WorldWideScience

Sample records for cluster chemistry structure

  1. Metal cluster compounds - chemistry and importance; clusters containing isolated main group element atoms, large metal cluster compounds, cluster fluxionality

    International Nuclear Information System (INIS)

    Walther, B.

    1988-01-01

    This part of the review on metal cluster compounds deals with clusters containing isolated main group element atoms, with high nuclearity clusters and metal cluster fluxionality. It will be obvious that main group element atoms strongly influence the geometry, stability and reactivity of the clusters. High nuclearity clusters are of interest in there own due to the diversity of the structures adopted, but their intermediate position between molecules and the metallic state makes them a fascinating research object too. These both sites of the metal cluster chemistry as well as the frequently observed ligand and core fluxionality are related to the cluster metal and surface analogy. (author)

  2. Fluoride Bridges as Structure-Directing Motifs in 3d-4f Cluster Chemistry

    DEFF Research Database (Denmark)

    Birk, Torben; Pedersen, Kasper; Thuesen, Christian Aa.

    2012-01-01

    The use of kinetically robust chromium(III) fluorido complexes as synthons for mixed 3d-4f clusters is reported. The tendency toward linear {CrIII–F–LnIII} units dictates the cluster topology. Specifically, we show that reaction of cis-[CrIIIF2(NN)2]NO3 (NN = 1,10-phenanthroline (“phen”) or 2......-nuclear complex and fac-[CrIIIF3L′], with L′ = 1,1,1-tris-((methylamino)methylethane) (“Me3tame”), reacts with [Ln(hfac)3(H2O)2] (hfacH = 1,1,1,5,5,5-hexafluoroacetylacetone) to yield an isostructural series of {Ln3Cr2} (10–14) trigonal bipyramids with no central ligand. The formation of the latter is accompanied...... by a partial solvolysis of the Cr(III) precursor but without formation of insoluble LnF3. The magnetic properties of the gadolinium containing clusters allow quantification of fluoride-mediated, antiferromagnetic Gd–Cr exchange interactions of magnitude between 0.14 cm–1 and 0.71 cm–1 (Ĥ = J12Ŝ1·Ŝ2...

  3. Bridging quantum chemistry and nuclear structure theory: Coupled-cluster calculations for closed- and open-shell nuclei

    International Nuclear Information System (INIS)

    Piecuch, Piotr; Wloch, Marta; Gour, Jeffrey R.; Dean, David J.; Papenbrock, Thomas; Hjorth-Jensen, Morten

    2005-01-01

    We review basic elements of the single-reference coupled-cluster theory and discuss large scale ab initio calculations of ground and excited states of 15O, 16O, and 17O using coupled-cluster methods and algorithms developed in quantum chemistry. By using realistic two-body interactions and the renormalized form of the Hamiltonian obtained with a no-core G-matrix approach, we obtain the converged results for 16O and promising preliminary results for 15O and 17O at the level of two-body interactions. The calculated properties other than energies include matter density, charge radius, and charge form factor. The relatively low costs of coupled-cluster calculations, which are characterized by the low-order polynomial scaling with the system size, enable us to probe large model spaces with up to 7 or 8 major oscillator shells, for which non-truncated shell-model calculations for nuclei with A = 15 17 active particles are presently not possible. We argue that the use of coupled-cluster methods and computer algorithms developed by quantum chemists to calculate properties of nuclei is an important step toward the development of accurate and affordable many-body theories that cross the boundaries of various physical sciences

  4. Contribution of radiation chemistry to cluster science

    International Nuclear Information System (INIS)

    Belloni, J.

    2006-01-01

    Nanoclusters are small objects made of a few atoms, with a size of a few nanometers at most, which constitute a state of matter, named mesoscopic, intermediary between the atom and the bulk metal. In the 70's, radiation chemistry experiments have demonstrated that metal clusters exhibited indeed, due to their very small size, specific properties distinct from the bulk metal. The properties, physical and chemical, change with the number of atoms they contain. Their optical absorption spectrum, for example, as well as their redox potential, depends on the nuclearity, and also on the environment. Radiation chemistry methods have been proven to be of high potentiality to induce small and size-monodispersed metal clusters, as nanocolloids or supported on various materials. Pulse radiolysis provides the means to study the dynamics of nucleation and growth of clusters, monoand bi-metallic, from the monomers to the stable nanoparticle and to observe directly their reactivity, especially to determine during the growth their nuclearity-dependent properties, such as the redox potential. These are of crucial importance for the understanding of the mechanism of the cluster growth itself, in the radiation-induced as well as in the chemical or photochemical reduction processes, and also of the mechanism of certain catalytic reactions. (authors)

  5. Exotic cluster structures on

    CERN Document Server

    Gekhtman, M; Vainshtein, A

    2017-01-01

    This is the second paper in the series of papers dedicated to the study of natural cluster structures in the rings of regular functions on simple complex Lie groups and Poisson-Lie structures compatible with these cluster structures. According to our main conjecture, each class in the Belavin-Drinfeld classification of Poisson-Lie structures on \\mathcal{G} corresponds to a cluster structure in \\mathcal{O}(\\mathcal{G}). The authors have shown before that this conjecture holds for any \\mathcal{G} in the case of the standard Poisson-Lie structure and for all Belavin-Drinfeld classes in SL_n, n<5. In this paper the authors establish it for the Cremmer-Gervais Poisson-Lie structure on SL_n, which is the least similar to the standard one.

  6. Sodium-water clusters and their role in radiation chemistry

    International Nuclear Information System (INIS)

    Dhar, S.; Kestner, N.R.

    1988-01-01

    Studies of sodium-water clusters are presented which could serve as models for the recently suggested intermediate species in the radiation chemistry of water. The ionization potentials and the lower excited states of sodium with n-water molecules are calculated by ab initio quantum chemistry methods. The ionization potential calculated at the SCF level for the water monomer is 4.10 eV, which becomes 4.34 at the MP2 correlation level. The experimental value is 4.379 ± 0.002 eV. Structural data is presented for the lower members of the sodium with n-water clusters. In addition the Hartree-Fock calculations indicate that there should be some strong charge transfer to solvent transitions at higher energies. (author)

  7. Computational Chemistry of Modified [MFe3S4] and [M2Fe2S4] Clusters: Assessment of Trends in Electronic Structure and Properties

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta; Ooi, Bee Lean; Christensen, Hans Erik Mølager

    2008-01-01

    The aim of this work is to understand the molecular evolution of iron−sulfur clusters in terms of electronic structure and function. Metal-substituted models of biological [Fe4S4] clusters in oxidation states [MxFe4−xS4]3+/2+/1+ have been studied by density functional theory (M = Cr, Mn, Fe, Co, ...

  8. Electron-induced chemistry in microhydrated sulfuric acid clusters

    Directory of Open Access Journals (Sweden)

    J. Lengyel

    2017-11-01

    Full Text Available We investigate the mixed sulfuric acid–water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT calculations. The microhydration of (H2SO4m(H2On clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4m(H2OnHSO4− and (H2OnH2SO4−. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4−  ⋅  ⋅  ⋅  H3O+ formation in the neutral H2SO4(H2On clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO42(H2On this process starts as early as n ≥ 2 water molecules. The (H2SO4m(H2OnHSO4− clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4−  ⋅  ⋅  ⋅  H3O+ ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2OnH2SO4− cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid–water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid–water aerosols are discussed.

  9. Electron-induced chemistry in microhydrated sulfuric acid clusters

    Science.gov (United States)

    Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

    2017-11-01

    We investigate the mixed sulfuric acid-water clusters in a molecular beam experiment with electron attachment and negative ion mass spectrometry and complement the experiment by density functional theory (DFT) calculations. The microhydration of (H2SO4)m(H2O)n clusters is controlled by the expansion conditions, and the electron attachment yields the main cluster ion series (H2SO4)m(H2O)nHSO4- and (H2O)nH2SO4-. The mass spectra provide an experimental evidence for the onset of the ionic dissociation of sulfuric acid and ion-pair (HSO4- ṡ ṡ ṡ H3O+) formation in the neutral H2SO4(H2O)n clusters with n ≥ 5 water molecules, in excellent agreement with the theoretical predictions. In the clusters with two sulfuric acid molecules (H2SO4)2(H2O)n this process starts as early as n ≥ 2 water molecules. The (H2SO4)m(H2O)nHSO4- clusters are formed after the dissociative electron attachment to the clusters containing the (HSO4- ṡ ṡ ṡ H3O+) ion-pair structure, which leads to the electron recombination with the H3O+ moiety generating H2O molecule and the H-atom dissociation from the cluster. The (H2O)nH2SO4- cluster ions point to an efficient caging of the H atom by the surrounding water molecules. The electron-energy dependencies exhibit an efficient electron attachment at low electron energies below 3 eV, and no resonances above this energy, for all the measured mass peaks. This shows that in the atmospheric chemistry only the low-energy electrons can be efficiently captured by the sulfuric acid-water clusters and converted into the negative ions. Possible atmospheric consequences of the acidic dissociation in the clusters and the electron attachment to the sulfuric acid-water aerosols are discussed.

  10. Structure correlation and chemistry

    International Nuclear Information System (INIS)

    Buergi, H.B.

    1998-01-01

    The main goal of crystal and molecular structure determination is to provide a starting point for understanding the physical, chemical and biological properties of matter. At present, results from nearly 300000 crystal structure studies are available in computer-readable form. Structure correlation attempts to extract knowledge and understanding from this body of information, which is not available from its parts. This article reviews some typical examples: libraries of prototypal molecular dimensions, mappings of chemical reaction pathways, correlations between structure on one hand and energy, reaction rate, catalytic activity or magnetism on the other. The knowledge gained from structure-correlation studies, together with quantum-chemical and other modeling techniques, provides conceptual and practical tools for designing molecules and materials with tailor-made properties. (orig.)

  11. Structure and bonding in clusters

    International Nuclear Information System (INIS)

    Kumar, V.

    1991-10-01

    We review here the recent progress made in the understanding of the electronic and atomic structure of small clusters of s-p bonded materials using the density functional molecular dynamics technique within the local density approximation. Starting with a brief description of the method, results are presented for alkali metal clusters, clusters of divalent metals such as Mg and Be which show a transition from van der Waals or weak chemical bonding to metallic behaviour as the cluster size grows and clusters of Al, Sn and Sb. In the case of semiconductors, we discuss results for Si, Ge and GaAs clusters. Clusters of other materials such as P, C, S, and Se are also briefly discussed. From these and other available results we suggest the possibility of unique structures for the magic clusters. (author). 69 refs, 7 figs, 1 tab

  12. Electronic structure of metal clusters

    International Nuclear Information System (INIS)

    Wertheim, G.K.

    1989-01-01

    Photoemission spectra of valence electrons in metal clusters, together with threshold ionization potential measurements, provide a coherent picture of the development of the electronic structure from the isolated atom to the large metallic cluster. An insulator-metal transition occurs at an intermediate cluster size, which serves to define the boundary between small and large clusters. Although the outer electrons may be delocalized over the entire cluster, a small cluster remains insulating until the density of states near the Fermi level exceeds 1/kT. In large clusters, with increasing cluster size, the band structure approaches that of the bulk metal. However, the bands remain significantly narrowed even in a 1000-atom cluster, giving an indication of the importance of long-range order. The core-electron binding-energy shifts of supported metal clusters depend on changes in the band structure in the initial state, as well as on various final-state effects, including changes in core hole screening and the coulomb energy of the final-state charge. For cluster supported on amorphous carbon, this macroscopic coulomb shift is often dominant, as evidenced by the parallel shifts of the core-electron binding energy and the Fermi edge. Auger data confirm that final-state effects dominate in cluster of Sn and some other metals. Surface atom core-level shifts provide a valuable guide to the contributions of initial-state changes in band structure to cluster core-electron binding energy shifts, especially for Au and Pt. The available data indicate that the shift observed in supported, metallic clusters arise largely from the charge left on the cluster by photoemission. As the metal-insulator transition is approached from above, metallic screening is suppressed and the shift is determined by the local environment. (orig.)

  13. Cluster analysis of track structure

    International Nuclear Information System (INIS)

    Michalik, V.

    1991-01-01

    One of the possibilities of classifying track structures is application of conventional partition techniques of analysis of multidimensional data to the track structure. Using these cluster algorithms this paper attempts to find characteristics of radiation reflecting the spatial distribution of ionizations in the primary particle track. An absolute frequency distribution of clusters of ionizations giving the mean number of clusters produced by radiation per unit of deposited energy can serve as this characteristic. General computation techniques used as well as methods of calculations of distributions of clusters for different radiations are discussed. 8 refs.; 5 figs

  14. Contribution of radiation chemistry to the study of metal clusters.

    Science.gov (United States)

    Belloni, J

    1998-11-01

    Radiation chemistry dates from the discovery of radioactivity one century ago by H. Becquerel and P. and M. Curie. The complex phenomena induced by ionizing radiation have been explained progressively. At present, the methodology of radiation chemistry, particularly in the pulsed mode, provides a powerful means to study not only the early processes after the energy absorption, but more generally a broad diversity of chemical and biochemical reaction mechanisms. Among them, the new area of metal cluster chemistry illustrates how radiation chemistry contributed to this field in suggesting fruitful original concepts, in guiding and controlling specific syntheses, and in the detailed elaboration of the mechanisms of complex and long-unsolved processes, such as the dynamics of nucleation, electron transfer catalysis and photographic development.

  15. Determination of atomic cluster structure with cluster fusion algorithm

    DEFF Research Database (Denmark)

    Obolensky, Oleg I.; Solov'yov, Ilia; Solov'yov, Andrey V.

    2005-01-01

    We report an efficient scheme of global optimization, called cluster fusion algorithm, which has proved its reliability and high efficiency in determination of the structure of various atomic clusters.......We report an efficient scheme of global optimization, called cluster fusion algorithm, which has proved its reliability and high efficiency in determination of the structure of various atomic clusters....

  16. On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

    Science.gov (United States)

    Turi, László

    2016-04-01

    We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

  17. On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

    Energy Technology Data Exchange (ETDEWEB)

    Turi, László, E-mail: turi@chem.elte.hu [Department of Physical Chemistry, Eötvös Loránd University, P.O. Box 32, H-1518 Budapest 112 (Hungary)

    2016-04-21

    We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

  18. Cluster structure in Cf nuclei

    International Nuclear Information System (INIS)

    Singh, Shailesh K.; Biswal, S.K.; Bhuyan, M.; Patra, S.K.; Gupta, R.K.

    2014-01-01

    Due to the availability of advance experimental facilities, it is possible to probe the nuclei upto their nucleon level very precisely and analyzed the internal structure which will help us to resolve some mysterious problem of the decay of nuclei. Recently, the relativistic nuclear collision, confirmed the α cluster type structure in the 12 C which is the mile stone for the cluster structure in nuclei. The clustering phenomena in light and intermediate elements in nuclear chart is very interesting. There is a lot of work done by our group in the clustering behaviour of the nuclei. In this paper, the various prospectus of clustering in the isotopes of Cf nucleus including fission state is discussed. Here, 242 Cf isotope for the analysis, which is experimentally known is taken. The relativistic mean field model with well established NL3 parameter set is taken. For getting the exact ground state configuration of the isotopes, the calculation for minimizing the potential energy surface is performed by constraint method. The clustering structure of other Cf isotopes is discussed

  19. Cluster structure of light nuclei

    Science.gov (United States)

    Iachello, Francesco

    2018-02-01

    Matter and charge densities of kα structures with k=2 (8Be), k=3 (12C) and k=4 (16O) calculated within the framework of the algebraic cluster model (ACM) are briefly reviewed and explicitly displayed. Their parameters are determined from a comparison with electron scattering data.

  20. Chemistry and structure of technetium complexes

    International Nuclear Information System (INIS)

    Baldas, J.; Boas, J.F.; Bonnyman, J.; Williams, G.A.

    1983-01-01

    The structures of tris(2-aminobenzenethiolato) technetium(VI) and dichlorobis(diethyldithiocarbamato) thionitrosyltechnetium(V) have been determined by single crystal x-ray diffraction analysis. The preparation and chemistry of thiocyanato complexes of technetium have been investigated

  1. Fine structure of cluster decays

    International Nuclear Information System (INIS)

    Dumitrescu, O.

    1993-07-01

    Within the one level R-matrix approach the hindrance factors of the radioactive decays in which are emitted α and 14 C - nuclei are calculated. The generalization to radioactive decays in which are emitted heavier clusters such as e.g. 20 O, 24 Ne, 25 Ne, 28 Mg. 30 Mg, 32 Si and 34 Si is straightforward. The interior wave functions are supposed to be given by the shell model with effective residual interactions (e.g. the large scale shell model code-OXBASH - in the Michigan State University version for nearly spherical nuclei or by the enlarged superfluid model - ESM - recently proposed for deformed nuclei). The exterior wave functions are calculated from a cluster - nucleus double - folding model potential obtained with the M3Y interaction. As examples of the cluster decay fine structure we analyzed the particular cases of α - decay of 241 Am and 14 C -decay of 233 Ra. Good agreement with the experimental data is obtained. (author). 78 refs, 2 figs, 6 tabs

  2. Macropolyhedral boron-containing cluster chemistry. Cluster opening and B-frame rearrangement in the reaction of B16H20 with [{(IrCl2(eta(5)-C5Me5)}(2)]. Synchrotron X-ray structures of [(eta(5)-C5Me5)(2)Ir2B16H17Cl] and [(eta(5)-C5Me5)(2)Ir2B16H15Cl

    Czech Academy of Sciences Publication Activity Database

    Carr, MJ.; Perera, SD.; Jelínek, Tomáš; Kilner, C. A.; Clegg, W.; Štíbr, Bohumil; Kennedy, J.D.

    2006-01-01

    Roč. 44, - (2006), s. 5221-5224 ISSN 1477-9226 R&D Projects: GA AV ČR(CZ) IAA400320601; GA ČR GA203/05/2646 Grant - others:EPSRC(GB) J/56929; EPSRC(GB) GR/L/49505; EPSRC(GB) R/61949 Institutional research plan: CEZ:AV0Z40320502 Keywords : intercluster bonding intimagy * matallaborane clusters * crystal-structures Subject RIV: CA - Inorganic Chemistry Impact factor: 3.012, year: 2006

  3. Structure and clusters of light unstable nuclei

    International Nuclear Information System (INIS)

    En'yo, Yoshiko

    2010-01-01

    As it is known, cluster structures are often observed in light nuclei. In the recent evolution of unstable nuclear research (on nuclei having unbalanced number of neutron and proton) further new types of clusters are coming to be revealed. In this report, structures of light unstable nuclei and some of the theoretical models to describe them are reviewed. The following topics are picked up. 1. Cluster structure and theoretical models, 2. Cluster structure of unstable nuclei (low excited state). 3. Cluster structure of neutron excess beryllium isotopes. 4. Cluster gas like state in C isotope. 5. Dineutron structure of He isotopes. Numbers of strange nuclear structures of light nuclei are illustrated. Antisymmetrized molecular dynamics (AMD) is the recently developed theoretical framework which has been successfully used in heavy ion reactions and nuclear structure studies. Successful application of AMD to the isotopes of Be, B and C are illustrated. (S. Funahashi)

  4. Cluster structures in light nuclei

    International Nuclear Information System (INIS)

    Horiuchi, H.

    2000-01-01

    Complete text of publication follows. Clustering in neutron-rich nuclei is discussed. To understand the novel features (1,2,3) of the clustering in neutron-rich nuclei, the basic features of the clustering in stable nuclei (4) are briefly reviewed. In neutron-rich nuclei, the requirement of the stability of clusters is questioned and the threshold rule is no more obeyed. Examples of clustering in Be and B isotopes (4,5) are discussed in some detail. Possible existence of novel type of clustering near neutron dripline is suggested (1). (author)

  5. Quantum chemistry of the minimal CdSe clusters

    Science.gov (United States)

    Yang, Ping; Tretiak, Sergei; Masunov, Artëm E.; Ivanov, Sergei

    2008-08-01

    Colloidal quantum dots are semiconductor nanocrystals (NCs) which have stimulated a great deal of research and have attracted technical interest in recent years due to their chemical stability and the tunability of photophysical properties. While internal structure of large quantum dots is similar to bulk, their surface structure and passivating role of capping ligands (surfactants) are not fully understood to date. We apply ab initio wavefunction methods, density functional theory, and semiempirical approaches to study the passivation effects of substituted phosphine and amine ligands on the minimal cluster Cd2Se2, which is also used to benchmark different computational methods versus high level ab initio techniques. Full geometry optimization of Cd2Se2 at different theory levels and ligand coverage is used to understand the affinities of various ligands and the impact of ligands on cluster structure. Most possible bonding patterns between ligands and surface Cd/Se atoms are considered, including a ligand coordinated to Se atoms. The degree of passivation of Cd and Se atoms (one or two ligands attached to one atom) is also studied. The results suggest that B3LYP/LANL2DZ level of theory is appropriate for the system modeling, whereas frequently used semiempirical methods (such as AM1 and PM3) produce unphysical results. The use of hydrogen atom for modeling of the cluster passivating ligands is found to yield unphysical results as well. Hence, the surface termination of II-VI semiconductor NCs with hydrogen atoms often used in computational models should probably be avoided. Basis set superposition error, zero-point energy, and thermal corrections, as well as solvent effects simulated with polarized continuum model are found to produce minor variations on the ligand binding energies. The effects of Cd-Se complex structure on both the electronic band gap (highest occupied molecular orbital-lowest unoccupied molecular orbital energy difference) and ligand binding

  6. Rearrangement of cluster structure during fission processes

    DEFF Research Database (Denmark)

    Lyalin, Andrey G.; Obolensky, Oleg I.; Solov'yov, Andrey V.

    2004-01-01

    Results of molecular dynamics simulations of fission reactions $Na_10^2+ -->Na_7^++ Na_3^+ and Na_18^2+--> 2Na_9^+ are presented. The dependence of the fission barriers on the isomer structure of the parent cluster is analysed. It is demonstrated that the energy necessary for removing homothetic...... groups of atoms from the parent cluster is largely independent of the isomer form of the parent cluster. The importance of rearrangement of the cluster structure during the fission process is elucidated. This rearrangement may include transition to another isomer state of the parent cluster before actual...

  7. Alpha condensates and nonlocalized cluster structures

    International Nuclear Information System (INIS)

    Funaki, Yasuro

    2014-01-01

    We discuss a container structure for non-gaslike cluster states, in which single Tohsaki-Horiuchi-Schuck-ROpke (THSR) wave functions are shown to be almost 100% equivalent to the full solutions of the corresponding RGM/GCM equations, for the inversion doublet band states in 20 Ne, α-linear-chain states, and α + α + A cluster states in 9 Λ Be. The recognition of the fact that the THSR wave function describes well not only gaslike cluster states but also non-gaslike cluster states is a recent remarkable development of nuclear cluster physics. This fact tells us that the cluster structure is composed of cluster-mean-field motion under the constraint of inter-cluster Pauli repulsion, in which we call the cluster-mean-field potential the container. We demonstrate that the evolution of the cluster structure of a nucleus is governed by the size parameter of the cluster-mean-field potential (container), for 16 O nucleus

  8. Chalcone: A Privileged Structure in Medicinal Chemistry.

    Science.gov (United States)

    Zhuang, Chunlin; Zhang, Wen; Sheng, Chunquan; Zhang, Wannian; Xing, Chengguo; Miao, Zhenyuan

    2017-06-28

    Privileged structures have been widely used as an effective template in medicinal chemistry for drug discovery. Chalcone is a common simple scaffold found in many naturally occurring compounds. Many chalcone derivatives have also been prepared due to their convenient synthesis. These natural products and synthetic compounds have shown numerous interesting biological activities with clinical potentials against various diseases. This review aims to highlight the recent evidence of chalcone as a privileged scaffold in medicinal chemistry. Multiple aspects of chalcone will be summarized herein, including the isolation of novel chalcone derivatives, the development of new synthetic methodologies, the evaluation of their biological properties, and the exploration of the mechanisms of action as well as target identification. This review is expected to be a comprehensive, authoritative, and critical review of the chalcone template to the chemistry community.

  9. Clustering methods for the optimization of atomic cluster structure

    Science.gov (United States)

    Bagattini, Francesco; Schoen, Fabio; Tigli, Luca

    2018-04-01

    In this paper, we propose a revised global optimization method and apply it to large scale cluster conformation problems. In the 1990s, the so-called clustering methods were considered among the most efficient general purpose global optimization techniques; however, their usage has quickly declined in recent years, mainly due to the inherent difficulties of clustering approaches in large dimensional spaces. Inspired from the machine learning literature, we redesigned clustering methods in order to deal with molecular structures in a reduced feature space. Our aim is to show that by suitably choosing a good set of geometrical features coupled with a very efficient descent method, an effective optimization tool is obtained which is capable of finding, with a very high success rate, all known putative optima for medium size clusters without any prior information, both for Lennard-Jones and Morse potentials. The main result is that, beyond being a reliable approach, the proposed method, based on the idea of starting a computationally expensive deep local search only when it seems worth doing so, is capable of saving a huge amount of searches with respect to an analogous algorithm which does not employ a clustering phase. In this paper, we are not claiming the superiority of the proposed method compared to specific, refined, state-of-the-art procedures, but rather indicating a quite straightforward way to save local searches by means of a clustering scheme working in a reduced variable space, which might prove useful when included in many modern methods.

  10. Structure of small rare earth clusters

    International Nuclear Information System (INIS)

    Rayane, D.; Benamar, A.; Tribollet, B.; Broyer, M.; Melinon, P.

    1991-01-01

    Rare earth clusters are produced by the inert gas condensation technique. The observed size distribution shows large peaks at n=13, 19, 23, 26, 29, 32, 34, 37, 39, 45, .... The beginning of this sequence (up to 34) has been already observed in argon clusters and recently by our group in barium clusters; this sequence may be interpreted in terms of icosahedral structures corresponding to the addition of caps on a core icosahedron of 13 atoms. (orig.)

  11. Geometric structure of percolation clusters.

    Science.gov (United States)

    Xu, Xiao; Wang, Junfeng; Zhou, Zongzheng; Garoni, Timothy M; Deng, Youjin

    2014-01-01

    We investigate the geometric properties of percolation clusters by studying square-lattice bond percolation on the torus. We show that the density of bridges and nonbridges both tend to 1/4 for large system sizes. Using Monte Carlo simulations, we study the probability that a given edge is not a bridge but has both its loop arcs in the same loop and find that it is governed by the two-arm exponent. We then classify bridges into two types: branches and junctions. A bridge is a branch iff at least one of the two clusters produced by its deletion is a tree. Starting from a percolation configuration and deleting the branches results in a leaf-free configuration, whereas, deleting all bridges produces a bridge-free configuration. Although branches account for ≈43% of all occupied bonds, we find that the fractal dimensions of the cluster size and hull length of leaf-free configurations are consistent with those for standard percolation configurations. By contrast, we find that the fractal dimensions of the cluster size and hull length of bridge-free configurations are given by the backbone and external perimeter dimensions, respectively. We estimate the backbone fractal dimension to be 1.643 36(10).

  12. Structural stability of nano-sized clusters

    NARCIS (Netherlands)

    De Hosson, JTM; Palasantzas, G; Vystavel, T; Koch, S; Ovidko,; Pande, CS; Krishnamoorti, R; Lavernia, E; Skandan, G

    2004-01-01

    This contribution presents challenges to control the microstructure in nano-structured materials via a relatively new approach, i.e. using a so-called nanocluster source. An important aspect is that the cluster size distribution is monodisperse and that the kinetic energy of the clusters during

  13. Electron-induced chemistry in microhydrated sulfuric acid clusters

    Czech Academy of Sciences Publication Activity Database

    Lengyel, Jozef; Pysanenko, Andriy; Fárník, Michal

    2017-01-01

    Roč. 17, č. 22 (2017), s. 14171-14180 ISSN 1680-7324 R&D Projects: GA ČR(CZ) GA17-04068S Grant - others:Austrian Science Fund (FWF)(AT) M1983-N34 Institutional support: RVO:61388955 Keywords : induced aerosol formation * particle formation * atmospheric implication Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry

  14. Identifying At-Risk Students in General Chemistry via Cluster Analysis of Affective Characteristics

    Science.gov (United States)

    Chan, Julia Y. K.; Bauer, Christopher F.

    2014-01-01

    The purpose of this study is to identify academically at-risk students in first-semester general chemistry using affective characteristics via cluster analysis. Through the clustering of six preselected affective variables, three distinct affective groups were identified: low (at-risk), medium, and high. Students in the low affective group…

  15. Experimental studies of the chemistry of metal clusters

    International Nuclear Information System (INIS)

    Parks, E.K.; Riley, S.J.

    1988-01-01

    The procedures for studying chemical reactions of metal clusters in a continuous-flow reactor are described, and examples of such studies are given. Experiments to be discussed include kinetics and thermodynamics measurements, and determination of the composition of clusters saturated with various adsorbate reagents. Specific systems to be covered include the reaction of iron clusters with ammonia and with hydrogen, the reaction of nickel clusters with hydrogen and with ammonia, and the reaction of platinum clusters with ethylene. The last two reactions are characterized by complex, multi-step processes that lead to adsorbate decomposition and hydrogen desorption from the clusters. Methods for probing these processes will be discussed. 26 refs., 8 figs

  16. Cu cluster shell structure at elevated temperatures

    DEFF Research Database (Denmark)

    Christensen, Ole Bøssing; Jacobsen, Karsten Wedel; Nørskov, Jens Kehlet

    1991-01-01

    Equilibrium structures of small (3–29)-atom Cu clusters are determined by simulated annealing, and finite-temperature ensembles are simulated by Monte Carlo techniques using the effective-medium theory for the energy calculation. Clusters with 8, 18, and 20 atoms are found to be particularly stable....... The equilibrium geometrical structures are determined and found to be determined by a Jahn-Teller distortion, which is found to affect the geometry also at high temperatures. The ‘‘magic’’ clusters retain their large stability even at elevated temperatures....

  17. Structural Chemistry of Human RNA Methyltransferases.

    Science.gov (United States)

    Schapira, Matthieu

    2016-03-18

    RNA methyltransferases (RNMTs) play important roles in RNA stability, splicing, and epigenetic mechanisms. They constitute a promising target class that is underexplored by the medicinal chemistry community. Information of relevance to drug design can be extracted from the rich structural coverage of human RNMTs. In this work, the structural chemistry of this protein family is analyzed in depth. Unlike most methyltransferases, RNMTs generally feature a substrate-binding site that is largely open on the cofactor-binding pocket, favoring the design of bisubstrate inhibitors. Substrate purine or pyrimidines are often sandwiched between hydrophobic walls that can accommodate planar ring systems. When the substrate base is laying on a shallow surface, a 5' flanking base is sometimes anchored in a druggable cavity. The cofactor-binding site is structurally more diverse than in protein methyltransferases and more druggable in SPOUT than in Rossman-fold enzymes. Finally, conformational plasticity observed both at the substrate and cofactor binding sites may be a challenge for structure-based drug design. The landscape drawn here may inform ongoing efforts toward the discovery of the first human RNMT inhibitors.

  18. Organoactinide chemistry: synthesis, structure, and solution dynamics

    International Nuclear Information System (INIS)

    Brennan, J.G.

    1985-12-01

    This thesis considers three aspects of organoactinide chemistry. In chapter one, a bidentate phosphine ligand was used to kinetically stabilize complexes of the type Cp 2 MX 2 . Ligand redistribution processes are present throughout the synthetic work, as has often been observed in uranium cyclopentadienyl chemistry. The effects of covalent M-L bonding on the solution and solid state properties of U(III) coordination complexes are considered. In particular, the nature of the more subtle interaction between the metal and the neutral ligand are examined. Using relative basicity data obtained in solution, and solid state structural data (and supplemented by gas phase photoelectron measurements), it is demonstrated that the more electron rich U(III) centers engage in significant U → L π-donation. Trivalent uranium is shown to be capable of acting either as a one- or two-electron reducing agent toward a wide variety of unsaturated organic and inorganic molecules, generating molecular classes unobtainable via traditional synthetic approaches, as well as offering an alternative synthetic approach to molecules accessible via metathesis reactions. Ligand redistribution processes are again observed, but given the information concerning ligand lability, this reactivity pattern is applied to the synthesis of pure materials inaccessible from redox chemistry. 214 refs., 33 figs., 10 tabs

  19. Clustering aspects in nuclear structure functions

    International Nuclear Information System (INIS)

    Hirai, M.; Saito, K.; Watanabe, T.; Kumano, S.

    2011-01-01

    For understanding an anomalous nuclear effect experimentally observed for the beryllium-9 nucleus at the Thomas Jefferson National Accelerator Facility, clustering aspects are studied in structure functions of deep inelastic lepton-nucleus scattering by using momentum distributions calculated in antisymmetrized (or fermionic) molecular dynamics (AMD) and also in a simple shell model for comparison. According to AMD, the 9 Be nucleus consists of two α-like clusters with a surrounding neutron. The clustering produces high-momentum components in nuclear wave functions, which affects nuclear modifications of the structure functions. We investigated whether clustering features could appear in the structure function F 2 of 9 Be along with studies for other light nuclei. We found that nuclear modifications of F 2 are similar in both AMD and shell models within our simple convolution description although there are slight differences in 9 Be. It indicates that the anomalous 9 Be result should be explained by a different mechanism from the nuclear binding and Fermi motion. If nuclear-modification slopes d(F 2 A /F 2 D )/dx are shown by the maximum local densities, the 9 Be anomaly can be explained by the AMD picture, namely by the clustering structure, whereas it certainly cannot be described in the simple shell model. This fact suggests that the large nuclear modification in 9 Be should be explained by large densities in the clusters. For example, internal nucleon structure could be modified in the high-density clusters. The clustering aspect of nuclear structure functions is an unexplored topic which is interesting for future investigations.

  20. Web document clustering using hyperlink structures

    Energy Technology Data Exchange (ETDEWEB)

    He, Xiaofeng; Zha, Hongyuan; Ding, Chris H.Q; Simon, Horst D.

    2001-05-07

    With the exponential growth of information on the World Wide Web there is great demand for developing efficient and effective methods for organizing and retrieving the information available. Document clustering plays an important role in information retrieval and taxonomy management for the World Wide Web and remains an interesting and challenging problem in the field of web computing. In this paper we consider document clustering methods exploring textual information hyperlink structure and co-citation relations. In particular we apply the normalized cut clustering method developed in computer vision to the task of hyperdocument clustering. We also explore some theoretical connections of the normalized-cut method to K-means method. We then experiment with normalized-cut method in the context of clustering query result sets for web search engines.

  1. The atomic structure of transition metal clusters

    International Nuclear Information System (INIS)

    Riley, S.J.

    1995-01-01

    Chemical reactions are used to probe the atomic (geometrical) structure of isolated clusters of transition metal atoms. The number of adsorbate molecules that saturate a cluster, and/or the binding energy of molecules to cluster surfaces, are determined as a function of cluster size. Systematics in these properties often make it possible to propose geometrical structures consistent with the experimental observations. We will describe how studies of the reactions of cobalt and nickel clusters with ammonia, water, and nitrogen provide important and otherwise unavailable structural information. Specifically, small (less than 20 atoms) clusters of cobalt and nickel atoms adopt entirely different structures, the former having packing characteristic of the bulk and the latter having pentagonal symmetry. These observations provide important input for model potentials that attempt to describe the local properties of transition metals. In particular, they point out the importance of a proper treatment of d-orbital binding in these systems, since cobalt and nickel differ so little in their d-orbital occupancy

  2. Structure prediction of AlnOm clusters

    International Nuclear Information System (INIS)

    Smok, P

    2011-01-01

    Genetic algorithm simulations, using Buckingham potential to represent the anion-anion and cation-anion short-range interactions, were performed in order to predict the equilibrium positions of the Al and O ions in Al n O m clusters. In order to find the equilibrium structures of compounds a self-organizing genetic algorithm were constructed. The calculation were carried out for several clusters Al n O m , with different numbers of aluminium and oxygen atoms.

  3. Cluster structures influenced by interaction with a surface.

    Science.gov (United States)

    Witt, Christopher; Dieterich, Johannes M; Hartke, Bernd

    2018-05-30

    Clusters on surfaces are vitally important for nanotechnological applications. Clearly, cluster-surface interactions heavily influence the preferred cluster structures, compared to clusters in vacuum. Nevertheless, systematic explorations and an in-depth understanding of these interactions and how they determine the cluster structures are still lacking. Here we present an extension of our well-established non-deterministic global optimization package OGOLEM from isolated clusters to clusters on surfaces. Applying this approach to intentionally simple Lennard-Jones test systems, we produce a first systematic exploration that relates changes in cluster-surface interactions to resulting changes in adsorbed cluster structures.

  4. Groundwater Chemistry Regulated by Hydrochemical Processes and Geological Structures: A Case Study in Tongchuan, China

    Directory of Open Access Journals (Sweden)

    Xinyan Li

    2018-03-01

    Full Text Available Knowledge of hydrochemical processes in groundwater helps to identify the relationship between geochemical processes and groundwater quality as well as to understand the hydrochemical evaluation of groundwater, which is important for the sustainable management of groundwater resources. This study aims to identify the chemical characteristics of groundwater in the area of Tongchuan City, China. A total of 58 groundwater samples were collected. A hierarchical cluster analysis divided samples into three clusters and six sub-clusters (cluster 1a, 1b, 2a, 2b, 3a, 3b according to hydrochemical facies. Graphical plots of multiple ionic ratios, saturation indices, and ion exchange indices were employed to examine hydrochemical processes that result in different hydrochemical facies of each cluster. Results show the predominance of carbonate and silicate weathering in cluster 1, silicate weathering in cluster 2, and carbonate weathering in cluster 3. Ionic exchange is a ubiquitous process among all clusters. The distribution of clusters is related to the regional geology, which may result in different hydrochemical processes. Two stratigraphic sections identify the differences in hydrochemical processes resulting from complex stratum structures and varied aquifer media. Cluster 2a shows an interesting difference in water chemistry along the groundwater flow path. Further study by oxygen and hydrogen isotope indicated that mixing between Quaternary and the Permian aquifers resulting from faulting is the main reason for the distinctive characteristic of cluster 2a.

  5. Computed structure of small benzene clusters

    NARCIS (Netherlands)

    van de Waal, B.W.

    1986-01-01

    The structures of small benzene clusters (C6H6)n, n = 2–7, have been calculated employing potential-energy minimization with respect to molecular translational and rotational coordinates, using exp-6-1 non-bonded atom-atom potential functions. The influence of the adopted point-charge model is

  6. Construction Cluster Volume I [Wood Structural Framing].

    Science.gov (United States)

    Pennsylvania State Dept. of Justice, Harrisburg. Bureau of Correction.

    The document is the first of a series, to be integrated with a G.E.D. program, containing instructional materials at the basic skills level for the construction cluster. It focuses on wood structural framing and contains 20 units: (1) occupational information; (2) blueprint reading; (3) using leveling instruments and laying out building lines; (4)…

  7. Structural properties of small rhodium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Soon, Yee Yeen; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    2015-04-24

    We report a systematic study of the structural properties of rhodium clusters at the atomistic level. A novel global-minimum search algorithm, known as parallel tempering multicanonical basin hopping plus genetic algorithm (PTMBHGA), is used to obtain the geometrical structures with lowest minima at the semi-empirical level where Gupta potential is used to describe the atomic interaction among the rhodium atoms. These structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA). The structures are optimized for different spin multiplicities. The ones with lowest energies will be taken as ground-state structures. In most cases, we observe only minor changes in the geometry and bond length of the clusters as a result of DFT-level re-optimization. Only in some limited cases, the initial geometries obtained from the PTMBHGA are modified by the re-optimization. The variation of structural properties, such as ground-state geometry, symmetry and binding energy, with respect to the cluster size is studied and agreed well with other results available in the literature.

  8. Star Cluster Structure from Hierarchical Star Formation

    Science.gov (United States)

    Grudic, Michael; Hopkins, Philip; Murray, Norman; Lamberts, Astrid; Guszejnov, David; Schmitz, Denise; Boylan-Kolchin, Michael

    2018-01-01

    Young massive star clusters (YMCs) spanning 104-108 M⊙ in mass generally have similar radial surface density profiles, with an outer power-law index typically between -2 and -3. This similarity suggests that they are shaped by scale-free physics at formation. Recent multi-physics MHD simulations of YMC formation have also produced populations of YMCs with this type of surface density profile, allowing us to narrow down the physics necessary to form a YMC with properties as observed. We show that the shallow density profiles of YMCs are a natural result of phase-space mixing that occurs as they assemble from the clumpy, hierarchically-clustered configuration imprinted by the star formation process. We develop physical intuition for this process via analytic arguments and collisionless N-body experiments, elucidating the connection between star formation physics and star cluster structure. This has implications for the early-time structure and evolution of proto-globular clusters, and prospects for simulating their formation in the FIRE cosmological zoom-in simulations.

  9. Density structures inside the plasmasphere: Cluster observations

    DEFF Research Database (Denmark)

    Darrouzet, F.; Decreau, P.M.E.; De Keyser, J.

    2004-01-01

    The electron density profiles derived from the EFW and WHISPER instruments on board the four Cluster spacecraft reveal density structures inside the plasmasphere and at its outer boundary, the plasmapause. We have conducted a statistical study to characterize these density structures. We focus...... on the plasmasphere crossing on I I April 2002, during which Cluster observed several density irregularities inside the plasmasphere, as well as a plasmaspheric plume. We derive the density gradient vectors from simultaneous density measurements by the four spacecraft. We also determine the normal velocity...... of the boundaries of the plume and of the irregularities from the time delays between those boundaries in the four individual density profiles, assuming they are planar. These new observations yield novel insights about the occurrence of density irregularities, their geometry and their dynamics. These in...

  10. Structural motifs of pre-nucleation clusters.

    Science.gov (United States)

    Zhang, Y; Türkmen, I R; Wassermann, B; Erko, A; Rühl, E

    2013-10-07

    Structural motifs of pre-nucleation clusters prepared in single, optically levitated supersaturated aqueous aerosol microparticles containing CaBr2 as a model system are reported. Cluster formation is identified by means of X-ray absorption in the Br K-edge regime. The salt concentration beyond the saturation point is varied by controlling the humidity in the ambient atmosphere surrounding the 15-30 μm microdroplets. This leads to the formation of metastable supersaturated liquid particles. Distinct spectral shifts in near-edge spectra as a function of salt concentration are observed, in which the energy position of the Br K-edge is red-shifted by up to 7.1 ± 0.4 eV if the dilute solution is compared to the solid. The K-edge positions of supersaturated solutions are found between these limits. The changes in electronic structure are rationalized in terms of the formation of pre-nucleation clusters. This assumption is verified by spectral simulations using first-principle density functional theory and molecular dynamics calculations, in which structural motifs are considered, explaining the experimental results. These consist of solvated CaBr2 moieties, rather than building blocks forming calcium bromide hexahydrates, the crystal system that is formed by drying aqueous CaBr2 solutions.

  11. Chemistry and kinetics of size-selected cobalt cluster cations at thermal energies. I. Reactions with CO

    Science.gov (United States)

    Guo, B. C.; Kerns, K. P.; Castleman, A. W., Jr.

    1992-06-01

    The chemistry and kinetics of size-selected Co+n cluster-ion (n=2-8) reactions with CO are studied using a selected ion drift tube affixed with a laser vaporization source operated under well-defined thermal conditions. All reactions studied in the present work are found to be association reactions. Their absolute rate constants, which are determined quantitatively, are found to have a strong dependence on cluster size. Similar to the cases of reactions with many other reactants such as H2 and CH4, Co+4 and Co+5 display a higher reactivity toward the CO molecule than do clusters of neighboring size. The multiple-collision conditions employed in the present work have enabled a determination of the maximum coordination number of CO molecules bound onto each Co+n cluster. It is found that the tetramer tends to bond 12 CO molecules, the pentamer 14 CO, hexamer 16 CO, and so on. The results are interpreted in terms of Lauher's calculation and the polyhedral skeletal electron pair theory. All the measured maximum coordination numbers correlate extremely well with the predictions of these theories, except for the trimer where the measured number is one CO less than the predicted value. The good agreement between experiment and theory enables one to gain some insight into the geometric structure of the clusters. Based on the present findings, the cobalt tetramer cation is interpreted to have a tetrahedral structure, the pentamer a trigonal bipyramid, and the hexamer an octahedral structure. Other cluster structures are also discussed.

