density incorporation of new atoms on a crystallographically precise framework. Leveraging the broad palette of known atomic layer deposition (ALD) chemistries, ALD in MOFs (AIM) is one such targeted approach to construct diverse, highly functional, few-atom clusters. In this paper, we demonstrate the saturating reaction of trimethylindium (InMe 3) with the node hydroxyls and ligated water of NU-1000, which takes place without significant loss of MOF crystallinity or internal surface area. We computationally identify the elementary steps by which trimethylated trivalent metal compounds (ALD precursors) react with this Zr-based MOFmore » node to generate a uniform and well characterized new surface layer on the node itself, and we predict a final structure that is fully consistent with experimental X-ray pair distribution function (PDF) analysis. Finally, we further demonstrate tunable metal loading through controlled number density of the reactive handles (–OH and –OH 2) achieved through node dehydration at elevated temperatures.« less

Comparative study of local atomic structures in Zr2CuxNi1-x (x = 0, 0.5, 1) metallic glasses

NASA Astrophysics Data System (ADS)

Huang, Yuxiang; Huang, Li; Wang, C. Z.; Kramer, M. J.; Ho, K. M.

2015-11-01

Extensive analysis has been performed to understand the key structural motifs accounting for the difference in glass forming ability in the Zr-Cu and Zr-Ni binary alloy systems. Here, the reliable atomic structure models of Zr2CuxNi1-x (x = 0, 0.5, 1) are constructed using the combination of X-ray diffraction experiments, ab initio molecular dynamics simulations and a constrained reverse Monte Carlo method. We observe a systematic variation of the interatomic distance of different atomic pairs with respect to the alloy composition. The ideal icosahedral content in all samples is limited, despite the high content of five-fold symmetry motifs. We also demonstrate that the population of Z-clusters in Zr2Cu glass is much higher than that in the Zr2Ni and Zr2Cu0.5Ni0.5 samples. And Z12 ⟨0, 0, 12, 0⟩ Voronoi polyhedra clusters prefer to form around Cu atoms, while Ni-centered clusters are more like Z11 ⟨0, 2, 8, 1⟩ clusters, which is less energetically stable compared to Z12 clusters. These two different structural properties may account for the higher glass forming ability of Zr2Cu alloy than that of Zr2Ni alloy.

Mass-invariance of the iron enrichment in the hot haloes of massive ellipticals, groups, and clusters of galaxies

NASA Astrophysics Data System (ADS)

Mernier, F.; de Plaa, J.; Werner, N.; Kaastra, J. S.; Raassen, A. J. J.; Gu, L.; Mao, J.; Urdampilleta, I.; Truong, N.; Simionescu, A.

2018-05-01

X-ray measurements find systematically lower Fe abundances in the X-ray emitting haloes pervading groups (kT ≲ 1.7 keV) than in clusters of galaxies. These results have been difficult to reconcile with theoretical predictions. However, models using incomplete atomic data or the assumption of isothermal plasmas may have biased the best fit Fe abundance in groups and giant elliptical galaxies low. In this work, we take advantage of a major update of the atomic code in the spectral fitting package SPEX to re-evaluate the Fe abundance in 43 clusters, groups, and elliptical galaxies (the CHEERS sample) in a self-consistent analysis and within a common radius of 0.1r500. For the first time, we report a remarkably similar average Fe enrichment in all these systems. Unlike previous results, this strongly suggests that metals are synthesised and transported in these haloes with the same average efficiency across two orders of magnitude in total mass. We show that the previous metallicity measurements in low temperature systems were biased low due to incomplete atomic data in the spectral fitting codes. The reasons for such a code-related Fe bias, also implying previously unconsidered biases in the emission measure and temperature structure, are discussed.

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

NASA Astrophysics Data System (ADS)

Liu, Siqi; Xu, Yi-Jun

2016-03-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters-TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability.

Single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers: Reactant- and stoichiometry-dependent syntheses, effective photocatalytic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinfang, E-mail: zjf260@jiangnan.edu.cn; Wang, Chao; Wang, Yinlin

2015-11-15

The systematic study on the reaction variables affecting single cyanide-bridged Mo(W)/S/Cu cluster-based coordination polymers (CPs) is firstly demonstrated. Five anionic single cyanide-bridged Mo(W)/S/Cu cluster-based CPs {[Pr_4N][WS_4Cu_3(CN)_2]}{sub n} (1), {[Pr_4N][WS_4Cu_4(CN)_3]}{sub n} (2), {[Pr_4N][WOS_3Cu_3(CN)_2]}{sub n} (3), {[Bu_4N][WOS_3Cu_3(CN)_2]}{sub n} (4) and {[Bu_4N][MoOS_3Cu_3(CN)_2]}{sub n} (5) were prepared by varying the molar ratios of the starting materials, and the specific cations, cluster building blocks and central metal atoms in the cluster building blocks. 1 possesses an anionic 3D diamondoid framework constructed from 4-connected T-shaped clusters [WS{sub 4}Cu{sub 3}]{sup +} and single CN{sup −} bridges. 2 is fabricated from 6-connected planar ‘open’ clusters [WS{sub 4}Cu{sub 4}]{supmore » 2+} and single CN{sup −} bridges, forming an anionic 3D architecture with an “ACS” topology. 3 and 4 exhibit novel anionic 2-D double-layer networks, both constructed from nest-shaped clusters [WOS{sub 3}Cu{sub 3}]{sup +} linked by single CN{sup −} bridges, but containing the different cations [Pr{sub 4}N]{sup +} and [Bu{sub 4}N]{sup +}, respectively. 5 is constructed from nest-shaped clusters [MoOS{sub 3}Cu{sub 3}]{sup +} and single CN{sup −} bridges, with an anionic 3D diamondoid framework. The anionic frameworks of 1-5, all sustained by single CN{sup −} bridges, are non-interpenetrating and exhibit huge potential void volumes. Employing differing molar ratios of the reactants and varying the cluster building blocks resulted in differing single cyanide-bridged Mo(W)/S/Cu cluster-based CPs, while replacing the cation ([Pr{sub 4}N]{sup +} vs. [Bu{sub 4}N]{sup +}) was found to have negligible impact on the nature of the architecture. Unexpectedly, replacement of the central metal atom (W vs. Mo) in the cluster building blocks had a pronounced effect on the framework. Furthermore, the photocatalytic activities of heterothiometallic cluster-based CPs were firstly explored by monitoring the photodegradation of methylene blue (MB) under visible light irradiation, which reveals that 2 exhibits effective photocatalytic properties. - Highlights: • Reaction variables affecting Mo(W)/S/Cu cluster-based CPs is firstly explored. • Replacing central metal atom had a pronounced effect on W/S/Cu cluster-based CPs. • Photocatalytic activities of Mo(W)/S/Cu cluster-based CPs are firstly investigated.« less

Polar Intermetallics Pr 5Co 2Ge 3 and Pr 7Co 2Ge 4 With Planar Hydrocarbon-Like Metal Clusters

DOE PAGES

Lin, Qisheng; Aguirre, Kaiser; Saunders, Scott M.; ...

2017-06-19

Planar hydrocarbon-like metal clusters may foster new insights linking organic molecules with conjugated π-π bonding interactions and inorganic structures in terms of their bonding characteristics. However, such clusters are uncommon in polar intermetallics. Herein, we report two polar intermetallic phases, Pr 5Co 2Ge 3 and Pr 7Co 2Ge 4, both of which feature such planar metal clusters, viz., ethylene-like [Co 2Ge 4] clusters plus the concatenated forms and polyacene-like [Co 2Ge 2] n ribbons in Pr 5Co 2Ge 3, and 1,2,4,5-tetramethylbenzene-like [Co4Ge6] cluster in Pr 7Co 2Ge 4. Just as in the related planar organic structures, these metal-metalloid species aremore » dominated by covalent bonding interactions. Both compounds magnetically order at low temperature with net ferromagnetic components: Pr 5Co 2Ge 3 via a series of transitions below 150 K; and Pr 7Co 2Ge 4 via a single ferromagnetic transition at 19 K. Spin-polarized electronic structure calculations for Pr 7Co 2Ge 4 reveal strong spin-orbit coupling within Pr and considerable magnetic contributions from Co atoms. This work suggests that similar structural chemistry can emerge for other rare earth-late transition metal-main group systems.« less

Structure of mono- and bimetallic heterogeneous catalysts based on noble metals obtained by means of fluid technology and metal-vapor synthesis

NASA Astrophysics Data System (ADS)

Said-Galiev, E. E.; Vasil'kov, A. Yu.; Nikolaev, A. Yu.; Lisitsyn, A. I.; Naumkin, A. V.; Volkov, I. O.; Abramchuk, S. S.; Lependina, O. L.; Khokhlov, A. R.; Shtykova, E. V.; Dembo, K. A.; Erkey, C.

2012-10-01

Monometallic nanocomposites are obtained with the use of supercritical carbon dioxide (fluid technique) and metal-vapor synthesis (MVS), while bimetallic nanocomposites of Pt and Au noble metals and γ-Al2O3 oxide matrix are synthesized by a combination of these two methods. The structures, concentrations, and chemical states of metal atoms in composites are studied by means of small-angle X-ray scattering (SAXS), transparent electron microscopy (TEM), X-ray fluorescent analysis (XFA), and X-ray photoelectron spectroscopy (XPS). The neutral state of metal atoms in clusters is shown by XPS and their size distribution is found according to SAXS; as is shown, it is determined by the pore sizes of the oxide matrices and lies in the range of 1 to 50 nm. The obtained composites manifest themselves as effective catalysts in the oxidation of CO to CO2.

Nanophase materials assembled from clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Siegel, R.W.

1992-02-01

The preparation of metal and ceramic atom clusters by means of the gas-condensation method, followed by their in situ collection and consolidation under high-vacuum conditions, has recently led to the synthesis of a new class of ultrafine-grained materials. These nanophase materials, with typical average grain sizes of 5 to 50 nm and, hence, a large fraction of their atoms in interfaces, exhibit properties that are often considerably improved relative to those of conventional materials. Furthermore, their synthesis and processing characteristics should enable the design of new materials with unique properties. Some examples are ductile ceramics that can be formed andmore » sintered to full density at low temperatures without the need for binding or sintering aids, and metals with dramatically increased strength. The synthesis of these materials is briefly described along with what is presently known of their structure and properties. Their future impact on materials science and technology is also considered.« less

Photo-induced transformation process at gold clusters-semiconductor interface: Implications for the complexity of gold clusters-based photocatalysis

PubMed Central

Liu, Siqi; Xu, Yi-Jun

2016-01-01

The recent thrust in utilizing atomically precise organic ligands protected gold clusters (Au clusters) as photosensitizer coupled with semiconductors for nano-catalysts has led to the claims of improved efficiency in photocatalysis. Nonetheless, the influence of photo-stability of organic ligands protected-Au clusters at the Au/semiconductor interface on the photocatalytic properties remains rather elusive. Taking Au clusters–TiO2 composites as a prototype, we for the first time demonstrate the photo-induced transformation of small molecular-like Au clusters to larger metallic Au nanoparticles under different illumination conditions, which leads to the diverse photocatalytic reaction mechanism. This transformation process undergoes a diffusion/aggregation mechanism accompanied with the onslaught of Au clusters by active oxygen species and holes resulting from photo-excited TiO2 and Au clusters. However, such Au clusters aggregation can be efficiently inhibited by tuning reaction conditions. This work would trigger rational structural design and fine condition control of organic ligands protected-metal clusters-semiconductor composites for diverse photocatalytic applications with long-term photo-stability. PMID:26947754

First-principles study of hydrogen adsorption in metal-doped COF-10

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu Miaomiao; Sun Qiang; Department of Physics, Virginia Commonwealth University, Richmond, Virginia 23284

2010-10-21

Covalent organic frameworks (COFs), due to their low-density, high-porosity, and high-stability, have promising applications in gas storage. In this study we have explored the potential of COFs doped with Li and Ca metal atoms for storing hydrogen under ambient thermodynamic conditions. Using density functional theory we have performed detailed calculations of the sites Li and Ca atoms occupy in COF-10 and their interaction with hydrogen molecules. The binding energy of Li atom on COF-10 substrate is found to be about 1.0 eV and each Li atom can adsorb up to three H{sub 2} molecules. However, at high concentration, Li atomsmore » cluster and, consequently, their hydrogen storage capacity is reduced due to steric hindrance between H{sub 2} molecules. On the other hand, due to charge transfer from Li to the substrate, O sites provide additional enhancement for hydrogen adsorption. With increasing concentration of doped metal atoms, the COF-10 substrate provides an additional platform for storing hydrogen. Similar conclusions are reached for Ca doped COF-10.« less

Medium-induced change of the optical response of metal clusters in rare-gas matrices

NASA Astrophysics Data System (ADS)

Xuan, Fengyuan; Guet, Claude

2017-10-01

Interaction with the surrounding medium modifies the optical response of embedded metal clusters. For clusters from about ten to a few hundreds of silver atoms, embedded in rare-gas matrices, we study the environment effect within the matrix random phase approximation with exact exchange (RPAE) quantum approach, which has proved successful for free silver clusters. The polarizable surrounding medium screens the residual two-body RPAE interaction, adds a polarization term to the one-body potential, and shifts the vacuum energy of the active delocalized valence electrons. Within this model, we calculate the dipole oscillator strength distribution for Ag clusters embedded in helium droplets, neon, argon, krypton, and xenon matrices. The main contribution to the dipole surface plasmon red shift originates from the rare-gas polarization screening of the two-body interaction. The large size limit of the dipole surface plasmon agrees well with the classical prediction.

Dissociation kinetics of metal clusters on multiple electronic states including electronic level statistics into the vibronic soup

NASA Astrophysics Data System (ADS)

Shvartsburg, Alexandre A.; Siu, K. W. Michael

2001-06-01

Modeling the delayed dissociation of clusters had been over the last decade a frontline development area in chemical physics. It is of fundamental interest how statistical kinetics methods previously validated for regular molecules and atomic nuclei may apply to clusters, as this would help to understand the transferability of statistical models for disintegration of complex systems across various classes of physical objects. From a practical perspective, accurate simulation of unimolecular decomposition is critical for the extraction of true thermochemical values from measurements on the decay of energized clusters. Metal clusters are particularly challenging because of the multitude of low-lying electronic states that are coupled to vibrations. This has previously been accounted for assuming the average electronic structure of a conducting cluster approximated by the levels of electron in a cavity. While this provides a reasonable time-averaged description, it ignores the distribution of instantaneous electronic structures in a "boiling" cluster around that average. Here we set up a new treatment that incorporates the statistical distribution of electronic levels around the average picture using random matrix theory. This approach faithfully reflects the completely chaotic "vibronic soup" nature of hot metal clusters. We found that the consideration of electronic level statistics significantly promotes electronic excitation and thus increases the magnitude of its effect. As this excitation always depresses the decay rates, the inclusion of level statistics results in slower dissociation of metal clusters.

Structural and chemical orders in N i 64.5 Z r 35.5 metallic glass by molecular dynamics simulation

DOE PAGES

Tang, L.; Wen, T. Q.; Wang, N.; ...

2018-03-06

The atomic structure of Ni 64.5Zr 35.5 metallic glass has been investigated by molecular dynamics (MD) simulations. The calculated structure factors from the MD glassy sample at room temperature agree well with the X-ray diffraction (XRD) and neutron diffraction (ND) experimental data. Using the pairwise cluster alignment and clique analysis methods, we show that there are three types dominant short-range order (SRO) motifs around Ni atoms in the glass sample of Ni 64.5Zr 35.5, i.e., Mixed- Icosahedron(ICO)-Cube, Twined-Cube and icosahedron-like clusters. Furthermore, chemical order and medium-range order (MRO) analysis show that the Mixed-ICOCube and Twined-Cube clusters exhibit the characteristics ofmore » the crystalline B2 phase. In conclusion, our simulation results suggest that the weak glass-forming ability (GFA) of Ni 64.5Zr 35.5 can be attributed to the competition between the glass forming ICO SRO and the crystalline Mixed-ICO-Cube and Twined-Cube motifs.« less

Structural and chemical orders in N i 64.5 Z r 35.5 metallic glass by molecular dynamics simulation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang, L.; Wen, T. Q.; Wang, N.

The atomic structure of Ni 64.5Zr 35.5 metallic glass has been investigated by molecular dynamics (MD) simulations. The calculated structure factors from the MD glassy sample at room temperature agree well with the X-ray diffraction (XRD) and neutron diffraction (ND) experimental data. Using the pairwise cluster alignment and clique analysis methods, we show that there are three types dominant short-range order (SRO) motifs around Ni atoms in the glass sample of Ni 64.5Zr 35.5, i.e., Mixed- Icosahedron(ICO)-Cube, Twined-Cube and icosahedron-like clusters. Furthermore, chemical order and medium-range order (MRO) analysis show that the Mixed-ICOCube and Twined-Cube clusters exhibit the characteristics ofmore » the crystalline B2 phase. In conclusion, our simulation results suggest that the weak glass-forming ability (GFA) of Ni 64.5Zr 35.5 can be attributed to the competition between the glass forming ICO SRO and the crystalline Mixed-ICO-Cube and Twined-Cube motifs.« less

Structural and chemical orders in N i64.5Z r35.5 metallic glass by molecular dynamics simulation

NASA Astrophysics Data System (ADS)

Tang, L.; Wen, T. Q.; Wang, N.; Sun, Y.; Zhang, F.; Yang, Z. J.; Ho, K. M.; Wang, C. Z.

2018-03-01

The atomic structure of N i64.5Z r35.5 metallic glass has been investigated by molecular dynamics (MD) simulations. The calculated structure factors from the MD glassy sample at room temperature agree well with the x-ray diffraction (XRD) and neutron diffraction (ND) experimental data. Using the pairwise cluster alignment and clique analysis methods, we show that there are three types of dominant short-range order (SRO) motifs around Ni atoms in the glass sample of N i64.5Z r35.5 , i.e., mixed-icosahedron(ICO)-cube, intertwined-cube, and icosahedronlike clusters. Furthermore, chemical order and medium-range order (MRO) analysis show that the mixed-ICO-cube and intertwined-cube clusters exhibit the characteristics of the crystalline B2 phase. Our simulation results suggest that the weak glass-forming ability (GFA) of N i64.5Z r35.5 can be attributed to the competition between the glass forming ICO SRO and the crystalline mixed-ICO-cube and intertwined-cube motifs.

The Preparation of an Ultrastable Mesoporous Cr(III)-MOF via Reductive Labilization

DTIC Science & Technology

2015-09-02

of metal clusters from a template MOF with a known structure. Fe(III)-MOFs can serve as practical structural templates because iron resembles chromium ...clusters in PCN-333 are able to accommodate both di- and trivalent metal ions by varying the charges of the terminal ligands, the bridging oxygen atoms, and...molecules in trivalent aqua complexes27 Inert complexes Labile complexes M(OH2) Cr(OH2)6 3+ Ir(OH2)6 3+ V(OH2)6 3+ Fe(OH2)6 3+ Ti(OH2)6 3+ k (s1) 2.4 10

Endohedral beryllium atoms in germanium clusters with eight and fewer vertices: how small can a cluster be and still encapsulate a central atom?

PubMed

Uţă, M M; King, R B

2012-05-31

Structures of the beryllium-centered germanium clusters Be@Ge(n)(z) (n = 8, 7, 6; z = -4, -2, 0, +2) have been investigated by density functional theory to provide some insight regarding the smallest metal cluster that can encapsulate an interstitial atom. The lowest energy structures of the eight-vertex Be@Ge(8)(z) clusters (z = -4, -2, 0, +2) all have the Be atom at the center of a closed polyhedron, namely, a D(4d) square antiprism for Be@Ge(8)(4-), a D(2d) bisdisphenoid for Be@Ge(8)(2-), an ideal O(h) cube for Be@Ge(8), and a C(2v) distorted cube for Be@Ge(8)(2+). The Be-centered cubic structures predicted for Be@Ge(8) and Be@Ge(8)(2+) differ from the previously predicted lowest energy structures for the isoelectronic Ge(8)(2-) and Ge(8). This appears to be related to the larger internal volume of the cube relative to other closed eight-vertex polyhedra. The lowest energy structures for the smaller seven- and six-vertex clusters Be@Ge(n)(z) (n = 7, 6; z = -4, -2, 0, +2) no longer have the Be atom at the center of a closed Ge(n) polyhedron. Instead, either the Ge(n) polyhedron has opened up to provide a larger volume for the Be atom or the Be atom has migrated to the surface of the polyhedron. However, higher energy structures are found in which the Be atom is located at the center of a Ge(n) (n = 7, 6) polyhedron. Examples of such structures are a centered C(2v) capped trigonal prismatic structure for Be@Ge(7)(2-), a centered D(5h) pentagonal bipyramidal structure for Be@Ge(7), a centered D(3h) trigonal prismatic structure for Be@Ge(6)(4-), and a centered octahedral structure for Be@Ge(6). Cluster buildup reactions of the type Be@Ge(n)(z) + Ge(2) → Be@Ge(n+2)(z) (n = 6, 8; z = -4, -2, 0, +2) are all predicted to be highly exothermic. This suggests that interstitial clusters having an endohedral atom inside a bare post transition element polyhedron with eight or fewer vertices are less than the optimum size. This is consistent with the experimental observation of several types of 10-vertex polyhedral bare post transition element clusters with interstitial atoms but the failure to observe such clusters with external polyhedra having eight or fewer vertices.

Photophysical characterization of fluorescent metal nanoclusters synthesized using oligonucleotides, proteins and small molecule ligands

NASA Astrophysics Data System (ADS)

Yeh, Hsin-Chih; Sharma, Jaswinder; Yoo, Hyojong; Martinez, Jennifer S.; Werner, James H.

2010-02-01

The size transition from bulk conducting metals to insulating nanoparticles and eventually to single atoms passes through the relatively unexplored few-atom nanocluster region. With dimensions close to the Fermi wavelength, these nanoclusters demonstrate molecule-like properties distinct from bulk metals or atoms, such as discrete and size-tunable electronic transitions which lead to photoluminescence. Current research aims to elucidate the fundamental photophysical properties of metal nanoclusters made by different means and based on different encapsulation agents. Here, we report the study of the photophysical properties, including quantum yields, lifetimes, extinction coefficients, blinking dynamics and sizes, of silver and gold nanoclusters synthesized using oligonucleotides, a protein (bovine serum albumin) and a Good's buffer molecule (MES, 2-(N-morpholino) ethanesulfonic acid) as encapsulation agents. We also investigate the change of photoluminescence as a function of temperature. Furthermore, we show that the fluorescent metal clusters can be used as a donor in forming a resonance energy transfer pair with a commercial organic quencher. These new fluorophores have great potential as versatile tools for a broad range of applications in biological and chemical detection.

The First Non-Dispersive High-Resolution Spectroscopy of an X-ray-bright Galaxy Cluster

NASA Astrophysics Data System (ADS)

Yamaguchi, Hiroya; Hitomi Collaboration

2018-06-01

The Hitomi X-ray Observatory was equipped with the Soft X-ray Spectrometer (SXS), an X-ray microcalorimeter that achieved an energy resolution of 5 eV (@0.5-10 keV) for extended objects. This offered an unprecedented benchmark of atomic modeling and database for hot collisional plasmas, revealing both successes and challenges in the current atomic codes that are widely used by the X-ray astronomy community. I will review the Hitomi observations of the brightest part of the Perseus Cluster, whose X-ray spectrum is dominated by thermal emission from the intra-cluster medium (ICM). The SXS successfully measured the turbulent velocities and metal abundances of the ICM, which radically altered our understanding of the dynamics and chemical enrichment in this object. At the same time, the high-resolution X-ray data led to significant improvement in the atomic models, such as AtomDB and SPEX -- I will briefly overview how this improvement was made. Nevertheless, there are still significant discrepancies among the public atomic models, causing systematic uncertainties in measurements of the temperature, abundance, and degree of the resonance scattering. Requirements for future improvements will be summarized in this context.

Bimetallic Catalysts.

ERIC Educational Resources Information Center

Sinfelt, John H.

1985-01-01

Chemical reaction rates can be controlled by varying composition of miniscule clusters of metal atoms. These bimetallic catalysts have had major impact on petroleum refining, where work has involved heterogeneous catalysis (reacting molecules in a phase separate from catalyst.) Experimentation involving hydrocarbon reactions, catalytic…

Cooling rate dependence of structural order in Al90Sm10 metallic glass

NASA Astrophysics Data System (ADS)

Sun, Yang; Zhang, Yue; Zhang, Feng; Ye, Zhuo; Ding, Zejun; Wang, Cai-Zhuang; Ho, Kai-Ming

2016-07-01

The atomic structure of Al90Sm10 metallic glass is studied using molecular dynamics simulations. By performing a long sub-Tg annealing, we developed a glass model closer to the experiments than the models prepared by continuous cooling. Using the cluster alignment method, we found that "3661" cluster is the dominating short-range order in the glass samples. The connection and arrangement of "3661" clusters, which define the medium-range order in the system, are enhanced significantly in the sub-Tg annealed sample as compared with the fast cooled glass samples. Unlike some strong binary glass formers such as Cu64.5Zr35.5, the clusters representing the short-range order do not form an interconnected interpenetrating network in Al90Sm10, which has only marginal glass formability.

Metal cluster chemistry: Structure and stereochemistry in the polynuclear rhodium hydrides HnRhn[P(OR)3]2n

PubMed Central

Brown, R. K.; Williams, J. M.; Fredrich, M. F.; Day, V. W.; Sivak, A. J.; Muetterties, E. L.

1979-01-01

Crystallographic analyses of x-ray and neutron diffraction data have provided a definitive structural representation of {HRh[P(O-i-C3H7)3]2}2 and {HRh[P(OCH3)3]2}3. These polynuclear hydrides are generated from square planar H2Rh[P(OR)3]2 units by edge (hydrogen atom) sharing and by vertex (hydrogen atom) sharing to form the dimeric and trimeric structures, respectively. The square-planar units are held together through four-center and three-center two-electron Rh—H—Rh bonds in the dimer and trimer, respectively. The dimer and trimer molecules each add one molecule of hydrogen to form H[(i-C3H7O)3P]2RhH3Rh [P(O-i-C3H7)3]2 and H5Rh3[P(OCH3)3]6, respectively. NMR spectral information has served to define the stereochemical features of these polyhydrides. The significance of this chemistry in the metal cluster-metal surface analogy is described. PMID:16592645

An ab initio cluster study of the chemisorption of atomic cesium and hydrogen on reconstructed surfaces of gallium rich gallium arsenide

NASA Astrophysics Data System (ADS)

Schailey, Ronald

1999-11-01

Chemisorption properties of cesium and hydrogen atoms on the Ga-rich GaAs (100) (2 x 1), (2 x 2), and β(4 x 2) surfaces are investigated using ab initio self-consistent restricted open shell Hartree-Fock (ROHF) total energy calculations with Hay- Wadt effective core potentials. The effects of electron correlation have been included using many-body perturbation theory through second order, with the exception of β(4 x 2) symmetry due to computational limitations. The semiconductor surface is modeled by finite sized hydrogen saturated clusters. The effects of surface relaxation and reconstruction have been investigated in detail. Results are given for the energetics of chemisorption, charge population analysis, HOMO-LUMO gaps, and consequent possibilities of metallization for atomic cesium adsorption. For the chemisorption of atomic hydrogen, the experimentally verified mechanism of surface dimer bond breaking is investigated in detail.

Pd n Ag (4-n) and Pd n Pt (4-n) clusters on MgO (100): a density functional surface genetic algorithm investigation

DOE PAGES

Heard, Christopher J.; Heiles, Sven; Vajda, Stefan; ...

2014-08-07

We employed the novel surface mode of the Birmingham Cluster Genetic Algorithm (S-BCGA) for the global optimisation of noble metal tetramers upon an MgO(100) substrate at the GGA-DFT level of theory. The effect of element identity and alloying in surface-bound neutral subnanometre clusters is determined by energetic comparison between all compositions of Pd nAg (4-n) and Pd nPt (4-n). And while the binding strengths to the surface increase in the order Pt > Pd > Ag, the excess energy profiles suggest a preference for mixed clusters for both cases. The binding of CO is also modelled, showing that the adsorptionmore » site can be predicted solely by electrophilicity. Comparison to CO binding on a single metal atom shows a reversal of the 5s-d activation process for clusters, weakening the cluster surface interaction on CO adsorption. Charge localisation determines homotop, CO binding and surface site preferences. Furthermore, the electronic behaviour, which is intermediate between molecular and metallic particles allows for tunable features in the subnanometre size range.« less

Melting and Freezing of Metal Clusters

NASA Astrophysics Data System (ADS)

Aguado, Andrés; Jarrold, Martin F.

2011-05-01

Recent developments allow heat capacities to be measured for size-selected clusters isolated in the gas phase. For clusters with tens to hundreds of atoms, the heat capacities determined as a function of temperature usually have a single peak attributed to a melting transition. The melting temperatures and latent heats show large size-dependent fluctuations. In some cases, the melting temperatures change by hundreds of degrees with the addition of a single atom. Theory has played a critical role in understanding the origin of the size-dependent fluctuations, and in understanding the properties of the liquid-like and solid-like states. In some cases, the heat capacities have extra features (an additional peak or a dip) that reveal a more complex behavior than simple melting. In this article we provide a description of the methods used to measure the heat capacities and provide an overview of the experimental and theoretical results obtained for sodium and aluminum clusters.

Study of methods to increase cluster/dislocation loop densities in electrodes

NASA Astrophysics Data System (ADS)

Yang, Xiaoling; Miley, George H.

2009-03-01

Recent research has developed a technique for imbedding ultra-high density deuterium ``clusters'' (50 to 100 atoms per cluster) in various metals such as Palladium (Pd), Beryllium (Be) and Lithium (Li). It was found the thermally dehydrogenated PdHx retained the clusters and exhibited up to 12 percent lower resistance compared to the virginal Pd samplesootnotetextA. G. Lipson, et al. Phys. Solid State. 39 (1997) 1891. SQUID measurements showed that in Pd these condensed matter clusters approach metallic conditions, exhibiting superconducting propertiesootnotetextA. Lipson, et al. Phys. Rev. B 72, 212507 (2005ootnotetextA. G. Lipson, et al. Phys. Lett. A 339, (2005) 414-423. If the fabrication methods under study are successful, a large packing fraction of nuclear reactive clusters can be developed in the electrodes by electrolyte or high pressure gas loading. This will provide a much higher low-energy-nuclear- reaction (LENR) rate than achieved with earlier electrodeootnotetextCastano, C.H., et al. Proc. ICCF-9, Beijing, China 19-24 May, 2002..

The role of electronegativity on the extent of nitridation of group 5 metals as revealed by reactions of tantalum cluster cations with ammonia molecules.

PubMed

Arakawa, Masashi; Ando, Kota; Fujimoto, Shuhei; Mishra, Saurabh; Patwari, G Naresh; Terasaki, Akira

2018-05-10

Reactions of the free tantalum cation, Ta+, and tantalum cluster cations, Tan+ (n = 2-10), with ammonia are presented. The reaction of the monomer cation, Ta+, with two molecules of NH3 leads to the formation of TaN2H2+ along with release of two H2 molecules. The dehydrogenation occurs until the formal oxidation number of the tantalum atom reaches +5. On the other hand, all the tantalum cluster cations, Tan+, react with two molecules of NH3 and form TanN2+ with the release of three H2 molecules. Further exposure to ammonia showed that TanNmH+ and TanNm+ are produced through successive reactions; a pure nitride and three H2 molecules are formed for every other NH3 molecule. The nitridation occurred until the formal oxidation number of the tantalum atoms reaches +5 as in the case of TaN2H2+ in contrast to other group 5 elements, i.e., vanadium and niobium, which have been reported to produce nitrides with lower oxidation states. The present results on small gas-phase metal-nitride clusters show correlation with their bulk properties: tantalum is known to form bulk nitrides in the oxidation states of either +5 (Ta3N5) or +3 (TaN), whereas vanadium and niobium form nitrides in the oxidation state of +3 (VN and NbN). Along with DFT calculations, these findings reveal that nitridation is driven by the electron-donating ability of group 5 elements, i.e., electronegativity of the metal plays a key role in determining the composition of the metal nitrides.

Effect of pressure on β relaxation in La60Ni15Al25 metallic glass

NASA Astrophysics Data System (ADS)

Xu, H. Y.; Sheng, H. W.; Li, M. Z.

2018-03-01

The effect of pressure on β relaxation in La60Ni15Al25 metallic glass (MG) was investigated by activation-relaxation technique in combination with molecular dynamics simulation. It is found that the β relaxation behavior and the potential energy landscape are significantly modulated by pressure. With increasing pressure, the atomic motion in β relaxation in La60Ni15Al25 MG changes from hopping-dominated to the string-like-dominated motion with increased activation energy. Moreover, while the hopping motion is gradually suppressed as pressure is increased, the cooperative rearrangements with more atoms involved but very low activation energies are significantly enhanced by pressure. It is further found that the "subbasins" in the potential energy landscape in La60Ni15Al25 MG become deeper and steeper with increasing pressure, leading to the increase of activation energy. Meanwhile, some neighboring "subbasins" merge under pressure accompanied by the disappearance of energy barriers in-between, leading to events with very low activation energies in the β relaxation. The atomic structure analysis reveals that the transformation of atomic motions in β relaxation in La60Ni15Al25 MG under pressure is strongly correlated with the decrease of pentagon-rich atomic clusters and the increase of clusters with fewer pentagons. These findings provide a new understanding of the β relaxation mechanism and some clues for tuning β relaxation in MGs.

Thermal and adsorbate effects on the activity and morphology of size-selected Pdn/TiO2 model catalysts

NASA Astrophysics Data System (ADS)

Kaden, William E.; Kunkel, William A.; Roberts, F. Sloan; Kane, Matthew; Anderson, Scott L.

2014-03-01

Model catalysts containing size-selected Pdn (n = 1,2,4,7,10,16,20,25) deposited on rutile TiO2(110) deactivate during repeated CO oxidation temperature-programmed reaction (TPR) cycles, and the deactivation process has been probed using a combination of X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), low-energy ion scattering (ISS), temperature-dependent ion scattering (TD-ISS), annealing experiments, and temperature-programmed desorption following exposure to CO and O2 reactants. Results from such experiments suggest the cluster deactivation proceeds via an alloy-like, strong metal-support interaction (SMSI) effect that chemically modifies the clusters via electronic interactions between the supported metal atoms and Ti from the support. Threshold measurements show that this effect detrimentally affects CO-oxidation activity prior to the formation of an encapsulating overlayer by severely weakening the COPd bond strengths for binding configurations on top of the clusters. Oxidation appears to provide means of partially restoring the clusters to their initial state, but after sufficient exposure to reducing environments and elevated temperatures, all Pdn become covered by an overlayer and begin to electronically and chemically resemble freshly deposited atoms, which are completely inactive towards the probe reaction. In addition, we find evidence of oxygen spillover induced by co-adsorbed CO during TPRs for all active Pdn clusters.

Phosphorus vacancy cluster model for phosphorus diffusion gettering of metals in Si

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Renyu; Trzynadlowski, Bart; Dunham, Scott T.

2014-02-07

In this work, we develop models for the gettering of metals in silicon by high phosphorus concentration. We first performed ab initio calculations to determine favorable configurations of complexes involving phosphorus and transition metals (Fe, Cu, Cr, Ni, Ti, Mo, and W). Our ab initio calculations found that the P{sub 4}V cluster, a vacancy surrounded by 4 nearest-neighbor phosphorus atoms, which is the most favorable inactive P species in heavily doped Si, strongly binds metals such as Cu, Cr, Ni, and Fe. Based on the calculated binding energies, we build continuum models to describe the P deactivation and Fe getteringmore » processes with model parameters calibrated against experimental data. In contrast to previous models assuming metal-P{sub 1}V or metal-P{sub 2}V as the gettered species, the binding of metals to P{sub 4}V satisfactorily explains the experimentally observed strong gettering behavior at high phosphorus concentrations.« less

UTa 2O(S 2) 3Cl 6: A ribbon structure containing a heterobimetallic 5 d-5 f M 3 cluster

NASA Astrophysics Data System (ADS)

Wells, Daniel M.; Chan, George H.; Ellis, Donald E.; Ibers, James A.

2010-02-01

A new solid-state compound containing a heterobimetallic cluster of U and Ta, UTa 2O(S 2) 3Cl 6, has been synthesized and its structure has been characterized by single-crystal X-ray diffraction methods. UTa 2O(S 2) 3Cl 6 was synthesized from UCl 4 and Ta 1.2S 2 at 883 K. The O is believed to have originated in the Ta 1.2S 2 reactant. The compound crystallizes in the space group P1¯ of the triclinic system. The structure comprises a UTa 2 unit bridged by μ 2-S 2 and μ 3-O groups. Each Ta atom bonds to two μ 2-S 2, the μ 3-O, and two terminal Cl atoms. Each U atom bonds to two μ 2-S 2, the μ 3-O, and four Cl atoms. The Cl atoms bridge in pairs to neighboring U atoms to form a ribbon structure. The bond distances are normal and are consistent with formal oxidation states of +IV/+V/-II/-I/-I for U/Ta/O/S/Cl, respectively. The optical absorbance spectrum displays characteristic transition peaks near the absorption edge. Density functional theory was used to assign these peaks to transitions between S 1- valence-band states and empty U 5 f-6 d hybrid bands. Density-of-states analysis shows overlap between Ta 5 d and U bands, consistent with metal-metal interactions.

Vapor-liquid-solid mechanisms: Challenges for nanosized quantum cluster/dot/wire materials

NASA Astrophysics Data System (ADS)

Cheyssac, P.; Sacilotti, M.; Patriarche, G.

2006-08-01

The growth mechanism model of a nanoscaled material is a critical step that has to be refined for a better understanding of a nanostructure's dot/wire fabrication. To do so, the growth mechanism will be discussed in this paper and the influence of the size of the metallic nanocluster starting point, referred to later as "size effect," will be studied. Among many of the so-called size effects, a tremendous decrease of the melting point of the metallic nanocluster changes the physical properties as well as the physical/mechanical interactions inside the growing structure composed of a metallic dot on top of a column. The thermodynamic size effect is related to the bending or curvature of chains of atoms, giving rise to the weakening of bonds between them; this size or curvature effect is described and approached to crystal nanodot/wire growth. We will describe this effect as that of a "cooking machine" when the number of atoms decreases from ˜1023at./cm3 for a bulk material to a few tens of them in a 1-2nm diameter sphere. The decrease of the number of atoms in a metallic cluster from such an enormous quantity is accompanied by a lowering of the melting temperature that extends from 200 up to 1000K, depending on the metallic material and its size under study. In this respect, the vapor-liquid-solid (VLS) model, which is the most utilized growth mechanism for quantum nanowires and nanodots, is critically exposed to size or curvature effects (CEs). More precisely, interactions in the vicinity of the growth regions should be reexamined. Some results illustrating the growth of micrometer-/nanometer-sized materials are presented in order to corroborate the CE/VLS models utilized by many research groups in today's nanosciences world. Examples of metallic clusters and semiconducting wires will be presented. The results and comments presented in this paper can be seen as a challenge to be overcome. From them, we expect that in a near future an improved model can be exposed to the scientific community.

Understanding the Cu-Zn brass alloys using a short-range-order cluster model: significance of specific compositions of industrial alloys

PubMed Central

Hong, H. L.; Wang, Q.; Dong, C.; Liaw, Peter K.

2014-01-01

Metallic alloys show complex chemistries that are not yet understood so far. It has been widely accepted that behind the composition selection lies a short-range-order mechanism for solid solutions. The present paper addresses this fundamental question by examining the face-centered-cubic Cu-Zn α-brasses. A new structural approach, the cluster-plus-glue-atom model, is introduced, which suits specifically for the description of short-range-order structures in disordered systems. Two types of formulas are pointed out, [Zn-Cu12]Zn1~6 and [Zn-Cu12](Zn,Cu)6, which explain the α-brasses listed in the American Society for Testing and Materials (ASTM) specifications. In these formulas, the bracketed parts represent the 1st-neighbor cluster, and each cluster is matched with one to six 2nd-neighbor Zn atoms or with six mixed (Zn,Cu) atoms. Such a cluster-based formulism describes the 1st- and 2nd-neighbor local atomic units where the solute and solvent interactions are ideally satisfied. The Cu-Ni industrial alloys are also explained, thus proving the universality of the cluster-formula approach in understanding the alloy selections. The revelation of the composition formulas for the Cu-(Zn,Ni) industrial alloys points to the common existence of simple composition rules behind seemingly complex chemistries of industrial alloys, thus offering a fundamental and practical method towards composition interpretations of all kinds of alloys. PMID:25399835

Understanding the Cu-Zn brass alloys using a short-range-order cluster model: Significance of specific compositions of industrial alloys

DOE PAGES

Hong, H. L.; Wang, Q.; Dong, C.; ...

2014-11-17

Metallic alloys show complex chemistries that are not yet understood so far. It has been widely accepted that behind the composition selection lies a short-range-order mechanism for solid solutions. The present paper addresses this fundamental question by examining the face-centered-cubic Cu-Zn α-brasses. A new structural approach, the cluster-plus-glue-atom model, is introduced, which suits specifically for the description of short-range-order structures in disordered systems. Two types of formulas are pointed out, [Zn-Cu 12]Zn 1~6 and [Zn-Cu 12](Zn,Cu) 6, which explain the α-brasses listed in the American Society for Testing and Materials (ASTM) specifications. In these formulas, the bracketed parts represent themore » 1 st-neighbor cluster, and each cluster is matched with one to six 2 nd-neighbor Zn atoms or with six mixed (Zn,Cu) atoms. Such a cluster-based formulism describes the 1 st- and 2 nd-neighbor local atomic units where the solute and solvent interactions are ideally satisfied. The Cu-Ni industrial alloys are also explained, thus proving the universality of the cluster-formula approach in understanding the alloy selections. As a result, the revelation of the composition formulas for the Cu-(Zn,Ni) industrial alloys points to the common existence of simple composition rules behind seemingly complex chemistries of industrial alloys, thus offering a fundamental and practical method towards composition interpretations of all kinds of alloys.« less

Local atomic order of a metallic glass made visible by scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Luo, Yuansu; Samwer, Konrad

2018-06-01

Exploring the atomic level structure in amorphous materials by STM becomes extremely difficult due to the localized electronic states. Here we carried out STM studies on a quasi-low-dimensional film of metallic glass Zr65Cu27.5Al7.5 which is ‘ultrathin’ compared with the localization length and/or the length scale of short range order. The local electronic structure must appear more inherent, having states at E f available for tip-sample tunneling current. To enhance imaging contrasts between long-range and short-range orders, the highly oriented pyrolytic graphite was chosen as substrate, so that the structural heterogeneity arising from competition between the glass former ability and the epitaxy can be ascertained. A chemical order predicted for this system was observed in atomic ordered regimes (1–2 monolayers), accompanied with a superstructure with the period Zr–Cu(Al)–Zr along three hexagonal axes. The result implies a chemical short range order in disordered regimes, where polyhedral clusters are dominant with the solute atom Cu(Al) in the center. An attempt for the structural modelling was made based on high resolution STM images, giving icosahedral order on the surface and different Voronoi clusters in 3D space.

Molecular vibrations in metal-single-molecule-metal junctions

NASA Astrophysics Data System (ADS)

Yokota, Kazumichi; Taniguchi, Masateru; Kawai, Tomoji

2010-03-01

Molecular vibrations in a metal-single-molecule-metal junction were studied based on density functional theory using a single benzenedithiolate molecule connected between gold clusters. We found that the difference in vibrational energy between an isolated benzenedithiol and the single-molecule junction is less than 3% in the energy range above 540 cm -1, where sulfur atoms contribute little to molecular vibrations. The finding implies that we can predict the peak energy in the inelastic electron tunneling spectrum of the single-molecule junction in the high energy range by vibrational analyses of isolated molecules.

Graphene/MoS2 heterostructures as templates for growing two-dimensional metals: Predictions from ab initio calculations

NASA Astrophysics Data System (ADS)

Šljivančanin, Željko; Belić, Milivoj

2017-09-01

Preparation of single-atom-thick layers of ordinary metals has been a challenging task since their closely packed atoms lack layered structure with highly anisotropic bonding. Using computational modeling based on density functional theory we showed that graphene/MoS2 heterostructures can be used as suitable templates to grow stable two-dimensional (2D) clusters, as well as extended monoatomic layers of metals with nonlayered structure in the bulk. Considering gold and lithium as two metals with markedly different properties, we found that Li intercalants strengthen coupling between graphene (G) and MoS2, mainly due to electrostatic attraction of 2D materials with positively charged Li atoms. However, intercalation with large Au atoms gives rise to a significant increase in the distance between G and MoS2 and thus, weakens their interaction. In addition to strong preference for 2D growth, we demonstrated that Au intercalants weakly interact with both G and MoS2, and hence G /MoS2 vertical heterostructures could be a promising framework to prepare gold 2D structures with electronic properties closely resembling those of the hypothetical free-standing hexagonal gold monolayer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Qisheng; Aguirre, Kaiser; Saunders, Scott M.

Planar hydrocarbon-like metal clusters may foster new insights linking organic molecules with conjugated π-π bonding interactions and inorganic structures in terms of their bonding characteristics. However, such clusters are uncommon in polar intermetallics. Herein, we report two polar intermetallic phases, Pr 5Co 2Ge 3 and Pr 7Co 2Ge 4, both of which feature such planar metal clusters, viz., ethylene-like [Co 2Ge 4] clusters plus the concatenated forms and polyacene-like [Co 2Ge 2] n ribbons in Pr 5Co 2Ge 3, and 1,2,4,5-tetramethylbenzene-like [Co4Ge6] cluster in Pr 7Co 2Ge 4. Just as in the related planar organic structures, these metal-metalloid species aremore » dominated by covalent bonding interactions. Both compounds magnetically order at low temperature with net ferromagnetic components: Pr 5Co 2Ge 3 via a series of transitions below 150 K; and Pr 7Co 2Ge 4 via a single ferromagnetic transition at 19 K. Spin-polarized electronic structure calculations for Pr 7Co 2Ge 4 reveal strong spin-orbit coupling within Pr and considerable magnetic contributions from Co atoms. This work suggests that similar structural chemistry can emerge for other rare earth-late transition metal-main group systems.« less

A bronze matryoshka: the discrete intermetalloid cluster [Sn@Cu12@Sn20](12-) in the ternary phases A12Cu12Sn21 (A = Na, K).