  12. Unraveling the atomic structure of ultrafine iron clusters

    KAUST Repository

    Wang, Hongtao; Li, Kun; Yao, Yingbang; Wang, Qingxiao; Cheng, Yingchun; Schwingenschlö gl, Udo; Zhang, Xixiang; Yang, Wei

    2012-01-01

    Unraveling the atomic structures of ultrafine iron clusters is critical to understanding their size-dependent catalytic effects and electronic properties. Here, we describe the stable close-packed structure of ultrafine Fe clusters for the first

  13. Combining research in physical chemistry and chemical education: Part A. The femtosecond molecular dynamics of small gas-phase anion clusters. Part B. Surveying student beliefs about chemistry and the development of physical chemistry learning tutorials

    Science.gov (United States)

    Barbera, Jack

    2007-12-01

    This dissertation combines work in the areas of experimental physical chemistry and chemical education. In the area of physical chemistry, femtosecond pump-probe spectroscopy is used to interrogate the time-dependence for energy redistribution, solvent reorientation, and dissociation dynamics in small gas-phase anion clusters. The chemical education research addressed in this manuscript include the development and validation of a survey to measure students' beliefs about chemistry and the learning of chemistry and the development and testing of learning tutorials for use in undergraduate physical chemistry courses in thermodynamics and kinetics. In the first part of this dissertation, the Cu(CD3OD) dynamics are investigated using a combination of femtosecond pump-probe experiments and ab initio calculations. Dissociation of this complex into Cu and CD3OD occurs on two distinct time scales: 3 and 30 ps, which arise, respectively, from the coupling of intermolecular solvent rotations and excited methyl rotor rotation into the Cu-O dissociation component upon electron photodetachment of the precursor anion. In the second part of this dissertation, the time-resolved recombination of photodissociated IBr-(CO2)n (n = 5 - 10) cluster anions is investigated. Upon excitation to the A' 2pi 1/2 state of the chromophore, the bare anion results in I- and Br products, upon solvation with CO2, the IBr- chromophore regains near-IR absorption after recombination and vibrational relaxation on the ground electronic state. The recombination times vary with the number of solvent molecules from 12 ps for n = 5 to 900 ps for n = 10. Extensive electronic structure and non-adiabatic molecular dynamic simulations provide a framework to understand this behavior. In the third part of this dissertation, the modification and validation of the Colorado Learning Attitudes about Science Survey (CLASS) for use in chemistry is presented in detail. The CLASS survey is designed to measure student

  14. Alpha cluster structure in 16O

    International Nuclear Information System (INIS)

    Dias Rodrigueres, M.R.; Borello-Lewin, T.; Miyake, H.; Duarte, J.L.M.; Lima Rodrigues, C.; De Souza, M.A.; Horodynski-Matsushigue, L.B.; Neto de Faria, P.; Cappuzzello, F.; Nicolosi, D.; Bondi, M.; Carbone, D.; Tropea, S.; Cavallaro, M.; Cunsolo, A.; Agodi, C.; De Napoli, M.; Foti, A.; Ukita, G.M.

    2014-01-01

    The main purpose of the present work is the investigation of the α-cluster phenomenon in 16 O. The 12 C( 6 Li,d) 16 O reaction was measured at a bombarding energy of 25.5 MeV employing the Sao Paulo Pelletron-Enge-Spectrograph facility and the nuclear emulsion detection technique. Resonant states around 4α threshold were measured and an energy resolution of 15 keV has allowed us to define states that were previously unresolved. The angular distributions of the absolute cross sections were determined in a range of 4-40 degrees in the center of mass system. The upper limit for the resonance widths was obtained, indicating that the α cluster structure information in this region should be revised. (authors)

  15. Alpha Cluster Structure in 16O

    Science.gov (United States)

    Dias Rodrigues, Márcia Regina; Borello-Lewin, Thereza; Miyake, Hideaki; Cappuzzello, Francesco; Cavallaro, Manuela; Duarte, José Luciano Miranda; Lima Rodrigues, Cleber; de Souza, Marco Antonio; Horodynski-Matsushigue, Brighitta; Cunsolo, Angelo; Foti, Antonio; Mitsuo Ukita, Gilberto; Neto de Faria, Pedro; Agodi, Clementina; De Napoli, Marzio; Nicolosi, Dario; Bondì, Dario; Carbone, Diana; Tropea, Stefania

    2014-03-01

    The main purpose of the present work is the investigation of the α-cluster phenomenon in 16O. The 12C(6Li,d)16O reaction was measured at a bombarding energy of 25.5 MeV employing the São Paulo Pelletron-Enge-Spectrograph facility and the nuclear emulsion detection technique. Resonant states around 4α threshold were measured and an energy resolution of 15 keV allows to define states previously unresolved. The angular distributions of the absolute cross sections were determined in a range of 4-40 degree in the center of mass system. The upper limit for the resonance widths was obtained, indicating that the a cluster structure information in this region should be revised.

  16. Modified genetic algorithms to model cluster structures in medium-size silicon clusters

    International Nuclear Information System (INIS)

    Bazterra, Victor E.; Ona, Ofelia; Caputo, Maria C.; Ferraro, Marta B.; Fuentealba, Patricio; Facelli, Julio C.

    2004-01-01

    This paper presents the results obtained using a genetic algorithm (GA) to search for stable structures of medium size silicon clusters. In this work the GA uses a semiempirical energy function to find the best cluster structures, which are further optimized using density-functional theory. For small clusters our results agree well with previously reported structures, but for larger ones different structures appear. This is the case of Si 36 where we report a different structure, with significant lower energy than those previously found using limited search approaches on common structural motifs. This demonstrates the need for global optimization schemes when searching for stable structures of medium-size silicon clusters

  17. Teaching Beginning Chemistry Students Simple Lewis Dot Structures

    Science.gov (United States)

    Nassiff, Peter; Czerwinski, Wendy A.

    2015-01-01

    Students beginning their initial study of chemistry often have a difficult time mastering simple Lewis dot structures. Textbooks show students how to manipulate Lewis structures by moving valence electron dots around the chemical structure so each atom has an octet or duet. However, an easier method of teaching Lewis structures for simple…

  18. Ground-state structures of Hafnium clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Wei Chun; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technoloty, Multimedia University, Melaca Campus, 75450 Melaka (Malaysia)

    2015-04-24

    Hafnium (Hf) is a very large tetra-valence d-block element which is able to form relatively long covalent bond. Researchers are interested to search for substitution to silicon in the semi-conductor industry. We attempt to obtain the ground-state structures of small Hf clusters at both empirical and density-functional theory (DFT) levels. For calculations at the empirical level, charge-optimized many-body functional potential (COMB) is used. The lowest-energy structures are obtained via a novel global-minimum search algorithm known as parallel tempering Monte-Carlo Basin-Hopping and Genetic Algorithm (PTMBHGA). The virtue of using COMB potential for Hf cluster calculation lies in the fact that by including the charge optimization at the valence shells, we can encourage the formation of proper bond hybridization, and thus getting the correct bond order. The obtained structures are further optimized using DFT to ensure a close proximity to the ground-state.

  19. Inferring hierarchical clustering structures by deterministic annealing

    International Nuclear Information System (INIS)

    Hofmann, T.; Buhmann, J.M.

    1996-01-01

    The unsupervised detection of hierarchical structures is a major topic in unsupervised learning and one of the key questions in data analysis and representation. We propose a novel algorithm for the problem of learning decision trees for data clustering and related problems. In contrast to many other methods based on successive tree growing and pruning, we propose an objective function for tree evaluation and we derive a non-greedy technique for tree growing. Applying the principles of maximum entropy and minimum cross entropy, a deterministic annealing algorithm is derived in a meanfield approximation. This technique allows us to canonically superimpose tree structures and to fit parameters to averaged or open-quote fuzzified close-quote trees

  20. Bonding, structure and solid-state chemistry

    CERN Document Server

    Ladd, Mark

    2016-01-01

    This book is aimed at undergraduate students in both chemistry and those degree subjects in which chemistry forms a significant part. It does not reflect any particular academic year, and so finds a place during the normal span of degree studies in the physical sciences. An A-level standard in science and mathematics is presumed; additional mathematical treatments are discussed in Appendices. An introductory first chapter leads into the main subject matter, which is treated through four chapters in terms of the principle bonding forces of cohesion in the solid state; a further chapter discusses nanosize materials. Important applications of the study topics are interspersed at appropriate points within the text. Each chapter is provided with a set of problems of varying degrees of difficulty, so as to assist the reader in gaining a facility with the subject matter and its applications. The problems are supplemented by detailed tutorial solutions, some of which present additional relevant material that indicate...

  1. K-nearest uphill clustering in the protein structure space

    KAUST Repository

    Cui, Xuefeng

    2016-08-26

    The protein structure classification problem, which is to assign a protein structure to a cluster of similar proteins, is one of the most fundamental problems in the construction and application of the protein structure space. Early manually curated protein structure classifications (e.g., SCOP and CATH) are very successful, but recently suffer the slow updating problem because of the increased throughput of newly solved protein structures. Thus, fully automatic methods to cluster proteins in the protein structure space have been designed and developed. In this study, we observed that the SCOP superfamilies are highly consistent with clustering trees representing hierarchical clustering procedures, but the tree cutting is very challenging and becomes the bottleneck of clustering accuracy. To overcome this challenge, we proposed a novel density-based K-nearest uphill clustering method that effectively eliminates noisy pairwise protein structure similarities and identifies density peaks as cluster centers. Specifically, the density peaks are identified based on K-nearest uphills (i.e., proteins with higher densities) and K-nearest neighbors. To our knowledge, this is the first attempt to apply and develop density-based clustering methods in the protein structure space. Our results show that our density-based clustering method outperforms the state-of-the-art clustering methods previously applied to the problem. Moreover, we observed that computational methods and human experts could produce highly similar clusters at high precision values, while computational methods also suggest to split some large superfamilies into smaller clusters. © 2016 Elsevier B.V.

  2. Enhancing prospective chemistry teachers cognitive structures in the topics of bonding and hybridization by internet-assisted chemistry applications

    OpenAIRE

    Özge Özyalçın Oskay, Sinem Dinçol

    2011-01-01

    The purpose of this study is to determine the effects of internet-assisted chemistry applications on prospective chemistry teachers’ cognitive structures in the topics of bonding and hybridization. The sample of the study consisted of 36 prospective chemistry teachers attending Hacettepe University, Faculty of Education, the Department of Chemistry Education in 2010-2011 academic year and taking Basic Chemistry I lesson. In the study, students were separated into experimental and control gr...

  3. Structure and physical properties of silicon clusters and of vacancy clusters in bulk silicon

    International Nuclear Information System (INIS)

    Sieck, A.

    2000-01-01

    In this thesis the growth-pattern of free silicon clusters and vacancy clusters in bulk silicon is investigated. The aim is to describe and to better understand the cluster to bulk transition. Silicon structures in between clusters and solids feature new interesting physical properties. The structure and physical properties of silicon clusters can be revealed by a combination of theory and experiment, only. Low-energy clusters are determined with different optimization techniques and a density-functional based tight-binding method. Additionally, infrared and Raman spectra, and polarizabilities calculated within self-consistent field density-functional theory are provided for the smaller clusters. For clusters with 25 to 35 atoms an analysis of the shape of the clusters and the related mobilities in a buffer gas is given. Finally, the clusters observed in low-temperature experiments are identified via the best match between calculated properties and experimental data. Silicon clusters with 10 to 15 atoms have a tricapped trigonal prism as a common subunit. Clusters with up to about 25 atoms follow a prolate growth-path. In the range from 24 to 30 atoms the geometry of the clusters undergoes a transition towards compact spherical structures. Low-energy clusters with up to 240 atoms feature a bonding pattern strikingly different from the tetrahedral bonding in the solid. It follows that structures with dimensions of several Angstroem have electrical and optical properties different from the solid. The calculated stabilities and positron-lifetimes of vacancy clusters in bulk silicon indicate the positron-lifetimes of about 435 ps detected in irradiated silicon to be related to clusters of 9 or 10 vacancies. The vacancies in these clusters form neighboring hexa-rings and, therefore, minimize the number of dangling bonds. (orig.)

  4. Weighted voting-based consensus clustering for chemical structure databases

    Science.gov (United States)

    Saeed, Faisal; Ahmed, Ali; Shamsir, Mohd Shahir; Salim, Naomie

    2014-06-01

    The cluster-based compound selection is used in the lead identification process of drug discovery and design. Many clustering methods have been used for chemical databases, but there is no clustering method that can obtain the best results under all circumstances. However, little attention has been focused on the use of combination methods for chemical structure clustering, which is known as consensus clustering. Recently, consensus clustering has been used in many areas including bioinformatics, machine learning and information theory. This process can improve the robustness, stability, consistency and novelty of clustering. For chemical databases, different consensus clustering methods have been used including the co-association matrix-based, graph-based, hypergraph-based and voting-based methods. In this paper, a weighted cumulative voting-based aggregation algorithm (W-CVAA) was developed. The MDL Drug Data Report (MDDR) benchmark chemical dataset was used in the experiments and represented by the AlogP and ECPF_4 descriptors. The results from the clustering methods were evaluated by the ability of the clustering to separate biologically active molecules in each cluster from inactive ones using different criteria, and the effectiveness of the consensus clustering was compared to that of Ward's method, which is the current standard clustering method in chemoinformatics. This study indicated that weighted voting-based consensus clustering can overcome the limitations of the existing voting-based methods and improve the effectiveness of combining multiple clusterings of chemical structures.

  5. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    The chemical research and development efforts related to the design and ultimate operation of molten-salt breeder reactor systems are concentrated on fuel- and coolant-salt chemistry, including the development of analytical methods for use in these systems. The chemistry of tellurium in fuel salt is being studied to help elucidate the role of this element in the intergranular cracking of Hastelloy N. Studies were continued of the effect of oxygen-containing species on the equilibrium between dissolved UF 3 and dissolved UF 4 , and, in some cases, between the dissolved uranium fluorides and graphite, and the UC 2 . Several aspects of coolant-salt chemistry are under investigation. Hydroxy and oxy compounds that could be formed in molten NaBF 4 are being synthesized and characterized. Studies of the chemistry of chromium (III) compounds in fluoroborate melts were continued as part of a systematic investigation of the corrosion of structural alloys by coolant salt. An in-line voltammetric method for determining U 4+ /U 3+ ratios in fuel salt was tested in a forced-convection loop over a six-month period. (LK)

  6. Aggregation kinetics and structure of cryoimmunoglobulins clusters

    CERN Document Server

    De Spirito, M; Bassi, F A; Di Stasio, E; Giardina, B; Arcovito, G

    2002-01-01

    Cryoimmunoglobulins are pathological antibodies characterized by a temperature-dependent reversible insolubility. Rheumatoid factors (RF) are immunoglobulins possessing anti-immunoglobulin activity and usually consist of an IgM antibody that recognizes IgG as antigen. These proteins are present in sera of patients affected by a large variety of different pathologies, such as HCV infection, neoplastic and autoimmune diseases. Aggregation and precipitation of cryoimmunoglobulins, leading to vasculiti, are physical phenomena behind such pathologies. A deep knowledge of the physico-chemical mechanisms regulating such phenomena plays a fundamental role in biological and clinical applications. In this work, a preliminary investigation of the aggregation kinetics and of the final macro- molecular structure of the aggregates is presented. Through static light scattering techniques, the gyration radius R/sub g/ and the fractal dimension D/sub m/ of the growing clusters have been determined. However, while the initial ...

  7. NATO Advanced Research Workshop on Physics and Chemistry of Finite Systems : from Clusters to Crystals

    CERN Document Server

    Khanna, S; Rao, B

    1992-01-01

    Recent innovations in experimental techniques such as molecular and cluster beam epitaxy, supersonic jet expansion, matrix isolation and chemical synthesis are increasingly enabling researchers to produce materials by design and with atomic dimension. These materials constrained by sire, shape, and symmetry range from clusters containing as few as two atoms to nanoscale materials consisting of thousands of atoms. They possess unique structuraI, electronic, magnetic and optical properties that depend strongly on their size and geometry. The availability of these materials raises many fundamental questions as weIl as technological possibilities. From the academic viewpoint, the most pertinent question concerns the evolution of the atomic and electronic structure of the system as it grows from micro clusters to crystals. At what stage, for example, does the cluster look as if it is a fragment of the corresponding crystal. How do electrons forming bonds in micro-clusters transform to bands in solids? How do the s...

  8. Structure based alignment and clustering of proteins (STRALCP)

    Science.gov (United States)

    Zemla, Adam T.; Zhou, Carol E.; Smith, Jason R.; Lam, Marisa W.

    2013-06-18

    Disclosed are computational methods of clustering a set of protein structures based on local and pair-wise global similarity values. Pair-wise local and global similarity values are generated based on pair-wise structural alignments for each protein in the set of protein structures. Initially, the protein structures are clustered based on pair-wise local similarity values. The protein structures are then clustered based on pair-wise global similarity values. For each given cluster both a representative structure and spans of conserved residues are identified. The representative protein structure is used to assign newly-solved protein structures to a group. The spans are used to characterize conservation and assign a "structural footprint" to the cluster.

  9. Clustering of low-valence particles: structure and kinetics.

    Science.gov (United States)

    Markova, Olga; Alberts, Jonathan; Munro, Edwin; Lenne, Pierre-François

    2014-08-01

    We compute the structure and kinetics of two systems of low-valence particles with three or six freely oriented bonds in two dimensions. The structure of clusters formed by trivalent particles is complex with loops and holes, while hexavalent particles self-organize into regular and compact structures. We identify the elementary structures which compose the clusters of trivalent particles. At initial stages of clustering, the clusters of trivalent particles grow with a power-law time dependence. Yet at longer times fusion and fission of clusters equilibrates and clusters form a heterogeneous phase with polydispersed sizes. These results emphasize the role of valence in the kinetics and stability of finite-size clusters.

  10. Linkage of molecular units in the chemistry of niobium and tantalum cluster halides

    International Nuclear Information System (INIS)

    Perrin, C.; Sergent, M.

    1991-01-01

    In low valency niobium and tantalum halides, interunit linkages are observed between the (Me 6 X 12 )X 6 units. They are insulators and interesting magnetic properties are observed, due to the intrinsic potential magnetism of the Me 6 cluster and depending on the inserted cations, for instance rare earths in MM'Nb 6 Cl 18 (M = monovalent cation, M' = rare earth). Of special interest are the niobium iodides which exhibit (Me 6 X 8 )X 6 units, an exception in the niobium chemistry; interesting properties have been reported for some of these iodides

  11. Theoretical study of structures of Ga5N5 cluster

    International Nuclear Information System (INIS)

    Song Bin; Cao Peilin

    2002-01-01

    The structures and energies of a Ga 5 N 5 cluster have been calculated using a full-potential linear-muffin-tin-orbital (FP-LMTO) method, combined with molecular dynamics technique. Twenty-four structures for a Ga 5 N 5 cluster have been obtained. The most stable structure is a C 1 planar structure with a N 3 subunit. The Ga 5 N 5 clusters show a preference for a N 3 subunit, revealing the same behavior as in the Ga 3 N 3 and Ga 4 N 4 clusters. The existence of strong N-N bonds dominates the structure of a Ga 5 N 5 cluster. Through the calculation of the density of states we found that the most stable structure of Ga 5 N 5 clusters presented semiconductor-like properties

  12. Synthetic modeling chemistry of iron-sulfur clusters in nitric oxide signaling.

    Science.gov (United States)

    Fitzpatrick, Jessica; Kim, Eunsuk

    2015-08-18

    Nitric oxide (NO) is an important signaling molecule that is involved in many physiological and pathological functions. Iron-sulfur proteins are one of the main reaction targets for NO, and the [Fe-S] clusters within these proteins are converted to various iron nitrosyl species upon reaction with NO, of which dinitrosyl iron complexes (DNICs) are the most prevalent. Much progress has been made in identifying the origin of cellular DNIC generation. However, it is not well-understood which other products besides DNICs may form during [Fe-S] cluster degradation nor what effects DNICs and other degradation products can have once they are generated in cells. Even more elusive is an understanding of the manner by which cells cope with unwanted [Fe-S] modifications by NO. This Account describes our synthetic modeling efforts to identify cluster degradation products derived from the [2Fe-2S]/NO reaction in order to establish their chemical reactivity and repair chemistry. Our intent is to use the chemical knowledge that we generate to provide insight into the unknown biological consequences of cluster modification. Our recent advances in three different areas are described. First, new reaction conditions that lead to the formation of previously unrecognized products during the reaction of [Fe-S] clusters with NO are identified. Hydrogen sulfide (H2S), a gaseous signaling molecule, can be generated from the reaction between [2Fe-2S] clusters and NO in the presence of acid or formal H• (e(-)/H(+)) donors. In the presence of acid, a mononitrosyl iron complex (MNIC) can be produced as the major iron-containing product. Second, cysteine analogues can efficiently convert MNICs back to [2Fe-2S] clusters without the need for any other reagents. This reaction is possible for cysteine analogues because of their ability to labilize NO from MNICs and their capacity to undergo C-S bond cleavage, providing the necessary sulfide for [2Fe-2S] cluster formation. Lastly, unique dioxygen

  13. Recent development in clusters of rare earths and actinides. Chemistry and materials

    International Nuclear Information System (INIS)

    Zheng, Zhiping

    2017-01-01

    This book contains the following eight contributions: 1. Lanthanide Hydroxide Cluster Complexes via Ligand-Controlled Hydrolysis of the Lanthanide Ions (Zhonghao Zhang, Yanan Zhang, and Zhiping Zheng); 2. Synthesis and Structures of Lanthanide-Transition Metal Clusters (Xiu-Ying Zheng, Xiang-Jian Kong, and La-Sheng Long); 3. Hydrothermal Synthesis of Lanthanide and Lanthanide-Transition-Metal Cluster Organic Frameworks via Synergistic Coordination Strategy (Jian-Wen Cheng and Guo-Yu Yang); 4. Oxo Clusters of 5f Elements (Sarah Hickam and Peter C.); 5. Construction and Luminescence Properties of 4f and d-4f Clusters with Salen-Type Schiff Base Ligands (Xiaoping Yang, Shiqing Wang, Chengri Wang, Shaoming Huang, and Richard A.); 6. 4f-Clusters for Cryogenic Magnetic Cooling (Yan-Cong Chen, Jun-Liang Liu, and Ming-Liang Tong); 7. Lanthanide Clusters Toward Single-Molecule Magnets (Tian Han, You-Song Ding, and Yan-Zhen Zheng); 8. Molecular Rare Earth Hydride Clusters (Takanori Shima and Zhaomin Hou).

  14. Recent development in clusters of rare earths and actinides. Chemistry and materials

    Energy Technology Data Exchange (ETDEWEB)

    Zheng, Zhiping (ed.) [Arizona Univ., Tucson, AZ (United States). Dept. of Chemistry and Biochemistry

    2017-02-01

    This book contains the following eight contributions: 1. Lanthanide Hydroxide Cluster Complexes via Ligand-Controlled Hydrolysis of the Lanthanide Ions (Zhonghao Zhang, Yanan Zhang, and Zhiping Zheng); 2. Synthesis and Structures of Lanthanide-Transition Metal Clusters (Xiu-Ying Zheng, Xiang-Jian Kong, and La-Sheng Long); 3. Hydrothermal Synthesis of Lanthanide and Lanthanide-Transition-Metal Cluster Organic Frameworks via Synergistic Coordination Strategy (Jian-Wen Cheng and Guo-Yu Yang); 4. Oxo Clusters of 5f Elements (Sarah Hickam and Peter C.); 5. Construction and Luminescence Properties of 4f and d-4f Clusters with Salen-Type Schiff Base Ligands (Xiaoping Yang, Shiqing Wang, Chengri Wang, Shaoming Huang, and Richard A.); 6. 4f-Clusters for Cryogenic Magnetic Cooling (Yan-Cong Chen, Jun-Liang Liu, and Ming-Liang Tong); 7. Lanthanide Clusters Toward Single-Molecule Magnets (Tian Han, You-Song Ding, and Yan-Zhen Zheng); 8. Molecular Rare Earth Hydride Clusters (Takanori Shima and Zhaomin Hou).

  15. K-nearest uphill clustering in the protein structure space

    KAUST Repository

    Cui, Xuefeng; Gao, Xin

    2016-01-01

    The protein structure classification problem, which is to assign a protein structure to a cluster of similar proteins, is one of the most fundamental problems in the construction and application of the protein structure space. Early manually curated

  16. Geometric and electronic structures of small GaN clusters

    Energy Technology Data Exchange (ETDEWEB)

    Song Bin; Cao Peilin

    2004-08-02

    The geometric and electronic structures of Ga{sub x}N{sub y} (x+y{<=}8) clusters have been calculated using a full-potential linear-muffin-tin-orbital method, combined with molecular dynamics and simulated annealing techniques. It is found that the structures, binding energies and HOMO-LUMO gaps of these clusters strongly depend on their size and composition. The lowest energy structures of these clusters are obtained, and the trends in the geometries are discussed. The binding energy of the cluster increases as the size of cluster increases. N-rich cluster has larger binding energy than Ga-rich ones. The HOMO-LUMO gaps of these clusters are evaluated.

  17. Voting-based consensus clustering for combining multiple clusterings of chemical structures

    Directory of Open Access Journals (Sweden)

    Saeed Faisal

    2012-12-01

    Full Text Available Abstract Background Although many consensus clustering methods have been successfully used for combining multiple classifiers in many areas such as machine learning, applied statistics, pattern recognition and bioinformatics, few consensus clustering methods have been applied for combining multiple clusterings of chemical structures. It is known that any individual clustering method will not always give the best results for all types of applications. So, in this paper, three voting and graph-based consensus clusterings were used for combining multiple clusterings of chemical structures to enhance the ability of separating biologically active molecules from inactive ones in each cluster. Results The cumulative voting-based aggregation algorithm (CVAA, cluster-based similarity partitioning algorithm (CSPA and hyper-graph partitioning algorithm (HGPA were examined. The F-measure and Quality Partition Index method (QPI were used to evaluate the clusterings and the results were compared to the Ward’s clustering method. The MDL Drug Data Report (MDDR dataset was used for experiments and was represented by two 2D fingerprints, ALOGP and ECFP_4. The performance of voting-based consensus clustering method outperformed the Ward’s method using F-measure and QPI method for both ALOGP and ECFP_4 fingerprints, while the graph-based consensus clustering methods outperformed the Ward’s method only for ALOGP using QPI. The Jaccard and Euclidean distance measures were the methods of choice to generate the ensembles, which give the highest values for both criteria. Conclusions The results of the experiments show that consensus clustering methods can improve the effectiveness of chemical structures clusterings. The cumulative voting-based aggregation algorithm (CVAA was the method of choice among consensus clustering methods.

  18. Weighted similarity-based clustering of chemical structures and bioactivity data in early drug discovery.

    Science.gov (United States)

    Perualila-Tan, Nolen Joy; Shkedy, Ziv; Talloen, Willem; Göhlmann, Hinrich W H; Moerbeke, Marijke Van; Kasim, Adetayo

    2016-08-01

    The modern process of discovering candidate molecules in early drug discovery phase includes a wide range of approaches to extract vital information from the intersection of biology and chemistry. A typical strategy in compound selection involves compound clustering based on chemical similarity to obtain representative chemically diverse compounds (not incorporating potency information). In this paper, we propose an integrative clustering approach that makes use of both biological (compound efficacy) and chemical (structural features) data sources for the purpose of discovering a subset of compounds with aligned structural and biological properties. The datasets are integrated at the similarity level by assigning complementary weights to produce a weighted similarity matrix, serving as a generic input in any clustering algorithm. This new analysis work flow is semi-supervised method since, after the determination of clusters, a secondary analysis is performed wherein it finds differentially expressed genes associated to the derived integrated cluster(s) to further explain the compound-induced biological effects inside the cell. In this paper, datasets from two drug development oncology projects are used to illustrate the usefulness of the weighted similarity-based clustering approach to integrate multi-source high-dimensional information to aid drug discovery. Compounds that are structurally and biologically similar to the reference compounds are discovered using this proposed integrative approach.

  19. Anatomy of a cluster IDP. Part 2: Noble gas abundances, trace element geochemistry, isotopic abundances, and trace organic chemistry of several fragments from L2008#5

    Science.gov (United States)

    Thomas, K. L.; Clemett, S. J.; Flynn, G. J.; Keller, L. P.; Mckay, David S.; Messenger, S.; Nier, A. O.; Schlutter, D. J.; Sutton, S. R.; Walker, R. M.

    1994-01-01

    The topics discussed include the following: noble gas content and release temperatures; trace element abundances; heating summary of cluster fragments; isotopic measurements; and trace organic chemistry.

  20. The three-cluster structures in 7Li

    International Nuclear Information System (INIS)

    Beck, R.; Krivec, R.; Mihailovic, M.V.; Kernforschungszentrum Karlsruhe G.m.b.H.

    1981-01-01

    A cluster model for the description of light nuclei is investigated which includes the interplay of three-cluster structures with the two-cluster ones and allows molecule-like vibrations of clusters. It is applied to the nucleus 7 Li in order to study the influence of the trhee-cluster structures of the type ( 4 He- 2 H-n) on the low-lying states previously described by two-cluster structures ( 4 He- 3 H) and ( 6 Li-n). An effective central interaction is used in the calculation. The structure of the nucleus 7 Li is described by the two-cluster configuration ( 4 He- 3 H) and the three-cluster configurations ( 4 He- 2 H(Isub(d))-n), with Isub(d) = 0, 1, and the total spin I = 1/2, 3/2. In the wave function of three-cluster structure the pair of values L 1 = 0, L 2 = 1 only is included. The effective nuclear potential V2 of Volkov is used in the calculation. The energy of the ground state described by a single configuration of the two-cluster structure ( 4 He- 3 H) is lowered by 0.66 MeV when this configuration is coupled to two three-cluster configurations and the molecule-like vibration is allowed through solving the Hill-Wheeler equation. Both mechanism have approximately equal effects. The ground-state energy (-38.14 MeV) is 0.3 MeV lower than in the model which describes the 7 Li by a superposition of two-cluster structures ( 4 He- 3 H) and ( 6 Li-n). (orig./HSI)

  1. Equilibrium structure and atomic vibrations of Nin clusters

    Science.gov (United States)

    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.

  2. Quantum cluster algebra structures on quantum nilpotent algebras

    CERN Document Server

    Goodearl, K R

    2017-01-01

    All algebras in a very large, axiomatically defined class of quantum nilpotent algebras are proved to possess quantum cluster algebra structures under mild conditions. Furthermore, it is shown that these quantum cluster algebras always equal the corresponding upper quantum cluster algebras. Previous approaches to these problems for the construction of (quantum) cluster algebra structures on (quantized) coordinate rings arising in Lie theory were done on a case by case basis relying on the combinatorics of each concrete family. The results of the paper have a broad range of applications to these problems, including the construction of quantum cluster algebra structures on quantum unipotent groups and quantum double Bruhat cells (the Berenstein-Zelevinsky conjecture), and treat these problems from a unified perspective. All such applications also establish equality between the constructed quantum cluster algebras and their upper counterparts.

  3. A General Chemistry Experiment Incorporating Synthesis and Structural Determination

    Science.gov (United States)

    van Ryswyk, Hal

    1997-07-01

    An experiment for the general chemistry laboratory is described wherein gas chromatography-mass spectroscopy (GC-MS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) are used to characterize the products of a series of microscale reactions on vanillin. A single sophisticated instrument can be incorporated into the laboratory given sufficient attention to the use of sampling accessories and software macros. Synthetic experiments coupled with modern instrumental techniques can be used in the general chemistry laboratory to illustrate the concepts of synthesis, structure, bonding, and spectroscopy.

  4. Ionization probes of molecular structure and chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Johnson, P.M. [State Univ. of New York, Stony Brook (United States)

    1993-12-01

    Various photoionization processes provide very sensitive probes for the detection and understanding of the spectra of molecules relevant to combustion processes. The detection of ionization can be selective by using resonant multiphoton ionization or by exploiting the fact that different molecules have different sets of ionization potentials. Therefore, the structure and dynamics of individual molecules can be studied even in a mixed sample. The authors are continuing to develop methods for the selective spectroscopic detection of molecules by ionization, and to use these methods for the study of some molecules of combustion interest.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2014-04-15

    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 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

  6. Fragmentation mechanism reflecting the cluster structure of {sup 19}B

    Energy Technology Data Exchange (ETDEWEB)

    Takemoto, H.; Horiuchi, H. [Kyoto Univ., Dept. of Physics, Kyoto (Japan); Ono, A.

    1999-08-01

    Clustering structure of neutron dripline nucleus {sup 19}B which was predicted theoritically is investigated by studying the fragmentation reaction of {sup 19}B. We compare {sup 19}B fragmentation with {sup 13}B fragmentation in {sup 19}B + {sup 14}N and {sup 13}B + {sup 14}N reactions by using antisymmetrized molecular dynamics, where {sup 13}B has no clustering feature in its structure. We find that the cluster structure of the {sup 19}B nucleus is reflected in its fragmentation as the simultaneous production of He and Li isotopes. Furthermore we investigate the dependence of the cluster decay of {sup 19}B on the incident energy, and find that the cluster structure of {sup 19}B in its ground state is more reflected in lower incident-energy reactions. (author)

  7. Studies of coal structure using carbene chemistry

    Energy Technology Data Exchange (ETDEWEB)

    1990-01-01

    The object of this grant was to react coal, derivatized forms of coal, and solvent swelled coal with carbenes (divalent carbon species) under mild conditions. These carbenes were to be prepared by treating the coal with several diazo compounds and then thermally decomposing them at relatively low temperatures (80--130{degree}C). The carbenes were to be chosen to show varying selectively toward aromatic rings containing heteroatom functionalities and toward polynuclear aromatic systems. In some instances, where selectivities toward aromatic and heteroaromatic ring systems were not known, model studies were to be carried out. Because of the generally mild conditions employed and the good selectivity anticipated, and actually observed with one particular system, it was expected that this methodology would provide structural information about the coal, along with data on the extent of occurrence and type of aromatic systems. After carbene reactions, treatment of the coal samples was to include extractions and thermolysis. Physical studies included thermogravimetric analysis, diffuse reflectance FT-IR spectroscopy, NMR ({sup 1}H and {sup 13}C) spectroscopy, gas chromatography, GC/MS and GC/FT-IR. 7 figs., 10 tabs.

  8. Unraveling the atomic structure of ultrafine iron clusters

    KAUST Repository

    Wang, Hongtao

    2012-12-18

    Unraveling the atomic structures of ultrafine iron clusters is critical to understanding their size-dependent catalytic effects and electronic properties. Here, we describe the stable close-packed structure of ultrafine Fe clusters for the first time, thanks to the superior properties of graphene, including the monolayer thickness, chemical inertness, mechanical strength, electrical and thermal conductivity. These clusters prefer to take regular planar shapes with morphology changes by local atomic shuffling, as suggested by the early hypothesis of solid-solid transformation. Our observations differ from observations from earlier experimental study and theoretical model, such as icosahedron, decahedron or cuboctahedron. No interaction was observed between Fe atoms or clusters and pristine graphene. However, preferential carving, as observed by other research groups, can be realized only when Fe clusters are embedded in graphene. The techniques introduced here will be of use in investigations of other clusters or even single atoms or molecules.

  9. Coexistence of Cluster Structure and Mean-field-type Structure in Medium-weight Nuclei

    International Nuclear Information System (INIS)

    Taniguchi, Yasutaka; Horiuchi, Hisashi; Kimura, Masaaki

    2006-01-01

    We have studied the coexistence of cluster structure and mean-field-type structure in 20Ne and 40Ca using Antisymmetrized Molecular Dynamics (AMD) + Generator Coordinate Method (GCM). By energy variation with new constraint for clustering, we calculate cluster structure wave function. Superposing cluster structure wave functions and mean-field-type structure wave function, we found that 8Be-12C, α-36Ar and 12C-28Si cluster structure are important components of K π = 0 3 + band of 20Ne, that of normal deformed band of 40Ca and that of super deformed band of 40Ca, respectively

  10. The clustered nucleus-cluster structures in stable and unstable nuclei

    International Nuclear Information System (INIS)

    Freer, Martin

    2007-01-01

    The subject of clustering has a lineage which runs throughout the history of nuclear physics. Its attraction is the simplification of the often uncorrelated behaviour of independent particles to organized and coherent quasi-crystalline structures. In this review the ideas behind the development of clustering in light nuclei are investigated, mostly from the stand-point of the harmonic oscillator framework. This allows a unifying description of alpha-conjugate and neutron-rich nuclei, alike. More sophisticated models of clusters are explored, such as antisymmetrized molecular dynamics. A number of contemporary topics in clustering are touched upon; the 3α-cluster state in 12 C, nuclear molecules and clustering at the drip-line. Finally, an understanding of the 12 C+ 12 C resonances in 24 Mg, within the framework of the theoretical ideas developed in the review, is presented

  11. Progress in organic and physical chemistry structures and mechanisms

    CERN Document Server

    Zaikov, Gennady E; Lobanov, Anton V

    2013-01-01

    Progress in Organic and Physical Chemistry: Structures and Mechanisms provides a collection of new research in the field of organic and physical properties, including new research on: The physical principles of the conductivity of electrical conducting polymer compounds The dependence on constants of electromagnetic interactions upon electron spacial-energy characteristics Effects of chitosan molecultural weight on rehological behavior of chitosan modified nanoclay at hight hydrated state Bio-structural energy criteria of functional states in normal and pathological conditions Potentiometric study on the international between devalent cations and sodium carboxylates in aqueous solutions Structural characteristic changes in erythrocyte membranes of mice bearing Alzheimer's-like disease caused by the olfactory bulbetomy This volume is intended to provide an overview of new studies and research for engineers, faculty, researchers, and upper-level students in the field of organic and physical chemistry.

  12. Structure and Spectrum of Dust Coulomb Clusters

    International Nuclear Information System (INIS)

    Cheung, F.M.H.; Ford, C.; Barkby, S.; Samarian, A.A.; Vladimirov, S.V.

    2005-01-01

    In our study, the dynamics of Coulomb cluster systems were simulated for different number of particles. The spectra of energy states of dust Coulomb clusters corresponding to various packing sequences were obtained. The broadening of the spectrum due to inter-ring twist was discovered. It was found that the inter-ring twist will lead to a change in the energy spectrum of Coulomb cluster. This change was accompanied by a distortion of stable shells such that particles are able to compensate for any additional Coulomb energy (owing to the inter-ring twist) by further reducing their radial distance as much as possible. The overall effect is a change in the shape of the outer-shell from circular to elliptical

  13. The energetics and structure of nickel clusters: Size dependence

    International Nuclear Information System (INIS)

    Cleveland, C.L.; Landman, U.

    1991-01-01

    The energetics of nickel clusters over a broad size range are explored within the context of the many-body potentials obtained via the embedded atom method. Unconstrained local minimum energy configurations are found for single crystal clusters consisting of various truncations of the cube or octahedron, with and without (110) faces, as well as some monotwinnings of these. We also examine multitwinned structures such as icosahedra and various truncations of the decahedron, such as those of Ino and Marks. These clusters range in size from 142 to over 5000 atoms. As in most such previous studies, such as those on Lennard-Jones systems, we find that icosahedral clusters are favored for the smallest cluster sizes and that Marks' decahedra are favored for intermediate sizes (all our atomic systems larger than about 2300 atoms). Of course very large clusters will be single crystal face-centered-cubic (fcc) polyhedra: the onset of optimally stable single-crystal nickel clusters is estimated to occur at 17 000 atoms. We find, via comparisons to results obtained via atomistic calculations, that simple macroscopic expressions using accurate surface, strain, and twinning energies can usefully predict energy differences between different structures even for clusters of much smaller size than expected. These expressions can be used to assess the relative energetic merits of various structural motifs and their dependence on cluster size

  14. Structure-based classification and ontology in chemistry

    Directory of Open Access Journals (Sweden)

    Hastings Janna

    2012-04-01

    Full Text Available Abstract Background Recent years have seen an explosion in the availability of data in the chemistry domain. With this information explosion, however, retrieving relevant results from the available information, and organising those results, become even harder problems. Computational processing is essential to filter and organise the available resources so as to better facilitate the work of scientists. Ontologies encode expert domain knowledge in a hierarchically organised machine-processable format. One such ontology for the chemical domain is ChEBI. ChEBI provides a classification of chemicals based on their structural features and a role or activity-based classification. An example of a structure-based class is 'pentacyclic compound' (compounds containing five-ring structures, while an example of a role-based class is 'analgesic', since many different chemicals can act as analgesics without sharing structural features. Structure-based classification in chemistry exploits elegant regularities and symmetries in the underlying chemical domain. As yet, there has been neither a systematic analysis of the types of structural classification in use in chemistry nor a comparison to the capabilities of available technologies. Results We analyze the different categories of structural classes in chemistry, presenting a list of patterns for features found in class definitions. We compare these patterns of class definition to tools which allow for automation of hierarchy construction within cheminformatics and within logic-based ontology technology, going into detail in the latter case with respect to the expressive capabilities of the Web Ontology Language and recent extensions for modelling structured objects. Finally we discuss the relationships and interactions between cheminformatics approaches and logic-based approaches. Conclusion Systems that perform intelligent reasoning tasks on chemistry data require a diverse set of underlying computational

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

    Energy Technology Data Exchange (ETDEWEB)

    Arslan, Ilke [Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Dixon, David A. [Univ. of Alabama, Tuscaloosa, AL (United States); Gates, Bruce C. [Univ. of California, Davis, CA (United States); Katz, Alexander [Univ. of California, Berkeley, CA (United States)

    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-the 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

  16. Structure and properties of small sodium clusters

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Solov'yov, Andrey V.; Greiner, Walter

    2002-01-01

    and the results of other theoretical work. We have systematically calculated the optimized geometries of neutral and singly charged sodium clusters having up to 20 atoms, their multipole moments (dipole and quadrupole), static polarizabilities, binding energies per atom, ionization potentials, and frequencies...

  17. Ligand-protected gold clusters: the structure, synthesis and applications

    International Nuclear Information System (INIS)

    Pichugina, D A; Kuz'menko, N E; Shestakov, A F

    2015-01-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Au n with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au 15 and Au 25 ) and on anchorage to a support surface (Au 25 /SiO 2 , Au 20 /C, Au 10 /FeO x ) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR) n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters M x Au n L m (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR) x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active

  18. Ligand-protected gold clusters: the structure, synthesis and applications

    Science.gov (United States)

    Pichugina, D. A.; Kuz'menko, N. E.; Shestakov, A. F.

    2015-11-01

    Modern concepts of the structure and properties of atomic gold clusters protected by thiolate, selenolate, phosphine and phenylacetylene ligands are analyzed. Within the framework of the superatom theory, the 'divide and protect' approach and the structure rule, the stability and composition of a cluster are determined by the structure of the cluster core, the type of ligands and the total number of valence electrons. Methods of selective synthesis of gold clusters in solution and on the surface of inorganic composites based, in particular, on the reaction of Aun with RS, RSe, PhC≡C, Hal ligands or functional groups of proteins, on stabilization of clusters in cavities of the α-, β and γ-cyclodextrin molecules (Au15 and Au25) and on anchorage to a support surface (Au25/SiO2, Au20/C, Au10/FeOx) are reviewed. Problems in this field are also discussed. Among the methods for cluster structure prediction, particular attention is given to the theoretical approaches based on the density functional theory (DFT). The structures of a number of synthesized clusters are described using the results obtained by X-ray diffraction analysis and DFT calculations. A possible mechanism of formation of the SR(AuSR)n 'staple' units in the cluster shell is proposed. The structure and properties of bimetallic clusters MxAunLm (M=Pd, Pt, Ag, Cu) are discussed. The Pd or Pt atom is located at the centre of the cluster, whereas Ag and Cu atoms form bimetallic compounds in which the heteroatom is located on the surface of the cluster core or in the 'staple' units. The optical properties, fluorescence and luminescence of ligand-protected gold clusters originate from the quantum effects of the Au atoms in the cluster core and in the oligomeric SR(AuSR)x units in the cluster shell. Homogeneous and heterogeneous reactions catalyzed by atomic gold clusters are discussed in the context of the reaction mechanism and the nature of the active sites. The bibliography includes 345 references.

  19. Macropolyhedral boron-containing cluster chemistry [S2B16H17](-). A new eighteen-vertex thiaborane anion

    Czech Academy of Sciences Publication Activity Database

    Carr, MJ.; Clegg, W.; Kennedy, J.D.; Londesborough, Michael Geoffrey Stephen; Kilner, C. A.

    2010-01-01

    Roč. 75, č. 8 (2010), s. 807-812 ISSN 0010-0765 Institutional research plan: CEZ:AV0Z40320502 Keywords : borane cluster * thiaborane * macropolyhedral Subject RIV: CA - Inorganic Chemistry Impact factor: 0.853, year: 2010

  20. Mixed-metal cluster chemistry. 28. Core enlargement of tungsten-iridium clusters with alkynyl, ethyndiyl, and butadiyndiyl reagents.