PubMed

Stegmaier, Saskia; Fässler, Thomas F

2011-12-14

The synthesis and crystal structure of the first ternary A-Cu-Sn intermetallic phases for the heavier alkali metals A = Na to Cs is reported. The title compounds A(12)Cu(12)Sn(21) show discrete 33-atom intermetalloid Cu-Sn clusters {Sn@Cu(12)@Sn(20)}, which are composed of {Sn(20)} pentagonal dodecahedra surrounding {Cu(12)} icosahedra with single Sn atoms at the center. Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21) were characterized by single-crystal XRD studies, and the successful synthesis of analogous A-Cu-Sn compounds with A = Rb and Cs is deduced from powder XRD data. The isotypic A(12)Cu(12)Sn(21) phases crystallize in the cubic space group Pn ̅3m (No. 224), with the Cu-Sn clusters adopting a face centered cubic arrangement. A formal charge of 12- can be assigned to the {Sn@Cu(12)@Sn(20)} cluster unit, and the interpretation of the title compounds as salt-like intermetallic phases featuring discrete anionic intermetalloid [Sn@Cu(12)@Sn(20)](12-) clusters separated by alkali metal cations is supported by electronic structure calculations. For both Na(12)Cu(12)Sn(21) and K(12)Cu(12)Sn(21), DFT band structure calculations (TB-LMTO-ASA) reveal a band gap. The discrete [Sn@Cu(12)@Sn(20)](12-) cluster is analyzed in consideration of the molecular orbitals obtained from hybrid DFT calculations (Gaussian 09) for the cluster anion. The [Sn@Cu(12)@Sn(20)](12-) cluster MOs can be classified with labels indicating the numbers of radial and angular nodes, in the style of spherical shell models of cluster bonding. © 2011 American Chemical Society

C 60 as a chemical Faraday cage for three ferromagnetic Fe atoms

NASA Astrophysics Data System (ADS)

Gao, Guohua; Kang, Hong Seok

2008-09-01

Based on calculations using density functional theory, we show that C 60 can act as a chemical Faraday cage in which a highly magnetic metal cluster with a high chemical reactivity can be encapsulated. As an example, we find that C 60 can encapsulate a Fe 3 cluster, while it is much less likely to encapsulate a Fe 2 cluster. Spin multiplicity (=9) of the Fe 3@C 60 is very high, being comparable to that (=11) of a free Fe 3 cluster. Geometrically, the triangular plane of the cluster is perpendicular to a S6 axis of the fullerene.

Community-level physiological profiles of microorganisms inhabiting soil contaminated with heavy metals

NASA Astrophysics Data System (ADS)

Kuźniar, Agnieszka; Banach, Artur; Stępniewska, Zofia; Frąc, Magdalena; Oszust, Karolina; Gryta, Agata; Kłos, Marta; Wolińska, Agnieszka

2018-01-01

The aim of the study was to assess the differences in the bacterial community physiological profiles in soils contaminated with heavy metals versus soils without metal contaminations. The study's contaminated soil originated from the surrounding area of the Szopienice non-ferrous metal smelter (Silesia Region, Poland). The control was soil unexposed to heavy metals. Metal concentration was appraised by flame atomic absorption spectrometry, whereas the the community-level physiological profile was determined with the Biolog EcoPlatesTM system. The soil microbiological activity in both sites was also assessed via dehydrogenase activity. The mean concentrations of metals (Cd and Zn) in contaminated soil samples were in a range from 147.27 to 12265.42 mg kg-1, and the heavy metal contamination brought about a situation where dehydrogenase activity inhibition was observed mostly in the soil surface layers. Our results demonstrated that there is diversity in the physiological profiles of microorganisms inhabiting contaminated and colntrol soils; therefore, for assessment purposes, these were treated as two clusters. Cluster I included colntrol soil samples in which microbial communities utilised most of the available substrates. Cluster II incorporated contaminated soil samples in which a smaller number of the tested substrates was utilised by the contained microorganisms. The physiological profiles of micro-organisms inhabiting the contaminated and the colntrol soils are distinctly different.

Magnetic nanostructures.

PubMed

Bennemann, K

2010-06-23

Characteristic results of magnetism in small particles, thin films and tunnel junctions are presented. As a consequence of the reduced atomic coordination in small clusters and thin films the electronic states and density of states are modified. Thus, magnetic moments and magnetization are affected. Generally, in clusters and thin films magnetic anisotropy plays a special role. In tunnel junctions the interplay of magnetism, spin currents and superconductivity are of particular interest. In ring-like mesoscopic systems Aharonov-Bohm-induced currents are studied. Results are given for single transition metal clusters, cluster ensembles, thin films, mesoscopic structures and tunnel systems. © 2010 IOP Publishing Ltd

Application of Density Functional Theory to Systems Containing Metal Atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.

2006-01-01

The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+n, MNO+, and MCO+2. The DFT works well for frequencies and geometries, even in case with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of successes as well as failures of DFT will be given.

Mass Spectroscopy of Neutral Metal Oxide Clusters Using a Desk-Top Soft X-Ray Laser

NASA Astrophysics Data System (ADS)

Dong, F.; Heinbuch, S.; Bernstein, E. R.; Rocca, J. J.

We report the use of a compact 46.9 nm capillary discharge soft x-ray laser in the study of metal-oxide nanoclusters using mass spectroscopy. Transition metal oxides are widely used as heterogeneous catalysts and catalytic supports in industrial processes. There are numerous applications for transition metal oxide catalysts, and although they are widely used, there is a lack of fundamental understanding of the complicated processes that occur on the metal oxide surface during catalysis. Conventional nanocluster spectroscopy techniques have used 193 nm radiation from an ArF excimer laser corresponding to a photon energy of 6.4 eV in order to photoionize a sample. Typical metal oxide nanocluster ionization energies fall into the range of 7-12 eV while some have even higher energies. Therefore a single 6.4 eV photon can not ionize the cluster making multiphoton processes the dominant ionization method. A major problem associated with mass spectroscopy can become evident during the multiphoton ionization of clusters. Specifically, the clusters may fragment during the ionization process and the identification of the neutral parent cluster can become difficult. In the present experiment neutral vanadium, niobium and tantalum oxide clusters are studied by single photon ionization with the 26.5 eV photons produced by a capillary discharge soft x-ray laser.1 During ionization, the metal oxide clusters are observed to be almost free of serious fragmentation. The most stable neutral cluster of vanadium, niobium, and tantalum oxide growth in a saturated oxygen condition are identified as MO2, M2O4/M2O5, M3O7, M4O10, M5O12, M6O15, M7O17, M8O20, and M9O22, which can be represented as a form (MO2)0,1(M2O5)y. M2O5 is identified as a basic unit to build-up the three kinds of metal oxide clusters. In the case of niobium and tantalum oxide clusters, the oxygen-deficient clusters with a structure of (MO2)2(M2O5)y are detected for groups that contain an even number of metal atoms. For vanadium oxide clusters, the oxygen-deficient clusters are detected for every family, indicating a stable structure of (VO2)x(V2O5)y. The stoichiometry of oxygen-rich clusters can be expressed as (MO2)0,1(M2O5)yO1-3 and their structures are consistent with chemically bonded species.

Determining whether metals nucleate homogeneously on graphite: A case study with copper

DOE PAGES

Appy, David; Lei, Huaping; Han, Yong; ...

2014-11-05

In this study, we observe that Cu clusters grow on surface terraces of graphite as a result of physical vapor deposition in ultrahigh vacuum. We show that the observation is incompatible with a variety of models incorporating homogeneous nucleation and calculations of atomic-scale energetics. An alternative explanation, ion-mediated heterogeneous nucleation, is proposed and validated, both with theory and experiment. This serves as a case study in identifying when and whether the simple, common observation of metal clusters on carbon-rich surfaces can be interpreted in terms of homogeneous nucleation. We describe a general approach for making system-specific and laboratory-specific predictions.

Cooling rate dependence of structural order in Al 90Sm 10 metallic glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yang; Zhang, Yue; Zhang, Feng

2016-07-07

Here, the atomic structure of Al 90Sm 10 metallic glass is studied using molecular dynamics simulations. By performing a long sub-T g annealing, we developed a glass model closer to the experiments than the models prepared by continuous cooling. Using the cluster alignment method, we found that “3661” cluster is the dominating short-range order in the glass samples. The connection and arrangement of “3661” clusters, which define the medium-range order in the system, are enhanced significantly in the sub-T g annealed sample as compared with the fast cooled glass samples. Unlike some strong binary glass formers such as Cu 64.5Zrmore » 35.5, the clusters representing the short-range order do not form an interconnected interpenetrating network in Al 90Sm 10, which has only marginal glass formability.« less

Cooling rate dependence of structural order in Al{sub 90}Sm{sub 10} metallic glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yang; Ames Laboratory, US Department of Energy, Ames, Iowa 50011; Zhang, Yue

2016-07-07

The atomic structure of Al{sub 90}Sm{sub 10} metallic glass is studied using molecular dynamics simulations. By performing a long sub-T{sub g} annealing, we developed a glass model closer to the experiments than the models prepared by continuous cooling. Using the cluster alignment method, we found that “3661” cluster is the dominating short-range order in the glass samples. The connection and arrangement of “3661” clusters, which define the medium-range order in the system, are enhanced significantly in the sub-T{sub g} annealed sample as compared with the fast cooled glass samples. Unlike some strong binary glass formers such as Cu{sub 64.5}Zr{sub 35.5},more » the clusters representing the short-range order do not form an interconnected interpenetrating network in Al{sub 90}Sm{sub 10,} which has only marginal glass formability.« less

Ferromagnetism and spin glass ordering in transition metal alloys (invited)

NASA Astrophysics Data System (ADS)

Crane, S.; Carnegie, D. W., Jr.; Claus, H.

1982-03-01

Magnetic properties of transition metal alloys near the percolation threshold are often complicated by metallurgical effects. Alloys like AuFe, VFe, CuNi, RhNi, and PdNi are in general not random solid solutions but have various degrees of atomic clustering or short-range order (SRO), depending on the heat treatment. First, it is shown how the magnetic ordering temperature of these alloys varies with the degree of clustering or SRO. Second, by systematically changing this degree of clustering or SRO, important information can be obtained about the magnetic phase diagram. In all these alloys below the percolation limit, the onset of ferromagnetic order is probably preceded by a spin glass-type ordering. However, details of the magnetic phase diagram near the critical point can be quite different alloy systems.

The role of charge transfer in the oxidation state change of Ce atoms in the TM13-CeO2(111) systems (TM = Pd, Ag, Pt, Au): a DFT + U investigation.

PubMed

Tereshchuk, Polina; Freire, Rafael L H; Ungureanu, Crina G; Seminovski, Yohanna; Kiejna, Adam; Da Silva, Juarez L F

2015-05-28

Despite extensive studies of transition metal (TM) clusters supported on ceria (CeO2), fundamental issues such as the role of the TM atoms in the change in the oxidation state of Ce atoms are still not well understood. In this work, we report a theoretical investigation based on static and ab initio molecular dynamics density functional theory calculations of the interaction of 13-atom TM clusters (TM = Pd, Ag, Pt, Au) with the unreduced CeO2(111) surface represented by a large surface unit cell and employing Hubbard corrections for the strong on-site Coulomb correlation in the Ce f-electrons. We found that the TM13 clusters form pyramidal-like structures on CeO2(111) in the lowest energy configurations with the following stacking sequence, TM/TM4/TM8/CeO2(111), while TM13 adopts two-dimensional structures at high energy structures. TM13 induces a change in the oxidation state of few Ce atoms (3 of 16) located in the topmost Ce layer from Ce(IV) (itinerant Ce f-states) to Ce(III) (localized Ce f-states). There is a charge flow from the TM atoms to the CeO2(111) surface, which can be explained by the electronegativity difference between the TM (Pd, Ag, Pt, Au) and O atoms, however, the charge is not uniformly distributed on the topmost O layer due to the pressure induced by the TM13 clusters on the underlying O ions, which yields a decrease in the ionic charge of the O ions located below the cluster and an increase in the remaining O ions. Due to the charge flow mainly from the TM8-layer to the topmost O-layer, the charge cannot flow from the Ce(IV) atoms to the O atoms with the same magnitude as in the clean CeO2(111) surface. Consequently, the effective cationic charge decreases mainly for the Ce atoms that have a bond with the O atoms not located below the cluster, and hence, those Ce atoms change their oxidation state from IV to III. This increases the size of the Ce(III) compared with the Ce(IV) cations, which builds-in a strain within the topmost Ce layer, and hence, also affecting the location of the Ce(III) cations and the structure of the TM13 clusters.

Structural and electronic properties for atomic clusters

NASA Astrophysics Data System (ADS)

Sun, Yan

We have studied the structural and electronic properties for different groups of atomic clusters by doing a global search on the potential energy surface using the Taboo Search in Descriptors Space (TSDS) method and calculating the energies with Kohn-Sham Density Functional Theory (KS-DFT). Our goal was to find the structural and electronic principles for predicting the structure and stability of clusters. For Ben (n = 3--20), we have found that the evolution of geometric and electronic properties with size reflects a change in the nature of the bonding from van der Waals to metallic and then bulk-like. The cluster sizes with extra stability agree well with the predictions of the jellium model. In the 4d series of transition metal (TM) clusters, as the d-type bonding becomes more important, the preferred geometric structure changes from icosahedral (Y, Zr), to distorted compact structures (Nb, Mo), and FCC or simple cubic crystal fragments (Tc, Ru, Rh) due to the localized nature of the d-type orbital. Analysis of relative isomer energies and their electronic density of states suggest that these clusters tend to follow a maximum hardness principle (MHP). For A4B12 clusters (A is divalent, B is monovalent), we found unusually large (on average 1.95 eV) HOMO-LUMO gap values. This shows the extra stability at an electronic closed shell (20 electrons) predicted by the jellium model. The importance of symmetry, closed electronic and ionic shells in stability is shown by the relative stability of homotops of Mg4Ag12 which also provides support for the hypothesis that clusters that satisfy more than one stability criterion ("double magic") should be particularly stable.

Two-dimensional triangular lattice and its application to lithium-intercalated layered compounds

NASA Astrophysics Data System (ADS)

Decerqueira, R. O.

1982-08-01

Good rechargeable batteries are being searched for use in electric vehicles and in energy storage during off-peak consumption periods and from solar sources. The interest in lithium intercalation compounds has been recently enhanced by the search for such batteries. The process of intercalation of lithium in several transition metal dichalcogenides can provide an emf of several volts. The progress achieved in the last decade in the investigation of these intercalates has been facilitated by the availability of the dichalcogenides as single crystals and by their chemical stability. The transition-metal dichalcogenides and their Li-intercalates are studied, with emphasis on the Li/su xTa/sub yTi/sub l-y/S2 series. The interactions between the Li atoms and the applicability of a lattice gas model to the problem of ordering of these atoms is discussed. A formulation is presented of the cluster-variation aproximation to the lattice gas problem. The single-site and the nearest-neighbor triangle basic clusters are considered as models for Li/sub x TiS2. Also a theory is presented for the effects of a random distribution of different species of host atoms, as in Ta/sub y/Ti/sub l-y/S2.

Molecular dynamics simulations with electronic stopping can reproduce experimental sputtering yields of metals impacted by large cluster ions

NASA Astrophysics Data System (ADS)

Tian, Jiting; Zhou, Wei; Feng, Qijie; Zheng, Jian

2018-03-01

An unsolved problem in research of sputtering from metals induced by energetic large cluster ions is that molecular dynamics (MD) simulations often produce sputtering yields much higher than experimental results. Different from the previous simulations considering only elastic atomic interactions (nuclear stopping), here we incorporate inelastic electrons-atoms interactions (electronic stopping, ES) into MD simulations using a friction model. In this way we have simulated continuous 45° impacts of 10-20 keV C60 on a Ag(111) surface, and found that the calculated sputtering yields can be very close to the experimental results when the model parameter is appropriately assigned. Conversely, when we ignore the effect of ES, the yields are much higher, just like the previous studies. We further expand our research to the sputtering of Au induced by continuous keV C60 or Ar100 bombardments, and obtain quite similar results. Our study indicates that the gap between the experimental and the simulated sputtering yields is probably induced by the ignorance of ES in the simulations, and that a careful treatment of this issue is important for simulations of cluster-ion-induced sputtering, especially for those aiming to compare with experiments.

Energetics of charged metal clusters containing vacancies

NASA Astrophysics Data System (ADS)

Pogosov, Valentin V.; Reva, Vitalii I.

2018-01-01

We study theoretically large metal clusters containing vacancies. We propose an approach, which combines the Kohn-Sham results for monovacancy in a bulk of metal and analytical expansions in small parameters cv (relative concentration of vacancies) and RN,v -1, RN ,v being cluster radii. We obtain expressions of the ionization potential and electron affinity in the form of corrections to electron work function, which require only the characteristics of 3D defect-free metal. The Kohn-Sham method is used to calculate the electron profiles, ionization potential, electron affinity, electrical capacitance; dissociation, cohesion, and monovacancy-formation energies of the small perfect clusters NaN, MgN, AlN (N ≤ 270) and the clusters containing a monovacancy (N ≥ 12) in the stabilized-jellium model. The quantum-sized dependences for monovacancy-formation energies are calculated for the Schottky scenario and the "bubble blowing" scenario, and their asymptotic behavior is also determined. It is shown that the asymptotical behaviors of size dependences for these two mechanisms differ from each other and weakly depend on the number of atoms in the cluster. The contribution of monovacancy to energetics of charged clusters and the size dependences of their characteristics and asymptotics are discussed. It is shown that the difference between the characteristics for the neutral and charged clusters is entirely determined by size dependences of ionization potential and electron affinity. Obtained analytical dependences may be useful for the analysis of the results of photoionization experiments and for the estimation of the size dependences of the vacancy concentration including the vicinity of the melting point.

Single d-metal atoms on F(s) and F(s+) defects of MgO(001): a theoretical study across the periodic table.

PubMed

Neyman, Konstantin M; Inntam, Chan; Matveev, Alexei V; Nasluzov, Vladimir A; Rösch, Notker

2005-08-24

Single d-metal atoms on oxygen defects F(s) and F(s+) of the MgO(001) surface were studied theoretically. We employed an accurate density functional method combined with cluster models, embedded in an elastic polarizable environment, and we applied two gradient-corrected exchange-correlation functionals. In this way, we quantified how 17 metal atoms from groups 6-11 of the periodic table (Cu, Ag, Au; Ni, Pd, Pt; Co, Rh, Ir; Fe, Ru, Os; Mn, Re; and Cr, Mo, W) interact with terrace sites of MgO. We found bonding with F(s) and F(s+) defects to be in general stronger than that with O2- sites, except for Mn-, Re-, and Fe/F(s) complexes. In M/F(s) systems, electron density is accumulated on the metal center in a notable fashion. The binding energy on both kinds of O defects increases from 3d- to 4d- to 5d-atoms of a given group, at variance with the binding energy trend established earlier for the M/O2- complexes, 4d < 3d < 5d. Regarding the evolution of the binding energy along a period, group 7 atoms are slightly destabilized compared to their group 6 congeners in both the F(s) and F(s+) complexes; for later transition elements, the binding energy increases gradually up to group 10 and finally decreases again in group 11, most strongly on the F(s) site. This trend is governed by the negative charge on the adsorbed atoms. We discuss implications for an experimental detection of metal atoms on oxide supports based on computed core-level energies.

The Herschel Virgo Cluster Survey - XVI. A cluster inventory

NASA Astrophysics Data System (ADS)

Davies, J. I.; Bianchi, S.; Baes, M.; Bendo, G. J.; Clemens, M.; De Looze, I.; di Serego Alighieri, S.; Fritz, J.; Fuller, C.; Pappalardo, C.; Hughes, T. M.; Madden, S.; Smith, M. W. L.; Verstappen, J.; Vlahakis, C.

2014-03-01

Herschel far-infrared (FIR) observations are used to construct Virgo cluster galaxy luminosity functions and to show that the cluster lacks the very bright and the numerous faint sources detected in field galaxy surveys. The FIR spectral energy distributions are fitted to obtain dust masses and temperatures and the dust mass function. The cluster is overdense in dust by about a factor of 100 compared to the field. The same emissivity (β)-temperature relation applies for different galaxies as that found for different regions of M31. We use optical and H I data to show that Virgo is overdense in stars and atomic gas by about a factor of 100 and 20, respectively. Metallicity values are used to measure the mass of metals in the gas phase. The mean metallicity is ˜0.7 solar, and ˜50 per cent of the metals are in the dust. For the cluster as a whole, the mass density of stars in galaxies is eight times that of the gas and the gas mass density is 130 times that of the metals. We use our data to consider the chemical evolution of the individual galaxies, inferring that the measured variations in the effective yield are due to galaxies having different ages, being affected to varying degrees by gas loss. Four galaxy scaling relations are considered: mass-metallicity, mass-velocity, mass-star formation rate and mass-radius - we suggest that initial galaxy mass is the prime driver of a galaxy's ultimate destiny. Finally, we use X-ray observations and galaxy dynamics to assess the dark and baryonic matter content compared to the cosmological model.

From Single Atoms to Nanoparticles — Spectroscopy on the Atomic Level

NASA Astrophysics Data System (ADS)

Nilius, Niklas

2003-12-01

The scanning tunneling microscope is not only a well-established tool for a topographic characterization of the sample surface on the atomic scale. It also provides a variety of spectroscopic techniques to examine electronic, magnetic, vibrational and optical properties of a localized system. The following presentation gives an overview, how scanning tunneling spectroscopy, inelastic electron tunneling spectroscopy and photon emission spectroscopy with the STM can be employed to investigate spatially confined metal systems and their interaction with molecular gases. The experiments were performed on single Pd and Au atoms, mono-atomic chains and individual Ag clusters on a NiAl support and a Al2O3 thin film.

The Gaia-ESO Survey: evidence of atomic diffusion in M67?

NASA Astrophysics Data System (ADS)

Bertelli Motta, C.; Pasquali, A.; Richer, J.; Michaud, G.; Salaris, M.; Bragaglia, A.; Magrini, L.; Randich, S.; Grebel, E. K.; Adibekyan, V.; Blanco-Cuaresma, S.; Drazdauskas, A.; Fu, X.; Martell, S.; Tautvaišienė, G.; Gilmore, G.; Alfaro, E. J.; Bensby, T.; Flaccomio, E.; Koposov, S. E.; Korn, A. J.; Lanzafame, A. C.; Smiljanic, R.; Bayo, A.; Carraro, G.; Casey, A. R.; Costado, M. T.; Damiani, F.; Franciosini, E.; Heiter, U.; Hourihane, A.; Jofré, P.; Lardo, C.; Lewis, J.; Monaco, L.; Morbidelli, L.; Sacco, G. G.; Sousa, S. G.; Worley, C. C.; Zaggia, S.

2018-07-01

Investigating the chemical homogeneity of stars born from the same molecular cloud at virtually the same time is very important for our understanding of the chemical enrichment of the interstellar medium and with it the chemical evolution of the Galaxy. One major cause of inhomogeneities in the abundances of open clusters is stellar evolution of the cluster members. In this work, we investigate variations in the surface chemical composition of member stars of the old open cluster M67 as a possible consequence of atomic diffusion effects taking place during the main-sequence phase. The abundances used are obtained from high-resolution UVES/FLAMES spectra within the framework of the Gaia-ESO Survey. We find that the surface abundances of stars on the main sequence decrease with increasing mass reaching a minimum at the turn-off. After deepening of the convective envelope in subgiant branch stars, the initial surface abundances are restored. We found the measured abundances to be consistent with the predictions of stellar evolutionary models for a cluster with the age and metallicity of M67. Our findings indicate that atomic diffusion poses a non-negligible constraint on the achievable precision of chemical tagging methods.

The Gaia-ESO Survey: Evidence of atomic diffusion in M67?

NASA Astrophysics Data System (ADS)

Motta, C. Bertelli; Pasquali, A.; Richer, J.; Michaud, G.; Salaris, M.; Bragaglia, A.; Magrini, L.; Randich, S.; Grebel, E. K.; Adibekyan, V.; Blanco-Cuaresma, S.; Drazdauskas, A.; Fu, X.; Martell, S.; TautvaišienÄ--, G.; Gilmore, G.; Alfaro, E. J.; Bensby, T.; Flaccomio, E.; Koposov, S. E.; Korn, A. J.; Lanzafame, A. C.; Smiljanic, R.; Bayo, A.; Carraro, G.; Casey, A. R.; Costado, M. T.; Damiani, F.; Franciosini, E.; Heiter, U.; Hourihane, A.; Jofré, P.; Lardo, C.; Lewis, J.; Monaco, L.; Morbidelli, L.; Sacco, G. G.; Sousa, S. G.; Worley, C. C.; Zaggia, S.

2018-04-01

Investigating the chemical homogeneity of stars born from the same molecular cloud at virtually the same time is very important for our understanding of the chemical enrichment of the interstellar medium and with it the chemical evolution of the Galaxy. One major cause of inhomogeneities in the abundances of open clusters is stellar evolution of the cluster members. In this work, we investigate variations in the surface chemical composition of member stars of the old open cluster M67 as a possible consequence of atomic diffusion effects taking place during the main-sequence phase. The abundances used are obtained from high-resolution UVES/FLAMES spectra within the framework of the Gaia-ESO Survey. We find that the surface abundances of stars on the main sequence decrease with increasing mass reaching a minimum at the turn-off. After deepening of the convective envelope in sub-giant branch stars, the initial surface abundances are restored. We found the measured abundances to be consistent with the predictions of stellar evolutionary models for a cluster with the age and metallicity of M67. Our findings indicate that atomic diffusion poses a non-negligible constraint on the achievable precision of chemical tagging methods.

Reactions of Metal-Metal Multiple Bonds. 14. Synthesis and Characterization of Triangulo-W3 and Mo2W-oxo Capped Alkoxide Clusters. Comproportionation of M-M Triple Bonds, sigma(2)pi(4) and d(o) Metal-oxo Groups: M Triple Bond M + M Triple Bond O Yields M3(micron 3-O).

DTIC Science & Technology

1984-05-02

the syntheses of dinuclear and trinuclear complexes employing metal -alkylidyne or -alkylidene fragments.8 Reaction 1 also has a parallel with the...1 0 which was previously examined. The mixed metal complex is undoubtedly disordered with respect to the disposition of molybdenum and tungsten atoms...than for the analogous Mo3 complex suggests greater metal - metal overlap and possibly stronger bonding interactions in the W3 complex which would not

Modeling of the HiPco process for carbon nanotube production. II. Reactor-scale analysis

NASA Technical Reports Server (NTRS)

Gokcen, Tahir; Dateo, Christopher E.; Meyyappan, M.

2002-01-01

The high-pressure carbon monoxide (HiPco) process, developed at Rice University, has been reported to produce single-walled carbon nanotubes from gas-phase reactions of iron carbonyl in carbon monoxide at high pressures (10-100 atm). Computational modeling is used here to develop an understanding of the HiPco process. A detailed kinetic model of the HiPco process that includes of the precursor, decomposition metal cluster formation and growth, and carbon nanotube growth was developed in the previous article (Part I). Decomposition of precursor molecules is necessary to initiate metal cluster formation. The metal clusters serve as catalysts for carbon nanotube growth. The diameter of metal clusters and number of atoms in these clusters are some of the essential information for predicting carbon nanotube formation and growth, which is then modeled by the Boudouard reaction with metal catalysts. Based on the detailed model simulations, a reduced kinetic model was also developed in Part I for use in reactor-scale flowfield calculations. Here this reduced kinetic model is integrated with a two-dimensional axisymmetric reactor flow model to predict reactor performance. Carbon nanotube growth is examined with respect to several process variables (peripheral jet temperature, reactor pressure, and Fe(CO)5 concentration) with the use of the axisymmetric model, and the computed results are compared with existing experimental data. The model yields most of the qualitative trends observed in the experiments and helps to understanding the fundamental processes in HiPco carbon nanotube production.

Electronic structure of clathrates Bax@AlySi46-y ; thermoelectric devices

NASA Astrophysics Data System (ADS)

Eguchi, Haruki; Nagano, Takatoshi; Takenaka, Hiroyuki; Tsumuraya, Kazuo

2002-03-01

Clathrates have received much attention as a candidate of high performance thermoelectric devices. This is because they have a) low thermal conductivity due to rattle effect of the alkali or heavy alkali-earth metals such as Ba atoms in the cages of clusters of the clathrates, and b) adjustablity of the Fermi levels through replacement of frame Si atoms with acceptor Al atoms and addition of the cage atoms as donors. We present the dispersion curves with LDA and GGA approximations for the exchange correlation of electrons using the planewave based pseudopotential methods and predict the electronic properties of the clathrates.

Defect charge states in Si doped hexagonal boron-nitride monolayer

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Molepo, M. P.; Andrew, R. C.; Chetty, N.

2016-02-01

We perform ab initio density functional theory calculations to investigate the energetics, electronic and magnetic properties of isolated stoichiometric and non-stoichiometric substitutional Si complexes in a hexagonal boron-nitride monolayer. The Si impurity atoms substituting the boron atom sites SiB giving non-stoichiometric complexes are found to be the most energetically favourable, and are half-metallic and order ferromagnetically in the neutral charge state. We find that the magnetic moments and magnetization energies increase monotonically when Si defects form a cluster. Partial density of states and standard Mulliken population analysis indicate that the half-metallic character and magnetic moments mainly arise from the Si 3p impurity states. The stoichiometric Si complexes are energetically unfavorable and non-magnetic. When charging the energetically favourable non-stoichiometric Si complexes, we find that the formation energies strongly depend on the impurity charge states and Fermi level position. We also find that the magnetic moments and orderings are tunable by charge state modulation q  =  -2, -1, 0, +1, +2. The induced half-metallic character is lost (retained) when charging isolated (clustered) Si defect(s). This underlines the potential of a Si doped hexagonal boron-nitride monolayer for novel spin-based applications.

Nanosheet Supported Single-Metal Atom Bifunctional Catalyst for Overall Water Splitting.

PubMed

Ling, Chongyi; Shi, Li; Ouyang, Yixin; Zeng, Xiao Cheng; Wang, Jinlan

2017-08-09

Nanosheet supported single-atom catalysts (SACs) can make full use of metal atoms and yet entail high selectivity and activity, and bifunctional catalysts can enable higher performance while lowering the cost than two separate unifunctional catalysts. Supported single-atom bifunctional catalysts are therefore of great economic interest and scientific importance. Here, on the basis of first-principles computations, we report a design of the first single-atom bifunctional eletrocatalyst, namely, isolated nickel atom supported on β 12 boron monolayer (Ni 1 /β 12 -BM), to achieve overall water splitting. This nanosheet supported SAC exhibits remarkable electrocatalytic performance with the computed overpotential for oxygen/hydrogen evolution reaction being just 0.40/0.06 V. The ab initio molecular dynamics simulation shows that the SAC can survive up to 800 K elevated temperature, while enacting a high energy barrier of 1.68 eV to prevent isolated Ni atoms from clustering. A viable experimental route for the synthesis of Ni 1 /β 12 -BM SAC is demonstrated from computer simulation. The desired nanosheet supported single-atom bifunctional catalysts not only show great potential for achieving overall water splitting but also offer cost-effective opportunities for advancing clean energy technology.

Observation of novel photochemistry in the multiphoton ionization of Mo(CO) sub 6 van der Waals clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Peifer, W.R.; Garvey, J.F.

1989-07-27

van der Waals clusters of Mo(CO){sub 6} generated in the free-jet expansion of a pulsed beam of seeded helium are subjected to multiphoton ionization and the product ions analyzed by quadrupole mass spectrometry. Oxomolybdenum and dioxomolybdenum ions are observed to be produced with high efficiency. This behavior is in striking contrast to that of metal carbonyl monomers and covalently bound cluster carbonyls, which under complete ligand loss prior to ionization. The observed photochemistry is ascribed to reactions between a photoproduced molybdenum atom and the ligands of neighboring Mo(CO){sub 6} solvent molecules within the van der Waals cluster.

Ab initio simulations of the structure, energetics and mobility of radiation-induced point defects in bcc Nb

NASA Astrophysics Data System (ADS)

Cerdeira, M. A.; Palacios, S. L.; González, C.; Fernández-Pello, D.; Iglesias, R.

2016-09-01

The formation, binding and migration energetics of helium clusters inside a niobium crystal have been analysed via ab initio simulations. The effect of placing several He atoms within an n-vacancy previously formed or as interstitials inside the initial perfect bulk matrix has been studied. DFT-based results show that He atoms prefer to aggregate forming small clusters at n-vacancy sites rather than at interstitial positions in the perfect crystal. The minimum formation energy is found when NHe is equal to the number of vacancies, n. It follows that vacancies act as almost perfect traps for He atoms, as is well known for other metals. The migration barriers of He atoms inside vacancies increase considerably when compared to what happens for vacancies alone. A secondary consequence is that the full set of energies obtained will be highly relevant as an input for new approaches to KMC simulations of defects in Nb.

Mn doped InSb studied at the atomic scale by cross-sectional scanning tunneling microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mauger, S. J. C.; Bocquel, J.; Koenraad, P. M., E-mail: p.m.koenraad@tue.nl

2015-11-30

We present an atomically resolved study of metal-organic vapor epitaxy grown Mn doped InSb. Both topographic and spectroscopic measurements have been performed by cross-sectional scanning tunneling microscopy (STM). The measurements on the Mn doped InSb samples show a perfect crystal structure without any precipitates and reveal that Mn acts as a shallow acceptor. The Mn concentration of the order of ∼10{sup 20 }cm{sup −3} obtained from the cross-sectional STM data compare well with the intended doping concentration. While the pair correlation function of the Mn atoms showed that their local distribution is uncorrelated beyond the STM resolution for observing individual dopants,more » disorder in the Mn ion location giving rise to percolation pathways is clearly noted. The amount of clustering that we see is thus as expected for a fully randomly disordered distribution of the Mn atoms and no enhanced clustering or second phase material was observed.« less

Molecular dynamics simulation of metallic impurity diffusion in liquid lead-bismuth eutectic (LBE)

NASA Astrophysics Data System (ADS)

Gao, Yun; Takahashi, Minoru; Cavallotti, Carlo; Raos, Guido

2018-04-01

Corrosion of stainless steels by lead-bismuth eutectic (LBE) is an important problem which depends, amongst other things, on the diffusion of the steel components inside this liquid alloy. Here we present the results of classical molecular dynamics simulations of the diffusion of Fe and Ni within LBE. The simulations complement experimental studies of impurity diffusion by our group and provide an atomic-level understanding of the relevant diffusion phenomena. They are based on the embedded atom method (EAM) to represent many-body interactions among atoms. The EAM potentials employed in our simulations have been validated against ab initio density functional calculations. We show that the experimental and simulation results for the temperature-dependent viscosity of LBE and the impurity diffusion coefficients can be reconciled by assuming that the Ni and Fe diffuse mainly as nanoscopic clusters below 1300 K. The average Fe and Ni cluster sizes decrease with increasing the temperature and there is essentially single-atom diffusion at higher temperatures.

Fe-S Clusters Emerging as Targets of Therapeutic Drugs

PubMed Central

2017-01-01

Fe-S centers exhibit strong electronic plasticity, which is of importance for insuring fine redox tuning of protein biological properties. In accordance, Fe-S clusters are also highly sensitive to oxidation and can be very easily altered in vivo by different drugs, either directly or indirectly due to catabolic by-products, such as nitric oxide species (NOS) or reactive oxygen species (ROS). In case of metal ions, Fe-S cluster alteration might be the result of metal liganding to the coordinating sulfur atoms, as suggested for copper. Several drugs presented through this review are either capable of direct interaction with Fe-S clusters or of secondary Fe-S clusters alteration following ROS or NOS production. Reactions leading to Fe-S cluster disruption are also reported. Due to the recent interest and progress in Fe-S biology, it is very likely that an increasing number of drugs already used in clinics will emerge as molecules interfering with Fe-S centers in the near future. Targeting Fe-S centers could also become a promising strategy for drug development. PMID:29445445

Synthesis and Structure of an Extended Cluster Lead(II) Carboxylate, [Pb{(CO)(9)Co(3)(&mgr;(3)-CCO(2))}(2)](n)(). Role of Core Metals in Cluster-Derived Hydrogenation Catalysts.

PubMed

Lei, Xinjian; Shang, Maoyu; Patil, Atul; Wolf, Eduardo E.; Fehlner, Thomas P.

1996-05-22

The reaction of lead acetate with (CO)(9)Co(3)(&mgr;(3)-CCOOH) leads to the formation of [Pb{(CO)(9)Co(3)(&mgr;(3)-CCO(2))}(2)](n)(), I, in high yield. The structure of I exhibits unusual six-coordinate Pb(II) centers with two asymmetrical chelating cluster carboxylates (C(22)Co(6)PbO(22); triclinic P&onemacr;; a = 8.119(1), b = 14.346(2), c = 14.660(2) Å; alpha = 102.18(1), beta = 99.01(1), gamma = 97.30(1) degrees; Z = 2). One oxygen of each cluster carboxylate ligand bridges between adjacent lead atoms such that a chainlike extended structure is found in the solid state without the presence of solvent or water. I is converted stepwise on pyrolysis into two metastable forms of solid materials (designated LT and HT), each of which has been characterized spectroscopically. The hydrogenation of 2-butenal as a test reaction shows that the LT catalyst exhibits selectivities similar to previous LT materials derived from other cobalt cluster metal carboxylates and that the HT material is totally inactive. The observed release of the lead core metal under HT activation conditions totally inactivates the catalyst and demonstrates exposure of the core metal in the HT form of these novel catalysts.

Enhanced Electromagnetic and Chemical/Biological Sensing. Properties of Atomic Cluster-Derived Materials

DTIC Science & Technology

2003-02-24

electron injection at interfaces, analysis of the voltage dependence of the electrostatic potential across molecules, the nature of binding at the...nanoscale titania into a metallic surface), analysis of the so-called band lineup between the molecular levels and the Fermi levels of the metal...observe the CNT’s in the electron microscope with the possibility to manipulate them externally and to apply potentials to them. These new

Two molecular wheels 12-MC-6 complexes: Synthesis, structure and magnetic property of [Co(μ{sub 2}-SEt){sub 2}]{sub 6} and [Fe(μ{sub 2}-SEt){sub 2}]{sub 6}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Jing; Jian, Fangfang, E-mail: ffj2003@163169.net; Huang, Baoxin

2013-08-15

The syntheses and structures of two ethyl mercaptan molecular wheels complexes, [M(μ{sub 2}-SCH{sub 2}CH{sub 3}){sub 2}]{sub 6} (M=Fe, Co), have been reported. Each metal atom is surrounded by four S atoms of the μ{sub 2}-SCH{sub 2}CH{sub 3} ligands in a distorted square plane fashion. The edge-sharing S{sub 4} square planes connect with each other to form a ring. Six metal atoms are located at the vertices of an almost hexagon, with M···M separations in the range of 2.903(1)∼2.936(2) Å for Fe and 2.889(2)∼2.962(2) Å for Co. The diameter of the ring, defined as the average distance between two opposing metalmore » atoms, is 5.850(1) Å for Fe and 5.780(1) Å for Co, respectively. The magnetic property behaves of cobalt(II) cluster complex is studied. Highlights: • Two new ethyl mercaptan cyclic hexanuclear complexes were reported. • The crystal structures shown center formation of M{sub 6}S{sub 12} molecular wheels. • The Co{sub 6} ring cluster complex represents as weak ferromagnet.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perez, Danny, E-mail: danny-perez@lanl.gov; Sandoval, Luis; Voter, Arthur F.

Due to its enviable properties, tungsten is a leading candidate plasma facing material in nuclear fusion reactors. However, like many other metals, tungsten is known to be affected by the high doses of helium atoms incoming from the plasma. Indeed, the implanted interstitial helium atoms cluster together and, upon reaching a critical cluster size, convert into substitutional nanoscale He bubbles. These bubbles then grow by absorbing further interstitial clusters from the matrix. This process can lead to deleterious changes in microstructure, degradation of mechanical properties, and contamination of the plasma. In order to better understand the growth process, we usemore » traditional and accelerated molecular dynamics simulations to investigate the interactions between interstitial He clusters and pre-existing bubbles. These interactions are characterized in terms of thermodynamics and kinetics. We show that the proximity of the bubble leads to an enhancement of the trap mutation rate and, consequently, to the nucleation of satellite bubbles in the neighborhood of existing ones. We also uncover a number of mechanisms that can lead to the subsequent annihilation of such satellite nanobubbles.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Perez, Danny; Sandoval, Luis; Uberuaga, Blas P.

Due to its enviable properties, tungsten is a leading candidate plasma facing material in nuclear fusion reactors. But, like many other metals, tungsten is known to be affected by the high doses of helium atoms incoming from the plasma. Indeed, the implanted interstitial helium atoms cluster together and, upon reaching a critical cluster size, convert into substitutional nanoscale He bubbles. These bubbles then grow by absorbing further interstitial clusters from the matrix. This process can lead to deleterious changes in microstructure, degradation of mechanical properties, and contamination of the plasma. In order to better understand the growth process, we usemore » traditional and accelerated molecular dynamics simulations to investigate the interactions between interstitial He clusters and pre-existing bubbles. These interactions are characterized in terms of thermodynamics and kinetics. We also show that the proximity of the bubble leads to an enhancement of the trap mutation rate and, consequently, to the nucleation of satellite bubbles in the neighborhood of existing ones. Finally, we uncover a number of mechanisms that can lead to the subsequent annihilation of such satellite nanobubbles.« less

Application of Density Functional Theory to Systems Containing Metal Atoms

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Arnold, James O. (Technical Monitor)

1997-01-01

The accuracy of density functional theory (DFT) for problems involving metal atoms is considered. The DFT results are compared with experiment as well as results obtained using the coupled cluster approach. The comparisons include geometries, frequencies, and bond energies. The systems considered include MO2, M(OH)+(sub n), MNO+, and MCO+(sub 2). The DFT works well for frequencies and geometries, even in cases with symmetry breaking; however, some examples have been found where the symmetry breaking is quite severe and the DFT methods do not work well. The calculation of bond energies is more difficult and examples of the successes as well as failures of DFT will be given.

Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters.

PubMed

Parnis, J Mark; Escobar-Cabrera, Eric; Thompson, Matthew G K; Jacula, J Paul; Lafleur, Rick D; Guevara-García, Alfredo; Martínez, Ana; Rayner, David M

2005-08-18

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 Nb8 and Nb10, 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 Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, 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 C2H4, C2H2, or C2. 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 calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of the structural variations present in the cluster species studied shows an increase in C-H bond lengths with cluster size that closely correlates with the increased thermodynamic drive to full dehydrogenation. This correlation strongly suggests that all steps in the reaction are barrierless, and that weakening of the C-H bonds is directly reflected in the thermodynamics of the overall dehydrogenation process. It is also demonstrated that reaction exergonicity in the initial partial dehydrogenation step must be carried through as excess internal energy into the second dehydrogenation step.

Optimizing the ionization and energy absorption of laser-irradiated clusters

NASA Astrophysics Data System (ADS)

Kundu, M.; Bauer, D.

2008-03-01

It is known that rare-gas or metal clusters absorb incident laser energy very efficiently. However, due to the intricate dependencies on all the laser and cluster parameters, it is difficult to predict under which circumstances ionization and energy absorption are optimal. With the help of three-dimensional particle-in-cell simulations of xenon clusters (up to 17256 atoms), it is shown that for a given laser pulse energy and cluster, an optimum wavelength exists that corresponds to the approximate wavelength of the transient, linear Mie-resonance of the ionizing cluster at an early stage of negligible expansion. In a single ultrashort laser pulse, the linear resonance at this optimum wavelength yields much higher absorption efficiency than in the conventional, dual-pulse pump-probe setup of linear resonance during cluster expansion.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM.

PubMed

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-18

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt 1 /Fe 2 O 3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water-gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe 2 O 3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H 2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H 2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H 2 O molecules to the CO or H 2 significantly accelerates the sintering of the Fe 2 O 3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal-support interaction.

Photoelectron spectroscopic study of the anionic transition metalorganic complexes [Fe(1,2)(COT)](-) and [Co(COT)](-).

PubMed

Li, Xiang; Eustis, Soren N; Bowen, Kit H; Kandalam, Anil

2008-09-28

The gas-phase, iron and cobalt cyclooctatetraene cluster anions, [Fe(1,2)(COT)](-) and [Co(COT)](-), were generated using a laser vaporization source and studied using mass spectrometry and anion photoelectron spectroscopy. Density functional theory was employed to compute the structures and spin multiplicities of these cluster anions as well as those of their corresponding neutrals. Both experimental and theoretically predicted electron affinities and photodetachment transition energies are in good agreement, authenticating the structures and spin multiplicities predicted by theory. The implied spin magnetic moments of these systems suggest that [Fe(COT)], [Fe(2)(COT)], and [Co(COT)] retain the magnetic moments of the Fe atom, the Fe(2) dimer, and the Co atom, respectively. Thus, the interaction of these transition metal, atomic and dimeric moieties with a COT molecule does not quench their magnetic moments, leading to the possibility that these combinations may be useful in forming novel magnetic materials.

The thermodynamic and kinetic interactions of He interstitial clusters with bubbles in W

DOE PAGES

Perez, Danny; Sandoval, Luis; Uberuaga, Blas P.; ...

2016-05-26

Due to its enviable properties, tungsten is a leading candidate plasma facing material in nuclear fusion reactors. But, like many other metals, tungsten is known to be affected by the high doses of helium atoms incoming from the plasma. Indeed, the implanted interstitial helium atoms cluster together and, upon reaching a critical cluster size, convert into substitutional nanoscale He bubbles. These bubbles then grow by absorbing further interstitial clusters from the matrix. This process can lead to deleterious changes in microstructure, degradation of mechanical properties, and contamination of the plasma. In order to better understand the growth process, we usemore » traditional and accelerated molecular dynamics simulations to investigate the interactions between interstitial He clusters and pre-existing bubbles. These interactions are characterized in terms of thermodynamics and kinetics. We also show that the proximity of the bubble leads to an enhancement of the trap mutation rate and, consequently, to the nucleation of satellite bubbles in the neighborhood of existing ones. Finally, we uncover a number of mechanisms that can lead to the subsequent annihilation of such satellite nanobubbles.« less

The thermodynamic and kinetic interactions of He interstitial clusters with bubbles in W

NASA Astrophysics Data System (ADS)

Perez, Danny; Sandoval, Luis; Uberuaga, Blas P.; Voter, Arthur F.

2016-05-01

Due to its enviable properties, tungsten is a leading candidate plasma facing material in nuclear fusion reactors. However, like many other metals, tungsten is known to be affected by the high doses of helium atoms incoming from the plasma. Indeed, the implanted interstitial helium atoms cluster together and, upon reaching a critical cluster size, convert into substitutional nanoscale He bubbles. These bubbles then grow by absorbing further interstitial clusters from the matrix. This process can lead to deleterious changes in microstructure, degradation of mechanical properties, and contamination of the plasma. In order to better understand the growth process, we use traditional and accelerated molecular dynamics simulations to investigate the interactions between interstitial He clusters and pre-existing bubbles. These interactions are characterized in terms of thermodynamics and kinetics. We show that the proximity of the bubble leads to an enhancement of the trap mutation rate and, consequently, to the nucleation of satellite bubbles in the neighborhood of existing ones. We also uncover a number of mechanisms that can lead to the subsequent annihilation of such satellite nanobubbles.

Molecular dynamics simulation of metal nanoislands growth

NASA Astrophysics Data System (ADS)

Kapralov, N. V.; Babich, E. S.; Redkov, A. V.

2017-11-01

We present the atomistic model and the simulation of a self-assembled growth of a silver nanoisland film and small groups of nanoislands on a glass substrate after thermal poling of the glass with a profiled electrode. The calculations were performed in molecular dynamics simulator LAMMPS taking into account the diffusion of the metal atoms towards and along the glass surface and their clustering. Lennard-Jones potential was used to describe metal-metal and metal-glass interaction. The potential parameters were determined to provide qualitative coincidence of the simulated configurations of the metal nanostructures and the experimental ones, such as an isolated nanoisland, a pair and a set of three nanoislands and a “plasmonic molecule”.

Unidentified line in x-ray spectra of the Andromeda galaxy and Perseus galaxy cluster.

PubMed

Boyarsky, A; Ruchayskiy, O; Iakubovskyi, D; Franse, J

2014-12-19

We report a weak line at 3.52±0.02  keV in x-ray spectra of the Andromeda galaxy and the Perseus galaxy cluster observed by the metal-oxide-silicon (MOS) and p-n (PN) CCD cameras of the XMM-Newton telescope. This line is not known as an atomic line in the spectra of galaxies or clusters. It becomes stronger towards the centers of the objects; is stronger for Perseus than for M31; is absent in the spectrum of a deep "blank sky" data set. Although for each object it is hard to exclude that the feature is due to an instrumental effect or an atomic line, it is consistent with the behavior of a dark matter decay line. Future (non-)detections of this line in multiple objects may help to reveal its nature.

Processes of conversion of a hot metal particle into aerogel through clusters

NASA Astrophysics Data System (ADS)

Smirnov, B. M.

2015-10-01

Processes are considered for conversion into a fractal structure of a hot metal micron-size particle that is located in a buffer gas or a gas flow and is heated by an external electric or electromagnetic source or by a plasma. The parameter of this heating is the particle temperature, which is the same in the entire particle volume because of its small size and high conductivity. Three processes determine the particle heat balance: particle radiation, evaporation of metal atoms from the particle surface, and heat transport to the surrounding gas due to its thermal conductivity. The particle heat balance is analyzed based on these processes, which are analogous to those for bulk metals with the small particle size, and its high temperature taken into account. Outside the particle, where the gas temperature is lower than on its surface, the formed metal vapor in a buffer gas flow is converted into clusters. Clusters grow as a result of coagulation until they become liquid, and then clusters form fractal aggregates if they are removed form the gas flow. Subsequently, associations of fractal aggregates join into a fractal structure. The rate of this process increases in medium electric fields, and the formed fractal structure has features of aerogels and fractal fibers. As a result of a chain of the above processes, a porous metal film may be manufactured for use as a filter or catalyst for gas flows.

Energetic ion bombardment of Ag surfaces by C60+ and Ga+ projectiles.

PubMed

Sun, Shixin; Szakal, Christopher; Winograd, Nicholas; Wucher, Andreas

2005-10-01

The ion bombardment-induced release of particles from a metal surface is investigated using energetic fullerene cluster ions as projectiles. The total sputter yield as well as partial yields of neutral and charged monomers and clusters leaving the surface are measured and compared with corresponding data obtained with atomic projectile ions of similar impact kinetic energy. It is found that all yields are enhanced by about one order of magnitude under bombardment with the C60+ cluster projectiles compared with Ga+ ions. In contrast, the electronic excitation processes determining the secondary ion formation probability are unaffected. The kinetic energy spectra of sputtered particles exhibit characteristic differences which reflect the largely different nature of the sputtering process for both types of projectiles. In particular, it is found that under C60+ impact (1) the energy spectrum of sputtered atoms peaks at significantly lower kinetic energies than for Ga+ bombardment and (2) the velocity spectra of monomers and dimers are virtually identical, a finding which is in pronounced contrast to all published data obtained for atomic projectiles. The experimental findings are in reasonable agreement with recent molecular dynamics simulations.

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co 1–xPt x Clusters under H 2 and CO + H 2 Atmospheres

DOE PAGES

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette; ...

2016-08-25

In this study, Co 1–xPt x clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al 2O 3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged cluster samples were characterized by grazing-incidence X-ray absorption spectroscopymore » (GIXAS) and then pretreated with diluted hydrogen and further exposed to the mixture of diluted CO and H 2 up to 225°C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the clusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the clusters. For example, a low Pt/Co ratio (x ≤ 0.5) facilitates the formation of Co(OH) 2, whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co 3O 4 composition instead through the formation of a Co–Pt core–shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co 1–xPt x alloy clusters. Finally, the obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.« less

Half-metallic ferromagnetism in substitutionally doped boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-11-01

We perform first-principles molecular dynamics simulations to investigate the magnetoelectronic response of substitutionally doped boronitrene to thermal excitation. We show that the local geometry, size, and edge termination of the substitutional complexes of boron, carbon, or nitrogen determine the thermodynamic stability of the monolayer. We find that hexagonal boron or triangular carbon clusters induce finite magnetic moments with 100% spin-polarized Fermi-level electrons in boronitrene. In such carbon substitutions, the spontaneous magnetic moment increases with the size of the embedded carbon cluster, and results in half-metallic ferrimagnetism above 750 K with a corresponding Curie point of 1250 K, above which the magnetization density vanishes. We predict an ultrahigh temperature half-metallic ferromagnetic phase in impurity-free boronitrene, when any three nearest-neighbor nitrogen atoms are substituted with boron, with unquenched magnetic moment up to its melting point.

Meteoric Metal Chemistry in the Martian Atmosphere

NASA Astrophysics Data System (ADS)

Plane, J. M. C.; Carrillo-Sanchez, J. D.; Mangan, T. P.; Crismani, M. M. J.; Schneider, N. M.; Määttänen, A.

2018-03-01

Recent measurements by the Imaging Ultraviolet Spectrograph (IUVS) instrument on NASA's Mars Atmosphere and Volatile EvolutioN mission show that a persistent layer of Mg+ ions occurs around 90 km in the Martian atmosphere but that neutral Mg atoms are not detectable. These observations can be satisfactorily modeled with a global meteoric ablation rate of 0.06 t sol-1, out of a cosmic dust input of 2.7 ± 1.6 t sol-1. The absence of detectable Mg at 90 km requires that at least 50% of the ablating Mg atoms ionize through hyperthermal collisions with CO2 molecules. Dissociative recombination of MgO+.(CO2)n cluster ions with electrons to produce MgCO3 directly, rather than MgO, also avoids a buildup of Mg to detectable levels. The meteoric injection rate of Mg, Fe, and other metals—constrained by the IUVS measurements—enables the production rate of metal carbonate molecules (principally MgCO3 and FeCO3) to be determined. These molecules have very large electric dipole moments (11.6 and 9.2 Debye, respectively) and thus form clusters with up to six H2O molecules at temperatures below 150 K. These clusters should then coagulate efficiently, building up metal carbonate-rich ice particles which can act as nucleating particles for the formation of CO2-ice clouds. Observable mesospheric clouds are predicted to occur between 65 and 80 km at temperatures below 95 K and above 85 km at temperatures about 5 K colder.

Ionized cluster beam deposition

NASA Technical Reports Server (NTRS)

Kirkpatrick, A. R.

1983-01-01

Ionized Cluster Beam (ICB) deposition, a new technique originated by Takagi of Kyoto University in Japan, offers a number of unique capabilities for thin film metallization as well as for deposition of active semiconductor materials. ICB allows average energy per deposited atom to be controlled and involves impact kinetics which result in high diffusion energies of atoms on the growth surface. To a greater degree than in other techniques, ICB involves quantitative process parameters which can be utilized to strongly control the characteristics of films being deposited. In the ICB deposition process, material to be deposited is vaporized into a vacuum chamber from a confinement crucible at high temperature. Crucible nozzle configuration and operating temperature are such that emerging vapor undergoes supercondensation following adiabatic expansion through the nozzle.

Transition-metal dispersion on carbon-doped boron nitride nanostructures: Applications for high-capacity hydrogen storage

NASA Astrophysics Data System (ADS)

Chen, Ming; Zhao, Yu-Jun; Liao, Ji-Hai; Yang, Xiao-Bao

2012-07-01

Using density-functional theory calculations, we investigated the adsorption of transition-metal (TM) atoms (TM = Sc, Ti, V, Cr, Mn, Fe, Co, and Ni) on carbon doped hexagonal boron nitride (BN) sheet and the corresponding cage (B12N12). With carbon substitution of nitrogen, Sc, V, Cr, and Mn atoms were energetically favorable to be dispersed on the BN nanostructures without clustering or the formation of TM dimers, due to the strong binding between TM atoms and substrate, which contains the half-filled levels above the valence bands maximum. The carbon doped BN nanostructures with dispersed Sc could store up to five and six H2, respectively, with the average binding energy of 0.3 ˜ 0.4 eV, indicating the possibility of fabricating hydrogen storage media with high capacity. We also demonstrated that the geometrical effect is important for the hydrogen storage, leading to a modulation of the charge distributions of d levels, which dominates the binding between H2 and TM atoms.

Theoretical investigation of M@Pb122- and M@Sn122- Zintl clusters (M = Lrn+, Lun+, La3+, Ac3+ and n = 0, 1, 2, 3).

PubMed

Joshi, Meenakshi; Chandrasekar, Aditi; Ghanty, Tapan K

2018-06-06

The positions of lawrencium (Lr), lutetium (Lu), actinium (Ac) and lanthanum (La) in the periodic table have been a controversial topic for quite some time. According to studies carried out by different groups with their justifications, these elements may potentially be placed in the d-block, p-block or all four in a 15 element f-block. The present work looks into this issue from a new perspective, which involves encapsulation of these four elements into Zintl ion clusters, Pb122- and Sn122-, followed by the determination of the structural, thermodynamic and electronic properties of these endohedral M@Pb122- and M@Sn122- clusters (M = Lrn+, Lun+ with n = 0, 1, 2, 3) using first principles based density functional theory (DFT). These parameters are compared with similar clusters encapsulated La3+ and Ac3+ ions in order to seek out similarities and differences to draw conclusions about their placement in the periodic table. For the first time the structural, energetic, and electronic properties of these metal atom/ion encapsulated Pb122- and Sn122- clusters have been investigated thoroughly. Structural parameters such as bond distances, geometry and symmetry, electronic properties viz. the density of states, the molecular orbital ordering, the electron localization function, bond critical point properties and charge distributions have been analyzed. Additionally, the thermodynamic property of the binding energy during the encapsulation process has also been calculated. All M@Pb12+ and M@Sn12+ (M = Lr and Lu) clusters form stable 18 bonding electron magic number systems with shell closing. They show negative values of binding energy and relatively large HOMO-LUMO energy gaps indicating the stability of such clusters. All the calculated parameters for Lr encapsulated clusters closely match with the corresponding calculated parameters of Lu encapsulated clusters, confirming the similarity between Lr and Lu metal atoms in various oxidation states, though their atomic ground state valence electronic configurations are different. The effect of spin orbit coupling has also been investigated using the ZORA approach. It is interesting to discover that La and Ac showed striking similarities to Lr and Lu with respect to all the properties investigated and have formed a stable 18-electron system.

Aluminum Cluster-Based Materials for Propulsion and Other Applications and Catalysis

DTIC Science & Technology

2012-04-04

CuMg8- and AuMg8- . It was shown that aromaticity, traditionally used to understand stability of organic systems , can also stabilize metallic...the helical chains of arsenic and K atoms. Extensions of these to other systems is currently under study. Since 2009, 12 group publications (GP... systems that are cyclic, planar and contain (4n+2) π electrons. Only recently has this concept been extended to all-metal systems , with the seminal

Structural Evolution and Kinetics in Cu-Zr Metallic Liquids from Molecular Dynamics Simulations (Postprint)

DTIC Science & Technology

2013-10-23

compensate for overcounting due to numerical issues inherent in the tessellation.16 The shape of the coordination polyhedron was determined by the shape...work by Yang et al.21 The total volume can be determined by finding the volume of the convex polyhedron whose vertices are given by the centers of...atoms in the nearest-neighbor shell. In order to determine the volume of the atoms inside the clusters, the convex hull polyhedron is first segmented

Bridging Zirconia Nodes within a Metal–Organic Framework via Catalytic Ni-Hydroxo Clusters to Form Heterobimetallic Nanowires

DOE Office of Scientific and Technical Information (OSTI.GOV)

Platero-Prats, Ana E.; League, Aaron B.; Bernales, Varinia

2017-07-24

Metal-organic frameworks (MOFs), with their well-ordered pore networks and tunable surface chemistries, offer a versatile platform for preparing well-defined nanostructures wherein functionality such as catalysis can be incorporated. We resolved the atomic structure of Ni-oxo species deposited in the MOF NU-1000 through atomic layer deposition using local and long-range structure probes, including X-ray absorption spectroscopy, pair distribution function analysis and difference envelope density analysis, with electron microscopy imaging and computational modeling.

Insight from first principles into the stability and magnetism of alkali-metal superoxide nanoclusters

NASA Astrophysics Data System (ADS)

Arcelus, Oier; Suaud, Nicolas; Katcho, Nebil A.; Carrasco, Javier

2017-05-01

Alkali-metal superoxides are gaining increasing interest as 2p magnetic materials for information and energy storage. Despite significant research efforts on bulk materials, gaps in our knowledge of the electronic and magnetic properties at the nanoscale still remain. Here, we focused on the role that structural details play in determining stability, electronic structure, and magnetic couplings of (MO2)n (M = Li, Na, and K, with n = 2-8) clusters. Using first-principles density functional theory based on the Perdew-Burke-Ernzerhof and Heyd-Scuseria-Ernzerhof functionals, we examined the effect of atomic structure on the relative stability of different polymorphs within each investigated cluster size. We found that small clusters prefer to form planar-ring structures, whereas non-planar geometries become more stable when increasing the cluster size. However, the crossover point depends on the nature of the alkali metal. Our analysis revealed that electrostatic interactions govern the highly ionic M-O2 bonding and ultimately control the relative stability between 2-D and 3-D geometries. In addition, we analyzed the weak magnetic couplings between superoxide molecules in (NaO2)4 clusters comparing model Hamiltonian methods based on Wannier function projections onto πg states with wave function-based multi-reference calculations.

Investigation on structure, electronic and magnetic properties of Cr doped (ZnO)12 clusters: First-principles calculations

NASA Astrophysics Data System (ADS)

Liu, Huan; Zhang, Jian-Min

2018-05-01

The structural, electronic, and magnetic properties of (ZnO)12 clusters doped with Cr atoms have been investigated by using spin-polarized first-principles calculations. The exohedral a3 isomer is favorable than endohedral a2 isomer. The isomer a1 and a5 respectively have the narrowest and biggest gap between highest unoccupied molecular orbital and the lowest unoccupied molecular orbital (HOMO-LUMO) of 0.473 and 1.291 eV among these five monodoped isomers. The magnetic moment may be related to the local environment around the Cr atom that the a2 isomer whose total magnetic moment is 6 μB while the other monodoped isomers which all isomers have nearly total magnetic moments 4 μB . For Cr-doped (ZnO)12 on a1 or a3 isomer, the DOS of spin-up channel cross the Fermi level EF showing a finite magnitude near the Fermi level which might be useful for half metallic character. For the bidoped cases, the exohedral isomers are found to be most favorable. Including all bipoed isomers of substitutional, exohedral and endohedral bidoped clusters, the total magnetic moment of the ferromagnetic (antiferromagnetic) state is 8 (0) μB and the HOMO-LUMO gap of antiferromagnetic state is slightly larger than that of ferromagnetic state. The magnetic coupling between the Cr atoms in bidoped configurations is mainly governed by the competition between direct Cr and Cr atoms antiferromagnetic interaction and the ferromagnetic interaction between two Cr atoms via O atom due to strong p-d hybridization. Most importantly, we show that the exohedral bidoped (ZnO)12 clusters favor the ferromagnetic state, which may have the future applications in spin-dependent magneto-optical and magneto-electrical devices.

Zinc and cadmium complexes of a plant metallothionein under radical stress: desulfurisation reactions associated with the formation of trans-lipids in model membranes.

PubMed

Torreggiani, Armida; Domènech, Jordi; Orihuela, Ruben; Ferreri, Carla; Atrian, Sílvia; Capdevila, Mercè; Chatgilialoglu, Chryssostomos

2009-06-08

Metallothioneins (MTs) are sulfur-rich proteins capable of binding metal ions to give metal clusters. The metal-MT aggregates used in this work were Zn- and Cd-QsMT, where QsMT is an MT from the plant Quercus suber. Reactions of reductive reactive species (H(*) atoms and e(aq)(-)), produced by gamma irradiation of water, with Zn- and Cd-QsMT were carried out in both aqueous solutions and vesicle suspensions, and were characterized by different approaches. By using a biomimetic model based on unsaturated lipid vesicle suspensions, the occurrence of tandem protein/lipid damage was shown. The reactions of reductive reactive species with methionine residues and/or sulfur-containing ligands afford diffusible sulfur-centred radicals, which migrate from the aqueous phase to the lipid bilayer and transform the cis double bond of the oleate moiety into the trans isomer. Tailored experiments allowed the reaction mechanism to be elucidated in some detail. The formation of sulfur-centred radicals is accompanied by the modification of the metal-QsMT complexes, which were monitored by various spectroscopic and spectrometric techniques (Raman, CD, and ESI-MS). Attack of the H(*) atom and e(aq)(-) on the metal-QsMT aggregates can induce significant structural changes such as partial deconstruction and/or rearrangement of the metal clusters and breaking of the protein backbone. Substantial differences were observed in the behaviour of the Zn- and Cd-QsMT aggregates towards the reactive species, depending on the different folding of the polypeptide in these two cases.

Allosteric control in a metalloprotein dramatically alters function

PubMed Central

Baxter, Elizabeth Leigh; Zuris, John A.; Wang, Charles; Vo, Phu Luong T.; Axelrod, Herbert L.; Cohen, Aina E.; Paddock, Mark L.; Nechushtai, Rachel; Onuchic, Jose N.; Jennings, Patricia A.

2013-01-01

Metalloproteins (MPs) comprise one-third of all known protein structures. This diverse set of proteins contain a plethora of unique inorganic moieties capable of performing chemistry that would otherwise be impossible using only the amino acids found in nature. Most of the well-studied MPs are generally viewed as being very rigid in structure, and it is widely thought that the properties of the metal centers are primarily determined by the small fraction of amino acids that make up the local environment. Here we examine both theoretically and experimentally whether distal regions can influence the metal center in the diabetes drug target mitoNEET. We demonstrate that a loop (L2) 20 Å away from the metal center exerts allosteric control over the cluster binding domain and regulates multiple properties of the metal center. Mutagenesis of L2 results in significant shifts in the redox potential of the [2Fe-2S] cluster and orders of magnitude effects on the rate of [2Fe-2S] cluster transfer to an apo-acceptor protein. These surprising effects occur in the absence of any structural changes. An examination of the native basin dynamics of the protein using all-atom simulations shows that twisting in L2 controls scissoring in the cluster binding domain and results in perturbations to one of the cluster-coordinating histidines. These allosteric effects are in agreement with previous folding simulations that predicted L2 could communicate with residues surrounding the metal center. Our findings suggest that long-range dynamical changes in the protein backbone can have a significant effect on the functional properties of MPs. PMID:23271805

Hidden relationships between metalloproteins unveiled by structural comparison of their metal sites

NASA Astrophysics Data System (ADS)

Valasatava, Yana; Andreini, Claudia; Rosato, Antonio

2015-03-01

Metalloproteins account for a substantial fraction of all proteins. They incorporate metal atoms, which are required for their structure and/or function. Here we describe a new computational protocol to systematically compare and classify metal-binding sites on the basis of their structural similarity. These sites are extracted from the MetalPDB database of minimal functional sites (MFSs) in metal-binding biological macromolecules. Structural similarity is measured by the scoring function of the available MetalS2 program. Hierarchical clustering was used to organize MFSs into clusters, for each of which a representative MFS was identified. The comparison of all representative MFSs provided a thorough structure-based classification of the sites analyzed. As examples, the application of the proposed computational protocol to all heme-binding proteins and zinc-binding proteins of known structure highlighted the existence of structural subtypes, validated known evolutionary links and shed new light on the occurrence of similar sites in systems at different evolutionary distances. The present approach thus makes available an innovative viewpoint on metalloproteins, where the functionally crucial metal sites effectively lead the discovery of structural and functional relationships in a largely protein-independent manner.

Methanol Oxidative Dehydrogenation on Oxide Catalysts: Molecular and Dissociative Routes and Hydrogen Addition Energies as Descriptors of Reactivity

DOE Office of Scientific and Technical Information (OSTI.GOV)

Deshlahra, Prashant; Iglesia, Enrique

The oxidative dehydrogenation (ODH) of alkanols on oxide catalysts is generally described as involving H-abstraction from alkoxy species formed via O–H dissociation. Kinetic and isotopic data cannot discern between such routes and those involving kinetically-relevant H-abstraction from undissociated alkanols. Here, we combine such experiments with theoretical estimates of activation energies and entropies to show that the latter molecular routes prevail over dissociative routes for methanol reactions on polyoxometalate (POM) clusters at all practical reaction temperatures. The stability of the late transition states that mediate H-abstraction depend predominantly on the stability of the O–H bond formed, making H-addition energies (HAE) accuratemore » and single-valued descriptors of reactivity. Density functional theory-derived activation energies depend linearly on HAE values at each O-atom location on clusters with a range of composition (H3PMo12, H4SiMo12, H3PW12, H4PV1Mo11, and H4PV1W11); both barriers and HAE values reflect the lowest unoccupied molecular orbital energy of metal centers that accept the electron and the protonation energy of O-atoms that accept the proton involved in the H-atom transfer. Bridging O-atoms form O–H bonds that are stronger than those of terminal atoms and therefore exhibit more negative HAE values and higher ODH reactivity on all POM clusters. For each cluster composition, ODH turnover rates reflect the reactivity-averaged HAE of all accessible O-atoms, which can be evaluated for each cluster composition to provide a rigorous and accurate predictor of ODH reactivity for catalysts with known structure. These relations together with oxidation reactivity measurements can then be used to estimate HAE values and to infer plausible structures for catalysts with uncertain active site structures.« less

Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide.

PubMed

Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

2015-12-18

Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants.

Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

DOE PAGES

Wang, Yanggang; Mei, Donghai; Glezakou, Vassiliki Alexandra; ...

2015-03-04

Ab initio Molecular Dynamics simulations and static Density Functional Theory calculations have been performed to investigate the reaction mechanism of CO oxidation on Au/CeO 2 catalyst. It is found that under reaction condition CO adsorption significantly labializes the surface atoms of the Au cluster and leads to the formation of isolated Au+-CO species that resides on the support in the vicinity of the Au particle. In this context, we identified a dynamic single-atom catalytic mechanism at the interfacial area for CO oxidation on Au/CeO 2 catalyst, which is a lower energy pathway than that of CO oxidation at the interfacemore » with the metal particle. This results from the ability of the single atom site to strongly couple with the redox properties of the support in a synergistic manner thereby lowering the barrier for redox reactions. We find that the single Au+ ion, which only exists under reaction conditions, breaks away from the Au cluster to catalyze CO oxidation and returns to the Au cluster after the catalytic cycle is completed. Generally, our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in a catalytic process.« less

Molecular oxygen adsorption and dissociation on Au12M clusters with M = Cu, Ag or Ir

NASA Astrophysics Data System (ADS)

Jiménez-Díaz, Laura M.; Pérez, Luis A.

2018-03-01

In this work, we present a density functional theory study of the structural and electronic properties of isolated neutral clusters of the type Au12M, with M = Cu, Ag, or Ir. On the other hand, there is experimental evidence that gold-silver, gold-copper and gold-iridium nanoparticles have an enhanced catalytic activity for the CO oxidation reaction. In order to address these phenomena, we also performed density functional calculations of the adsorption and dissociation of O2 on these nanoparticles. Moreover, to understand the effects of Cu, Ag, and Ir impurity atoms on the dissociation of O2, we also analyze this reaction in the corresponding pure gold cluster. The results indicate that the substitution of one gold atom in a Au13 cluster by Ag, Cu or Ir diminishes the activation energy barrier for the O2 dissociation by nearly 1 eV. This energy barrier is similar for Au12Ag and Au12Cu, whereas for Au12Ir is even lower. These results suggest that the addition of other transition metal atoms to gold nanoclusters can enhance their catalytic activity towards the CO oxidation reaction, independently of the effect that the substrate could have on supported nanoclusters.

The use of mosses as environmental metal pollution indicators.

PubMed

Aceto, Maurizio; Abollino, Ornella; Conca, Raffaele; Malandrino, Mery; Mentasti, Edoardo; Sarzanini, Corrado

2003-01-01

The possibility of using mosses as environmental indicators of metal pollution has been investigated. Mosses of the species Bryum argenteum were collected from different parts of Piedmont (Italy), ranging from highly polluted areas to nearly uncontaminated mountain areas. Periodical samplings were planned in every site on a monthly base, in order to check variations of metal uptake throughout one year; correlations with pluviometric and thermal patterns were investigated for all sampling stations. On every moss sample 20 elements, ranging from major (K, P, Al, Ca, Fe and Mg) to minor (Mn, Na, Ti and Zn) and trace (As, Ba, Cd, Co, Cr, Cu, Li, Ni, Pb and Sr), were quantitatively determined by inductively coupled plasma-atomic emission spectrometry or graphite furnace-atomic absorption spectrometry, depending on the needed sensitivity. Statistical analyses, carried out with principal component analysis and cluster analysis methods, revealed that a good correlation exists between metal content in mosses and pollution degree in the areas sampled.

Catalysis by Atomic-Sized Centers: Methane Activation for Partial Oxidation and Combustion

DTIC Science & Technology

2015-07-21

example, H adsorbed alone on an oxide surface will bind to oxygen to form a hydroxide . However, if a Lewis base (e.g. any electron donor) is...that on a gold surface, which is not surprising considering the bonding character between the cluster and metal surfaces. The high mobility verifies

Structural origin underlying poor glass forming ability of Al metallic glass

NASA Astrophysics Data System (ADS)

Li, F.; Liu, X. J.; Hou, H. Y.; Chen, G.; Chen, G. L.

2011-07-01

We performed molecular dynamics simulations to study the glass formation and local atomic structure of rapidly quenched Al. Both potential energy and structural parameters indicate that the glass transition temperature of amorphous Al is as low as 300 K, which may lead to the poor thermal stability of the amorphous Al as it is prone to crystallize even at room temperature. Voronoi polyhedra analysis reveals that the most popular polyhedron is the deformed body-centered cubic (bcc) cluster characterized by the index < 0, 3, 6, 4 > in the amorphous Al, while the icosahedron with the index < 0, 0, 12, 0 > is always predominant in bulk metallic glass formers with excellent glass forming ability (GFA). Moreover, these deformed-bcc short-range orders can make up medium-range orders via the linkage of vertex-, edge-, face-, intercrossed-shared atoms, which are believed to more easily transform into face-centered cubic (fcc) Al nanocrystal compared with the icosahedral clusters in terms of the symmetrical similarity between bcc and fcc structures. This finding could unveil the structural origin of poor GFA of Al-based alloys.

In-Plane Multimagnetron Approach

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johnson, Grant E.; Laskin, Julia

2017-04-01

Nanoparticles (NPs) and sub-nanometer clusters containing controlled amounts of different atoms are of interest for a variety of potential applications including catalysis,1, 2 optics,3, 4 magnetics,5-7 sensors,8, 9 and biotheraputics.10, 11 Alloy NPs may possess enhanced physical and chemical properties compared to single metal species due to the additional interplay between their different elemental components. By reducing the quantity of expensive precious metals in alloy NPs by substituting cheaper base metals, it may also be possible to achieve equivalent or even superior performance to pure noble metal NPs for applications such as heterogeneous catalysis at substantially reduced material costs.12 Inmore » addition, alloying of elements that are immiscible in bulk form is possible in NPs because the enthalpy of mixing decreases and becomes negative at small particle sizes.13, 14 As a result, a substantially broader array of alloy species may be generated in the form of NPs and sub-nanometer clusters.« less

Chain-like structure elements in Ni40Ta60 metallic glasses observed by scanning tunneling microscopy

PubMed Central

Pawlak, Rémy; Marot, Laurent; Sadeghi, Ali; Kawai, Shigeki; Glatzel, Thilo; Reimann, Peter; Goedecker, Stefan; Güntherodt, Hans-Joachim; Meyer, Ernst

2015-01-01

The structure of metallic glasses is a long-standing question because the lack of long-range order makes diffraction based techniques difficult to be applied. Here, we used scanning tunneling microscopy with large tunneling resistance of 6 GΩ at low temperature in order to minimize forces between probe and sample and reduce thermal fluctuations of metastable structures. Under these extremely gentle conditions, atomic structures of Ni40Ta60 metallic glasses are revealed with unprecedented lateral resolution. In agreement with previous models and experiments, icosahedral-like clusters are observed. The clusters show a high degree of mobility, which explains the need of low temperatures for stable imaging. In addition to icosahedrons, chain-like structures are resolved and comparative density functional theory (DFT) calculations confirm that these structures are meta-stable. The co-existence of icosahedral and chain-like structures might be an key ingredient for the understanding of the mechanical properties of metallic glasses. PMID:26268430

Destructive Clustering of Metal Nanoparticles in Chalcogenide and Oxide Glassy Matrices.

PubMed

Shpotyuk, M V; Shpotyuk, O I; Cebulski, J; Kozyukhin, S

2016-12-01

The energetic χ-criterion is developed to parameterize difference in the origin of high-order optical non-linearity associated with metallic atoms (Cu, Ag, Au) embedded destructively in oxide- and chalcogenide glasses. Within this approach, it is unambiguously proved that covalent-bonded networks of soft semiconductor chalcogenides exemplified by binary As(Ge)-S(Se) glasses differ essentially from those typical for hard dielectric oxides like vitreous silica by impossibility to accommodate pure agglomerates of metallic nanoparticles. In an excellence according to known experimental data, it is suggested that destructive clustering of nanoparticles is possible in Cu-, Ag-, and Au-ion-implanted dielectric oxide glass media, possessing a strongly negative χ-criterion. Some recent speculations trying to ascribe equally this ability to soft chalcogenide glasses despite an obvious difference in the corresponding bond dissociation energies have been disclosed and criticized as inconclusive.

Photobiomolecular deposition of metallic particles and films

DOEpatents

Hu, Zhong-Cheng

2005-02-08

The method of the invention is based on the unique electron-carrying function of a photocatalytic unit such as the photosynthesis system I (PSI) reaction center of the protein-chlorophyll complex isolated from chloroplasts. The method employs a photo-biomolecular metal deposition technique for precisely controlled nucleation and growth of metallic clusters/particles, e.g., platinum, palladium, and their alloys, etc., as well as for thin-film formation above the surface of a solid substrate. The photochemically mediated technique offers numerous advantages over traditional deposition methods including quantitative atom deposition control, high energy efficiency, and mild operating condition requirements.

Photobiomolecular metallic particles and films

DOEpatents

Hu, Zhong-Cheng

2003-05-06

The method of the invention is based on the unique electron-carrying function of a photocatalytic unit such as the photosynthesis system I (PSI) reaction center of the protein-chlorophyll complex isolated from chloroplasts. The method employs a photo-biomolecular metal deposition technique for precisely controlled nucleation and growth of metallic clusters/particles, e.g., platinum, palladium, and their alloys, etc., as well as for thin-film formation above the surface of a solid substrate. The photochemically mediated technique offers numerous advantages over traditional deposition methods including quantitative atom deposition control, high energy efficiency, and mild operating condition requirements.

Hidden electronic rule in the “cluster-plus-glue-atom” model

PubMed Central

Du, Jinglian; Dong, Chuang; Melnik, Roderick; Kawazoe, Yoshiyuki; Wen, Bin

2016-01-01

Electrons and their interactions are intrinsic factors to affect the structure and properties of materials. Based on the “cluster-cluster-plus-glue-atom” model, an electron counting rule for complex metallic alloys (CMAs) has been revealed in this work (i. e. the CPGAMEC rule). Our results on the cluster structure and electron concentration of CMAs with apparent cluster features, indicate that the valence electrons’ number per unit cluster formula for these CMAs are specific constants of eight-multiples and twelve-multiples. It is thus termed as specific electrons cluster formula. This CPGAMEC rule has been demonstrated as a useful guidance to direct the design of CMAs with desired properties, while its practical applications and underlying mechanism have been illustrated on the basis of CMAs’ cluster structural features. Our investigation provides an aggregate picture with intriguing electronic rule and atomic structural features of CMAs. PMID:27642002

Characterization of the reactive and dissociative behavior of transition metal oxide cluster ions in the gas phase.

PubMed

Maleknia, S; Brodbelt, J; Pope, K

1991-05-01

The reactive and dissociative behavior of molybdenum and tungsten oxide cluster ions has been studied in the gas phase using a triple quadrupole mass spectrometer. Cluster ions (MO3) n (-) were formed via a simple thermal desorption/electron capture negative ionization method, and their structures were characterized by collision-activated dissociation (CAD). Typically, the clusters fragment by losses of neutral (MO3) units. Reactions of the oxide cluster ions with ethylene oxide, cyclohexene oxide, ethylene sulfide cyclohexene sulfide, 2,3-butanedione, and 2,4-pentanedione were examined, and product ions were characterized by CAD. The clusters react with ethylene oxide by addition of ethylene oxide or net addition of oxygen, whereas the clusters react with ethylene sulfide via net addition of one or two sulfur atoms. Reactions of the clusters with the diones result in addition of one or two dione units, in some cases with dehydration.

Nucleophilic ring opening of bridging thietanes in open triosmium cluster complexes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adams, R.D.; Belinski, J.A.

1992-07-01

The complexes Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}] (1) and Os{sub 3}(CO){sub 9}({mu}{sub 3}-S)[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}] (2) were obtained from the reactions of Os{sub 3}(CO){sub 10}({mu}{sub 3}-S) with 3,3-dimethylthietane (DMT) and thietane, respectively, at -42 {degree}C in the presence of Me{sub 3}NO. Compound 1 was characterized by a single-crystal X-ray diffraction analysis and was found to contain a DMT group bridging two of the nonbonded metal atoms in the open cluster of three metal atoms by using both lone pairs of electrons on the sulfur atom. Compound 1 reacted with bis(triphenylphosphine)nitrogen(1+) chloride ([PPN]Cl) at 25 {degrees}C tomore » yield the salt [PPN][Os{sub 3}-(CO){sub 9}({mu}-SCH{sub 2}CMe{sub 2}CH{sub 2}Cl)({mu}{sub 3}-S)] (3; 76%), in which the chloride ion was added to one of the methylene groups of the DMT ring in a process that caused the ring to open by cleavage of one of the carbon-sulfur bonds. A 4-chloro-3,3-dimethylpropanethiolate ligand bridges the open edge of the anionic triosmium cluster. Compound 3 was converted to the neutral complex Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CMe{sub 2}CMe{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (4) by reaction with HCl at 25 {degrees}C. Compound 4 is structurally similar to 3, except that is contains a hydride ligand bridging one of the two metal-metal bonds. Compounds 1 and 2 react with HCl in CH{sub 2}Cl{sub 2} solvent to yield the neutral compounds 4 and Os{sub 3}(CO){sub 9}[{mu}-SCH{sub 2}CH{sub 2}CH{sub 2}Cl]({mu}{sub 3}-S)({mu}-H) (5) in 89% and 90% yields, respectively, in one step. 11 refs., 3 figs., 10 tabs.« less

Comparative study of energy of particles ejected from coulomb explosion of rare gas and metallic clusters irradiated by intense femtosecond laser field

NASA Astrophysics Data System (ADS)

Boucerredj, N.; Beggas, K.

2016-10-01

We present our study of high intensity femtosecond laser field interaction with large cluster of Kr and Na (contained 2.103 to 2.107 atoms). When laser intensity is above a critical value, it blows off all of electrons from the cluster and forms a non neutral ion cloud. The irradiation of these clusters by the intense laser field leads to highly excitation energy which can be the source of energetic electrons, electronic emission, highly charge, energetic ions and fragmentation process. During the Coulomb explosion of the resulting highly ionized, high temperature nanoplasma, ions acquire again their energy. It is shown that ultra fast ions are produced. The goal of our study is to investigate in detail a comparative study of the expansion and explosion then the ion energy of metallic and rare gas clusters irradiated by an intense femtosecond laser field. We have found that ions have a kinetic energy up to 105 eV and the Coulomb pressure is little than the hydrodynamic pressure. The Coulomb explosion of a cluster may provide a new high energy ion source.

Investigating the synthesis of ligated metal clusters in solution using a flow reactor and electrospray ionization mass spectrometry.

PubMed

Olivares, Astrid; Laskin, Julia; Johnson, Grant E

2014-09-18

The scalable synthesis of ligated subnanometer metal clusters containing an exact number of atoms is of interest due to the highly size-dependent catalytic, electronic, and optical properties of these species. While significant research has been conducted on the batch preparation of clusters through reduction synthesis in solution, the processes of metal complex reduction as well as cluster nucleation, growth, and postreduction etching are still not well understood. Herein, we demonstrate a prototype temperature-controlled flow reactor for qualitatively studying cluster formation in solution at steady-state conditions. Employing this technique, methanol solutions of a chloro(triphenylphosphine)gold precursor, 1,4-bis(diphenylphosphino)butane capping ligand, and borane-tert-butylamine reducing agent were combined in a mixing tee and introduced into a heated capillary with a known length. In this manner, the temperature dependence of the relative abundance of different ionic reactants, intermediates, and products synthesized in real time was characterized qualitatively using online mass spectrometry. A wide distribution of doubly and triply charged cationic gold clusters was observed as well as smaller singly charged organometallic complexes. The results demonstrate that temperature plays a crucial role in determining the relative population of cationic gold clusters and, in general, that higher temperature promotes the formation of doubly charged clusters and singly charged organometallic complexes while reducing the abundance of triply charged species. Moreover, the distribution of clusters observed at elevated temperatures is found to be consistent with that obtained at longer reaction times at room temperature, thereby demonstrating that heating may be used to access cluster distributions characteristic of different stages of batch reduction synthesis in solution.

Communication: Diverse nanoscale cluster dynamics: Diffusion of 2D epitaxial clusters

NASA Astrophysics Data System (ADS)

Lai, King C.; Evans, James W.; Liu, Da-Jiang

2017-11-01

The dynamics of nanoscale clusters can be distinct from macroscale behavior described by continuum formalisms. For diffusion of 2D clusters of N atoms in homoepitaxial systems mediated by edge atom hopping, macroscale theory predicts simple monotonic size scaling of the diffusion coefficient, DN ˜ N-β, with β = 3/2. However, modeling for nanoclusters on metal(100) surfaces reveals that slow nucleation-mediated diffusion displaying weak size scaling β < 1 occurs for "perfect" sizes Np = L2 and L(L+1) for integer L = 3,4,… (with unique square or near-square ground state shapes), and also for Np+3, Np+4,…. In contrast, fast facile nucleation-free diffusion displaying strong size scaling β ≈ 2.5 occurs for sizes Np+1 and Np+2. DN versus N oscillates strongly between the slowest branch (for Np+3) and the fastest branch (for Np+1). All branches merge for N = O(102), but macroscale behavior is only achieved for much larger N = O(103). This analysis reveals the unprecedented diversity of behavior on the nanoscale.

Rhodium clustering process on defective (8,0) SWCNT: Analysis of chemical and physical properties using density functional theory

NASA Astrophysics Data System (ADS)

Ambrusi, Ruben E.; Luna, C. Romina; Sandoval, Mario G.; Bechthold, Pablo; Pronsato, M. Estela; Juan, Alfredo

2017-12-01

The Spin-polarized density functional theory is used to study the effect of a single vacancy in a (8,0) single-walled carbon nanotube (SWCNT) on the Rh clustering process. The vacancy is considered oxygenated and non-oxygenated and, in each case, different Rhn cluster sizes (n = 1-4) are taken into account. For the analysis of these systems some physical and chemical properties are calculated, such as binding energy (Eb), work function (WF), magnetic moment, charge transfer, bond length, band gap (Eg), and density of state (DOS). From this analysis it can be concluded that: a single Rh atom and Rh2 dimer are adsorbed on vacancy without oxygen, whereas Rh3 and Rh4 clusters prefer to be adsorbed on oxygenated vacancy. In all cases, Rh adsorption induces a magnetic moment. When the Rh atom and Rh2 dimer are bonded to the defective SWCNT, it has been found that they show a semiconductor behavior that could be interesting to use in the spintronic area. In the case of Rh3 and Rh4 clusters our results show a metallic behavior suggesting that these systems are good candidates for nanotube contact.

Comparative study of cluster Ag17Cu2 by instantaneous normal mode analysis and by isothermal Brownian-type molecular dynamics simulation.

PubMed

Tang, Ping-Han; Wu, Ten-Ming; Yen, Tsung-Wen; Lai, S K; Hsu, P J

2011-09-07

We perform isothermal Brownian-type molecular dynamics simulations to obtain the velocity autocorrelation function and its time Fourier-transformed power spectral density for the metallic cluster Ag(17)Cu(2). The temperature dependences of these dynamical quantities from T = 0 to 1500 K were examined and across this temperature range the cluster melting temperature T(m), which we define to be the principal maximum position of the specific heat is determined. The instantaneous normal mode analysis is then used to dissect the cluster dynamics by calculating the vibrational instantaneous normal mode density of states and hence its frequency integrated value I(j) which is an ensemble average of all vibrational projection operators for the jth atom in the cluster. In addition to comparing the results with simulation data, we look more closely at the entities I(j) of all atoms using the point group symmetry and diagnose their temperature variations. We find that I(j) exhibit features that may be used to deduce T(m), which turns out to agree very well with those inferred from the power spectral density and specific heat. © 2011 American Institute of Physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, X. M.; Wang, X. D., E-mail: wangxd@zju.edu.cn, E-mail: jiangjz@zju.edu.cn; Yu, Q.

The atomic structures of Al{sub 89}Y{sub 11}, Al{sub 90}Y{sub 6.5}La{sub 3.5}, and Al{sub 82.8}Y{sub 6.07}Ni{sub 8}La{sub 3.13} metallic glasses have been studied by using high energy X-ray diffraction, X-ray absorption fine structure combined with the ab initio molecular dynamics and reverse Monte Carlo simulations. It is demonstrated that the partial replacement of Y atoms by La has limited improvement of the glass forming ability (GFA), although La atoms reduce the ordering around Y atoms and also the fractions of icosahedron-like polyhedra centered by Al atoms. In contrast, Ni atoms can significantly improve the GFA, which are inclined to locate inmore » the shell of polyhedra centered by Al, Y, and La atoms, mainly forming Ni-centered icosahedron-like polyhedra to enhance the spatial connectivity between clusters and suppress the crystallization.« less

Meteoric Metal Chemistry in the Martian Atmosphere

PubMed Central

Carrillo‐Sanchez, J. D.; Mangan, T. P.; Crismani, M. M. J.; Schneider, N. M.; Määttänen, A.

2018-01-01

Abstract Recent measurements by the Imaging Ultraviolet Spectrograph (IUVS) instrument on NASA's Mars Atmosphere and Volatile EvolutioN mission show that a persistent layer of Mg+ ions occurs around 90 km in the Martian atmosphere but that neutral Mg atoms are not detectable. These observations can be satisfactorily modeled with a global meteoric ablation rate of 0.06 t sol−1, out of a cosmic dust input of 2.7 ± 1.6 t sol−1. The absence of detectable Mg at 90 km requires that at least 50% of the ablating Mg atoms ionize through hyperthermal collisions with CO2 molecules. Dissociative recombination of MgO+.(CO2)n cluster ions with electrons to produce MgCO3 directly, rather than MgO, also avoids a buildup of Mg to detectable levels. The meteoric injection rate of Mg, Fe, and other metals—constrained by the IUVS measurements—enables the production rate of metal carbonate molecules (principally MgCO3 and FeCO3) to be determined. These molecules have very large electric dipole moments (11.6 and 9.2 Debye, respectively) and thus form clusters with up to six H2O molecules at temperatures below 150 K. These clusters should then coagulate efficiently, building up metal carbonate‐rich ice particles which can act as nucleating particles for the formation of CO2‐ice clouds. Observable mesospheric clouds are predicted to occur between 65 and 80 km at temperatures below 95 K and above 85 km at temperatures about 5 K colder. PMID:29780678

Reactions of mixed silver-gold cluster cations AgmAun+ (m+n=4,5,6) with CO: Radiative association kinetics and density functional theory computations

NASA Astrophysics Data System (ADS)

Neumaier, Marco; Weigend, Florian; Hampe, Oliver; Kappes, Manfred M.

2006-09-01

Near thermal energy reactive collisions of small mixed metal cluster cations AgmAun+ (m +n=4, 5, and 6) with carbon monoxide have been studied in the room temperature Penning trap of a Fourier transform ion-cyclotron-resonance mass spectrometer as a function of cluster size and composition. The tetrameric species AgAu3+ and Ag2Au2+ are found to react dissociatively by way of Au or Ag atom loss, respectively, to form the cluster carbonyl AgAu2CO+. In contrast, measurements on a selection of pentamers and hexamers show that CO is added with absolute rate constants that decrease with increasing silver content. Experimentally determined absolute rate constants for CO adsorption were analyzed using the radiative association kinetics model to obtain cluster cation-CO binding energies ranging from 0.77to1.09eV. High-level ab initio density functional theory (DFT) computations identifying the lowest-energy cluster isomers and the respective CO adsorption energies are in good agreement with the experimental findings clearly showing that CO binds in a "head-on" fashion to a gold atom in the mixed clusters. DFT exploration of reaction pathways in the case of Ag2Au2+ suggests that exoergicities are high enough to access the minimum energy products for all reactive clusters probed.

Adsorption of alkali and alkaline earth metal atoms and dimers on monolayer germanium carbide

NASA Astrophysics Data System (ADS)

Gökçe, Aytaç Gürhan; Ersan, Fatih

2017-01-01

First-principles plane wave calculations have been performed to study the adsorption of alkali and alkaline earth metals on monolayer germanium carbide (GeC). We found that the favourable adsorption sites on GeC sheet for single alkali and alkaline earth adatoms are generally different from graphene or germanene. Among them, Mg, Na and their dimers have weakly bounded to GeC due to their closed valence electron shells, so they may have high mobility on GeC. Two different levels of adatom coverage (? and ?) have been investigated and we concluded that different electronic structures and magnetic moments for both coverages owing to alkali and alkaline earth atoms have long range electrostatic interactions. Lithium atom prefers to adsorbed on hollow site similar to other group-IV monolayers and the adsorption results in metallisation of GeC instead of semiconducting behaviour. Na and K adsorption can induce 1 ? total magnetic moment on GeC structures and they have shown semiconductor property which may have potential use in spintronic devices. We also showed that alkali or alkaline earth metal atoms can form dimer on GeC sheet. Calculated adsorption energies suggest that clustering of alkali and alkaline earth atoms is energetically favourable. All dimer adsorbed GeC systems have nonmagnetic semiconductor property with varying band gaps from 0.391 to 1.311 eV which are very suitable values for various device applications.