    Science.gov (United States)

    Dalton, Gulliver T; Viau, Lydie; Waterman, Susan M; Humphrey, Mark G; Bruce, Michael I; Low, Paul J; Roberts, Rachel L; Willis, Anthony C; Koutsantonis, George A; Skelton, Brian W; White, Allan H

    2005-05-02

    Reaction of [WIr3(mu-CO)3(CO)8(eta-C5Me5)] (1c) with [W(C[triple bond]CPh)(CO)3(eta-C5H5)] afforded the edge-bridged tetrahedral cluster [W2Ir3(mu4-eta2-C2Ph)(mu-CO)(CO)9(eta-C5H5)(eta-C5Me5)] (3) and the edge-bridged trigonal-bipyramidal cluster [W3Ir3(mu4-eta2-C2Ph)(mu-eta2-C=CHPh)(Cl)(CO)8(eta-C5Me5)(eta-C5H5)2] (4) in poor to fair yield. Cluster 3 forms by insertion of [W(C[triple bond]CPh)(CO)3(eta-C5H5)] into Ir-Ir and W-Ir bonds, accompanied by a change in coordination mode from a terminally bonded alkynyl to a mu4-eta2 alkynyl ligand. Cluster 4 contains an alkynyl ligand interacting with two iridium atoms and two tungsten atoms in a mu4-eta2 fashion, as well as a vinylidene ligand bridging a W-W bond. Reaction of [WIr3(CO)11(eta-C5H5)] (1a) or 1c with [(eta-C5H5)(CO)2 Ru(C[triple bond]C)Ru(CO)2(eta-C5H5)] afforded [Ru2WIr3(mu5-eta2-C2)(mu-CO)3(CO)7(eta-C5H5)2(eta-C5R5)] [R = H (5a), Me (5c)] in low yield, a structural study of 5a revealing a WIr3 butterfly core capped and spiked by Ru atoms; the diruthenium ethyndiyl precursor has undergone Ru-C scission, with insertion of the C2 unit into a W-Ir bond of the cluster precursor. Reaction of [W2Ir2(CO)10(eta-C5H5)2] with the diruthenium ethyndiyl reagent gave [RuW2Ir2{mu4-eta2-(C2C[triple bond]C)Ru(CO)2(eta-C5H5)}(mu-CO)2(CO)6(eta-C5H5)3] (6) in low yield, a structural study of 6 revealing a butterfly W2Ir2 unit capped by a Ru(eta-C5H5) group resulting from Ru-C scission; the terminal C2 of a new ruthenium-bound butadiyndiyl ligand has been inserted into the W-Ir bond. Reaction between 1a, [WIr3(CO)11(eta-C5H4Me)] (1b), or 1c and [(eta-C5H5)(CO)3W(C[triple bond]CC[triple bond]C)W(CO)3(eta-C5H5)] afforded [W2Ir3{mu4-eta2-(C2C[triple bond]C)W(CO)3(eta-C5H5)}(mu-CO)2(CO)2(eta-C5H5)(eta-C5R5)] [R = H (7a), Me (7c); R5 = H4Me (7b)] in good yield, a structural study of 7c revealing it to be a metallaethynyl analogue of 3.

  1. Cluster structure of 20Ne and 40Ca

    International Nuclear Information System (INIS)

    Taniguchi, Yasutaka

    2004-01-01

    A d-constraint for calculating the wave functions of various kinds of configurations of cluster structure and optimizing the inside wave functions of the cluster was developed. The wave functions of various kinds of cluster structures were calculated by constraining and energy variation of the antisymmetrized molecular dynamics wave functions. The cluster structure of nucleus was reproduced by linear combination of the above wave functions by the generator coordinate method. By superposition of both wave functions calculated using d-constraint and β-constraint, K π =O 3 + rotation band of 20 Ne was reproduced. The excitation energies of 20 Ne were calculated. The result of calculation energies of α- 36 Ar structure of 40 Ca are higher values than expected them. Framework, AMD wave function, constraint, calculation results and discussions are stated. (S.Y.)

  2. Macropolyhedral boron-containing cluster chemistry. The unique nido-five-vertex-< B-2 >-nido-ten-vertex conjuncto structure of [(eta(5)-C5Me5)(2)Rh2B11H15] via an unexpected cluster-dismantling

    Czech Academy of Sciences Publication Activity Database

    Carr, MJ.; Perera, SD.; Jelínek, Tomáš; Štíbr, Bohumil; Clegg, W.; Kilner, C. A.; Kennedy, D. J.

    2007-01-01

    Roč. 34, - (2007), s. 3559-3561 ISSN 1359-7345 R&D Projects: GA ČR GA203/05/2646; GA AV ČR(CZ) IAA400320601 Grant - others:EPSRC(GB) J/56929; EPSRC(GB) GR/L/49505; EPSRC(GB) R/61949 Institutional research plan: CEZ:AV0Z40320502 Keywords : nuclear magnetic resonance Subject RIV: CA - Inorganic Chemistry Impact factor: 5.141, year: 2007

  3. Determination of the structures of small gold clusters on stepped magnesia by density functional calculations.

    Science.gov (United States)

    Damianos, Konstantina; Ferrando, Riccardo

    2012-02-21

    The structural modifications of small supported gold clusters caused by realistic surface defects (steps) in the MgO(001) support are investigated by computational methods. The most stable gold cluster structures on a stepped MgO(001) surface are searched for in the size range up to 24 Au atoms, and locally optimized by density-functional calculations. Several structural motifs are found within energy differences of 1 eV: inclined leaflets, arched leaflets, pyramidal hollow cages and compact structures. We show that the interaction with the step clearly modifies the structures with respect to adsorption on the flat defect-free surface. We find that leaflet structures clearly dominate for smaller sizes. These leaflets are either inclined and quasi-horizontal, or arched, at variance with the case of the flat surface in which vertical leaflets prevail. With increasing cluster size pyramidal hollow cages begin to compete against leaflet structures. Cage structures become more and more favourable as size increases. The only exception is size 20, at which the tetrahedron is found as the most stable isomer. This tetrahedron is however quite distorted. The comparison of two different exchange-correlation functionals (Perdew-Burke-Ernzerhof and local density approximation) show the same qualitative trends. This journal is © The Royal Society of Chemistry 2012

  4. Mo{sub 2}B{sub 4}O{sub 9} - connecting borate and metal-cluster chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, Martin K.; Huppertz, Hubert [Institut fuer Allgemeine, Anorganische und Theoretische Chemie, Universitaet Innsbruck (Austria); Janka, Oliver; Poettgen, Rainer [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Benndorf, Christopher [Institut fuer Anorganische und Analytische Chemie, Universitaet Muenster (Germany); Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Institut fuer Mineralogie, Kristallographie und Materialwissenschaften, Universitaet Leipzig (Germany); Oliveira, Marcos de Jr. [Sao Carlos Institute of Physics, University of Sao Paulo, Sao Carlos (Brazil); Eckert, Hellmut [Institut fuer Physikalische Chemie, Universitaet Muenster (Germany); Sao Carlos Institute of Physics, University of Sao Paulo, Sao Carlos (Brazil); Pielnhofer, Florian; Tragl, Amadeus-Samuel [Institut fuer Anorganische Chemie, Universitaet Regensburg (Germany); Weihrich, Richard [Institut fuer Materials Resource Management, Universitaet Augsburg (Germany); Joachim, Bastian [Institut fuer Mineralogie und Petrographie, Universitaet Innsbruck (Austria); Johrendt, Dirk [Department Chemie, Ludwig-Maximilians-Universitaet Muenchen (Germany)

    2017-06-01

    We report on the first thoroughly characterized molybdenum borate, which was synthesized in a high-pressure/high-temperature experiment at 12.3 GPa/1300 C using a Walker-type multianvil apparatus. Mo{sub 2}B{sub 4}O{sub 9} incorporates tetrahedral molybdenum clusters into an anionic borate crystal structure - a structural motif that has never been observed before in the wide field of borate crystal chemistry. The six bonding molecular orbitals of the [Mo{sub 4}] tetrahedron are completely filled with 12 electrons, which are fully delocalized over the four molybdenum atoms. This finding is in agreement with the results of the magnetic measurements, which confirmed the diamagnetic character of Mo{sub 2}B{sub 4}O{sub 9}. The two four-coordinated boron sites can be differentiated in the {sup 11}B MAS-NMR spectrum because of the strongly different degrees of local distortions. Experimentally obtained IR and Raman bands were assigned to vibrational modes based on DFT calculations. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  5. Clustering coefficient and community structure of bipartite networks

    Science.gov (United States)

    Zhang, Peng; Wang, Jinliang; Li, Xiaojia; Li, Menghui; Di, Zengru; Fan, Ying

    2008-12-01

    Many real-world networks display natural bipartite structure, where the basic cycle is a square. In this paper, with the similar consideration of standard clustering coefficient in binary networks, a definition of the clustering coefficient for bipartite networks based on the fraction of squares is proposed. In order to detect community structures in bipartite networks, two different edge clustering coefficients LC4 and LC3 of bipartite networks are defined, which are based on squares and triples respectively. With the algorithm of cutting the edge with the least clustering coefficient, communities in artificial and real world networks are identified. The results reveal that investigating bipartite networks based on the original structure can show the detailed properties that is helpful to get deep understanding about the networks.

  6. Dynamics of cluster structures in a financial market network

    Science.gov (United States)

    Kocheturov, Anton; Batsyn, Mikhail; Pardalos, Panos M.

    2014-11-01

    In the course of recent fifteen years the network analysis has become a powerful tool for studying financial markets. In this work we analyze stock markets of the USA and Sweden. We study cluster structures of a market network constructed from a correlation matrix of returns of the stocks traded in each of these markets. Such cluster structures are obtained by means of the P-Median Problem (PMP) whose objective is to maximize the total correlation between a set of stocks called medians of size p and other stocks. Every cluster structure is an undirected disconnected weighted graph in which every connected component (cluster) is a star, or a tree with one central node (called a median) and several leaf nodes connected with the median by weighted edges. Our main observation is that in non-crisis periods of time cluster structures change more chaotically, while during crises they show more stable behavior and fewer changes. Thus an increasing stability of a market graph cluster structure obtained via the PMP could be used as an indicator of a coming crisis.

  7. Structures of 38-atom gold-platinum nanoalloy clusters

    Energy Technology Data Exchange (ETDEWEB)

    Ong, Yee Pin; Yoon, Tiem Leong [School of Physics, Universiti Sains Malaysia, 11800 USM, Penang (Malaysia); Lim, Thong Leng [Faculty of Engineering and Technology, Multimedia University, Melaka Campus, 75450 Melaka (Malaysia)

    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 atoms 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.

  8. Structure and stability of small H clusters on graphene

    DEFF Research Database (Denmark)

    Sljivancanin, Zeljko; Andersen, Mie; Hammer, Bjørk

    2011-01-01

    The structure and stability of small hydrogen clusters adsorbed on graphene is studied by means of density functional theory (DFT) calculations. Clusters containing up to six H atoms are investigated systematically, with the clusters having either all H atoms on one side of the graphene sheet (cis......-clusters) or having the H atoms on both sides in an alternating manner (trans-clusters). The most stable cis-clusters found have H atoms in ortho- and para-positions with respect to each other (two H’s on neighboring or diagonally opposite carbon positions within one carbon hexagon), while the most stable trans......-clusters found have H atoms in ortho-trans-positions with respect to each other (two H’s on neighboring carbon positions, but on opposite sides of the graphene). Very stable trans-clusters with 13–22 H atoms were identified by optimizing the number of H atoms in ortho-trans-positions and thereby the number...

  9. α clustering with a hollow structure: Geometrical structure of α clusters from platonic solids to fullerene shape

    Science.gov (United States)

    Tohsaki, Akihiro; Itagaki, Naoyuki

    2018-01-01

    We study α -cluster structure based on the geometric configurations with a microscopic framework, which takes full account of the Pauli principle, and which also employs an effective internucleon force including finite-range three-body terms suitable for microscopic α -cluster models. Here, special attention is focused upon the α clustering with a hollow structure; all the α clusters are put on the surface of a sphere. All the platonic solids (five regular polyhedra) and the fullerene-shaped polyhedron coming from icosahedral structure are considered. Furthermore, two configurations with dual polyhedra, hexahedron-octahedron and dodecahedron-icosahedron, are also scrutinized. When approaching each other from large distances with these symmetries, α clusters create certain local energy pockets. As a consequence, we insist on the possible existence of α clustering with a geometric shape and hollow structure, which is favored from Coulomb energy point of view. Especially, two configurations, that is, dual polyhedra of dodecahedron-icosahedron and fullerene, have a prominent hollow structure compared with the other six configurations.

  10. STM-electroluminescence from clustered C3N4 nanodomains synthesized via green chemistry process.

    Science.gov (United States)

    Andrade, E P; Costa, B B A; Chaves, C R; de Paula, A M; Cury, L A; Malachias, A; Safar, G A M

    2018-01-01

    A Scanning Tunneling Microscopy/Spectroscopy (STM/STS) and synchrotron X-ray diffraction study on clustered C 3 N 4 nanoparticles (nanoflakes) is conducted on green-chemistry synthesized samples obtained from chitosan through high power sonication. Morphological aspects and the electronic characteristics are investigated. The observed bandgap of the nanoflakes reveals the presence of different phases in the material. Combining STM morphology, STS spectra and X-ray diffraction (XRD) results one finds that the most abundant phase is graphitic C 3 N 4 . A high density of defects is inferred from the XRD measurements. Additionally, STM-electroluminescence (STMEL) is detected in C 3 N 4 nanoflakes deposited on a gold substrate. The tunneling current creates photons that are three times more energetic than the tunneling electrons of the STM sample. We ponder about the two most probable models to explain the observed photon emission energy: either a nonlinear optical phenomenon or a localized state emission. Copyright © 2017 Elsevier B.V. All rights reserved.

  11. Flocculent and grand design spiral arm structure in cluster galaxies

    International Nuclear Information System (INIS)

    Elmegreen, D.M.

    1982-01-01

    A total of 829 spiral galaxies in 22 clusters having redshifts between z = 0.02 and 0.06 were classified according to the appearance of their spiral arm structures. The fraction of galaxies that have a grand design spiral structure was found to be higher among barred galaxies than among non-barred galaxies (at z = 0.02, 95 per cent of strongly barred galaxies have a grand design, compared with 67 per cent of non-barred or weakly barred galaxies). Cluster galaxies and distant non-cluster galaxies have the same fraction of grand design galaxies when resolution effects are considered. The grand design fraction among cluster galaxies is also similar to the fraction observed among nearby galaxies in binary systems and in groups. (author)

  12. The structure of rotational bands in alpha-cluster nuclei

    Directory of Open Access Journals (Sweden)

    Bijker Roelof

    2015-01-01

    Full Text Available In this contribution, I discuss an algebraic treatment of alpha-cluster nuclei based on the introduction of a spectrum generating algebra for the relative motion of the alpha-clusters. Particular attention is paid to the discrete symmetry of the geometric arrangement of the α-particles, and the consequences for the structure of the rotational bands in the 12C and 16O nuclei.

  13. Structural properties of silicon clusters: An empirical potential study

    International Nuclear Information System (INIS)

    Gong, X.G.; Zheng, Q.Q.; He Yizhen

    1993-09-01

    By using our newly proposed empirical interatomic potential for silicon, the structure and some dynamical properties of silicon cluster Si n (10 ≤ n ≤ 24) have been studied. It is found that the obtained results are close to those from ab-initio methods. From present results, we can gain a new insight into the understanding of the experimental data on the Si n clusters. (author). 20 refs, 6 figs

  14. Evolution of the electronic and ionic structure of Mg clusters with increase in cluster size

    DEFF Research Database (Denmark)

    Lyalin, Andrey G.; Solov'yov, Ilia; Solov'yov, Andrey V.

    2003-01-01

    The optimized structure and electronic properties of neutral and singly charged magnesium clusters have been investigated using ab initio theoretical methods based on density-functional theory and systematic post–Hartree-Fock many-body perturbation theory accounting for all electrons in the system....... We have investigated the appearance of the elements of the hcp structure and metallic evolution of the magnesium clusters, as well as the stability of linear chains and rings of magnesium atoms. The results obtained are compared with the available experimental data and the results of other...

  15. Enhancing prospective chemistry teachers cognitive structures in the topics of bonding and hybridization by internet-assisted chemistry applications

    Directory of Open Access Journals (Sweden)

    Özge Özyalçın Oskay, Sinem Dinçol

    2011-08-01

    Full Text Available The purpose of this study is to determine the effects of internet-assisted chemistry applications on prospective chemistry teachers’ cognitive structures in the topics of bonding and hybridization. The sample of the study consisted of 36 prospective chemistry teachers attending Hacettepe University, Faculty of Education, the Department of Chemistry Education in 2010-2011 academic year and taking Basic Chemistry I lesson. In the study, students were separated into experimental and control groups according to their pre-cognitive structures. Students were requested to answer two open ended questions. Answers by each student were gathered and evaluated by flow map method. “Bonding and hybridization” topics were taught to control group with traditional teaching method and to experimental group besides traditional method internet-assisted applications were conducted. The same open-ended questions were given to both groups and their cognitive structures were examined once more. The differences between control and experimental groups’ cognitive structures were examined. A significant difference was identified in favour of experimental group (p<0, 05. The mean score of the Experimental group was X=19.94, and the mean score of the Control group was X=13.88. In addition, subsequent to internet assisted chemistry applications differences in terms of concepts and descriptions in prospective chemistry teachers’ in experimental and control group cognitive structure have been determined. When post flow maps of prospective chemistry teachers in experimental group, on whom internet assisted chemistry applications were made, are formed, it has been determined that there are more statements about hybridization, hybridization types, molecule geometry and bond angles compared to control grou

  16. Modern electronic structure theory and applications in organic chemistry

    CERN Document Server

    Davidson, ER

    1997-01-01

    This volume focuses on the use of quantum theory to understand and explain experiments in organic chemistry. High level ab initio calculations, when properly performed, are useful in making quantitative distinctions between various possible interpretations of structures, reactions and spectra. Chemical reasoning based on simpler quantum models is, however, essential to enumerating the likely possibilities. The simpler models also often suggest the type of wave function likely to be involved in ground and excited states at various points along reaction paths. This preliminary understanding is n

  17. Agglomerative concentric hypersphere clustering applied to structural damage detection

    Science.gov (United States)

    Silva, Moisés; Santos, Adam; Santos, Reginaldo; Figueiredo, Eloi; Sales, Claudomiro; Costa, João C. W. A.

    2017-08-01

    The present paper proposes a novel cluster-based method, named as agglomerative concentric hypersphere (ACH), to detect structural damage in engineering structures. Continuous structural monitoring systems often require unsupervised approaches to automatically infer the health condition of a structure. However, when a structure is under linear and nonlinear effects caused by environmental and operational variability, data normalization procedures are also required to overcome these effects. The proposed approach aims, through a straightforward clustering procedure, to discover automatically the optimal number of clusters, representing the main state conditions of a structural system. Three initialization procedures are introduced to evaluate the impact of deterministic and stochastic initializations on the performance of this approach. The ACH is compared to state-of-the-art approaches, based on Gaussian mixture models and Mahalanobis squared distance, on standard data sets from a post-tensioned bridge located in Switzerland: the Z-24 Bridge. The proposed approach demonstrates more efficiency in modeling the normal condition of the structure and its corresponding main clusters. Furthermore, it reveals a better classification performance than the alternative ones in terms of false-positive and false-negative indications of damage, demonstrating a promising applicability in real-world structural health monitoring scenarios.

  18. Structure and stability of spiro-cyclic water clusters

    Indian Academy of Sciences (India)

    Administrator

    Abstract. The structure and stability of spiro-cyclic water clusters containing up to 32 water molecules have been ... due to its importance in various real life systems. 1–8. High level ... It is well-known from the crystal structure data- base that the ...

  19. Effects of Chemistry on Blunt-Body Wake Structure

    Science.gov (United States)

    Dogra, Virendra K.; Moss, James N.; Wilmoth, Richard G.; Taylor, Jeff C.; Hassan, H. A.

    1995-01-01

    Results of a numerical study are presented for hypersonic low-density flow about a 70-deg blunt cone using direct simulation Monte Carlo (DSMC) and Navier-Stokes calculations. Particular emphasis is given to the effects of chemistry on the near-wake structure and on the surface quantities and the comparison of the DSMC results with the Navier-Stokes calculations. The flow conditions simulated are those experienced by a space vehicle at an altitude of 85 km and a velocity of 7 km/s during Earth entry. A steady vortex forms in the near wake for these freestream conditions for both chemically reactive and nonreactive air gas models. The size (axial length) of the vortex for the reactive air calculations is 25% larger than that of the nonreactive air calculations. The forebody surface quantities are less sensitive to the chemistry than the base surface quantities. The presence of the afterbody has no effect on the forebody flow structure or the surface quantities. The comparisons of DSMC and Navier-Stokes calculations show good agreement for the wake structure and the forebody surface quantities.

  20. Unbiased structural search of small copper clusters within DFT

    International Nuclear Information System (INIS)

    Cogollo-Olivo, Beatriz H.; Seriani, Nicola; Montoya, Javier A.

    2015-01-01

    Highlights: • We have been able to identify novel metastable structures for small Cu clusters. • We have shown that a linear structure reported for Cu_3 is actually a local maximum. • Some of the structures reported in literature are actually unstable within DFT. • Some of the isomer structures found shows the limits of educated guesses. - Abstract: The atomic structure of small Cu clusters with 3–6 atoms has been investigated by density functional theory and random search algorithm. New metastable structures have been found that lie merely tens of meV/atom above the corresponding ground state, and could therefore be present at thermodynamic equilibrium at room temperature or slightly above. Moreover, we show that the previously proposed linear configuration for Cu_3 is in fact a local maximum of the energy. Finally, we argue that the random search algorithm also provides qualitative information about the attraction basin of each structure in the energy landscape.

  1. a Probabilistic Embedding Clustering Method for Urban Structure Detection

    Science.gov (United States)

    Lin, X.; Li, H.; Zhang, Y.; Gao, L.; Zhao, L.; Deng, M.

    2017-09-01

    Urban structure detection is a basic task in urban geography. Clustering is a core technology to detect the patterns of urban spatial structure, urban functional region, and so on. In big data era, diverse urban sensing datasets recording information like human behaviour and human social activity, suffer from complexity in high dimension and high noise. And unfortunately, the state-of-the-art clustering methods does not handle the problem with high dimension and high noise issues concurrently. In this paper, a probabilistic embedding clustering method is proposed. Firstly, we come up with a Probabilistic Embedding Model (PEM) to find latent features from high dimensional urban sensing data by "learning" via probabilistic model. By latent features, we could catch essential features hidden in high dimensional data known as patterns; with the probabilistic model, we can also reduce uncertainty caused by high noise. Secondly, through tuning the parameters, our model could discover two kinds of urban structure, the homophily and structural equivalence, which means communities with intensive interaction or in the same roles in urban structure. We evaluated the performance of our model by conducting experiments on real-world data and experiments with real data in Shanghai (China) proved that our method could discover two kinds of urban structure, the homophily and structural equivalence, which means clustering community with intensive interaction or under the same roles in urban space.

  2. Coexistence of cluster structure and superdeformation in 44Ti

    International Nuclear Information System (INIS)

    Kimura, Masaaki; Horiuchi, Hisashi

    2006-01-01

    The nucleus 44 Ti has low-lying levels of various kinds of mutually very different nuclear structure displaying the richness of the nuclear many-body dynamics. It is shown that the deformed-basis antisymmetrized molecular dynamics by the use of the Gogny D1S force reproduces successfully and unifiedly two types of coexistence phenomena in 44 Ti. Namely, on one hand, the coexistence of the mean-field structure and the cluster structure is confirmed by verifying the normally deformed structure of the K π =3 1 - band with a 1-particle-1-hole intrinsic configuration and the α+Ca40 cluster structure of the K π =0 2 - band. The mixed character of the mean-field-like structure and the α+Ca40 cluster structure of the ground band is also shown. On the other hand, the coexistence of the normal deformed mean-field and the superdeformed mean-field is confirmed by verifying the triaxial superdeformation of the K π =0 2 + band and the K π =2 1 + band which has a 4-particle-4-hole intrinsic configuration. Good reproduction of the experimental data is shown for many kinds of quantities including the energy spectra, electric transition rates, alpha spectroscopic factors. Preliminary discussions are given on the existence of hyperdeformed excited states, the relation between superdeformation and clustering and so on

  3. Coexistence of cluster structure and superdeformation in {sup 44}Ti

    Energy Technology Data Exchange (ETDEWEB)

    Kimura, Masaaki [Yukawa Institute for Theoretical Physics, Kyoto University, Kyoto 606-8502 (Japan)]. E-mail: masaaki@yukawa.kyoto-u.ac.jp; Horiuchi, Hisashi [Department of Physics, Kyoto University, Kyoto 606-8502 (Japan)

    2006-03-06

    The nucleus {sup 44}Ti has low-lying levels of various kinds of mutually very different nuclear structure displaying the richness of the nuclear many-body dynamics. It is shown that the deformed-basis antisymmetrized molecular dynamics by the use of the Gogny D1S force reproduces successfully and unifiedly two types of coexistence phenomena in {sup 44}Ti. Namely, on one hand, the coexistence of the mean-field structure and the cluster structure is confirmed by verifying the normally deformed structure of the K{sup {pi}}=3{sub 1}{sup -} band with a 1-particle-1-hole intrinsic configuration and the {alpha}+Ca40 cluster structure of the K{sup {pi}}=0{sub 2}{sup -} band. The mixed character of the mean-field-like structure and the {alpha}+Ca40 cluster structure of the ground band is also shown. On the other hand, the coexistence of the normal deformed mean-field and the superdeformed mean-field is confirmed by verifying the triaxial superdeformation of the K{sup {pi}}=0{sub 2}{sup +} band and the K{sup {pi}}=2{sub 1}{sup +} band which has a 4-particle-4-hole intrinsic configuration. Good reproduction of the experimental data is shown for many kinds of quantities including the energy spectra, electric transition rates, alpha spectroscopic factors. Preliminary discussions are given on the existence of hyperdeformed excited states, the relation between superdeformation and clustering and so on.

  4. A PROBABILISTIC EMBEDDING CLUSTERING METHOD FOR URBAN STRUCTURE DETECTION

    Directory of Open Access Journals (Sweden)

    X. Lin

    2017-09-01

    Full Text Available Urban structure detection is a basic task in urban geography. Clustering is a core technology to detect the patterns of urban spatial structure, urban functional region, and so on. In big data era, diverse urban sensing datasets recording information like human behaviour and human social activity, suffer from complexity in high dimension and high noise. And unfortunately, the state-of-the-art clustering methods does not handle the problem with high dimension and high noise issues concurrently. In this paper, a probabilistic embedding clustering method is proposed. Firstly, we come up with a Probabilistic Embedding Model (PEM to find latent features from high dimensional urban sensing data by “learning” via probabilistic model. By latent features, we could catch essential features hidden in high dimensional data known as patterns; with the probabilistic model, we can also reduce uncertainty caused by high noise. Secondly, through tuning the parameters, our model could discover two kinds of urban structure, the homophily and structural equivalence, which means communities with intensive interaction or in the same roles in urban structure. We evaluated the performance of our model by conducting experiments on real-world data and experiments with real data in Shanghai (China proved that our method could discover two kinds of urban structure, the homophily and structural equivalence, which means clustering community with intensive interaction or under the same roles in urban space.

  5. LARGE-SCALE FILAMENTARY STRUCTURES AROUND THE VIRGO CLUSTER REVISITED

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Suk; Rey, Soo-Chang; Lee, Youngdae; Lee, Woong; Chung, Jiwon [Department of Astronomy and Space Science, Chungnam National University, 99 Daehak-ro, Daejeon 305-764 (Korea, Republic of); Bureau, Martin [Sub-department of Astrophysics, Department of Physics, University of Oxford, Denys Wilkinson Building, Keble Road, Oxford OX1 3RH (United Kingdom); Yoon, Hyein; Chung, Aeree [Department of Astronomy and Yonsei University Observatory, Yonsei University, Seoul 120-749 (Korea, Republic of); Jerjen, Helmut [Research School of Astronomy and Astrophysics, The Australian National University, Cotter Road, Weston, ACT 2611 (Australia); Lisker, Thorsten [Astronomisches Rechen-Institut, Zentrum für Astronomie der Universität Heidelberg (ZAH), Mönchhofstraße 12-14, D-69120 Heidelberg (Germany); Jeong, Hyunjin; Sung, Eon-Chang, E-mail: screy@cnu.ac.kr, E-mail: star4citizen@kasi.re.kr [Korea Astronomy and Space Science institute, 776 Daedeokdae-ro, Daejeon 305-348 (Korea, Republic of)

    2016-12-20

    We revisit the filamentary structures of galaxies around the Virgo cluster, exploiting a larger data set, based on the HyperLeda database, than previous studies. In particular, this includes a large number of low-luminosity galaxies, resulting in better sampled individual structures. We confirm seven known structures in the distance range 4  h {sup −1} Mpc < SGY < 16  h {sup −1} Mpc, now identified as filaments, where SGY is the axis of the supergalactic coordinate system roughly along the line of sight. The Hubble diagram of the filament galaxies suggests they are infalling toward the main body of the Virgo cluster. We propose that the collinear distribution of giant elliptical galaxies along the fundamental axis of the Virgo cluster is smoothly connected to two of these filaments (Leo II A and B). Behind the Virgo cluster (16  h {sup −1} Mpc < SGY < 27  h {sup −1} Mpc), we also identify a new filament elongated toward the NGC 5353/4 group (“NGC 5353/4 filament”) and confirm a sheet that includes galaxies from the W and M clouds of the Virgo cluster (“W–M sheet”). In the Hubble diagram, the NGC 5353/4 filament galaxies show infall toward the NGC 5353/4 group, whereas the W–M sheet galaxies do not show hints of gravitational influence from the Virgo cluster. The filamentary structures identified can now be used to better understand the generic role of filaments in the build-up of galaxy clusters at z  ≈ 0.

  6. Probing cluster structures through sub-barrier transfer reactions

    Directory of Open Access Journals (Sweden)

    Rafferty D. C.

    2016-01-01

    Full Text Available Multinucleon transfer probabilities and excitation energy distributions have been measured in 16,18O, 19F + 208Pb at energies between 90% - 100% of the Coulomb barrier. A strong 2p2n enhancement is observed for all reactions, though most spectacularly in the 18O induced reaction. Results are interpreted in terms of the Semiclassical model, which seems to suggest α-cluster transfer in all studied systems. The relation to cluster-states in the projectile is discussed, with the experimental results consistent with previous structure studies. Dissipation of energy in the collisions of 18O is compared between different reaction modes, with cluster transfer associated with dissipation over a large number of internal states. Cluster transfer is shown to be a long range dissipation mechanism, which will inform the development of future models to treat these dynamic processes in reactions.

  7. Dilute 2α+t cluster structure in 11B

    International Nuclear Information System (INIS)

    Kawabata, T.; Akimune, H.; Fujita, H.; Fujita, Y.; Fujiwara, M.; Hara, K.; Hatanaka, K.; Itoh, M.; Kanada-En'yo, Y.; Kishi, S.; Nakanishi, K.; Sakaguchi, H.; Shimbara, Y.; Tamii, A.; Terashima, S.; Uchida, M.; Wakasa, T.; Yasuda, Y.; Yoshida, H.P.; Yosoi, M.

    2007-01-01

    The cluster structures of the excited states in 11 B are studied by analyzing the isoscalar monopole and quadrupole strengths in the 11 B(d,d') reaction at E d =200 MeV. The excitation strengths are compared with the predictions by the shell-model and antisymmetrized molecular-dynamics (AMD) calculations. It is found that the large monopole strength for the 3/2 3 - state at E x =8.56 MeV is well described by the AMD calculation and is an evidence for a developed 2α+t cluster structure

  8. Multidimensional structure of employee motivation - Clustering approach

    Science.gov (United States)

    Gąsior, Marcin; Skowron, Łukasz; Sak-Skowron, Monika

    2014-12-01

    Employees' motivation along with their satisfaction with work is one of the most significant factors determining functioning and the success of an organization on the market. The purpose of this article is to demonstrate that motivation to work is a phenomenon whose nature is different among subsequent employees not only in terms of its general level, but also internal structure, and checking whether among various possible structures of motivation there is repeatability which could prove the existence of specific regularities and enabling possible classification of employees. Reasoning with regard to internal structure of motivation was conducted on the basis of the designated 14 variables expressing it, which included both internal factors (feelings) and external (actions), both positive and negative in its meaning. The conducted research consisted in segmentation of the surveyed employees using the generalized method of k-means, in order to separate groups with the same subsequent intensity profiles, so designated variables. By way of research, five various groups of employees were found. Each has a unique, different profile of motivation, at the same time, in each of them a different satisfaction level of the employed was observed. The analysis leads to a conclusion that the motivation profile itself is not completely connected with the perceived satisfaction with work. While signs of motivation positive in nature are usually stronger among satisfied employees, and the weaker - among dissatisfied ones, we cannot speak about a similar regularity when it comes to factors of negative nature. Furthermore, the presented research shows that within negative factors, larger intensification can be observed among ones of internal nature, while among these of external nature - it is smaller.

  9. Stable structures for Al{sub 20} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Yao Changhong [Department of Physics and State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, Zhejiang 310027 (China)]. E-mail: phych@zju.edu.cn; Song Bin [Department of Physics and State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, Zhejiang 310027 (China); Cao Peilin [Department of Physics and State Key Laboratory of Silicon Materials, Zhejiang University, Hangzhou, Zhejiang 310027 (China)

    2005-06-20

    The low-lying energy structures of Al{sub 20} cluster are obtained by full-potential linear-muffin-tin-orbital molecular-dynamics (FP-LMTO-MD) method. A set of new low-lying energy structures including a new lowest energy structure, were found in our calculation. The waist-capped double icosahedral structure, which was considered as the global minimum previously, is merely one of the low-lying structures. Comparison and discussion between Al{sub 20} and Si{sub 20} have been made.

  10. Ab initio calculations and modelling of atomic cluster structure

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Lyalin, Andrey G.; Solov'yov, Andrey V.

    2004-01-01

    The optimized structure and electronic properties of small sodium and magnesium clusters have been investigated using it ab initio theoretical methods based on density-functional theory and post-Hartree-Fock many-body perturbation theory accounting for all electrons in the system. A new theoretical...

  11. A workshop report on nuclear reaction and cluster structure

    International Nuclear Information System (INIS)

    1985-01-01

    A work shop was held in June 1984 at RCNP (Research Center for Nuclear Physics), Osaka University, to discuss theory of nuclear reactions based on studies from microscopic or cluster structure viewpoints. About forty researchers participated in this work shop and 27 paperes were presented. All these papers with English abstracts are gathered in this collective report. (Aoki, K.)

  12. Electronic Structure of Au25 Clusters: Between Discrete and Continuous

    KAUST Repository

    Katsiev, Khabiboulakh

    2016-07-15

    Here, an approach based on synchrotron resonant photoemission is emplyed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states at the vicinity of the Fermi level. These observations are supported by DFT studies.

  13. Electronic Structure of Au25 Clusters: Between Discrete and Continuous

    KAUST Repository

    Katsiev, Khabiboulakh; Lozova, Nataliya; Wang, Lu; Katla, Saikrishna; Li, Ruipeng; Mei, Wai Ning; Skrabalak, Sara; Challa, Challa; Losovyj, Yaroslav

    2016-01-01

    Here, an approach based on synchrotron resonant photoemission is emplyed to explore the transition between quantization and hybridization of the electronic structure in atomically precise ligand-stabilized nanoparticles. While the presence of ligands maintains quantization in Au25 clusters, their removal renders increased hybridization of the electronic states at the vicinity of the Fermi level. These observations are supported by DFT studies.

  14. Nuclear chemistry on the Czech Technical University in Prague after introduction of structured study and foundation of the Centre for Radiochemistry and Radiation Chemistry

    International Nuclear Information System (INIS)

    John, J.

    2007-01-01

    In this presentation the author (head of the Centre for Radiochemistry and Radiation Chemistry) give a short review of history of the Department of Nuclear Chemistry and of the Centre for Radiochemistry and Radiation Chemistry of the Czech Technical University in Prague. Education in structured study in specialisation of nuclear chemistry in bachelor level, master level, as well as post-graduate study in nuclear chemistry with academic degree PhD. are realised. Some scientific results are presented

  15. Understanding surface structure and chemistry of single crystal lanthanum aluminate

    KAUST Repository

    Pramana, Stevin S.

    2017-03-02

    The surface crystallography and chemistry of a LaAlO3 single crystal, a material mainly used as a substrate to deposit technologically important thin films (e.g. for superconducting and magnetic devices), was analysed using surface X-ray diffraction and low energy ion scattering spectroscopy. The surface was determined to be terminated by Al-O species, and was significantly different from the idealised bulk structure. Termination reversal was not observed at higher temperature (600 °C) and chamber pressure of 10−10 Torr, but rather an increased Al-O occupancy occurred, which was accompanied by a larger outwards relaxation of Al from the bulk positions. Changing the oxygen pressure to 10−6 Torr enriched the Al site occupancy fraction at the outermost surface from 0.245(10) to 0.325(9). In contrast the LaO, which is located at the next sub-surface atomic layer, showed no chemical enrichment and the structural relaxation was lower than for the top AlO2 layer. Knowledge of the surface structure will aid the understanding of how and which type of interface will be formed when LaAlO3 is used as a substrate as a function of temperature and pressure, and so lead to improved design of device structures.

  16. A Structural View on Medicinal Chemistry Strategies against Drug Resistance.

    Science.gov (United States)

    Agnello, Stefano; Brand, Michael; Chellat, Mathieu F; Gazzola, Silvia; Riedl, Rainer

    2018-05-30

    The natural phenomenon of drug resistance represents a generic impairment that hampers the benefits of drugs in all major clinical indications. Antibacterials and antifungals are affected as well as compounds for the treatment of cancer, viral infections or parasitic diseases. Despite the very diverse set of biological targets and organisms involved in the development of drug resistance, underlying molecular processes have been identified to understand the emergence of resistance and to overcome this detrimental mechanism. Detailed structural information of the root causes for drug resistance is nowadays frequently available to design next generation drugs anticipated to suffer less from resistance. This knowledge-based approach is a prerequisite in the fight against the inevitable occurrence of drug resistance to secure the achievements of medicinal chemistry in the future. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. Exploring biological network structure with clustered random networks

    Directory of Open Access Journals (Sweden)

    Bansal Shweta

    2009-12-01

    Full Text Available Abstract Background Complex biological systems are often modeled as networks of interacting units. Networks of biochemical interactions among proteins, epidemiological contacts among hosts, and trophic interactions in ecosystems, to name a few, have provided useful insights into the dynamical processes that shape and traverse these systems. The degrees of nodes (numbers of interactions and the extent of clustering (the tendency for a set of three nodes to be interconnected are two of many well-studied network properties that can fundamentally shape a system. Disentangling the interdependent effects of the various network properties, however, can be difficult. Simple network models can help us quantify the structure of empirical networked systems and understand the impact of various topological properties on dynamics. Results Here we develop and implement a new Markov chain simulation algorithm to generate simple, connected random graphs that have a specified degree sequence and level of clustering, but are random in all other respects. The implementation of the algorithm (ClustRNet: Clustered Random Networks provides the generation of random graphs optimized according to a local or global, and relative or absolute measure of clustering. We compare our algorithm to other similar methods and show that ours more successfully produces desired network characteristics. Finding appropriate null models is crucial in bioinformatics research, and is often difficult, particularly for biological networks. As we demonstrate, the networks generated by ClustRNet can serve as random controls when investigating the impacts of complex network features beyond the byproduct of degree and clustering in empirical networks. Conclusion ClustRNet generates ensembles of graphs of specified edge structure and clustering. These graphs allow for systematic study of the impacts of connectivity and redundancies on network function and dynamics. This process is a key step in

  18. Structural and optical properties of Si-doped Ag clusters

    KAUST Repository

    Mokkath, Junais Habeeb

    2014-03-06

    The structural and optical properties of AgN and Ag N-1Si1 (neutral, cationic, and anionic) clusters (N = 5 to 12) are systematically investigated using the density functional based tight binding method and time-dependent density functional theory, providing insight into recent experiments. The gap between the highest occupied and lowest unoccupied molecular orbitals and therefore the optical spectrum vary significantly under Si doping, which enables flexible tuning of the chemical and optical properties of Ag clusters. © 2014 American Chemical Society.

  19. Dynamic analysis of clustered building structures using substructures methods

    International Nuclear Information System (INIS)

    Leimbach, K.R.; Krutzik, N.J.

    1989-01-01

    The dynamic substructure approach to the building cluster on a common base mat starts with the generation of Ritz-vectors for each building on a rigid foundation. The base mat plus the foundation soil is subjected to kinematic constraint modes, for example constant, linear, quadratic or cubic constraints. These constraint modes are also imposed on the buildings. By enforcing kinematic compatibility of the complete structural system on the basis of the constraint modes a reduced Ritz model of the complete cluster is obtained. This reduced model can now be analyzed by modal time history or response spectrum methods

  20. Structural and optical properties of Si-doped Ag clusters

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2014-01-01

    The structural and optical properties of AgN and Ag N-1Si1 (neutral, cationic, and anionic) clusters (N = 5 to 12) are systematically investigated using the density functional based tight binding method and time-dependent density functional theory, providing insight into recent experiments. The gap between the highest occupied and lowest unoccupied molecular orbitals and therefore the optical spectrum vary significantly under Si doping, which enables flexible tuning of the chemical and optical properties of Ag clusters. © 2014 American Chemical Society.

  1. Polyhedral boron-containing cluster chemistry: Aspects of architecture beyond the icosahedron

    Czech Academy of Sciences Publication Activity Database

    Shea, S. L.; Bould, J.; Londesborough, M. G. S.; Perea, S. D.; Franken, A.; Ormsby, D. L.; Jelínek, Tomáš; Štíbr, Bohumil; Holub, Josef; Kilner, C. A.; Thorton-Pett, M.; Kennedy, J. D.

    2003-01-01

    Roč. 75, č. 9 (2003), s. 1239-1248 ISSN 0033-4545 R&D Projects: GA MŠk LN00A028 Grant - others:UK EPRC(GB) J56929 Institutional research plan: CEZ:AV0Z4032918 Keywords : molecular chemistry * carbon hydrides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.471, year: 2003

  2. Using Cluster Analysis to Characterize Meaningful Learning in a First-Year University Chemistry Laboratory Course

    Science.gov (United States)

    Galloway, Kelli R.; Bretz, Stacey Lowery

    2015-01-01

    The Meaningful Learning in the Laboratory Instrument (MLLI) was designed to measure students' cognitive and affective learning in the university chemistry laboratory. The MLLI was administered at the beginning and the end of the first semester to first-year university chemistry students to measure their expectations and experiences for learning in…

  3. Structure of bimetallic clusters. Extended x-ray absorption fine structure (EXAFS) studies of Rh--Cu clusters

    International Nuclear Information System (INIS)

    Meitzner, G.; Via, G.H.; Lytle, F.W.; Sinfelt, J.H.

    1983-01-01

    An investigation of the structure of the bimetallic clusters present in rhodium--copper catalysts was conducted with the use of extended x-ray absorption fine structure (EXAFS) measurements. Two catalysts were studied, both employing silica as a support for the clusters and both containing 1 wt. % rhodium. In one catalyst the Cu:Rh atomic ratio was 1:2 and in the other 1:1. Studies were made of the EXAFS associated with the K absorption edges of the rhodium and copper. The results of the EXAFS studies indicate that copper concentrates at the surface of the rhodium--copper clusters. In this regard the results are similar to our earlier reported results on ruthenium--copper clusters. However, the extent of surface segregation of the copper appears to be less pronounced for rhodium--copper clusters. This result is reasonable on the basis that rhodium and copper, unlike ruthenium and copper, exhibit at least some miscibility in the bulk

  4. Structural chemistry of superconducting pnictides and pnictide oxides with layered structures

    Energy Technology Data Exchange (ETDEWEB)

    Johrendt, Dirk [Ludwig-Maximilians-Univ. Muenchen (Germany). Dept. Chemie und Biochemie; Hosono, Hideo [Tokyo Institute of Technology, Yokohama (Japan). Frontier Research Center; Hoffmann, Rolf-Dieter; Poettgen, Rainer [Muenster Univ. (Germany). Inst. fuer Anorganische und Analytische Chemie

    2011-07-01

    The basic structural chemistry of superconducting pnictides and pnictide oxides is reviewed. Crystal chemical details of selected compounds and group subgroup schemes are discussed with respect to phase transitions upon charge-density formation, the ordering of vacancies, or the ordered displacements of oxygen atoms. Furthermore, the influences of doping and solid solutions on the valence electron concentration are discussed in order to highlight the structural and electronic flexibility of these materials. (orig.)

  5. Structure and dynamics of molecular clusters. 2. Melting and freezing of CCl4 clusters

    International Nuclear Information System (INIS)

    Bartell, L.S.; Chen, Jian

    1992-01-01

    Phase transitions of a 225-molecule cluster of carbon tetrachloride have been studied by a molecular dynamics simulation. A five-site model potential function was developed to reproduce the density and heat of vaporization of the bulk liquid. Computations began with orientationally disordered molecules distributed in fcc lattice sites of a nearly spherical cluster. The cluster was heated from a low temperature to 200 K in 10-deg steps of 50 ps each and then cooled to 10 K. Translational and rotational transitions were monitored by following several indicators including the translational and rotational diffusion and rotational entropies of individual molecules. Melting began at the surface and propagated inward as the temperature increased. Solidification of the molten cluster proceeded from the center to the surface. At the high cooling rate of the simulation, however, molecules were unable to organize into a crystalline array and solidified into a glassy structure instead. Except for spatial order, the indicators of degree of liquefaction exhibited almost the same temperature dependence in the crystsl → liquid as in the liquid → glass transition, a behavior that could be rationalized on the basis of Lindemann's theory of melting. Results were compared with predictions of an illustrative model due to Reiss, Mirabel, and Whetten. Qualitatively, the model included all of the features of the simulation. Quantitatively, the model grossly underestimated the range over which the melting transition took place. 40 refs., 10 figs., 1 tab

  6. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1976-01-01

    Research progress is reported in programs on fuel-salt chemistry, properties of compounds in the Li--Te system, Te spectroscopy UF 4 --H equilibria, porous electrode studies of molten salts, fuel salt-coolant salt reactions, thermodynamic properties of transition-metal fluorides, and properties of sodium fluoroborate. Developmental work on analytical methods is summarized including in-line analysis of molten MSBR fuel, analysis of coolant-salts for tritium, analysis of molten LiF--BeF 2 --ThF 4 for Fe and analysis of LiF--BeF--ThF 4 for Te

  7. From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry.

    Science.gov (United States)

    Müller, Achim; Gouzerh, Pierre

    2012-11-21

    Following Nature's lessons, today chemists can cross the boundary of the small molecule world to construct multifunctional and highly complex molecular nano-objects up to protein size and even cell-like nanosystems showing responsive sensing. Impressive examples emerge from studies of the solutions of some oxoanions of the early transition metals especially under reducing conditions which enable the controlled linking of metal-oxide building blocks. The latter are available from constitutional dynamic libraries, thus providing the option to generate multifunctional unique nanoscale molecular systems with exquisite architectures, which even opens the way towards adaptive and evolutive (Darwinian) chemistry. The present review presents the first comprehensive report of current knowledge (including synthesis aspects not discussed before) regarding the related giant metal-oxide clusters mainly of the type {Mo(57)M'(6)} (M' = Fe(III), V(IV)) (torus structure), {M(72)M'(30)} (M = Mo, M' = V(IV), Cr(III), Fe(III), Mo(V)), {M(72)Mo(60)} (M = Mo, W) (Keplerates), {Mo(154)}, {Mo(176)}, {Mo(248)} ("big wheels"), and {Mo(368)} ("blue lemon") - all having the important transferable pentagonal {(M)M(5)} groups in common. These discoveries expanded the frontiers of inorganic chemistry to the mesoscopic world, while there is probably no collection of discrete inorganic compounds which offers such a versatile chemistry and the option to study new phenomena of interdisciplinary interest. The variety of different properties of the sphere- and wheel-type metal-oxide-based clusters can directly be related to their unique architectures: The spherical Keplerate-type capsules having 20 crown-ether-type pores and tunable internal functionalities allow the investigation of confined matter as well as that of sphere-surface-supramolecular and encapsulation chemistry - including related new aspects of the biologically important hydrophobic effects - but also of nanoscale ion transport and

  8. Chemistry and structure of giant molecular clouds in energetic environments

    Science.gov (United States)

    Anderson, Crystal Nicole

    2016-09-01

    Throughout the years many studies on Galactic star formation have been conducted. This resulted in the idea that giant molecular clouds (GMCs) are hierarchical in nature with substructures spanning a large range of sizes. The physical processes that determine how molecular clouds fragment, form clumps/cores and then stars depends strongly on both recent radiative and mechanical feed- back from massive stars and, on longer term, from enhanced cooling due to the buildup of metals. Radiative and mechanical energy input from stellar populations can alter subsequent star formation over a large part of a galaxy and hence is relevant to the evolution of galaxies. Much of our knowledge of star formation on galaxy wide scales is based on scaling laws and other parametric descriptions. But to understand the overall evolution of star formation in galaxies we need to watch the feedback processes at work on giant molecular cloud (GMC) scales. By doing this we can begin to answer how strong feedback environments change the properties of the substructure in GMCs. Tests of Galactic star formation theory to other galaxies has been a challenging process due to the lack of resolution with current instruments. Thus, only the nearest galaxies allow us to resolve GMCs and their substructures. The Large Magellanic Cloud (LMC), is one of the closest low metallicity dwarf galaxies (D˜ 50 kpc) and is close enough that current instruments can resolve the sub- structure of its GMCs to molecular gas tracers (e.g. HCO+, HCN, HNC, CS, C2H, N2H+) detected in the LMC at 1.5-40 pc scales and in NGC 5253 at 40 pc scales. I then compare the molecular gas detections to the Central Molecular Zone in our Galaxy. Dense molecular gas was detected in all of the sources. For the regions in the LMC, molecular lines of CS, N2H+, C 2H, HNC, HCO+ and HCN were all detected in N159W and N113 while only HCN, HCO+, HNC, and C2H were detected in 30Dor-10. Toward NGC 5253 only HCO+, HCN, C2H and CS were detected. I

  9. Beyond Low-Rank Representations: Orthogonal clustering basis reconstruction with optimized graph structure for multi-view spectral clustering.

    Science.gov (United States)

    Wang, Yang; Wu, Lin

    2018-07-01

    Low-Rank Representation (LRR) is arguably one of the most powerful paradigms for Multi-view spectral clustering, which elegantly encodes the multi-view local graph/manifold structures into an intrinsic low-rank self-expressive data similarity embedded in high-dimensional space, to yield a better graph partition than their single-view counterparts. In this paper we revisit it with a fundamentally different perspective by discovering LRR as essentially a latent clustered orthogonal projection based representation winged with an optimized local graph structure for spectral clustering; each column of the representation is fundamentally a cluster basis orthogonal to others to indicate its members, which intuitively projects the view-specific feature representation to be the one spanned by all orthogonal basis to characterize the cluster structures. Upon this finding, we propose our technique with the following: (1) We decompose LRR into latent clustered orthogonal representation via low-rank matrix factorization, to encode the more flexible cluster structures than LRR over primal data objects; (2) We convert the problem of LRR into that of simultaneously learning orthogonal clustered representation and optimized local graph structure for each view; (3) The learned orthogonal clustered representations and local graph structures enjoy the same magnitude for multi-view, so that the ideal multi-view consensus can be readily achieved. The experiments over multi-view datasets validate its superiority, especially over recent state-of-the-art LRR models. Copyright © 2018 Elsevier Ltd. All rights reserved.

  10. Unbiased structural search of small copper clusters within DFT

    Energy Technology Data Exchange (ETDEWEB)

    Cogollo-Olivo, Beatriz H., E-mail: bcogolloo@unicartagena.edu.co [Maestría en Ciencias Físicas, Universidad de Cartagena, 130001 Cartagena de Indias, Bolívar (Colombia); Seriani, Nicola, E-mail: nseriani@ictp.it [Condensed Matter and Statistical Physics Section, The Abdus Salam ICTP, Strada Costiera 11, 34151 Trieste (Italy); Montoya, Javier A., E-mail: jmontoyam@unicartagena.edu.co [Instituto de Matemáticas Aplicadas, Universidad de Cartagena, 130001 Cartagena de Indias, Bolívar (Colombia); Associates Program, The Abdus Salam ICTP, Strada Costiera 11, 34151 Trieste (Italy)

    2015-11-05

    Highlights: • We have been able to identify novel metastable structures for small Cu clusters. • We have shown that a linear structure reported for Cu{sub 3} is actually a local maximum. • Some of the structures reported in literature are actually unstable within DFT. • Some of the isomer structures found shows the limits of educated guesses. - Abstract: The atomic structure of small Cu clusters with 3–6 atoms has been investigated by density functional theory and random search algorithm. New metastable structures have been found that lie merely tens of meV/atom above the corresponding ground state, and could therefore be present at thermodynamic equilibrium at room temperature or slightly above. Moreover, we show that the previously proposed linear configuration for Cu{sub 3} is in fact a local maximum of the energy. Finally, we argue that the random search algorithm also provides qualitative information about the attraction basin of each structure in the energy landscape.

  11. Cluster shell model: I. Structure of 9Be, 9B

    Science.gov (United States)

    Della Rocca, V.; Iachello, F.

    2018-05-01

    We calculate energy spectra, electromagnetic transition rates, longitudinal and transverse electron scattering form factors and log ft values for beta decay in 9Be, 9B, within the framework of a cluster shell model. By comparing with experimental data, we find strong evidence for the structure of these nuclei to be two α-particles in a dumbbell configuration with Z2 symmetry, plus an additional nucleon.

  12. The Logical and Psychological Structure of Physical Chemistry and Its Relevance to the Organization/Sequencing of the Major Areas Covered in Physical Chemistry Textbooks

    Science.gov (United States)

    Tsaparlis, Georgios

    2014-01-01

    Jensen's scheme for the logical structure of chemistry is taken as reference to study the logical structure of physical chemistry. The scheme distinguishes three dimensions (composition and structure, energy, and time), with each dimension treated at one of the three levels (molar, molecular, and electrical). Such a structure places the outer…

  13. Structural Parameters of Star Clusters: Signal to Noise Effects

    Directory of Open Access Journals (Sweden)

    Narbutis D.

    2015-09-01

    Full Text Available We study the impact of photometric signal to noise on the accuracy of derived structural parameters of unresolved star clusters using MCMC model fitting techniques. Star cluster images were simulated as a smooth surface brightness distribution following a King profile convolved with a point spread function. The simulation grid was constructed by varying the levels of sky background and adjusting the cluster’s flux to a specified signal to noise. Poisson noise was introduced to a set of cluster images with the same input parameters at each node of the grid. Model fitting was performed using “emcee” algorithm. The presented posterior distributions of the parameters illustrate their uncertainty and degeneracies as a function of signal to noise. By defining the photometric aperture containing 80% of the cluster’s flux, we find that in all realistic sky background level conditions a signal to noise ratio of ~50 is necessary to constrain the cluster’s half-light radius to an accuracy better than ~20%. The presented technique can be applied to synthetic images simulating various observations of extragalactic star clusters.

  14. A microgrid cluster structure and its autonomous coordination control strategy

    DEFF Research Database (Denmark)

    Zhou, Xiaoping; Zhou, Leming; Chen, Yandong

    2018-01-01

    This paper proposes a microgrid cluster structure and its autonomous coordination control strategy. Unlike existing microgrids that are purely AC or DC, the microgrid cluster studied here is an interconnected system with multiple AC and DC microgrids, which enables mutual power support among...... control method combining the normalized droop-based control and adaptive control is proposed for PEU, which can effectively realize mutual power support among microgrids and reduce the bus voltage or frequency deviation in microgrids. In addition, the adaptive control strategy of PEU can ensure...... that the bigger the normalized index of microgrid is, the larger the active power exchange coefficient is, which can make all of microgrids operate around the rated state as much as possible. Besides, EP is mainly used to balance the system power, and the hierarchical coordinated control method of EP is proposed...

  15. Fine structure in the cluster decays of the translead nuclei

    International Nuclear Information System (INIS)

    Dumitrescu, O.; Cioaca, C.

    1994-06-01

    Within the one level R-matrix approach several hindrance factors for the radioactive decays in which are emitted α and other nuclei (such as 14 C and 20 O) are calculated. The interior wave functions are supposed to be given by the shell model with effective residual interactions. The exterior wave functions are calculated from a cluster - nucleus double - folding model potential with the M3Y interaction. As examples of the cluster decay fine structure we analyzed the particular cases of α - decay of 255 Fm, 14 C - decay of 223 Ra and 20 O - decay of 229 Th and 225 Fm. Good agreement with the experimental data is obtained. (author). 38 refs, 6 tabs

  16. NoFold: RNA structure clustering without folding or alignment.

    Science.gov (United States)

    Middleton, Sarah A; Kim, Junhyong

    2014-11-01

    Structures that recur across multiple different transcripts, called structure motifs, often perform a similar function-for example, recruiting a specific RNA-binding protein that then regulates translation, splicing, or subcellular localization. Identifying common motifs between coregulated transcripts may therefore yield significant insight into their binding partners and mechanism of regulation. However, as most methods for clustering structures are based on folding individual sequences or doing many pairwise alignments, this results in a tradeoff between speed and accuracy that can be problematic for large-scale data sets. Here we describe a novel method for comparing and characterizing RNA secondary structures that does not require folding or pairwise alignment of the input sequences. Our method uses the idea of constructing a distance function between two objects by their respective distances to a collection of empirical examples or models, which in our case consists of 1973 Rfam family covariance models. Using this as a basis for measuring structural similarity, we developed a clustering pipeline called NoFold to automatically identify and annotate structure motifs within large sequence data sets. We demonstrate that NoFold can simultaneously identify multiple structure motifs with an average sensitivity of 0.80 and precision of 0.98 and generally exceeds the performance of existing methods. We also perform a cross-validation analysis of the entire set of Rfam families, achieving an average sensitivity of 0.57. We apply NoFold to identify motifs enriched in dendritically localized transcripts and report 213 enriched motifs, including both known and novel structures. © 2014 Middleton and Kim; Published by Cold Spring Harbor Laboratory Press for the RNA Society.

  17. Tug of war between AO-hybridization and aromaticity in dictating structures of Li-doped alkali clusters

    Science.gov (United States)

    Alexandrova, Anastassia N.

    2012-04-01

    Hybridization of atomic orbitals is a widely appreciated phenomenon in organic chemistry. Here, we demonstrate that hybridization also can dramatically impact the shapes of small all-alkali metal clusters, and oppose σ-aromaticity in defining cluster shapes. The valence-iso-electronic LiNa4- and LiK4- clusters adopt different global minimum structures: LiNa4- is a planar C2v (1A1) species distorted from the perfect pentagon, and LiK4- is a planar square D4h (1A1g) species with Li being in the centre. This effect is rooted in the different degrees of the 2s-2p hybridization in Li in response to binding to Na versus K.

  18. Structure and energetics of clusters relevant to thorium tetrachloride melts

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Tosi, M.P.

    2000-08-01

    We study within an ionic model the structure and the energetics of neutral and charged clusters which may exist as structural units in molten ThCl 4 and in its liquid mixtures with alkali chlorides, with reference to Raman scattering experiments by Photiadis and Papatheodorou. As stressed by these authors, the most striking facts for ThCl 4 in comparison with other tetrachlorides (and in particular with ZrCl 4 ) are the appreciable ionic conductivity of the pure melt and the continuous structural changes which occur in the melt mixtures with varying composition. After adjusting our model to data on the isolated ThCl 4 tetrahedral molecule, we evaluate (i) the Th 2 Cl 8 dimer and the singly charged species obtained by chlorine-ion transfer between two such neutral dimers; (ii) the ThCl 6 and ThCl 7 clusters both as charged anions and as alkali -compensated species; and (iii) various oligomers carrying positive or negative double charges. Our study shows that the characteristic structural properties of the ThCl 4 compound and of the alkali-Th chloride systems are the consequence of the relatively high ionic character of the binding, which is already evident in the isolated ThCl 4 molecular monomer. (author)

  19. Ligand induced structural isomerism in phosphine coordinated gold clusters revealed by ion mobility mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Ligare, Marshall R.; Baker, Erin M.; Laskin, Julia; Johnson, Grant E.

    2017-01-01

    Structural isomerism in ligated gold clusters is revealed using electrospray ionization ion mobility spectrometry mass spectrometry. Phosphine ligated Au8 clusters are shown to adopt more “extended” type structures with increasing exchange of methyldiphenylphosphine (MePPh2) for triphenylphosphine (PPh3). These ligand-dependant structure-property relationships are critical to applications of clusters in catalysis.

  20. Chemistry

    International Nuclear Information System (INIS)

    Ferris, L.M.

    1975-01-01

    Research and development activities dealing with the chemical problems related to design and ultimate operation of molten-salt reactor systems are described. An experimental test stand was constructed to expose metallurgical test specimens to Te 2 vapor at defined temperatures and deposition rates. To better define the chemistry of fluoroborate coolant, several aspects are being investigated. The behavior of hydroxy and oxy compounds in molten NaBF 4 is being investigated to define reactions and compounds that may be involved in corrosion and/or could be involved in methods for trapping tritium. Two corrosion products of Hastelloy N, Na 3 CrF 6 and Na 5 Cr 3 F 14 , were identified from fluoroborate systems. The evaluation of fluoroborate and alternate coolants continued. Research on the behavior of hydrogen and its isotopes is summarized. The solubilities of hydrogen, deuterium, and helium in Li 2 BeF 4 are very low. The sorption of tritium on graphite was found to be significant (a few milligrams of tritium per kilogram of graphite), possibly providing a means of sequestering a portion of the tritium produced. Development of analytical methods continued with emphasis on voltammetric and spectrophotometric techniques for the in-line analysis of corrosion products such as Fe 2+ and Cr 3+ and the determination of the U 3+ /U 4+ ratio in MSBR fuel salt. Similar studies were conducted with the NaBF 4 --NaF coolant salt. Information developed during the previous operation of the CSTF has been assessed and used to formulate plans for evaluation of in-line analytical methods in future CSTF operations. Electroanalytical and spectrophotometric research suggests that an electroactive protonic species is present in molten NaBF 4 --NaF, and that this species rapidly equilibrates with a volatile proton-containing species. Data obtained from the CSTF indicated that tritium was concentrated in the volatile species. (JGB)

  1. PSPP: a protein structure prediction pipeline for computing clusters.

    Directory of Open Access Journals (Sweden)

    Michael S Lee

    2009-07-01

    Full Text Available Protein structures are critical for understanding the mechanisms of biological systems and, subsequently, for drug and vaccine design. Unfortunately, protein sequence data exceed structural data by a factor of more than 200 to 1. This gap can be partially filled by using computational protein structure prediction. While structure prediction Web servers are a notable option, they often restrict the number of sequence queries and/or provide a limited set of prediction methodologies. Therefore, we present a standalone protein structure prediction software package suitable for high-throughput structural genomic applications that performs all three classes of prediction methodologies: comparative modeling, fold recognition, and ab initio. This software can be deployed on a user's own high-performance computing cluster.The pipeline consists of a Perl core that integrates more than 20 individual software packages and databases, most of which are freely available from other research laboratories. The query protein sequences are first divided into domains either by domain boundary recognition or Bayesian statistics. The structures of the individual domains are then predicted using template-based modeling or ab initio modeling. The predicted models are scored with a statistical potential and an all-atom force field. The top-scoring ab initio models are annotated by structural comparison against the Structural Classification of Proteins (SCOP fold database. Furthermore, secondary structure, solvent accessibility, transmembrane helices, and structural disorder are predicted. The results are generated in text, tab-delimited, and hypertext markup language (HTML formats. So far, the pipeline has been used to study viral and bacterial proteomes.The standalone pipeline that we introduce here, unlike protein structure prediction Web servers, allows users to devote their own computing assets to process a potentially unlimited number of queries as well as perform

  2. Gold cluster carbonyls: saturated adsorption of CO on gold cluster cations, vibrational spectroscopy, and implications for their structures.

    Science.gov (United States)

    Fielicke, André; von Helden, Gert; Meijer, Gerard; Pedersen, David B; Simard, Benoit; Rayner, David M

    2005-06-15

    We report on the interaction of carbon monoxide with cationic gold clusters in the gas phase. Successive adsorption of CO molecules on the Au(n)(+) clusters proceeds until a cluster size specific saturation coverage is reached. Structural information for the bare gold clusters is obtained by comparing the saturation stoichiometry with the number of available equivalent sites presented by candidate structures of Au(n)(+). Our findings are in agreement with the planar structures of the Au(n)(+) cluster cations with n < or = 7 that are suggested by ion mobility experiments [Gilb, S.; Weis, P.; Furche, F.; Ahlrichs, R.; Kappes, M. M. J. Chem. Phys. 2001, 116, 4094]. By inference we also establish the structure of the saturated Au(n)(CO)(m)(+) complexes. In certain cases we find evidence suggesting that successive adsorption of CO can distort the metal cluster framework. In addition, the vibrational spectra of the Au(n)(CO)(m)(+) complexes in both the CO stretching region and in the region of the Au-C stretch and the Au-C-O bend are measured using infrared photodepletion spectroscopy. The spectra further aid in the structure determination of Au(n)(+), provide information on the structure of the Au(n)(+)-CO complexes, and can be compared with spectra of CO adsorbates on deposited clusters or surfaces.

  3. Human population structure detection via multilocus genotype clustering

    Directory of Open Access Journals (Sweden)

    Starmer Joshua

    2007-06-01

    Full Text Available Abstract Background We describe a hierarchical clustering algorithm for using Single Nucleotide Polymorphism (SNP genetic data to assign individuals to populations. The method does not assume Hardy-Weinberg equilibrium and linkage equilibrium among loci in sample population individuals. Results We show that the algorithm can assign sample individuals highly accurately to their corresponding ethnic groups in our tests using HapMap SNP data and it is also robust to admixed populations when tested with Perlegen SNP data. Moreover, it can detect fine-scale population structure as subtle as that between Chinese and Japanese by using genome-wide high-diversity SNP loci. Conclusion The algorithm provides an alternative approach to the popular STRUCTURE program, especially for fine-scale population structure detection in genome-wide association studies. This is the first successful separation of Chinese and Japanese samples using random SNP loci with high statistical support.

  4. Using Structure-Based Organic Chemistry Online Tutorials with Automated Correction for Student Practice and Review

    Science.gov (United States)

    O'Sullivan, Timothy P.; Hargaden, Gra´inne C.

    2014-01-01

    This article describes the development and implementation of an open-access organic chemistry question bank for online tutorials and assessments at University College Cork and Dublin Institute of Technology. SOCOT (structure-based organic chemistry online tutorials) may be used to supplement traditional small-group tutorials, thereby allowing…

  5. An Analysis of Prospective Chemistry Teachers' Cognitive Structures through Flow Map Method: The Subject of Oxidation and Reduction

    Science.gov (United States)

    Temel, Senar

    2016-01-01

    This study aims to analyse prospective chemistry teachers' cognitive structures related to the subject of oxidation and reduction through a flow map method. Purposeful sampling method was employed in this study, and 8 prospective chemistry teachers from a group of students who had taken general chemistry and analytical chemistry courses were…

  6. Structure and Mobility of Metal Clusters in MOFs: Au, Pd, and AuPd Clusters in MOF-74

    DEFF Research Database (Denmark)

    Vilhelmsen, Lasse; Walton, Krista S.; Sholl, David S.

    2012-01-01

    is just as important for nanocluster adsorption as open Zn or Mg metal sites. Using the large number of clusters generated by the GA, we developed a systematic method for predicting the mobility of adsorbed clusters. Through the investigation of diffusion paths a relationship between the cluster......Understanding the adsorption and mobility of metal–organic framework (MOF)-supported metal nanoclusters is critical to the development of these catalytic materials. We present the first theoretical investigation of Au-, Pd-, and AuPd-supported clusters in a MOF, namely MOF-74. We combine density...... functional theory (DFT) calculations with a genetic algorithm (GA) to reliably predict the structure of the adsorbed clusters. This approach allows comparison of hundreds of adsorbed configurations for each cluster. From the investigation of Au8, Pd8, and Au4Pd4 we find that the organic part of the MOF...

  7. Structural material anomaly detection system using water chemistry data

    International Nuclear Information System (INIS)

    Asakura, Yamato; Nagase, Makoto; Uchida, Shunsuke; Ohsumi, Katsumi.

    1992-01-01

    The concept of an advanced water chemistry diagnosis system for detection of anomalies and preventive maintenance of system components is proposed and put into a concrete form. Using the analogy to a medical inspection system, analyses of water chemistry change will make it possible to detect symptoms of anomalies in system components. Then, correlations between water chemistry change and anomaly occurrence in the components of the BWR primary cooling system are analyzed theoretically. These fragmentary correlations are organized and reduced to an algorithm for the on-line diagnosis system using on-line monitoring data, pH and conductivity. By using actual plant data, the on-line diagnosis model system is verified to be applicable for early and automatic finding of the anomaly cause and for timely supply of much diagnostic information to plant operators. (author)

  8. Functional clustering in hippocampal cultures: relating network structure and dynamics

    International Nuclear Information System (INIS)

    Feldt, S; Dzakpasu, R; Olariu, E; Żochowski, M; Wang, J X; Shtrahman, E

    2010-01-01

    In this work we investigate the relationship between gross anatomic structural network properties, neuronal dynamics and the resultant functional structure in dissociated rat hippocampal cultures. Specifically, we studied cultures as they developed under two conditions: the first supporting glial cell growth (high glial group), and the second one inhibiting it (low glial group). We then compared structural network properties and the spatio-temporal activity patterns of the neurons. Differences in dynamics between the two groups could be linked to the impact of the glial network on the neuronal network as the cultures developed. We also implemented a recently developed algorithm called the functional clustering algorithm (FCA) to obtain the resulting functional network structure. We show that this new algorithm is useful for capturing changes in functional network structure as the networks evolve over time. The FCA detects changes in functional structure that are consistent with expected dynamical differences due to the impact of the glial network. Cultures in the high glial group show an increase in global synchronization as the cultures age, while those in the low glial group remain locally synchronized. We additionally use the FCA to quantify the amount of synchronization present in the cultures and show that the total level of synchronization in the high glial group is stronger than in the low glial group. These results indicate an interdependence between the glial and neuronal networks present in dissociated cultures

  9. Galaxy clusters, type Ia supernovae and the fine structure constant

    Energy Technology Data Exchange (ETDEWEB)

    Holanda, R.F.L. [Departamento de Física, Universidade Estadual da Paraíba, street Baraúnas, Campina Grande, PB, 58429-500 (Brazil); Busti, V.C. [Departamento de Física Matemática, Instituto de Física, Universidade de São Paulo, CP 66318, São Paulo, SP, CEP 05508-090 Brazil (Brazil); Colaço, L.R. [Departamento de Física, Universidade Federal de Campina Grande, street Aprígio Veloso, Campina Grande, PB, 58429-900 (Brazil); Alcaniz, J.S. [Observatório Nacional, Street José Cristino, Rio de Janeiro, RJ, 20921-400 (Brazil); Landau, S.J., E-mail: holanda@uepb.edu.br, E-mail: viniciusbusti@gmail.com, E-mail: colacolrc@gmail.com, E-mail: alcaniz@on.br, E-mail: slandau@df.uba.ar [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Viamonte, Buenos Aires, 1053 Argentina (Argentina)

    2016-08-01

    As is well known, measurements of the Sunyaev-Zeldovich effect can be combined with observations of the X-ray surface brightness of galaxy clusters to estimate the angular diameter distance to these structures. In this paper, we show that this technique depends on the fine structure constant, α. Therefore, if α is a time-dependent quantity, e.g., α = α{sub 0}φ( z ), where φ is a function of redshift, we argue that current data do not provide the real angular diameter distance, D {sub A}( z ), to the cluster, but instead D {sub A}{sup data}( z ) = φ( z ){sup 2} D {sub A}( z ). We use this result to derive constraints on a possible variation of α for a class of dilaton runaway models considering a sample of 25 measurements of D {sub A}{sup data}( z ) in redshift range 0.023 < z < 0.784 and estimates of D {sub A}( z ) from current type Ia supernovae observations. We find no significant indication of variation of α with the present data.

  10. Electronic structure of Ni-- and Ni2--ethylene cluster complexes

    International Nuclear Information System (INIS)

    Basch, H.; Newton, M.D.; Moskowitz, J.W.

    1978-01-01

    The electronic structure of metal cluster--ethylene complexes has been investigated by carrying out ab initio bonding pair-correlated, self-consistent field, and configuration interaction (CI) calculations on the NiC 2 H 4 and Ni 2 C 2 H 4 species. The π-NiC 2 H 4 and π-Ni 2 C 2 H 4 cluster complexes are found to be bound, the former only with CI, while disigma-Ni 2 C 2 H 4 has only a repulsive Ni 2 --C 2 H 4 ground state potential curve. The bonding in the π-type cluster complexes can be described as follows: The metal atom configuration is 3d 9 4s 1 with the 4s hybridized (by the metal 4p) away from the ethylene molecule, thereby allowing the π orbital to form a dative sigma bond with the metal atom. The bonding interaction is promoted by the presence of a second nickel atom behind the first one, leading to a 4s orbital electron deficiency of the bonded nickel atom and thus making this nickel atom a better electron acceptor. Back donation from the occupied metal 3d into the ethylene π* molecular orbital also takes place to some extent, and thus both features of the classical Dewar--Chatt--Duncanson model are observed. The π-Ni 2 C 2 H 4 species is analyzed in terms of the addition of a bare nickel atom to a π-NiC 2 H 4 cluster complex, with concomitant stabilization of the orbitals of the bonded nickel atom. A study of the excited electronic states of π-NiC 2 H 4 shows that low-lying 4s→π* and 3d→π* (M→L) charge transfer transitions are predicted. The former is not observed experimentally, probably due to the diffuse nature of the 4s orbital. The relationship between small cluster--ethylene complex systems and ethylene chemisorption on a nickel metal surface is discussed

  11. Formation of global energy minimim structures in the growth process of Lennard-Jones clusters

    DEFF Research Database (Denmark)

    Solov'yov, Ilia; Koshelev, Andrey; Shutovich, Andrey

    2003-01-01

    that in this way all known global minimum structures of the Lennard-Jones (LJ) clusters can be found. Our method provides an efficient tool for the calculation and analysis of atomic cluster structure. With its use we justify the magic numbers sequence for the clusters of noble gases atoms and compare...

  12. The Structure of the Young Star Cluster NGC 6231. II. Structure, Formation, and Fate

    Science.gov (United States)

    Kuhn, Michael A.; Getman, Konstantin V.; Feigelson, Eric D.; Sills, Alison; Gromadzki, Mariusz; Medina, Nicolás; Borissova, Jordanka; Kurtev, Radostin

    2017-12-01

    The young cluster NGC 6231 (stellar ages ˜2-7 Myr) is observed shortly after star formation activity has ceased. Using the catalog of 2148 probable cluster members obtained from Chandra, VVV, and optical surveys (Paper I), we examine the cluster’s spatial structure and dynamical state. The spatial distribution of stars is remarkably well fit by an isothermal sphere with moderate elongation, while other commonly used models like Plummer spheres, multivariate normal distributions, or power-law models are poor fits. The cluster has a core radius of 1.2 ± 0.1 pc and a central density of ˜200 stars pc-3. The distribution of stars is mildly mass segregated. However, there is no radial stratification of the stars by age. Although most of the stars belong to a single cluster, a small subcluster of stars is found superimposed on the main cluster, and there are clumpy non-isotropic distributions of stars outside ˜4 core radii. When the size, mass, and age of NGC 6231 are compared to other young star clusters and subclusters in nearby active star-forming regions, it lies at the high-mass end of the distribution but along the same trend line. This could result from similar formation processes, possibly hierarchical cluster assembly. We argue that NGC 6231 has expanded from its initial size but that it remains gravitationally bound.

  13. (Electronic structure and reactivities of transition metal clusters)

    Energy Technology Data Exchange (ETDEWEB)

    1992-01-01

    The following are reported: theoretical calculations (configuration interaction, relativistic effective core potentials, polyatomics, CASSCF); proposed theoretical studies (clusters of Cu, Ag, Au, Ni, Pt, Pd, Rh, Ir, Os, Ru; transition metal cluster ions; transition metal carbide clusters; bimetallic mixed transition metal clusters); reactivity studies on transition metal clusters (reactivity with H{sub 2}, C{sub 2}H{sub 4}, hydrocarbons; NO and CO chemisorption on surfaces). Computer facilities and codes to be used, are described. 192 refs, 13 figs.

  14. Direct Atomic Scale Observation of the Structure and Chemistry of Order/Disorder Interfaces

    National Research Council Canada - National Science Library

    Srinivasan, R; Banerjee, R; Hwang, J. Y; Viswanathan, G. B; Tiley, J; Fraser, H. L

    2008-01-01

    ... distributed ordered intermetallic precipitates within a disordered matrix. The structure and chemistry at the precipitate/matrix interface plays a critical role in determining the effectiveness of the strengthening mechanism...

  15. Fast large-scale clustering of protein structures using Gauss integrals

    DEFF Research Database (Denmark)

    Harder, Tim; Borg, Mikael; Boomsma, Wouter

    2011-01-01

    trajectories. Results: We present Pleiades, a novel approach to clustering protein structures with a rigorous mathematical underpinning. The method approximates clustering based on the root mean square deviation by rst mapping structures to Gauss integral vectors – which were introduced by Røgen and co......-workers – and subsequently performing K-means clustering. Conclusions: Compared to current methods, Pleiades dramatically improves on the time needed to perform clustering, and can cluster a signicantly larger number of structures, while providing state-ofthe- art results. The number of low energy structures generated...

  16. Designing a Scalable Fault Tolerance Model for High Performance Computational Chemistry: A Case Study with Coupled Cluster Perturbative Triples.

    Science.gov (United States)

    van Dam, Hubertus J J; Vishnu, Abhinav; de Jong, Wibe A

    2011-01-11

    In the past couple of decades, the massive computational power provided by the most modern supercomputers has resulted in simulation of higher-order computational chemistry methods, previously considered intractable. As the system sizes continue to increase, the computational chemistry domain continues to escalate this trend using parallel computing with programming models such as Message Passing Interface (MPI) and Partitioned Global Address Space (PGAS) programming models such as Global Arrays. The ever increasing scale of these supercomputers comes at a cost of reduced Mean Time Between Failures (MTBF), currently on the order of days and projected to be on the order of hours for upcoming extreme scale systems. While traditional disk-based check pointing methods are ubiquitous for storing intermediate solutions, they suffer from high overhead of writing and recovering from checkpoints. In practice, checkpointing itself often brings the system down. Clearly, methods beyond checkpointing are imperative to handling the aggravating issue of reducing MTBF. In this paper, we address this challenge by designing and implementing an efficient fault tolerant version of the Coupled Cluster (CC) method with NWChem, using in-memory data redundancy. We present the challenges associated with our design, including an efficient data storage model, maintenance of at least one consistent data copy, and the recovery process. Our performance evaluation without faults shows that the current design exhibits a small overhead. In the presence of a simulated fault, the proposed design incurs negligible overhead in comparison to the state of the art implementation without faults.

  17. Size and composition dependence of the frozen structures in Co-based bimetallic clusters

    International Nuclear Information System (INIS)

    Li, Guojian; Wang, Qiang; Cao, Yongze; Du, Jiaojiao; He, Jicheng

    2012-01-01

    This Letter studies the size-dependent freezing of Co, Co–Ni, and Co–Cu clusters by using molecular dynamics with embedded atom method. Size effect occurs in these three types of clusters. The clusters with large sizes always freeze to form their bulk-like structures. However, the frozen structures for small sizes are generally related to their compositions. The icosahedral clusters are formed for Co clusters (for ⩽3.2 nm diameter) and also for Co–Ni clusters but at a larger size range (for ⩽4.08 nm). Upon the Co–Cu clusters, decahedral structure is obtained for small size (for 2.47 nm). The released energy induced the structural transformation plays a key role in the frozen structures. These results indicate that the preformed clusters with special structures can be tuned by controlling their compositions and sizes. -- Highlights: ► The size effect occurs in the Co, Co–Ni, and Co–Cu clusters. ► The clusters with large sizes always freeze to form their bulk-like structures. ► The frozen structures for small sizes are generally related to their compositions. ► Icosahedron is formed for Co and also for Co–Ni but at a larger size range. ► Upon the Co–Cu clusters, decahedral structure is obtained for small size.

  18. Structures and dynamical properties of Cn, Sin, Gen, and Snn clusters with n up to 13

    International Nuclear Information System (INIS)

    Lu, Zhong-Yi; Wang, Cai-Zhuang; Ho, Kai-Ming

    2000-01-01

    Car-Parrinello molecular dynamics simulated annealings were carried out for clusters Si n , Ge n , and Sn n (n≤13). We investigate the temperature regions in which these clusters transform from a ''liquidlike'' phase to a ''solidlike'' phase, and then from the ''solidlike'' phase to the ground-state structures. Additional simulated annealing was also performed for the cluster C 13 which is selected as a prototype of small carbon clusters. In addition to the discovery of structures for Sn and Ge clusters, our simulation results also provide insights into the dynamics of cluster formation. (c) 2000 The American Physical Society

  19. α cluster structures in unbound states in 19Ne

    Science.gov (United States)

    Otani, Reiji; Iwasaki, Masataka; Ito, Makoto

    2016-06-01

    Cluster structures in 19Ne are studied by the microscopic and macroscopic cluster models. In the microscopic calculation, the coupled-channels problem of (3He+16O) + (α+15O) is solved, and the adiabatic energy surfaces, which are the series of the energy eigenvalues as a function of the He-O distance, are investigated. In the adiabatic energy curves, the several local minima are generated in the spatial region of the small core distance, where the neutron hole inside of the He or O nucleus is strongly coupled to the residual nuclei. The energy spectra, which are constructed from the strong coupling states, nicely reproduce the the low-lying energy levels in the 19Ne nucleus. In the macroscopic approach, the α + 15O potential is evaluated from the elastic scattering of the α + 15N system, and the resonant levels of the α + 15O system are calculated under the absorbing boundary condition. The potential model predicts the existence of the resonances above the α threshold, which has a weak-coupling scheme of the α particle and one hole inside of the 16O nucleus. The extended microscopic calculations of (3He+16O) + (α+15O) + (5He+14O) are performed in order to see the coupling effect of the 5p-2h configuration, which corresponds to the shell model limit of the 5He + 14O cluster configuration. The extended calculation suggests that the 5He + 14O configuration plays an important role on the formation of the 3/2+ resonance at 0.5 MeV with respect to the α threshold.

  20. Structural profiles of human miRNA families from pairwise clustering

    DEFF Research Database (Denmark)

    Kaczkowski, Bogumil; Þórarinsson, Elfar; Reiche, Kristin

    2009-01-01

    secondary structure already predicted, little is known about the patterns of structural conservation among pre-miRNAs. We address this issue by clustering the human pre-miRNA sequences based on pairwise, sequence and secondary structure alignment using FOLDALIGN, followed by global multiple alignment...... of obtained clusters by WAR. As a result, the common secondary structure was successfully determined for four FOLDALIGN clusters: the RF00027 structural family of the Rfam database and three clusters with previously undescribed consensus structures. Availability: http://genome.ku.dk/resources/mirclust...

  1. THREE DISCRETE GROUPS WITH HOMOGENEOUS CHEMISTRY ALONG THE RED GIANT BRANCH IN THE GLOBULAR CLUSTER NGC 2808

    International Nuclear Information System (INIS)

    Carretta, E.

    2014-01-01

    We present the homogeneous reanalysis of Mg and Al abundances from high resolution UVES/FLAMES spectra for 31 red giants in the globular cluster NGC 2808. We found a well defined Mg-Al anticorrelation reaching a regime of subsolar Mg abundance ratios, with a spread of about 1.4 dex in [Al/Fe]. The main result from the improved statistics of our sample is that the distribution of stars is not continuous along the anticorrelation because they are neatly clustered into three distinct clumps, each with different chemical compositions. One group (P) shows a primordial composition of field stars of similar metallicity, and the other two (I and E) have increasing abundances of Al and decreasing abundances of Mg. The fraction of stars we found in the three components (P: 68%, I: 19%, E: 13%) is in excellent agreement with the ratios computed for the three distinct main sequences in NGC 2808: for the first time there is a clear correspondence between discrete photometric sequences of dwarfs and distinct groups of giants with homogeneous chemistry. The composition of the I group cannot be reproduced by mixing of matter with extreme processing in hot H-burning and gas with pristine, unprocessed composition, as also found in the recent analysis of three discrete groups in NGC 6752. This finding suggests that different classes of polluters were probably at work in NGC 2808 as well

  2. Complex chemistry

    International Nuclear Information System (INIS)

    Kim, Bong Gon; Kim, Jae Sang; Kim, Jin Eun; Lee, Boo Yeon

    2006-06-01

    This book introduces complex chemistry with ten chapters, which include development of complex chemistry on history coordination theory and Warner's coordination theory and new development of complex chemistry, nomenclature on complex with conception and define, chemical formula on coordination compound, symbol of stereochemistry, stereo structure and isomerism, electron structure and bond theory on complex, structure of complex like NMR and XAFS, balance and reaction on solution, an organo-metallic chemistry, biology inorganic chemistry, material chemistry of complex, design of complex and calculation chemistry.

  3. Structure and Stability of GeAun, n = 1-10 clusters: A Density Functional Study

    International Nuclear Information System (INIS)

    Priyanka,; Dharamvir, Keya; Sharma, Hitesh

    2011-01-01

    The structures of Germanium doped gold clusters GeAu 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 n clusters and have it compared with Silicon doped gold clusters and pure gold clusters. The ground state geometries of the GeAu 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 silicon doped gold cluster. The HUMO-LOMO gap for Au 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.

  4. antiSMASH 4.0-improvements in chemistry prediction and gene cluster boundary identification

    DEFF Research Database (Denmark)

    Blin, Kai; Wolf, Thomas; Chevrette, Marc G.

    2017-01-01

    Many antibiotics, chemotherapeutics, crop protection agents and food preservatives originate from molecules produced by bacteria, fungi or plants. In recent years, genome mining methodologies have been widely adopted to identify and characterize the biosynthetic gene clusters encoding...... the production of such compounds. Since 2011, the 'antibiotics and secondary metabolite analysis shell-antiSMASH' has assisted researchers in efficiently performing this, both as a web server and a standalone tool. Here, we present the thoroughly updated antiSMASH version 4, which adds several novel features...

  5. The N2O activation by Rh5 clusters. A quantum chemistry study.

    Science.gov (United States)

    Olvera-Neria, Oscar; Avilés, Roberto; Francisco-Rodríguez, Héctor; Bertin, Virineya; García-Cruz, Raúl; González-Torres, Julio César; Poulain, Enrique

    2015-04-01

    Nitrous oxide (N2O) is a by-product of exhaust pipe gases treatment produced by motor vehicles. Therefore, the N2O reduction to N2 is necessary to meet the actual environmental legislation. The N2O adsorption and dissociation assisted by the square-based pyramidal Rh5 cluster was investigated using the density functional theory and the zero-order regular approximation (ZORA). The Rh5 sextet ground state is the most active in N2O dissociation, though the quartet and octet states are also active because they are degenerate. The Rh5 cluster spontaneously activates the N2─O cleavage, and the reaction is highly exothermic ca. -75 kcal mol(-1). The N2─O breaking is obtained for the geometrical arrangement that maximizes the overlap and electron transfers between the N2O and Rh5 frontier orbitals. The Rh5 high activity is due to the Rh 3d orbitals are located between the N2O HOMO and LUMO orbitals, which makes possible the interactions between them. In particular, the O 2p states strongly interact with Rh 3d orbitals, which finally weaken the N2─O bond. The electron transfer is from the Rh5 HOMO orbital to the N2O antibonding orbital.

  6. Chemistry and the development of research into the structure of matter

    International Nuclear Information System (INIS)

    Coldanskij, V.

    1977-01-01

    Efforts have been made recently to explain the structure of the atomic nucleus and the structure of the electron shell of the atom using a unified quantum mechanics description. The applications are surveyed of the knowledge of the nucleus and electron shell structure in chemistry. Electron paramagnetic resonance, nuclear magnetic resonance and gamma resonance spectrometry are presented as examples. (J.B.)

  7. Chemistry and the development of research into the structure of matter

    Energy Technology Data Exchange (ETDEWEB)

    Coldanskii, V

    1977-06-01

    Efforts have been made recently to explain the structure of the atomic nucleus and the structure of the electron shell of the atom using a unified quantum mechanics description. The applications are surveyed of the knowledge of the nucleus and electron shell structure in chemistry. Electron paramagnetic resonance, nuclear magnetic resonance and gamma resonance spectrometry are presented as examples.

  8. Structure Determination of Unknown Organic Liquids Using NMR and IR Spectroscopy: A General Chemistry Laboratory

    Science.gov (United States)

    Pavel, John T.; Hyde, Erin C.; Bruch, Martha D.

    2012-01-01

    This experiment introduced general chemistry students to the basic concepts of organic structures and to the power of spectroscopic methods for structure determination. Students employed a combination of IR and NMR spectroscopy to perform de novo structure determination of unknown alcohols, without being provided with a list of possible…

  9. On the electronic and geometrical structures of small atomic clusters

    International Nuclear Information System (INIS)

    Malrieu, J.P.; Maynau, D.

    1987-01-01

    This paper recalls the main challenges and difficulties of the theoretical study of small clusters of atoms. It briefly summarizes some informations concerning rare-gas clusters and clusters of normal elements such as C or Si. The main discussion is devoted to the small clusters of the simplest metal (Li), comparing the agreement and discrepancies between two crude models - the jellium model and the tight-binding one - with the most refined ab initio calculations. 28 refs

  10. Cluster decay analysis and related structure effects of fissionable ...

    Indian Academy of Sciences (India)

    2015-08-01

    Aug 1, 2015 ... Collective clusterization approach of dynamical cluster decay model (DCM) has been ... fusion–fission process resulting in the emission of symmetric and/or ... represents the relative separation distance between two fragments or clusters ... decay constant λ or decay half-life T1/2 is defined as λ = (ln 2/T1/2) ...

  11. Electronic shell structure in multiply charged silver clusters

    International Nuclear Information System (INIS)

    Kandler, O.; Athanassenas, K.; Echt, O.; Kreisle, D.; Leisner, T.; Recknagel, E.