Using Density Functional Theory (DFT) for the Calculation of Atomization Energies

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The calculation of atomization energies using density functional theory (DFT), using the B3LYP hybrid functional, is reported. The sensitivity of the atomization energy to basis set is studied and compared with the coupled cluster singles and doubles approach with a perturbational estimate of the triples (CCSD(T)). Merging the B3LYP results with the G2(MP2) approach is also considered. It is found that replacing the geometry optimization and calculation of the zero-point energy by the analogous quantities computed using the B3LYP approach reduces the maximum error in the G2(MP2) approach. In addition to the 55 G2 atomization energies, some results for transition metal containing systems will also be presented.

Polymorphism in magic-sized Au144(SR)60 clusters

NASA Astrophysics Data System (ADS)

Jensen, Kirsten M. Ø.; Juhas, Pavol; Tofanelli, Marcus A.; Heinecke, Christine L.; Vaughan, Gavin; Ackerson, Christopher J.; Billinge, Simon J. L.

2016-06-01

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. Here we present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. The study reveals structural polymorphism in these archetypal nanoclusters. In addition to confirming the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. The discovery of polymorphism may open up a new dimension in nanoscale engineering.

Nanostructures nucleation in carbon-metal gaseous phase: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Galiullina, G. M.; Orekhov, N. D.; Stegailov, V. V.

2018-01-01

We perform nonequilibrium molecular dynamics simulation of carbon nanoclusters nucleation and early stages of growth from the gaseous phase. We analyze the catalytic effect of iron atoms on the nucleation kinetics and structure of the resultant nanoparticles. Reactive Force Field (ReaxFF) is used in the simulations for the description of bond formation and dissociation during the nucleation process at the nanoscale. The catalytic effect of iron reveals itself even on nanosecond simulation times: iron atoms accelerate the process of clustering but result in less graphitized carbon structures.

Ti12Xe: A twelve-coordinated Xe-containing molecule

NASA Astrophysics Data System (ADS)

Miao, Junjian; Xu, Wenwu; Zhu, Beien; Gao, Yi

2017-08-01

A twelve-coordinated Xe-containing molecule Ti12Xe has been predicted by DFT calculations with quasi-icosahedral symmetry. Structural and NBO analyses show the chemical bonding exists between the central Xe atom and peripheral Ti atoms, which leads to the high stability of the molecule to a considerable degree. First principle molecular dynamics simulations further reveal the particularly high thermal stability of Ti12Xe up to 1500 K. This unique species may disclose new physics and chemistry of xenon element and stir interest in the Xe-transition metal cluster physics and chemistry.

Field evaporation of ZnO: A first-principles study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xia, Yu, E-mail: yuxia@dal.ca; Karahka, Markus; Kreuzer, H. J.

2015-07-14

With recent advances in atom probe tomography of insulators and semiconductors, there is a need to understand high electrostatic field effects in these materials as well as the details of field evaporation. We use density functional theory to study field effects in ZnO clusters calculating the potential energy curves, the local field distribution, the polarizability, and the dielectric constant as a function of field strength. We confirm that, as in MgO, the HOMO-LUMO gap of a ZnO cluster closes at the evaporation field strength signaling field-induced metallization of the insulator. Following the structural changes in the cluster at the evaporationmore » field strength, we can identify the field evaporated species, in particular, we show that the most abundant ion, Zn{sup 2+}, is NOT post-ionized but leaves the surface as 2+ largely confirming the experimental observations. Our results also help to explain problems related to stoichiometry in the mass spectra measured in atom probe tomography.« less

Reversing Conventional Reactivity of Mixed Oxo/Alkyl Rare-Earth Complexes: Non-Redox Oxygen Atom Transfer.

PubMed

Hong, Jianquan; Tian, Haiwen; Zhang, Lixin; Zhou, Xigeng; Del Rosal, Iker; Weng, Linhong; Maron, Laurent

2018-01-22

The preferential substitution of oxo ligands over alkyl ones of rare-earth complexes is commonly considered as "impossible" due to the high oxophilicity of metal centers. Now, it has been shown that simply assembling mixed methyl/oxo rare-earth complexes to a rigid trinuclear cluster framework cannot only enhance the activity of the Ln-oxo bond, but also protect the highly reactive Ln-alkyl bond, thus providing a previously unrecognized opportunity to selectively manipulate the oxo ligand in the presence of numerous reactive functionalities. Such trimetallic cluster has proved to be a suitable platform for developing the unprecedented non-redox rare-earth-mediated oxygen atom transfer from ketones to CS 2 and PhNCS. Controlled experiments and computational studies shed light on the driving force for these reactions, emphasizing the importance of the sterical accessibility and multimetallic effect of the cluster framework in promoting reversal of reactivity of rare-earth oxo complexes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Template Synthesis, Metalation, and Self-Assembly of Protic Gold(I)/(NHC)2 Tectons Driven by Metallophilic Interactions.

PubMed

Ruiz, Javier; García, Lucía; Sol, Daniel; Vivanco, Marilín

2016-07-11

A new protocol for the synthesis of protic bis(N-heterocyclic carbene) complexes of Au(I) by a stepwise metal-controlled coupling of isocyanide and propargylamine is described. They are used as tectons for the construction of supramolecular architectures through metalation and self-assembly. Notably a unique polymeric chain of Cu(I) with alternate Au(I) /bis(imidazolate) bridging scaffolds and strong unsupported Cu(I) -Cu(I) interactions has been generated, as well as a 28-metal-atoms cluster containing a nanopiece of Cu2 O trapped by peripheral Au(I) /bis(imidazolate) moieties. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electronic Transport Behaviors due to Charge Density Waves in Ni-Nb-Zr-H Glassy Alloys

NASA Astrophysics Data System (ADS)

Fukuhara, Mikio; Umemori, Yoshimasa

2013-11-01

The amorphous Ni-Nb-Zr-H glassy alloy containing subnanometer-sized icosahedral Zr5 Nb5Ni3 clusters exhibited four types of electronic phenomena: a metal/insulator transition, an electric current-induced voltage oscillation (Coulomb oscillation), giant capacitor behavior and an electron avalanche with superior resistivity. These findings could be excluded by charge density waves that the low-dimensional component of clusters, in which the atoms are lined up in chains along the [130] direction, plays important roles in various electron transport phenomena.

Atomic and electronic basis for the serrations of refractory high-entropy alloys

NASA Astrophysics Data System (ADS)

Wang, William Yi; Shang, Shun Li; Wang, Yi; Han, Fengbo; Darling, Kristopher A.; Wu, Yidong; Xie, Xie; Senkov, Oleg N.; Li, Jinshan; Hui, Xi Dong; Dahmen, Karin A.; Liaw, Peter K.; Kecskes, Laszlo J.; Liu, Zi-Kui

2017-06-01

Refractory high-entropy alloys present attractive mechanical properties, i.e., high yield strength and fracture toughness, making them potential candidates for structural applications. Understandings of atomic and electronic interactions are important to reveal the origins for the formation of high-entropy alloys and their structure-dominated mechanical properties, thus enabling the development of a predictive approach for rapidly designing advanced materials. Here, we report the atomic and electronic basis for the valence-electron-concentration-categorized principles and the observed serration behavior in high-entropy alloys and high-entropy metallic glass, including MoNbTaW, MoNbVW, MoTaVW, HfNbTiZr, and Vitreloy-1 MG (Zr41Ti14Cu12.5Ni10Be22.5). We find that the yield strengths of high-entropy alloys and high-entropy metallic glass are a power-law function of the electron-work function, which is dominated by local atomic arrangements. Further, a reliance on the bonding-charge density provides a groundbreaking insight into the nature of loosely bonded spots in materials. The presence of strongly bonded clusters and weakly bonded glue atoms imply a serrated deformation of high-entropy alloys, resulting in intermittent avalanches of defects movement.

Synthesis and structure of an extended cluster lead(II) carboxylate, [Pb((CO){sub 9}Co{sub 3}({mu}{sub 3}-CCO{sub 2})){sub 2}]{sub n}. Role of core metals in cluster-derived hydrogenation catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xinjian Lei; Maoyu Shang; Fehlner, T.P.

The reaction of lead acetate with (CO){sub 9}Co{sub 3}({mu}{sub 3}-CCOOH) leads to the formation of [Pb((CO){sub 9}Co{sub 3}({mu}{sub 3}-CCO{sub 2})){sub 2}]{sub n}, I, in high yield. The structure of I exhibits unusual six-coordinate Pb(II) centers with two asymmetrical chelating cluster carboxylates (C{sub 22}Co{sub 6}PbO{sub 22}; triclinic P1; a = 8.119(1), b = 14.346(2), c = 14.660(2) {Angstrom}; {alpha} = 102.18(1), {beta} = 99.01(1), {gamma} = 97.30(1){degrees}; Z = 2). One oxygen of each cluster carboxylate ligand bridges between adjacent lead atoms such that a chainlike extended structure is found in the solid state without the presence of solvent or water.more » I is converted stepwide on pyrolysis into two metastable forms of solid materials (designated LT and HT), each of which has been characterized spectroscopically. The hydrogenation of 2-butenal as a test reaction shows that the LT catalyst exhibits selectivities similar to previous LT materials derived from other cobalt cluster metal carboxylates and that the HT material is totally inactive. The observed release of the lead core metal under HT activation conditions totally inactivates the catalyst and demonstrates exposure of the core metal in the HT form of these novel catalysts.« less

Theoretical studies on Grignard reagent formation: radical mechanism versus non-radical mechanism.

PubMed

Chen, Zhe-Ning; Fu, Gang; Xu, Xin

2012-12-21

Here we present a systematic theoretical investigation on the mechanisms of Grignard reagent formation (GRF) for CH(3)Cl reacting with Mg atom, Mg(2) and a series of Mg clusters (Mg(4)-Mg(20)). Our calculations reveal that the ground state Mg atom is inactive under matrix condition, whereas it is active under metal vapor synthesis (MVS) conditions. On the other hand, the excited state Mg ((3)P) atom, as produced by laser-ablation, can react with CH(3)Cl barrierlessly, and hence is active under matrix condition. We predict that the bimagnesium Grignard reagent, though often proposed, can barely be observed experimentally, due to its high reactivity towards additional CH(3)Cl to produce more stable Grignard reagent dimer, and that the cluster Grignard reagent RMg(4)X possesses a flat Mg(4) unit rather than a tetrahedral geometry. Our calculations further reveal that the radical pathway (T4) is prevalent on Mg, Mg(2) and Mg(n) clusters of small size, while the no-radical pathway (T2), which starts at Mg(4), becomes competitive with T4 as the cluster size increases. A structure-reactivity relationship between barrier heights and ionization potentials of Mg(n) is established. These findings not only resolve controversy in experiment and theory, but also provide insights which can be used in the design of effective synthesis approaches for the preparation of chiral Grignard reagents.

Molecular metal catalysts on supports: organometallic chemistry meets surface science.

PubMed

Serna, Pedro; Gates, Bruce C

2014-08-19

Recent advances in the synthesis and characterization of small, essentially molecular metal complexes and metal clusters on support surfaces have brought new insights to catalysis and point the way to systematic catalyst design. We summarize recent work unraveling effects of key design variables of site-isolated catalysts: the metal, metal nuclearity, support, and other ligands on the metals, also considering catalysts with separate, complementary functions on supports. The catalysts were synthesized with the goal of structural simplicity and uniformity to facilitate incisive characterization. Thus, they are essentially molecular species bonded to porous supports chosen for their high degree of uniformity; the supports are crystalline aluminosilicates (zeolites) and MgO. The catalytic species are synthesized in reactions of organometallic precursors with the support surfaces; the precursors include M(L)2(acetylacetonate)1-2, with M = Ru, Rh, Ir, or Au and the ligands L = C2H4, CO, or CH3. Os3(CO)12 and Ir4(CO)12 are used as precursors of supported metal clusters, and some such catalysts are made by ship-in-a-bottle syntheses to trap the clusters in zeolite cages. The simplicity and uniformity of the supported catalysts facilitate precise structure determinations, even in reactive atmospheres and during catalysis. The methods of characterizing catalysts in reactive atmospheres include infrared (IR), extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and nuclear magnetic resonance (NMR) spectroscopies, and complementary methods include density functional theory and atomic-resolution aberration-corrected scanning transmission electron microscopy for imaging of individual metal atoms. IR, NMR, XANES, and microscopy data demonstrate the high degrees of uniformity of well-prepared supported species. The characterizations determine the compositions of surface metal complexes and clusters, including the ligands and the metal-support bonding and structure, which identify the supports as ligands with electron-donor properties that influence reactivity and catalysis. Each of the catalyst design variables has been varied independently, illustrated by mononuclear and tetranuclear iridium on zeolite HY and on MgO and by isostructural rhodium and iridium (diethylene or dicarbonyl) complexes on these supports. The data provide examples resolving the roles of the catalyst design variables and place the catalysis science on a firm foundation of organometallic chemistry linked with surface science. Supported molecular catalysts offer the advantages of characterization in the absence of solvents and with surface-science methods that do not require ultrahigh vacuum. Families of supported metal complexes have been made by replacement of ligands with others from the gas phase. Spectroscopically identified catalytic reaction intermediates help to elucidate catalyst performance and guide design. The methods are illustrated for supported complexes and clusters of rhodium, iridium, osmium, and gold used to catalyze reactions of small molecules that facilitate identification of the ligands present during catalysis: alkene dimerization and hydrogenation, H-D exchange in the reaction of H2 with D2, and CO oxidation. The approach is illustrated with the discovery of a highly active and selective MgO-supported rhodium carbonyl dimer catalyst for hydrogenation of 1,3-butadiene to give butenes.

Electrochemical impedance spectroscopy on nanostructured carbon electrodes grown by supersonic cluster beam deposition

NASA Astrophysics Data System (ADS)

Bettini, Luca Giacomo; Bardizza, Giorgio; Podestà, Alessandro; Milani, Paolo; Piseri, Paolo

2013-02-01

Nanostructured porous films of carbon with density of about 0.5 g/cm3 and 200 nm thickness were deposited at room temperature by supersonic cluster beam deposition (SCBD) from carbon clusters formed in the gas phase. Carbon film surface topography, determined by atomic force microscopy, reveals a surface roughness of 16 nm and a granular morphology arising from the low kinetic energy ballistic deposition regime. The material is characterized by a highly disordered carbon structure with predominant sp2 hybridization as evidenced by Raman spectroscopy. The interface properties of nanostructured carbon electrodes were investigated by cyclic voltammetry and electrochemical impedance spectroscopy employing KOH 1 M solution as aqueous electrolyte. An increase of the double layer capacitance is observed when the electrodes are heat treated in air or when a nanostructured nickel layer deposited by SCBD on top of a sputter deposited film of the same metal is employed as a current collector instead of a plain metallic film. This enhancement is consistent with an improved charge injection in the active material and is ascribed to the modification of the electrical contact at the interface between the carbon and the metal current collector. Specific capacitance values up to 120 F/g have been measured for the electrodes with nanostructured metal/carbon interface.

Deposition of Size-Selected Cu Nanoparticles by Inert Gas Condensation

PubMed Central

2010-01-01

Nanometer size-selected Cu clusters in the size range of 1–5 nm have been produced by a plasma-gas-condensation-type cluster deposition apparatus, which combines a grow-discharge sputtering with an inert gas condensation technique. With this method, by controlling the experimental conditions, it was possible to produce nanoparticles with a strict control in size. The structure and size of Cu nanoparticles were determined by mass spectroscopy and confirmed by atomic force microscopy (AFM) and scanning electron transmission microscopy (STEM) measurements. In order to preserve the structural and morphological properties, the energy of cluster impact was controlled; the energy of acceleration of the nanoparticles was in near values at 0.1 ev/atom for being in soft landing regime. From SEM measurements developed in STEM-HAADF mode, we found that nanoparticles are near sized to those values fixed experimentally also confirmed by AFM observations. The results are relevant, since it demonstrates that proper optimization of operation conditions can lead to desired cluster sizes as well as desired cluster size distributions. It was also demonstrated the efficiency of the method to obtain size-selected Cu clusters films, as a random stacking of nanometer-size crystallites assembly. The deposition of size-selected metal clusters represents a novel method of preparing Cu nanostructures, with high potential in optical and catalytic applications. PMID:20652132

Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides.

PubMed

Wang, Zixing; Kochat, Vidya; Pandey, Prafull; Kashyap, Sanjay; Chattopadhyay, Soham; Samanta, Atanu; Sarkar, Suman; Manimunda, Praveena; Zhang, Xiang; Asif, Syed; Singh, Abhisek K; Chattopadhyay, Kamanio; Tiwary, Chandra Sekhar; Ajayan, Pulickel M

2017-08-01

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C 2 H 2 , B powder, and NH 3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Influence of Atomic Diffusion on Stellar Ages and Chemical Tagging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dotter, Aaron; Conroy, Charlie; Cargile, Phillip

2017-05-10

In the era of large stellar spectroscopic surveys, there is an emphasis on deriving not only stellar abundances but also the ages for millions of stars. In the context of Galactic archeology, stellar ages provide a direct probe of the formation history of the Galaxy. We use the stellar evolution code MESA to compute models with atomic diffusion—with and without radiative acceleration—and extra mixing in the surface layers. The extra mixing consists of both density-dependent turbulent mixing and envelope overshoot mixing. Based on these models we argue that it is important to distinguish between initial, bulk abundances (parameters) and current,more » surface abundances (variables) in the analysis of individual stellar ages. In stars that maintain radiative regions on evolutionary timescales, atomic diffusion modifies the surface abundances. We show that when initial, bulk metallicity is equated with current, surface metallicity in isochrone age analysis, the resulting stellar ages can be systematically overestimated by up to 20%. The change of surface abundances with evolutionary phase also complicates chemical tagging, which is the concept that dispersed star clusters can be identified through unique, high-dimensional chemical signatures. Stars from the same cluster, but in different evolutionary phases, will show different surface abundances. We speculate that calibration of stellar models may allow us to estimate not only stellar ages but also initial abundances for individual stars. In the meantime, analyzing the chemical properties of stars in similar evolutionary phases is essential to minimize the effects of atomic diffusion in the context of chemical tagging.« less

Atomically precise (catalytic) particles synthesized by a novel cluster deposition instrument

DOE PAGES

Yin, C.; Tyo, E.; Kuchta, K.; ...

2014-05-06

Here, we report a new high vacuum instrument which is dedicated to the preparation of well-defined clusters supported on model and technologically relevant supports for catalytic and materials investigations. The instrument is based on deposition of size selected metallic cluster ions that are produced by a high flux magnetron cluster source. Furthermore, we maximize the throughput of the apparatus by collecting and focusing ions utilizing a conical octupole ion guide and a linear ion guide. The size selection is achieved by a quadrupole mass filter. The new design of the sample holder provides for the preparation of multiple samples onmore » supports of various sizes and shapes in one session. After cluster deposition onto the support of interest, samples will be taken out of the chamber for a variety of testing and characterization.« less

Preparation of Carboxylato-Coordinated Titanium Alkoxides from Carboxylic Anhydrides: Alkoxido Group Transfer from Metal Atom to Carbonyl Group.

PubMed

Czakler, Matthias; Artner, Christine; Schubert, Ulrich

2012-07-01

Reaction of titanium(IV) isopropoxide, Ti(O i Pr) 4 , with an equimolar amount of phthalic anhydride resulted in the transfer of an isopropoxido group from the metal atom to one carbonyl group of the anhydride and coordination of the thus formed monoester to the titanium atom. One monoester ligand in Ti 2 (O i Pr) 6 (μ 2 -OOC-C 6 H 4 -COO i Pr)(η 1 -OOC-C 6 H 4 -COO i Pr)( i PrOH) is bridging and the other is η 1 -coordinated. When the reaction is performed in the presence of 1 mol-equiv. of acetic acid, the oxido cluster Ti 6 (μ 3 -O) 6 (O i Pr) 6 (μ 2 -OOC-C 6 H 4 -COO i Pr) 6 was instead obtained. The μ 3 -oxygen groups in the latter compound are due to esterification of acetic acid by the cleaved isopropyl alcohol.

Cooling rate dependence and local structure in aluminum monatomic metallic glass

NASA Astrophysics Data System (ADS)

Kbirou, M.; Trady, S.; Hasnaoui, A.; Mazroui, M.

2017-10-01

The local atomic structure in aluminium monatomic metallic glass is studied using molecular dynamics simulations combined with the embedded atom method (EAM). We have used a variety of analytical methods to characterise the atomic configurations of our system: the Pair Distribution Function (PDF), the Common Neighbour Analysis (CNA) and the Voronoi Tessellation Analysis. CNA was used to investigate the order change from liquid to amorphous phases, recognising that the amount of icosahedral clusters increases with the decrease of temperature. The Voronoi analysis revealed that the icosahedral-like polyhedral are the predominant ones. It has been observed that the PDF function shows a splitting in the second peak, which cannot be attributed to the only ideal icosahedral polyhedron 〈0, 0, 12, 0〉, but also to the formation of other Voronoi polyhedra 〈0, 1, 10, 2〉 . Further, the PDFs were then integrated giving the cumulative coordination number in order to compute the fractal dimension (df).

The linkage between ribosomal crystallography, metal ions, heteropolytungstates and functional flexibility

PubMed Central

Bashan, Anat; Yonath, Ada

2009-01-01

Crystallography of ribosomes, the universal cell nucleoprotein assemblies facilitating the translation of the genetic-code into proteins, met with severe problems owing to their large size, complex structure, inherent flexibility and high conformational variability. For the case of the small ribosomal subunit, which caused extreme difficulties, post crystallization treatment by minute amounts of a heteropolytungstate cluster allowed structure determination at atomic resolution. This cluster played a dual role in ribosomal crystallography: providing anomalous phasing power and dramatically increased the resolution, by stabilization of a selected functional conformation. Thus, four out of the fourteen clusters that bind to each of the crystallized small subunits are attached to a specific ribosomal protein in a fashion that may control a significant component of the subunit internal flexibility, by “gluing” symmetrical related subunits. Here we highlight basic issues in the relationship between metal ions and macromolecules and present common traits controlling in the interactions between polymetalates and various macromolecules, which may be extended towards the exploitation of polymetalates for therapeutical treatment. PMID:19915655

Reduction of N2 by supported tungsten clusters gives a model of the process by nitrogenase

PubMed Central

Murakami, Junichi; Yamaguchi, Wataru

2012-01-01

Metalloenzymes catalyze difficult chemical reactions under mild conditions. Mimicking their functions is a challenging task and it has been investigated using homogeneous systems containing metal complexes. The nitrogenase that converts N2 to NH3 under mild conditions is one of such enzymes. Efforts to realize the biological function have continued for more than four decades, which has resulted in several reports of reduction of N2, ligated to metal complexes in solutions, to NH3 by protonation under mild conditions. Here, we show that seemingly distinct supported small tungsten clusters in a dry environment reduce N2 under mild conditions like the nitrogenase. N2 is reduced to NH3 via N2H4 by addition of neutral H atoms, which agrees with the mechanism recently proposed for the N2 reduction on the active site of nitrogenase. The process on the supported clusters gives a model of the biological N2 reduction. PMID:22586517

Alloy formation and metal oxide segregation in Pt-Re/. gamma. -Al/sub 2/O/sub 3/ catalysts as investigated by temperature-programmed reduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wagstaff, N.; Prins, R.

1979-10-15

Temperature-programmed reduction has been used to characterize the finely dispersed metal compounds in a series of Pt-Re/..gamma..-Al/sub 2/O/sub 3/ catalysts. Strong evidence has been obtained that zerovalent Pt and Re atoms are in intimate contact with each other after catalyst reduction. The formation of bimetallic clusters supports the alloy explanation for the improved performance of this type of bimetallic reforming catalyst. Treatment of the reduced catalysts with oxygen above about 200/sup 0/C causes segregation of platinum and rhenium oxides. Adsorption of oxygen at temperatures up to 100/sup 0/C leaves the bimetallic clusters largely intact, but subsequent high-temperature treatment in themore » absence of extra oxygen leads to segregation of Pt and Re species. This suggests that in the presence of adsorbed oxygen the Pt-Re clusters are thermodynamically unstable, but that under mild conditions the rate of segregation is slow. 10 figures, 4 tables.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, T.R.

The cyclo-addition of two Mo/sub 2/Cl/sub 4/(P(C/sub 6/H/sub 5/)/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ molecules has produced a new type of tetrameric molybdenum cluster, Mo/sub 4/Cl/sub 8/L/sub 4/. Structural characterization of this dimer revealed weak molybdenum-methanol bonding which was consistent with the observed reactivity of the compound. New synthetic methods were devised for the preparation of Mo/sub 4/X/sub 8/L/sub 4/ clusters where X = Cl, Br, I, and L = PR/sub 3/, PO/sub 3/, RCN, CH/sub 3/OH. A scheme for the metal-metal bonding in these clusters was presented which was in agreement with the known structural features of Mo/sub 4/Cl/sub 8/(PR/submore » 3/)/sub 4/, R = C/sub 2/H/sub 5/, n-C/sub 4/H/sub 9/. The preparation of the analogous W/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ cluster from WCl/sub 4/ was accomplished by application of techniques used in the molybdenum syntheses. The single crystal x-ray structure revealed slight differences from the molybdenum analog which were rationalized in terms of the known behavior in dimeric tungsten and molybdenum species. The attempted preparation of a tetrameric tungsten cluster from W/sub 2/(mhp)/sub 4/ was unsuccessful (mhp = anion of 2-methyl-6-hydroxypyridine). Instead, the new tungsten dimer, W/sub 2/Cl/sub 2/(mhp)/sub 3/, was isolated which possessed a metal-metal bond order of 3.5. The x-ray crystal structure of the dimer revealed that the chlorine atoms was situated cis, one bound to each tungsten. Cyclic voltammetry showed that the compound could be reversibly reduced, presumably to a W/sub 2//sup 4 +/ dimer containing a quadruple metal-metal bond.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, T.R.

The cyclo-addition of two Mo/sub 2/Cl/sub 4/(P(C/sub 6/H/sub 5/)/sub 3/)/sub 2/(CH/sub 3/OH)/sub 2/ molecules has produced a new type of tetrameric molybdenum cluster, Mo/sub 4/Cl/sub 8/L/sub 4/. Structural characterization of this dimer revealed weak molybdenum-methanol bonding which was consistent with the observed reactivity of the compound. New synthetic methods were devised for the preparation of Mo/sub 4/X/sub 8/L/sub 4/ clusters where X = Cl, Br, I and L = PR/sub 3/, Po/sub 3/, RCN, CH/sub 3/OH. A scheme for the metal-metal bonding in these clusters was presented which was in agreement with the known structural features of Mo/sub 4/Cl/sub 8/(PR/submore » 3/)/sub 4/, R = C/sub 2/H/sub 5/, n-C/sub 4/H/sub 9/. The preparation of the analogous W/sub 4/Cl/sub 8/(PR/sub 3/)/sub 4/ cluster from WCl/sub 4/ was accomplished by application of techniques used in the molybdenum syntheses. The single crystal x-ray structure revealed slight differences from the molybdenum analog which were rationalized in terms of the known behavior in dimeric tungsten and molybdenum species. The attempted preparation of a tetrameric tungsten cluster from W/sub 2/(mhp)/sub 4/ was unsuccessful (mhp = anion of 2-methyl-6-hydroxypyridine). Instead, the new tungsten dimer, W/sub 2/Cl/sub 2/(mhp)/sub 3/, was isolated which possessed a metal-metal bond order of 3.5. The x-ray crystal structure of the dimer revealed that the chlorine atoms were situated cis, one bound to each tungsten. Cyclic voltammetry showed that the compound could be reversibly reduced, presumably to a W/sub 2//sup 4 +/ dimer containing a quadruple metal-metal bond.« less

First Principles Studies of Electronic and Optical Excitations in Noble Metal and Titania Clusters

NASA Astrophysics Data System (ADS)

Baishya, Kopinjol

Clusters are metastable structures that form a bridge between the atomic and the bulk phase. Due to their small size, quantum confinement effects are very important in clusters. They also have large surface to volume ratio, and as such, surface effects are also important. Due to these effects the properties of clusters are quite different from those of the bulk. When the size of a cluster is increased, its properties change from atomic to bulk values usually in nontrivial ways, often displaying interesting effects. By studying the evolution of cluster properties as a function of size one can try to understand the evolution and origin of bulk properties. This thesis concentrates on two main topics, noble-metal clusters of Ag and Cu, and TiO2 nanocrystals. I present my study of the optical properties of these systems calculated using first principles methods. Noble metal clusters have intriguing physical and chemical properties due to their electronic structure that contains a fully filled and localized d orbital energetically and spatially very close to the half filled s orbital. In Chapters 3 and 4 of this thesis, I present a detailed study of the role of d electrons on the optical properties of Ag and Cu clusters. I also show that the optical spectra of these clusters can be explained remarkably well by the classical Mie-Gans theory which uses the bulk dielectric constant of the material to predict their optical absorption spectra. The fact that the concept of the bulk dielectric constant survives up to the sub-nanometer size range is one of the main findings of this thesis. TiO2 is arguably the most studied single-crystalline material in the field of surface science of metal oxides. In chapter 5 of this thesis I present results and analyses on the electronic and optical excitations in rutile TiO2 nanocrystals. The motivation for this study stems from the following observation: In modeling optical prooperties of DSSC configurations with various organic molecules, a typical approach has been to use a finite, appropriately passivated TiO2 nanocrystal in order to limit the computational demand. In real systems on the other hand, the size of nanocrystalline TiO2 is of the order of several hundreds of nanometers, and hence, they can be considered to be essentially bulk-like. The question is then, whether finite TiO2 nanoparticles can accurately model the optical properties of bulk TiO2. I show in my thesis that the optical absorption absorption spectra of such TiO2 nanocrystals do not have the particular features seen in the imaginary part of the bulk dielectric function of TiO 2 associated with the van Hove singularities in the electronic density of states. Instead, the absorption spectra of bulk-terminated TiO2 nanocrystals can be reproduced quite well by the Mie-Gans theory.

Atomic structure and transport properties of Cu50Zr45Al5 metallic liquids and glasses: Molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Zhang, Y.; Mattern, N.; Eckert, J.

2011-11-01

We have simulated the atomic structure and the transport properties of Cu50Zr45Al5 metallic liquids and glasses within a wide cooling temperature range from 2000 to 300 K, using molecular dynamics simulations. High fractions of Cu- and Al-centered full icosahedra and Zr-centered icosahedra-like clusters have been detected in both supercooled liquids and glasses. The heat capacity and linear thermal expansion coefficients of both liquids and glasses are also calculated, which have not been reported for this off-eutectic composition previously. The critical temperature (Tc) of Cu50Zr45Al5 liquids is determined to be 874.7 K by investigating the self-diffusivity using the mode coupling theory. A dynamics cross-over is detected in the vicinity of Tc, which can be reflected by different diffusion mechanisms and a remarkable deviation from the Einstein-Stokes relation. The results further suggest a fragile to strong transition of Cu50Zr45Al5 liquids between 1500 K and 1300 K upon cooling, which may result from a drastic increase of stable clusters within this temperature range.

Physical Processes at Turnoff

NASA Astrophysics Data System (ADS)

Michaud, Georges

Stellar evolution models taking into account atomic diffusion including radiative accelerations of 28 species have been calculated for Pop II stars of 0.5 to 1.2 solar mass with [Fe/H] from -4.31 to -0.71. Overabundances are expected in some turnoff stars with effective temperatures larger than 5900 K. They depend strongly on the metallicity of the cluster. At the metallicity of M92 they reach a factor of 10 for many species at 12 Gyr but a factor of at most 2 at 13.5 Gyr. Series of models were also calculated with turbulence to determine to what extent turbulence reduces predicted abundance anomalies. The level of abundance anomalies observed in turnoff stars may then determine a level of turbulence. Even in the presence of turbulence however allowance for diffusive processes leads to a 10%-12% reduction in age at a given turnoff luminosity. For M 92 an age of 13.5 Gyr is determined which is about 1.5 Gyr younger than obtained in the absence of diffusion. In clusters atomic diffusion is now known to play a role in white dwarfs HB stars for age determination and for abundance anomalies in some turnoff stars.

Physical Processes at Turnoff

NASA Astrophysics Data System (ADS)

Michaud, Georges

Stellar evolution models taking into account atomic diffusion including radiative accelerations of 28 species have been calculated for Pop II stars of 0.5 to 1.2 solar mass with [Fe/H] from -4.31 to -0.71. Overabundances are expected in some turnoff stars with effective temperatures larger than 5900 K. They depend strongly on the metallicity of the cluster. At the metallicity of M92 they reach a factor of 10 for many species at 12 Gyr but a factor of at most 2 at 13.5 Gyr. Series of models were also calculated with turbulence to determine to what extent turbulence reduces predicted abundance anomalies. The level of abundance anomalies observed in turnoff stars may then determine a level of turbulence. Even in the presence of turbulence however allowance for diffusive processes leads to a 10%-12% reduction in age at a given turnoff luminosity. For M 92 an age of 13.5 Gyr is determined which is about 1.5 Gyr younger than obtained in the absence of diffusion. In clusters atomic diffusion is now known to play a role in white dwarfs HB stars for age determination and for abundance anomalies in some turnoff stars

Processes at the turnoff

NASA Astrophysics Data System (ADS)

Michaud, Georges; Richard, Olivier; Richer, Jacques

2005-01-01

Stellar evolution models taking into account atomic diffusion including radiative accelerations of 28 species have been calculated for Pop II stars of 0.5 to 1.2 solar mass with [Fe/H] from -4.31 to -0.71. Overabundances are expected in some turnoff stars with effective temperatures larger than 5900 K. They depend strongly on the metallicity of the cluster. At the metallicity of M92 they reach a factor of 10 for many species at 12 Gyr but a factor of at most 2 at 13.5 Gyr. Series of models were also calculated with turbulence to determine to what extent turbulence reduces predicted abundance anomalies. The level of abundance anomalies observed in turnoff stars may then determine a level of turbulence. Even in the presence of turbulence however allowance for diffusive processes leads to a 10%-12% reduction in age at a given turnoff luminosity. For M 92 an age of 13.5 Gyr is determined which is about 1.5 Gyr younger than obtained in the absence of diffusion. In clusters atomic diffusion is now known to play a role in white dwarfs HB stars for age determination and for abundance anomalies in some turnoff stars.

Trigonal Mn3 and Co3 Clusters Supported by Weak-Field Ligands: A Structural, Spectroscopic, Magnetic, and Computational Investigation into the Correlation of Molecular and Electronic Structure

PubMed Central

Fout, Alison R.; Xiao, Dianne J.; Zhao, Qinliang; Harris, T. David; King, Evan R.; Eames, Emily V.; Zheng, Shao-Liang; Betley, Theodore A.

2012-01-01

Transamination of divalent transition metal starting materials (M2(N(SiMe3)2)4, M = Mn, Co) with hexadentate ligand platforms RLH6 (RLH6 = MeC(CH2NPh-o-NR)3 where R = H, Ph, Mes (Mes = Mesityl)) or H,CyLH6 = 1,3,5-C6H9(NHPh-o-NH2)3 with added pyridine or tertiary phosphine co-ligands afforded trinuclear complexes of the type (RL)Mn3(py)3 and (RL)Co3(PMe2R’)3 (R’ = Me, Ph). While the sterically less encumbered ligand varieties, HL or PhL, give rise to local square-pyramidal geometries at each of the bound metal atoms, with four anilides forming an equatorial plane and an exogenous pyridine or phosphine in the apical site, the mesityl-substituted ligand (MesL) engenders local tetrahedral coordination. Both the neutral Mn3 and Co3 clusters feature S = 1/2 ground states, as determined by dc magnetometry, 1H NMR spectroscopy, and low-temperature EPR spectroscopy. Within the Mn3 clusters, the long internuclear Mn–Mn separations suggest minimal direct metal-metal orbital overlap. Accordingly, fits to variable-temperature magnetic susceptibility data reveal the presence of weak antiferromagnetic superexchange interactions through the bridging anilide ligands with exchange couplings ranging from J = −16.8 to −42 cm−1. Conversely, the short Co–Co interatomic distances suggest a significant degree of direct metal-metal orbital overlap, akin to the related Fe3 clusters. With the Co3 series, the S = 1/2 ground state can be attributed to population of a single molecular orbital manifold that arises from mixing of the metal- and o-phenylenediamide (OPDA) ligand-based frontier orbitals. Chemical oxidation of the neutral Co3 clusters affords diamagnetic cationic clusters of the type [(RL)Co3(PMe2R)3]+. DFT calculations on the neutral (S = ½) and cationic (S = 0) Co3 clusters reveal that oxidation occurs at an oribital with contributions from both the Co3 core and OPDA subunits. The predicted bond elongations within the ligand OPDA units are corroborated by the ligand bond perturbations observed by X-ray crystallography. PMID:22991939

Structural features and the microscopic dynamics of the three-component Zr{sub 47}Cu{sub 46}Al{sub 7} system: Equilibrium melt, supercooled melt, and amorphous alloy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khusnutdinoff, R. M., E-mail: khrm@mail.ru; Mokshin, A. V., E-mail: anatolii.mokshin@mail.ru; Klumov, B. A.

2016-08-15

The structural and dynamic properties of the three-component Zr{sub 47}Cu{sub 46}Al{sub 7} system are subjected to a molecular dynamics simulation in the temperature range T = 250–3000 K at a pressure p = 1.0 bar. The temperature dependences of the Wendt–Abraham parameter and the translation order parameter are used to determine the glass transition temperature in the Zr{sub 47}Cu{sub 46}Al{sub 7} system, which is found to be T{sub c} ≈ 750 K. It is found that the bulk amorphous Zr{sub 47}Cu{sub 46}Al{sub 7} alloy contains localized regions with an ordered atomic structures. Cluster analysis of configuration simulation data reveals themore » existence of quasi-icosahedral clusters in amorphous metallic Zr–Cu–Al alloys. The spectral densities of time radial distribution functions of the longitudinal (C̃{sub L}(k, ω)) and transverse (C̃{sub T}(k, ω)) fluxes are calculated in a wide wavenumber range in order to study the mechanisms of formation of atomic collective excitations in the Zr{sub 47}Cu{sub 46}Al{sub 7} system. It was found that a linear combination of three Gaussian functions is sufficient to reproduce the (C̃{sub L}(k, ω)) spectra, whereas at least four Gaussian contributions are necessary to exactly describe the (C̃{sub T}(k, ω)) spectra of the supercooled melt and the amorphous metallic alloy. It is shown that the collective atomic excitations in the equilibrium melt at T = 3000 K and in the amorphous metallic alloy at T = 250 K are characterized by two dispersion acoustic-like branches related with longitudinal and transverse polarizations.« less

Polymorphism in magic-sized Au144(SR)60 clusters

DOE PAGES

Jensen, Kirsten M. O.; Juhas, Pavol; Tofanelli, Marcus A.; ...

2016-06-14

Ultra-small, magic-sized metal nanoclusters represent an important new class of materials with properties between molecules and particles. However, their small size challenges the conventional methods for structure characterization. We present the structure of ultra-stable Au144(SR)60 magic-sized nanoclusters obtained from atomic pair distribution function analysis of X-ray powder diffraction data. Our study reveals structural polymorphism in these archetypal nanoclusters. Additionally, in order to confirm the theoretically predicted icosahedral-cored cluster, we also find samples with a truncated decahedral core structure, with some samples exhibiting a coexistence of both cluster structures. Although the clusters are monodisperse in size, structural diversity is apparent. Finally,more » the discovery of polymorphism may open up a new dimension in nanoscale engineering.« less

First-Principles Study of Structural, Electronic and Magnetic Properties of Metal-Centered Tetrahexahedral V15+ Cluster

PubMed Central

Ren, Hongjiang; Huang, Xinwei; Li, Shuna

2017-01-01

The V-centered bicapped hexagonal antiprism structure (A), as the most stable geometry of the cationic V15+ cluster, is determined by using infrared multiple photo dissociation (IR-MPD) in combination with density functional theory computations. It is found that the A structure can be stabilized by 18 delocalized 3c-2e σ-bonds on outer V3 triangles of the bicapped hexagonal antiprism surface and 12 delocalized 4c-2e σ-bonds on inner trigonal pyramidal V4 moiety, and the features are related to the strong p-d hybridization of the cluster. The total magnetic moments on the cluster are predicted to be 2.0 µB, which come mainly from the central vanadium atom. PMID:28665337

Tantalum induced butterfly-like clusters on Si (111)-7 × 7 surface: STM/STS study at low coverage

NASA Astrophysics Data System (ADS)

Shukrynau, Pavel; Mutombo, Pingo; Švec, Martin; Hietschold, Michael; Cháb, Vladimír

2012-02-01

The adsorption of the small amounts of tantalum on Si (111)-7 × 7 reconstructed surface is investigated systematically using scanning tunneling microscopy and tunneling spectroscopy combined with first-principles density functional theory calculations. We find out that the moderate annealing of the Ta covered surface results in the formation of clusters of the butterfly-like shape. The clusters are sporadically distributed over the surface and their density is metal coverage dependent. Filled and empty state STM images of the clusters differ strongly suggesting the existence of covalent bonds within the cluster. Tunneling spectroscopy measurements reveal small energy gap, showing semiconductor-like behavior of the constituent atoms. The cluster model based on experimental images and theoretical calculations has been proposed and discussed. Presented results show that Ta joins the family of adsorbates, that are known to form magic clusters on Si (111)-7 × 7, but its magic cluster has the structural and electronic properties that are different from those reported before.

Electronic structure of semiconducting alkali-metal silicides and germanides

NASA Astrophysics Data System (ADS)

Tegze, M.; Hafner, J.

1989-11-01

We present self-consistent linearized-muffin-tin-orbital calculations of the electronic structure of three alkali-metal germanides and silicides (KGe, NaGe, and NaSi). Like the alkali-metal-lead compounds investigated in our earlier work [M. Tegze and J. Hafner, Phys. Rev. B 39, 8263 (1989)] the Ge and Si compounds of the alkali metals form complex structures based on the packing of tetrahedral Ge4 and Si4 clusters. Our calculations show that all three compounds are narrow-gap semiconductors. The width of the energy gap depends on two main factors: the ratio of the intracluster to the intercluster interactions between the group-IV elements (which increases from Pb to Si) and the strength of the interactions between the alkali-metal atoms (which varies with the size ratio).

Rapid reversible borane to boryl hydride exchange by metal shuttling on the carborane cluster surface† †Electronic supplementary information (ESI) available. CCDC 1545735 and 1545736. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c7sc01846k

PubMed Central

Eleazer, Bennett J.; Smith, Mark D.

2017-01-01

In this work, we introduce a novel concept of a borane group vicinal to a metal boryl bond acting as a supporting hemilabile ligand in exohedrally metalated three-dimensional carborane clusters. The (POBOP)Ru(Cl)(PPh3) pincer complex (POBOP = 1,7-OP(i-Pr)2-m-2-carboranyl) features extreme distortion of the two-center-two-electron Ru–B bond due to the presence of a strong three-center-two-electron B–H···Ru vicinal interaction. Replacement of the chloride ligand with a hydride afforded the (POBOP)Ru(H)(PPh3) pincer complex, which possesses B–Ru, B–H···Ru, and Ru–H bonds. This complex was found to exhibit a rapid exchange between hydrogen atoms of the borane and the terminal hydride through metal center shuttling between two boron atoms of the carborane cage. This exchange process, which involves sequential cleavage and formation of strong covalent metal–boron and metal–hydrogen bonds, is unexpectedly facile at temperatures above –50 °C corresponding to an activation barrier of 12.2 kcal mol–1. Theoretical calculations suggested two equally probable pathways for the exchange process through formally Ru(0) or Ru(iv) intermediates, respectively. The presence of this hemilabile vicinal B–H···Ru interaction in (POBOP)Ru(H)(PPh3) was found to stabilize a latent coordination site at the metal center promoting efficient catalytic transfer dehydrogenation of cyclooctane under nitrogen and air at 170 °C. PMID:28970919

Astrophysics Meets Atomic Physics: Fe I Line Identifications and Templates for Old Stellar Populations from Warm and Hot Stellar UV Spectra

NASA Astrophysics Data System (ADS)

Peterson, Ruth

2017-08-01

Imaging surveys from the ultraviolet to the infrared are recording ever more distant astronomical sources. Needed to interpret them are high-resolution ultraviolet spectral templates at all metallicities for both old and intermediate-age stars, and the atomic physics data essential to model their spectra. To this end we are proposing new UV spectra of four warm and hot stars spanning a wide range of metallicity. These will provide observational templates of old and young metal-poor turnoff stars, and the laboratory source for the identification of thousands of lines of neutral iron that appear in stellar spectra but are not identified in laboratory spectra. By matching existing and new stellar spectra to calculations of energy levels, line wavelengths, and gf-values, Peterson & Kurucz (2015) and Peterson, Kurucz, & Ayres (2017) identified 124 Fe I levels with energies up to 8.4eV. These provided 3000 detectable Fe I lines from 1600A to 5.4mu, and yielded empirical gf-values for 640 of these. Here we propose high-resolution UV spectra reaching 1780A for the first time at the turnoff, to detect and identify the strongest Fe I lines at 1800 - 1850A. This should add 250 new Fe I levels. These spectra, plus one at lower resolution reaching 1620A, will also provide empirical UV templates for turnoff stars at high redshifts as well as low. This is essential to deriving age and metallicity independently for globular clusters and old galaxies out to z 3. It will also improve abundances of trace elements in metal-poor stars, constraining nucleosynthesis at early epochs and aiding the reconstruction of the populations of the Milky Way halo and of nearby globular clusters.

Structural and electronic properties of copper-doped chalcogenide glasses

NASA Astrophysics Data System (ADS)

Guzman, David M.; Strachan, Alejandro

2017-10-01

Using ab initio molecular dynamics based on density functional theory, we study the atomic and electronic structure, and transport properties of copper-doped germanium-based chalcogenide glasses. These mixed ionic-electronic conductor materials exhibit resistance or threshold switching under external electric field depending on slight variations of chemical composition. Understanding the origin of the transport character is essential for the functionalization of glassy chalcogenides for nanoelectronics applications. To this end, we generated atomic structures for GeX3 and GeX6 (X = S, Se, Te) at different copper concentrations and characterized the atomic origin of electronic states responsible for transport and the tendency of copper clustering as a function of metal concentration. Our results show that copper dissolution energies explain the tendency of copper to agglomerate in telluride glasses, consistent with filamentary conduction. In contrast, copper is less prone to cluster in sulfides and selenides leading to hysteresisless threshold switching where the nature of transport is dominated by electronic midgap defects derived from polar chalcogen bonds and copper atoms. Simulated I -V curves show that at least 35% by weight of copper is required to achieve the current demands of threshold-based devices for memory applications.

Study of MoNbO(y) (y = 2-5) anion and neutral clusters using photoelectron spectroscopy and density functional theory calculations: impact of spin contamination on single point calculations.