    1991-01-01

    Silver clusters are generated by standard laser vaporization technique and ionized via multiphoton ionization. Time-of-flight mass spectrometry reveals singly, doubly and triply charged clusters, Ag n z+ (z=1, 2, 3). The spectra show, for all charge states, intensity variations, indicating enhanced stabilities for cluster sizes with closed electronic configurations in accord with the spherical jellium model. (orig.)

  12. Spectral shifts and structures of phenol center dot center dot center dot Ar-n clusters

    Czech Academy of Sciences Publication Activity Database

    Armentano, A.; Černý, Jiří; Riese, M.; Taherkhani, M.; Ben Yezzar, M.; Muller-Dethlefs, K.

    2011-01-01

    Roč. 13, č. 13 (2011), s. 6077-6084 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z50520701 Keywords : VAN-DER-WAALS * BENZENE-ARGON CLUSTERS * INFRARED-SPECTRA Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

  13. Role of protein-glutathione contacts in defining glutaredoxin-3 [2Fe-2S] cluster chirality, ligand exchange and transfer chemistry.

    Science.gov (United States)

    Sen, Sambuddha; Cowan, J A

    2017-10-01

    Monothiol glutaredoxins (Grx) serve as intermediate cluster carriers in iron-sulfur cluster trafficking. The [2Fe-2S]-bound holo forms of Grx proteins display cysteinyl coordination from exogenous glutathione (GSH), in addition to contact from protein-derived Cys. Herein, we report mechanistic studies that investigate the role of exogenous glutathione in defining cluster chirality, ligand exchange, and the cluster transfer chemistry of Saccharomyces cerevisiae Grx3. Systematic perturbations were introduced to the glutathione-binding site by substitution of conserved charged amino acids that form crucial electrostatic contacts with the glutathione molecule. Native Grx3 could also be reconstituted in the absence of glutathione, with either DTT, BME or free L-cysteine as the source of the exogenous Fe-S ligand contact, while retaining full functional reactivity. The delivery of the [2Fe-2S] cluster to Grx3 from cluster donor proteins such as Isa, Nfu, and a [2Fe-2S](GS) 4 complex, revealed that electrostatic contacts are of key importance for positioning the exogenous glutathione that in turn influences the chiral environment of the cluster. All Grx3 derivatives were reconstituted by standard chemical reconstitution protocols and found to transfer cluster to apo ferredoxin 1 (Fdx1) at rates comparable to native protein, even when using DTT, BME or free L-cysteine as a thiol source in place of GSH during reconstitution. Kinetic analysis of cluster transfer from holo derivatives to apo Fdx1 has led to a mechanistic model for cluster transfer chemistry of native holo Grx3, and identification of the likely rate-limiting step for the reaction.

  14. Electronic structure and properties of designer clusters and cluster-assemblies

    International Nuclear Information System (INIS)

    Khanna, S.N.; Jena, P.

    1995-01-01

    Using self-consistent calculations based on density functional theory, we demonstrate that electronic shell filling and close atomic packing criteria can be used to design ultra-stable clusters. Interaction of these clusters with each other and with gas atoms is found to be weak confirming their chemical inertness. A crystal composed of these inert clusters is expected to have electronic properties that are markedly different from crystals where atoms are the building blocks. The recent observation of ferromagnetism in potassium clusters assembled in zeolite cages is discussed. (orig.)

  15. Actinide chemistry using singlet-paired coupled cluster and its combinations with density functionals

    Science.gov (United States)

    Garza, Alejandro J.; Sousa Alencar, Ana G.; Scuseria, Gustavo E.

    2015-12-01

    Singlet-paired coupled cluster doubles (CCD0) is a simplification of CCD that relinquishes a fraction of dynamic correlation in order to be able to describe static correlation. Combinations of CCD0 with density functionals that recover specifically the dynamic correlation missing in the former have also been developed recently. Here, we assess the accuracy of CCD0 and CCD0+DFT (and variants of these using Brueckner orbitals) as compared to well-established quantum chemical methods for describing ground-state properties of singlet actinide molecules. The f0 actinyl series (UO22+, NpO23+, PuO24+), the isoelectronic NUN, and thorium (ThO, ThO2+) and nobelium (NoO, NoO2) oxides are studied.

  16. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O) n=1-5 clusters.

    Science.gov (United States)

    Linton, Kirsty A; Wright, Timothy G; Besley, Nicholas A

    2018-03-13

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO + (H 2 O) n =1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO + (H 2 O) that is too high and incorrectly predict the lowest energy structure of NO + (H 2 O) 2 , and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO + Ab initio molecular dynamics (AIMD) simulations were performed to study the NO + (H 2 O) 5 [Formula: see text] H + (H 2 O) 4 + HONO reaction to investigate the formation of HONO from NO + (H 2 O) 5 Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO + (H 2 O) 5 complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  17. THE STRUCTURE OF THE STAR-FORMING CLUSTER RCW 38

    Energy Technology Data Exchange (ETDEWEB)

    Winston, E. [ESA-ESTEC (SRE-SA), Keplerlaan 1, 2201 AZ Noordwijk ZH (Netherlands); Wolk, S. J.; Bourke, T. L.; Spitzbart, B. [Harvard Smithsonian Center for Astrophysics, 60 Garden Street, Cambridge, MA 02138 (United States); Megeath, S. T. [Ritter Observatory, Department of Physics and Astronomy, University of Toledo, 2801 West Bancroft Avenue, Toledo, OH 43606 (United States); Gutermuth, R., E-mail: ewinston@rssd.esa.int [Five Colleges Astronomy Department, Smith College, Northampton, MA 01027 (United States)

    2011-12-20

    We present a study of the structure of the high-mass star-forming region RCW 38 and the spatial distribution of its young stellar population. Spitzer Infrared Array Camera (IRAC) photometry (3-8 {mu}m) is combined with Two Micron All Sky Survey near-IR data to identify young stellar objects (YSOs) by IR-excess emission from their circumstellar material. Chandra X-ray data are used to identify class III pre-main-sequence stars lacking circumstellar material. We identify 624 YSOs: 23 class 0/I and 90 flat spectrum protostars, 437 class II stars, and 74 class III stars. We also identify 29 (27 new) O star candidates over the IRAC field. Seventy-two stars exhibit IR-variability, including 7 class 0/I and 12 flat spectrum YSOs. A further 177 tentative candidates are identified by their location in the IRAC [3.6] versus [3.6]-[5.8] color-magnitude diagram. We find strong evidence of subclustering in the region. Three subclusters were identified surrounding the central cluster, with massive and variable stars in each subcluster. The central region shows evidence of distinct spatial distributions of the protostars and pre-main-sequence stars. A previously detected IR cluster, DB2001{sub O}bj36, has been established as a subcluster of RCW 38. This suggests that star formation in RCW 38 occurs over a more extended area than previously thought. The gas-to-dust ratio is examined using the X-ray derived hydrogen column density, N{sub H} and the K-band extinction, and found to be consistent with the diffuse interstellar medium, in contrast with Serpens and NGC 1333. We posit that the high photoionizing flux of massive stars in RCW 38 affects the agglomeration of the dust grains.

  18. Shell structures and chaos in nuclei and large metallic clusters

    International Nuclear Information System (INIS)

    Heiss, W.D.; University of the Witwatersrand, Johannesburg; Nazmitdinov, R.G.; Radu, S.; University of the Witwatersrand, Johannesburg

    1995-01-01

    A reflection-asymmetric deformed oscillator potential is analyzed from the classical and quantum mechanical point of view. The connection between occurrence of shell structures and classical periodic orbits is studied using the ''removal of resonances method'' in a classical analysis. In this approximation, the effective single particle potential becomes separable and the frequencies of the classical trajectories are easily determined. It turns out that the winding numbers calculated in this way are in good agreement with the ones found from the corresponding quantum mechanical spectrum using the particle number dependence of the fluctuating part of the total energy. When the octupole term is switched on it is found that prolate shapes are stable against chaos and can exhibit shells where spherical and oblate cases become chaotic. An attempt is made to explain this difference in the quantum mechanical context by looking at the distribution of exceptional points which results from the matrix structure of the respective Hamiltonians. In a similar way we analyze the modified Nilsson model and discuss its consequences for metallic clusters. (orig.)

  19. Analysis of NFU-1 metallocofactor binding-site substitutions-impacts on iron-sulfur cluster coordination and protein structure and function.

    Science.gov (United States)

    Wesley, Nathaniel A; Wachnowsky, Christine; Fidai, Insiya; Cowan, J A

    2017-11-01

    Iron-sulfur (Fe/S) clusters are ancient prosthetic groups found in numerous metalloproteins and are conserved across all kingdoms of life due to their diverse, yet essential functional roles. Genetic mutations to a specific subset of mitochondrial Fe/S cluster delivery proteins are broadly categorized as disease-related under multiple mitochondrial dysfunction syndrome (MMDS), with symptoms indicative of a general failure of the metabolic system. Multiple mitochondrial dysfunction syndrome 1 (MMDS1) arises as a result of the missense mutation in NFU1, an Fe/S cluster scaffold protein, which substitutes a glycine near the Fe/S cluster-binding pocket to a cysteine (p.Gly208Cys). This substitution has been shown to promote protein dimerization such that cluster delivery to NFU1 is blocked, preventing downstream cluster trafficking. However, the possibility of this additional cysteine, located adjacent to the cluster-binding site, serving as an Fe/S cluster ligand has not yet been explored. To fully understand the consequences of this Gly208Cys replacement, complementary substitutions at the Fe/S cluster-binding pocket for native and Gly208Cys NFU1 were made, along with six other variants. Herein, we report the results of an investigation on the effect of these substitutions on both cluster coordination and NFU1 structure and function. The data suggest that the G208C substitution does not contribute to cluster binding. Rather, replacement of the glycine at position 208 changes the oligomerization state as a result of global structural alterations that result in the downstream effects manifest as MMDS1, but does not perturb the coordination chemistry of the Fe-S cluster. © 2017 Federation of European Biochemical Societies.

  20. Of the crystal chemistry of Ruddlesden-Porter type structures in high Tc ceramic superconductors

    International Nuclear Information System (INIS)

    Dwivedi, A.; Cormack, A.N.

    1990-01-01

    This paper reports on atomistic computer simulation employed to examine the energetics and crystal chemistry of some Ruddlesden-Popper type oxide superconductors. Similar structural patterns have been noticed in the superconducting oxides. The formation of Ruddlesden-Popper type layers (alternating slabs of rocksalt and perovskite structures) is similar in many respects to that seen in the system Sr-Ti-O. However, there are some significant differences, for example, the rocksalt and perovskite blocks in the new superconducting compounds are not necessarily electrically neutral unlike in the Sr-Ti-O system and this may well lead to significant differences in their structural chemistry

  1. Structure and chemistry of model catalysts in ultrahigh vacuum

    Science.gov (United States)

    Walker, Joshua D.

    The study of catalysis is a key area of focus not only in the industrial sector but also in the nature and biological systems. The market for catalysis is a multi-billion dollar industry. Many of the materials and products we use on a daily basis are formed through a catalytic process. The quest to understanding and improving catalytic mechanisms is ongoing. Many model catalysts use transition metals as a support for chemical reactions to take place due to their selectivity and activity. Palladium, gold, and copper metals are studied in this work and show the ability to be catalytically reactive. It is important to understand the characteristics and properties of these surfaces. A well-known example of catalysis is the conversion of carbon monoxide (CO), a very harmful gas to carbon dioxide (CO2) which is less harmful. This reaction is mainly seen in the automotive industry. This reaction is investigated in this work on a Au(111) single crystal, which is normally inert but becomes reactivity with the adsorption of oxygen on the surface. Temperature Programmed Desorption (TPD) is used to understand some of the chemistry and effects with and without the addition of H2O. The oxidation of CO is shown to be enhanced by the addition of water, but warrants further analysis too fully understand the different mechanisms and reaction pathways existing. The field of nano-electronics is rapidly growing as technology continues to challenge scientists to create innovative ideas. The trend to produce smaller electronic products is increasing as consumer demands persist. It has been shown previously that 1,4-phenlyene diisocyanobenzene (1,4-PDI) on Au(111) react to form one-dimensional oligomer chains comprising alternating gold and 1,4-PDI units on the Au(111) surface. A similar compound 1,3-phenlyene diisocyanobenzene (1,3-PDI) was studied in order to investigate whether the oligomerization found for 1,4-PDI is a general phenomenon and to ultimately explore the effect of

  2. Complete Tem-Tomography: 3D Structure of Gems Cluster

    Science.gov (United States)

    Matsuno, J.; Miyake, A.; Tsuchiyama, A.; Messenger, S.; Nakamura-Messenger, K.

    2015-01-01

    GEMS (glass with embedded metal and sulfide) grains in interplanetary dust particles (IDPs) are considered to be one of the ubiquitous and fundamental building blocks of solids in the Solar System. They have been considered to be interstellar silicate dust that survived various metamorphism or alteration processes in the protoplanetary disk but the elemental and isotopic composition measurements suggest that most of them have been formed in the protoplanetary disk as condensates from high temperature gas. This formation model is also supported by the formation of GEMS-like grains with respect to the size, mineral assemblage, texture and infrared spectrum by condensation experiments from mean GEMS composition materials. Previous GEMS studies were performed only with 2D observation by transmission electron microscopy (TEM) or scanning TEM (STEM). However, the 3D shape and structure of GEMS grains and the spatial distribution of Fe/FeS's has critical information about their formation and origin. Recently, the 3D structure of GEMS grains in ultrathin sections of cluster IDPs was revealed by electron tomography using a TEM/STEM (JEM-2100F, JEOL). However, CT images of thin sections mounted on Cu grids acquired by conventional TEM-tomography are limited to low tilt angles (e. g., less than absolute value of 75 deg. In fact, previous 3D TEM observations of GEMS were affected by some artifacts related to the limited tilt range in the TEM used. Complete tomographic images should be acquired by rotating the sample tilt angle over a range of more than absolute value of 80 deg otherwise the CT images lose their correct structures. In order to constrain the origin and formation process of GEMS grains more clearly, we performed complete electron tomography for GEMS grains. Here we report the sample preparation method we have developed for this study, and the preliminary results.

  3. Structurally Based Therapeutic Evaluation: A Therapeutic and Practical Approach to Teaching Medicinal Chemistry.

    Science.gov (United States)

    Alsharif, Naser Z.; And Others

    1997-01-01

    Explains structurally based therapeutic evaluation of drugs, which uses seven therapeutic criteria in translating chemical and structural knowledge into therapeutic decision making in pharmaceutical care. In a Creighton University (Nebraska) medicinal chemistry course, students apply the approach to solve patient-related therapeutic problems in…

  4. Chemical Structure and Properties: A Modified Atoms-First, One-Semester Introductory Chemistry Course

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Jakubowski, Henry V.; McKenna, Anna G.; McIntee, Edward J.; Jones, T. Nicholas; Fazal, M. A.; Peterson, Alicia A.

    2015-01-01

    A one-semester, introductory chemistry course is described that develops a primarily qualitative understanding of structure-property relationships. Starting from an atoms-first approach, the course examines the properties and three-dimensional structure of metallic and ionic solids before expanding into a thorough investigation of molecules. In…

  5. Investigation of glutathione-derived electrostatic and hydrogen-bonding interactions and their role in defining Grx5 [2Fe-2S] cluster optical spectra and transfer chemistry.

    Science.gov (United States)

    Sen, Sambuddha; Bonfio, Claudia; Mansy, Sheref S; Cowan, J A

    2018-03-01

    Human glutaredoxin 5 (Grx5) is one of the core components of the Isc (iron-sulfur cluster) assembly and trafficking machinery, and serves as an intermediary cluster carrier, putatively delivering cluster from the Isu scaffold protein to target proteins. The tripeptide glutathione is intimately involved in this role, providing cysteinyl coordination to the iron center of the Grx5-bound [2Fe-2S] cluster. Grx5 has a well-defined glutathione-binding pocket with protein amino acid residues providing many ionic and hydrogen binding contacts to the bound glutathione. In this report, we investigated the importance of these interactions in cluster chirality and exchange reactivity by systematically perturbing the crucial contacts by use of natural and non-natural amino acid substitutions to disrupt the binding contacts from both the protein and glutathione. Native Grx5 could be reconstituted with all of the glutathione analogs used, as well as other thiol ligands, such as DTT or L-cysteine, by in vitro chemical reconstitution, and the holo proteins were found to transfer [2Fe-2S] cluster to apo ferredoxin 1 at comparable rates. However, the circular dichroism spectra of these derivatives displayed prominent differences that reflect perturbations in local cluster chirality. These studies provided a detailed molecular understanding of glutathione-protein interactions in holo Grx5 that define both cluster spectroscopy and exchange chemistry.

  6. Connecting Structure-Property and Structure-Function Relationships across the Disciplines of Chemistry and Biology: Exploring Student Perceptions

    Science.gov (United States)

    Kohn, Kathryn P.; Underwood, Sonia M.; Cooper, Melanie M.

    2018-01-01

    While many university students take science courses in multiple disciplines, little is known about how they perceive common concepts from different disciplinary perspectives. Structure-property and structure-function relationships have long been considered important explanatory concepts in the disciplines of chemistry and biology, respectively.…

  7. Atomic structures and covalent-to-metallic transition of lead clusters Pbn (n=2-22)

    International Nuclear Information System (INIS)

    Wang Baolin; Zhao Jijun; Chen Xiaoshuang; Shi Daning; Wang Guanghou

    2005-01-01

    The lowest-energy structures and electronic properties of the lead clusters are studied by density-functional-theory calculations with Becke-Lee-Yang-Parr gradient correction. The lowest-energy structures of Pb n (n=2-22) clusters are determined from a number of structural isomers, which are generated from empirical genetic algorithm simulations. The competition between atom-centered compact structures and layered stacking structures leads to the alternative appearance of the two types of structures as global minimum. The size evolution of geometric and electronic properties from covalent bonding towards bulk metallic behavior in Pb clusters is discussed

  8. clusters

    Indian Academy of Sciences (India)

    2017-09-27

    Sep 27, 2017 ... Author for correspondence (zh4403701@126.com). MS received 15 ... lic clusters using density functional theory (DFT)-GGA of the DMOL3 package. ... In the process of geometric optimization, con- vergence thresholds ..... and Postgraduate Research & Practice Innovation Program of. Jiangsu Province ...

  9. clusters

    Indian Academy of Sciences (India)

    environmental as well as technical problems during fuel gas utilization. ... adsorption on some alloys of Pd, namely PdAu, PdAg ... ried out on small neutral and charged Au24,26,27, Cu,28 ... study of Zanti et al.29 on Pdn (n = 1–9) clusters.

  10. Structural properties of gold clusters at different temperatures

    CSIR Research Space (South Africa)

    Mahladisa, MA

    2005-09-01

    Full Text Available A series of gold clusters consisting of aggregates of from 13 to 147 atoms was studied using the Sutton-Chen type many-body potential in molecular dynamics simulations. The properties of these clusters at temperatures from 10 K to 1000 K were...

  11. Cluster model calculations of the solid state materials electron structure

    International Nuclear Information System (INIS)

    Pelikan, P.; Biskupic, S.; Banacky, P.; Zajac, A.; Svrcek, A.; Noga, J.

    1997-01-01

    Materials of the general composition ACuO 2 are the parent compounds of so called infinite layer superconductors. In the paper presented the electron structure of the compounds CaCuO 2 , SrCuO2, Ca 0.86 Sr 0.14 CuO2 and Ca 0.26 Sr 0.74 CuO 2 were calculated. The cluster models consisting of 192 atoms were computed using quasi relativistic version of semiempirical INDO method. The obtained results indicate the strong ionicity of Ca/Sr-O bonds and high covalency of Cu-bonds. The width of energy gap at the Fermi level increases as follows: Ca 0.26 Sr 0.74 CuO 2 0.86 Sr 0.14 CuO2 2 . This order correlates with the fact that materials of the composition Ca x Sr 1-x CuO 2 have have the high temperatures of the superconductive transition (up to 110 K). Materials partially substituted by Sr 2+ have also the higher density of states in the close vicinity at the Fermi level that ai the additional condition for the possibility of superconductive transition. It was calculated the strong influence of the vibration motions to the energy gap at the Fermi level. (authors). 1 tabs., 2 figs., 10 refs

  12. The far from equilibrium structure of argon clusters doped with krypton or xenon.

    Science.gov (United States)

    Lindblad, A; Bergersen, H; Rander, T; Lundwall, M; Ohrwall, G; Tchaplyguine, M; Svensson, S; Björneholm, O

    2006-04-28

    Heterogeneous clusters created by doping Ar host clusters with Kr or Xe are shown to have radically different structures from the mixed clusters of the same type created by co-expansion of Ar-Kr or Ar-Xe gas mixtures. In contrast to the co-expansion case, the doped mixed clusters can be produced with Kr or Xe on the surface and Ar in the bulk. With the doping technique it is thus possible to control the surface composition of a specific cluster. A study of the cluster properties as a function of the doping pressure is also reported for the case of Ar clusters doped with Xe. The clusters have been studied by means of synchrotron radiation based X-ray photoelectron spectroscopy.

  13. D Nearest Neighbour Search Using a Clustered Hierarchical Tree Structure

    Science.gov (United States)

    Suhaibah, A.; Uznir, U.; Anton, F.; Mioc, D.; Rahman, A. A.

    2016-06-01

    Locating and analysing the location of new stores or outlets is one of the common issues facing retailers and franchisers. This is due to assure that new opening stores are at their strategic location to attract the highest possible number of customers. Spatial information is used to manage, maintain and analyse these store locations. However, since the business of franchising and chain stores in urban areas runs within high rise multi-level buildings, a three-dimensional (3D) method is prominently required in order to locate and identify the surrounding information such as at which level of the franchise unit will be located or is the franchise unit located is at the best level for visibility purposes. One of the common used analyses used for retrieving the surrounding information is Nearest Neighbour (NN) analysis. It uses a point location and identifies the surrounding neighbours. However, with the immense number of urban datasets, the retrieval and analysis of nearest neighbour information and their efficiency will become more complex and crucial. In this paper, we present a technique to retrieve nearest neighbour information in 3D space using a clustered hierarchical tree structure. Based on our findings, the proposed approach substantially showed an improvement of response time analysis compared to existing approaches of spatial access methods in databases. The query performance was tested using a dataset consisting of 500,000 point locations building and franchising unit. The results are presented in this paper. Another advantage of this structure is that it also offers a minimal overlap and coverage among nodes which can reduce repetitive data entry.

  14. Three-dimensional cluster formation and structure in heterogeneous dose distribution of intensity modulated radiation therapy.

    Science.gov (United States)

    Chao, Ming; Wei, Jie; Narayanasamy, Ganesh; Yuan, Yading; Lo, Yeh-Chi; Peñagarícano, José A

    2018-05-01

    To investigate three-dimensional cluster structure and its correlation to clinical endpoint in heterogeneous dose distributions from intensity modulated radiation therapy. Twenty-five clinical plans from twenty-one head and neck (HN) patients were used for a phenomenological study of the cluster structure formed from the dose distributions of organs at risks (OARs) close to the planning target volumes (PTVs). Initially, OAR clusters were searched to examine the pattern consistence among ten HN patients and five clinically similar plans from another HN patient. Second, clusters of the esophagus from another ten HN patients were scrutinized to correlate their sizes to radiobiological parameters. Finally, an extensive Monte Carlo (MC) procedure was implemented to gain deeper insights into the behavioral properties of the cluster formation. Clinical studies showed that OAR clusters had drastic differences despite similar PTV coverage among different patients, and the radiobiological parameters failed to positively correlate with the cluster sizes. MC study demonstrated the inverse relationship between the cluster size and the cluster connectivity, and the nonlinear changes in cluster size with dose thresholds. In addition, the clusters were insensitive to the shape of OARs. The results demonstrated that the cluster size could serve as an insightful index of normal tissue damage. The clinical outcome of the same dose-volume might be potentially different. Copyright © 2018 Elsevier B.V. All rights reserved.

  15. Understanding the structural properties and thermal stabilities of Au–Pd–Pt trimetallic clusters

    International Nuclear Information System (INIS)

    Zhao, Zheng; Li, Mingjiang; Cheng, Daojian; Zhu, Jiqin

    2014-01-01

    Highlights: • Structural properties of Au–Pd–Pt clusters are studied by Monte Carlo simulation. • Melting of Au–Pd–Pt clusters is studied by molecular dynamics simulation. • Au atoms are systematically segregated on the surface of the Au–Pd–Pt clusters. • Linear decrease in cluster melting point with the inverse cluster diameter. - Abstract: In this work, surface segregation phenomena of Au–Pd–Pt trimetallic clusters are investigated by using semi-grand Monte Carlo simulations based on the Gupta potential. It is found that Au atoms are systematically segregated on the surface of the Au–Pd–Pt clusters (6–24 at.% higher than the overall Au concentration), due to the competition among the surface energies of Au, Pd, and Pt. The melting properties of Au–Pd–Pt trimetallic clusters with different composition and size are investigated by using molecular dynamics simulations, based on the same Gupta potential. It is found that the Au–Pd–Pt trimetallic cluster with the highest melting point corresponds to the one with the most stable structure. In addition, linear decrease in cluster melting point with the inverse cluster diameter is predicted for both pure and trimetallic clusters, which is well-known as the Pawlow’s law

  16. Design of compound libraries based on natural product scaffolds and protein structure similarity clustering (PSSC)

    NARCIS (Netherlands)

    Balamurugan, Rengarajan; Dekker, Frank J; Waldmann, Herbert; Dekker, Frans

    Recent advances in structural biology, bioinformatics and combinatorial chemistry have significantly impacted the discovery of small molecules that modulate protein functions. Natural products which have evolved to bind to proteins may serve as biologically validated starting points for the design

  17. Tight-binding study of the structural and magnetic properties of vanadium clusters

    International Nuclear Information System (INIS)

    Zhao Jijun; Lain, K.D.

    1995-01-01

    The structural and magnetic properties of small vanadium clusters are studied in the framework of tight-binding theory. According to parameters of the cluster dimer and bulk solid, we developed a tight-binding interatomic potential and calculated the bonding energies for the different possible structures to determine the ground state atomic configurations of the small vanadium clusters. The theoretical bonding energies for the vanadium clusters agree with the experiment much better than the simple droplet model. However, the calculated values for the clusters of odd atomic number are somewhat higher than the measured ones, corresponding to the pair occupation of delocalized 4s 1 electrons. Based on the optimized geometries, we study the magnetic properties of these clusters through a parametrized Hubbard Hamiltonian. We find the small V clusters of ground-state structures exhibit antiferromagnetic behavior while the alignment of local moments in the clusters with the unoptimized structures may show either ferromagnetic or antiferromagnetic characteristics. The average magnetic moments of the clusters decrease nonmonotonically as cluster size increases and the theoretical results are consistent with the upper limits obtained from a recent experiment. (orig.)

  18. Ioniclike energy structure of neutral core-excited states in free Kr clusters

    International Nuclear Information System (INIS)

    Peredkov, S.; Sorensen, S.L.; Kivimaeki, A.; Schulz, J.; Maartensson, N.; Oehrwall, G.; Lundwall, M.; Rander, T.; Lindblad, A.; Bergersen, H.; Svensson, S.; Bjoerneholm, O.; Tchaplyguine, M.

    2005-01-01

    The development of electronic states in krypton clusters is investigated by high-resolution core-level electron spectroscopy. The energy ordering of bulk versus surface 3d -1 np(n>5) core-excited states in neutral clusters is demonstrated to be reversed to the 3d -1 5p level situation. The cluster 3d -1 6p,7p states are proven to be at a lower energy than the corresponding atomic levels. These findings reveal the ioniclike energy structure of the neutral cluster core-excited levels. The phenomenon is explained by a spatial spread of the excited orbitals over the cluster lattice

  19. Structural, electronic and magnetic properties of small bimetallic zirconium–palladium clusters: Ab initio study

    International Nuclear Information System (INIS)

    Bezi Javan, Masoud

    2015-01-01

    Highlights: • Electronic and magnetic properties of small Zr n Pd m (n + m ⩽ 5) have been investigated. • Binding energies of the Zr n clusters are significantly higher than Pd n clusters. • Binding energy of the Pd n clusters increase with substituting one or more Zr atom. • HOMO–LUMO gap of the Zr n Pd m clusters increase in comparison with pure states. - Abstract: Structural, electronic and magnetic properties of small bimetallic zirconium–palladium clusters, Zr n Pd m (n + m ⩽ 5), have been investigated using density functional theory with considering generalized gradient approximation and PBE functional. We have determined the ground state conformations of the bimetallic zirconium–palladium clusters by substitution of Zr and Pd atoms in the optimized lowest energy structures of pure zirconium and palladium clusters. Results reveal that binding energies of the pure Zr n clusters are significantly higher than Pd n clusters with the same number of atoms. Also it is found that binding energy of the Zr n and Pd n clusters increase with growth of the number of consisting atoms in the clusters. Results indicate that, for both Zr n and Pd n clusters the binding energy of planar forms is lower than three-dimensional structures. We have also found that the binding energy of the Pd n clusters increase with substituting one or more Zr atoms in these clusters. We have also studied the HOMO–LUMO energy gap and magnetic moment of the pure and combined Zr and Pd clusters. The energy gap analysis of the pure and combined Pd and Zr clusters show that in generally the HOMO–LUMO gap of the bimetallic Zr n Pd m clusters increase in comparison with their corresponding pure clusters with the same number of atoms. According to the spin polarization DFT calculations all of the Zr n Pd m (n + m ⩽ 5) have net magnetic moments as instance the Zr 2 , Pd 2 and ZrPd clusters show a total magnetic moment value of 2 μ B . Some more discussions around charge population

  20. Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

    Energy Technology Data Exchange (ETDEWEB)

    Vlcek, Lukas [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Uhlik, Filip [Charles Univ., Prague (Czech Republic); Moucka, Filip [Purkinje Univ. (Czech Republic); Nezbeda, Ivo [Purkinje Univ. (Czech Republic); Academy of Sciences of the Czech Republic (ASCR), Prague (Czech Republic); Chialvo, Ariel A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

    2015-12-16

    We evaluate the ability of selected classical molecular models to describe the thermodynamic and structural aspects of gas-phase hydration of alkali halide ions and the formation of small water clusters. To understand the effect of many-body interactions (polarization) and charge penetration effects on the accuracy of a force field, we perform Monte Carlo simulations with three rigid water models using different functional forms to account for these effects: (i) point charge non-polarizable SPC/E, (ii) Drude point charge polarizable SWM4- DP, and (iii) Drude Gaussian charge polarizable BK3. Model predictions are compared with experimental Gibbs free energies and enthalpies of ion hydration, and with microscopic structural properties obtained from quantum DFT calculations. We find that all three models provide comparable predictions for pure water clusters and cation hydration, but differ significantly in their description of anion hydration. None of the investigated classical force fields can consistently and quantitatively reproduce the experimental gas phase hydration thermodynamics. The outcome of this study highlights the relation between the functional form that describes the effective intermolecular interactions and the accuracy of the resulting ion hydration properties.

  1. The structure of nearby clusters of galaxies Hierarchical clustering and an application to the Leo region

    CERN Document Server

    Materne, J

    1978-01-01

    A new method of classifying groups of galaxies, called hierarchical clustering, is presented as a tool for the investigation of nearby groups of galaxies. The method is free from model assumptions about the groups. The scaling of the different coordinates is necessary, and the level from which one accepts the groups as real has to be determined. Hierarchical clustering is applied to an unbiased sample of galaxies in the Leo region. Five distinct groups result which have reasonable physical properties, such as low crossing times and conservative mass-to-light ratios, and which follow a radial velocity- luminosity relation. Only 4 out of 39 galaxies were adopted as field galaxies. (27 refs).

  2. From clusters to biomolecules: electric dipole, structure and dynamics

    International Nuclear Information System (INIS)

    Broyer, M; Antoine, R; Compagnon, I; Rayane, D; Dugourd, P

    2007-01-01

    In this paper, it is demonstrated that the electric dipole of complex molecules or clusters can be measured by beam deviation in an inhomogeneous electric field. This measurement, associated to appropriate theoretical calculations and simulations, allows us to determine the geometry of these systems and their dynamical behaviour as a function of temperature. Selected examples for mixed clusters (metal-fullerene, metal-benzene, salt) and biomolecules (hydrogen bound amino acids and glycine based polypeptides) are discussed

  3. Scalla: Structured Cluster Architecture for Low Latency Access

    Energy Technology Data Exchange (ETDEWEB)

    Hanushevsky, Andrew; Wang, Daniel L.; /SLAC

    2012-03-20

    Scalla is a distributed low-latency file access system that incorporates novel techniques that minimize latency and maximize scalability over a large distributed system with a distributed namespace. Scalla's techniques have shown to be effective in nearly a decade of service for the high-energy physics community using commodity hardware and interconnects. We describe the two components used in Scalla that are instrumental in its ability to provide low-latency, fault-tolerant name resolution and load distribution, and enable its use as a high-throughput, low-latency communication layer in the Qserv system, the Large Synoptic Survey Telescope's (LSST's) prototype astronomical query system. Scalla arguably exceeded its three main design objectives: low latency, scaling, and recoverability. In retrospect, these objectives were met using a simple but effective design. Low latency was met by uniformly using linear or constant time algorithms in all high-use paths, avoiding locks whenever possible, and using compact data structures to maximize the memory caching efficiency. Scaling was achieved by architecting the system as a 64-ary tree. Nodes can be added easily and as the number of nodes increases, search performance increases at an exponential rate. Recoverability is inherent in that no permanent state information is maintained and whatever state information is needed it can be quickly constructed or reconstructed in real time. This allows dynamic changes in a cluster of servers with little impact on over-all performance or usability. Today, Scalla is being deployed in environments and for uses that were never conceived in 2001. This speaks well for the systems adaptability but the underlying reason is that the system can meet its three fundamental objectives at the same time.

  4. Chemistry and structure of lunar and synthetic armalcolite

    International Nuclear Information System (INIS)

    Wechsler, B.A.; Prewitt, C.T.; Papike, J.J.

    1976-01-01

    A study of the chemical trends displayed by lunar armalcolites has been made in conjunction with single-crystal X-ray structure refinements of lunar and synthetic armalcolite in order to assess the possible importance of Ti 3+ in lunar armalcolite and to characterize the effects of cation substitutions on the structure. The apparent cation deficiences found in lunar armalcolites analyzed with the electron microprobe most likely reflect the presence of Ti 3+ , although the existence of vacancies cannot be ruled out. Structure refinements of an Apollo 17 armalcolite are consistent with either interpretation. These results support experimental evidence suggesting the presence of Ti 3+ in armalcolite and indicate that virtually all lunar armalcolites probably contain approximately 4-11 mol.% Ti 2 3+ Ti 4+ 0 5 component in solid solution. The cation distribution in lunar armalcolite is essentially completely ordered. However, synthetic crystals quenched from near 1200 0 C have been found to retain significant cation disorder. (Auth.)

  5. Isotope chemistry and molecular structure. The WINIMAX weighting factor

    International Nuclear Information System (INIS)

    Lee, M.W.; Bigeleisen, J.

    1979-01-01

    The modulating coefficients for the finite polynomial expansion of the logarithm of the reduced partition function, lnb (u), of a harmonic oscillator have been obtained for the range of 0 6 . It is shown that this weighting function is near optimum to insure minimum amplitudes of oscillation in the expansion of lnb (u) as a function of the order of the expansion and to include most of the important molecular structure information contained in the moments of the eigenvalues. Beyond Σu/sub i/ 6 , there is little new structural information

  6. Titanium embedded cage structure formation in AlnTi+ clusters and their interaction with Ar

    International Nuclear Information System (INIS)

    Torres, M. B.; Vega, A.; Balbás, L. C.; Aguilera-Granja, F.

    2014-01-01

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al n Ti + [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n c determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al n Ti + , experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al n Ti + (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n c = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n c = 21) and their neutral counterparts (n c = 20). For the Al n Ti + · Ar complexes, and for n n Ti + clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support to the experimental technique used. For n c = 21, the smallest size of endohedral Ti doped cationic clusters, the Ar binding energy decreases drastically, whereas the Ar-cluster distance increases substantially, point to Ar physisorption, as assumed by the experimentalists. Calculated Ar adsorption energies agree well with available experimental binding

  7. Structure of s - p bonded metal clusters with 8, 20 and 40 valence electrons

    International Nuclear Information System (INIS)

    Kumar, V.

    1992-10-01

    From studies on some clusters of metals and semiconductors, there appear some similarities in the structure of clusters with a given number of atoms and having the number of valence electrons corresponding to a shell closing. Here we present results of the atomic and electronic structure of a few other clusters with 20 and 40 valence electrons, namely Sb 4 , Sn 5 and Sb 8 using the density functional molecular dynamics method. We suggest that the similarities in the structure and deviation from them may help to understand bonding characteristics in clusters and its evolution to bulk behaviour. Our results on Sb 8 cluster are preliminary but indicate that above room temperature its structure is two weakly interacting tetrahedra which is in general agreement with the observation of predominently antimony tetramers at T > 300 K. (author). 16 refs, 2 figs

  8. Atomic and electronic structure of clusters from car-Parrinello method

    International Nuclear Information System (INIS)

    Kumar, V.

    1994-06-01

    With the development of ab-initio molecular dynamics method, it has now become possible to study the static and dynamical properties of clusters containing up to a few tens of atoms. Here I present a review of the method within the framework of the density functional theory and pseudopotential approach to represent the electron-ion interaction and discuss some of its applications to clusters. Particular attention is focussed on the structure and bonding properties of clusters as a function of their size. Applications to clusters of alkali metals and Al, non-metal - metal transition in divalent metal clusters, molecular clusters of carbon and Sb are discussed in detail. Some results are also presented on mixed clusters. (author). 121 refs, 24 ifigs

  9. Effects of manganese doping on the structure evolution of small-sized boron clusters

    Science.gov (United States)

    Zhao, Lingquan; Qu, Xin; Wang, Yanchao; Lv, Jian; Zhang, Lijun; Hu, Ziyu; Gu, Guangrui; Ma, Yanming

    2017-07-01

    Atomic doping of clusters is known as an effective approach to stabilize or modify the structures and properties of resulting doped clusters. We herein report the effect of manganese (Mn) doping on the structure evolution of small-sized boron (B) clusters. The global minimum structures of both neutral and charged Mn doped B cluster \\text{MnB}nQ (n  =  10-20 and Q  =  0, ±1) have been proposed through extensive first-principles swarm-intelligence based structure searches. It is found that Mn doping has significantly modified the grow behaviors of B clusters, leading to two novel structural transitions from planar to tubular and then to cage-like B structures in both neutral and charged species. Half-sandwich-type structures are most favorable for small \\text{MnB}n-/0/+ (n  ⩽  13) clusters and gradually transform to Mn-centered double-ring tubular structures at \\text{MnB}16-/0/+ clusters with superior thermodynamic stabilities compared with their neighbors. Most strikingly, endohedral cages become the ground-state structures for larger \\text{MnB}n-/0/+ (n  ⩾  19) clusters, among which \\text{MnB}20+ adopts a highly symmetric structure with superior thermodynamic stability and a large HOMO-LUMO gap of 4.53 eV. The unique stability of the endohedral \\text{MnB}\\text{20}+ cage is attributed to the geometric fit and formation of 18-electron closed-shell configuration. The results significantly advance our understanding about the structure and bonding of B-based clusters and strongly suggest transition-metal doping as a viable route to synthesize intriguing B-based nanomaterials.

  10. Modelling of Krn+ Clusters (n = 2 - 20) I. Structures and Energetics

    Czech Academy of Sciences Publication Activity Database

    Kalus, R.; Paidarová, Ivana; Hrivňák, D.; Paška, P.; Gadea, F. X.

    2003-01-01

    Roč. 294, č. 2 (2003), s. 141-153 ISSN 0301-0104 R&D Projects: GA ČR GA203/00/1025; GA ČR GA203/01/1274 Institutional research plan: CEZ:AV0Z4040901 Keywords : cluster modelling * rare-gas ions * an initio potential Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.070, year: 2003

  11. Click chemistry for the conservation of cellular structures and fluorescent proteins: ClickOx.

    Science.gov (United States)

    Löschberger, Anna; Niehörster, Thomas; Sauer, Markus

    2014-05-01

    Reactive oxygen species (ROS), including hydrogen peroxide, are known to cause structural damage not only in living, but also in fixed, cells. Copper-catalyzed azide-alkyne cycloaddition (click chemistry) is known to produce ROS. Therefore, fluorescence imaging of cellular structures, such as the actin cytoskeleton, remains challenging when combined with click chemistry protocols. In addition, the production of ROS substantially weakens the fluorescence signal of fluorescent proteins. This led us to develop ClickOx, which is a new click chemistry protocol for improved conservation of the actin structure and better conservation of the fluorescence signal of green fluorescent protein (GFP)-fusion proteins. Herein we demonstrate that efficient oxygen removal by addition of an enzymatic oxygen scavenger system (ClickOx) considerably reduces ROS-associated damage during labeling of nascent DNA with ATTO 488 azide by Cu(I)-catalyzed click chemistry. Standard confocal and super-resolution fluorescence images of phalloidin-labeled actin filaments and GFP/yellow fluorescent protein-labeled cells verify the conservation of the cytoskeleton microstructure and fluorescence intensity, respectively. Thus, ClickOx can be used advantageously for structure preservation in conventional and most notably in super-resolution microscopy methods. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Structure activity study on the quinone/quinone methide chemistry of flavonoids

    NARCIS (Netherlands)

    Awad, H.M.; Boersma, M.G.; Boeren, S.; Bladeren, van P.J.; Vervoort, J.; Rietjens, I.M.C.M.

    2001-01-01

    A structure-activity study on the quinone/quinone methide chemistry of a series of 3',4'-dihydroxyflavonoids was performed. Using the glutathione trapping method followed by HPLC, 1H NMR, MALDI-TOF, and LC/MS analysis to identify the glutathionyl adducts, the chemical behavior of the

  13. The role of supramolecular chemistry in stimuli responsive and hierarchically structured functional organic materials

    NARCIS (Netherlands)

    Schenning, A.P.H.J.; Bastiaansen, C.W.M.; Broer, D.J.; Debije, M.G.

    2014-01-01

    ABSTRACT: In this review, we show the important role of supramolecular chemistry in the fabrication of stimuli responsive and hierarchically structured liquid crystalline polymer networks. Supramolecular interactions can be used to create three dimensional order or as molecular triggers in materials

  14. A contribution to the study of the structure, reactivity and bioinorganic chemistry of iron

    International Nuclear Information System (INIS)

    Toma, H.E.

    1984-01-01

    The research work on inorganic and biological chemistry of iron developed at the University of Sao Paulo (SP, Brazil) is reviewed. Considerations are made about: π interactions, electronic structure and spectroscopy of cyanoferrates; solvation studies and kinetics of substitution reactions involving iron complexes; reactivity of coordinating ligands and iron interactions with biomolecules. (C.L.B.) [pt

  15. Structural fragment clustering reveals novel structural and functional motifs in α-helical transmembrane proteins

    Directory of Open Access Journals (Sweden)

    Vassilev Boris

    2010-04-01

    Full Text Available Abstract Background A large proportion of an organism's genome encodes for membrane proteins. Membrane proteins are important for many cellular processes, and several diseases can be linked to mutations in them. With the tremendous growth of sequence data, there is an increasing need to reliably identify membrane proteins from sequence, to functionally annotate them, and to correctly predict their topology. Results We introduce a technique called structural fragment clustering, which learns sequential motifs from 3D structural fragments. From over 500,000 fragments, we obtain 213 statistically significant, non-redundant, and novel motifs that are highly specific to α-helical transmembrane proteins. From these 213 motifs, 58 of them were assigned to function and checked in the scientific literature for a biological assessment. Seventy percent of the motifs are found in co-factor, ligand, and ion binding sites, 30% at protein interaction interfaces, and 12% bind specific lipids such as glycerol or cardiolipins. The vast majority of motifs (94% appear across evolutionarily unrelated families, highlighting the modularity of functional design in membrane proteins. We describe three novel motifs in detail: (1 a dimer interface motif found in voltage-gated chloride channels, (2 a proton transfer motif found in heme-copper oxidases, and (3 a convergently evolved interface helix motif found in an aspartate symporter, a serine protease, and cytochrome b. Conclusions Our findings suggest that functional modules exist in membrane proteins, and that they occur in completely different evolutionary contexts and cover different binding sites. Structural fragment clustering allows us to link sequence motifs to function through clusters of structural fragments. The sequence motifs can be applied to identify and characterize membrane proteins in novel genomes.