PubMed

Waller, Sarah E; Mann, Jennifer E; Rothgeb, David W; Jarrold, Caroline C

2012-10-04

Results of a study combining anion photoelectron spectroscopy and density functional theory calculations on the heteronuclear MoNbO(y)(-) (y = 2-5) transition metal suboxide cluster series are reported and analyzed. The photoelectron spectra, which exhibit broad electronic bands with partially resolved vibrational structure, were compared to spectral simulations generated from calculated spectroscopic parameters for all computationally determined energetically competitive structures. Although computational results on the less oxidized clusters could not be satisfactorily reconciled with experimental spectra, possibly because of heavy spin contamination found in a large portion of the computational results, the results suggest that (1) neutral cluster electron affinity is a strong indicator of whether O-atoms are bound in M-O-M bridge positions or M═O terminal positions, (2) MoNbO(y) anions and neutrals have structures that can be described as intermediate with respect to the unary (homonuclear) Mo(2)O(y) and Nb(2)O(y) clusters, and (3) structures in which O-atoms preferentially bind to the Nb center are slightly more stable than alternative structures. Several challenges associated with the calculations are considered, including spin contamination, which appears to cause spurious single point calculations used to determine vertical detachment energies.

Adsorption of Atoms of 3 d Metals on the Surfaces of Aluminum and Magnesium Oxide Films

NASA Astrophysics Data System (ADS)

Ramonova, A. G.; Kibizov, D. D.; Kozyrev, E. N.; Zaalishvili, V. B.; Grigorkina, G. S.; Fukutani, K.; Magkoev, T. T.

2018-01-01

The adsorption and formation of submonolayer structures of Ti, Cr, Fe, Ni, Cu on the surfaces of aluminum and magnesium oxide films formed on Mo(110) under ultrahigh vacuum conditions are studied via X-ray, ultraviolet photo-, and Auger electron spectroscopy (XPS, UVES, AES); spectroscopy of energy losses of high-resolution electrons (SELHRE); spectroscopy of the backscattering of low-energy ions (SBSLEI); infrared absorption spectroscopy (IAS); and the diffraction of slow electrons (DSE). Individual atoms and small clusters of all the investigated metals deposited on oxides acquire a positive charge, due presumably to interaction with surface defects. As the concentration of adatoms increases when the adsorption centers caused by defects are filled, charge transfer from adatoms to substrates is reduced. This is accompanied by further depolarization caused by the lateral interaction of adatoms.

Communication: Diverse nanoscale cluster dynamics: Diffusion of 2D epitaxial clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, King C.; Evans, James W.; Liu, Da -Jiang

The dynamics of nanoscale clusters can be distinct from macroscale behavior described by continuum formalisms. For diffusion of 2D clusters of N atoms in homoepitaxial systems mediated by edge atom hopping, macroscale theory predicts simple monotonic size scaling of the diffusion coefficient, D N ~ N –β, with β = 3/2. However, modeling for nanoclusters on metal(100) surfaces reveals that slow nucleation-mediated diffusion displaying weak size scaling β < 1 occurs for “perfect” sizes N p = L 2 and L(L+1) for integer L = 3,4,… (with unique square or near-square ground state shapes), and also for N p+3, Nmore » p+4,…. In contrast, fast facile nucleation-free diffusion displaying strong size scaling β ≈ 2.5 occurs for sizes N p+1 and N p+2. D N versus N oscillates strongly between the slowest branch (for N p+3) and the fastest branch (for N p+1). All branches merge for N = O(10 2), but macroscale behavior is only achieved for much larger N = O(10 3). Here, this analysis reveals the unprecedented diversity of behavior on the nanoscale.« less

Communication: Diverse nanoscale cluster dynamics: Diffusion of 2D epitaxial clusters

DOE PAGES

Lai, King C.; Evans, James W.; Liu, Da -Jiang

2017-11-27

The dynamics of nanoscale clusters can be distinct from macroscale behavior described by continuum formalisms. For diffusion of 2D clusters of N atoms in homoepitaxial systems mediated by edge atom hopping, macroscale theory predicts simple monotonic size scaling of the diffusion coefficient, D N ~ N –β, with β = 3/2. However, modeling for nanoclusters on metal(100) surfaces reveals that slow nucleation-mediated diffusion displaying weak size scaling β < 1 occurs for “perfect” sizes N p = L 2 and L(L+1) for integer L = 3,4,… (with unique square or near-square ground state shapes), and also for N p+3, Nmore » p+4,…. In contrast, fast facile nucleation-free diffusion displaying strong size scaling β ≈ 2.5 occurs for sizes N p+1 and N p+2. D N versus N oscillates strongly between the slowest branch (for N p+3) and the fastest branch (for N p+1). All branches merge for N = O(10 2), but macroscale behavior is only achieved for much larger N = O(10 3). Here, this analysis reveals the unprecedented diversity of behavior on the nanoscale.« less

{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Niobium Atoms Close to 300.

PubMed

Wu, Yan-Lan; Li, Xin-Xiong; Qi, Yan-Jie; Yu, Hao; Jin, Lu; Zheng, Shou-Tian

2018-05-29

A protein-sized (ca. 4.2 ᵡ 4.2 ᵡ 3.6 nm3) non-biologically derived molecule {Nb288O768(OH)48(CO3)12} (Nb288) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb288 is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb288 can be described as a giant windmill-like cluster aggregate of six brand-new, nanoscale high-nuclearity PONb units {Nb47O128(OH)6(CO3)2} (Nb47) joined together by six additional Nb ions. Interestingly, the in situ generated 47-nuclearity Nb47 units can be isolated and bridged by copper complexes to form an inorganic-organic hybrid three-dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb47 cluster also provides a new type of topology to very limited family of Nb-O clusters. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobalt doping of the MOF-5 framework and its effect on gas-adsorption properties.

PubMed

Botas, Juan A; Calleja, Guillermo; Sánchez-Sánchez, Manuel; Orcajo, M Gisela

2010-04-20

Partial isomorphic substitution of Zn in IRMOF metal clusters by cobalt ions is described for the first time. Specifically, different numbers of Co(2+) ions have been incorporated during solvothermal crystallization into the Zn-based MOF-5 (IRMOF-1) framework, which is one of the most studied MOF materials. The amount of Zn that can be substituted seems to be limited, being no more than 25% of total metal content, that is, no more than one Co atom inside every metal cluster formed by four transition-metal ions, on average. Several characterization techniques, including X-ray diffraction, DR UV-visible spectroscopy, N(2) adsorption isotherms, and thermogravimetrical analysis, strongly support the effective incorporation of Co into the material framework. As-synthesized CoMOF-5 has cobalt ions in octahedral coordination, changing to tetrahedral by simple evacuation, presumably by the removal of two diethylformamide molecules per Co ion. Moreover, the H(2), CH(4), and CO(2) uptake of MOF-5 materials systematically increases with the Co content, particularly at high pressure. Such an increase is moderate anyway, considering that Co is incorporated into unexposed metal sites that are less accessible to gas molecules.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

a Moessbauer Effect and Fenske-Hall Molecular Orbital Study of the Electronic Properties of Organoiron Clusters.

NASA Astrophysics Data System (ADS)

Buhl, Margaret Linn

The electronic properties of trinuclear iron, tetranuclear iron butterfly, iron-cobalt, and iron-copper clusters have been studied experimentally at 78K by the Mossbauer effect and theoretically by Fenske-Hall molecular orbital calculations. The Mossbauer effect isomer shift is very sensitive to the differences in the iron s-electron densities in these clusters and, as expected, decreases as the sum of the iron 4s Mulliken population and the Clementi and Raimondi effective nuclear charge increases. The molecular orbital wave functions and the Mulliken atomic charges are used to calculate the electric field gradient at the metal nuclei and the iron Mossbauer effect quadrupole splittings. The valence contribution was found to be the major component of the electric field gradient in all the clusters studied. In general the calculated value of Delta E_ {Q} is larger than the observed value, as a result of neglect of the valence Sternheimer factor, R. The metal charge depends upon its electronegativity and upon the nature of its Lewis base ligands. The carbonyl ligand carbon charge becomes more positive as the metal electronegativity increases. The oxygen charge becomes more negative as the anionic cluster charge increases, and in so doing, yields the maximum anionic charge separation. The electronic properties of the terminal carbonyl ligands are similar to those of carbon monoxide, whereas the electronic properties of the bridging carbonyl ligands are similar to those of the carbonyl group found in aldehydes and ketones.

Metal Adatoms and Clusters on Ultrathin Zirconia Films

PubMed Central

2016-01-01

Nucleation and growth of transition metals on zirconia has been studied by scanning tunneling microscopy (STM) and density functional theory (DFT) calculations. Since STM requires electrical conductivity, ultrathin ZrO2 films grown by oxidation of Pt3Zr(0001) and Pd3Zr(0001) were used as model systems. DFT studies were performed for single metal adatoms on supported ZrO2 films as well as the (1̅11) surface of monoclinic ZrO2. STM shows decreasing cluster size, indicative of increasing metal–oxide interaction, in the sequence Ag < Pd ≈ Au < Ni ≈ Fe. Ag and Pd nucleate mostly at steps and domain boundaries of ZrO2/Pt3Zr(0001) and form three-dimensional clusters. Deposition of low coverages of Ni and Fe at room temperature leads to a high density of few-atom clusters on the oxide terraces. Weak bonding of Ag to the oxide is demonstrated by removing Ag clusters with the STM tip. DFT calculations for single adatoms show that the metal–oxide interaction strength increases in the sequence Ag < Au < Pd < Ni on monoclinic ZrO2, and Ag ≈ Au < Pd < Ni on the supported ultrathin ZrO2 film. With the exception of Au, metal nucleation and growth on ultrathin zirconia films follow the usual rules: More reactive (more electropositive) metals result in a higher cluster density and wet the surface more strongly than more noble metals. These bind mainly to the oxygen anions of the oxide. Au is an exception because it can bind strongly to the Zr cations. Au diffusion may be impeded by changing its charge state between −1 and +1. We discuss differences between the supported ultrathin zirconia films and the surfaces of bulk ZrO2, such as the possibility of charge transfer to the substrate of the films. Due to their large in-plane lattice constant and the variety of adsorption sites, ZrO2{111} surfaces are more reactive than many other oxygen-terminated oxide surfaces. PMID:27213024

Assessment of interaction-strength interpolation formulas for gold and silver clusters

NASA Astrophysics Data System (ADS)

Giarrusso, Sara; Gori-Giorgi, Paola; Della Sala, Fabio; Fabiano, Eduardo

2018-04-01

The performance of functionals based on the idea of interpolating between the weak- and the strong-interaction limits the global adiabatic-connection integrand is carefully studied for the challenging case of noble-metal clusters. Different interpolation formulas are considered and various features of this approach are analyzed. It is found that these functionals, when used as a correlation correction to Hartree-Fock, are quite robust for the description of atomization energies, while performing less well for ionization potentials. Future directions that can be envisaged from this study and a previous one on main group chemistry are discussed.

Activation of CO2 by supported Cu clusters.

PubMed

Iyemperumal, Satish Kumar; Deskins, N Aaron

2017-11-01

Catalytic reduction of carbon dioxide to useful chemicals is a potent way to mitigate this greenhouse gas, but the challenge lies in finding active reduction catalysts. Using density functional theory we studied CO 2 activation over TiO 2 -supported Cu clusters of size 1-4 atoms. The linear to bent transformation of CO 2 is necessary for activation, and we found that all the clusters stabilized bent CO 2 , along with a significant gain of electrons on the CO 2 (indicative of activation). On all the TiO 2 supported Cu clusters, the interfacial sites were found to stabilize the bent CO 2 adsorption, where the active site of adsorption on Cu dimer, trimer and tetramer was on the Cu atom farthest away from the TiO 2 surface. Particularly, the Cu dimer stabilized bent CO 2 very strongly, although this species was found to be unstable on the surface. A synthesis technique that could stabilize the Cu dimer could therefore lead to a very active catalyst. Furthermore we found (using vibrational and charge analysis) that the active sites for the CO 2 activation predominantly had 0 and +1 oxidation states; the oxidation state of Cu is known to directly affect CO 2 reduction activity. Our study shows TiO 2 -supported small Cu clusters can be active catalysts for CO 2 reduction and also provides further motivation for theoretical and experimental studies of metal clusters.

Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

PubMed

Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

2010-06-21

The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

Role of string-like collective atomic motion on diffusion and structural relaxation in glass forming Cu-Zr alloys

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Hao; Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta T6G 2V4; Zhong, Cheng

2015-04-28

We investigate Cu-Zr liquid alloys using molecular dynamics simulation and well-accepted embedded atom method potentials over a wide range of chemical composition and temperature as model metallic glass-forming (GF) liquids. As with other types of GF materials, the dynamics of these complex liquids are characterized by “dynamic heterogeneity” in the form of transient polymeric clusters of highly mobile atoms that are composed in turn of atomic clusters exhibiting string-like cooperative motion. In accordance with the string model of relaxation, an extension of the Adam-Gibbs (AG) model, changes in the activation free energy ΔG{sub a} with temperature of both the Cumore » and Zr diffusion coefficients D, and the alpha structural relaxation time τ{sub α} can be described to a good approximation by changes in the average string length, L. In particular, we confirm that the strings are a concrete realization of the abstract “cooperatively rearranging regions” of AG. We also find coexisting clusters of relatively “immobile” atoms that exhibit predominantly icosahedral local packing rather than the low symmetry packing of “mobile” atoms. These two distinct types of dynamic heterogeneity are then associated with different fluid structural states. Glass-forming liquids are thus analogous to polycrystalline materials where the icosahedrally packed regions correspond to crystal grains, and the strings reside in the relatively disordered grain boundary-like regions exterior to these locally well-ordered regions. A dynamic equilibrium between localized (“immobile”) and wandering (“mobile”) particles exists in the liquid so that the dynamic heterogeneity can be considered to be type of self-assembly process. We also characterize changes in the local atomic free volume in the course of string-like atomic motion to better understand the initiation and propagation of these fluid excitations.« less

Methane combustion reactivity during the metal→metallic oxide transformation of Pd-Pt catalysts: Effect of oxygen pressure

NASA Astrophysics Data System (ADS)

Qi, Wenjie; Ran, Jingyu; Zhang, Zhien; Niu, Juntian; Zhang, Peng; Fu, Lijuan; Hu, Bo; Li, Qilai

2018-03-01

Density functional theory combined with kinetic models were used to probe different kinetics consequences by which methane activation on different oxygen chemical potential surfaces as oxygen pressure increased. The metallic oxide → metal transformation temperature of Pd-Pt catalysts increased with the increase of the Pd content or/and O2 pressure. The methane conversion rate on Pt catalyst increased and then decreased to a constant value when increasing the O2 pressure, and Pd catalyst showed a poor activity performance in the case of low O2 pressure. Moreover, its activity increased as the oxygen chemical potential for O2 pressure increased in the range of 2.5-10 KPa. For metal clusters, the Csbnd H bond and Odbnd O bond activation steps occurred predominantly on *-* site pairs. The methane conversion rate was determined by O2 pressure because the adsorbed O atoms were rapidly consumed by other adsorbed species in this kinetic regime. As the O2 pressure increased, the metallic active sites for methane activation were decreased and there was no longer lack of adsorbed O atoms, resulting in the decrease of the methane conversion rate. Furthermore, when the metallic surfaces were completely covered by adsorbed oxygen atoms at higher oxygen chemical potentials, Pt catalyst showed a poor activity due to a high Csbnd H bond activation barrier on O*sbnd O*. In the case of high O2 pressure, Pd atoms preferred to segregate to the active surface of Pd-Pt catalysts, leading to the formation of PdO surfaces. The increase of Pd segregation promoted a subsequent increase in active sites and methane conversion rate. The PdO was much more active than metallic and O* saturated surfaces for methane activation, inferred from the theory and experimental study. Pd-rich bimetallic catalyst (75% molar Pd) showed a dual high methane combustion activity on O2-poor and O2-rich conditions.

Trends in magnetism of free Rh clusters via relativistic ab-initio calculations.

PubMed

Šipr, O; Ebert, H; Minár, J

2015-02-11

A fully relativistic ab-initio study on free Rh clusters of 13-135 atoms is performed to identify general trends concerning their magnetism and to check whether concepts which proved to be useful in interpreting magnetism of 3d metals are applicable to magnetism of 4d systems. We found that there is no systematic relation between local magnetic moments and coordination numbers. On the other hand, the Stoner model appears well-suited both as a criterion for the onset of magnetism and as a guide for the dependence of local magnetic moments on the site-resolved density of states at the Fermi level. Large orbital magnetic moments antiparallel to spin magnetic moments were found for some sites. The intra-atomic magnetic dipole Tz term can be quite large at certain sites but as a whole it is unlikely to affect the interpretation of x-ray magnetic circular dichroism experiments based on the sum rules.

Stability investigation of a high number density Pt1/Fe2O3 single-atom catalyst under different gas environments by HAADF-STEM

NASA Astrophysics Data System (ADS)

Duan, Sibin; Wang, Rongming; Liu, Jingyue

2018-05-01

Catalysis by supported single metal atoms has demonstrated tremendous potential for practical applications due to their unique catalytic properties. Unless they are strongly anchored to the support surfaces, supported single atoms, however, are thermodynamically unstable, which poses a major obstacle for broad applications of single-atom catalysts (SACs). In order to develop strategies to improve the stability of SACs, we need to understand the intrinsic nature of the sintering processes of supported single metal atoms, especially under various gas environments that are relevant to important catalytic reactions. We report on the synthesis of high number density Pt1/Fe2O3 SACs using a facial strong adsorption method and the study of the mobility of these supported Pt single atoms at 250 °C under various gas environments that are relevant to CO oxidation, water–gas shift, and hydrogenation reactions. Under the oxidative gas environment, Fe2O3 supported Pt single atoms are stable even at high temperatures. The presence of either CO or H2 molecules in the gas environment, however, facilitates the movement of the Pt atoms. The strong interaction between CO and Pt weakens the binding between the Pt atoms and the support, facilitating the movement of the Pt single atoms. The dissociation of H2 molecules on the Pt atoms and their subsequent interaction with the oxygen species of the support surfaces dislodge the surface oxygen anchored Pt atoms, resulting in the formation of Pt clusters. The addition of H2O molecules to the CO or H2 significantly accelerates the sintering of the Fe2O3 supported Pt single atoms. An anchoring-site determined sintering mechanism is further proposed, which is related to the metal–support interaction.

Synthesis of Nine-atom Deltahedral Zintl Ions of Germanium and their Functionalization with Organic Groups

PubMed Central

Gillett-Kunnath, Miriam M.; Sevov, Slavi C.

2012-01-01

Although the first studies of Zintl ions date between the late 1890's and early 1930's they were not structurally characterized until many years later.1,2 Their redox chemistry is even younger, just about ten years old, but despite this short history these deltahedral clusters ions E9n- (E = Si, Ge, Sn, Pb; n = 2, 3, 4) have already shown interesting and diverse reactivity and have been at the forefront of rapidly developing and exciting new chemistry.3-6 Notable milestones are the oxidative coupling of Ge94- clusters to oligomers and infinite chains,7-19 their metallation,14-16,20-25 capping by transition-metal organometallic fragments,26-34 insertion of a transition-metal atom at the center of the cluster which is sometimes combined with capping and oligomerization,35-47 addition of main-group organometallic fragments as exo-bonded substituents,48-50 and functionalization with various organic residues by reactions with organic halides and alkynes.51-58 This latter development of attaching organic fragments directly to the clusters has opened up a new field, namely organo-Zintl chemistry, that is potentially fertile for further synthetic explorations, and it is the step-by-step procedure for the synthesis of germanium-divinyl clusters described herein. The initial steps outline the synthesis of an intermetallic precursor of K4Ge9 from which the Ge94- clusters are extracted later in solution. This involves fused-silica glass blowing, arc-welding of niobium containers, and handling of highly air-sensitive materials in a glove box. The air-sensitive K4Ge9 is then dissolved in ethylenediamine in the box and then alkenylated by a reaction with Me3SiC≡CSiMe3. The reaction is followed by electrospray mass spectrometry while the resulting solution is used for obtaining single crystals containing the functionalized clusters [H2C=CH-Ge9-CH=CH2]2-. For this purpose the solution is centrifuged, filtered, and carefully layered with a toluene solution of 18-crown-6. Left undisturbed for a few days, the so-layered solutions produced orange crystalline blocks of [K(18-crown-6)]2[Ge9(HCCH2)2]•en which were characterized by single-crystal X-ray diffraction. The process highlights standard reaction techniques, work-up, and analysis towards functionalized deltahedral Zintl clusters. It is hoped that it will help towards further development and understanding of these compounds in the community at large. PMID:22349121

Heavy Metal Contamination in Groundwater around Industrial Estate vs Residential Areas in Coimbatore, India

PubMed Central

Mohankumar, K.; Rao, N. Prasada

2016-01-01

Introduction Water is the vital resource, necessary for all aspects of human and ecosystem survival and health. Depending on the quality, bore water may be used for human consumption, irrigation purposes and livestock watering. The quality of bore water can vary widely depending on the quality of ground water that is its source. Pollutants are being added to the ground water system through human and natural processes. Solid waste from industrial units is being dumped near the factories, which react with percolating rainwater and reaches the ground water. The percolating water picks up a large number of heavy metals and reaches the aquifer system and contaminates the ground water. The usage of the contaminated bore water causes the diseases. Mercury, Arsenic and Cadmium are used or released by many industries. Aim This study was conducted to investigate the pollution of bore water in the industrial region (Kurichi Industrial Cluster) of Coimbatore, in the state of Tamilnadu, India. Materials and Methods Four samples were taken from residential areas around Kurichi Industrial Cluster and analysed to find the concentrations of Mercury, Arsenic and Cadmium. Four more samples were taken from other residential regions far from the industrial estate and served as control. Samples were analysed using Atomic absorption spectrophotometry method. Results We found that the ground water of the areas surrounding the industrial cluster does not contain significant amount of those metals. Instead, Heavy metal contamination of ground water were observed in some residential areas of coimbatore. Conclusion The regulatory measures to contain and prevent ground water contamination by industries undertaken by Tamilnadu pollution control board may have lead to absence of heavy metal contamination in Kurichi Industrial cluster, Coimbatore, India. PMID:27190788

Atomic Scale Imaging of Nucleation and Growth Trajectories of an Interfacial Bismuth Nanodroplet.

PubMed

Li, Yingxuan; Bunes, Benjamin R; Zang, Ling; Zhao, Jie; Li, Yan; Zhu, Yunqing; Wang, Chuanyi

2016-02-23

Because of the lack of experimental evidence, much confusion still exists on the nucleation and growth dynamics of a nanostructure, particularly of metal. The situation is even worse for nanodroplets because it is more difficult to induce the formation of a nanodroplet while imaging the dynamic process with atomic resolution. Here, taking advantage of an electron beam to induce the growth of Bi nanodroplets on a SrBi2Ta2O9 platelet under a high resolution transmission electron microscope (HRTEM), we directly observed the detailed growth pathways of Bi nanodroplets from the earliest stage of nucleation that were previously inaccessible. Atomic scale imaging reveals that the dynamics of nucleation involves a much more complex trajectory than previously predicted based on classical nucleation theory (CNT). The monatomic Bi layer was first formed in the nucleation process, which induced the formation of the prenucleated clusters. Following that, critical nuclei for the nanodroplets formed both directly from the addition of atoms to the prenucleated clusters by the classical growth process and indirectly through transformation of an intermediate liquid film based on the Stranski-Krastanov growth mode, in which the liquid film was induced by the self-assembly of the prenucleated clusters. Finally, the growth of the Bi nanodroplets advanced through the classical pathway and sudden droplet coalescence. This study allows us to visualize the critical steps in the nucleation process of an interfacial nanodroplet, which suggests a revision of the perspective of CNT.

Al-centered icosahedral ordering in Cu46Zr46Al8 bulk metallic glass

NASA Astrophysics Data System (ADS)

Fang, H. Z.; Hui, X.; Chen, G. L.; Liu, Z. K.

2009-03-01

Icosahedral short-range order, of which Al atoms are caged in the center of icosahedra with Cu and Zr atoms being the vertices, has been evidenced in the Cu46Zr46Al8 glassy structure by ab initio molecular dynamics simulation. These Al-centered clusters distribute irregularly in the three-dimensional space and form a "backbone" structure of the Cu46Zr46Al8 glass alloy. It is suggested that this kind of local structural feature is attributed to the requirement of efficient dense packing and the chemical affinity between Zr-Zr, Zr-Al, and Cu-Zr atoms. Our calculated results are found to be in good agreement with the experimental data.

Complex magnetic orders in small cobalt-benzene molecules.

PubMed

González, J W; Alonso-Lanza, T; Delgado, F; Aguilera-Granja, F; Ayuela, A

2017-06-07

Organometallic clusters based on transition metal atoms are interesting because of their possible applications in spintronics and quantum information processing. In addition to the enhanced magnetism at the nanoscale, the organic ligands may provide a natural shield against unwanted magnetic interactions with the matrices required for applications. Here we show that the organic ligands may lead to non-collinear magnetic order as well as the expected quenching of the magnetic moments. We use different density functional theory (DFT) methods to study the experimentally relevant three cobalt atoms surrounded by benzene rings (Co 3 Bz 3 ). We found that the benzene rings induce a ground state with non-collinear magnetization, with the magnetic moments localized on the cobalt centers and lying on the plane formed by the three cobalt atoms. We further analyze the magnetism of such a cluster using an anisotropic Heisenberg model where the involved parameters are obtained by a comparison with the DFT results. These results may also explain the recent observation of the null magnetic moment of Co 3 Bz 3 + . Moreover, we propose an additional experimental verification based on electron paramagnetic resonance.

Effects of electronic excitation in 150 keV Ni ion irradiation of metallic systems

NASA Astrophysics Data System (ADS)

Zarkadoula, Eva; Samolyuk, German; Weber, William J.

2018-01-01

We use the two-temperature model in molecular dynamic simulations of 150 keV Ni ion cascades in nickel and nickel-based alloys to investigate the effect of the energy exchange between the atomic and the electronic systems during the primary stages of radiation damage. We find that the electron-phonon interactions result in a smaller amount of defects and affect the cluster formation, resulting in smaller clusters. These results indicate that ignoring the local heating due to the electrons results in the overestimation of the amount of damage and the size of the defect clusters. A comparison of the average defect production to the Norgett-Robinson-Torrens (NRT) prediction over a range of energies is provided.

Iridium clusters in KLTL zeolite: Structure and catalytic selectivity for n-hexane aromatization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triantafillou, N.D.; Miller, J.T.; Gates, B.C.

Catalysts consisting of Ir clusters in zeolite KLTL were prepared by reduction of [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2} in the zeolite with H{sub 2} at temperatures 300 or 500{degrees}C. The catalysts were tested for reactions of n-hexane and H{sub 2} at 400, 440 and 480{degrees}C and were characterized by temperature-programmed reduction, hydrogen chemisorption, transmission electron microscopy, infrared spectroscopy of adsorbed CO, and extended X-ray absorption fine structure spectroscopy. The clusters consist of 4 to 6 Ir atoms on average and are sufficiently small to reside within the pores of the zeolite. The infrared spectra characteristic of terminal CO suggest that themore » support environment is slightly basic and that the Ir clusters are electron rich relative to the bulk metal. Notwithstanding the small cluster size, the support basicity, and the confining geometry of the LTL zeolite pore structure, the catalytic performance is similar to those of other Ir catalysts, with a poor selectivity for aromatization and a high selectivity for hydrogenolysis. These results are consistent with the inference that the principal requirements for selective naphtha aromatization catalysts are both a nonacidic support and a metal with a low hydrogenolsis activity, i.e., Pt. 47 refs., 6 figs., 3 tabs.« less

Ab initio molecular dynamics simulation of binary Cu64Zr36 bulk metallic glass: Validation of the cluster-plus-glue-atom model

NASA Astrophysics Data System (ADS)

Tian, Hua; Zhang, Chong; Wang, Lu; Zhao, JiJun; Dong, Chuang; Wen, Bin; Wang, Qing

2011-06-01

We have performed ab initio molecular dynamics simulation of Cu64Zr36 alloy at descending temperatures (from 2000 K to 400 K) and discussed the evolution of short-range order with temperature. The pair-correlation functions, coordination numbers, and chemical compositions of the most abundant local clusters have been analyzed. We found that icosahedral short-range order exists in the liquid, undercooled, and glass states, and it becomes dominant in the glass states. Moreover, we demonstrated the existence of Cu-centered Cu8Zr5 icosahedral clusters as the major local structural unit in the Cu64Zr36 amorphous alloy. This finding agrees well with our previous cluster model of Cu-Zr-based BMG as well as experimental evidences from synchrotron x ray and neutron diffraction measurements.

Irradiation-induced Ag nanocluster nucleation in silicate glasses: Analogy with photography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Espiau de Lamaestre, R.; Fontainebleau Research Center, Corning SA, 77210 Avon; Bea, H.

2007-11-15

The synthesis of Ag nanoclusters in soda lime silicate glasses and silica was studied by optical absorption and electron spin resonance experiments under both low (gamma ray) and high (MeV ion) deposited energy density irradiation conditions. Both types of irradiation create electrons and holes whose density and thermal evolution--notably via their interaction with defects--are shown to determine the clustering and growth rates of Ag nanocrystals. We thus establish the influence of redox interactions of defects and silver (poly)ions. The mechanisms are similar to the latent image formation in photography: Irradiation-induced photoelectrons are trapped within the glass matrix, notably on dissolvedmore » noble metal ions and defects, which are thus neutralized (reverse oxidation reactions are also shown to exist). Annealing promotes metal atom diffusion, which, in turn, leads to cluster nuclei formation. The cluster density depends not only on the irradiation fluence but also--and primarily--on the density of deposited energy and the redox properties of the glass. Ion irradiation (i.e., large deposited energy density) is far more effective in cluster formation, despite its lower neutralization efficiency (from Ag{sup +} to Ag{sup 0}) as compared to gamma photon irradiation.« less

Theoretical study of electron correlation effects in transition metal dimers

NASA Technical Reports Server (NTRS)

Das, G. P.; Jaffe, R. L.

1984-01-01

Introduction of partially localized orbitals is shown to reduce the number of terms needed to describe the bonding in transition metal clusters. Using this formalism, it is possible to compute the various intra- and inter-atomic electron correlation contributions to the bond energy. Calculations demonstrate the relative importance of several kinds of electron correlation terms involving the 3p, 3d, and 4s electrons. Improved interaction potentials are obtained for the dimers V(2) and Cr(2) when additional correlation is added to the CAS SCF results of Walch, Bauschlicher, Roos, and Nelin (1983).

Temperature-Dependent Evolution of the Oxidation States of Cobalt and Platinum in Co 1–x Pt x Clusters under H 2 and CO + H 2 Atmospheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Bing; Khadra, Ghassan; Tuaillon-Combes, Juliette

2016-09-29

Co1-xPtx clusters of 2.9-nm size with a range of atomically precise Pt/Co atomic ratios (x = 0, 0.25, 0.5, 0.75, 1) were synthesized using the mass-selected low-energy cluster beam deposition (LECBD) technique and soft-landed onto an amorphous alumina thin film prepared by atomic layer deposition (ALD). Utilizing ex situ X-ray photoemission spectroscopy (XPS), the oxidation state of the as-made clusters supported on Al2O3 was determined after both a 1-h-long exposure to air and aging for several weeks while exposed to air. Next, the aged duster samples were characterized by grazing-incidence X-ray absorption spectroscopy (GIXAS) and then pretreated with diluted hydrogenmore » and further exposed to the mixture of diluted CO and H-2 up to 225 degrees C at atmospheric pressure, and the temperature-dependent evolutions of the particle size/shape and the oxidation states of the individual metal components within the dusters were monitored using in situ grazing-incidence small-angle X-ray scattering and X-ray absorption spectroscopy (GISAXS/GIXAS). The changes in the oxidation states of Co and Pt exhibited a nonlinear dependence on the Pt/Co atomic ratio of the dusters. For example, a low Pt/Co ratio (x <= 0.5) facilitates the formation of Co(OH)(2), whereas a high Pt/Co ratio (x = 0.75) stabilizes the Co3O4 composition instead through the formation of a Co-Pt core-shell structure where the platinum shell inhibits the reduction of cobalt in the core of the Co1-xPtx alloy dusters. The obtained results indicate methods for optimizing the composition and structure of binary alloy clusters for catalysis.« less

Di-μ3-chlorido-tetra-μ2-chlorido-dichloridobis(dimethyl­formamide-κO)hexa­kis­(1H-imidazole-κN 3)tetra­cadmium

PubMed Central

Zhu, Run-Qiang

2011-01-01

The centrosymmetric mol­ecule of the title complex, [Cd4Cl8(C3H4N2)6(C3H7NO)2], contains four CdII atoms, six imidazole, two dimethyl­formamide and eight chloride ligands. The structure shows a novel chloride-bridged tetra­nuclear cadmium quasi-cubane cluster. The coordination geometry of all CdII atoms is distorted octa­hedral, with the two metal atoms in the asymmetric unit in different coordination environments. One of the Cd2+ ions is coordinated by five Cl− ions and by one N atom from an imidazole ligand, while the second is coordinated by three chloride ligands, two N atoms from two imidazole ligands and one O atom from a dimethyl­formamide mol­ecule. Inter­molecular N—H⋯Cl hydrogen bonds link the mol­ecules into a two-dimensional polymeric structure parallel to the ab plane. PMID:22058708

A DFT study of volatile organic compounds adsorption on transition metal deposited graphene

NASA Astrophysics Data System (ADS)

Kunaseth, Manaschai; Poldorn, Preeyaporn; Junkeaw, Anchalee; Meeprasert, Jittima; Rungnim, Chompoonut; Namuangruk, Supawadee; Kungwan, Nawee; Inntam, Chan; Jungsuttiwong, Siriporn

2017-02-01

Recently, elevated global emission of volatile organic compounds (VOCs) was associated to the acceleration and increasing severity of climate change worldwide. In this work, we investigated the performance of VOCs removal via modified carbon-based adsorbent using density functional theory. Here, four transition metals (TMs) including Pd, Pt, Ag, and Au were deposited onto single-vacancy defective graphene (SDG) surface to increase the adsorption efficiency. Five prototypical VOCs including benzene, furan, pyrrole, pyridine, and thiophene were used to study the adsorption capability of metal-deposited graphene adsorbent. Calculation results revealed that Pd, Pt, Au, and Ag atoms and nanoclusters bind strongly onto the SDG surface. In this study, benzene, furan and pyrrole bind in the π-interaction mode using delocalized π-electron in aromatic ring, while pyridine and thiophene favor X- interaction mode, donating lone pair electron from heteroatom. In terms of adsorption, pyridine VOC adsorption strengths to the TM-cluster doped SDG surfaces are Pt4 (-2.11 eV) > Pd4 (-2.05 eV) > Ag4 (-1.53 eV) > Au4 (-1.87 eV). Our findings indicate that TM-doped SDG is a suitable adsorbent material for VOC removal. In addition, partial density of states analysis suggests that benzene, furan, and pyrrole interactions with TM cluster are based on p-orbitals of carbon atoms, while pyridine and thiophene interactions are facilitated by hybridized sp2-orbitals of heteroatoms. This work provides a key insight into the fundamentals of VOCs adsorption on carbon-based adsorbent.

Understanding the evolution of luminescent gold quantum clusters in protein templates.

PubMed

Chaudhari, Kamalesh; Xavier, Paulrajpillai Lourdu; Pradeep, Thalappil

2011-11-22

We show that the time-dependent biomineralization of Au(3+) by native lactoferrin (NLf) and bovine serum albumin (BSA) resulting in near-infrared (NIR) luminescent gold quantum clusters (QCs) occurs through a protein-bound Au(1+) intermediate and subsequent emergence of free protein. The evolution was probed by diverse tools, principally, using matrix-assisted laser desorption ionization mass spectrometry (MALDI MS), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The importance of alkaline pH in the formation of clusters was probed. At neutral pH, a Au(1+)-protein complex was formed (starting from Au(3+)) with the binding of 13-14 gold atoms per protein. When the pH was increased above 12, these bound gold ions were further reduced to Au(0) and nucleation and growth of cluster commenced, which was corroborated by the beginning of emission; at this point, the number of gold atoms per protein was ~25, suggesting the formation of Au(25). During the cluster evolution, at certain time intervals, for specific molar ratios of gold and protein, occurrence of free protein was noticed in the mass spectra, suggesting a mixture of products and gold ion redistribution. By providing gold ions at specific time of the reaction, monodispersed clusters with enhanced luminescence could be obtained, and the available quantity of free protein could be utilized efficiently. Monodispersed clusters would be useful in obtaining single crystals of protein-protected noble metal quantum clusters where homogeneity of the system is of primary concern. © 2011 American Chemical Society

Cooling rate dependence of structural order in Ni 62 Nb 38 metallic glass

DOE PAGES

Wen, Tongqi; Sun, Yang; Ye, Beilin; ...

2018-01-31

In this article, molecular dynamics (MD) simulations are performed to study the structure of Ni 62Nb 38 bulk metallic glass at the atomistic level. Structural analysis based on the cluster alignment method is carried out and a new Ni-centered distorted-icosahedra (DISICO) motif is excavated. We show that the short-range order and medium-range order in the glass are enhanced with lower cooling rate. Almost 50% of the clusters around the Ni atoms in the well-annealed Ni 62Nb 38 glass sample from our MD simulations can be classified as DISICO. It is revealed that the structural distortion with respect to the perfectmore » icosahedra is driven by chemical ordering in the distorted region of the DISICO motif. The relationship between the structure, energy, and dynamics in this glass-forming alloy during the cooling and annealing processes is also established.« less

Stabilization of Oxidized Copper Nanoclusters in Confined Spaces

DOE PAGES

Akter, Nusnin; Wang, Mengen; Zhong, Jian-Qiang; ...

2018-01-04

Copper is an important industrial catalyst. The ability to manipulate the oxidation state of copper clusters in a controlled way is critical to understanding structure–reactivity relations of copper catalysts at the molecular level. Experimentally, cupric oxide surfaces or even small domains can only be stabilized at elevated temperatures and in the presence of oxygen, as copper can be easily reduced under reaction conditions. Herein bilayer silica films grown on a metallic substrate are used to trap diluted copper oxide clusters. By combining in situ experiments with first principles calculations, it is found that the confined space created by the silicamore » film leads to an increase in the energy barrier for Cu diffusion. Dispersed copper atoms trapped by the silica film can be easily oxidized by surface oxygen chemisorbed on the metallic substrate, which results in the formation and stabilization of Cu 2+ cations.« less

Cooling rate dependence of structural order in Ni 62 Nb 38 metallic glass

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wen, Tongqi; Sun, Yang; Ye, Beilin

In this article, molecular dynamics (MD) simulations are performed to study the structure of Ni 62Nb 38 bulk metallic glass at the atomistic level. Structural analysis based on the cluster alignment method is carried out and a new Ni-centered distorted-icosahedra (DISICO) motif is excavated. We show that the short-range order and medium-range order in the glass are enhanced with lower cooling rate. Almost 50% of the clusters around the Ni atoms in the well-annealed Ni 62Nb 38 glass sample from our MD simulations can be classified as DISICO. It is revealed that the structural distortion with respect to the perfectmore » icosahedra is driven by chemical ordering in the distorted region of the DISICO motif. The relationship between the structure, energy, and dynamics in this glass-forming alloy during the cooling and annealing processes is also established.« less

Cooling rate dependence of structural order in Ni62Nb38 metallic glass

NASA Astrophysics Data System (ADS)

Wen, Tongqi; Sun, Yang; Ye, Beilin; Tang, Ling; Yang, Zejin; Ho, Kai-Ming; Wang, Cai-Zhuang; Wang, Nan

2018-01-01

Molecular dynamics (MD) simulations are performed to study the structure of Ni62Nb38 bulk metallic glass at the atomistic level. Structural analysis based on the cluster alignment method is carried out and a new Ni-centered distorted-icosahedra (DISICO) motif is excavated. We show that the short-range order and medium-range order in the glass are enhanced with lower cooling rate. Almost 50% of the clusters around the Ni atoms in the well-annealed Ni62Nb38 glass sample from our MD simulations can be classified as DISICO. It is revealed that the structural distortion with respect to the perfect icosahedra is driven by chemical ordering in the distorted region of the DISICO motif. The relationship between the structure, energy, and dynamics in this glass-forming alloy during the cooling and annealing processes is also established.

Carbon nitride supported Fe2 cluster catalysts with superior performance for alkene epoxidation.

PubMed

Tian, Shubo; Fu, Qiang; Chen, Wenxing; Feng, Quanchen; Chen, Zheng; Zhang, Jian; Cheong, Weng-Chon; Yu, Rong; Gu, Lin; Dong, Juncai; Luo, Jun; Chen, Chen; Peng, Qing; Draxl, Claudia; Wang, Dingsheng; Li, Yadong

2018-06-15

Sub-nano metal clusters often exhibit unique and unexpected properties, which make them particularly attractive as catalysts. Herein, we report a "precursor-preselected" wet-chemistry strategy to synthesize highly dispersed Fe 2 clusters that are supported on mesoporous carbon nitride (mpg-C 3 N 4 ). The obtained Fe 2 /mpg-C 3 N 4 sample exhibits superior catalytic performance for the epoxidation of trans-stilbene to trans-stilbene oxide, showing outstanding selectivity of 93% at high conversion of 91%. Molecular oxygen is the only oxidant and no aldehyde is used as co-reagent. Under the same condition, by contrast, iron porphyrin, single-atom Fe, and small Fe nanoparticles (ca. 3 nm) are nearly reactively inert. First-principles calculations reveal that the unique reactivity of the Fe 2 clusters originates from the formation of active oxygen species. The general applicability of the synthesis approach is further demonstrated by producing other diatomic clusters like Pd 2 and Ir 2 , which lays the foundation for discovering diatomic cluster catalysts.

Density-functional study of the structures and properties of holmium-doped silicon clusters HoSi n (n = 3-9) and their anions.

PubMed

Hou, Liyuan; Yang, Jucai; Liu, Yuming

2017-04-01

The structures and properties of Ho-doped Si clusters, including their adiabatic electron affinities (AEAs), simulated photoelectron spectra (PESs), stabilities, magnetic moments, and charge-transfer characteristics, were systematically investigated using four density-functional methods. The results show that the double-hybrid functional (which includes an MP2 correlation component) can accurately predict the ground-state structure and properties of Ho-doped Si clusters. The ground-state structures of HoSi n (n = 3-9) are sextuplet electronic states. The structures of these Ho-doped Si clusters (aside from HoSi 7 ) are substitutional. The ground-state structures of HoSi n - are quintuplet electronic states. Their predicted AEAs are in excellent agreement with the experimental ones. The mean absolute error in the theoretical AEAs of HoSi n (n = 4-9) is only 0.04 eV. The simulated PESs for HoSi n - (n = 5-9) are in good agreement with the experimental PESs. Based on its simulated PES and theoretical AEA, we reassigned the experimental PES of HoSi 4 - and obtained an experimental AEA of 2.2 ± 0.1 eV. The dissociation energies of Ho from HoSi n and HoSi n - (n = 3-9) were evaluated to test the relative stabilities of the clusters. HOMO-LUMO gap analysis indicated that doping the Si clusters with the rare-earth metal atom significantly increases their photochemical reactivity. Natural population analysis showed that the magnetic moments of HoSi n (n = 3-9) and their anions derive mainly from the Ho atom. It was also found that the magnetic moments of Ho in the HoSi n clusters are larger than the magnetic moment of an isolated Ho atom.

Detection of one-dimensional migration of single self-interstitial atoms in tungsten using high-voltage electron microscopy

PubMed Central

Amino, T.; Arakawa, K.; Mori, H.

2016-01-01

The dynamic behaviour of atomic-size disarrangements of atoms—point defects (self-interstitial atoms (SIAs) and vacancies)—often governs the macroscopic properties of crystalline materials. However, the dynamics of SIAs have not been fully uncovered because of their rapid migration. Using a combination of high-voltage transmission electron microscopy and exhaustive kinetic Monte Carlo simulations, we determine the dynamics of the rapidly migrating SIAs from the formation process of the nanoscale SIA clusters in tungsten as a typical body-centred cubic (BCC) structure metal under the constant-rate production of both types of point defects with high-energy electron irradiation, which must reflect the dynamics of individual SIAs. We reveal that the migration dimension of SIAs is not three-dimensional (3D) but one-dimensional (1D). This result overturns the long-standing and well-accepted view of SIAs in BCC metals and supports recent results obtained by ab-initio simulations. The SIA dynamics clarified here will be one of the key factors to accurately predict the lifetimes of nuclear fission and fusion materials. PMID:27185352

Growth kinetics of indium metal atoms on Si(1 1 2) surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raj, Vidur; Chauhan, Amit Kumar Singh; Gupta, Govind, E-mail: govind@nplindia.org

Graphical abstract: Controlled growth of indium atoms on Si(1 1 2) surface has been carried out systematically and the influence of substrate temperature on the kinetics is analysed under various growth conditions. Temperature induced anomalous layer-to-clusters transformation during thermal desorption has also been reported. - Highlights: • Controlled growth of indium atoms on Si(1 1 2) surface & their thermal stability. • Influence of substrate temperature on the kinetics under various growth conditions. • Temperature induced layer-to-clusters transformation during thermal desorption. - Abstract: The growth kinetics and desorption behavior of indium (In) atoms grown on high index Si(1 1 2)more » surface at different substrate temperatures has been studied. Auger electron spectroscopy analysis revealed that In growth at room temperature (RT) and high substrate temperature (HT) ∼250 °C follows Frank–van der Merve growth mode whereas at temperatures ≥450 °C, In growth evolves through Volmer–Weber growth mode. Thermal desorption studies of RT and 250 °C grown In/Si(1 1 2) systems show temperature induced rearrangement of In atoms over Si(1 1 2) surface leading to clusters to layer transformation. The monolayer and bilayer desorption energies for RT grown In/Si(1 1 2) system are calculated to be 2.5 eV and 1.52 eV, while for HT-250 °C the values are found to be 1.6 eV and 1.3 eV, respectively. This study demonstrates the effect of temperature on growth kinetics as well as on the multilayer/monolayer desorption pathway of In on Si(1 1 2) surface.« less

Unified mechanism of alkali and alkaline earth catalyzed gasification reactions of carbon by CO2 and H2O

USGS Publications Warehouse

Chen, S.G.; Yang, R.T.

1997-01-01

From molecular orbital calculations, a unified mechanism is proposed for the gasification reactions of graphite by CO2 and H2O, both uncatalyzed and catalyzed by alkali and alkaline earth catalysts. In this mechanism, there are two types of oxygen intermediates that are bonded to the active edge carbon atoms: an in-plane semiquinone type, Cf(O), and an off-plane oxygen bonded to two saturated carbon atoms that are adjacent to the semiquinone species, C(O)Cf(O). The rate-limiting step is the decomposition of these intermediates by breaking the C-C bonds that are connected to Cf(O). A new rate equation is derived for the uncatalyzed reactions, and that for the catalyzed reactions is readily available from the proposed mechanism. The proposed mechanism can account for several unresolved experimental observations: TPD and TK (transient kinetics) desorption results of the catalyzed systems, the similar activation energies for the uncatalyzed and catalyzed reactions, and the relative activities of the alkali and alkaline earth elements. The net charge of the edge carbon active site is substantially changed by gaining electron density from the alkali or alkaline earth element (by forming C-O-M, where M stands for metal). The relative catalytic activities of these elements can be correlated with their abilities of donating electrons and changing the net charge of the edge carbon atom. As shown previously (Chen, S. G.; Yang, R. T. J. Catal. 1993, 141, 102), only clusters of the alkali compounds are active. This derives from the ability of the clusters to dissociate CO2 and H2O to form O atoms and the mobility of the dissociated O atoms facilitated by the clusters.

Theoretical study of hydrogen storage in metal hydrides.

PubMed

Oliveira, Alyson C M; Pavão, A C

2018-05-04

Adsorption, absorption and desorption energies and other properties of hydrogen storage in palladium and in the metal hydrides AlH 3 , MgH 2 , Mg(BH 4 ) 2 , Mg(BH 4 )(NH 2 ) and LiNH 2 were analyzed. The DFT calculations on cluster models show that, at a low concentration, the hydrogen atom remains adsorbed in a stable state near the palladium surface. By increasing the hydrogen concentration, the tetrahedral and the octahedral sites are sequentially occupied. In the α phase the tetrahedral site releases hydrogen more easily than at the octahedral sites, but the opposite occurs in the β phase. Among the hydrides, Mg(BH 4 ) 2 shows the highest values for both absorption and desorption energies. The absorption energy of LiNH 2 is higher than that of the palladium, but its desorption energy is too high, a recurrent problem of the materials that have been considered for hydrogen storage. The release of hydrogen, however, can be favored by using transition metals in the material structure, as demonstrated here by doping MgH 2 with 3d and 4d-transition metals to reduce the hydrogen atomic charge and the desorption energy.

Stability chart of small mixed 4He-3He clusters

NASA Astrophysics Data System (ADS)

Guardiola, R.; Navarro, J.

2003-11-01

A stability chart of mixed 4He and 3He clusters has been obtained by means of the diffusion Monte Carlo method, using both the Aziz HFD-B and the Tang-Toennies-Yiu atom-atom interaction. The investigated clusters contain up to eight 4He atoms and up to 20 3He atoms. One single 4He binds 20 3He atoms, and two 4He bind 1, 2, 8, and more than 14 3He atoms. All clusters with three or more 4He atoms are bound, although the combinations 4He33He9,10,11 and 4He34He9 are metastable. Clusters with 2, 8, and 20 3He atoms are particularly stable and define magic 3He numbers.

Room-temperature current blockade in atomically defined single-cluster junctions

NASA Astrophysics Data System (ADS)

Lovat, Giacomo; Choi, Bonnie; Paley, Daniel W.; Steigerwald, Michael L.; Venkataraman, Latha; Roy, Xavier

2017-11-01

Fabricating nanoscopic devices capable of manipulating and processing single units of charge is an essential step towards creating functional devices where quantum effects dominate transport characteristics. The archetypal single-electron transistor comprises a small conducting or semiconducting island separated from two metallic reservoirs by insulating barriers. By enabling the transfer of a well-defined number of charge carriers between the island and the reservoirs, such a device may enable discrete single-electron operations. Here, we describe a single-molecule junction comprising a redox-active, atomically precise cobalt chalcogenide cluster wired between two nanoscopic electrodes. We observe current blockade at room temperature in thousands of single-cluster junctions. Below a threshold voltage, charge transfer across the junction is suppressed. The device is turned on when the temporary occupation of the core states by a transiting carrier is energetically enabled, resulting in a sequential tunnelling process and an increase in current by a factor of ∼600. We perform in situ and ex situ cyclic voltammetry as well as density functional theory calculations to unveil a two-step process mediated by an orbital localized on the core of the cluster in which charge carriers reside before tunnelling to the collector reservoir. As the bias window of the junction is opened wide enough to include one of the cluster frontier orbitals, the current blockade is lifted and charge carriers can tunnel sequentially across the junction.

Nano-jewellery: C5Au12--a gold-plated diamond at molecular level.

PubMed

Naumkin, F

2006-06-07

A mixed carbon-metal cluster is designed by combining the tetrahedral C(5) radical (with a central atom-the skeleton of the C(5)H(12) molecule) and the spherical Au(12) layer (the external atomic shell of the Au(13) cluster). The C(5)Au(12) cluster and its negative and positive ionic derivatives, C(5)Au(12)(+/-), are investigated ab initio (DFT) in terms of optimized structures and relative energies of a few spin-states, for the icosahedral-like and octahedral-like isomers. The cluster is predicted to be generally more stable in its octahedral shape (similar to C(5)H(12)) which prevails for the negative ion and may compete with the icosahedral shape for the neutral system and positive ion. Adiabatic ionization energies (AIE) and electron affinities (AEA) of C(5)Au(12), vertical electron-detachment (VDE) energies of C(5)Au(12)(-), and vertical ionization and electron-attachment energies (VIE, VEA) of C(5)Au(12) are calculated as well, and compared with those for the corresponding isomers of the Au(13) cluster. The AIE and VIE values are found to be close for the two systems, while the AEA and VDE values are significantly reduced for the radical-based species. A simple fragment-based model is proposed for the decomposition of the total interaction into carbon-gold and gold-gold components.

Dislocation creation and void nucleation in FCC ductile metals under tensile loading: a general microscopic picture.

PubMed

Pang, Wei-Wei; Zhang, Ping; Zhang, Guang-Cai; Xu, Ai-Guo; Zhao, Xian-Geng

2014-11-10

Numerous theoretical and experimental efforts have been paid to describe and understand the dislocation and void nucleation processes that are fundamental for dynamic fracture modeling of strained metals. To date an essential physical picture on the self-organized atomic collective motions during dislocation creation, as well as the essential mechanisms for the void nucleation obscured by the extreme diversity in structural configurations around the void nucleation core, is still severely lacking in literature. Here, we depict the origin of dislocation creation and void nucleation during uniaxial high strain rate tensile processes in face-centered-cubic (FCC) ductile metals. We find that the dislocations are created through three distinguished stages: (i) Flattened octahedral structures (FOSs) are randomly activated by thermal fluctuations; (ii) The double-layer defect clusters are formed by self-organized stacking of FOSs on the close-packed plane; (iii) The stacking faults are formed and the Shockley partial dislocations are created from the double-layer defect clusters. Whereas, the void nucleation is shown to follow a two-stage description. We demonstrate that our findings on the origin of dislocation creation and void nucleation are universal for a variety of FCC ductile metals with low stacking fault energies.

Enhancement of magnetocaloric effect in the Gd 2Al phase by Co alloying

DOE PAGES

Huang, Z. Y.; Fu, H.; Hadimani, R. L.; ...

2014-11-14

We observe that Cu clusters grow on surface terraces of graphite as a result of physical vapor deposition in ultrahigh vacuum. We show that the observation is incompatible with a variety of models incorporating homogeneous nucleation and high level calculations of atomic-scale energetics. An alternative explanation, ion-mediated heterogeneous nucleation, is proposed and validated, both with theory and experiment. This serves as a case study in identifying when and whether the simple, common observation of metal clusters on carbon-rich surfaces can be interpreted in terms of homogeneous nucleation. We describe a general approach for making system-specific and laboratory-specific predictions.

Vibrational properties of gold nanoparticles obtained by green synthesis

NASA Astrophysics Data System (ADS)

Alvarez, Ramón A. B.; Cortez-Valadez, M.; Bueno, L. Oscar Neira; Britto Hurtado, R.; Rocha-Rocha, O.; Delgado-Beleño, Y.; Martinez-Nuñez, C. E.; Serrano-Corrales, Luis Ivan; Arizpe-Chávez, H.; Flores-Acosta, M.

2016-10-01

This study reports the synthesis and characterization of gold nanoparticles through an ecological method to obtain nanostructures from the extract of the plant Opuntia ficus-indica. Colloidal nanoparticles show sizes that vary between 10-20 nm, and present various geometric morphologies. The samples were characterized through optical absorption, Raman Spectroscopy and Transmission Electron Microscopy (TEM). Additionally, low energy metallic clusters of Aun (n=2-20 atoms) were modeled by computational quantum chemistry. The theoretical results were obtained with Density Functional Theory (DFT). The predicted results of Au clusters show a tendency and are correlated with the experimental results concerning the optical absorption bands and Raman spectroscopy in gold nanoparticles.

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

NASA Astrophysics Data System (ADS)

Lai, King C.; Liu, Da-Jiang; Evans, James W.

2017-12-01

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal (100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN˜ N-β with β =3 /2 . However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N <9 ; (ii) slow nucleation-mediated diffusion with small β <1 for "perfect" sizes N = Np= L2 or L (L +1 ) , for L =3 ,4 , ... having unique ground-state shapes, for moderate sizes 9 ≤N ≤O (102) ; the same also applies for N =Np+3 , Np+ 4 , ... (iii) facile diffusion but with large β >2 for N =Np+1 and Np+2 also for moderate sizes 9 ≤N ≤O (102) ; (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲β <3 /2 , reflecting the quasifacetted structure of clusters, for larger N =O (102) to N =O (103) ; (v) classic scaling with β =3 /2 for very large N =O (103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where we show that diffusivity cycles quasiperiodically from the slowest branch for Np+3 (not Np) to the fastest branch for Np+1 . Behavior is quantified by kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground-state and low-lying excited state cluster configurations, and also of kink populations.

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai, King C.; Liu, Da -Jiang; Evans, James W.

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal(100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN ~ N -β with β = 3/2. However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N < 9; (ii) slow nucleation-mediated diffusion with small β < 1 for “perfect” sizes N = N p = L 2 or L(L+1), for L = 3, 4,… having unique ground state shapes, for moderate sizes 9 ≤ N ≤ O(10 2); the samemore » also applies for N = N p +3, N p + 4,… (iii) facile diffusion but with large β > 2 for N = Np + 1 and N p + 2 also for moderate sizes 9 ≤ N ≤ O(10 2); (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲ β < 3/2, reflecting the quasi-facetted structure of clusters, for larger N = O(10 2) to N = O(10 3); and (v) classic scaling with β = 3/2 for very large N = O(103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where show that diffusivity cycles quasi-periodically from the slowest branch for N p + 3 (not Np) to the fastest branch for Np + 1. Behavior is quantified by Kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back-correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground state and low-lying excited state cluster configurations, and also of kink populations.« less

Diffusion of two-dimensional epitaxial clusters on metal (100) surfaces: Facile versus nucleation-mediated behavior and their merging for larger sizes

DOE PAGES

Lai, King C.; Liu, Da -Jiang; Evans, James W.

2017-12-05

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal(100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN ~ N -β with β = 3/2. However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N < 9; (ii) slow nucleation-mediated diffusion with small β < 1 for “perfect” sizes N = N p = L 2 or L(L+1), for L = 3, 4,… having unique ground state shapes, for moderate sizes 9 ≤ N ≤ O(10 2); the samemore » also applies for N = N p +3, N p + 4,… (iii) facile diffusion but with large β > 2 for N = Np + 1 and N p + 2 also for moderate sizes 9 ≤ N ≤ O(10 2); (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲ β < 3/2, reflecting the quasi-facetted structure of clusters, for larger N = O(10 2) to N = O(10 3); and (v) classic scaling with β = 3/2 for very large N = O(103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where show that diffusivity cycles quasi-periodically from the slowest branch for N p + 3 (not Np) to the fastest branch for Np + 1. Behavior is quantified by Kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back-correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground state and low-lying excited state cluster configurations, and also of kink populations.« less

Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

Fine-Tuning the Activity of Metal–Organic Framework Supported Cobalt Catalysts for the Oxidative Dehydrogenation of Propane

DOE PAGES

Li, Zhanyong; Peters, Aaron W.; Platero-Prats, Ana E.; ...

2017-10-04

Few-atom cobalt-oxide clusters, when dispersed on a Zr-based metal–organic framework (MOF) NU-1000, have previously been shown to be active for the oxidative dehydrogenation (ODH) of propane at low temperatures (< 230 °C), affording a selective and stable propene production catalyst. In our current work, a series of promoter ions with varying Lewis acidity, including Ni(II), Zn(II), Al(III), Ti(IV) and Mo(VI), are anchored as metal-oxide,hydroxide clusters to NU-1000 via SIM (solvothermal deposition within MOFs–specifically the nodes) followed by incorporation of Co(II) ions via vapor-phase AIM (atomic layer deposition (ALD) in MOFs). This process yields a series of NU-1000-supported bimetallic-oxo,hydroxo,aqua clusters. Usingmore » difference envelope density (DED) analyses, the spatial locations of the promoter ions and catalytic cobalt ions are determined. For all samples the SIM-anchored promoter ions are sited between pairs of Zr 6 nodes along the MOF c-axis (channel-aligned axis) whereas the location of the AIM-anchored cobalt ions varies depending on the identity of promoter metal ion. With Ni(II)-, Al(III)-, or Ti(IV)-containing clusters as promoters, the oxy-cobalt species are sited atop the promoter sites; with Mo(VI) they grow exclusively on the MOF nodes sites (hexa-Zr(IV)- oxo,hydroxo,aqua units); with Zn(II) they grow on both the node and promoter. The NU-1000- supported bimetallic-oxide clusters are active for propane ODH after thermal activation under O 2 to open a cobalt coordination site and to oxidize Co(II) to Co(III), as evidenced by operando Xray absorption spectroscopy at the Co K-edge. The cobalt component is exclusively responsible for the observed catalysis. In accord with the decreasing Lewis acidity of the promoter ion, catalytic activity increases in the order: Mo(VI)« less

Neutral and charged gallium clusters: structures, physical properties and implications for the melting features

NASA Astrophysics Data System (ADS)

Núñez, Sara; López, José M.; Aguado, Andrés

2012-09-01

We report the putative Global Minimum (GM) structures and electronic properties of GaN+, GaN and GaN- clusters with N = 13-37 atoms, obtained from first-principles density functional theory structural optimizations. The calculations include spin polarization and employ an exchange-correlation functional which accounts for van der Waals dispersion interactions (vdW-DFT). We find a wide diversity of structural motifs within the located GM, including decahedral, polyicosahedral, polytetrahedral and layered structures. The GM structures are also extremely sensitive to the number of electrons in the cluster, so that the structures of neutral and charged clusters differ for most sizes. The main magic numbers (clusters with an enhanced stability) are identified and interpreted in terms of electronic and geometric shell closings. The theoretical results are consistent with experimental abundance mass spectra of GaN+ and with photoelectron spectra of GaN-. The size dependence of the latent heats of melting, the shape of the heat capacity peaks, and the temperature dependence of the collision cross-sections, all measured for GaN+ clusters, are properly interpreted in terms of the calculated cohesive energies, spectra of configurational excitations, and cluster shapes, respectively. The transition from ``non-melter'' to ``magic-melter'' behaviour, experimentally observed between Ga30+ and Ga31+, is traced back to a strong geometry change. Finally, the higher-than-bulk melting temperatures of gallium clusters are correlated with a more typically metallic behaviour of the clusters as compared to the bulk, contrary to previous theoretical claims.We report the putative Global Minimum (GM) structures and electronic properties of GaN+, GaN and GaN- clusters with N = 13-37 atoms, obtained from first-principles density functional theory structural optimizations. The calculations include spin polarization and employ an exchange-correlation functional which accounts for van der Waals dispersion interactions (vdW-DFT). We find a wide diversity of structural motifs within the located GM, including decahedral, polyicosahedral, polytetrahedral and layered structures. The GM structures are also extremely sensitive to the number of electrons in the cluster, so that the structures of neutral and charged clusters differ for most sizes. The main magic numbers (clusters with an enhanced stability) are identified and interpreted in terms of electronic and geometric shell closings. The theoretical results are consistent with experimental abundance mass spectra of GaN+ and with photoelectron spectra of GaN-. The size dependence of the latent heats of melting, the shape of the heat capacity peaks, and the temperature dependence of the collision cross-sections, all measured for GaN+ clusters, are properly interpreted in terms of the calculated cohesive energies, spectra of configurational excitations, and cluster shapes, respectively. The transition from ``non-melter'' to ``magic-melter'' behaviour, experimentally observed between Ga30+ and Ga31+, is traced back to a strong geometry change. Finally, the higher-than-bulk melting temperatures of gallium clusters are correlated with a more typically metallic behaviour of the clusters as compared to the bulk, contrary to previous theoretical claims. Electronic supplementary information (ESI) available: Atomic coordinates (in xyz format and Å units) and point group symmetries for the global minimum structures reported in this paper. See DOI: 10.1039/c2nr31222k

The application of aberration-corrected electron microscopy to the characterization of gold-based catalysts

NASA Astrophysics Data System (ADS)

Herzing, Andrew A.

Electron microscopy has long been used to study the morphology of heterogeneous catalysts. Recent advances in electron optics now allow for the correction of the inherent spherical aberration (Cs) produced by the objective lens in the scanning transmission electron microscope (STEM, resulting in a significantly improved spatial resolution as well as the ability to use a much larger probe-current than was previously possible. In this thesis, the combination of high-angle annular dark-field (HAADF) imaging and microanalysis by x-ray energy dispersive spectroscopy (XEDS) in an aberration-corrected STEM has been applied for the first time to the characterization of gold-based heterogeneous catalysts. Multi-variate statistical analysis (MSA) has been employed in order to further improve the STEM-XEDS spectrum image data acquired with this technique. In addition, supplemental analysis using electron-energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFTEM) in an aberration-corrected instrument has also been attempted. These techniques have proven extremely valuable in providing complimentary information to more traditional catalyst characterization techniques such as x-ray photoelectron spectroscopy and x-ray diffraction in four specific problems relating to catalysis. Firstly, the atomic-scale resolution of Cs-corrected HAADF imaging has been utilized to study Au/FeOx catalysts in order to determine the size and structure of the Au clusters present on the support surface. It was discovered that, while both inactive and active catalysts for low-temperature CO oxidation contained large Au particles (> 5 nm) and individual Au atoms, the active catalyst also contained sub-nm clusters comprised of only a few Au atoms. Secondly, novel CeO2 support materials for Au and Au-Pd catalysts were synthesized by precipitation with supercritical CO2. These supports were found to produce significantly more active catalysts than those based on CeO2 prepared using more traditional methods. The combination of STEM-HAADF imaging and XEDS mapping has been used to characterize these catalysts and a strong correlation between the catalytic activity and the enhanced degree of metal dispersion over the support is demonstrated. Thirdly, a systematic series of Au-Pd/Al2O3 catalysts has been studied in order to characterize the effects of various heat treatments on the development of core-shell morphologies within the bi-metallic particles and its subsequent effect on their catalytic performance for H2O 2 synthesis. STEM-XEDS spectrum imaging was employed in order to determine the degree of alloying and segregation behavior within the individual Au-Pd particles as a function of calcination/reduction temperature. It was found that the as prepared catalyst contained homogeneous Au-Pd alloy particles and that a Pd-rich shell/Au-rich core morphology gradually developed upon calcination. Subsequent reduction of the catalyst caused a large fraction of the particles to invert and form Pd-rich core/Au-rich shell structures. These changes are related to both the activity and stability of the catalyst. Finally, the washing of activated carbon support materials in acid was found to be extremely beneficial for producing Au-Pd catalysts for the direct synthesis of H2O2. STEM-HAADF imaging revealed that the acid-washing treatment increased the dispersion of the metal on the carbon supports. Aberration-corrected STEM-XEDS spectrum imaging demonstrated a strong size dependence of the Au-Pd particle composition. Crucially, the acid-washing pre-treatment enhanced the alloying of Au and Pd by suppressing the formation of large (> 25 nm) Au-rich particles. In summary, the application of aberration-corrected HAADF imaging and STEM-XEDS spectrum imaging to the characterization of Au-based catalysts has enhanced the understanding of the structural and chemical features that determine their catalytic behavior. Specifically, they have allowed us to achieve the following: (a) image individual metal atoms and clusters of just a few atoms dispersed in a real, high surface area catalyst, (b) detect and follow the development of core-shell structures in Au-Pd bi-metallic catalysts, (c) determine composition/size correlations in Au-Pd catalysts, (d) detect minor alloying elements in bi-metallic catalysts, (e) and chemically map atomic or near atomic dispersions of metals on oxide supports.

Quantum chemical molecular dynamics simulation of single-walled carbon nanotube cap nucleation on an iron particle.

PubMed

Ohta, Yasuhito; Okamoto, Yoshiko; Page, Alister J; Irle, Stephan; Morokuma, Keiji

2009-11-24

The atomic scale details of single-walled carbon nanotube (SWNT) nucleation on metal catalyst particles are elusive to experimental observations. Computer simulation of metal-catalyzed SWNT nucleation is a challenging topic but potentially of great importance to understand the factors affecting SWNT diameters, chirality, and growth efficiency. In this work, we use nonequilibrium density functional tight-binding molecular dynamics simulations and report nucleation of sp(2)-carbon cap structures on an iron particle consisting of 38 atoms. One C(2) molecule was placed every 1.0 ps around an Fe(38) cluster for 30 ps, after which a further 410 ps of annealing simulation without carbon supply was performed. We find that sp(2)-carbon network nucleation and annealing processes occur in three sequential and repetitive stages: (A) polyyne chains on the metal surface react with each other to evolve into a Y-shaped polyyne junction, which preferentially form a five-membered ring as a nucleus; (B) polyyne chains on the first five-membered ring form an additional fused five- or six-membered ring; and (C) pentagon-to-hexagon self-healing rearrangement takes place with the help of short-lived polyyne chains, stabilized by the mobile metal atoms. The observed nucleation process resembles the formation of a fullerene cage. However, the metal particle plays a key role in differentiating the nucleation process from fullerene cage formation, most importantly by keeping the growing cap structure from closing into a fullerene cage and by keeping the carbon edge "alive" for the addition of new carbon material.

The atomic-scale nucleation mechanism of NiTi metallic glasses upon isothermal annealing studied via molecular dynamics simulations.

PubMed

Li, Yang; Li, JiaHao; Liu, BaiXin

2015-10-28

Nucleation is one of the most essential transformation paths in phase transition and exerts a significant influence on the crystallization process. Molecular dynamics simulations were performed to investigate the atomic-scale nucleation mechanisms of NiTi metallic glasses upon devitrification at various temperatures (700 K, 750 K, 800 K, and 850 K). Our simulations reveal that at 700 K and 750 K, nucleation is polynuclear with high nucleation density, while at 800 K it is mononuclear. The underlying nucleation mechanisms have been clarified, manifesting that nucleation can be induced either by the initial ordered clusters (IOCs) or by the other precursors of nuclei evolved directly from the supercooled liquid. IOCs and other precursors stem from the thermal fluctuations of bond orientational order in supercooled liquids during the quenching process and during the annealing process, respectively. The simulation results not only elucidate the underlying nucleation mechanisms varied with temperature, but also unveil the origin of nucleation. These discoveries offer new insights into the devitrification mechanism of metallic glasses.

A new hexanuclear iron-selenium nitrosyl cluster: primary exploration of the preparation methods, structure, and spectroscopic and electrochemical properties.

PubMed

Wang, Rongming; Xu, Wei; Zhang, Jian; Li, Lijuan

2010-06-07

A new hexanuclear iron-selenium nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)Se(6)(NO)(6)] (1), and a hexanuclear iron-sulfur nitrosyl cluster, [(n-Bu)(4)N](2)[Fe(6)S(6)(NO)(6)] (2), were synthesized by the solvent-thermal reactions of [(n-Bu)(4)N][Fe(CO)(3)NO] with selenium or sulfur in methanol, while a tetranuclear iron-sulfur nitrosyl cluster, (Me(4)N)[Fe(4)S(3)(NO)(7)] (3), was also prepared by the solvent-thermal reaction of FeCl(2).4H(2)O with thiourea in the presence of (CH(3))(4)NCl, NaNO(2), and methanol. Complexes 1-3 were characterized by IR, UV-vis, (1)H NMR, electrochemistry, and single-crystal X-ray diffraction analysis. IR spectra of complexes 1 and 2 show the characteristic NO stretching frequencies at 1694 and 1698 cm(-1), respectively, while the absorptions of complex 3 appear at 1799, 1744, and 1710 cm(-1). The UV-vis spectra of complexes 1-3 show different bands in the range of 259-562 nm, which are assigned to the transitions between orbitals delocalized over the Fe-S cluster, the ligand-to-metal charge transfer, pi*(NO)-d(Fe), and the metal-to-ligand charge transfer, d(Fe)-pi*(NO). Single-crystal X-ray structural analysis reveals that complex 1 crystallizes in the monoclinic P2(1)/n space group with two molecules per unit cell. Two parallel "chair-shaped" structures, consisting of three iron and three selenium atoms, are connected by Fe-Se bonds with an average distance of 2.341 A; each iron center is bonded to three selenium atoms and a nitrogen atom from the nitrosyl ligand with a pseudotetrahedral center geometry. Cyclic voltammograms of complexes 1 and 2 display two cathodic and three anodic current peaks with an unusually strong cathodic peak. Further electrochemical investigations demonstrated that the intensity of the unusually strong peak is a result of at least three processes. One is the quasi-reversible reduction, and the other two are from an irreversible electrochemical process, in which the compound goes through a typical electron transfer and chemical reaction mechanism. Compound 3 shows three quasi-reversible reductions.

Effects of electronic excitation in 150 keV Ni ion irradiation of metallic systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zarkadoula, Eva; Samolyuk, German; Weber, William J.

We use the two-temperature model in molecular dynamic simulations of 150 keV Ni ion cascades in nickel and nickel-based alloys to investigate the effect of the energy exchange between the atomic and the electronic systems during the primary stages of radiation damage. We find that the electron-phonon interactions result in a smaller amount of defects and affect the cluster formation, resulting in smaller clusters. These results indicate that ignoring the local heating due to the electrons results in the overestimation of the amount of damage and the size of the defect clusters. A comparison of the average defect production tomore » the Norgett-Robinson-Torrens (NRT) prediction over a range of energies is provided.« less

Toward better understanding of the support effect: Test cases for CO dissociation on Fen/TiO2(1 1 0), n = 4, 5

NASA Astrophysics Data System (ADS)

Jedidi, Abdesslem; Aziz, Saadullah G.; Cavallo, Luigi; Minot, Christian

2017-09-01

The Fischer-Tropsch reaction is initiated by direct CO dissociation for Iron catalyst even though a H-assisted mechanism may be easier on other metals. In the gas phase, the CO dissociation is only favorable for Fe-clusters composed by more than 11 atoms. We show here the remarkable effect of the support TiO2(1 1 0), making this dissociation exothermic for Fe4 and Fe5 clusters. The main factor for the CO activation is the electron transfer to the reducible support. The role of the TiO2(1 1 0) support is to transform the neutral cluster into a positively charged one for which CO dissociation is easier.

Effects of electronic excitation in 150 keV Ni ion irradiation of metallic systems

DOE PAGES

Zarkadoula, Eva; Samolyuk, German; Weber, William J.

2018-01-18

We use the two-temperature model in molecular dynamic simulations of 150 keV Ni ion cascades in nickel and nickel-based alloys to investigate the effect of the energy exchange between the atomic and the electronic systems during the primary stages of radiation damage. We find that the electron-phonon interactions result in a smaller amount of defects and affect the cluster formation, resulting in smaller clusters. These results indicate that ignoring the local heating due to the electrons results in the overestimation of the amount of damage and the size of the defect clusters. A comparison of the average defect production tomore » the Norgett-Robinson-Torrens (NRT) prediction over a range of energies is provided.« less

Cluster analysis of polymers using laser-induced breakdown spectroscopy with K-means

NASA Astrophysics Data System (ADS)

Yangmin, GUO; Yun, TANG; Yu, DU; Shisong, TANG; Lianbo, GUO; Xiangyou, LI; Yongfeng, LU; Xiaoyan, ZENG

2018-06-01

Laser-induced breakdown spectroscopy (LIBS) combined with K-means algorithm was employed to automatically differentiate industrial polymers under atmospheric conditions. The unsupervised learning algorithm K-means were utilized for the clustering of LIBS dataset measured from twenty kinds of industrial polymers. To prevent the interference from metallic elements, three atomic emission lines (C I 247.86 nm , H I 656.3 nm, and O I 777.3 nm) and one molecular line C–N (0, 0) 388.3 nm were used. The cluster analysis results were obtained through an iterative process. The Davies–Bouldin index was employed to determine the initial number of clusters. The average relative standard deviation values of characteristic spectral lines were used as the iterative criterion. With the proposed approach, the classification accuracy for twenty kinds of industrial polymers achieved 99.6%. The results demonstrated that this approach has great potential for industrial polymers recycling by LIBS.

Dense cloud cores revealed by CO in the low metallicity dwarf galaxy WLM.

PubMed

Rubio, Monica; Elmegreen, Bruce G; Hunter, Deidre A; Brinks, Elias; Cortés, Juan R; Cigan, Phil

2015-09-10

Understanding stellar birth requires observations of the clouds in which they form. These clouds are dense and self-gravitating, and in all existing observations they are molecular, with H2 the dominant species and carbon monoxide (CO) the best available tracer. When the abundances of carbon and oxygen are low compared with that of hydrogen, and the opacity from dust is also low, as in primeval galaxies and local dwarf irregular galaxies, CO forms slowly and is easily destroyed, so it is difficult for it to accumulate inside dense clouds. Here we report interferometric observations of CO clouds in the local group dwarf irregular galaxy Wolf-Lundmark-Melotte (WLM), which has a metallicity that is 13 per cent of the solar value and 50 per cent lower than the previous CO detection threshold. The clouds are tiny compared to the surrounding atomic and H2 envelopes, but they have typical densities and column densities for CO clouds in the Milky Way. The normal CO density explains why star clusters forming in dwarf irregulars have similar densities to star clusters in giant spiral galaxies. The low cloud masses suggest that these clusters will also be low mass, unless some galaxy-scale compression occurs, such as an impact from a cosmic cloud or other galaxy. If the massive metal-poor globular clusters in the halo of the Milky Way formed in dwarf galaxies, as is commonly believed, then they were probably triggered by such an impact.

Competition between drum and quasi-planar structures in RhB18-: motifs for metallo-boronanotubes and metallo-borophenes.

PubMed

Jian, Tian; Li, Wan-Lu; Chen, Xin; Chen, Teng-Teng; Lopez, Gary V; Li, Jun; Wang, Lai-Sheng

2016-12-01

Metal-doped boron clusters provide new opportunities to design nanoclusters with interesting structures and bonding. A cobalt-doped boron cluster, CoB 18 - , has been observed recently to be planar and can be viewed as a motif for metallo-borophenes, whereas the D 9d drum isomer as a motif for metallo-boronanotubes is found to be much higher in energy. Hence, whether larger doped boron drums are possible is still an open question. Here we report that for RhB 18 - the drum and quasi-planar structures become much closer in energy and co-exist experimentally, revealing a competition between the metallo-boronanotube and metallo-borophene structures. Photoelectron spectroscopy of RhB 18 - shows a complicated spectral pattern, suggesting the presence of two isomers. Quantum chemistry studies indicate that the D 9d drum isomer and a quasi-planar isomer ( C s ) compete for the global minimum. The enhanced stability of the drum isomer in RhB 18 - is due to the less contracted Rh 4d orbitals, which can have favorable interactions with the B 18 drum motif. Chemical bonding analyses show that the quasi-planar isomer of RhB 18 - is aromatic with 10 π electrons, whereas the observed RhB 18 - drum cluster sets a new record for coordination number of eighteen among metal complexes. The current finding shows that the size of the boron drum can be tuned by appropriate metal dopants, suggesting that even larger boron drums with 5d, 6d transition metal, lanthanide or actinide metal atoms are possible.

Structures of small Pd Pt bimetallic clusters by Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Cheng, Daojian; Huang, Shiping; Wang, Wenchuan

2006-11-01

Segregation phenomena of Pd-Pt bimetallic clusters with icosahedral and decahedral structures are investigated by using Monte Carlo method based on the second-moment approximation of the tight-binding (TB-SMA) potentials. The simulation results indicate that the Pd atoms generally lie on the surface of the smaller clusters. The three-shell onion-like structures are observed in 55-atom Pd-Pt bimetallic clusters, in which a single Pd atom is located in the center, and the Pt atoms are in the middle shell, while the Pd atoms are enriched on the surface. With the increase of Pd mole fraction in 55-atom Pd-Pt bimetallic clusters, the Pd atoms occupy the vertices of clusters first, then edge and center sites, and finally the interior shell. It is noticed that some decahedral structures can be transformed into the icosahedron-like structure at 300 and 500 K. Comparisons are made with previous experiments and theoretical studies of Pd-Pt bimetallic clusters.

Mechanical gate control for atom-by-atom cluster assembly with scanning probe microscopy.

PubMed

Sugimoto, Yoshiaki; Yurtsever, Ayhan; Hirayama, Naoki; Abe, Masayuki; Morita, Seizo

2014-07-11

Nanoclusters supported on substrates are of great importance in physics and chemistry as well as in technical applications, such as single-electron transistors and nanocatalysts. The properties of nanoclusters differ significantly from those of either the constituent atoms or the bulk solid, and are highly sensitive to size and chemical composition. Here we propose a novel atom gating technique to assemble various atom clusters composed of a defined number of atoms at room temperature. The present gating operation is based on the transfer of single diffusing atoms among nanospaces governed by gates, which can be opened in response to the chemical interaction force with a scanning probe microscope tip. This method provides an alternative way to create pre-designed atom clusters with different chemical compositions and to evaluate their chemical stabilities, thus enabling investigation into the influence that a single dopant atom incorporated into the host clusters has on a given cluster stability.

Impact of deformation on the atomic structures and dynamics of a Cu-Zr metallic glass: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Zhang, Y.; Mendelev, M. I.; Wang, C. Z.; Ott, R.; Zhang, F.; Besser, M. F.; Ho, K. M.; Kramer, M. J.

2014-11-01

Despite numerous studies on the atomic structures of Cu-Zr metallic glasses (MGs), their inherent structural ordering, e.g., medium-range order (MRO), remains difficult to describe. Specifically lacking is an understanding of how the MRO responds to deformation and the associated changes in atomic mobility. In this paper, we focus on the impact of deformation on MRO and associated effect on diffusion in a well-relaxed C u64.5Z r35.5 MG by molecular dynamics simulations. The Cu-Zr MG exhibits a larger elastic limit of 0.035 and a yield stress of 3.5 GPa. The cluster alignment method was employed to characterize the icosahedral short-range order (ISRO) and Bergman-type medium-range order (BMRO) in the models upon loading and unloading. From this analysis, we find the disruption of both ISRO and BMRO occurs as the strain reaches about 0.02, well below the elastic limit. Within the elastic limit, the total fractions of ISRO or BMRO can be fully recovered upon unloading. The diffusivity increases six to eight times in regions undergoing plastic deformation, which is due to the dramatic disruption of the ISRO and BMRO. By mapping the spatial distributions of the mobile atoms, we demonstrate the increase in atomic mobility is due to the extended regions of disrupted ISRO and more importantly BMRO.

Structures of 38-atom gold-platinum nanoalloy clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ong, Yee Pin; Yoon, Tiem Leong; Lim, Thong Leng

2015-04-24

Bimetallic nanoclusters, such as gold-platinum nanoclusters, are nanomaterials promising wide range of applications. We perform a numerical study of 38-atom gold-platinum nanoalloy clusters, Au{sub n}Pt{sub 38−n} (0 ≤ n ≤ 38), to elucidate the geometrical structures of these clusters. The lowest-energy structures of these bimetallic nanoclusters at the semi-empirical level are obtained via a global-minimum search algorithm known as parallel tempering multi-canonical basin hopping plus genetic algorithm (PTMBHGA), in which empirical Gupta many-body potential is used to describe the inter-atomic interactions among the constituent atoms. The structures of gold-platinum nanoalloy clusters are predicted to be core-shell segregated nanoclusters. Gold atomsmore » are observed to preferentially occupy the surface of the clusters, while platinum atoms tend to occupy the core due to the slightly smaller atomic radius of platinum as compared to gold’s. The evolution of the geometrical structure of 38-atom Au-Pt clusters displays striking similarity with that of 38-atom Au-Cu nanoalloy clusters as reported in the literature.« less

Nanometer scale atomic structure of zirconium based bulk metallic glass

NASA Astrophysics Data System (ADS)

Hwang, Jinwoo

We have studied the nanometer scale structure of bulk metallic glass (BMG) using fluctuation electron microscopy (FEM). The nanometer scale medium range order (MRO) in BMG is of significant interest because of its possible relationship to the properties, but the experimental study of the MRO is difficult because conventional diffraction techniques are not sensitive to the MRO scale. FEM is a quantitative transmission electron microscopy technique which measures the nanoscale structural fluctuation associated with MRO in amorphous materials, and provides information about the size, distribution, and internal structure of MRO. In this work, we developed an improved method for FEM using energy-filtered STEM nanodiffraction with highly coherent probes with size up to 11nm in a state-of-the-art Cs- corrected STEM. We also developed an effective way to eliminate the effect of sample thickness variation to the FEM data by using Z-contrast images as references. To study the detailed structure of MRO, we developed a hybrid reverse Monte Carlo (H-RMC) simulation which combines an empirical atomic potential and the FEM data. H-RMC generated model structures that match the experimental data at short and medium range. In addition, the subtle rotational symmetries in the FEM nanodiffraction patterns were analyzed by angular correlation function to reveal more details of the internal structure of MRO. Our experiments and simulations show that Zr-based BMG contains pseudo-planar, crystal-like MRO as well as icosahedral clusters in its nanoscale structure. We found that some icosahedral clusters may be connected, and that structural relaxation by annealing increases the population of icosahedral clusters.

High reactivity of nanosized niobium oxide cluster cations in methane activation: A comparison with vanadium oxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, Xun-Lei, E-mail: dingxl@ncepu.edu.cn, E-mail: chemzyx@iccas.ac.cn; Wang, Dan; Wu, Xiao-Nan

2015-09-28

The reactions between methane and niobium oxide cluster cations were studied and compared to those employing vanadium oxides. Hydrogen atom abstraction (HAA) reactions were identified over stoichiometric (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters for N as large as 14 with a time-of-flight mass spectrometer. The reactivity of (Nb{sub 2}O{sub 5}){sub N}{sup +} clusters decreases as the N increases, and it is higher than that of (V {sub 2}O{sub 5}){sub N}{sup +} for N ≥ 4. Theoretical studies were conducted on (Nb{sub 2}O{sub 5}){sub N}{sup +} (N = 2–6) by density functional calculations. HAA reactions on these clusters are all favorablemore » thermodynamically and kinetically. The difference of the reactivity with respect to the cluster size and metal type (Nb vs V) was attributed to thermodynamics, kinetics, the electron capture ability, and the distribution of the unpaired spin density. Nanosized Nb oxide clusters show higher HAA reactivity than V oxides, indicating that niobia may serve as promising catalysts for practical methane conversion.« less

Clusters, Assemble: Growth of Intermetallic Compounds from Metal Flux Reactions.

PubMed

Latturner, Susan E

2018-01-16

Metal flux synthesis involves the reaction of metals and metalloids in a large excess of a low-melting metal that acts as a solvent. This technique makes use of an unusual temperature regime (above the temperatures used for solvothermal methods and below the temperatures used in traditional solid state synthesis) and facilitates the growth of products as large crystals. It has proven to be a fruitful method to discover new intermetallic compounds. However, little is known about the chemistry occurring within a molten metal solvent; without an understanding of the nature of precursor formation and assembly, it is difficult to predict product structures and target properties. Organic chemists have a vast toolbox of well-known reagents and reaction mechanisms to use in directing their synthesis toward a desired molecular structure. This is not yet the case for the synthesis of inorganic extended structures. We have carried out extensive explorations of the growth of new magnetic intermetallic compounds from a variety of metal fluxes. This Account presents a review of some of our results and recent reports by other groups; this work indicates that products with common building blocks and homologous series with identical structural motifs are repeatedly seen in metal flux chemistry. For instance, fluorite-type layers comprised of transition metals coordinated by eight main group metal atoms are found in the Th 2 (Au x Si 1-x )[AuAl 2 ] n Si 2 and R[AuAl 2 ] n Al 2 (Au x Si 1-x ) 2 series grown from aluminum flux, the Ce n PdIn 3n+2 series grown from indium flux, and CePdGa 6 and Ce 2 PdGa 10 grown from gallium flux. Similarly, our investigations of reactions of heavy main group metals, M, in rare earth/transition metal eutectic fluxes reveal that the R/T/M/M' products usually feature M-centered rare earth clusters M@R 8-12 , which share faces to form layers and networks that surround transition metal building blocks. These structural trends, temperature dependence of products formed in the flux, and interconversions observed by differential scanning calorimetry support the idea that these clusters likely form in the melt, existing as precursors and assembling into different crystalline products depending on time, temperature, and reaction ratio. Proof of this mechanism will require future investigations using techniques such as pair distribution function analysis of flux melts to observe cluster formation and in situ diffraction during cooling to detect various phases as they crystallize and interconvert. These data will aid in understanding the parameters that control cluster formation and assembly in metal melts, allow for prediction of products of flux reactions, and will potentially enable the tailoring of reaction conditions to promote the formation of structures with desirable properties.

Solving local structure around dopants in metal nanoparticles with ab initio modeling of X-ray absorption near edge structure

DOE PAGES

Timoshenko, J.; Shivhare, A.; Scott, R. W.; ...

2016-06-30

We adopted ab-initio X-ray Absorption Near Edge Structure (XANES) modelling for structural refinement of local environments around metal impurities in a large variety of materials. Our method enables both direct modelling, where the candidate structures are known, and the inverse modelling, where the unknown structural motifs are deciphered from the experimental spectra. We present also estimates of systematic errors, and their influence on the stability and accuracy of the obtained results. We illustrate our approach by following the evolution of local environment of palladium atoms in palladium-doped gold thiolate clusters upon chemical and thermal treatments.

Theoretical characterization on the size-dependent electron and hole trapping activity of chloride-passivated CdSe nanoclusters

NASA Astrophysics Data System (ADS)

Cui, Yingqi; Cui, Xianhui; Zhang, Li; Xie, Yujuan; Yang, Mingli

2018-04-01

Ligand passivation is often used to suppress the surface trap states of semiconductor quantum dots (QDs) for their continuous photoluminescence output. The suppression process is related to the electrophilic/nucleophilic activity of surface atoms that varies with the structure and size of QD and the electron donating/accepting nature of ligand. Based on first-principles-based descriptors and cluster models, the electrophilic/nucleophilic activities of bare and chloride-coated CdSe clusters were studied to reveal the suppression mechanism of Cl-passivated QDs and compared to experimental observations. The surface atoms of bare clusters have higher activity than inner atoms and their activity decreases with cluster size. In the ligand-coated clusters, the Cd atom remains as the electrophilic site, while the nucleophilic site of Se atoms is replaced by Cl atoms. The activities of Cd and Cl atoms in the coated clusters are, however, remarkably weaker than those in bare clusters. Cluster size, dangling atoms, ligand coverage, electronegativity of ligand atoms, and solvent (water) were found to have considerable influence on the activity of surface atoms. The suppression of surface trap states in Cl-passivated QDs was attributed to the reduction of electrophilic/nucleophilic activity of Cd/Se/Cl atoms. Both saturation to under-coordinated surface atoms and proper selection for the electron donating/accepting strength of ligands are crucial for eliminating the charge carrier traps. Our calculations predicted a similar suppressing effect of chloride ligands with experiments and provided a simple but effective approach to assess the charge carrier trapping behaviors of semiconductor QDs.

Melting of size-selected gallium clusters with 60-183 atoms.

PubMed

Pyfer, Katheryne L; Kafader, Jared O; Yalamanchali, Anirudh; Jarrold, Martin F

2014-07-10

Heat capacities have been measured as a function of temperature for size-selected gallium cluster cations with between 60 and 183 atoms. Almost all clusters studied show a single peak in the heat capacity that is attributed to a melting transition. The peaks can be fit by a two-state model incorporating only fully solid-like and fully liquid-like species, and hence no partially melted intermediates. The exceptions are Ga90(+), which does not show a peak, and Ga80(+) and Ga81(+), which show two peaks. For the clusters with two peaks, the lower temperature peak is attributed to a structural transition. The melting temperatures for clusters with less than 50 atoms have previously been shown to be hundreds of degrees above the bulk melting point. For clusters with more than 60 atoms the melting temperatures decrease, approaching the bulk value (303 K) at around 95 atoms, and then show several small upward excursions with increasing cluster size. A plot of the latent heat against the entropy change for melting reveals two groups of clusters: the latent heats and entropy changes for clusters with less than 94 atoms are distinct from those for clusters with more than 93 atoms. This observation suggests that a significant change in the nature of the bonding or the structure of the clusters occurs at 93-94 atoms. Even though the melting temperatures are close to the bulk value for the larger clusters studied here, the latent heats and entropies of melting are still far from the bulk values.

Atomic Scale Medium Range Order and Relaxation Dynamics in Metallic Glass

NASA Astrophysics Data System (ADS)

Zhang, Pei

We studied the atomic scale structure of bulk metallic glass (BMG) with the combination of fluctuation electron microscopy (FEM) and hybrid reverse Monte Carlo (HRMC) simulation. Medium range order (MRO), which occupies the length scale between short range order (SRO) and long-range order, plays an important role on the properties of metallic glass, but the characterization of MRO in experiment is difficult because conventional techniques are not sensitive to the structure at MRO scale. Compared with the X-ray and neutron which can measure SRO by two-body correlation functions, FEM is an effective way to detect MRO structure through three and four-body correlation functions, providing information about the size, distribution, and internal structure of MRO combing HRMC modeling. Thickness estimation is necessary in FEM experiment and HRMC calculation, so in Chapter 3, we measured the elastic and inelastic mean free paths of metallic glass alloys based on focused ion beam prepared thin samples with measured thickness gradients. We developed a model based on the Wentzel atomic model to predict the elastic mean free path for other amorphous materials. In Chapter 4, we studied the correlation of MRO and glass forming ability ZrCuAl alloy. Results from Variable resolution fluctuation microscopy show that in Zr50Cu35Al15 the crystal-like clusters shrink but become more ordered, while icosahedral-like clusters grow. Compared with Zr50Cu45Al5, Zr50Cu35Al15 with poorer glass forming ability exhibits more stable crystal-like structure under annealing, indicating that destabilizing crystal-like structures is important to achieve better glass forming ability in this alloy. In Chapter 5, we studied the crystallization and MRO structural in deformed and quenched Ni60Nb40 metallic glass. The deformed Ni60Nb40 contains fewer icosahedral-like Voronoi clusters and more crystal-like and bcc-like Voronoi clusters. The crystal-like and bcc-like medium range order clusters may be the structural origin for its lower crystallization temperature compared with quenched alloy. Dynamics heterogeneity is proposed to be the microscopic origin of the dynamic nature of glass transition. Some experimental evidence and simulation have indicated that different regions of materials indeed relax at fast or slow rate. However, the spatial distribution of relaxation time visualized from the experiment as the direct evidence of heterogeneous dynamics is still challenging. We proposed to measure the structural dynamics of supercooled metallic glasses with electron correlation microscopy (ECM) technique at the nanometer scale. ECM was developed as a way to measure structural relaxation times of liquids with nanometer-scale spatial resolution using the coherent electron scattering equivalent of photon correlation spectroscopy. In chapter 6, we studied the experimental requirements of ECM to obtain reliable results. For example, the trajectory length must be at least 40 times the relaxation time to obtain a well-converged g2( t), and the time per frame must be less than 0.1 time the relaxation time to obtain sufficient sampling. ECM experiment was firstly realized in scanning transmission electron microscopy (STEM) mode and applied to measure the structural relaxation time of Pd based metallic glass. In order to overcome the drift problem and capture the spatial information, we developed ECM experiment in dark field (DF) mode. In Chapter 7, through DF-ECM, we visualized the spatially heterogeneous dynamics by in-situ heating Pt57.5Cu14.7Ni 5.3P22.5 nanowire into supercooled liquid state, and quantify the size of the heterogeneity by four-point correlation function. The thickness effect and temporal evolution of the heterogeneous domain were also discussed. Additionally, a fast near-surface dynamics was discovered, providing an effective mechanism for surface crystallization of liquids by homogeneous nucleation.