  16. Structure, Bonding and Surface Chemistry of Metal Oxide Nanoclusters

    Science.gov (United States)

    2015-06-23

    an electrospray ionization time-of-flight (ESI-TOF) mass spectrometer to the lab (PerSeptive Biosystems Mariner), which provides a different...with this Project Faculty: Professor Michael A. Duncan (one month summer salary) Prof. Heather Abbott -Lyons, summer visiting faculty and...Distribution approved for public release. 4. H. L. Abbott , A. D. Brathwaite and M. A. Duncan, "Infrared spectroscopy and structures of mass-selected

  17. GPCR crystal structures: Medicinal chemistry in the pocket.

    Science.gov (United States)

    Shonberg, Jeremy; Kling, Ralf C; Gmeiner, Peter; Löber, Stefan

    2015-07-15

    Recent breakthroughs in GPCR structural biology have significantly increased our understanding of drug action at these therapeutically relevant receptors, and this will undoubtedly lead to the design of better therapeutics. In recent years, crystal structures of GPCRs from classes A, B, C and F have been solved, unveiling a precise snapshot of ligand-receptor interactions. Furthermore, some receptors have been crystallized in different functional states in complex with antagonists, partial agonists, full agonists, biased agonists and allosteric modulators, providing further insight into the mechanisms of ligand-induced GPCR activation. It is now obvious that there is enormous diversity in the size, shape and position of the ligand binding pockets in GPCRs. In this review, we summarise the current state of solved GPCR structures, with a particular focus on ligand-receptor interactions in the binding pocket, and how this can contribute to the design of GPCR ligands with better affinity, subtype selectivity or efficacy. Copyright © 2015 Elsevier Ltd. All rights reserved.

  18. Electronic structure of the BiSI cluster

    International Nuclear Information System (INIS)

    Audzijonis, A.; Gaigalas, G.; Zigas, L.; Pauliukas, A.; Zaltauskas, R.; Cerskus, A.; Narusis, J.; Kvedaravicius, A.

    2007-01-01

    The energy levels of valence bands (VB) and core levels (CL) of the BiSI crystals have been investigated theoretically. The molecular model of this crystal was used for calculation of VB and CL by the unrestricted Hartree-Fock method using GAMESS program, with Hw and MINI basis set. The molecular cluster consisting of 20 molecules of BiSI was used for calculations of averaged total density of states including atom vibrations. The spectra of averaged total density of states from VB of BiSI cluster has been compared with experimental X-ray photoelectron spectra (XPS) of VB of SbSI crystal. The results clarify that the atomic vibrations is one of possible reasons for the smoother appearance of the experimental XPS. The investigation of vibrational spectrum reveals new experimental information about the reflection spectrum of BiSI crystals. The cluster model calculations have shown that the splitting of the CL in the BiSI may be caused by the photoelectron emission from the atoms at the surface that is in different valence states. The cluster model calculation showed that splitting energy of CL depends on difference of ionic charges of the same atoms at the edges of BiSI cluster

  19. Electronic structure of the BiSI cluster

    Energy Technology Data Exchange (ETDEWEB)

    Audzijonis, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Gaigalas, G. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, LT-01108 Vilnius (Lithuania); Zigas, L. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania)]. E-mail: kkol@vpu.lt; Pauliukas, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Zaltauskas, R. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Cerskus, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Narusis, J. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania); Institute of Theoretical Physics and Astronomy, Vilnius University, A. Gostauto 12, LT-01108 Vilnius (Lithuania); Kvedaravicius, A. [Department of Physics, Vilnius Pedagogical University, Studentu 39, LT-08106 Vilnius (Lithuania)

    2007-03-15

    The energy levels of valence bands (VB) and core levels (CL) of the BiSI crystals have been investigated theoretically. The molecular model of this crystal was used for calculation of VB and CL by the unrestricted Hartree-Fock method using GAMESS program, with Hw and MINI basis set. The molecular cluster consisting of 20 molecules of BiSI was used for calculations of averaged total density of states including atom vibrations. The spectra of averaged total density of states from VB of BiSI cluster has been compared with experimental X-ray photoelectron spectra (XPS) of VB of SbSI crystal. The results clarify that the atomic vibrations is one of possible reasons for the smoother appearance of the experimental XPS. The investigation of vibrational spectrum reveals new experimental information about the reflection spectrum of BiSI crystals. The cluster model calculations have shown that the splitting of the CL in the BiSI may be caused by the photoelectron emission from the atoms at the surface that is in different valence states. The cluster model calculation showed that splitting energy of CL depends on difference of ionic charges of the same atoms at the edges of BiSI cluster.

  20. THE STRUCTURAL EVOLUTION OF FORMING AND EARLY STAGE STAR CLUSTERS

    International Nuclear Information System (INIS)

    Jaehnig, Karl O.; Da Rio, Nicola; Tan, Jonathan C.

    2015-01-01

    We study the degree of angular substructure in the stellar position distribution of young members of Galactic star-forming regions, looking for correlations with distance from cluster center, surface number density of stars, and local dynamical age. To this end we adopt the catalog of members in 18 young (∼1-3 Myr) clusters from the Massive Young Star-Forming Complex Study in Infrared and X-ray Survey and the statistical analysis of the angular dispersion parameter, δ ADP, N . We find statistically significant correlation between δ ADP, N and physical projected distance from the center of the clusters, with the centers appearing smoother than the outskirts, consistent with more rapid dynamical processing on local dynamical, free-fall or orbital timescales. Similarly, smoother distributions are seen in regions of higher surface density, or older dynamical ages. These results indicate that dynamical processing that erases substructure is already well-advanced in young, sometimes still-forming, clusters. Such observations of the dissipation of substructure have the potential to constrain theoretical models of the dynamical evolution of young and forming clusters

  1. Structural transition of (InSb)n clusters at n = 6-10

    Science.gov (United States)

    Lu, Qi Liang; Luo, Qi Quan; Huang, Shou Guo; Li, Yi De

    2016-10-01

    An optimization strategy combining global semi-empirical quantum mechanical search with all-electron density functional theory was adopted to determine the lowest energy structure of (InSb)n clusters with n = 6-10. A new structural growth pattern of the clusters was observed. The lowest energy structures of (InSb)6 and (InSb)8 were different from that of previously reported results. Competition existed between core-shell and cage-like structures of (InSb)8. The structural transition of (InSb)n clusters occurred at size n = 8-9. For (InSb)9 and (InSb)10 clusters, core-shell structure were more energetically favorable than the cage. The corresponding electronic properties were investigated.

  2. Theoretical study of the structure of a Ga{sub 6}N{sub 6} cluster

    Energy Technology Data Exchange (ETDEWEB)

    Song Bin; Cao Peilin; Li Baoxing

    2003-08-25

    The structures and energies of a Ga{sub 6}N{sub 6} cluster have been calculated using a full-potential linear-muffin-tin-orbital (FP-LMTO) method, combined with molecular dynamics and simulated annealing techniques. We obtained 19 structures for a Ga{sub 6}N{sub 6} cluster. The most stable structure we obtained is a C{sub s} three-dimensional structure with a N{sub 2} and N{sub 3} subunits. The calculated results show that the existence of strong N-N bonds still dominates the structure of a Ga{sub 6}N{sub 6} cluster, supporting the previous result made by Kandalam et al. [J. Phys. Chem. B 106 (2002) 1945]. Through the calculation of the density of states we found that the most stable structure of Ga{sub 6}N{sub 6} clusters presented semiconductor-like properties.

  3. Detection of secondary structure elements in proteins by hydrophobic cluster analysis.

    Science.gov (United States)

    Woodcock, S; Mornon, J P; Henrissat, B

    1992-10-01

    Hydrophobic cluster analysis (HCA) is a protein sequence comparison method based on alpha-helical representations of the sequences where the size, shape and orientation of the clusters of hydrophobic residues are primarily compared. The effectiveness of HCA has been suggested to originate from its potential ability to focus on the residues forming the hydrophobic core of globular proteins. We have addressed the robustness of the bidimensional representation used for HCA in its ability to detect the regular secondary structure elements of proteins. Various parameters have been studied such as those governing cluster size and limits, the hydrophobic residues constituting the clusters as well as the potential shift of the cluster positions with respect to the position of the regular secondary structure elements. The following results have been found to support the alpha-helical bidimensional representation used in HCA: (i) there is a positive correlation (clearly above background noise) between the hydrophobic clusters and the regular secondary structure elements in proteins; (ii) the hydrophobic clusters are centred on the regular secondary structure elements; (iii) the pitch of the helical representation which gives the best correspondence is that of an alpha-helix. The correspondence between hydrophobic clusters and regular secondary structure elements suggests a way to implement variable gap penalties during the automatic alignment of protein sequences.

  4. Modern quantum chemistry introduction to advanced electronic structure theory

    CERN Document Server

    Szabo, Attila

    1996-01-01

    The aim of this graduate-level textbook is to present and explain, at other than a superficial level, modem ab initio approaches to the calculation of the electronic structure and properties of molecules. The first three chapters contain introductory material culminating in a thorough discussion of the Hartree-Fock approximation.The remaining four chapters describe a variety of more sophisticated approaches, which improve upon this approximation.Among the highlights of the seven chapters are (1) a review of the mathematics (mostly matrix algebra) required for the rest of the book, (2) an intr

  5. Chemistry and Structure-Activity Relationships of Psychedelics.

    Science.gov (United States)

    Nichols, David E

    2018-01-01

    This chapter will summarize structure-activity relationships (SAR) that are known for the classic serotonergic hallucinogens (aka psychedelics), focusing on the three chemical types: tryptamines, ergolines, and phenethylamines. In the brain, the serotonin 5-HT 2A receptor plays a key role in regulation of cortical function and cognition, and also appears to be the principal target for hallucinogenic/psychedelic drugs such as LSD. It is one of the most extensively studied of the 14 known types of serotonin receptors. Important structural features will be identified for activity and, where possible, those that the psychedelics have in common will be discussed. Because activation of the 5-HT 2A receptor is the principal mechanism of action for psychedelics, compounds with 5-HT 2A agonist activity generally are quickly discarded by the pharmaceutical industry. Thus, most of the research on psychedelics can be related to activation of 5-HT 2A receptors. Therefore, much of the discussion will include not only clinical or anecdotal studies, but also will consider data from animal models as well as a certain amount of molecular pharmacology where it is known.

  6. Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters using Density Functional Theory

    Science.gov (United States)

    2017-05-05

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--17-9724 Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters...TELEPHONE NUMBER (include area code) b. ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Equilibrium Structures and Absorption...and electronic excited-state absorption spectra for eqilibrium structures of SixOy molecular clusters using density function theory (DFT) and time

  7. Carbon based nanostructures: diamond clusters structured with nanotubes

    Directory of Open Access Journals (Sweden)

    O.A. Shenderova

    2003-01-01

    Full Text Available Feasibility of designing composites from carbon nanotubes and nanodiamond clusters is discussed based on atomistic simulations. Depending on nanotube size and morphology, some types of open nanotubes can be chemically connected with different facets of diamond clusters. The geometrical relation between different types of nanotubes and different diamond facets for construction of mechanically stable composites with all bonds saturated is summarized. Potential applications of the suggested nanostructures are briefly discussed based on the calculations of their electronic properties using environment dependent self-consistent tight-binding approach.

  8. Physics and Chemistry of Creating New Titanates with Perovskite Structure

    Science.gov (United States)

    Politova, E. D.; Kaleva, G. M.; Golubko, N. V.; Mosunov, A. V.; Sadovskaya, N. V.; Bel'kova, D. A.; Strebkov, D. A.; Stefanovich, S. Yu.; Kiselev, D. A.; Kislyuk, A. M.

    2018-06-01

    The phase formation, structural features, and dielectric, ferroelectric, and piezoelectric properties of ceramics with compositions from the region of the morphotropic phase boundary in the (Na0.5Bi0.5)TiO3-BaTiO3-Bi(Mg0.5Ti0.5)O3 system modified by different low-melting additives (Bi2O3, V2O5, KCl, NaCl-LiF, LiF, CuO, and MnO2) are studied. First-order phase transitions are detected near 700-800 and 400 K that display relaxor behavior and are indicative of the presence of polar regions in a nonpolar matrix. Prospects for improving the piezoelectric properties of the modified ceramic samples are confirmed.

  9. Dark energy and the structure of the Coma cluster of galaxies

    Science.gov (United States)

    Chernin, A. D.; Bisnovatyi-Kogan, G. S.; Teerikorpi, P.; Valtonen, M. J.; Byrd, G. G.; Merafina, M.

    2013-05-01

    Context. We consider the Coma cluster of galaxies as a gravitationally bound physical system embedded in the perfectly uniform static dark energy background as implied by ΛCDM cosmology. Aims: We ask if the density of dark energy is high enough to affect the structure of a large and rich cluster of galaxies. Methods: We base our work on recent observational data on the Coma cluster, and apply our theory of local dynamical effects of dark energy, including the zero-gravity radius RZG of the local force field as the key parameter. Results: 1) Three masses are defined that characterize the structure of a regular cluster: the matter mass MM, the dark-energy effective mass MDE (antigravity affects the structure of the Coma cluster strongly at large radii R ≳ 14 Mpc and should be considered when its total mass is derived.

  10. Structure and dynamics of ion clusters in linear octupole traps: Phase diagrams, chirality, and melting mechanisms

    International Nuclear Information System (INIS)

    Yurtsever, E.; Onal, E. D.; Calvo, F.

    2011-01-01

    The stable structures and melting dynamics of clusters of identical ions bound by linear octupole radiofrequency traps are theoretically investigated by global optimization methods and molecular dynamics simulations. By varying the cluster sizes in the range of 10-1000 ions and the extent of trap anisotropy by more than one order of magnitude, we find a broad variety of stable structures based on multiple rings at small sizes evolving into tubular geometries at large sizes. The binding energy of these clusters is well represented by two contributions arising from isotropic linear and octupolar traps. The structures generally exhibit strong size effects, and chiral arrangements spontaneously emerge in many crystals. Sufficiently large clusters form nested, coaxial tubes with different thermal stabilities. As in isotropic octupolar clusters, the inner tubes melt at temperatures that are lower than the overall melting point.

  11. Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

    KAUST Repository

    Lucassen, Arnas; Park, Sungwoo; Hansen, Nils; Sarathy, Mani

    2014-01-01

    This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model's capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

  12. Combustion chemistry of alcohols: Experimental and modeled structure of a premixed 2-methylbutanol flame

    KAUST Repository

    Lucassen, Arnas

    2014-06-14

    This paper presents a detailed investigation of 2-methylbutanol combustion chemistry in low-pressure premixed flames. This chemistry is of particular interest to study because this compound is potentially a lignocellulosic-based, next-generation biofuel. The detailed chemical structure of a stoichiometric low-pressure (25 Torr) flame was determined using flame-sampling molecular-beam mass spectrometry. A total of 55 species were identified and subsequently quantitative mole fraction profiles as function of distance from the burner surface were determined. In an independent effort, a detailed flame chemistry model for 2-methylbutanol was assembled based on recent knowledge gained from combustion chemistry studies for butanol isomers ([Sarathy et al. Combust. Flame 159 (6) (2012) 2028-2055]) and iso-pentanol (3-methylbutanol) [Sarathy et al. Combust. Flame 160 (12) (2013) 2712-2728]. Experimentally determined and modeled mole fraction profiles were compared to demonstrate the model\\'s capabilities. Examples of individual mole fraction profiles are discussed together with the most significant fuel consumption pathways to highlight the combustion chemistry of 2-methylbutanol. Discrepancies between experimental and modeling results are used to suggest areas where improvement of the kinetic model would be needed. © 2014.

  13. Study of structure and spectroscopy of water–hydroxide ion clusters ...

    Indian Academy of Sciences (India)

    Experimen- talists are interested in determining the bonding,1–18 structure and spectroscopy of these systems and the- oreticians have contributed to the logical explanation of experimental findings. There are different types of systems ranging from atomic clusters, especially noble gas clusters (modelled by Lennard Jones ...

  14. Ground state structures and properties of Si3Hn (n= 1–6) clusters

    Indian Academy of Sciences (India)

    The ground state structures and properties of Si3H (1 ≤ ≤ 6) clusters have been calculated using Car–Parrinello molecular dynamics with simulated annealing and steepest descent optimization methods. We have studied cohesive energy per particle and first excited electronic level gap of the clusters as a function of ...

  15. Electronic structure and chemistry of the heaviest elements

    International Nuclear Information System (INIS)

    Pershina, V.; Fricke, B.

    1998-04-01

    Progress in the development of relativistic molecular codes has allowed for an adequate description of the electronic structure of the very heavy element compounds, and for the interpretation and prediction of their molecular properties. Most of the theoretical investigations for compounds, interesting from the experimental point of view, have been carried out using the LDF methods. The studied species were group 4, 5 and 6 gas-phase compounds of the transactinides along with their lighter homologs, and their complexes in aqueous solutions. As a result of these calculations, trends within the transition-element groups and within the beginning of the transactinide series for molecular properties such as ionicity, covalence, stability towards oxidation or reduction, crystal-field and spin-orbit effects, bonding, and the influence of relativistic effects on them have been established. In combination with some other models, these calculations allowed for predicting properties measured experimentally: volatility of compounds, redox potentials in solutions and complex formation. Especially promising were predictions of equilibria of reaction using the DS-DV method. Agreement between results of the calculations and experiment confirmed the necessity of doing relativistic MO calculations and the unreliability of the straightforward extrapolations of properties within the chemical groups. (orig.)

  16. Metastable Structures in Cluster Catalysis from First-Principles: Structural Ensemble in Reaction Conditions and Metastability Triggered Reactivity.

    Science.gov (United States)

    Sun, Geng; Sautet, Philippe

    2018-02-28

    Reactivity studies on catalytic transition metal clusters are usually performed on a single global minimum structure. With the example of a Pt 13 cluster under a pressure of hydrogen, we show from first-principle calculations that low energy metastable structures of the cluster can play a major role for catalytic reactivity and that hence consideration of the global minimum structure alone can severely underestimate the activity. The catalyst is fluxional with an ensemble of metastable structures energetically accessible at reaction conditions. A modified genetic algorithm is proposed to comprehensively search for the low energy metastable ensemble (LEME) structures instead of merely the global minimum structure. In order to reduce the computational cost of density functional calculations, a high dimensional neural network potential is employed to accelerate the exploration. The presence and influence of LEME structures during catalysis is discussed by the example of H covered Pt 13 clusters for two reactions of major importance: hydrogen evolution reaction and methane activation. The results demonstrate that although the number of accessible metastable structures is reduced under reaction condition for Pt 13 clusters, these metastable structures can exhibit high activity and dominate the observed activity due to their unique electronic or structural properties. This underlines the necessity of thoroughly exploring the LEME structures in catalysis simulations. The approach enables one to systematically address the impact of isomers in catalysis studies, taking into account the high adsorbate coverage induced by reaction conditions.

  17. Ionospheric plasma density structures associated with magnetopause motion: a case study using the Cluster spacecraft and the EISCAT Svalbard Radar

    Directory of Open Access Journals (Sweden)

    F. Pitout

    2004-07-01

    Full Text Available On 5 January 2003, the footprint of the Cluster spacecraft, then orbiting in the dayside magnetosphere near the magnetopause, was in the close vicinity of the EISCAT Svalbard Radar (ESR in the dayside afternoon sector. This configuration made possible the study of the magnetopause motion and its direct consequences on the ionospheric plasma at high latitude. Cluster observed multiple magnetopause crossings despite its high latitude, while on the ground the magnetic activity was very low, whereas the ionospheric plasma sounded by the ESR exhibited poleward moving plasma density structures. In this paper, we compare the satellite and radar data, in order to show that the plasma density structures are directly related to the magnetopause motion and its associated pulsed ionospheric flow. We propose that the variations in electric field make the convection velocity vary enough to alter the electron population by accelerating the chemistry in the F-region and act as a source of electron depletion. The magnetopause motion is in this case, a source of plasma density structures in the polar dayside ionosphere.

  18. Evolution of galaxy cluster scaling and structural properties from XMM observations: probing the physics of structure formation

    International Nuclear Information System (INIS)

    Anokhin, Sergey

    2008-01-01

    Clusters of galaxies are the largest gravitationally bound objects in the Universe. It is possible to study the hierarchical structure formation based on these youngest objects in the Universe. In order to complete the results found with hot clusters, we choose the cold distant galaxy clusters selected from The Southern SHARC catalogue. In the same time, we studied archived galaxy clusters to test the theory and treatment analysis. To study these weak cluster of galaxies, we optimized our treatment analysis: in particular, searching for the best background subtraction and modeling it for our surface brightness profile and spectra. Our results are in a good agreement with Scaling Relation obtained from hot galaxy clusters. (author) [fr

  19. Developing and Implementing a Reorganized Undergraduate Chemistry Curriculum Based on the Foundational Chemistry Topics of Structure, Reactivity, and Quantitation

    Science.gov (United States)

    Schaller, Chris P.; Graham, Kate J.; Johnson, Brian J.; Fazal, M. A.; Jones, T. Nicholas; McIntee, Edward J.; Jakubowski, Henry V.

    2014-01-01

    The recent revision of undergraduate curricular guidelines from the American Chemical Society Committee on Professional Training (ACS-CPT) has generated interest in examining new ways of organizing course sequences both for chemistry majors and for nonmajors. A radical reconstruction of the foundation-level chemistry curriculum is presented in…

  20. A catalogue of masses, structural parameters and velocity dispersion profiles of 112 Milky Way globular clusters

    Science.gov (United States)

    Baumgardt, H.; Hilker, M.

    2018-05-01

    We have determined masses, stellar mass functions and structural parameters of 112 Milky Way globular clusters by fitting a large set of N-body simulations to their velocity dispersion and surface density profiles. The velocity dispersion profiles were calculated based on a combination of more than 15,000 high-precision radial velocities which we derived from archival ESO/VLT and Keck spectra together with ˜20, 000 published radial velocities from the literature. Our fits also include the stellar mass functions of the globular clusters, which are available for 47 clusters in our sample, allowing us to self-consistently take the effects of mass segregation and ongoing cluster dissolution into account. We confirm the strong correlation between the global mass functions of globular clusters and their relaxation times recently found by Sollima & Baumgardt (2017). We also find a correlation of the escape velocity from the centre of a globular cluster and the fraction of first generation stars (FG) in the cluster recently derived for 57 globular clusters by Milone et al. (2017), but no correlation between the FG star fraction and the global mass function of a globular cluster. This could indicate that the ability of a globular cluster to keep the wind ejecta from the polluting star(s) is the crucial parameter determining the presence and fraction of second generation stars and not its later dynamical mass loss.

  1. The structural chemistry of metallocorroles: combined X-ray crystallography and quantum chemistry studies afford unique insights.

    Science.gov (United States)

    Thomas, Kolle E; Alemayehu, Abraham B; Conradie, Jeanet; Beavers, Christine M; Ghosh, Abhik

    2012-08-21

    Although they share some superficial structural similarities with porphyrins, corroles, trianionic ligands with contracted cores, give rise to fundamentally different transition metal complexes in comparison with the dianionic porphyrins. Many metallocorroles are formally high-valent, although a good fraction of them are also noninnocent, with significant corrole radical character. These electronic-structural characteristics result in a variety of fascinating spectroscopic behavior, including highly characteristic, paramagnetically shifted NMR spectra and textbook cases of charge-transfer spectra. Although our early research on corroles focused on spectroscopy, we soon learned that the geometric structures of metallocorroles provide a fascinating window into their electronic-structural characteristics. Thus, we used X-ray structure determinations and quantum chemical studies, chiefly using DFT, to obtain a comprehensive understanding of metallocorrole geometric and electronic structures. This Account describes our studies of the structural chemistry of metallocorroles. At first blush, the planar or mildly domed structure of metallocorroles might appear somewhat uninteresting particularly when compared to metalloporphyrins. Metalloporphyrins, especially sterically hindered ones, are routinely ruffled or saddled, but the missing meso carbon apparently makes the corrole skeleton much more resistant to nonplanar distortions. Ruffling, where the pyrrole rings are alternately twisted about the M-N bonds, is energetically impossible for metallocorroles. Saddling is also uncommon; thus, a number of sterically hindered, fully substituted metallocorroles exhibit almost perfectly planar macrocycle cores. Against this backdrop, copper corroles stand out as an important exception. As a result of an energetically favorable Cu(d(x2-y2))-corrole(π) orbital interaction, copper corroles, even sterically unhindered ones, are inherently saddled. Sterically hindered substituents

  2. PREFACE: 10th International Conference on Clustering Aspects of Nuclear Structure and Dynamics (CLUSTER'12)

    Science.gov (United States)

    Lovas, R. G.; Dombrádi, Zs; Kiss, G. G.; Kruppa, A. T.; Lévai, G.

    2013-04-01

    As Editors of this Proceedings volume and organizers as well as participants of the Conference, let us sum up a few facts about the Conference and let us add some subjective notes. The conference was held at Köolcsey Centre, a prestigious site of scientific and business meetings and cultural events in the city of Debrecen, Hungary, 24-28 September 2012. The city was chosen as the home of the Institute of Nuclear Research of the Hungarian Academy of Sciences, the home institution of the organizers. The Institute was visited by some of the participants. The organizing team was complemented by some belonging to the University of Debrecen, which made it possible to hold the conference dinner in the marvellous covered 'ceremonial court' of the University. The participants were taken for an excursion and wine tasting to a wine cellar at Tokaj, centre of, historically, the most significant wine producing area in Hungary. By coincidence, the closing day coincided with the day of what is called the Researchers' Night in the European Union. That night, (or rather, that evening) every year there is a public lecture in the Institute of Nuclear Research for a general audience, mainly secondary-school pupils. The public lecture scheduled on this occasion was held by one of the participants of the conference who represented the world outside Hungary and yet was able to deliver a talk in Hungarian. He is Professor Kálmán Varga, Vanderbilt University. The title of his talk was Simulation of Nanosystems ( http://kutatokejszakaja.hu/2012/esemenynaptar/esemeny.php?id=112&menu_id=4). There were 115 registered participants, representing 22 countries of Europe, Africa, Asia, Central, South and North America. We had 44 plenary talks and 47 talks presented in parallel sessions. In the Programme list the talks are arranged following the session structure of the Conference. In this list the invited speakers are marked by asterisks. All the talks in the plenary sessions were invited talks

  3. Ground state structures and properties of Si3Hn (n = 1–6) clusters

    Indian Academy of Sciences (India)

    Unknown

    Keywords. Car–Parrinello molecular dynamics; hydrogenated silicon clusters; electronic structure calcula- ... the molecular dynamics simulation, allows us to describe dynamics of ... work through charge density analysis (Balamurugan and.

  4. Program package for calculating matrix elements of two-cluster structures in nuclei

    International Nuclear Information System (INIS)

    Krivec, R.; Mihailovic, M.V.; Kernforschungszentrum Karlsruhe G.m.b.H.

    1982-01-01

    Matrix elements of operators between Slater determinants of two-cluster structures must be expanded into partial waves for the purpose of angular momentum projection. The expansion coefficients contain integrals over the spherical angles theta and phi. (orig.)

  5. Mapping RNA Structure In Vitro with SHAPE Chemistry and Next-Generation Sequencing (SHAPE-Seq).

    Science.gov (United States)

    Watters, Kyle E; Lucks, Julius B

    2016-01-01

    Mapping RNA structure with selective 2'-hydroxyl acylation analyzed by primer extension (SHAPE) chemistry has proven to be a versatile method for characterizing RNA structure in a variety of contexts. SHAPE reagents covalently modify RNAs in a structure-dependent manner to create adducts at the 2'-OH group of the ribose backbone at nucleotides that are structurally flexible. The positions of these adducts are detected using reverse transcriptase (RT) primer extension, which stops one nucleotide before the modification, to create a pool of cDNAs whose lengths reflect the location of SHAPE modification. Quantification of the cDNA pools is used to estimate the "reactivity" of each nucleotide in an RNA molecule to the SHAPE reagent. High reactivities indicate nucleotides that are structurally flexible, while low reactivities indicate nucleotides that are inflexible. These SHAPE reactivities can then be used to infer RNA structures by restraining RNA structure prediction algorithms. Here, we provide a state-of-the-art protocol describing how to perform in vitro RNA structure probing with SHAPE chemistry using next-generation sequencing to quantify cDNA pools and estimate reactivities (SHAPE-Seq). The use of next-generation sequencing allows for higher throughput, more consistent data analysis, and multiplexing capabilities. The technique described herein, SHAPE-Seq v2.0, uses a universal reverse transcription priming site that is ligated to the RNA after SHAPE modification. The introduced priming site allows for the structural analysis of an RNA independent of its sequence.

  6. Enhanced magnetostriction derived from magnetic single domain structures in cluster-assembled SmCo films

    Science.gov (United States)

    Bai, Yulong; Yang, Bo; Guo, Fei; Lu, Qingshan; Zhao, Shifeng

    2017-11-01

    Cluster-assembled SmCo alloy films were prepared by low energy cluster beam deposition. The structure, magnetic domain, magnetization, and magnetostriction of the films were characterized. It is shown that the as-prepared films are assembled in compact and uniformly distributed spherical cluster nanoparticles, most of which, after vacuum in situ annealing at 700 K, aggregated to form cluster islands. These cluster islands result in transformations from superparamagnetic states to magnetic single domain (MSD) states in the films. Such MSD structures contribute to the enhanced magnetostrictive behaviors with a saturation magnetostrictive coefficient of 160 × 10-6 in comparison to 105 × 10-6 for the as-prepared films. This work demonstrates candidate materials that could be applied in nano-electro-mechanical systems, low power information storage, and weak magnetic detecting devices.

  7. Structure and Dynamics of the Globular Cluster Palomar 13

    Science.gov (United States)

    Bradford, J. D.; Geha, M.; Muñoz, R. R.; Santana, F. A.; Simon, J. D.; Côté, P.; Stetson, P. B.; Kirby, E.; Djorgovski, S. G.

    2011-12-01

    We present Keck/DEIMOS spectroscopy and Canada-France-Hawaii Telescope/MegaCam photometry for the Milky Way globular cluster Palomar 13. We triple the number of spectroscopically confirmed members, including many repeat velocity measurements. Palomar 13 is the only known globular cluster with possible evidence for dark matter, based on a Keck/High Resolution Echelle Spectrometer 21 star velocity dispersion of σ = 2.2 ± 0.4 km s-1. We reproduce this measurement, but demonstrate that it is inflated by unresolved binary stars. For our sample of 61 stars, the velocity dispersion is σ = 0.7+0.6 -0.5 km s-1. Combining our DEIMOS data with literature values, our final velocity dispersion is σ = 0.4+0.4 -0.3 km s-1. We determine a spectroscopic metallicity of [Fe/H] = -1.6 ± 0.1 dex, placing a 1σ upper limit of σ[Fe/H] ~ 0.2 dex on any internal metallicity spread. We determine Palomar 13's total luminosity to be MV = -2.8 ± 0.4, making it among the least luminous known globular clusters. The photometric isophotes are regular out to the half-light radius and mildly irregular outside this radius. The outer surface brightness profile slope is shallower than typical globular clusters (Σvpropr η, η = -2.8 ± 0.3). Thus at large radius, tidal debris is likely affecting the appearance of Palomar 13. Combining our luminosity with the intrinsic velocity dispersion, we find a dynamical mass of M 1/2 = 1.3+2: 7 -1.3 × 103 M ⊙ and a mass-to-light ratio of M/LV = 2.4+5.0 -2.4 M ⊙/L ⊙. Within our measurement errors, the mass-to-light ratio agrees with the theoretical predictions for a single stellar population. We conclude that, while there is some evidence for tidal stripping at large radius, the dynamical mass of Palomar 13 is consistent with its stellar mass and neither significant dark matter, nor extreme tidal heating, is required to explain the cluster dynamics. The data presented herein were obtained at the W. M. Keck Observatory, which is operated as a

  8. Kendall’s tau and agglomerative clustering for structure determination of hierarchical Archimedean copulas

    Directory of Open Access Journals (Sweden)

    Górecki J.

    2017-01-01

    Full Text Available Several successful approaches to structure determination of hierarchical Archimedean copulas (HACs proposed in the literature rely on agglomerative clustering and Kendall’s correlation coefficient. However, there has not been presented any theoretical proof justifying such approaches. This work fills this gap and introduces a theorem showing that, given the matrix of the pairwise Kendall correlation coefficients corresponding to a HAC, its structure can be recovered by an agglomerative clustering technique.

  9. Theoretical study of structures of Ga{sub 5}N{sub 5} cluster

    Energy Technology Data Exchange (ETDEWEB)

    Song Bin; Cao Peilin

    2002-12-23

    The structures and energies of a Ga{sub 5}N{sub 5} cluster have been calculated using a full-potential linear-muffin-tin-orbital (FP-LMTO) method, combined with molecular dynamics technique. Twenty-four structures for a Ga{sub 5}N{sub 5} cluster have been obtained. The most stable structure is a C{sub 1} planar structure with a N{sub 3} subunit. The Ga{sub 5}N{sub 5} clusters show a preference for a N{sub 3} subunit, revealing the same behavior as in the Ga{sub 3}N{sub 3} and Ga{sub 4}N{sub 4} clusters. The existence of strong N-N bonds dominates the structure of a Ga{sub 5}N{sub 5} cluster. Through the calculation of the density of states we found that the most stable structure of Ga{sub 5}N{sub 5} clusters presented semiconductor-like properties.

  10. Rule of five in 2015 and beyond: Target and ligand structural limitations, ligand chemistry structure and drug discovery project decisions.

    Science.gov (United States)

    Lipinski, Christopher A

    2016-06-01

    The rule of five (Ro5), based on physicochemical profiles of phase II drugs, is consistent with structural limitations in protein targets and the drug target ligands. Three of four parameters in Ro5 are fundamental to the structure of both target and drug binding sites. The chemical structure of the drug ligand depends on the ligand chemistry and design philosophy. Two extremes of chemical structure and design philosophy exist; ligands constructed in the medicinal chemistry synthesis laboratory without input from natural selection and natural product (NP) metabolites biosynthesized based on evolutionary selection. Exceptions to Ro5 are found mostly among NPs. Chemistry chameleon-like behavior of some NPs due to intra-molecular hydrogen bonding as exemplified by cyclosporine A is a strong contributor to NP Ro5 outliers. The fragment derived, drug Navitoclax is an example of the extensive expertise, resources, time and key decisions required for the rare discovery of a non-NP Ro5 outlier. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Geometric structure of chemistry-relevant graphs zigzags and central circuits

    CERN Document Server

    Deza, Michel-Marie; Shtogrin, Mikhail Ivanovitch

    2015-01-01

    The central theme of the present book is zigzags and central-circuits of three- or four-regular plane graphs, which allow a double covering or covering of the edgeset to be obtained. The book presents zigzag and central circuit structures of geometric fullerenes and several other classes of graph of interest in the fields of chemistry and mathematics. It also discusses the symmetries, parameterization and the Goldberg–Coxeter construction for those graphs. It is the first book on this subject, presenting full structure theory of such graphs. While many previous publications only addressed particular questions about selected graphs, this book is based on numerous computations and presents extensive data (tables and figures), as well as algorithmic and computational information. It will be of interest to researchers and students of discrete geometry, mathematical chemistry and combinatorics, as well as to lay mathematicians.

  12. M31 GLOBULAR CLUSTER STRUCTURES AND THE PRESENCE OF X-RAY BINARIES

    International Nuclear Information System (INIS)

    Agar, J. R. R.; Barmby, P.

    2013-01-01

    The Andromeda galaxy, M31, has several times the number of globular clusters found in the Milky Way. It contains a correspondingly larger number of low-mass X-ray binaries (LMXBs) associated with globular clusters, and as such can be used to investigate the cluster properties that lead to X-ray binary formation. The best tracer of the spatial structure of M31 globulars is the high-resolution imaging available from the Hubble Space Telescope (HST), and we have used HST data to derive structural parameters for 29 LMXB-hosting M31 globular clusters. These measurements are combined with structural parameters from the literature for a total of 41 (of 50 known) LMXB clusters and a comparison sample of 65 non-LMXB clusters. Structural parameters measured in blue bandpasses are found to be slightly different (smaller core radii and higher concentrations) than those measured in red bandpasses; this difference is enhanced in LMXB clusters and could be related to stellar population differences. Clusters with LMXBs show higher collision rates for their mass compared to clusters without LMXBs, and collision rates estimated at the core radius show larger offsets than rates estimated at the half-light radius. These results are consistent with the dynamical formation scenario for LMXBs. A logistic regression analysis finds that, as expected, the probability of a cluster hosting an LMXB increases with increasing collision rate and proximity to the galaxy center. The same analysis finds that probability of a cluster hosting an LMXB decreases with increasing cluster mass at a fixed collision rate, although we caution that this could be due to sample selection effects. Metallicity is found to be a less important predictor of LMXB probability than collision rate, mass, or distance, even though LMXB clusters have a higher metallicity on average. This may be due to the interaction of location and metallicity: a sample of M31 LMXBs with a greater range in galactocentric distance would

  13. Relative influence of soil chemistry and topography on soil available micronutrients by structural equation modeling

    OpenAIRE

    Zhu, Hongfen; Zhao, Ying; Nan, Feng; Duan, Yonghong; Bi, Rutian

    2016-01-01

    Soil chemical and topographic properties are two important factors influencing available micronutrient distribution of soil in the horizontal dimension. The objective of this study was to explore the relative influence of soil chemistry (including soil pH, soil organic matter, total nitrogen, available phosphorus, and available potassium) and topography (including elevation, slope, aspect, and wetness index) on the availability of micronutrients (Fe, Mn, Cu, Zn, and B) using structural equati...

  14. Electronic structure of vacancies and vacancy clusters in simple metals

    International Nuclear Information System (INIS)

    Manninen, M.; Nieminen, R.M.

    1978-05-01

    The self-consistent density functional approach has been applied in a study of electronic properties of vacancies and vacancy clusters in simple metals. The electron density profiles and potentials have been obtained for spherical voids of varying size. The formation energies and residual resistivities have been calculated for vacancies using both perturbational and variational inclusion of discrete lattice effects. The relation of the void properties to the plane surface ones is studied, and the inadequacy of the jellium-based methods to high-index faces is demonstrated. (author)

  15. Cluster structure in the correlation coefficient matrix can be characterized by abnormal eigenvalues

    Science.gov (United States)

    Nie, Chun-Xiao

    2018-02-01

    In a large number of previous studies, the researchers found that some of the eigenvalues of the financial correlation matrix were greater than the predicted values of the random matrix theory (RMT). Here, we call these eigenvalues as abnormal eigenvalues. In order to reveal the hidden meaning of these abnormal eigenvalues, we study the toy model with cluster structure and find that these eigenvalues are related to the cluster structure of the correlation coefficient matrix. In this paper, model-based experiments show that in most cases, the number of abnormal eigenvalues of the correlation matrix is equal to the number of clusters. In addition, empirical studies show that the sum of the abnormal eigenvalues is related to the clarity of the cluster structure and is negatively correlated with the correlation dimension.

  16. Variance in water chemistry parameters in isolated wetlands of Florida, USA, and relationships with macroinvertebrate and diatom community structure

    Science.gov (United States)

    Eighty small isolated wetlands throughout Florida were sampled in 2005 to explore within-site variability of water chemistry parameters and relate water chemistry to macroinvertebrate and diatom community structure. Three samples or measures of water were collected within each si...

  17. Quadrupole and octupole collectivity and cluster structures in neon isotopes

    Science.gov (United States)

    Marević, P.; Ebran, J.-P.; Khan, E.; Nikšić, T.; Vretenar, D.

    2018-02-01

    The lowest positive- and negative-parity bands of 20Ne and neutron-rich even-even Ne isotopes are investigated using a theoretical framework based on energy density functionals. Starting from a self-consistent relativistic Hartree-Bogoliubov calculation of axially symmetric and reflection-asymmetric deformation energy surfaces, the collective symmetry-conserving states are built using projection techniques and the generator coordinate method. Overall a good agreement with the experimental excitation energies and transition rates is obtained. In particular, the model provides an accurate description of the excitation spectra and transition probabilities in 20Ne. The contribution of cluster configurations to the low-energy states is discussed, as well as the transitional character of the ground state. The analysis is extended to 22Ne and the shape-coexisting isotope 24Ne, and to the drip-line nuclei 32Ne and 34Ne. The role of valence neutrons in the formation of molecular-type bonds between clusters is discussed.

  18. Effects of clustering structure on volumetric properties of amino acids in (DMSO + water) mixtures

    International Nuclear Information System (INIS)

    Huang Aimin; Liu Chunli; Ma Lin; Tong Zhangfa; Lin Ruisen

    2012-01-01

    Graphical abstract: Together with static light scattering measurement, volumetric properties of glycine, L-alanine and L-serine were determined and utilized to reveal the microscopic solvent structure of (DMSO + water) mixtures and its influence on the interaction between DMSO and amino acids from a clustering point of view. The results demonstrated that the interaction between amino acids and DMSO was greatly related to the clustering structure of the mixed solvent and that amino acids interacted with already established solvent clusters. Hydrophobic aggregating of DMSO lead to a decrease in the hydrophobic effect of DMSO and the hydrophobic–hydrophilic and hydrophobic–hydrophobic interaction with amino acids, which was reflected by the solvation of proteins. Highlights: ► Determine volumetric properties of three amino acids in aqueous DMSO in details. ► Static light scattering measurement for clustering structure of aqueous DMSO. ► Volumetric behaviour of amino acids depends on clustering structure of aqueous DMSO. ► Clustering structure of aqueous DMSO influences solvation of protein and cellulose. - Abstract: For a better understanding on the functions of DMSO in biological systems at a relatively lower concentration, apparent molar volumes of three typical amino acids, glycine, L-alanine and L-serine in (DMSO + water) mixtures were determined and the transfer volumes from water to the mixtures were evaluated. Together with static light scattering measurement, the results were utilised to reveal the microscopic solvent structure of (DMSO + water) mixtures and its influence on the interaction between DMSO and amino acids from a clustering point of view. The results demonstrate that the interaction between amino acids and DMSO is greatly related to the clustering structure of the mixed solvent and that amino acids interacted with already established solvent clusters. The linear dependence of transfer volume of amino acids on DMSO concentration up to 2

  19. The structures of P{sub 8} and P{sub 9} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Song Bin; Cao Peilin; Zhao Wei; Li Baoxing [Zhejiang Univ., Hangzhou, ZJ (China). Dept. of Physics

    2001-08-01

    Full-potential linear-muffin-tin-orbital molecular-dynamics (FP-LMTO MD) calculations have been performed to investigate the structures and energies of P{sub 8} and P{sub 9} clusters. We get fourteen stable structures for P{sub 8} and fifteen stable structures for P{sub 9}. The results confirm that ''cuneane'' structure is the most stable isomer of P{sub 8} clusters. However, the distortion of a D{sub 3h} prism, which has not been reported so far, is the most stable among the fifteen P{sub 9} isomers. (orig.)

  20. Application of the AMPLE cluster-and-truncate approach to NMR structures for molecular replacement

    Energy Technology Data Exchange (ETDEWEB)

    Bibby, Jaclyn [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Keegan, Ronan M. [Research Complex at Harwell, STFC Rutherford Appleton Laboratory, Didcot OX11 0FA (United Kingdom); Mayans, Olga [University of Liverpool, Liverpool L69 7ZB (United Kingdom); Winn, Martyn D. [Science and Technology Facilities Council Daresbury Laboratory, Warrington WA4 4AD (United Kingdom); Rigden, Daniel J., E-mail: drigden@liv.ac.uk [University of Liverpool, Liverpool L69 7ZB (United Kingdom)

    2013-11-01

    Processing of NMR structures for molecular replacement by AMPLE works well. AMPLE is a program developed for clustering and truncating ab initio protein structure predictions into search models for molecular replacement. Here, it is shown that its core cluster-and-truncate methods also work well for processing NMR ensembles into search models. Rosetta remodelling helps to extend success to NMR structures bearing low sequence identity or high structural divergence from the target protein. Potential future routes to improved performance are considered and practical, general guidelines on using AMPLE are provided.

  1. Structure, reactivity and electronic properties of Mn doped Ni{sub 13} clusters

    Energy Technology Data Exchange (ETDEWEB)

    Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit, E-mail: abhijit.mookerjee61@gmail.com

    2013-06-15

    In this work we have studied the structural and magnetic properties of Ni{sub 13} cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H{sub 2} molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni{sub 12}Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni{sub 12}MnH{sub 2}. Our analysis of the stability and HOMO–LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H{sub 2} absorption in the doped Ni{sub 13−m}Mn{sub m} alloy clusters. This has been reported earlier for smaller Ni{sub n} clusters [1].

  2. Structure, reactivity and electronic properties of Mn doped Ni13 clusters

    International Nuclear Information System (INIS)

    Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

    2013-01-01

    In this work we have studied the structural and magnetic properties of Ni 13 cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H 2 molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni 12 Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni 12 MnH 2 . Our analysis of the stability and HOMO–LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H 2 absorption in the doped Ni 13−m Mn m alloy clusters. This has been reported earlier for smaller Ni n clusters [1

  3. Structure, reactivity and electronic properties of Mn doped Ni13 clusters

    Science.gov (United States)

    Banerjee, Radhashyam; Datta, Soumendu; Mookerjee, Abhijit

    2013-06-01

    In this work we have studied the structural and magnetic properties of Ni13 cluster mono- and bi-doped with Mn atoms. We have noted their tendency of being reactive toward the H2 molecule. We have found unusually enhanced stability in the mono-doped cluster (i.e. of the Ni12Mn) and the diminished stability of the corresponding chemisorbed cluster, Ni12MnH2. Our analysis of the stability and HOMO-LUMO gap explains this unusual behavior. Interestingly, we have also seen the quenching in the net magnetic moment upon H2 absorption in the doped NiMnm alloy clusters. This has been reported earlier for smaller Nin clusters [1].