An Atomically Precise Au10 Ag2 Nanocluster with Red-Near-IR Dual Emission.

PubMed

Lei, Zhen; Guan, Zong-Jie; Pei, Xiao-Li; Yuan, Shang-Fu; Wan, Xian-Kai; Zhang, Jin-Yuan; Wang, Quan-Ming

2016-08-01

A red-near-IR dual-emissive nanocluster with the composition [Au10 Ag2 (2-py-C≡C)3 (dppy)6 ](BF4 )5 (1; 2-py-C≡C is 2-pyridylethynyl, dppy=2-pyridyldiphenylphosphine) has been synthesized. Single-crystal X-ray structural analysis reveals that 1 has a trigonal bipyramidal Au10 Ag2 core that contains a planar Au4 (2-py-C≡C)3 unit sandwiched by two Au3 Ag(dppy)3 motifs. Cluster 1 shows intense red-NIR dual emission in solution. The visible emission originates from metal-to-ligand charge transfer (MLCT) from silver atoms to phosphine ligands in the Au3 Ag(dppy)3 motifs, and the intense NIR emission is associated with the participation of 2-pyridylethynyl in the frontier orbitals of the cluster, which is confirmed by a time-dependent density functional theory (TD-DFT) calculation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Plentiful magnetic moments in oxygen deficient SrTiO 3

DOE PAGES

Ganesh, Panchapakesan; Lopez-Bezanilla, Alejandro; Littlewood, Peter B.

2015-10-06

In this research, correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO 3. Hole and electron doping of oxygen deficient SrTiO 3 yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defect sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO 3–δ is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments inmore » the absence of vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono- and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.« less

Comparative study of mono- and dinuclear complexes of late 3d-metal chlorides with N,N-dimethylformamide in the gas phase.

PubMed

Duchácková, Lucie; Roithová, Jana; Milko, Petr; Zabka, Jan; Tsierkezos, Nikos; Schröder, Detlef

2011-02-07

Mono- and binuclear complexes of N,N-dimethylformamide (DMF) with chlorides of the divalent, late 3d metals M = Co, Ni, Cu, and Zn are investigated by means of electrospray ionization (ESI). Specifically, ESI leads to monocations of the type [(DMF)(n)MCl](+) and [(DMF)(n)M(2)Cl(3)](+), of which the species with n = 2 and 3 were selected for in-depth studies. The latter include collision-induced dissociation experiments, gas-phase infrared spectroscopy, and calculations using density functional theory. The mononuclear complexes [(DMF)(n)MCl](+) almost exclusively lose neutral DMF upon collisional activation with the notable exception of the copper complex, for which also a reduction from Cu(II) to Cu(I) concomitant with the release of atomic chlorine is observed. For the dinuclear clusters, there exists a competition between loss of a DMF ligand and cluster degradation via loss of neutral MCl(2) with decreasing cluster stability from cobalt to zinc. For the specific case of [(DMF)(n)ZnCl](+) and [(DMF)(n)Zn(2)Cl(3)](+), ion-mobility mass spectrometry indicates the existence of two isomeric cluster ions in the case of [(DMF)(2)Zn(2)Cl(3)](+) which corroborates parallel theoretical predictions.

Rydberg States of Alkali Metal Atoms on Superfluid Helium Droplets - Theoretical Considerations

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Lackner, Florian; Hauser, Andreas W.; Ernst, Wolfgang E.

2017-06-01

The bound states of electrons on the surface of superfluid helium have been a research topic for several decades. One of the first systems treated was an electron bound to an ionized helium cluster. Here, a similar system is considered, which consists of a helium droplet with an ionized dopant inside and an orbiting electron on the outside. In our theoretical investigation we select alkali metal atoms (AK) as central ions, stimulated by recent experimental studies of Rydberg states for Na, Rb, and Cs attached to superfluid helium nanodroplets. Experimental spectra , obtained by electronic excitation and subsequent ionization, showed blueshifts for low lying electronic states and redshifts for Rydberg states. In our theoretical treatment the diatomic AK^+-He potential energy curves are first computed with ab initio methods. These potentials are then used to calculate the solvation energy of the ion in a helium droplet as a function of the number of atoms. Additional potential terms, derived from the obtained helium density distribution, are added to the undisturbed atomic pseudopotential in order to simulate a 'modified' potential felt by the outermost electron. This allows us to compute a new set of eigenstates and eigenenergies, which we compare to the experimentally observed energy shifts for highly excited alkali metal atoms on helium nanodroplets. A. Golov and S. Sekatskii, Physica B, 1994, 194, 555-556 E. Loginov, C. Callegari, F. Ancilotto, and M. Drabbels, J. Phys. Chem. A, 2011, 115, 6779-6788 F. Lackner, G. Krois, M. Koch, and W. E. Ernst, J. Phys. Chem. Lett., 2012, 3, 1404-1408 F. Lackner, G. Krois, M. Theisen, M. Koch, and W. E. Ernst, Phys. Chem. Chem. Phys., 2011, 13, 18781-18788

Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

PubMed

Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

2016-02-18

Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

A note on the accuracy of KS-DFT densities

NASA Astrophysics Data System (ADS)

Ranasinghe, Duminda S.; Perera, Ajith; Bartlett, Rodney J.

2017-11-01

The accuracy of the density of wave function methods and Kohn-Sham (KS) density functionals is studied using moments of the density, ⟨rn ⟩ =∫ ρ (r )rnd τ =∫0∞4 π r2ρ (r ) rnd r ,where n =-1 ,-2,0,1,2 ,and 3 provides information about the short- and long-range behavior of the density. Coupled cluster (CC) singles, doubles, and perturbative triples (CCSD(T)) is considered as the reference density. Three test sets are considered: boron through neon neutral atoms, two and four electron cations, and 3d transition metals. The total density and valence only density are distinguished by dropping appropriate core orbitals. Among density functionals tested, CAMQTP00 and ωB97x show the least deviation for boron through neon neutral atoms. They also show accurate eigenvalues for the HOMO indicating that they should have a more correct long-range behavior for the density. For transition metals, some density functional approximations outperform some wave function methods, suggesting that the KS determinant could be a better starting point for some kinds of correlated calculations. By using generalized many-body perturbation theory (MBPT), the convergence of second-, third-, and fourth-order KS-MBPT for the density is addressed as it converges to the infinite-order coupled cluster result. For the transition metal test set, the deviations in the KS density functional theory methods depend on the amount of exact exchange the functional uses. Functionals with exact exchange close to 25% show smaller deviations from the CCSD(T) density.

Theory of Positron Annihilation in Helium-Filled Bubbles in Plutonium

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sterne, P A; Pask, J E

2003-02-13

Positron annihilation lifetime spectroscopy is a sensitive probe of vacancies and voids in materials. This non-destructive measurement technique can identify the presence of specific defects in materials at the part-per-million level. Recent experiments by Asoka-Kumar et al. have identified two lifetime components in aged plutonium samples--a dominant lifetime component of around 182 ps and a longer lifetime component of around 350-400ps. This second component appears to increase with the age of the sample, and accounts for only about 5 percent of the total intensity in 35 year-old plutonium samples. First-principles calculations of positron lifetimes are now used extensively to guidemore » the interpretation of positron lifetime data. At Livermore, we have developed a first-principles finite-element-based method for calculating positron lifetimes for defects in metals. This method is capable of treating system cell sizes of several thousand atoms, allowing us to model defects in plutonium ranging in size from a mono-vacancy to helium-filled bubbles of over 1 nm in diameter. In order to identify the defects that account for the observed lifetime values, we have performed positron lifetime calculations for a set of vacancies, vacancy clusters, and helium-filled vacancy clusters in delta-plutonium. The calculations produced values of 143ps for defect-free delta-Pu and 255ps for a mono-vacancy in Pu, both of which are inconsistent with the dominant experimental lifetime component of 182ps. Larger vacancy clusters have even longer lifetimes. The observed positron lifetime is significantly shorter than the calculated lifetimes for mono-vacancies and larger vacancy clusters, indicating that open vacancy clusters are not the dominant defect in the aged plutonium samples. When helium atoms are introduced into the vacancy cluster, the positron lifetime is reduced due to the increased density of electrons available for annihilation. For a mono-vacancy in Pu containing one helium atom, the calculated lifetime is 190 ps, while a di-vacancy containing two helium atoms has a positron lifetime of 205 ps. In general, increasing the helium density in a vacancy cluster or He-filled bubble reduces the positron lifetime, so that the same lifetime value can arise fi-om a range of vacancy cluster sizes with different helium densities. In order to understand the variation of positron lifetime with vacancy cluster size and helium density in the defect, we have performed over 60 positron lifetime calculations with vacancy cluster sizes ranging from 1 to 55 vacancies and helium densities ranging fi-om zero to five helium atoms per vacancy. The results indicate that the experimental lifetime of 182 ps is consistent with the theoretical value of 190 ps for a mono-vacancy with a single helium atom, but that slightly better agreement is obtained for larger clusters of 6 or more vacancies containing 2-3 helium atoms per vacancy. For larger vacancy clusters with diameters of about 3-5 nm or more, the annihilation with helium electrons dominates the positron annihilation rate; the observed lifetime of 180ps is then consistent with a helium concentration in the range of 3 to 3.5 Hehacancy, setting an upper bound on the helium concentration in the vacancy clusters. In practice, the single lifetime component is most probably associated with a family of helium-filled bubbles rather than with a specific unique defect size. The longer 350-400ps lifetime component is consistent with a relatively narrow range of defect sizes and He concentration. At zero He concentration, the lifetime values are matched by small vacancy clusters containing 6-12 vacancies. With increasing vacancy cluster size, a small amount of He is required to keep the lifetime in the 350-400 ps range, until the value saturates for larger helium bubbles of more than 50 vacancies (bubble diameter > 1.3 nm) at a helium concentration close to 1 He/vacancy. These results, taken together with the experimental data, indicate that the features observed in TEM data by Schwartz et al are not voids, but are in fact helium-filled bubbles with a helium pressure of around 2-3 helium atoms per vacancy, depending on the bubble size. This is consistent with the conclusions of recently developed models of He-bubble growth in aged plutonium.« less

An introduction to mass cytometry: fundamentals and applications.

PubMed

Tanner, Scott D; Baranov, Vladimir I; Ornatsky, Olga I; Bandura, Dmitry R; George, Thaddeus C

2013-05-01

Mass cytometry addresses the analytical challenges of polychromatic flow cytometry by using metal atoms as tags rather than fluorophores and atomic mass spectrometry as the detector rather than photon optics. The many available enriched stable isotopes of the transition elements can provide up to 100 distinguishable reporting tags, which can be measured simultaneously because of the essential independence of detection provided by the mass spectrometer. We discuss the adaptation of traditional inductively coupled plasma mass spectrometry to cytometry applications. We focus on the generation of cytometry-compatible data and on approaches to unsupervised multivariate clustering analysis. Finally, we provide a high-level review of some recent benchmark reports that highlight the potential for massively multi-parameter mass cytometry.

Photoionization of rare gas clusters

NASA Astrophysics Data System (ADS)

Zhang, Huaizhen

This thesis concentrates on the study of photoionization of van der Waals clusters with different cluster sizes. The goal of the experimental investigation is to understand the electronic structure of van der Waals clusters and the electronic dynamics. These studies are fundamental to understand the interaction between UV-X rays and clusters. The experiments were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory. The experimental method employs angle-resolved time-of-flight photoelectron spectrometry, one of the most powerful methods for probing the electronic structure of atoms, molecules, clusters and solids. The van der Waals cluster photoionization studies are focused on probing the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. The angular distribution has been known to be a sensitive probe of the electronic structure in atoms and molecules. However, it has not been used in the case of van der Waals clusters. We carried out outer-valence levels, inner-valence levels and core-levels cluster photoionization experiments. Specifically, this work reports on the first quantitative measurements of the angular distribution parameters of rare gas clusters as a function of average cluster sizes. Our findings for xenon clusters is that the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the corresponding free atoms. However, distinct differences in the angular distribution point at cluster-size-dependent effects were found. For krypton clusters, in the photon energy range where atomic photoelectrons have a high angular anisotropy, our measurements show considerably more isotropic angular distributions for the cluster photoelectrons, especially right above the 3d and 4p thresholds. For the valence electrons, a surprising difference between the two spin-orbit components was found. For argon clusters, we found that the angular distribution parameter values of the two-spin-orbit components from Ar 2p clusters are slightly different. When comparing the beta values for Ar between atoms and clusters, we found different results between Ar 3s atoms and clusters, and between Ar 3p atoms and clusters. Argon cluster resonance from surface and bulk were also measured. Furthermore, the angular distribution parameters of Ar cluster photoelectrons and Ar atom photoelectrons in the 3s → np ionization region were obtained.

Atomically precise cluster catalysis towards quantum controlled catalysts

PubMed Central

Watanabe, Yoshihide

2014-01-01

Catalysis of atomically precise clusters supported on a substrate is reviewed in relation to the type of reactions. The catalytic activity of supported clusters has generally been discussed in terms of electronic structure. Several lines of evidence have indicated that the electronic structure of clusters and the geometry of clusters on a support, including the accompanying cluster-support interaction, are strongly correlated with catalytic activity. The electronic states of small clusters would be easily affected by cluster–support interactions. Several studies have suggested that it is possible to tune the electronic structure through atomic control of the cluster size. It is promising to tune not only the number of cluster atoms, but also the hybridization between the electronic states of the adsorbed reactant molecules and clusters in order to realize a quantum-controlled catalyst. PMID:27877723

The Intrinsic Ferromagnetism in a MnO2 Monolayer.

PubMed

Kan, M; Zhou, J; Sun, Q; Kawazoe, Y; Jena, P

2013-10-17

The Mn atom, because of its special electronic configuration of 3d(5)4s(2), has been widely used as a dopant in various two-dimensional (2D) monolayers such as graphene, BN, silicene and transition metal dichalcogenides (TMDs). The distributions of doped Mn atoms in these systems are highly sensitive to the synthesis process and conditions, thus suffering from problems of low solubility and surface clustering. Here we show for the first time that the MnO2 monolayer, synthetized 10 years ago, where Mn ions are individually held at specific sites, exhibits intrinsic ferromagnetism with a Curie temperature of 140 K, comparable to the highest TC value achieved experimentally for Mn-doped GaAs. The well-defined atomic configuration and the intrinsic ferromagnetism of the MnO2 monolayer suggest that it is superior to other magnetic monolayer materials.

Theoretical realization of cluster-assembled hydrogen storage materials based on terminated carbon atomic chains.

PubMed

Liu, Chun-Sheng; An, Hui; Guo, Ling-Ju; Zeng, Zhi; Ju, Xin

2011-01-14

The capacity of carbon atomic chains with different terminations for hydrogen storage is studied using first-principles density functional theory calculations. Unlike the physisorption of H(2) on the H-terminated chain, we show that two Li (Na) atoms each capping one end of the odd- or even-numbered carbon chain can hold ten H(2) molecules with optimal binding energies for room temperature storage. The hybridization of the Li 2p states with the H(2)σ orbitals contributes to the H(2) adsorption. However, the binding mechanism of the H(2) molecules on Na arises only from the polarization interaction between the charged Na atom and the H(2). Interestingly, additional H(2) molecules can be bound to the carbon atoms at the chain ends due to the charge transfer between Li 2s2p (Na 3s) and C 2p states. More importantly, dimerization of these isolated metal-capped chains does not affect the hydrogen binding energy significantly. In addition, a single chain can be stabilized effectively by the C(60) fullerenes termination. With a hydrogen uptake of ∼10 wt.% on Li-coated C(60)-C(n)-C(60) (n = 5, 8), the Li(12)C(60)-C(n)-Li(12)C(60) complex, keeping the number of adsorbed H(2) molecules per Li and stabilizing the dispersion of individual Li atoms, can serve as better building blocks of polymers than the (Li(12)C(60))(2) dimer. These findings suggest a new route to design cluster-assembled hydrogen storage materials based on terminated sp carbon chains.

Central Doping of a Foreign Atom into the Silver Cluster for Catalytic Conversion of CO2 toward C-C Bond Formation.

PubMed

Liu, Yuanyuan; Chai, Xiaoqi; Cai, Xiao; Chen, Mingyang; Jin, Rongchao; Ding, Weiping; Zhu, Yan

2018-06-19

Clusters with an exact number of atoms are of particular research interest in catalysis. Their catalytic behaviors can be potentially altered with the addition or removal of a single atom. Herein we explore the effects of the single-foreign-atom (Au, Pd and Pt) doping into the core of an Ag cluster with 25-atoms on the catalytic properties, where the foreign atom is protected by 24 Ag atoms (i.e., Au@Ag24, Pd@Ag24, and Pt@Ag24). The central doping of a single atom into the Ag25 cluster is found to have a substantial influence on the catalytic performance in the carboxylation reaction of CO2 with terminal alkyne through C-C bond formation to produce propiolic acid. Our studies reveal that the catalytic properties of the cluster catalysts can be dramatically changed with the subtle alteration by a single atom away from the active sites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple valence superatoms.

PubMed

Reveles, J U; Khanna, S N; Roach, P J; Castleman, A W

2006-12-05

We recently demonstrated that, in gas phase clusters containing aluminum and iodine atoms, an Al(13) cluster behaves like a halogen atom, whereas an Al(14) cluster exhibits properties analogous to an alkaline earth atom. These observations, together with our findings that Al(13)(-) is inert like a rare gas atom, have reinforced the idea that chosen clusters can exhibit chemical behaviors reminiscent of atoms in the periodic table, offering the exciting prospect of a new dimension of the periodic table formed by cluster elements, called superatoms. As the behavior of clusters can be controlled by size and composition, the superatoms offer the potential to create unique compounds with tailored properties. In this article, we provide evidence of an additional class of superatoms, namely Al(7)(-), that exhibit multiple valences, like some of the elements in the periodic table, and hence have the potential to form stable compounds when combined with other atoms. These findings support the contention that there should be no limitation in finding clusters, which mimic virtually all members of the periodic table.

Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

PubMed

Lin, Qisheng; Miller, Gordon J

2018-01-16

Intermetallic compounds represent an extensive pool of candidates for energy related applications stemming from magnetic, electric, optic, caloric, and catalytic properties. The discovery of novel intermetallic compounds can enhance understanding of the chemical principles that govern structural stability and chemical bonding as well as finding new applications. Valence electron-poor polar intermetallics with valence electron concentrations (VECs) between 2.0 and 3.0 e - /atom show a plethora of unprecedented and fascinating structural motifs and bonding features. Therefore, establishing simple structure-bonding-property relationships is especially challenging for this compound class because commonly accepted valence electron counting rules are inappropriate. During our efforts to find quasicrystals and crystalline approximants by valence electron tuning near 2.0 e - /atom, we observed that compositions close to those of quasicrystals are exceptional sources for unprecedented valence electron-poor polar intermetallics, e.g., Ca 4 Au 10 In 3 containing (Au 10 In 3 ) wavy layers, Li 14.7 Mg 36.8 Cu 21.5 Ga 66 adopting a type IV clathrate framework, and Sc 4 Mg x Cu 15-x Ga 7.5 that is incommensurately modulated. In particular, exploratory syntheses of AAu 3 T (A = Ca, Sr, Ba and T = Ge, Sn) phases led to interesting bonding features for Au, such as columns, layers, and lonsdaleite-type tetrahedral frameworks. Overall, the breadth of Au-rich polar intermetallics originates, in part, from significant relativistics effect on the valence electrons of Au, effects which result in greater 6s/5d orbital mixing, a small effective metallic radius, and an enhanced Mulliken electronegativity, all leading to ultimate enhanced binding with nearly all metals including itself. Two other successful strategies to mine electron-poor polar intermetallics include lithiation and "cation-rich" phases. Along these lines, we have studied lithiated Zn-rich compounds in which structural complexity can be realized by small amounts of Li replacing Zn atoms in the parent binary compounds CaZn 2 , CaZn 3 , and CaZn 5 ; their phase formation and bonding schemes can be rationalized by Fermi surface-Brillouin zone interactions between nearly free-electron states. "Cation-rich", electron-poor polar intermetallics have emerged using rare earth metals as the electropositive ("cationic") component together metal/metalloid clusters that mimic the backbones of aromatic hydrocarbon molecules, which give evidence of extensive electronic delocalization and multicenter bonding. Thus, we can identify three distinct, valence electron-poor, polar intermetallic systems that have yielded unprecedented phases adopting novel structures containing complex clusters and intriguing bonding characteristics. In this Account, we summarize our recent specific progress in the developments of novel Au-rich BaAl 4 -type related structures, shown in the "gold-rich grid", lithiation-modulated Ca-Li-Zn phases stabilized by different bonding characteristics, and rare earth-rich polar intermetallics containing unprecedented hydrocarbon-like planar Co-Ge metal clusters and pronounced delocalized multicenter bonding. We will focus mainly on novel structural motifs, bonding analyses, and the role of valence electrons for phase stability.

Synthesis and characterization of transition metal clusters: From the isolation of ligand-stabilized solid fragments to the tuning of magnetic anisotropy and host-guest selectivity, and, Approaches to science teaching: Development of an observation instrument with a measurement model based on item response theory

NASA Astrophysics Data System (ADS)

Hee, Allan George

Part I. The work presented herein describes efforts to develop general techniques for the synthesis of transition metal clusters and the manipulation of their properties. In Chapter 2, it is demonstrated that a modified metal atom reactor allows for the vaporization, passivation, and isolation of metal-chalcogenide clusters from their parent binary solids. Among the clusters produced by this method were Cr6S8(PEt3)6, Fe4S 4(PEt3)4, Co6S8(PEt 3)6, Cu6S4(PEt3)6, Cu12S6(PEt3)8, and Cu26Se 13(PEt3)14. To create single-molecule magnets with higher demagnetization barriers, we are developing metal-cyanide systems which exhibit highly adjustable magnetic behavior. Chapter 3 reports an attempt to introduce magnetic anisotropy into a MnCr6 cluster. Replacement of CrIII with Mo III resulted in the assembly of K[(Me3tacn)6MnMo 6(CN)18](ClO4)3 (Me3tacn = N,N',N″ -trimethyl-1,4,7-triazacyclononane)---the first well-documented example of a cyano-bridged single-molecule magnet. Recently, it was demonstrated that replacing Me3tacn with the less sterically hindering tach (tach = cis,cis-1,3,5-triaminocyclohexane) in the face-centered cubic cluster [(tach)8Cr8Ni 6(CN)24]Br12 provides greater access to the cluster cavity. Chapter 4 describes my efforts to probe the selectivity of this cluster toward inclusion of various guests. Part II. Successful implementation of student-centered curricula reforms requires the creation of a measurement instrument for monitoring whether the curricula are being used as intended. The creation and development of an observation instrument would greatly contribute to this effort. To develop a theoretically sound construct map, it is necessary to review the literature and conduct our own investigations of approaches to science teaching. Chapter 2 presents the findings of these investigations and their contributions to our understanding of the construct. Using these findings, the Science Teaching Observation Protocol (STOP) was created and designed to measure two subconstructs: intentions and strategies. Chapter 3 details the first pilot test of STOP and analysis of the collected data. In Chapter 4, the theoretical shortcomings of the instrument are analyzed and discussed. Modified versions of the intention and strategy subconstruct maps are presented.

Unusual behavior in magnesium-copper cluster matter produced by helium droplet mediated deposition.

PubMed

Emery, S B; Xin, Y; Ridge, C J; Buszek, R J; Boatz, J A; Boyle, J M; Little, B K; Lindsay, C M

2015-02-28

We demonstrate the ability to produce core-shell nanoclusters of materials that typically undergo intermetallic reactions using helium droplet mediated deposition. Composite structures of magnesium and copper were produced by sequential condensation of metal vapors inside the 0.4 K helium droplet baths and then gently deposited onto a substrate for analysis. Upon deposition, the individual clusters, with diameters ∼5 nm, form a cluster material which was subsequently characterized using scanning and transmission electron microscopies. Results of this analysis reveal the following about the deposited cluster material: it is in the un-alloyed chemical state, it maintains a stable core-shell 5 nm structure at sub-monolayer quantities, and it aggregates into unreacted structures of ∼75 nm during further deposition. Surprisingly, high angle annular dark field scanning transmission electron microscopy images revealed that the copper appears to displace the magnesium at the core of the composite cluster despite magnesium being the initially condensed species within the droplet. This phenomenon was studied further using preliminary density functional theory which revealed that copper atoms, when added sequentially to magnesium clusters, penetrate into the magnesium cores.

Excited State Energetics and Dynamics of Large Molecules, Complexes and Clusters

DTIC Science & Technology

1988-07-01

tetracene. Ar (n=l-5) complexes, providing central information on microscopic solvent shifts. These studies were extended to M-metal atom com - plexes...corresponding to the bare molecule. At higher 2. Experimental stagnation pressures of Ar (p = 80-150 Toff) the contributions of van der Waals DPB. Ar, com - Our...gas aromatic-molecule complexes were docu- So - S1 transition of the trans-stilbene (TS)-Ar com - mented experimentally to lie in the rango - 30- plex

Mechanistic Investigations of Branched Macromolecules and Metal Nanocomposites for Nonlinear Optical Applications

DTIC Science & Technology

2009-09-26

gold which show a band gap opening. them with alkyl or aryl thiolates and they are often referred as monolayer protected gold clusters (MPC...workers16-18, as well as Tsukuda and co-workers19 with several thiolate capped MPCs. The PI’s laboratory has observed luminescence mainly in the near...properties for sizes between ~50 and ~1000 atoms is not well understood. Careful analysis of absorption spectra for thiolate stabilized gold MPC

An intramolecular antiferromagnetically coupled pentanuclear Mn(II) cluster containing acetate and tetracarboxylate linkers: Synthesis, structure and magnetism

NASA Astrophysics Data System (ADS)

Wu, Jian; Liu, Wei-Cong; Wu, Xi-Ren; Liu, Jian-Qiang; Sakiyama, Hiroshi; Yadav, Reena; Kumar, Abhinav

2016-06-01

A new Mn(II) complex {[Mn5(CH3COO)2(L)2(DMF)8](DMF)}n (1), (H4L = 3,5-bis(3‧,5‧-dicarboxylphenyl)-1H-1,2,3-triazole), has been synthesized and structurally characterized. The complex 1 have pentanuclear Mn(II) core, where the two sides of metal centers (Mn2 and Mn3) have trigonal bipyramidal arrangement and the middle metal center (Mn1) have octahedral environment utilizing two O atoms from adjacent bridging bidentate carboxylate groups and four O atoms from four coordinated DMF molecules. The planar arrangement of pentanuclear Mn(II) atoms are linked by L linkage to generate two dimensional sheet. The magnetic property of the compound indicates χMT value for the five Mn(II) unit to be 21.3 cm3 K mol-1 at 300 K, which is close to the spin-only value (21.9 cm3 K mol-1) for the pentamer having S = 5/2. Also, the Hirshfeld surface analyses have been performed which indicated the absence of weak Mn···Mn interaction thereby corroborating the results of observed magnetic properties.

Ir/KLTL zeolites: Structural characterization and catalysis on n-hexane reforming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triantafillou, N.D.; Gates, B.C.

Ir/KLTL zeolite catalysts were prepared by incipient wetness impregnation of LTL zeolites with [Ir(NH{sub 3}){sub 5}Cl]Cl{sub 2}. The catalysts were characterized by extended X-ray absorption fine structure (EX-AFS) spectroscopy, infrared spectroscopy, and H{sub 2} chemisorption. EXAFS data show that the average Ir cluster size (after treatment at 300{degrees}C in H{sub 2}) increased from about 7 to 20 {Angstrom} as the zeolite K:Al atomic ratio increased from 0.34 to 1.56. Infrared spectra of adsorbed CO show that the electron donation to the Ir increased as the K:Al ratio increased. In contrast to the performance reported for Pt/KLTL zeolites with metal clustersmore » as small as those observed in the present experiments, the Ir/KLTL catalyst has a low selectivity for dehydrocyclization of n-hexane at 440-480{degrees}C and 1 atm with a H{sub 2}: n-hexane feed molar ratio of 6. Instead, the catalysts are selective for hydrogenolysis. The selectivity is insensitive to the K:Al ratio, but the activity for dehydrocyclization is a maximum at a K:Al atomic ratio of about 1. The results show that even the smallest Ir clusters to which electron donation is significant still behave essentially like metallic Ir in the catalytic reactions. 49 refs., 4 figs., 7 tabs.« less

SGO: A fast engine for ab initio atomic structure global optimization by differential evolution

NASA Astrophysics Data System (ADS)

Chen, Zhanghui; Jia, Weile; Jiang, Xiangwei; Li, Shu-Shen; Wang, Lin-Wang

2017-10-01

As the high throughout calculations and material genome approaches become more and more popular in material science, the search for optimal ways to predict atomic global minimum structure is a high research priority. This paper presents a fast method for global search of atomic structures at ab initio level. The structures global optimization (SGO) engine consists of a high-efficiency differential evolution algorithm, accelerated local relaxation methods and a plane-wave density functional theory code running on GPU machines. The purpose is to show what can be achieved by combining the superior algorithms at the different levels of the searching scheme. SGO can search the global-minimum configurations of crystals, two-dimensional materials and quantum clusters without prior symmetry restriction in a relatively short time (half or several hours for systems with less than 25 atoms), thus making such a task a routine calculation. Comparisons with other existing methods such as minima hopping and genetic algorithm are provided. One motivation of our study is to investigate the properties of magnetic systems in different phases. The SGO engine is capable of surveying the local minima surrounding the global minimum, which provides the information for the overall energy landscape of a given system. Using this capability we have found several new configurations for testing systems, explored their energy landscape, and demonstrated that the magnetic moment of metal clusters fluctuates strongly in different local minima.

Dislocation creation and void nucleation in FCC ductile metals under tensile loading: A general microscopic picture

PubMed Central

Pang, Wei-Wei; Zhang, Ping; Zhang, Guang-Cai; Xu, Ai-Guo; Zhao, Xian-Geng

2014-01-01

Numerous theoretical and experimental efforts have been paid to describe and understand the dislocation and void nucleation processes that are fundamental for dynamic fracture modeling of strained metals. To date an essential physical picture on the self-organized atomic collective motions during dislocation creation, as well as the essential mechanisms for the void nucleation obscured by the extreme diversity in structural configurations around the void nucleation core, is still severely lacking in literature. Here, we depict the origin of dislocation creation and void nucleation during uniaxial high strain rate tensile processes in face-centered-cubic (FCC) ductile metals. We find that the dislocations are created through three distinguished stages: (i) Flattened octahedral structures (FOSs) are randomly activated by thermal fluctuations; (ii) The double-layer defect clusters are formed by self-organized stacking of FOSs on the close-packed plane; (iii) The stacking faults are formed and the Shockley partial dislocations are created from the double-layer defect clusters. Whereas, the void nucleation is shown to follow a two-stage description. We demonstrate that our findings on the origin of dislocation creation and void nucleation are universal for a variety of FCC ductile metals with low stacking fault energies. PMID:25382029

Meta-atom cluster acoustic metamaterial with broadband negative effective mass density

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Huaijun; Zhai, Shilong; Ding, Changlin

2014-02-07

We design a resonant meta-atom cluster, via which a two-dimensional (2D) acoustic metamaterial (AM) with broadband negative effective mass density from 1560 Hz to 5580 Hz is fabricated. Experimental results confirm that there is only weak interaction among the meta-atoms in the cluster. And then the meta-atoms in the cluster independently resonate, resulting in the cluster becoming equivalent to a broadband resonance unit. Extracted effective refractive indices from reflection and transmission measurements of the 2D AM appear to be negative from 1500 Hz to 5480 Hz. The broadband negative refraction has also been demonstrated by our further experiments. We expectmore » that this meta-atom cluster AM will significantly contribute to the design of broadband negative effective mass density AM.« less

Mechanistic Insights into Ring Cleavage and Contraction of Benzene over a Titanium Hydride Cluster.

PubMed

Kang, Xiaohui; Luo, Gen; Luo, Lun; Hu, Shaowei; Luo, Yi; Hou, Zhaomin

2016-09-14

Carbon-carbon bond cleavage of benzene by transition metals is of great fundamental interest and practical importance, as this transformation is involved in the production of fuels and other important chemicals in the industrial hydrocracking of naphtha on solid catalysts. Although this transformation is thought to rely on cooperation of multiple metal sites, molecular-level information on the reaction mechanism has remained scarce to date. Here, we report the DFT studies of the ring cleavage and contraction of benzene by a molecular trinuclear titanium hydride cluster. Our studies suggest that the reaction is initiated by benzene coordination, followed by H2 release, C6H6 hydrometalation, repeated C-C and C-H bond cleavage and formation to give a MeC5H4 unit, and insertion of a Ti atom into the MeC5H4 unit with release of H2 to give a metallacycle product. The C-C bond cleavage and ring contraction of toluene can also occur in a similar fashion, though some details are different due to the presence of the methyl substituent. Obviously, the facile release of H2 from the metal hydride cluster to provide electrons and to alter the charge population at the metal centers, in combination with the flexible metal-hydride connections and dynamic redox behavior of the trimetallic framework, has enabled this unusual transformation to occur. This work has not only provided unprecedented insights into the activation and transformation of benzene over a multimetallic framework but it may also offer help in the design of new molecular catalysts for the activation and transformation of inactive aromatics.

All-gas-phase synthesis of UiO-66 through modulated atomic layer deposition

NASA Astrophysics Data System (ADS)

Lausund, Kristian Blindheim; Nilsen, Ola

2016-11-01

Thin films of stable metal-organic frameworks (MOFs) such as UiO-66 have enormous application potential, for instance in microelectronics. However, all-gas-phase deposition techniques are currently not available for such MOFs. We here report on thin-film deposition of the thermally and chemically stable UiO-66 in an all-gas-phase process by the aid of atomic layer deposition (ALD). Sequential reactions of ZrCl4 and 1,4-benzenedicarboxylic acid produce amorphous organic-inorganic hybrid films that are subsequently crystallized to the UiO-66 structure by treatment in acetic acid vapour. We also introduce a new approach to control the stoichiometry between metal clusters and organic linkers by modulation of the ALD growth with additional acetic acid pulses. An all-gas-phase synthesis technique for UiO-66 could enable implementations in microelectronics that are not compatible with solvothermal synthesis. Since this technique is ALD-based, it could also give enhanced thickness control and the possibility to coat irregular substrates with high aspect ratios.

Atomic layer deposition in a metal–organic framework: Synthesis, characterization, and performance of a solid acid

DOE PAGES

Rimoldi, Martino; Bernales, Varinia; Borycz, Joshua; ...

2017-01-05

NU-1000, a zirconium-based metal-organic framework featuring mesoporous channels, has been post-synthetically metalated via atomic layer deposition in MOF (AIM) employing dimethylaluminum iso-propoxide ([AlMe 2 iOPr] 2 – DMAI), a milder precursor than widely used trimethylaluminum (AlMe 3 - TMA). The aluminum-modified NU-1000 (Al-NU-1000) has been characterized with a comprehensive suite of techniques that points to the formation of aluminum oxide clusters well dispersed through the framework and stabilized by confinement within small pores intrinsic to the NU-1000 structure. Experimental evidence allows for identification of spectroscopic similarities between Al-NU-1000 and γ-Al 2O 3. Density functional theory modeling provides structures and simulatedmore » spectra the relevance of which can be assessed via comparison to experimental IR and EXAFS data. As a result, the catalytic performance of Al-NU-1000 has been benchmarked against γ-Al 2O 3, with promising results in terms of selectivity.« less

Helium behavior in oxide dispersion strengthened (ODS) steel: Insights from ab initio modeling

NASA Astrophysics Data System (ADS)

Sun, Dan; Li, Ruihuan; Ding, Jianhua; Huang, Shaosong; Zhang, Pengbo; Lu, Zheng; Zhao, Jijun

2018-02-01

Using first-principles calculations, we systemically investigate the energetics and stability behavior of helium (He) atoms and small Hen (n = 2-4) clusters inside oxide dispersion strengthened (ODS) steel, as well as the incorporation of large amount of He atoms inside Y2O3 crystal. From the energetic point of view, He atom inside Y2O3 cluster is most stable, followed by the interstitial sites at the α-Fe/Y2O3 interface, and the tetrahedral interstitial sites inside α-Fe region. We further consider Hen (n = 2-4) clusters at the tetrahedral interstitial site surrounded by four Y atoms, which is the most stable site in the ODS steel model. The incorporation energies of all these Hen clusters are lower than that of single He atom in α-Fe, while the binding energy between two He atoms is relatively small. With insertion of 15 He atoms into 80-atom unit cell of Y2O3 crystal, the incorporation energy of He atoms is still lower than that of He4 cluster in α-Fe crystal. These theoretical results suggest that He atoms tend to aggregate inside Y2O3 clusters or at the α-Fe/Y2O3 interface, which is beneficial to prevent the He embrittlement in ODS steels.

Charge transfer interactions in oligomer coated gold nanoclusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Newmai, M. Boazbou; Kumar, Pandian Senthil, E-mail: duplasmonics@gmail.com

Gold nanoclusters were synthesized by a bottom-up synergistic approach of in-situ oligomerization of the monomer, N-vinyl pyrrolidone (NVP) and simultaneous weak reduction of Au-NVP complexes in the absence of any other external energy sources, thereby making these tiny gold clusters as the most elemental building blocks to construct further novel nano/microstructures with application potentials. It is well-known that metal clusters with less than 2 nm size do not show the usual surface plasmon band, because of the presence of a band-gap at the fermi level. Nevertheless, our present oligomer coated gold clusters show a discrete intense band at around 630 nm, whichmore » could very well be attributed to the charge transfer between the oligomer chain and the surface Au atoms. Such kind of sacrificial plasmon induced charge transfer interaction, observed for the very first time to the best of our knowledge, were also strongly corroborated through the enhancement / shifting of specific vibrational / rotational peaks as observed from the FTIR and Raman measurements as a function of the metal oxidation states, thus representing a new prototype for an efficient solar energy conversion probe.« less

Improvement in dehydrogenation of MXH4 where M = Na, Li and X = Al, B confined in CNTs: a DFT investigation

NASA Astrophysics Data System (ADS)

Meenakshi; Agnihotri, Deepak; Jeet, Kiran; Sharma, Hitesh

2016-11-01

Nanoconfinement improves dehydrogenation kinetics of complex metal hydrides. The present paper reports effect of confinement of MXH4, where M = Na, Li and X = Al, B inside carbon nanotubes (CNTs) (n, 0) n = 9-11 chirality and diameter of 7.47 Å, 7.87 Å, 8.73 Å, respectively, using Density Functional calculations. The MXH4 interacts strongly with the surface atoms of CNT (11, 0) and is found to be the smallest stable system for confinement of MXH4 clusters. The Hydrogen release energy (E Hre) of NaAlH4 decreases sharply by 68.3 % , w.r.t. pure NaAlH4 cluster when confined inside CNT(11, 0). Similarly, in CNT (11, 0) E Hre decreases by 38.1 % for LiAlH4, 12.7 % for NaBH4 and 19.1 % for LiBH4. Thus, resulting confinement had a profound effect in improving the energetics of complex metal hydride nanoparticles without catalyst.

Preparation and analysis of particulate metal deposits

NASA Technical Reports Server (NTRS)

Poppa, H.; Moorhead, D.; Heinemann, K.

1985-01-01

Small particles and clusters of palladium were grown by deposition from the vapor phase under ultrahigh vacuum conditions. Amorphous and crystalline support films of Al2O3 and ultrathin amorphous carbon films were used as substrate materials. The growth of the metal deposit was monitored in situ by scanning transmission diffraction of energy-filtered 100 kV electrons and high resolution transmission electron microscopy (TEM) analysis was performed in a separate instrument. It was established by in situ TEM, however, that the transfer of specimens in this case did not unduly affect the size and distribution of deposit particles. It was found that the cleanness, stoichiometry, crystallinity and structural perfection of the support surface play an essential role in determining the crystalline perfection and structure of the particles. The smallest palladium clusters reproducibly prepared contained not more than six atoms but size determinations below 1 nm average particle diameter are very problematic with conventional TEM. Palladium particles grown on carbon supports feature an impurity-stabilized mosaic structure.

Many-body expansion of the Fock matrix in the fragment molecular orbital method

NASA Astrophysics Data System (ADS)

Fedorov, Dmitri G.; Kitaura, Kazuo

2017-09-01

A many-body expansion of the Fock matrix in the fragment molecular orbital method is derived up to three-body terms for restricted Hartree-Fock and density functional theory in the atomic orbital basis and compared to the expansion in the basis of fragment molecular orbitals (MOs). The physical nature of many-body corrections is revealed in terms of charge transfer terms. An improvement of the fragment MO expansion is proposed by adding exchange to the embedding. The accuracy of all developed methods is demonstrated in comparison to unfragmented results for polyalanines, a water cluster, Trp-cage (PDB: 1L2Y) and crambin (PDB: 1CRN) proteins, a zeolite cluster, a Si nano-wire, and a boron nitride ribbon. The physical nature of metallicity is discussed, and it is shown what kinds of metallic systems can be treated by fragment-based methods. The density of states is calculated for a fully closed and a partially open nano-ring of boron nitride with a diameter of 105 nm.

In situ study of heavy ion irradiation response of immiscible Cu/Fe multilayers

DOE PAGES

Chen, Youxing; Li, Nan; Bufford, Daniel Charles; ...

2016-04-09

By providing active defect sinks that capture and annihilate radiation induced defect clusters immiscible metallic multilayers with incoherent interfaces can effectively reduce defect density in ion irradiated metals. Although it is anticipated that defect density within the layers should vary as a function of distance to the layer interface, there is, to date, little in situ TEM evidence to validate this hypothesis. In our study monolithic Cu films and Cu/Fe multilayers with individual layer thickness, h, of 100 and 5 nm were subjected to in situ Cu ion irradiation at room temperature to nominally 1 displacement-per-atom inside a transmission electronmore » microscope. Rapid formation and propagation of defect clusters were observed in monolithic Cu, whereas fewer defects with smaller dimensions were generated in Cu/Fe multilayers with smaller h. Moreover, in situ video shows that the cumulative defect density in Cu/Fe 100 nm multilayers indeed varies, as a function of distance to the layer interfaces, supporting a long postulated hypothesis.« less

Iridium clusters in KLTL zeolite: Synthesis, structural characterization, and catalysis of toluene hydrogenation and n-hexane dehydrocyclization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, A.; Jentoft, R.E.; Gates, B.C.

Iridium clusters incorporating about six atoms each, on average, were prepared in KLTL zeolite by decarbonylation (in H{sub 2} at 400{degrees}C) of iridium carbonyl clusters formed by treatment of adsorbed [Ir(CO){sub 2}(acac)] in CO at 1 atm and 175{degrees}C. The supported species were characterized by infrared and extended X-ray absorption fine structure (EXAFS) spectroscopies. The iridium carbonyls formed from [Ir(CO){sub 2}(acac)] were predominantly [HIr{sub 4}(CO){sub 11}]{sup -} with a small amount of [Ir(CO){sub 4}]{sup -}. The synthesis chemistry of iridium carbonyls in the basic KLTL zeolite parallels that in basic solutions. Shifts of the {nu}{sub CO} bands of the iridiummore » carbonyl clusters relative to those of the same clusters in solution indicate strong interactions between the clusters and zeolite cations. The decarbonylated sample, approximated as Ir{sub 6}/KLTL zeolite, is catalytically active for toluene hydrogenation at 60-100{degrees}C, with the activity being approximately the same as those of Ir{sub 4} and Ir{sub 6} clusters supported on metal oxides, but an order of magnitude less than that of a conventional supported iridium catalyst consisting of aggregates of about 50 atoms each, on average. The catalyst is also active for conversion of n-hexane + H{sub 2} at 340-420{degrees}C, but the selectivity for aromatization is low and that for hydrogenolysis is high, consistent with earlier results for conventionally prepared (salt-derived) iridium clusters of about the same size supported in KLTL zeolite. The zeolite-supported iridium clusters are the first prepared from both salt and organometallic precursors; the results indicate that the organometallic and conventional preparation routes lead to supported iridium clusters having similar structures and catalytic properties. 59 refs., 6 figs., 7 tabs.« less

Change of Energy of the Cubic Subnanocluster of Iron Under Influence of Interstitial and Substitutional Atoms.

PubMed

Nedolya, Anatoliy V; Bondarenko, Natalya V

2016-12-01

Energy change of an iron face-centred cubic subnanocluster was evaluated using molecular mechanics method depending on the position of a carbon interstitial atom and substitutional atoms of nickel. Calculations of all possible positions of impurity atoms show that the energy change of the system are discrete and at certain positions of the atoms are close to continuous.In terms of energy, when all impurity atoms are on the same edge of an atomic cluster, their positions are more advantageous. The presence of nickel atoms on the edge of a cubic cluster resulted in decrease of potential barrier for a carbon atom and decrease in energy in the whole cluster. A similar drift of a carbon atom from central octahedral interstitial site to the surface in the direction <011> occurred under the influence of surface factors.Such configuration corresponds to decreasing symmetry and increasing the number of possible energy states of a subnanocluster, and it corresponds to the condition of spontaneous crystallization process in an isolated system.Taking into account accidental positions of the nickel atom in the iron cluster, such behaviour of the carbon atom can explain the mechanism of growth of a new phase and formation of new clusters in the presence of other kind of atoms because of surface influence.

Exploring the atomic structure of 1.8nm monolayer-protected gold clusters with aberration-corrected STEM.

PubMed

Liu, Jian; Jian, Nan; Ornelas, Isabel; Pattison, Alexander J; Lahtinen, Tanja; Salorinne, Kirsi; Häkkinen, Hannu; Palmer, Richard E

2017-05-01

Monolayer-protected (MP) Au clusters present attractive quantum systems with a range of potential applications e.g. in catalysis. Knowledge of the atomic structure is needed to obtain a full understanding of their intriguing physical and chemical properties. Here we employed aberration-corrected scanning transmission electron microscopy (ac-STEM), combined with multislice simulations, to make a round-robin investigation of the atomic structure of chemically synthesised clusters with nominal composition Au 144 (SCH 2 CH 2 Ph) 60 provided by two different research groups. The MP Au clusters were "weighed" by the atom counting method, based on their integrated intensities in the high angle annular dark field (HAADF) regime and calibrated exponent of the Z dependence. For atomic structure analysis, we compared experimental images of hundreds of clusters, with atomic resolution, against a variety of structural models. Across the size range 123-151 atoms, only 3% of clusters matched the theoretically predicted Au 144 (SR) 60 structure, while a large proportion of the clusters were amorphous (i.e. did not match any model structure). However, a distinct ring-dot feature, characteristic of local icosahedral symmetry, was observed in about 20% of the clusters. Copyright © 2017. Published by Elsevier B.V.

Studies of cluster-assembled materials: From gas phase to condensed phase

NASA Astrophysics Data System (ADS)

Gao, Lin

Clusters, defined as "a number of similar things that occur together" in Webster's dictionary, has different meanings depending on the given subject. To physicists and chemists, the word cluster means "a group of atoms or molecules formed by interactions ranging from very weak van der Waals interactions to strong ionic bonds." Unlike molecules, which are made by nature and are stable under ambient conditions, clusters discovered in a laboratory are often metastable. Molecules have specific stoichiometry, whereas the cluster's composition can usually be altered atom by atom. Thus, clusters can be taken as intrinsically "artificial molecules" with considerably more tunabilities in their properties. Research into the relative stability and instability of clusters has in recent years become a very active research area, especially following the study by Khanna and Castleman that first suggested that by varying size and composition, clusters can expand the periodic table to the 3 rd-dimension; that is, clusters can mimic the chemistry of atoms and may, therefore, be used as the building blocks of new materials. The discovery of Met-Cars has drawn worldwide interests and has been actively investigated by researchers from a variety of fields, including physics, chemistry and material science. However, the unsuccessful search for a solvent capable of isolating Met-Cars has impeded progress in characterizing the material in the condensed state and, hence, limited its potential applications as a novel nanoscale material. An alternative method involving the deposition of mass-gated species and the subsequent structural investigation via Transmission Electron Microscopy (TEM) has been employed. With particularly interesting results, soft-landed deposits of zirconium Met-Cars were found to form a face-centered-cubic (FCC) structure with a lattice parameter ˜ 15A. The production of Met-Cars is conducted with the direct laser vaporization (DLV) of metal/graphite composite pellets. After being mass gated in a reflectron equipped time-of-flight mass spectrometer (TOF-MS) and deposited onto TEM grids, the resultant specimens can be loaded onto high-resolution TEM investigation via electron diffraction. In conclusion, soft-landing of mass selected clusters has been shown to be a successful approach to obtain structural information on Zr-Met-Car cluster-assembled materials collected from the gas phase. TEM images indicate the richness of the morphologies associated with these cluster crystals. However, passivation methods are expected to be examined further to overcome the limited stabilities of these novel clusters. From this initial study, it's shown the promising opportunity to study other Met-Cars species and more cluster-based materials. Experimental results of reactions run with a solvothermal synthesis method obtained while searching for new Zr-C cluster assembled materials, are reported. One unexpected product in single crystal form was isolated and tentatively identified by X-ray diffraction to be [Zr6i O(OH)O12·2(Bu)4], with space group P2 1/n and lattice parameters of a = 12.44 A, b = 22.06 A, c = 18.40 A, alpha = 90°, beta = 105°, gamma = 90°, V = 4875 A3 and R 1 = 3.15% for the total observed data (I ≥ 2 sigma I) and oR2 = 2.82%. This novel hexanuclear Zr(IV)-oxo-hydroxide cluster anion may be the first member in polyoxometalates class with metal atoms from the IVB group and having Oh symmetry. Alternatively, it may be the first member in {[(Zr6Z)X 12]X6}m- class with halides replaced by oxo- and hydroxyl groups and with an increased oxidation state of Zr. It is predicted to bear application potentials directed by both families. This work could suggest a direction in which the preparation of Zr-C cluster-assembled materials in a liquid environment may be eventually fulfilled. 1,3-Bis(diethylphosphino)propane (depp) protected small gold clusters are studied via multiple techniques, including Electrospray Ionization Mass Spectrometry (ESI-MS), Ultraviolet-Visible Spectroscopy (Uv-Vis), Nuclear Magnetic Resonance (NMR) for solution phase and Transmission Electron Microscopy (TEM) for the condensed phase. In particular, undeca-, dodeca- and trideca-gold clusters protected by depp and halogen ligands, i.e. [Au11-13(depp) 4Cl2-4]+, are found to be all predominant and persist in solution for months, while they gradually and spontaneously grow into a monomial trideca-gold clusters series. The unique preferred ligand combination, depp along with Cl, is discussed in terms of the ligand-core interaction and the closed-shell electronic configurations of the Au n (n = 11-13) cores, which enables them to serve as building units for larger cluster-assembled nanoparticles and form Self-Assembled Arrays (SAAs), as discovered by TEM measurements. Such spontaneous-growth behavior and the resultant SAAs observations are correlated by icosahedra-close-packing modes of clusters, following "magic numbers" rules. ˜7 shells of such cluster packing are proposed to be in the SAAs.

The cluster compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} containing Mo{sub 14} clusters and the new mono- and bi-capped trioctahedral Mo{sub 15} and Mo{sub 16} clusters: Synthesis, crystal structure, and electrical and magnetic properties

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gall, Philippe; Guizouarn, Thierry; Gougeon, Patrick, E-mail: Patrick.Gougeon@univ-rennes1.fr

2015-07-15

Single crystals of the new quaternary compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} were obtained by solid state reaction. The crystal structure was determined by single-crystal X-ray diffraction. In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} crystallizes in the orthorhombic space group Pbca with unit-cell parameters a=9.4432(14) Å, b=11.4828(12) Å, c=20.299(4) Å and Z=4. Full-matrix least-squares refinement on F{sup 2} using 3807 independent reflections for 219 refinable parameters resulted in R{sub 1}=0.0259 and wR{sub 2}=0.0591. The crystal structure contains in addition to Mo{sub 14} clusters the first examples of mono- and bi-capped trioctahedral Mo{sub 14} i.e. Mo{sub 15} and Mo{sub 16} clusters.more » The oxygen framework derives from a stacking along the a direction of close-packed layers with sequence (…ABAC…). The Mo–Mo distances range between 2.6938(5) and 2.8420(6) Å and the Mo–O distances between 1.879(5) and 2.250(3) Å, as usually observed in molybdenum oxide clusters. The indium atoms form In{sub 4}{sup 6+} bent chains with In–In distances of 2.6682(5) and 2.6622(8) Å and the Ti atoms are in highly distorted octahedral sites of oxygen atoms with Ti–O distances ranging between 1.865(4) and 2.161(4) Å. Magnetic susceptibility measurements confirm the presence of Ti{sup 4+} cations and the absence of localized moments on the Mo network. Electrical resistivity measurements on a single crystal of In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} show a semimetallic behavior. - Graphical abstract: We present here the synthesis, the crystal structure, and the electrical and magnetic properties of the new compound In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} in which Mo{sub 14} clusters coexist statistically with mono- and bi-capped trioctahedral Mo{sub 14} that is Mo{sub 15} and Mo{sub 16} clusters. - Highlights: • Single crystals of In{sub 4}Ti{sub 1.5}Mo{sub 0.5}Mo{sub 14}O{sub 26} were obtained by solid state reaction. • The crystal structure contains Mo{sub 14}, Mo{sub 15} and Mo{sub 16} clusters. • The indium atoms form In{sub 4}{sup 6+} bent chains. • Poorly metallic behavior. • Absence of localized moments on the Mo network as well as on the Ti atoms.« less

The study of structures and properties of PdnHm(n=1-10, m=1,2) clusters by density functional theory

NASA Astrophysics Data System (ADS)

Wen, Jun-Qing; Chen, Guo-Xiang; Zhang, Jian-Min; Wu, Hua

2018-04-01

The geometrical evolution, local relative stability, magnetism and charge transfer characteristics of PdnHm(n = 1-10, m = 1,2) have been systematically calculated by using density functional theory. The studied results show that the most stable geometries of PdnH and PdnH2 (n = 1-10) can be got by doping one or two H atoms on the sides of Pdn clusters except Pd6H and Pd6H2. It is found that doping one or two H atoms on Pdn clusters cannot change the basic framework of Pdn. The analysis of stability shows that Pd2H, Pd4H, Pd7H, Pd2H2, Pd4H2 and Pd7H2 clusters have higher local relative stability than neighboring clusters. The analysis of magnetic properties demonstrates that absorption of hydrogen atoms decreases the average atomic magnetic moments compared with pure Pdn clusters. More charges transfer from H atoms to Pd atoms for Pd6H and Pd6H2 clusters, demonstrating the adsorption of hydrogen atoms change from side adsorption to surface adsorption.

Triosmium Clusters on a Support: Determination of Structure by X-Ray Absorption Spectroscopy and High-Resolution Microscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shareghe, Mehraeen; Chi, Miaofang; Browning, Nigel D.

2011-01-01

The structures of small, robust metal clusters on a solid support were determined by a combination of spectroscopic and microscopic methods: extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning transmission electron microscopy (STEM), and aberration-corrected STEM. The samples were synthesized from [Os{sub 3}(CO){sub 12}] on MgO powder to provide supported clusters intended to be triosmium. The results demonstrate that the supported clusters are robust in the absence of oxidants. Conventional high-angle annular dark-field (HAADF) STEM images demonstrate a high degree of uniformity of the clusters, with root-mean-square (rms) radii of 2.03 {+-} 0.06 {angstrom}. The EXAFS OsOs coordination number ofmore » 2.1 {+-} 0.4 confirms the presence of triosmium clusters on average and correspondingly determines an average rms cluster radius of 2.02 {+-} 0.04 {angstrom}. The high-resolution STEM images show the individual Os atoms in the clusters, confirming the triangular structures of their frames and determining OsOs distances of 2.80 {+-} 0.14 {angstrom}, matching the EXAFS value of 2.89 {+-} 0.06 {angstrom}. IR and EXAFS spectra demonstrate the presence of CO ligands on the clusters. This set of techniques is recommended as optimal for detailed and reliable structural characterization of supported clusters.« less

Comparing Ultraviolet Spectra against Calculations: Year 2 Results

NASA Technical Reports Server (NTRS)

Peterson, Ruth C.

2004-01-01

The five-year goal of this effort is to calculate high fidelity mid-W spectra for individual stars and stellar systems for a wide range of ages, abundances, and abundance ratios. In this second year, the comparison of our calculations against observed high-resolution mid- W spectra was extended to stars as metal-rich as the Sun, and to hotter and cooler stars, further improving the list of atomic line parameters used in the calculations. We also published the application of our calculations based on the earlier list of line parameters to the observed mid-UV and optical spectra of a mildly metal-poor globular cluster in the nearby Andromeda galaxy, Messier 3 1.

Acceleration of metal-atom diffusion in electric field at metal/insulator interfaces: First-principles study

NASA Astrophysics Data System (ADS)

Nagasawa, Riki; Asayama, Yoshihiro; Nakayama, Takashi

2018-04-01

Metal-atom diffusion from metal electrodes into SiO2 in electric fields was studied using first-principles calculations. It was shown in the case without electric field that the diffusion barrier of a metal atom is mainly made of the cohesive energy of bulk metal layers, while the shape of the diffusion potential reflects the hybridization of the metal-atom state with metal-induced gap states (MIGSs) and the electron transfer between the metal atom and the electrode. We found that the metal-atom diffusion is markedly accelerated by the applied electric field, such that the diffusion barrier ϕB(E) decreases almost linearly with increasing electric field strength E. By analyzing the physical origins of the metal-atom diffusion, we derived the universal formula to estimate the diffusion barrier in the electric field, which is closely related to MIGSs.

Synthesis and first use of pyridine-2,6-diylbis(pyrazine-2-ylmethanone) in metal cluster chemistry: a {Mn(III)3Na2} complex with an ideal trigonal bipyramidal geometry.

PubMed

Giannopoulos, Dimosthenis P; Wilson-Konderka, Cody; Gagnon, Kevin J; Teat, Simon J; Escuer, Albert; Metallinos, Costa; Stamatatos, Theocharis C

2015-03-07

The successful organic synthesis of a new dipyrazole/pyridine-dicarbonyl organic molecule, namely pyridine-2,6-diylbis(pyrazine-2-ylmethanone) [(pz)CO(py)CO(pz)], followed by its employment in Mn coordination chemistry has yielded the neutral cluster compound [Mn3Na2O(N3)3(L)3] (1), where L(2-) is the (pz)C(CH2COCH3)(O(-))(py)C(CH2COCH3)(O(-))(pz) dianion. The latter group was formed in situ, presumably by the nucleophilic attack of the carbanion (-)CH2COCH3 to the carbonyl carbon atoms of (pz)CO(py)CO(pz), in the presence of Mn(n+) ions under basic conditions and in solvent Me2CO. Complex 1 possesses an almost ideal trigonal bipyramidal topology, with the two Na(I) ions occupying the apical positions and the three Mn(III) ions residing in the equatorial trigonal plane. The bridging ligation about the metal ions is provided by a μ3-O(2-) ion and six μ-OR(-) groups from the L(2-) ligand, while peripheral ligation is completed by three terminal azido groups and the pyridine N and carbonyl O atoms of L(2-). Magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the paramagnetic Mn(III) centres; the use of an anisotropic, equilateral Mn(III)3 triangle model allowed us to fit the magnetic data and obtain the best-fit parameters: J = -10.8 cm(-1), D = -5.3 cm(-1), and g = 1.99. The combined results demonstrate the rich chemical reactivity of carbonyl groups and the ability of poly-ketone ligands to stabilize cluster compounds with unprecedented structural motifs and interesting architectures.

Nanothermodynamics of iron clusters: Small clusters, icosahedral and fcc-cuboctahedral structures

NASA Astrophysics Data System (ADS)

Angelié, C.; Soudan, J.-M.

2017-05-01

The study of the thermodynamics and structures of iron clusters has been carried on, focusing on small clusters and initial icosahedral and fcc-cuboctahedral structures. Two combined tools are used. First, energy intervals are explored by the Monte Carlo algorithm, called σ-mapping, detailed in the work of Soudan et al. [J. Chem. Phys. 135, 144109 (2011), Paper I]. In its flat histogram version, it provides the classical density of states, gp(Ep), in terms of the potential energy of the system. Second, the iron system is described by a potential which is called "corrected EAM" (cEAM), explained in the work of Basire et al. [J. Chem. Phys. 141, 104304 (2014), Paper II]. Small clusters from 3 to 12 atoms in their ground state have been compared first with published Density Functional Theory (DFT) calculations, giving a complete agreement of geometries. The series of 13, 55, 147, and 309 atom icosahedrons is shown to be the most stable form for the cEAM potential. However, the 147 atom cluster has a special behaviour, since decreasing the energy from the liquid zone leads to the irreversible trapping of the cluster in a reproducible amorphous state, 7.38 eV higher in energy than the icosahedron. This behaviour is not observed at the higher size of 309 atoms. The heat capacity of the 55, 147, and 309 atom clusters revealed a pronounced peak in the solid zone, related to a solid-solid transition, prior to the melting peak. The corresponding series of 13, 55, and 147 atom cuboctahedrons has been compared, underscoring the unstability towards the icosahedral structure. This unstability occurs clearly in several steps for the 147 atom cluster, with a sudden transformation at a transition state. This illustrates the concerted icosahedron-cuboctahedron transformation of Buckminster Fuller-Mackay, which is calculated for the cEAM potential. Two other clusters of initial fcc structures with 24 and 38 atoms have been studied, as well as a 302 atom cluster. Each one relaxes towards a more stable structure without regularity. The 38 atom cluster exhibits a nearly glassy relaxation, through a cascade of six metastable states of long life. This behaviour, as that of the 147 atom cluster towards the amorphous state, shows that difficulties to reach ergodicity in the lower half of the solid zone are related to particular features of the potential energy landscape, and not necessarily to a too large size of the system. Comparisons of the cEAM iron system with published results about Lennard-Jones systems and DFT calculations are made. The results of the previous clusters have been combined with that of Paper II to plot the cohesive energy Ec and the melting temperature Tm in terms of the cluster atom number Nat. The Nat -1 /3 linear dependence of the melting temperature (Pawlow law) is observed again for Nat > 150. In contrast, for Nat < 150, the curve diverges strongly from the Pawlow law, giving it an overall V-shape, with a linear increase of Tm when Nat goes from 55 to 13 atoms. Surprisingly, the 38 atom cluster is anomalously below the overall curve.

Localized atomic segregation in the spalled area of a Zr50Cu40Al10 bulk metallic glasses induced by laser-shock experiment

NASA Astrophysics Data System (ADS)

Jodar, B.; Loison, D.; Yokoyama, Y.; Lescoute, E.; Nivard, M.; Berthe, L.; Sangleboeuf, J.-C.

2018-02-01

Laser-shock experiments were performed on a ternary {Zr50{Cu}40{Al}10} bulk metallic glass. A spalling process was studied through post-mortem analyses conducted on a recovered sample and spall. Scanning electron microscopy magnification of fracture surfaces revealed the presence of a peculiar feature known as cup-cone. Cups are found on sample fracture surface while cones are observed on spall. Two distinct regions can be observed on cups and cones: a smooth viscous-like region in the center and a flat one with large vein-pattern in the periphery. Energy dispersive spectroscopy measurements conducted on these features emphasized atomic distribution discrepancies both on the sample and spall. We propose a mechanism for the initiation and the growth of these features but also a process for atomic segregation during spallation. Cup and cones would originate from cracks arising from shear bands formation (softened paths). These shear bands result from a quadrupolar-shaped atomic disorder engendered around an initiation site by shock wave propagation. This disorder turns into a shear band when tensile front reaches spallation plane. During the separation process, temperature gain induced by shock waves and shear bands generation decreases material viscosity leading to higher atomic mobility. Once in a liquid-like form, atomic clusters migrate and segregate due to inertial effects originating from particle velocity variation (interaction of release waves). As a result, a high rate of copper is found in sample cups and high zirconium concentration is found on spall cones.

Magnetic properties of Mg12O12 nanocage doped with transition metal atoms (Mn, Fe, Co and Ni): DFT study

NASA Astrophysics Data System (ADS)

Javan, Masoud Bezi

2015-07-01

Binding energy of the Mg12O12 nanocage doped with transition metals (TM=Mn, Fe, Co and Ni) in endohedrally, exohedrally and substitutionally forms were studied using density functional theory with the generalized gradient approximation exchange-correlation functional along 6 different paths inside and outside of the Mg12O12 nanocage. The most stable structures were determined with full geometry optimization near the minimum of the binding energy curves of all the examined paths inside and outside of the Mg12O12 nanocage. The results reveal that for all stable structures, the Ni atom has a larger binding energy than the other TM atoms. It is also found that for all complexes additional peaks contributed by TM-3d, 4s and 4p states appear in the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) gap of the host MgO cluster. The mid-gap states are mainly due to the hybridization between TM-3d, 4s and 4p orbitals and the cage π orbitals. The magnetic moment of the endohedrally doped TM atoms in the Mg12O12 are preserved to some extent due to the interaction between the TM and Mg12O12 nanocage, in contrast to the completely quenched magnetic moment of the Fe and Ni atoms in the Mg11(TM)O12 complexes. Furthermore, charge population analysis shows that charge transfer occurs from TM atom to the cage for endohedrally and substitutionally doping.

Size and Site Dependence of the Catalytic Activity of Iridium Clusters toward Ethane Dehydrogenation.

PubMed

Ge, Yingbin; Jiang, Hao; Kato, Russell; Gummagatta, Prasuna

2016-12-01

This research focuses on optimizing transition metal nanocatalyst immobilization and activity to enhance ethane dehydrogenation. Ethane dehydrogenation, catalyzed by thermally stable Ir n (n = 8, 12, 18) atomic clusters that exhibit a cuboid structure, was studied using the B3LYP method with triple-ζ basis sets. Relativistic effects and dispersion corrections were included in the calculations. In the dehydrogenation reaction Ir n + C 2 H 6 → H-Ir n -C 2 H 5 → (H) 2 -Ir n -C 2 H 4 , the first H-elimination is the rate-limiting step, primarily because the reaction releases sufficient heat to facilitate the second H-elimination. The catalytic activity of the Ir clusters strongly depends on the Ir cluster size and the specific catalytic site. Cubic Ir 8 is the least reactive toward H-elimination in ethane: Ir 8 + C 2 H 6 → H-Ir 8 -C 2 H 5 has a large (65 kJ/mol) energy barrier, whereas Ir 12 (3 × 2 × 2 cuboid) and Ir 18 (3 × 3 × 2 cuboid) lower this energy barrier to 22 and 3 kJ/mol, respectively. The site dependence is as prominent as the size effect. For example, the energy barrier for the Ir 18 + C 2 H 6 → H-Ir 18 -C 2 H 5 reaction is 3, 48, and 71 kJ/mol at the corner, edge, or face-center sites of the Ir 18 cuboid, respectively. Energy release due to Ir cluster insertion into an ethane C-H bond facilitates hydrogen migration on the Ir cluster surface, and the second H-elimination of ethane. In an oxygen-rich environment, oxygen molecules may be absorbed on the Ir cluster surface. The oxygen atoms bonded to the Ir cluster surface may slightly increase the energy barrier for H-elimination in ethane. However, the adsorption of oxygen and its reaction with H atoms on the Ir cluster releases sufficient heat to yield an overall thermodynamically favored reaction: Ir n + C 2 H 6 + 1 / 2 O 2 → Ir n + C 2 H 4 + H 2 O. These results will be useful toward reducing the energy cost of ethane dehydrogenation in industry.

Spectroscopy of metal "superatom" nanoclusters and high-Tc superconducting pairing

NASA Astrophysics Data System (ADS)

Halder, Avik; Kresin, Vitaly V.

2015-12-01

A unique property of metal nanoclusters is the "superatom" shell structure of their delocalized electrons. The electronic shell levels are highly degenerate and therefore represent sharp peaks in the density of states. This can enable exceptionally strong electron pairing in certain clusters composed of tens to hundreds of atoms. In a finite system, such as a free nanocluster or a nucleus, pairing is observed most clearly via its effect on the energy spectrum of the constituent fermions. Accordingly, we performed a photoionization spectroscopy study of size-resolved aluminum nanoclusters and observed a rapid rise in the near-threshold density of states of several clusters (A l37 ,44 ,66 ,68 ) with decreasing temperature. The characteristics of this behavior are consistent with compression of the density of states by a pairing transition into a high-temperature superconducting state with Tc≳100 K. This value exceeds that of bulk aluminum by two orders of magnitude. These results highlight the potential of novel pairing effects in size-quantized systems and the possibility to attain even higher critical temperatures by optimizing the particles' size and composition. As a new class of high-temperature superconductors, such metal nanocluster particles are promising building blocks for high-Tc materials, devices, and networks.

Structure and Stability of GeAu{sub n}, n = 1-10 clusters: A Density Functional Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Priyanka,; Dharamvir, Keya; Sharma, Hitesh

2011-12-12

The structures of Germanium doped gold clusters GeAu{sub n} (n = 1-10) have been investigated using ab initio calculations based on density functional theory (DFT). We have obtained ground state geometries of GeAu{sub n} clusters and have it compared with Silicon doped gold clusters and pure gold clusters. The ground state geometries of the GeAu{sub n} clusters show patterns similar to silicon doped gold clusters except for n = 5, 6 and 9. The introduction of germanium atom increases the binding energy of gold clusters. The binding energy per atom of germanium doped cluster is smaller than the corresponding siliconmore » doped gold cluster. The HUMO-LOMO gap for Au{sub n}Ge clusters have been found to vary between 0.46 eV-2.09 eV. The mullikan charge analysis indicates that charge of order of 0.1e always transfers from germanium atom to gold atom.« less

Atomic dynamics and the problem of the structural stability of free clusters of solidified inert gases

NASA Astrophysics Data System (ADS)

Verkhovtseva, É. T.; Gospodarev, I. A.; Grishaev, A. V.; Kovalenko, S. I.; Solnyshkin, D. D.; Syrkin, E. S.; Feodos'ev, S. B.

2003-05-01

The dependence of the rms amplitudes of atoms in free clusters of solidified inert gases on the cluster size is investigated theoretically and experimentally. Free clusters are produced by homogeneous nucleation in an adiabatically expanding supersonic stream. Electron diffraction is used to measure the rms amplitudes of the atoms; the Jacobi-matrix method is used for theoretical calculations. A series of distinguishing features of the atomic dynamics of microclusters was found. This was necessary to determine the character of the formation and the stability conditions of the crystal structure. It wass shown that for clusters consisting of less than N˜103 atoms, as the cluster size decreases, the rms amplitudes grow much more rapidly than expected from the increase in the specific contribution of the surface. It is also established that an fcc structure of a free cluster, as a rule, contains twinning defects (nuclei of an hcp phase). One reason for the appearance of such defects is the so-called vertex instability (anomalously large oscillation amplitudes) of the atoms in coordination spheres.

Ultra-small Ag clusters in zeolite A4: Antibacterial and thermochromic applications

NASA Astrophysics Data System (ADS)

Horta-Fraijo, P.; Cortez-Valadez, M.; Flores-Lopez, N. S.; Britto Hurtado, R.; Vargas-Ortiz, R. A.; Perez-Rodriguez, A.; Flores-Acosta, M.

2018-03-01

The physical and chemical properties of metal clusters depend on their atomic structure, therefore, it is important to determine the lowest-energy structures of the clusters in order to understand and utilize their properties. In this work, we use the Density Functional Theory (DFT) at the generalized gradient approximation level Becke's three-parameter and the gradient corrected functional of Lee, Yang and Puar (B3LYP) in combination with the basis set LANL2DZ (the effective core potentials and associated double-zeta valence) to determine some of the structural, electronic and vibrational properties of the planar silver clusters (Agn clusters n = 2-24). Additionally, the study reports the experimental synthesis of small silver clusters in synthetic zeolite A4. The synthesis was possible using the ion exchange method with some precursors like silver nitrate (AgNO3) and synthetic zeolite A4. The silver clusters in zeolite powder underwent thermal treatment at 450 °C to release the remaining water or humidity on it. The morphology of the particles was determined by Transmission Electron microscopy. The nanomaterials obtained show thermochromic properties. The structural parameters were correlated theoretically and experimentally.

Intriguing structures and magic sizes of heavy noble metal nanoclusters around size 55 governed by relativistic effect and covalent bonding

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, X. J.; Xue, X. L.; Guo, Z. X.

Nanoclusters usually display exotic physical and chemical properties due to their intriguing geometric structures in contrast to their bulk counterparts. By means of first-principles calculations within density functional theory, we find that heavy noble metal Pt N nanoclusters around the size N = 55 begin to prefer an open configuration, rather than previously reported close-packed icosahedron or core-shell structures. Particularly, for Pt N, the widely supposed icosahedronal magic cluster is changed to a three-atomic-layered structure with D 6h symmetry, which can be well addressed by our recently established generalized Wulff construction principle (GWCP). But, the magic number of Pt Nmore » clusters around 55 is shifted to a new odd number of 57. The high symmetric three-layered Pt-57 motif is mainly stabilized by the enhanced covalent bonding contributed by both spin-orbital coupling effect and the open d orbital (5d 96s 1) of Pt, which result in a delicate balance between the enhanced Pt-Pt covalent bonding of the interlayers and negligible d dangling bonds on the cluster edges. Our findings about Pt N clusters are also applicable to Ir N clusters, but qualitatively different from their earlier neighboring element Os and their later neighboring element Au. The magic numbers for Os and Au are even, being 56 and 58, respectively. Finally, the findings of the new odd magic number 57 are the important supplementary of the recently established GWCP.« less

Electronic structure studies of Ni( 1 0 0 ) surface reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption

NASA Astrophysics Data System (ADS)

Kirsch, Janet E.; Harris, Suzanne

2003-01-01

Solid-state Fenske-Hall band structure calculations have been used to study the different surface structures which result from adsorption of a half monolayer of C, N, or O atoms on the Ni(1 0 0) surface. C or N atoms sit nearly coplanar with the surface Ni atoms and induce the "clock" reconstruction of the surface. In contrast, adsorbed O atoms sit slightly above the Ni(1 0 0) surface plane and have little effect on the overall surface structure. The local environments of the C, N, and O atoms on these surfaces are similar to their environments in a series of late transition metal carbonyl clusters, suggesting that some of the same electronic factors may play a role in favoring the different structures. Results of the calculations indicate that when adsorbates occupy coplanar sites on Ni(1 0 0), much of the Ni-Ni bonding within the surface layer and between the surface- and second-layers is disrupted. On the C- and N-covered surfaces the disruption is more than compensated for by the formation of strong adsorbate-Ni bonds and by new Ni-Ni surface bonds resulting from the clock reconstruction. When O is forced into a coplanar site, however, both the higher electron count and increased electronegativity of the O atoms lead to severe disruption of the surface bonding and weak Ni-O bonds. When O atoms sit above the surface, they form more polar Ni-O bonds, contribute less electron density to the Ni surface bands, and cause less disruption to Ni-Ni surface bonds. These results suggest that, similar to the organometallic clusters, the site preferences of C, N, and O atoms are directly related to their electron count, and in turn to the relative occupation of both Ni-Ni and X-Ni (X=C, N, O) antibonding bands.

Multivariate analysis of selected metals in tannery effluents and related soil.

PubMed

Tariq, Saadia R; Shah, Munir H; Shaheen, N; Khalique, A; Manzoor, S; Jaffar, M

2005-06-30

Effluent and relevant soil samples from 38 tanning units housed in Kasur, Pakistan, were obtained for metal analysis by flame atomic absorption spectrophotometric method. The levels of 12 metals, Na, Ca, K, Mg, Fe, Mn, Cr, Co, Cd, Ni, Pb and Zn were determined in the two media. The data were evaluated towards metal distribution and metal-to-metal correlations. The study evidenced enhanced levels of Cr (391, 16.7 mg/L) and Na (25,519, 9369 mg/L) in tannery effluents and relevant soil samples, respectively. The effluent versus soil trace metal content relationship confirmed that the effluent Cr was strongly correlated with soil Cr. For metal source identification the techniques of principal component analysis, and cluster analysis were applied. The principal component analysis yielded two factors for effluents: factor 1 (49.6% variance) showed significant loading for Ca, Fe, Mn, Cr, Cd, Ni, Pb and Zn, referring to a tanning related source for these metals, and factor 2 (12.6% variance) with higher loadings of Na, K, Mg and Co, was associated with the processes during the skin/hide treatment. Similarly, two factors with a cumulative variance of 34.8% were obtained for soil samples: factor 1 manifested the contribution from Mg, Mn, Co, Cd, Ni and Pb, which though soil-based is basically effluent-derived, while factor 2 was found associated with Na, K, Ca, Cr and Zn which referred to a tannery-based source. The dendograms obtained from cluster analysis, also support the observed results. The study exhibits a gross pollution of soils with Cr at levels far exceeding the stipulated safe limit laid down for tannery effluents.

The Robustness of Cluster Expansion: Assessing the Role of Relaxation

NASA Astrophysics Data System (ADS)

Nguyen, Andrew H.; Rosenbrock, Conrad W.; Hart, Gus L. W.

Cluster expansion (CE) has been used widely in combination with first-principles calculations to predict stable structures of metal alloys. CE treats alloys as a purely configuration problem, i.e., a problem in the distribution of the alloying elements on a fixed lattice. CE models are usually built from data taken from ``relaxed'' first-principles calculations where the individual atoms assume positions that minimize the total energy. A perennial question in the cluster expansion community is how the accuracy of the CE is affected by relaxations--technically, the formalism of CE breaks down when the underlying lattice is not preserved--but practitioners often argue that there is a one-to-one correspondence between relaxed and unrelaxed structures so that the formalism holds. We quantify the effect of relaxation on the robustness of cluster expansions by comparing CE fits for relaxed and unrelaxed data sets. Our results give a heuristic for when CE models can be trusted. Onr (MURI N00014-13-1-0635).

Dual role of CO in the stability of subnano Pt clusters at the Fe3O4(001) surface

PubMed Central

Bliem, Roland; van der Hoeven, Jessi E. S.; Hulva, Jan; Pavelec, Jiri; Gamba, Oscar; de Jongh, Petra E.; Schmid, Michael; Blaha, Peter; Diebold, Ulrike; Parkinson, Gareth S.

2016-01-01

Interactions between catalytically active metal particles and reactant gases depend strongly on the particle size, particularly in the subnanometer regime where the addition of just one atom can induce substantial changes in stability, morphology, and reactivity. Here, time-lapse scanning tunneling microscopy (STM) and density functional theory (DFT)-based calculations are used to study how CO exposure affects the stability of Pt adatoms and subnano clusters at the Fe3O4(001) surface, a model CO oxidation catalyst. The results reveal that CO plays a dual role: first, it induces mobility among otherwise stable Pt adatoms through the formation of Pt carbonyls (Pt1–CO), leading to agglomeration into subnano clusters. Second, the presence of the CO stabilizes the smallest clusters against decay at room temperature, significantly modifying the growth kinetics. At elevated temperatures, CO desorption results in a partial redispersion and recovery of the Pt adatom phase. PMID:27457953

A new analysis of charge transfer and polarization for ligand-metal bonding - Model studies of Al4CO and Al4NH3

NASA Technical Reports Server (NTRS)

Bagus, P. S.; Hermann, K.; Bauschlicher, C. W., Jr.

1984-01-01

The nature of the bonding of CO and NH3 ligands to Al is analyzed, and the intra-unit charge polarization and inter-unit donation for the interaction of ligands with metals are studied. The consequences of metal-to-ligand and ligand-to-metal charge transfer are separately considered by performing a constrained space orbital variation (CSOV) with the electrons of the metal member of the complex in the field of frozen ligand. The electrons of the metal atoms are then frozen in the relaxed distribution given by the CSOV SCF wave function and the ligand electrons are allowed to relax. Quantitative measures of the importance of inter-unit charge transfers and intra-unit polarization are obtained using results of SCF studies of Al4CO and Al4NH3 clusters chosen to simulate the adsorption of the ligands at an on-top side of the Al(111) surface. The electrostatic attraction of the effective dipole moments of the metal and ligand units makes an important contribution to the bond.

Dynamic formation of single-atom catalytic active sites on ceria-supported gold nanoparticles

PubMed Central

Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra; Li, Jun; Rousseau, Roger

2015-01-01

Catalysis by gold supported on reducible oxides has been extensively studied, yet issues such as the nature of the catalytic site and the role of the reducible support remain fiercely debated topics. Here we present ab initio molecular dynamics simulations of an unprecedented dynamic single-atom catalytic mechanism for the oxidation of carbon monoxide by ceria-supported gold clusters. The reported dynamic single-atom catalytic mechanism results from the ability of the gold cation to strongly couple with the redox properties of the ceria in a synergistic manner, thereby lowering the energy of redox reactions. The gold cation can break away from the gold nanoparticle to catalyse carbon monoxide oxidation, adjacent to the metal/oxide interface and subsequently reintegrate back into the nanoparticle after the reaction is completed. Our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in catalysis. PMID:25735407

Atomic origins of water-vapour-promoted alloy oxidation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luo, Langli; Su, Mao; Yan, Pengfei

The presence of water vapor, intentional or unavoidable, is crucial to many materials applications, such as steam generator, turbine engine, fuel cell, catalyst, and corrosion 1-6. Phenomenologically, water vapor has been noticed to accelerate oxidation of metals/alloys 7,8, however, the atomistic mechanisms remain elusive. Herein, through direct in situ atomic-scale transmission electron microscopy observation and density functional theory calculation, we reveal that water vapor enhanced oxidation of Ni-Cr alloy is associated with proton dissolution promoted vacancy formation, migration and clustering. Protons derived from water dissociation occupy interstitial position in the oxide lattice, which consequently leads to the lowering of bothmore » vacancy formation energy and the cation diffusion barrier. The atomic scale observations reveal a water vapor derived proton mediated oxide growth mechanism, which provides insights for reckoning many technological processes concerning materials in moist environment at elevated temperatures.« less

Early Transition Metal Oxides as Catalysts: Crossing Scales from Clusters to Single Crystals to Functioning Materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lai-Sheng Wang

2009-07-07

The overall goal of this program is to investigate the electronic structure and chemical bonding of early transition metal oxide clusters and use them as well-defined molecular models to obtain insight into properties and mechanisms of oxide catalysts, as well as to provide accurate spectroscopic and molecular information to verify theoretical methods used to predict materials properties. A laser vaporization cluster source is used to produce metal oxide clusters with different sizes, structures, and compositions. Well-defined inorganic polyoxometalate clusters in solution are transported in the gas phase using electrospray. Two state-of-the-art photoelectron spectroscopy apparatuses are used to interrogate the oxidemore » clusters and polyoxometalate anions in the gas phase to obtain spectroscopic and electronic structure information. The experimental effort is assisted by theoretical calculations to understanding the structures, chemical bonding, and catalytical properties of the transition metal oxide clusters. The research approach combines novel and flexible experimental techniques and advanced theoretical/computational methodologies and seeks molecular-level information to aiding the design of new catalysts, as well as mechanistic understanding. We have focused on the investigation of tungsten oxide clusters containing three W atoms: W{sub 3}O{sub x}{sup -} (x = 7-11). A number of interesting findings have been made. We observed that the oxygen-poor W{sub 3}O8 cluster contains a localized W{sup 4+} center, which can be used as a molecular model for O-deficient defect sites. A chemisorption energy was obtained through density functional calculations for W{sub 3}O8 + O{sub 2} {yields} W{sub 3}O{sub 10} as -78 kcal/mol. We further found that the neutral stoichiometric W{sub 2}O{sub 6} and W{sub 3}O{sub 9} clusters do not react with O{sub 2} and they only form physi-sorbed complexes, W{sub 2}O{sub 6}(O{sub 2}) and W{sub 3}O{sub 9}(O{sub 2}). However, the negatively charged W{sub 2}O{sub 6}{sup -} and W{sub 3}O{sub 9}{sup -} clusters are found to form chemisorbed complexes due to the presence of the extra electron. Thus, the W{sub 2}O{sub 6}{sup -} and W{sub 3}O{sub 9}{sup -} negative clusters can be viewed as models for O{sub 2} interaction with a reduced W site (W{sup 5+}) on the oxide surface. These studies also led to the surprising observation of the first d-orbital aromatic clusters in W{sub 3}O{sub 9}{sup 2-} and Mo{sub 3}O{sub 9}{sup 2-}, which each contains a completely delocalized three-center two-electron bond made entirely made of the metal d orbitals. This last result was highlighted in both Chem & Eng. News and Nature. We further studied a series of small metalate anions using electrospray, including the hydroxo and methoxo oxometalate MO{sub 3}(OH){sup -} and MO{sub 3}(OCH{sub 3}){sup -}, and the dimetalates: M{sub 2}O{sub 7}{sup 2-}, MM{prime}O{sub 7}{sup 2-}, and M{sub 2}O{sub 7}{sup -} (M, M{prime} = Cr, Mo, and W).« less

Many particle spectroscopy of atoms, molecules, clusters and surfaces: international conference MPS-2016

NASA Astrophysics Data System (ADS)

Grum-Grzhimailo, Alexei N.; Popov, Yuri V.; Gryzlova, Elena V.; Solov'yov, Andrey V.

2017-07-01

The conference on Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces (MPS-2016) brought together near to a hundred scientists in the field of electronic, photonic, atomic and molecular collisions, and spectroscopy from around the world. We deliver an Editorial of a topical issue presenting original research results from some of the participants on both experimental and theoretical studies involving many particle spectroscopy of atoms, molecules, clusters and surfaces. Contribution to the Topical Issue "Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces", edited by A.N. Grum-Grzhimailo, E.V. Gryzlova, Yu.V. Popov, and A.V. Solov'yov.

Observation of a barium xenon exciplex within a large argon cluster.

PubMed

Briant, M; Gaveau, M-A; Mestdagh, J-M

2010-07-21

Spectroscopic measurements provide fluorescence and excitation spectra of a single barium atom codeposited with xenon atoms on argon clusters of average size approximately 2000. The spectra are studied as a function of the number of xenon atoms per cluster. The excitation spectrum with approximately 10 xenon atoms per cluster is qualitatively similar to that observed when no xenon atom is present on the cluster. It consists of two bands located on each side of the 6s6p (1)P-6s(2) (1)S resonance line of the free barium. In contrast, the fluorescence spectrum differs qualitatively since a barium-xenon exciplex is observed, which has no counterpart in xenon free clusters. In particular an emission is observed, which is redshifted by 729 cm(-1) with respect to the Ba(6s6p (1)P-6s(2) (1)S) resonance line.

Cluster adsorption on amorphous and crystalline surfaces - A molecular dynamics study of model Pt on Cu and model Pd on Pt

NASA Technical Reports Server (NTRS)

Garofalini, S. H.; Halicioglu, T.; Pound, G. M.

1981-01-01

Molecular dynamics was used to study the structure, dispersion and short-time behavior of ten-atom clusters adsorbed onto amorphous and crystalline substrates, in which the cluster atoms differed from the substrate atoms. Two adatom-substrate model systems were chosen; one, in which the interaction energy between adatom pairs was greater than that between substrate pairs, and the other, in which the reverse was true. At relatively low temperature ranges, increased dispersion of cluster atoms occurred: (a) on the amorphous substrate as compared to the FCC(100) surface, (b) with increasing reduced temperature, and (c) with adatom-substrate interaction energy stronger than adatom-adatom interaction. Two-dimensional clusters (rafts) on the FCC(100) surface displayed migration of edge atoms only, indicating a mechanism for the cluster rotation and shape changes found in experimental studies.

Lasers '81

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, C.B.

1982-01-01

Progress in lasers is discussed. The subjects addressed include: excimer lasers, surface spectroscopy, modern laser spectroscopy, free electron lasers, cavities and propagation, lasers in medicine, X-ray and gamma ray lasers, laser spectroscopy of small molecules and clusters, optical bistability, excitons, nonlinear optics in the X-ray and gamma ray regions, collective atomic phenomena, tunable IR lasers, far IR/submillimeter lasers, and laser-assisted collisions. Also treated are: special applications, multiphoton processes in atoms and small molecules, nuclear pumped lasers, material processing and applications, polarization, high energy lasers, laser chemistry, IR molecular lasers, laser applications of collision and dissociation phenomena, solid state laser materials,more » phase conjugation, advances in laser technology for fusion, metal vapor lasers, picosecond phenomena, laser ranging and geodesy, and laser photochemistry of complex molecules.« less

Approximate treatment of semicore states in GW calculations with application to Au clusters.

PubMed

Xian, Jiawei; Baroni, Stefano; Umari, P

2014-03-28

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G0W0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au20 and Au32, that would be otherwise very difficult to deal with.

A comparison of the bonding in organoiron clusters

NASA Astrophysics Data System (ADS)

Buhl, Margaret L.; Long, Gary J.

1994-12-01

The Mössbauer effect hyperfine parameters and the results of the Fenske-Hall molecular orbit (mo) calculations have been used to study the electronic properties of trinuclear iron, tetranuclear iron butterfly, Fe-Co, and Fe-Cu carbonyl clusters. The more negative Fe charge and the larger Fe 4s population in an Fe(CO)4 fragment as compared with that in an Fe(CO)3 or an Fe(CO)2 fragment is a result of the CO ligands rather than the near-neighbor metals. The clusters which contain heterometals have more negative isomer shifts. The isomer shift correlated well with the sum of the Fe 4s orbital population and the Zeff these electrons experience. The mo wave functions and the atomic charges generally give a larger calculated Δ E Q than is observed, indicating the need to include Sternheimer factors in the calculation. The valence contribution dominates the EFG.

Approximate treatment of semicore states in GW calculations with application to Au clusters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xian, Jiawei; Baroni, Stefano; CNR-IOM Democritos, Theory-Elettra group, Trieste

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G{sub 0}W{sub 0} level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore statesmore » are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au{sub 20} and Au{sub 32}, that would be otherwise very difficult to deal with.« less

Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study.

PubMed

Yu, Yang; Li, Chen; Yin, Bing; Li, Jian-Li; Huang, Yuan-He; Wen, Zhen-Yi; Jiang, Zhen-Yi

2013-08-07

The structures, relative stabilities, vertical electron detachment energies, and magnetic properties of a series of trinuclear clusters are explored via combined broken-symmetry density functional theory and ab initio study. Several exchange-correlation functionals are utilized to investigate the effects of different halogen elements and central atoms on the properties of the clusters. These clusters are shown to possess stronger superhalogen properties than previously reported dinuclear superhalogens. The calculated exchange coupling constants indicate the antiferromagnetic coupling between the transition metal ions. Spin density analysis demonstrates the importance of spin delocalization in determining the strengths of various couplings. Spin frustration is shown to occur in some of the trinuclear superhalogens. The coexistence of strong superhalogen properties and spin frustration implies the possibility of trinuclear superhalogens working as the building block of new materials of novel magnetic properties.

Probing the Structural, Electronic, and Magnetic Properties of Ag n V (n = 1-12) Clusters.

PubMed

Xiong, Ran; Die, Dong; Xiao, Lu; Xu, Yong-Gen; Shen, Xu-Ying

2017-12-16

The structural, electronic, and magnetic properties of Ag n V (n = 1-12) clusters have been studied using density functional theory and CALYPSO structure searching method. Geometry optimizations manifest that a vanadium atom in low-energy Ag n V clusters favors the most highly coordinated location. The substitution of one V atom for an Ag atom in Ag n + 1 (n ≥ 5) cluster modifies the lowest energy structure of the host cluster. The infrared spectra, Raman spectra, and photoelectron spectra of Ag n V (n = 1-12) clusters are simulated and can be used to determine the most stable structure in the future. The relative stability, dissociation channel, and chemical activity of the ground states are analyzed through atomic averaged binding energy, dissociation energy, and energy gap. It is found that V atom can improve the stability of the host cluster, Ag 2 excepted. The most possible dissociation channels are Ag n V = Ag + Ag n - 1 V for n = 1 and 4-12 and Ag n V = Ag 2  + Ag n - 2 V for n = 2 and 3. The energy gap of Ag n V cluster with odd n is much smaller than that of Ag n + 1 cluster. Analyses of magnetic property indicate that the total magnetic moment of Ag n V cluster mostly comes from V atom and varies from 1 to 5 μ B . The charge transfer between V and Ag atoms should be responsible for the change of magnetic moment.

Embedded cluster metal-polymeric micro interface and process for producing the same

DOEpatents

Menezes, Marlon E.; Birnbaum, Howard K.; Robertson, Ian M.

2002-01-29

A micro interface between a polymeric layer and a metal layer includes isolated clusters of metal partially embedded in the polymeric layer. The exposed portion of the clusters is smaller than embedded portions, so that a cross section, taken parallel to the interface, of an exposed portion of an individual cluster is smaller than a cross section, taken parallel to the interface, of an embedded portion of the individual cluster. At least half, but not all of the height of a preferred spherical cluster is embedded. The metal layer is completed by a continuous layer of metal bonded to the exposed portions of the discontinuous clusters. The micro interface is formed by heating a polymeric layer to a temperature, near its glass transition temperature, sufficient to allow penetration of the layer by metal clusters, after isolated clusters have been deposited on the layer at lower temperatures. The layer is recooled after embedding, and a continuous metal layer is deposited upon the polymeric layer to bond with the discontinuous metal clusters.