  4. Structure investigation of metal ions clustering in dehydrated gel using x-ray anomalous dispersion effect

    CERN Document Server

    Soejima, Y; Sugiyama, M; Annaka, M; Nakamura, A; Hiramatsu, N; Hara, K

    2003-01-01

    The structure of copper ion clusters in dehydrated N-isopropylacrylamide/sodium acrylate (NIPA/SA) gel has been studied by means of small angle X-ray scattering (SAXS) method. In order to distinguish the intensity scattered by Cu ions, the X-ray anomalous dispersion effect around the Cu K absorption edge has been coupled with SAXS. It is found that the dispersion effect dependent on the incident X-ray energy is remarkable only at the momentum transfer q = 0.031 A sup - sup 1 , where a SAXS peak is observed. The results indicate that copper ions form clusters in the dehydrated gel, and that the mean size of clusters is the same as that of SA clusters produced by microphase separation. It is therefore naturally presumed that copper ions are adsorbed into the SA molecules. On the basis of the presumption, a mechanism is proposed for microphase-separation and clustering of Cu ions.

  5. Ab initio random structure search for 13-atom clusters of fcc elements

    International Nuclear Information System (INIS)

    Chou, J P; Hsing, C R; Wei, C M; Cheng, C; Chang, C M

    2013-01-01

    The 13-atom metal clusters of fcc elements (Al, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au) were studied by density functional theory calculations. The global minima were searched for by the ab initio random structure searching method. In addition to some new lowest-energy structures for Pd 13 and Au 13 , we found that the effective coordination numbers of the lowest-energy clusters would increase with the ratio of the dimer-to-bulk bond length. This correlation, together with the electronic structures of the lowest-energy clusters, divides the 13-atom clusters of these fcc elements into two groups (except for Au 13 , which prefers a two-dimensional structure due to the relativistic effect). Compact-like clusters that are composed exclusively of triangular motifs are preferred for elements without d-electrons (Al) or with (nearly) filled d-band electrons (Ni, Pd, Cu, Ag). Non-compact clusters composed mainly of square motifs connected by some triangular motifs (Rh, Ir, Pt) are favored for elements with unfilled d-band electrons. (paper)

  6. Cluster Structure of 12C and 11Be

    International Nuclear Information System (INIS)

    Freer, M.; Fujita, H.; Buthelezi, Z.; Carter, J.; Fearick, R.W.; Foertsch, S.V.; Neveling, R.; Perez, S.M.; Papka, P.; Smit, F.D.; Swartz, J.A.; Usman, I.; Haigh, P.J.; Ashwood, N.I.; Bloxham, T.; Curtis, N.; McEwan, P.; Bohlen, H.G.; Dorsch, T.; Kokalova, Tz.

    2010-01-01

    The structure of the nucleus 12 C is discussed, in particular the spectrum of states above the α-decay threshold. A search for the 2 + excitation of the Hoyle-state is reported. The structural link between halo-like states and molecular states is explored in the case of 11 Be.

  7. Anionic water pentamer and hexamer clusters: An extensive study of structures and energetics

    Science.gov (United States)

    Ünal, Aslı; Bozkaya, Uǧur

    2018-03-01

    An extensive study of structures and energetics for anionic pentamer and hexamer clusters is performed employing high level ab initio quantum chemical methods, such as the density-fitted orbital-optimized linearized coupled-cluster doubles (DF-OLCCD), coupled-cluster singles and doubles (CCSD), and coupled-cluster singles and doubles with perturbative triples [CCSD(T)] methods. In this study, sixteen anionic pentamer clusters and eighteen anionic hexamer clusters are reported. Relative, binding, and vertical detachment energies (VDE) are presented at the complete basis set limit (CBS), extrapolating energies of aug4-cc-pVTZ and aug4-cc-pVQZ custom basis sets. The largest VDE values obtained at the CCSD(T)/CBS level are 9.9 and 11.2 kcal mol-1 for pentamers and hexamers, respectively, which are in very good agreement with the experimental values of 9.5 and 11.1 kcal mol-1. Our binding energy results, at the CCSD(T)/CBS level, indicate strong bindings in anionic clusters due to hydrogen bond interactions. The average binding energy per water molecules is -5.0 and -5.3 kcal mol-1 for pentamers and hexamers, respectively. Furthermore, our results demonstrate that the DF-OLCCD method approaches to the CCSD(T) quality for anionic clusters. The inexpensive analytic gradients of DF-OLCCD compared to CCSD or CCSD(T) make it very attractive for high-accuracy studies.

  8. Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

    Science.gov (United States)

    Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

    2018-05-23

    Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

  9. Evolution of the electronic structure and properties of neutral and charged aluminum clusters: A comprehensive analysis

    International Nuclear Information System (INIS)

    Rao, B.K.; Jena, P.

    1999-01-01

    Density-functional theory with generalized gradient approximation for the exchange-correlation potential has been used to calculate the global equilibrium geometries and electronic structure of neutral, cationic, and anionic aluminum clusters containing up to 15 atoms. The total energies of these clusters are then used to study the evolution of their binding energy, relative stability, fragmentation channels, ionization potential, and vertical and adiabatic electron affinities as a function of size. The geometries are found to undergo a structural change from two dimensional to three dimensional when the cluster contains 6 atoms. An interior atom emerges only when clusters contain 11 or more atoms. The geometrical changes are accompanied by corresponding changes in the coordination number and the electronic structure. The latter is reflected in the relative concentration of the s and p electrons of the highest occupied molecular orbital. Aluminum behaves as a monovalent atom in clusters containing less than seven atoms and as a trivalent atom in clusters containing seven or more atoms. The binding energy evolves monotonically with size, but Al 7 , Al 7 + , Al 7 - , Al 11 - , and Al 13 - exhibit greater stability than their neighbors. Although the neutral clusters do not conform to the jellium model, the enhanced stability of these charged clusters is demonstrated to be due to the electronic shell closure. The fragmentation proceeds preferably by the ejection of a single atom irrespective of the charge state of the parent clusters. While odd-atom clusters carry a magnetic moment of 1μ B as expected, clusters containing even number of atoms carry 2μ B for n≤10 and 0 ampersand hthinsp;μ B for n>10. The calculated results agree very well with all available experimental data on magnetic properties, ionization potentials, electron affinities, and fragmentation channels. The existence of isomers of Al 13 cluster provides a unique perspective on the anomaly in the

  10. Electronic structure and optical properties of the thiolate-protected Au28(SMe)20 cluster.

    Science.gov (United States)

    Knoppe, Stefan; Malola, Sami; Lehtovaara, Lauri; Bürgi, Thomas; Häkkinen, Hannu

    2013-10-10

    The recently reported crystal structure of the Au28(TBBT)20 cluster (TBBT: p-tert-butylbenzenethiolate) is analyzed with (time-dependent) density functional theory (TD-DFT). Bader charge analysis reveals a novel trimeric Au3(SR)4 binding motif. The cluster can be formulated as Au14(Au2(SR)3)4(Au3(SR)4)2. The electronic structure of the Au14(6+) core and the ligand-protected cluster were analyzed, and their stability can be explained by formation of distorted eight-electron superatoms. Optical absorption and circular dichroism (CD) spectra were calculated and compared to the experiment. Assignment of handedness of the intrinsically chiral cluster is possible.

  11. A-dependence of structure functions and multiquark clusters in nuclei

    International Nuclear Information System (INIS)

    Kondratyuk, L.; Shmatikov, M.

    1984-01-01

    Assuming existence of 12q-clusters (bags) in nuclei the structure functions of deep inelastic scattering of leptons on nuclei are discussed. Universal momentum distribution of quarks in a multiquark cluster is used with high-momentum component falling exponentially PHIsub(q)sup(2)(k) approximately esup(-k/ksub(0)) with k 0 approximately equal to 50-60 MeV/c. The admixture of 12q-cluster W required for the description of SLAG data increases from 10% for 4 He to 30% for Au. The A-dependence of W agrees well with the A-dependence of cumulative particle spectra

  12. Semiparametric Bayesian analysis of accelerated failure time models with cluster structures.

    Science.gov (United States)

    Li, Zhaonan; Xu, Xinyi; Shen, Junshan

    2017-11-10

    In this paper, we develop a Bayesian semiparametric accelerated failure time model for survival data with cluster structures. Our model allows distributional heterogeneity across clusters and accommodates their relationships through a density ratio approach. Moreover, a nonparametric mixture of Dirichlet processes prior is placed on the baseline distribution to yield full distributional flexibility. We illustrate through simulations that our model can greatly improve estimation accuracy by effectively pooling information from multiple clusters, while taking into account the heterogeneity in their random error distributions. We also demonstrate the implementation of our method using analysis of Mayo Clinic Trial in Primary Biliary Cirrhosis. Copyright © 2017 John Wiley & Sons, Ltd.

  13. Iron-sulfur clusters as biological sensors: the chemistry of reactions with molecular oxygen and nitric oxide.

    Science.gov (United States)

    Crack, Jason C; Green, Jeffrey; Thomson, Andrew J; Le Brun, Nick E

    2014-10-21

    Iron-sulfur cluster proteins exhibit a range of physicochemical properties that underpin their functional diversity in biology, which includes roles in electron transfer, catalysis, and gene regulation. Transcriptional regulators that utilize iron-sulfur clusters are a growing group that exploit the redox and coordination properties of the clusters to act as sensors of environmental conditions including O2, oxidative and nitrosative stress, and metabolic nutritional status. To understand the mechanism by which a cluster detects such analytes and then generates modulation of DNA-binding affinity, we have undertaken a combined strategy of in vivo and in vitro studies of a range of regulators. In vitro studies of iron-sulfur cluster proteins are particularly challenging because of the inherent reactivity and fragility of the cluster, often necessitating strict anaerobic conditions for all manipulations. Nevertheless, and as discussed in this Account, significant progress has been made over the past decade in studies of O2-sensing by the fumarate and nitrate reduction (FNR) regulator and, more recently, nitric oxide (NO)-sensing by WhiB-like (Wbl) and FNR proteins. Escherichia coli FNR binds a [4Fe-4S] cluster under anaerobic conditions leading to a DNA-binding dimeric form. Exposure to O2 converts the cluster to a [2Fe-2S] form, leading to protein monomerization and hence loss of DNA binding ability. Spectroscopic and kinetic studies have shown that the conversion proceeds via at least two steps and involves a [3Fe-4S](1+) intermediate. The second step involves the release of two bridging sulfide ions from the cluster that, unusually, are not released into solution but rather undergo oxidation to sulfane (S(0)) subsequently forming cysteine persulfides that then coordinate the [2Fe-2S] cluster. Studies of other [4Fe-4S] cluster proteins that undergo oxidative cluster conversion indicate that persulfide formation and coordination may be more common than previously

  14. Structuring heterogeneous biological information using fuzzy clustering of k-partite graphs

    Directory of Open Access Journals (Sweden)

    Theis Fabian J

    2010-10-01

    Full Text Available Abstract Background Extensive and automated data integration in bioinformatics facilitates the construction of large, complex biological networks. However, the challenge lies in the interpretation of these networks. While most research focuses on the unipartite or bipartite case, we address the more general but common situation of k-partite graphs. These graphs contain k different node types and links are only allowed between nodes of different types. In order to reveal their structural organization and describe the contained information in a more coarse-grained fashion, we ask how to detect clusters within each node type. Results Since entities in biological networks regularly have more than one function and hence participate in more than one cluster, we developed a k-partite graph partitioning algorithm that allows for overlapping (fuzzy clusters. It determines for each node a degree of membership to each cluster. Moreover, the algorithm estimates a weighted k-partite graph that connects the extracted clusters. Our method is fast and efficient, mimicking the multiplicative update rules commonly employed in algorithms for non-negative matrix factorization. It facilitates the decomposition of networks on a chosen scale and therefore allows for analysis and interpretation of structures on various resolution levels. Applying our algorithm to a tripartite disease-gene-protein complex network, we were able to structure this graph on a large scale into clusters that are functionally correlated and biologically meaningful. Locally, smaller clusters enabled reclassification or annotation of the clusters' elements. We exemplified this for the transcription factor MECP2. Conclusions In order to cope with the overwhelming amount of information available from biomedical literature, we need to tackle the challenge of finding structures in large networks with nodes of multiple types. To this end, we presented a novel fuzzy k-partite graph partitioning

  15. New Constraints on Spatial Variations of the Fine Structure Constant from Clusters of Galaxies

    Directory of Open Access Journals (Sweden)

    Ivan De Martino

    2016-12-01

    Full Text Available We have constrained the spatial variation of the fine structure constant using multi-frequency measurements of the thermal Sunyaev-Zeldovich effect of 618 X-ray selected clusters. Although our results are not competitive with the ones from quasar absorption lines, we improved by a factor 10 and ∼2.5 previous results from Cosmic Microwave Background power spectrum and from galaxy clusters, respectively.

  16. Chemical probes of metal cluster structure--Fe, Co, Ni, and Cu

    International Nuclear Information System (INIS)

    Parks, E.K.; Zhu, L.; Ho, J.; Riley, S.J.

    1992-01-01

    Chemical reactivity is one of the few methods currently available for investigating the geometrical structure of isolated transition metal clusters. In this paper we summarize what is currently known about the structures of clusters of four transition metals, Fe, Co, Ni, and Cu, in the size range from 13 to 180 atoms. Chemical probes used to determine structural information include reactions with H 2 (D 2 ), H 2 0, NH 3 and N 2 . Measurements at both low coverage and at saturation are discussed

  17. Structures, Vibrational And Electronic Properties Of (F2O)N (N=2-4) Clusters

    International Nuclear Information System (INIS)

    Bahat, M.

    2008-01-01

    Recently, molecular clusters are the subject of several experimental and computational studies by means of their bonding structures. We studied, first time, small difluorine monoxide clusters such as dimer (linear, cyclic, bifurcated), trimer and tetramer structures using B3LYP variant of density functional theory with cc-pVDZ basis set. On the basis of the optimized geometry, various energy properties such as binding energy, molecular orbital energies, two and three body interaction energies have been calculated. Additionally dipole moment, polarizability, anisotropic polarizability and hyper polarizability have been calculated and compared with monomer structure

  18. Communication: Multireference equation of motion coupled cluster: A transform and diagonalize approach to electronic structure

    Czech Academy of Sciences Publication Activity Database

    Nooijen, M.; Demel, Ondřej; Datta, D.; Kong, L.; Shamasundar, K. R.; Lotrich, V.; Huntington, L. M.; Neese, F.

    2014-01-01

    Roč. 140, č. 8 (2014), 081102 ISSN 0021-9606 R&D Projects: GA ČR GPP208/10/P041; GA ČR GAP208/11/2222 Institutional support: RVO:61388955 Keywords : Electronic states * Electronic structure * Equations of motion Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.952, year: 2014

  19. Atomic Scale Structure-Chemistry Relationships at Oxide Catalyst Surfaces and Interfaces

    Science.gov (United States)

    McBriarty, Martin E.

    Oxide catalysts are integral to chemical production, fuel refining, and the removal of environmental pollutants. However, the atomic-scale phenomena which lead to the useful reactive properties of catalyst materials are not sufficiently understood. In this work, the tools of surface and interface science and electronic structure theory are applied to investigate the structure and chemical properties of catalytically active particles and ultrathin films supported on oxide single crystals. These studies focus on structure-property relationships in vanadium oxide, tungsten oxide, and mixed V-W oxides on the surfaces of alpha-Al2O3 and alpha-Fe2O 3 (0001)-oriented single crystal substrates, two materials with nearly identical crystal structures but drastically different chemical properties. In situ synchrotron X-ray standing wave (XSW) measurements are sensitive to changes in the atomic-scale geometry of single crystal model catalyst surfaces through chemical reaction cycles, while X-ray photoelectron spectroscopy (XPS) reveals corresponding chemical changes. Experimental results agree with theoretical calculations of surface structures, allowing for detailed electronic structure investigations and predictions of surface chemical phenomena. The surface configurations and oxidation states of V and W are found to depend on the coverage of each, and reversible structural shifts accompany chemical state changes through reduction-oxidation cycles. Substrate-dependent effects suggest how the choice of oxide support material may affect catalytic behavior. Additionally, the structure and chemistry of W deposited on alpha-Fe 2O3 nanopowders is studied using X-ray absorption fine structure (XAFS) measurements in an attempt to bridge single crystal surface studies with real catalysts. These investigations of catalytically active material surfaces can inform the rational design of new catalysts for more efficient and sustainable chemistry.

  20. Structure evolution during the cooling and coalesced cooling processes of Cu-Co bimetallic clusters

    International Nuclear Information System (INIS)

    Li Guojian; Wang Qiang; Li Donggang; Lue Xiao; He Jicheng

    2008-01-01

    Constant-temperature molecular dynamics with general EAM was employed to study the structure evolutions during the cooling and coalesced cooling processes of Cu-Co bimetallic clusters. It shows that the desired particle morphologies and structures can be obtained by controlling the composition and distribution of hetero atoms during synthesis process

  1. Electric dipole, polarizability and structure of cesium chloride clusters with one-excess electron

    International Nuclear Information System (INIS)

    Jraij, A.; Allouche, A.R.; Rabilloud, F.; Korek, M.; Aubert-Frecon, M.; Rayane, D.; Compagnon, I.; Antoine, R.; Broyer, M.; Dugourd, Ph.

    2006-01-01

    The measurement of the electric dipole of gas phase one-excess electron Cs n Cl n-1 clusters is reported together with a theoretical ab initio prediction of stable structures, dipole moments and electronic polarizabilities for these species in their ground state. Results are in agreement with NaCl cubic structures

  2. Multi-level flow-based Markov clustering for design structure matrices

    NARCIS (Netherlands)

    Wilschut, T.; Etman, P.L.F.; Rooda, J.E.; Adan, I.J.B.F.

    2016-01-01

    For decomposition and integration of systems one requires extensive knowledge on system structure. A Design Structure Matrix (DSM) can provide a simple, compact and visual representation of dependencies between system elements. By permuting the rows and columns of a DSM using a clustering algorithm,

  3. The stabilities and electron structures of Al-Mg clusters with 18 and 20 valence electrons

    Science.gov (United States)

    Yang, Huihui; Chen, Hongshan

    2017-07-01

    The spherical jellium model predicts that metal clusters having 18 and 20 valence electrons correspond to the magic numbers and will show specific stabilities. We explore in detail the geometric structures, stabilities and electronic structures of Al-Mg clusters containing 18 and 20 valence electrons by using genetic algorithm combined with density functional theories. The stabilities of the clusters are governed by the electronic configurations and Mg/Al ratios. The clusters with lower Mg/Al ratios are more stable. The molecular orbitals accord with the shell structures predicted by the jellium model but the 2S level interweaves with the 1D levels and the 2S and 1D orbitals form a subgroup. The clusters having 20 valence electrons form closed 1S21P61D102S2 shells and show enhanced stability. The Al-Mg clusters with a valence electron count of 18 do not form closed shells because one 1D orbital is unoccupied. The ionization potential and electron affinity are closely related to the electronic configurations; their values are determined by the subgroups the HOMO or LUMO belong to. Supplementary material in the form of one pdf file available from the Journal web page at http://https://doi.org/10.1140/epjd/e2017-80042-9

  4. Structures, stabilities, and electronic properties for rare-earth lanthanum doped gold clusters

    International Nuclear Information System (INIS)

    Zhao, Ya-Ru

    2015-01-01

    The structures, stabilities, and electronic properties of rare-earth lanthanum doped gold La 2 Au n (n = 1-9) and pure gold Au n (n ≤ 11) clusters have been investigated by using density functional theory. The optimized geometries show that the lowest energy structures of La 2 Au n clusters favour the 3D structure at n ≥ 3. The lanthanum atoms can strongly enhance the stabilities of gold clusters and tend to occupy the most highly coordinated position. By analysing the gap, vertical ionization potential, and chemical hardness, it is found that the La 2 Au 6 isomer possesses higher stability for small-sized La 2 Au n clusters (n = 1-9). The charges in the La 2 Au n clusters transfer from La atoms to the Au n host. In addition, Wiberg bond indices analysis reveals that the intensity of different bonds of La 2 Au n clusters exhibits a sequence of La-La bond > La-Au bond > Au-Au bond.

  5. A facility for using cluster research to study environmental problems

    Energy Technology Data Exchange (ETDEWEB)

    1991-11-01

    This report begins by describing the general application of cluster based research to environmental chemistry and the development of a Cluster Structure and Dynamics Research Facility (CSDRF). Next, four important areas of cluster research are described in more detail, including how they can impact environmental problems. These are: surface-supported clusters, water and contaminant interactions, time-resolved dynamic studies in clusters, and cluster structures and reactions. These facilities and equipment required for each area of research are then presented. The appendices contain workshop agenda and a listing of the researchers who participated in the workshop discussions that led to this report.

  6. A facility for using cluster research to study environmental problems

    International Nuclear Information System (INIS)

    1991-11-01

    This report begins by describing the general application of cluster based research to environmental chemistry and the development of a Cluster Structure and Dynamics Research Facility (CSDRF). Next, four important areas of cluster research are described in more detail, including how they can impact environmental problems. These are: surface-supported clusters, water and contaminant interactions, time-resolved dynamic studies in clusters, and cluster structures and reactions. These facilities and equipment required for each area of research are then presented. The appendices contain workshop agenda and a listing of the researchers who participated in the workshop discussions that led to this report

  7. Impacts of operating conditions and solution chemistry on osmotic membrane structure and performance

    KAUST Repository

    Wong, Mavis C.Y.; Martinez, Kristina; Ramon, Guy Z.; Hoek, Eric M.V.

    2012-01-01

    Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane's water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane's structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications. © 2011 Elsevier B.V.

  8. Some aspects of the chemistry of fast reactor fuel, structural material and decontamination

    International Nuclear Information System (INIS)

    Ganesan, V.

    2012-01-01

    The chemistry of materials pertaining to fast reactors is both fascinating and challenging considering the nature of materials involved such as the fuel, coolant, control and shielding materials in addition to the interactions between the structural materials and the fuel/coolant depending on the nature and conditions involved. The different chemical forms of fuel materials, the need to operate up to high burnups with consequent interactions of the fuel with clad materials, the need to close the fuel cycle by recovery of the fuel materials from spent fuels for refabrication and the necessity to manage the waste, throw a host of challenges which make their study scientifically interesting and technologically important. The use of liquid sodium as coolant in fast reactor heat transport systems combined with its inherent chemical reactivity opens up an interesting branch of chemistry involving liquid sodium especially in contact with structural materials during normal operation of the reactor and with fuels in the event of fuel pin failure. The phenomenon of sodium wetting and the associated corrosion of structural materials in contact with it combined with the need to carryout decontamination of such materials make it interesting to examine and evaluate their suitability for reuse without compromising on their structural integrity. Boron being the material of choice for control and shielding applications in fast reactors with varying isotopic enrichment and the technological challenge to produce large quantities of boron carbide makes it unique. Some of these aspects are addressed in this paper. (author)

  9. Impacts of operating conditions and solution chemistry on osmotic membrane structure and performance

    KAUST Repository

    Wong, Mavis C.Y.

    2012-02-01

    Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane\\'s water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane\\'s structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications. © 2011 Elsevier B.V.

  10. Searching for filaments and large-scale structure around DAFT/FADA clusters

    Science.gov (United States)

    Durret, F.; Márquez, I.; Acebrón, A.; Adami, C.; Cabrera-Lavers, A.; Capelato, H.; Martinet, N.; Sarron, F.; Ulmer, M. P.

    2016-04-01

    Context. Clusters of galaxies are located at the intersection of cosmic filaments and are still accreting galaxies and groups along these preferential directions. However, because of their relatively low contrast on the sky, filaments are difficult to detect (unless a large amount of spectroscopic data are available), and unambiguous detections have been limited until now to relatively low redshifts (zDAFT/FADA survey for which we had deep wide field photometric data. For each cluster, based on a colour-magnitude diagram, we selected galaxies that were likely to belong to the red sequence, and hence to be at the cluster redshift, and built density maps. By computing the background for each of these maps and drawing 3σ contours, we estimated the elongations of the structures detected in this way. Whenever possible, we identified the other structures detected on the density maps with clusters listed in NED. Results: We find clear elongations in twelve clusters out of thirty, with sizes that can reach up to 7.6 Mpc. Eleven other clusters have neighbouring structures, but the zones linking them are not detected in the density maps at a 3σ level. Three clusters show no extended structure and no neighbours, and four clusters are of too low contrast to be clearly visible on our density maps. Conclusions: The simple method we have applied appears to work well to show the existence of filaments and/or extensions around a number of clusters in the redshift range 0.4 cluster samples such as the clusters detected in the CFHTLS and SDSS-Stripe 82 surveys in the near future. Based on our own data (see Guennou et al. 2014) and archive data obtained with MegaPrime/MegaCam, a joint project of CFHT and CEA/DAPNIA, at the Canada-France-Hawaii Telescope (CFHT) which is operated by the National Research Council (NRC) of Canada, the Institut National des Sciences de l'Univers of the Centre National de la Recherche Scientifique of France, and

  11. Beyond Academic Tracking: Using Cluster Analysis and Self-Organizing Maps to Investigate Secondary Students' Chemistry Self-Concept

    Science.gov (United States)

    Nielsen, Sara E.; Yezierski, Ellen J.

    2016-01-01

    Academic tracking, placing students in different classes based on past performance, is a common feature of the American secondary school system. A longitudinal study of secondary students' chemistry self-concept scores was conducted, and one feature of the study was the presence of academic tracking. Though academic tracking is one way to group…

  12. Thermodynamics of Small Alkali Metal Halide Cluster Ions: Comparison of Classical Molecular Simulations with Experiment and Quantum Chemistry

    Czech Academy of Sciences Publication Activity Database

    Vlček, L.; Uhlík, F.; Moučka, F.; Nezbeda, Ivo; Chialvo, L.

    2015-01-01

    Roč. 119, č. 3 (2015), s. 488-500 ISSN 1089-5639 Institutional support: RVO:67985858 Keywords : monte-carlo simulations * molecular-dynamic simulations * classical drude oscillators Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.883, year: 2015

  13. Structural, magnetic and electronic properties of FexCoyIrz (x + y + z = 5, 6) clusters: an ab initio study

    KAUST Repository

    Devi, Assa Aravindh Sasikala

    2014-05-01

    Investigations on freestanding binary and ternary clusters of Fe (x) Co (y) Ir (z) (x + y + z = 5, 6) are carried out using ab initio density functional theory techniques. The geometry, chemical order, binding energy, magnetic moment and electronic structure of the clusters are analyzed for the entire range of composition. Composition dependent structural transition is observed in the five atom clusters, while octahedral geometry prevailed in clusters with six atoms. Both the clusters show increment in binding energy with the increase in number of heterogeneous bonds. Analysis based on the chemical order parameter indicates that clusters favor mixing rather than segregation. The clusters exhibit ferromagnetic ordering and the inter-dependence of optimal cluster geometry to the magnetic moments and electronic structure is observed.

  14. Influence of system temperature on the micro-structures and dynamics of dust clusters in dusty plasmas

    Energy Technology Data Exchange (ETDEWEB)

    Song, Y. L.; Huang, F., E-mail: huangfeng@cau.edu.cn [College of Science, China Agricultural University, Beijing 100083 (China); He, Y. F.; Wu, L. [College of Information and Electrical Engineering, China Agricultural University, Beijing 100083 (China); Liu, Y. H. [School of Physics and Optoelectronic Engineering, Ludong University, Yantai 264025 (China); Chen, Z. Y. [Department of Physics, Beijing University of Chemical Technology, Beijing 100029 (China); Yu, M. Y. [Institute for Fusion Theory and Simulation, Zhejiang University, Hangzhou 310027 (China); Institute for Theoretical Physics I, Ruhr University, D-44801 Bochum (Germany)

    2015-06-15

    Influence of the system temperature on the micro-structures and dynamics of dust clusters in dusty plasmas is investigated through laboratory experiment and molecular dynamics simulation. The micro-structures, defect numbers, and pair correlation function of the dust clusters are studied for different system temperatures. The dust grains' trajectories, the mean square displacement, and the corresponding self-diffusion coefficient of the clusters are calculated for different temperatures for illustrating the phase properties of the dust clusters. The simulation results confirm that with the increase in system temperature, the micro-structures and dynamics of dust clusters are gradually changed, which qualitatively agree with experimental results.

  15. Impact of the Fused Deposition (FDM Printing Process on Polylactic Acid (PLA Chemistry and Structure

    Directory of Open Access Journals (Sweden)

    Michael Arthur Cuiffo

    2017-06-01

    Full Text Available Polylactic acid (PLA is an organic polymer commonly used in fused deposition (FDM printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier transform infrared (FTIR spectroscopy and photoacousitc FTIR spectroscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS in order to characterize both the bulk and surface chemistry of the source material and printed samples. Scanning electron microscopy (SEM and differential scanning calorimetry (DSC were used to characterize morphology, cold crystallinity, and the glass transition and melting temperatures following printing. Analysis revealed calcium carbonate-based additives which were reacted with organic ligands and potentially trace metal impurities, both before and following printing. These additives became concentrated in voids in the printed structure. This finding is important for biomedical applications as carbonate will impact subsequent cell growth on printed tissue scaffolds. Results of chemical analysis also provided evidence of the hygroscopic nature of the source material and oxidation of the printed surface, and SEM imaging revealed micro- and submicron-scale roughness that will also impact potential applications.

  16. A block structure Laplacian for hyperspectral image data clustering

    CSIR Research Space (South Africa)

    Lunga, D

    2013-12-01

    Full Text Available and points to new directions that boost unsupervised pattern classification. In particular, the paper offers design insights on the generation of a well structured graph Laplacian based on an affinity function that induces context-dependence to create compact...

  17. Investigation of the Structures and Energy Landscapes of Thiocyanate-Water Clusters

    Directory of Open Access Journals (Sweden)

    Lewis C. Smeeton

    2017-03-01

    Full Text Available The Basin Hopping search method is used to find the global minima (GM and map the energy landscapes of thiocyanate-water clusters, (SCN−(H2On with 3–50 water molecules, with empirical potentials describing the ion-water and water-water interactions. (It should be noted that beyond n = 23, the lowest energy structures were only found in 1 out of 8 searches so they are unlikely to be the true GM but are indicative low energy structures. As for pure water clusters, the low energy isomers of thiocyanate-water clusters show a preponderance of fused water cubes and pentagonal prisms, with the weakly solvated thiocyanate ion lying on the surface, replacing two water molecules along an edge of a water polyhedron and with the sulfur atom in lower coordinated sites than nitrogen. However, by comparison with Density Functional Theory (DFT calculations, the empirical potential is found to overestimate the strength of the thiocyanate-water interaction, especially O–H⋯S, with low energy DFT structures having lower coordinate N and (especially S atoms than for the empirical potential. In the case of these finite ion-water clusters, the chaotropic (“disorder-making” thiocyanate ion weakens the water cluster structure but the water molecule arrangement is not significantly changed.

  18. Quantum dynamics of small H2 and D2 clusters in the large cage of structure II clathrate hydrate: Energetics, occupancy, and vibrationally averaged cluster structures

    Science.gov (United States)

    Sebastianelli, Francesco; Xu, Minzhong; Bačić, Zlatko

    2008-12-01

    We report diffusion Monte Carlo (DMC) calculations of the quantum translation-rotation (T-R) dynamics of one to five para-H2 (p-H2) and ortho-D2 (o-D2) molecules inside the large hexakaidecahedral (51264) cage of the structure II clathrate hydrate, which was taken to be rigid. These calculations provide a quantitative description of the size evolution of the ground-state properties, energetics, and the vibrationally averaged geometries, of small (p-H2)n and (o-D2)n clusters, n=1-5, in nanoconfinement. The zero-point energy (ZPE) of the T-R motions rises steeply with the cluster size, reaching 74% of the potential well depth for the caged (p-H2)4. At low temperatures, the rapid increase of the cluster ZPE as a function of n is the main factor that limits the occupancy of the large cage to at most four H2 or D2 molecules, in agreement with experiments. Our DMC results concerning the vibrationally averaged spatial distribution of four D2 molecules, their mean distance from the cage center, the D2-D2 separation, and the specific orientation and localization of the tetrahedral (D2)4 cluster relative to the framework of the large cage, agree very well with the low-temperature neutron diffraction experiments involving the large cage with the quadruple D2 occupancy.

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

    Science.gov (United States)

    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

  20. Relation between financial market structure and the real economy: comparison between clustering methods.

    Science.gov (United States)

    Musmeci, Nicoló; Aste, Tomaso; Di Matteo, T

    2015-01-01

    We quantify the amount of information filtered by different hierarchical clustering methods on correlations between stock returns comparing the clustering structure with the underlying industrial activity classification. We apply, for the first time to financial data, a novel hierarchical clustering approach, the Directed Bubble Hierarchical Tree and we compare it with other methods including the Linkage and k-medoids. By taking the industrial sector classification of stocks as a benchmark partition, we evaluate how the different methods retrieve this classification. The results show that the Directed Bubble Hierarchical Tree can outperform other methods, being able to retrieve more information with fewer clusters. Moreover,we show that the economic information is hidden at different levels of the hierarchical structures depending on the clustering method. The dynamical analysis on a rolling window also reveals that the different methods show different degrees of sensitivity to events affecting financial markets, like crises. These results can be of interest for all the applications of clustering methods to portfolio optimization and risk hedging [corrected].

  1. Relation between financial market structure and the real economy: comparison between clustering methods.

    Directory of Open Access Journals (Sweden)

    Nicoló Musmeci

    Full Text Available We quantify the amount of information filtered by different hierarchical clustering methods on correlations between stock returns comparing the clustering structure with the underlying industrial activity classification. We apply, for the first time to financial data, a novel hierarchical clustering approach, the Directed Bubble Hierarchical Tree and we compare it with other methods including the Linkage and k-medoids. By taking the industrial sector classification of stocks as a benchmark partition, we evaluate how the different methods retrieve this classification. The results show that the Directed Bubble Hierarchical Tree can outperform other methods, being able to retrieve more information with fewer clusters. Moreover,we show that the economic information is hidden at different levels of the hierarchical structures depending on the clustering method. The dynamical analysis on a rolling window also reveals that the different methods show different degrees of sensitivity to events affecting financial markets, like crises. These results can be of interest for all the applications of clustering methods to portfolio optimization and risk hedging [corrected].

  2. Organic chemistry

    International Nuclear Information System (INIS)

    2003-08-01

    This book with sixteen chapter explains organic chemistry on linkage isomerism such as alkane, cycloalkane, alkene, aromatic compounds, stereo selective isomerization, aromatic compounds, stereo selective isomerization, organic compounds, stereo selective isomerization, organic halogen compound, alcohol, ether, aldehyde and ketone, carboxylic acid, dicarboxylic acid, fat and detergent, amino, carbohydrate, amino acid and protein, nucleotide and nucleic acid and spectroscopy, a polymer and medical chemistry. Each chapter has introduction structure and characteristic and using of organic chemistry.

  3. The resonating group method three cluster approach to the ground state 9 Li nucleus structure

    International Nuclear Information System (INIS)

    Filippov, G.F.; Pozdnyakov, Yu.A.; Terenetsky, K.O.; Verbitsky, V.P.

    1994-01-01

    The three-cluster approach for light atomic nuclei is formulated in frame of the algebraic version of resonating group method. Overlap integral and Hamiltonian matrix elements on generating functions are obtained for 9 Li nucleus. All permissible by Pauli principle 9 Li different cluster nucleon permutations were taken into account in the calculations. The results obtained can be easily generalised on any three-cluster system up to 12 C. Matrix elements obtained in the work were used in the variational calculations of the ground state energetic and geometric 9 Li characteristics. It is shown that 9 Li ground state is not adequate to the shell model limit and has pronounced three-cluster structure. (author). 16 refs., 4 tab., 2 figs

  4. From bismuth oxide/hydroxide precursor clusters towards stable oxides: Proton transfer reactions and structural reorganization govern the stability of [Bi18O13(OH)10]-nitrate clusters

    Science.gov (United States)

    Walther, M.; Zahn, D.

    2018-01-01

    Structural relaxation and stability of a Bi18-cluster as obtained from association of [Bi6O4(OH)4](NO3)6 precursor clusters in DMSO solution is investigated from a combination of quantum chemical calculations and μs-scale molecular dynamics simulations using empirical interaction potentials. The Bi18-cluster undergoes a OH⋯OH proton transfer reaction, followed by considerable structural relaxation. While the aggregation of the Bi18-cluster is induced by the dissociation of a single nitrate ion leading to [Bi6O4(OH)4](NO3)5+ as an activated precursor species that can bind two more Bi6-clusters, we find the [Bi18O13(OH)10](NO3)18-x+x species (explored for x = 1-6) rather inert against either nitrate dissociation, collision with Bi6-precursors or combinations thereof.

  5. The electronic structure of the F-center in alkali-halides-The Bethe cluster - lattice

    International Nuclear Information System (INIS)

    Queiroz, S.L.A. de.

    1977-07-01

    The electronic structure of the F-center in alkali-halides with the NaCl structure has been studied using the Bethe Cluster lattice method. The central cluster has been taken as constituted by the vacancy and the nearest- and second-neighbors to it, respectively cations and anions. The optical transitions have been calculated and compared to experimental data on the location of the peak of the F-absorption band. The agreement obtained indicates that this method may be used to study properties of this defect in alkali halides. (Author) [pt

  6. Accurate Energies and Structures for Large Water Clusters Using the X3LYP Hybrid Density Functional

    OpenAIRE

    Su, Julius T.; Xu, Xin; Goddard, William A., III

    2004-01-01

    We predict structures and energies of water clusters containing up to 19 waters with X3LYP, an extended hybrid density functional designed to describe noncovalently bound systems as accurately as covalent systems. Our work establishes X3LYP as the most practical ab initio method today for calculating accurate water cluster structures and energies. We compare X3LYP/aug-cc-pVTZ energies to the most accurate theoretical values available (n = 2−6, 8), MP2 with basis set superposition error (BSSE)...

  7. Probing the structure and dynamics of cage-like clusters: from water to Met-Cars

    International Nuclear Information System (INIS)

    Castleman, A.W. Jr.

    1995-01-01

    Our recent work on metal compounds led to the discovery of a new class of metal-carbon clusters which are of finite size and have specific geometry, but exhibit varying electronic character because of the different metals of which they can be comprised. We term these metallo-carbohedrenes or Met-Cars for short. This paper reviews the progress made in elucidating the structures if these two classes of clusters which seem to be quite different, but have some interesting common features involving structural considerations. (orig.)

  8. From Globular Clusters to Tidal Dwarfs: Structure Formation in the Tidal Tails of Merging Galaxies

    Science.gov (United States)

    Knierman, Karen A.; Gallagher, Sarah C.; Charlton, Jane C.; Hunsberger, Sally D.; Whitmore, Bradley; Kundu, Arunav; Hibbard, J. E.; Zaritsky, Dennis

    2003-09-01

    Using V and I images obtained with the Wide Field Planetary Camera 2 (WFPC2) of the Hubble Space Telescope, we investigate compact stellar structures within tidal tails. Six regions of tidal debris in the four classic ``Toomre sequence'' mergers: NGC 4038/39 (``Antennae''), NGC 3256, NGC 3921, and NGC 7252 (``Atoms for Peace'') have been studied in order to explore how the star formation depends on the local and global physical conditions. These mergers sample a range of stages in the evolutionary sequence and tails with and without embedded tidal dwarf galaxies. The six tails are found to contain a variety of stellar structures, with sizes ranging from those of globular clusters up to those of dwarf galaxies. From V and I WFPC2 images, we measure the luminosities and colors of the star clusters. NGC 3256 is found to have a large population of blue clusters (0.2<~V-I<~0.9), particularly in its western tail, similar to those found in the inner region of the merger. In contrast, NGC 4038/39 has no clusters in the observed region of the tail, only less luminous point sources likely to be individual stars. NGC 3921 and NGC 7252 have small populations of clusters along their tails. A significant cluster population is clearly associated with the prominent tidal dwarf candidates in the eastern and western tails of NGC 7252. The cluster-rich western tail of NGC 3256 is not distinguished from the others by its dynamical age or by its total H I mass. However, the mergers that have few clusters in the tail all have tidal dwarf galaxies, while NGC 3256 does not have prominent tidal dwarfs. We speculate that star formation in tidal tails may manifest itself either in small structures like clusters along the tail or in large structures such as dwarf galaxies, but not in both. Also, NGC 3256 has the highest star formation rate of the four mergers studied, which may contribute to the high number of star clusters in its tidal tails. Based in part on observations obtained with the

  9. Electronic structure and geometries of small compound metal clusters: Progress report, August 1, 1987-July 31, 1988

    International Nuclear Information System (INIS)

    Jena, P.; Rao, B.K.; Khanna, S.N.

    1988-04-01

    Our research during this reporting period has focused on studying electronic structure and properties of both gas-phase clusters and clusters as models of crystals and defects. We have also concentrated on developing new theoretical techniques that can allow us to study large clusters in a computationally effective manner. Following is a summary of results

  10. Electronic structure and geometries of small compound metal clusters: Progress report, August 1, 1988--July 31, 1989

    International Nuclear Information System (INIS)

    Jena, P.; Rao, B.K.; Khanna, S.N.

    1989-04-01

    Our research during this reporting period has focused on the following two aspects of cluster research. Electronic structure and stability of charged clusters and studies of evolution of magnetic properties with increasing cluster size. Following is a summary of our results

  11. Structure and Sequence Analyses of Clustered Protocadherins Reveal Antiparallel Interactions that Mediate Homophilic Specificity.

    Science.gov (United States)

    Nicoludis, John M; Lau, Sze-Yi; Schärfe, Charlotta P I; Marks, Debora S; Weihofen, Wilhelm A; Gaudet, Rachelle

    2015-11-03

    Clustered protocadherin (Pcdh) proteins mediate dendritic self-avoidance in neurons via specific homophilic interactions in their extracellular cadherin (EC) domains. We determined crystal structures of EC1-EC3, containing the homophilic specificity-determining region, of two mouse clustered Pcdh isoforms (PcdhγA1 and PcdhγC3) to investigate the nature of the homophilic interaction. Within the crystal lattices, we observe antiparallel interfaces consistent with a role in trans cell-cell contact. Antiparallel dimerization is supported by evolutionary correlations. Two interfaces, located primarily on EC2-EC3, involve distinctive clustered Pcdh structure and sequence motifs, lack predicted glycosylation sites, and contain residues highly conserved in orthologs but not paralogs, pointing toward their biological significance as homophilic interaction interfaces. These two interfaces are similar yet distinct, reflecting a possible difference in interaction architecture between clustered Pcdh subfamilies. These structures initiate a molecular understanding of clustered Pcdh assemblies that are required to produce functional neuronal networks. Copyright © 2015 Elsevier Ltd. All rights reserved.

  12. Mixing and matching siderophore clusters: structure and biosynthesis of serratiochelins from Serratia sp. V4.

    Science.gov (United States)

    Seyedsayamdost, Mohammad R; Cleto, Sara; Carr, Gavin; Vlamakis, Hera; João Vieira, Maria; Kolter, Roberto; Clardy, Jon

    2012-08-22

    Interrogation of the evolutionary history underlying the remarkable structures and biological activities of natural products has been complicated by not knowing the functions they have evolved to fulfill. Siderophores-soluble, low molecular weight compounds-have an easily understood and measured function: acquiring iron from the environment. Bacteria engage in a fierce competition to acquire iron, which rewards the production of siderophores that bind iron tightly and cannot be used or pirated by competitors. The structures and biosyntheses of "odd" siderophores can reveal the evolutionary strategy that led to their creation. We report a new Serratia strain that produces serratiochelin and an analog of serratiochelin. A genetic approach located the serratiochelin gene cluster, and targeted mutations in several genes implicated in serratiochelin biosynthesis were generated. Bioinformatic analyses and mutagenesis results demonstrate that genes from two well-known siderophore clusters, the Escherichia coli enterobactin cluster and the Vibrio cholera vibriobactin cluster, were shuffled to produce a new siderophore biosynthetic pathway. These results highlight how modular siderophore gene clusters can be mixed and matched during evolution to generate structural diversity in siderophores.

  13. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters

    Science.gov (United States)

    Linton, Kirsty A.; Wright, Timothy G.; Besley, Nicholas A.

    2018-03-01

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO+.(H2O)n=1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO+.(H2O) that is too high and incorrectly predict the lowest energy structure of NO+.(H2O)2, and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO+. Ab initio molecular dynamics (AIMD) simulations were performed to study the NO+.(H2O)5 H+.(H2O)4 + HONO reaction to investigate the formation of HONO from NO+.(H2O)5. Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO+.(H2O)5 complex following its formation. This article is part of the theme issue `Modern theoretical chemistry'.

  14. Stable structures of Al510–800 clusters and lowest energy sequence of truncated octahedral Al clusters up to 10,000 atoms

    International Nuclear Information System (INIS)

    Wu, Xia; He, Chengdong

    2012-01-01

    Highlights: ► The stable structures of Al 510–800 clusters are obtained with the NP-B potential. ► Al 510–800 clusters adopt truncated octahedral (TO) growth pattern based on complete TOs at Al 405 , Al 586 , and Al 711 . ► The lowest energy sequence of complete TOs up to the size 10,000 is proposed. -- Abstract: The stable structures of Al 510–800 clusters are obtained using dynamic lattice searching with constructed cores (DLSc) method by the NP-B potential. According to the structural growth rule, octahedra and truncated octahedra (TO) configurations are adopted as the inner cores in DLSc method. The results show that in the optimized structures two complete TO structures are found at Al 586 and Al 711 . Furthermore, Al 510–800 clusters adopt TO growth pattern on complete TOs at Al 405 , Al 586 , and Al 711 , and the configurations of the surface atoms are investigated. On the other hand, Al clusters with complete TO motifs are studied up to the size 10,000 by the geometrical construction method. The structural characteristics of complete TOs are denoted by the term “family”, and the growth sequence of Al clusters is investigated. The lowest energy sequence of complete TOs is proposed.

  15. Magnetism, structure and chemical order in small CoPd clusters: A first-principles study

    Energy Technology Data Exchange (ETDEWEB)

    Mokkath, Junais Habeeb, E-mail: Junais.Mokkath@kaust.edu.sa

    2014-01-15

    The structural, electronic and magnetic properties of small Co{sub m}Pd{sub n}(N=m+n=8,m=0−N) nanoalloy clusters are studied in the framework of a generalized-gradient approximation to density-functional theory. The optimized cluster structures have a clear tendency to maximize the number of nearest-neighbor CoCo pairs. The magnetic order is found to be ferromagnetic-like (FM) for all the ground-state structures. Antiferromagnetic-like spin arrangements were found in some low-lying isomers. The average magnetic moment per atom μ{sup ¯}{sub N} increases approximately linearly with Co content. A remarkable enhancement of the local Co moments is observed as a result of Pd doping. This is a consequence of the increase in the number of Co d holes, due to CoPd charge transfer, combined with the reduced local coordination. The influence of spin–orbit interactions on the cluster properties is also discussed. - Highlights: • This work analyses the structural and magnetic properties of CoPd nanoclusters. • The magnetic order is found to be ferromagnetic-like for all the ground-state structures. • The average magnetic moment per atom increases approximately linearly with Co content. • The influence of spin–orbit interactions on the cluster properties is discussed.

  16. Automated Clustering Analysis of Immunoglobulin Sequences in Chronic Lymphocytic Leukemia Based on 3D Structural Descriptors

    DEFF Research Database (Denmark)

    Marcatili, Paolo; Mochament, Konstantinos; Agathangelidis, Andreas

    2016-01-01

    study, we used the structure prediction tools PIGS and I-TASSER for creating the 3D models and the TM-align algorithm to superpose them. The innovation of the current methodology resides in the usage of methods adapted from 3D content-based search methodologies to determine the local structural...... determine it are extremely laborious and demanding. Hence, the ability to gain insight into the structure of Igs at large relies on the availability of tools and algorithms for producing accurate Ig structural models based on their primary sequence alone. These models can then be used to determine...... to achieve an optimal solution to this task yet their results were hindered mainly due to the lack of efficient clustering methods based on the similarity of 3D structure descriptors. Here, we present a novel workflow for robust Ig 3D modeling and automated clustering. We validated our protocol in chronic...

  17. A study of new rare-earth metal group-13 chalcohalides. Structures, chemistry, and optical properties

    International Nuclear Information System (INIS)

    Dorhout, P.K.; Van Calcar, P.M.

    1998-01-01

    Full text: Several new quaternary compounds from the rare-earth metal group-13 chalcohalide family have been prepared from alkaline earth halide flux reactions of binary and elemental starting materials. One compound, for example, Ca 2 La 6G a 2 S 1 4 , crystallizes as needles in an hexagonal cell while another, more disordered structure, La 11 Ga 19 Cl 6 S 42 , crystallizes as monoclinic plates. The former is a condensed structure with channels that contain the alkaline earth element while the latter forms a layered structure containing rare-earth halide clusters within interlayer galleries. These compounds are new members of a family of rare-earth metal main-group chalcogenides which show promise as electroluminescent materials. Structural and spectroscopic studies of these and related compounds will be discussed

  18. Mental State Talk Structure in Children’s Narratives: A Cluster Analysis

    Directory of Open Access Journals (Sweden)

    Giuliana Pinto

    2017-01-01

    Full Text Available This study analysed children’s Theory of Mind (ToM as assessed by mental state talk in oral narratives. We hypothesized that the children’s mental state talk in narratives has an underlying structure, with specific terms organized in clusters. Ninety-eight children attending the last year of kindergarten were asked to tell a story twice, at the beginning and at the end of the school year. Mental state talk was analysed by identifying terms and expressions referring to perceptual, physiological, emotional, willingness, cognitive, moral, and sociorelational states. The cluster analysis showed that children’s mental state talk is organized in two main clusters: perceptual states and affective states. Results from the study confirm the feasibility of narratives as an outlet to inquire mental state talk and offer a more fine-grained analysis of mental state talk structure.

  19. New conception of the spatial structure of the galactic clusters: Pleiades, Praesepe and Coma Berenices

    International Nuclear Information System (INIS)

    Pejkov, Z.I.

    1990-01-01

    The spatial structure of the galactic cluster Pleiads, Praesepe and Coma Berenices in the dependence on different star magnitude intervals and on different limiting star magnitudes is investigated on the basis of the star density distribution functions which were published by Kholopov and Artyukhina. It is shown that the spatial structure of these clusters, similarly to the globular ones, systematically changes with the star magnitude of the included stars, starting from the brightest stars of the upper part of the main sequance and descending along the 'V, B-V' diagram for the clusters. This change consists in an increase of the spatial zones radii, following the same law, whith the transition to the fainter stars

  20. Influence of Structure and Charge State on the Mechanism of CO Oxidation on Gold Clusters

    Science.gov (United States)

    Johnson, Grant; Burgel, Christian; Reilly, Nelly; Mitric, Roland; Kimble, Michele; Tyo, Eric; Castleman, A. W.; Bonacic-Koutecky, Vlasta

    2008-05-01

    Gas-phase reactivity experiments and high level theoretical calculations have been employed to study the interaction of both positively and negatively charged gold oxide clusters with carbon monoxide (CO). We demonstrate that for negatively charged clusters CO is oxidized to CO2 by an Eley-Ridel-like (ER-) mechanism involving the attack of CO on oxygen rather than gold. In contrast, for positively charged clusters, the oxidation reaction may also occur by a Langmuir-Hinshelwood-like (LH-) mechanism involving the initial binding of CO to a gold atom followed by subsequent migration to an oxygen site. The LH mechanism is made possible through the large energy gain associated with the adsorption of two CO molecules onto cationic gold clusters. Structure-reactivity relationships are also established which demonstrate that terminally bound oxygen atoms are the most active sites for CO oxidation. Bridge bonded oxygen atoms and molecularly bound O2 units are shown to be inert. We also establish an inverse relationship between the binding energy of CO to gold clusters and the energy of the clusters lowest unoccupied molecular orbital (LUMO).

  1. On the structure and stability of Arn and Arn+ clusters at finite temperature

    International Nuclear Information System (INIS)

    Schulte, J.

    1991-01-01

    For Ar 2-29 and Ar 2-29 + clusters at 20 K in the polarization model presented here the electrodynamical dipole-dipole many-body problem is solved selfconsistently with the Monte-Carlo method (MC) at 20 K, i.e. the instantaneous dipole-dipole interaction is solved to infinite perturbation order and in cluster expansion to the order of the cluster size. The long range many-body dipole-dipole interaction is coupled to exchange interaction by a modified effective dipole polarizability. This model will be compared to the dimer model and classical MC simulation of Ar n . The resulting different magic numbers in the binding energies are discussed in this connection with different experimental techniques of cluster ionization. By the mean square cluster diameter a shape parameter is introduced and it is found that with this parameter structural form transition in cluster growth can be resolved, and surprinsingly do not correlate with the magic numbers. (orig.)

  2. Study of structure formation scenarios with X-ray and SZ observed galaxy clusters

    International Nuclear Information System (INIS)

    Democles, Jessica

    2010-01-01

    Galaxy clusters are the largest structures formed by gravitational collapse. They are cited as cosmological probes for their dependence on the matter density parameter Ω_M, the normalization of the power spectrum of density fluctuations σ_8 and the Dark Energy parameters Ω_D_E and w_D_E. This thesis takes advantage of the multi-wavelength observation of galaxy clusters in order to optimize their cosmological exploitation. In particular, it deals with two aspects: the statistical characterization of cluster catalogues and the existence of scaling relations between their mass and their observables. It presents an observation model for SZ detected cluster catalogues, as it is the case for the Planck and SPT experiments. This model characterizes of the catalogues in terms of completeness, photometry and contamination. Its direct application to the theoretical distribution of clusters enables us to compute the observed cluster abundance. A Fisher analysis estimates the potential of cosmological parameter constraints associated with this abundance. We notice that one of the main limitations of constraints comes from the uncertainty of the scaling relation. Dissipative physics of the baryons are the main feature of the complexification of the scaling relations. The data analysis of two fossil groups observed with XMM-Newton shed light on the influence of dissipative physics on both the scaling relations and the matter distribution of gas and dark matter at group scale. (author) [fr

  3. Managing expectations: assessment of chemistry databases generated by automated extraction of chemical structures from patents.

    Science.gov (United States)

    Senger, Stefan; Bartek, Luca; Papadatos, George; Gaulton, Anna

    2015-12-01

    First public disclosure of new chemical entities often takes place in patents, which makes them an important source of information. However, with an ever increasing number of patent applications, manual processing and curation on such a large scale becomes even more challenging. An alternative approach better suited for this large corpus of documents is the automated extraction of chemical structures. A number of patent chemistry databases generated by using the latter approach are now available but little is known that can help to manage expectations when using them. This study aims to address this by comparing two such freely available sources, SureChEMBL and IBM SIIP (IBM Strategic Intellectual Property Insight Platform), with manually curated commercial databases. When looking at the percentage of chemical structures successfully extracted from a set of patents, using SciFinder as our reference, 59 and 51 % were also found in our comparison in SureChEMBL and IBM SIIP, respectively. When performing this comparison with compounds as starting point, i.e. establishing if for a list of compounds the databases provide the links between chemical structures and patents they appear in, we obtained similar results. SureChEMBL and IBM SIIP found 62 and 59 %, respectively, of the compound-patent pairs obtained from Reaxys. In our comparison of automatically generated vs. manually curated patent chemistry databases, the former successfully provided approximately 60 % of links between chemical structure and patents. It needs to be stressed that only a very limited number of patents and compound-patent pairs were used for our comparison. Nevertheless, our results will hopefully help to manage expectations of users of patent chemistry databases of this type and provide a useful framework for more studies like ours as well as guide future developments of the workflows used for the automated extraction of chemical structures from patents. The challenges we have encountered

  4. Stability analysis and structural rules of titanium dioxide clusters (TiO2)n with n = 1-9

    International Nuclear Information System (INIS)

    Zhang Weiwei; Han Ye; Yao Shuyu; Sun Haiqing

    2011-01-01

    Highlights: · We investigated the structure and stability of (TiO 2 ) n clusters with n = 1-9. · Some initial structures are introduced and proved to be the real global minimum. · We summarized the structural rules for small (TiO 2 ) n clusters. · The bonding features for the energy increment or decrement of the clusters are investigated. · A general shift of stability and reactivity with size for (TiO 2 ) n clusters. - Abstract: Atomic clusters have been considered as models for fundamental mechanistic insight into complex surfaces and catalysts. The structure and stability of (TiO 2 ) n clusters with n = 1-9 are investigated using the b3lyp hybrid density functional method in this paper. Some of the clusters are proposed initially and proved to be the real global minima. The stability and band gap of the clusters as a function of size are also investigated. The structural rules of the clusters are first summarized. The lowest-lying (TiO 2 ) n isomers tend to form some compact rather than quasi-linear or circular structures. The oxygen atom in 4-fold coordination and the titanium atom in 4-fold coordination favor the cluster stability. The 5-fold coordinated Ti-atom, the Ti-Ti bond and the terminal Ti-O bond lead to stability penalty for the clusters. No evidence for a regular variation in stability or reactivity with size of the clusters has shown. The structural rules can serve as guiding factors for formation research and structure design of (TiO 2 ) n and other transition metal oxide clusters.

  5. Organic chemistry as a language and the implications of chemical linguistics for structural and retrosynthetic analyses.

    Science.gov (United States)

    Cadeddu, Andrea; Wylie, Elizabeth K; Jurczak, Janusz; Wampler-Doty, Matthew; Grzybowski, Bartosz A

    2014-07-28

    Methods of computational linguistics are used to demonstrate that a natural language such as English and organic chemistry have the same structure in terms of the frequency of, respectively, text fragments and molecular fragments. This quantitative correspondence suggests that it is possible to extend the methods of computational corpus linguistics to the analysis of organic molecules. It is shown that within organic molecules bonds that have highest information content are the ones that 1) define repeat/symmetry subunits and 2) in asymmetric molecules, define the loci of potential retrosynthetic disconnections. Linguistics-based analysis appears well-suited to the analysis of complex structural and reactivity patterns within organic molecules. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Structure and chemistry of the Si(111)/AlN interface

    Science.gov (United States)

    Radtke, G.; Couillard, M.; Botton, G. A.; Zhu, D.; Humphreys, C. J.

    2012-01-01

    We investigate the atomic structure and the chemistry of the Si(111)/AlN interface for an AlN film grown at low-temperature (735 °C) by metalorganic vapor phase epitaxy. A heterogeneous interface is formed from the alternation of crystallographically abrupt and partly amorphous regions. The polarity of the AlN film, along with the projected atomic structure of the crystalline interface, is retrieved using high-angle annular dark field imaging, and a model, based on these experimental observations, is proposed for the bonding at the interface. Electron energy-loss spectrum-imaging, however, also reveals a chemical intermixing, placing our growth conditions at the onset of SiNx interlayer formation.

  7. Probing chemistry within the membrane structure of wood with soft X-ray spectral microscopy

    International Nuclear Information System (INIS)

    Cody, George D.

    2000-01-01

    Scanning Transmission Soft X-ray spectral microscopy on Carbon's 1s absorption edge reveals the distribution of structural biopolymers within cell membrane regions of modern cedar and oak. Cellulose is extremely susceptible to beam damage. Spectroscopic studies of beam damage reveals that the chemical changes resulting from secondary electron impact may be highly selective and is consistent with hydroxyl eliminations and structural rearrangement of pyranose rings in alpha-cellulose to hydroxyl substituted γ pyrones. A study of acetylated cellulose demonstrates significantly different chemistry; principally massive decarboxylation. Defocusing the beam to a 2 μm spot size allows for the acquisition of 'pristine' cellulose spectra. Spectral deconvolution is used to assess the distribution of lignin and cellulose in the different regions of the cell membrane. Using the intensity of the hydroxylated aromatic carbons 1s-π * transition, the ratio of coniferyl and syringyl based lignin within the middle lamellae and secondary cell wall of oak, an angiosperm can be determined

  8. Structure and chemistry of passivated SiC/SiO{sub 2} interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Houston Dycus, J.; Xu, Weizong; LeBeau, James M. [Department of Materials Science and Engineering, North Carolina State University, Raleigh, North Carolina 27695-7907 (United States); Lichtenwalner, Daniel J.; Hull, Brett; Palmour, John W. [Power Devices R& D, Wolfspeed, A Cree Company, Research Triangle Park, North Carolina 27709 (United States)

    2016-05-16

    Here, we report on the chemistry and structure of 4H-SiC/SiO{sub 2} interfaces passivated either by nitric oxide annealing or Ba deposition. Using aberration corrected scanning transmission electron microscopy and spectroscopy, we find that Ba and N remain localized at SiC/SiO{sub 2} interface after processing. Further, we find that the passivating species can introduce significant changes to the near-interface atomic structure of SiC. Specifically, we quantify significant strain for nitric oxide annealed sample where Si dangling bonds are capped by N. In contrast, strain is not observed at the interface of the Ba treated samples. Finally, we place these results in the context of field effect mobility.

  9. Structures, Energetics and Spectroscopic Fingerprints of Water Clusters n=2-24

    Energy Technology Data Exchange (ETDEWEB)

    Yoo, Soohaeng; Xantheas, Sotiris S.

    2017-06-08

    This chapter discusses the structures, energetics, and vibrational spectra of the first few (n$24) water clusters obtained from high-level electronic structure calculations. The results are discussed in the perspective of being used to parameterize/assess the accuracy of classical and quantum force fields for water. To this end, a general introduction with the classification of those force fields is presented. Several low-lying families of minima for the medium cluster sizes are considered. The transition from the “all surface” to the “fully coordinated” cluster structures occurring at nD17 and its spectroscopic signature is presented. The various families of minima for nD20 are discussed together with the low energy networks of the pentagonal dodecahedron (H2O)20 water cage. Finally, the low-energy networks of the tetrakaidecahedron (T-cage) (H2O)24 cluster are shown and their significance in the construction of periodic lattices of structure I (sI) of the hydrate lattices is discussed.

  10. Kendall’s tau and agglomerative clustering for structure determination of hierarchical Archimedean copulas

    Czech Academy of Sciences Publication Activity Database

    Górecki, J.; Hofert, M.; Holeňa, Martin

    2017-01-01

    Roč. 5, č. 1 (2017), s. 75-87 ISSN 2300-2298 R&D Projects: GA ČR GA17-01251S Institutional support: RVO:67985807 Keywords : structure determination * agglomerative clustering * Kendall’s tau * Archimedean copula Subject RIV: IN - Informatics, Computer Science OBOR OECD: Statistics and probability

  11. Experimental analysis of clustering structures in magnetic and MR fluids using ultrasound

    International Nuclear Information System (INIS)

    Bramantya, M A; Takuma, H; Faiz, M; Sawada, T; Motozawa, M

    2009-01-01

    The formation of clustering structures in magnetic and MR fluids has an influence on ultrasonic propagation. We propose a qualitative analysis of these structures by measuring properties of ultrasonic propagation. Since magnetic and MR fluids are opaque, the non-contact inspection using this ultrasonic technique can be very useful for analyzing the inner structures of magnetic and MR fluids. We measured ultrasonic propagation velocity in a hydrocarbon-based magnetic fluid and MR fluid precisely. Based on these results, the clustering structures of these fluids were analyzed experimentally in terms of elapsed time dependence, effect of external magnetic field strength and angle, and hysteresis phenomena. A comparison of ultrasonic velocity propagation between magnetic and MR fluid was discussed.

  12. Computational Design of Clusters for Catalysis

    Science.gov (United States)

    Jimenez-Izal, Elisa; Alexandrova, Anastassia N.

    2018-04-01

    When small clusters are studied in chemical physics or physical chemistry, one perhaps thinks of the fundamental aspects of cluster electronic structure, or precision spectroscopy in ultracold molecular beams. However, small clusters are also of interest in catalysis, where the cold ground state or an isolated cluster may not even be the right starting point. Instead, the big question is: What happens to cluster-based catalysts under real conditions of catalysis, such as high temperature and coverage with reagents? Myriads of metastable cluster states become accessible, the entire system is dynamic, and catalysis may be driven by rare sites present only under those conditions. Activity, selectivity, and stability are highly dependent on size, composition, shape, support, and environment. To probe and master cluster catalysis, sophisticated tools are being developed for precision synthesis, operando measurements, and multiscale modeling. This review intends to tell the messy story of clusters in catalysis.

  13. Non-standard base pairing and stacked structures in methyl xanthine clusters

    Czech Academy of Sciences Publication Activity Database

    Callahan, M. P.; Gengeliczki, Z.; Svadlenak, N.; Valdes, Haydee; Hobza, Pavel; de Vries, M. S.

    2008-01-01

    Roč. 10, č. 19 (2008), s. 2819-2826 ISSN 1463-9076 R&D Projects: GA MŠk LC512 Grant - others:NSF(US) CHE-0615401 Institutional research plan: CEZ:AV0Z40550506 Keywords : non-standard base pairing * stacked structures * in methyl xanthine Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 4.064, year: 2008

  14. Analysis of the Structures and Properties of (GaSb)n (n = 4-9) Clusters through Density Functional Theory.

    Science.gov (United States)

    Lu, Qi Liang; Luo, Qi Quan; Huang, Shou Guo; Li, Yi De; Wan, Jian Guo

    2016-07-07

    An optimization strategy combining global semiempirical quantum mechanical search with all-electron density functional theory was adopted to determine the lowest energy structure of (GaSb)n clusters up to n = 9. The growth pattern of the clusters differed from those of previously reported group III-V binary clusters. A cagelike configuration was found for cluster sizes n ≤ 7. The structure of (GaSb)6 deviated from that of other III-V clusters. Competition existed between core-shell and hollow cage structures of (GaSb)7. Novel noncagelike structures were energetically preferred over the cages for the (GaSb)8 and (GaSb)9 clusters. Electronic properties, such as vertical ionization potential, adiabatic electron affinities, HOMO-LUMO gaps, and average on-site charges on Ga or Sb atoms, as well as binding energies, were computed.

  15. Self-selection in size and structure in argon clusters formed on amorphous carbon

    Energy Technology Data Exchange (ETDEWEB)

    Krainyukova, Nina V.; Waal, Benjamin W. van de

    2004-07-01

    Argon clusters formed on an amorphous carbon substrate as deposited from the vapor phase were studied by means of transmission high energy electron diffraction using the liquid helium cryostat. Electron diffractograms were analysed on the basis of assumption that there exist a cluster size distribution in samples formed on substrate and multi-shell structures such as icosahedra, decahedra, fcc and hcp were probed for different sizes up to {approx}15 000 atoms. The experimental data were considered as a result of a superposition of diffracted intensities from clusters of different sizes and structures. The comparative analysis was based on the R-factor minimization that was found to be equal to 0.014 for the best fit between experiment and modelling. The total size and structure distribution function shows the presence of 'non-crystallographic' structures such as icosahedra and decahedra with five-fold symmetry that was found to prevail and a smaller amount of fcc and hcp structures. Possible growth mechanisms as well as observed general tendency to self-selection in sizes and structures are presumably governed by confined pore-like geometry in an amorphous carbon substrate.

  16. The structure of small clusters ejected by ion bombardment of solids

    International Nuclear Information System (INIS)

    Ali, M.; Smith, R.

    1993-01-01

    The structure of small clusters predicted by the many-body potentials used in Molecular Dynamics (MD) simulations of semiconductor processes is investigated. The potential minima are determined by using global optimisation algorithms which also find the local minima. It is shown that there are many such local minima for the Tersoff type potentials. If an MD simulation requires an accurate description of the small cluster geometries and energetics, then the potential can describe them provided they are included in the fitting process. (Author)

  17. Structure and reactivity of molybdenum oxide cluster ions in the gas phase

    International Nuclear Information System (INIS)

    Goncharov, V.B.; Fialko, E.F.

    2002-01-01

    A set of cluster ions of molybdenum oxides Mo x O y + (x = 1-5, y = 1-15) was prepared using a combination of the ionic cyclotron resonance method and Knudsen effusion source. Dependence of concentration of different molybdenum oxide ions on the time of retention and their interaction with carbon monoxide was studied. It is shown that Mo x O y + ions with x>3 contain cyclic fragment Mo 3 O 9 in their structure. Oxygen binding energies within ionic clusters Mo x O y + were estimated [ru

  18. The Formation of Competitive Advantages for Corporate Structures Based on the Cluster Integration

    Directory of Open Access Journals (Sweden)

    Ekaterina Vasilyevna Pustynnikova

    2017-06-01

    Full Text Available The article studies the cluster forms of integration as well as the development of corporate and cluster connections. At present, economic knowledge is rather focused on the development of integrated regional systems recognized as one of the most effective forms of integration. In turn, the processes, based on the interdependence and cooperation of economic entities located on the same territory, determine the possibility of stable economic relations, synergetic effect and growth of the competitive advantages of these territories. Such development tendencies reflect corporate interests and define trends for the integration of corporations in the context of regional and industrial limitations. Thus, one of the main aspects of integration is focused on the establishment of sustainable cost-beneficial relationships between corporate entities. The dialectical unity of the coordination and cooperation of corporate structures in economic clusters expands the traditional boundaries of economic benefits. Considering the government of corporate structure on the basis of internal approach, we can see that the benefits from the fragmented leadership may be neutralized due to unevenness of expenses. The corporate-cluster approach of corporate structure government allows not only to coordinate actions at the micro-level but also to generate more sustainable economic relations at the industrial, market and regional levels. It is reflected in the synergistic effect. The coordination of economic processes and geographic concentration contribute to system flexibility and adaptability in the market conditions as well as stimulate economic processes. Therefore, all cluster participants benefit from mutually beneficial cooperation. This, in turn, contributes to the decrease of total expenses and hastens the responses of entities on different market changes. The authors’ hypothesis assumes the coordination of interests in the economic cluster that allows to create

  19. Coupled-cluster calculations for ground and excited states of closed- and open-shell nuclei using methods of quantum chemistry

    International Nuclear Information System (INIS)

    Wloch, Marta; Gour, Jeffrey R; Piecuch, Piotr; Dean, David J; Hjorth-Jensen, Morten; Papenbrock, Thomas

    2005-01-01

    We discuss large-scale ab initio calculations of ground and excited states of 16 O and preliminary calculations for 15 O and 17 O using coupled-cluster methods and algorithms developed in quantum chemistry. By using realistic two-body interactions and the renormalized form of the Hamiltonian obtained with a no-core G-matrix approach, we are able to obtain the virtually converged results for 16 O and promising results for 15 O and 17 O at the level of two-body interactions. The calculated properties other than binding and excitation energies include charge radius and charge form factor. The relatively low costs of coupled-cluster calculations, which are characterized by the low-order polynomial scaling with the system size, enable us to probe large model spaces with up to seven or eight major oscillator shells, for which nontruncated shell-model calculations for nuclei with A = 15-17 active particles are presently not possible

  20. From Globular Clusters to Tidal Dwarfs: Structure Formation in Tidal Tails

    Science.gov (United States)

    Knierman, K.; Hunsberger, S.; Gallagher, S.; Charlton, J.; Whitmore, B.; Hibbard, J.; Kundu, A.; Zaritsky, D.

    1999-12-01

    Galaxy interactions trigger star formation in tidal debris. How does this star formation depend on the local and global physical conditions? Using WFPC2/HST images, we investigate the range of structure within tidal tails of four classic ``Toomre Sequence'' mergers: NGC 4038/9 (``Antennae''), NGC 7252 (``Atoms for Peace''), NGC 3921, and NGC 3256. These tails contain a variety of stellar associations with sizes from globular clusters up to dwarf Irregulars. We explore whether there is a continuum between the two extremes. Our eight fields sample seven tidal tails at a variety of stages in the evolutionary sequence. Some of these tails are rich in HI while others are HI poor. Large tidal dwarfs are embedded in three of the tails. Using V and I WFPC2 images, we measure luminosities and colors of substructures within the tidal tails. The properties of globular cluster candidates in the tails will be contrasted with those of the hundreds of young clusters in the central regions of these mergers. We address whether globular clusters form and survive in the tidal tails and whether tidal dwarfs are composed of only young stars. By comparing the properties of structures in the tails of the four mergers with different ages, we examine systematic evolution of structure along the evolutionary sequence and as a function of HI content. We acknowledge support from NASA through STScI, and from NSF for an REU supplement for Karen Knierman.

  1. Correlation of bistranded clustered abasic DNA lesion processing with structural and dynamic DNA helix distortion

    Science.gov (United States)

    Bignon, Emmanuelle; Gattuso, Hugo; Morell, Christophe; Dehez, François; Georgakilas, Alexandros G.; Monari, Antonio; Dumont, Elise

    2016-01-01

    Clustered apurinic/apyrimidinic (AP; abasic) DNA lesions produced by ionizing radiation are by far more cytotoxic than isolated AP lesion entities. The structure and dynamics of a series of seven 23-bp oligonucleotides featuring simple bistranded clustered damage sites, comprising of two AP sites, zero, one, three or five bases 3′ or 5′ apart from each other, were investigated through 400 ns explicit solvent molecular dynamics simulations. They provide representative structures of synthetically engineered multiply damage sites-containing oligonucleotides whose repair was investigated experimentally (Nucl. Acids Res. 2004, 32:5609-5620; Nucl. Acids Res. 2002, 30: 2800–2808). The inspection of extrahelical positioning of the AP sites, bulge and non Watson–Crick hydrogen bonding corroborates the experimental measurements of repair efficiencies by bacterial or human AP endonucleases Nfo and APE1, respectively. This study provides unprecedented knowledge into the structure and dynamics of clustered abasic DNA lesions, notably rationalizing the non-symmetry with respect to 3′ to 5′ position. In addition, it provides strong mechanistic insights and basis for future studies on the effects of clustered DNA damage on the recognition and processing of these lesions by bacterial or human DNA repair enzymes specialized in the processing of such lesions. PMID:27587587

  2. A pilot cluster randomized controlled trial of structured goal-setting following stroke.

    Science.gov (United States)

    Taylor, William J; Brown, Melanie; William, Levack; McPherson, Kathryn M; Reed, Kirk; Dean, Sarah G; Weatherall, Mark

    2012-04-01

    To determine the feasibility, the cluster design effect and the variance and minimal clinical importance difference in the primary outcome in a pilot study of a structured approach to goal-setting. A cluster randomized controlled trial. Inpatient rehabilitation facilities. People who were admitted to inpatient rehabilitation following stroke who had sufficient cognition to engage in structured goal-setting and complete the primary outcome measure. Structured goal elicitation using the Canadian Occupational Performance Measure. Quality of life at 12 weeks using the Schedule for Individualised Quality of Life (SEIQOL-DW), Functional Independence Measure, Short Form 36 and Patient Perception of Rehabilitation (measuring satisfaction with rehabilitation). Assessors were blinded to the intervention. Four rehabilitation services and 41 patients were randomized. We found high values of the intraclass correlation for the outcome measures (ranging from 0.03 to 0.40) and high variance of the SEIQOL-DW (SD 19.6) in relation to the minimally importance difference of 2.1, leading to impractically large sample size requirements for a cluster randomized design. A cluster randomized design is not a practical means of avoiding contamination effects in studies of inpatient rehabilitation goal-setting. Other techniques for coping with contamination effects are necessary.

  3. Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

    Energy Technology Data Exchange (ETDEWEB)

    Kulagin, N.A., E-mail: nkulagin@bestnet.kharkov.u [Kharkiv National University for Radio Electronics, Avenue Shakespeare 6-48, 61045 Kharkiv (Ukraine)

    2011-03-15

    Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr{sup +4} ions in oxides, Cu{sup +2} in HTSC, Nd{sup +2} in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10{sup -9} m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: External influence and variation of technology induce changes in valence of nl ions in compounds. Wave function of cluster presented as anti-symmetrical set of ions wave functions. The main equation describes the self-consistent field depending on state of all electrons of cluster. Level scheme of Cr{sup 4+} ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. Plasma treatment effects in appearance of systems of unit crystallites with size of about 10{sup -6}-10{sup -9} m.

  4. Electronic structure and dynamics of ordered clusters with ME or RE ions on oxide surface

    International Nuclear Information System (INIS)

    Kulagin, N.A.

    2011-01-01

    Selected data of ab initio simulation of the electronic structure and spectral properties of either cluster with ions of iron, rare earth or actinium group elements have been presented here. Appearance of doped Cr +4 ions in oxides, Cu +2 in HTSC, Nd +2 in solids has been discussed. Analysis of experimental data for plasma created ordered structures of crystallites with size of about 10 -9 m on surface of separate oxides are given, too. Change in the spectroscopic properties of clusters and nano-structures on surface of strontium titanate crystals discussed shortly using the X-ray line spectroscopy experimental results. - Research highlights: → External influence and variation of technology induce changes in valence of nl ions in compounds. → Wave function of cluster presented as anti-symmetrical set of ions wave functions. → The main equation describes the self-consistent field depending on state of all electrons of cluster. → Level scheme of Cr 4+ ions in octo- and tetra-site corresponds to doped oxides spectra after treatment. → Plasma treatment effects in appearance of systems of unit crystallites with size of about 10 -6 -10 -9 m.

  5. Structures of Pt clusters on graphene doped with nitrogen, boron, and silicon: a theoretical study

    Institute of Scientific and Technical Information of China (English)

    Dai Xian-Qi; Tang Ya-Nan; Dai Ya-Wei; Li Yan-Hui; Zhao Jian-Hua; Zhao Bao; Yang Zong-Xian

    2011-01-01

    The structures of Pt clusters on nitrogen-, boron-, silicon- doped graphenes are theoretically studied using densityfunctional theory. These dopants (nitrogen, boron and silicon) each do not induce a local curvature in the graphene and the doped graphenes all retain their planar form. The formation energy of the silicon-graphene system is lower than those of the nitrogen-, boron-doped graphenes, indicating that the silicon atom is easier to incorporate into the graphene.All the substitutional impurities enhance the interaction between the Pt atom and the graphene. The adsorption energy of a Pt adsorbed on the silicon-doped graphene is much higher than those on the nitrogen- and boron-doped graphenes.The doped silicon atom can provide more charges to enhance the Pt-graphene interaction and the formation of Pt clusters each with a large size. The stable structures of Pt clusters on the doped-graphenes are dimeric, triangle and tetrahedron with the increase of the Pt coverage. Of all the studied structures, the tetrahedron is the most stable cluster which has the least influence on the planar surface of doped-graphene.

  6. Structure of boron clusters revisited, Bn with n = 14-20

    Science.gov (United States)

    Tai, Truong Ba; Tam, Nguyen Minh; Nguyen, Minh Tho

    2012-03-01

    We reinvestigate the structures of neutral boron clusters Bn, with n = 14-20. G3B3 calculations confirm that a transition between 2D and 3D shape occurs at B20, which has a tubular form. In disagreement with Boustani et al. (Phys. Rev. B, 83 (2011) 193405), we find a planar B19 cluster. Standard heats of formation are obtained and used to evaluate the clusters stability. The average binding energy tends to increase with increasing size toward a limit. Higher stability is found B14, B16, B18 and B20. All Bn have negative NICS-values. The bonding nature and electron delocalization of B20 are re-examined using CMO and LOL.

  7. A density functional study of structures and stability of SinCN clusters

    International Nuclear Information System (INIS)

    Gai Zhigang; Yang Li; Zhao Jie; Chu Shibo

    2011-01-01

    In this paper, density functional theory (DFT) B3LYP method with 6-311G * basis set has been used to investigate geometric configurations, vibrational frequencies and ground state energies of Si n CN (n = 2 ∼ 6) clusters. The energies and spin multiplicities of ground states and substable states have been discussed, respectively. Harmonic frequencies and infrared spectra intensity for these clusters are given in order to aid in the characterization of the stable structures. The results show that the zero point energy (ZPE), thermocapacity and entropies are nearly in proportion to increased n, whose average enhancement are 0.80 kcal/mol, 5.20 cal/mol · K and 12.72 cal/ mol · K, respectively. The stability of Si n CN (n = 2 ∼ 6) clusters with even n are greater than that with odd n. (authors)

  8. Clustering of 770,000 genomes reveals post-colonial population structure of North America

    Science.gov (United States)

    Han, Eunjung; Carbonetto, Peter; Curtis, Ross E.; Wang, Yong; Granka, Julie M.; Byrnes, Jake; Noto, Keith; Kermany, Amir R.; Myres, Natalie M.; Barber, Mathew J.; Rand, Kristin A.; Song, Shiya; Roman, Theodore; Battat, Erin; Elyashiv, Eyal; Guturu, Harendra; Hong, Eurie L.; Chahine, Kenneth G.; Ball, Catherine A.

    2017-02-01

    Despite strides in characterizing human history from genetic polymorphism data, progress in identifying genetic signatures of recent demography has been limited. Here we identify very recent fine-scale population structure in North America from a network of over 500 million genetic (identity-by-descent, IBD) connections among 770,000 genotyped individuals of US origin. We detect densely connected clusters within the network and annotate these clusters using a database of over 20 million genealogical records. Recent population patterns captured by IBD clustering include immigrants such as Scandinavians and French Canadians; groups with continental admixture such as Puerto Ricans; settlers such as the Amish and Appalachians who experienced geographic or cultural isolation; and broad historical trends, including reduced north-south gene flow. Our results yield a detailed historical portrait of North America after European settlement and support substantial genetic heterogeneity in the United States beyond that uncovered by previous studies.

  9. Electronic and atomic structure of the AlnHn+2 clusters

    DEFF Research Database (Denmark)

    Martinez, Jose Ignacio; Alonso, J.A.

    2008-01-01

    The electronic and atomic structure of the family of hydrogenated Al clusters AlnHn+2 with n=4-11 has been studied using the density functional theory with the generalized gradient approximation (GGA) for exchange and correlation. All these clusters have substantial gaps between the highest...... a polyhedron of n vertices and n H atoms form strong H-Al terminal bonds; one pair of electrons is involved in each of those bonds. The remaining n+1 electron pairs form a delocalized cloud over the surface of the Al cage. The clusters fulfilling the Wade-Mingos rule have wider HOMO-LUMO gaps...... and are chemically more stable. The trends in the gap have some reflections in the form of the photoabsorption spectra, calculated in the framework of time-dependent density functional theory using the GGA single-particle energies and orbitals and a local density approximation exchange-correlation kernel....

  10. Molecular comparison of the structural proteins encoding gene clusters of two related Lactobacillus delbrueckii bacteriophages.

    Science.gov (United States)

    Vasala, A; Dupont, L; Baumann, M; Ritzenthaler, P; Alatossava, T

    1993-01-01

    Virulent phage LL-H and temperate phage mv4 are two related bacteriophages of Lactobacillus delbrueckii. The gene clusters encoding structural proteins of these two phages have been sequenced and further analyzed. Six open reading frames (ORF-1 to ORF-6) were detected. Protein sequencing and Western immunoblotting experiments confirmed that ORF-3 (g34) encoded the main capsid protein Gp34. The presence of a putative late promoter in front of the phage LL-H g34 gene was suggested by primer extension experiments. Comparative sequence analysis between phage LL-H and phage mv4 revealed striking similarities in the structure and organization of this gene cluster, suggesting that the genes encoding phage structural proteins belong to a highly conservative module. Images PMID:8497043

  11. Magneto-structural properties and magnetic anisotropy of small transition-metal clusters: a first-principles study

    International Nuclear Information System (INIS)

    Blonski, Piotr; Hafner, Juergen

    2011-01-01

    Ab initio density-functional calculations including spin-orbit coupling (SOC) have been performed for Ni and Pd clusters with three to six atoms and for 13-atom clusters of Ni, Pd, and Pt, extending earlier calculations for Pt clusters with up to six atoms (2011 J. Chem. Phys. 134 034107). The geometric and magnetic structures have been optimized for different orientations of the magnetization with respect to the crystallographic axes of the cluster. The magnetic anisotropy energies (MAE) and the anisotropies of spin and orbital moments have been determined. Particular attention has been paid to the correlation between the geometric and magnetic structures. The magnetic point group symmetry of the clusters varies with the direction of the magnetization. Even for a 3d metal such as Ni, the change in the magnetic symmetry leads to small geometric distortions of the cluster structure, which are even more pronounced for the 4d metal Pd. For a 5d metal the SOC is strong enough to change the energetic ordering of the structural isomers. SOC leads to a mixing of the spin states corresponding to the low-energy spin isomers identified in the scalar-relativistic calculations. Spin moments are isotropic only for Ni clusters, but anisotropic for Pd and Pt clusters, orbital moments are anisotropic for the clusters of all three elements. The magnetic anisotropy energies have been calculated. The comparison between MAE and orbital anisotropy invalidates a perturbation analysis of magnetic anisotropy for these small clusters.

  12. From Globular Clusters to Tidal Dwarfs: Structure Formation in the Tidal Tails of Merging Pairs

    Science.gov (United States)

    Knierman, K. A.; Gallagher, S. C.; Charlton, J. C.; Hunsberger, S. D.; Whitmore, B. C.; Kundu, A.; Hibbard, J. E.; Zaritsky, D. F.

    2001-05-01

    Using V and I images obtained with the Wide Field Planetary Camera 2 (WFPC2) of the Hubble Space Telescope, we investigate compact stellar structures within tidal tails. Six regions of tidal debris in the four classic ``Toomre Sequence'' mergers: NGC 4038/9 (``Antennae''), NGC 3256, NGC 3921, and NGC 7252 (``Atoms for Peace'') have been studied in order to explore how the star formation depends upon the local and global physical conditions. These mergers sample a range of stages in the evolutionary sequence, and include HI--rich and HI--poor environments. The six tails are found to contain a variety of stellar structures, with sizes ranging from those of globular clusters up to those of dwarf galaxies. From V and I WFPC2 images, we measure the luminosities and colors of the star clusters. NGC 3256 is found to have a large population of young clusters lying along both tails, similar to those found in the inner region of the merger. In contrast, NGC 4038/9 has no clusters in the observed region of the tail, only less luminous point sources likely to be individual stars. NGC 3921 and NGC 7252 have small populations of clusters that are concentrated in certain regions of the tail, and particularly in the prominent tidal dwarfs in the eastern and western tails of NGC 7252. The two cluster--rich tails of NGC 3256 are not distinguished from the others by their ages or by their total HI masses. We acknowledge support from NASA through STScI, and from NSF for an REU supplement for Karen Knierman.

  13. Influence of Cr doping on the stability and structure of small cobalt oxide clusters

    Energy Technology Data Exchange (ETDEWEB)

    Tung, Nguyen Thanh; Lievens, Peter; Janssens, Ewald, E-mail: ewald.janssens@fys.kuleuven.be [Laboratory of Solid-State Physics and Magnetism, KU Leuven, B-3001 Leuven (Belgium); Tam, Nguyen Minh; Nguyen, Minh Tho [Department of Chemistry, KU Leuven, B-3001 Leuven (Belgium)

    2014-07-28

    The stability of mass-selected pure cobalt oxide and chromium doped cobalt oxide cluster cations, Co{sub n}O{sub m}{sup +} and Co{sub n−1}CrO{sub m}{sup +} (n = 2, 3; m = 2–6 and n = 4; m = 3–8), has been investigated using photodissociation mass spectrometry. Oxygen-rich Co{sub n}O{sub m}{sup +} clusters (m ⩾ n + 1 for n = 2, 4 and m ⩾ n + 2 for n = 3) prefer to photodissociate via the loss of an oxygen molecule, whereas oxygen poorer clusters favor the evaporation of oxygen atoms. Substituting a single Co atom by a single Cr atom alters the dissociation behavior. All investigated Co{sub n−1}CrO{sub m}{sup +} clusters, except CoCrO{sub 2}{sup +} and CoCrO{sub 3}{sup +}, prefer to decay by eliminating a neutral oxygen molecule. Co{sub 2}O{sub 2}{sup +}, Co{sub 4}O{sub 3}{sup +}, Co{sub 4}O{sub 4}{sup +}, and CoCrO{sub 2}{sup +} are found to be relatively difficult to dissociate and appear as fragmentation product of several larger clusters, suggesting that they are particularly stable. The geometric structures of pure and Cr doped cobalt oxide species are studied using density functional theory calculations. Dissociation energies for different evaporation channels are calculated and compared with the experimental observations. The influence of the dopant atom on the structure and the stability of the clusters is discussed.

  14. The 2009 Nobel Prize in Chemistry: Thomas A. Steitz and the structure of the ribosome.

    Science.gov (United States)

    Zhao, Peter

    2011-06-01

    Over the past 200 years, there have been countless groundbreaking discoveries in biology and medicine at Yale University. However, one particularly noteworthy discovery with profoundly important and broad consequences happened here in just the past two decades. In 2009, Thomas Steitz, the Sterling Professor of Molecular Biophysics & Biochemistry, was awarded the Nobel Prize in Chemistry for "studies of the structure and function of the ribosome," along with Venkatraman Ramakrishnan of the MRC Laboratory of Molecular Biology and Ada E. Yonath of the Weizmann Institute of Science. This article covers the historical context of Steitz's important discovery, the techniques his laboratory used to study the ribosome, and the impact that this research has had, and will have, on the future of biological and medical research.

  15. Probing the chemistry, electronic structure and redox energetics in pentavalent organometallic actinide complexes

    Energy Technology Data Exchange (ETDEWEB)

    Graves, Christopher R [Los Alamos National Laboratory; Vaughn, Anthony E [Los Alamos National Laboratory; Morris, David E [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory

    2008-01-01

    Complexes of the early actinides (Th-Pu) have gained considerable prominence in organometallic chemistry as they have been shown to undergo chemistries not observed with their transition- or lanthanide metal counterparts. Further, while bonding in f-element complexes has historically been considered to be ionic, the issue of covalence remains a subject of debate in the area of actinide science, and studies aimed at elucidating key bonding interactions with 5f-orbitals continue to garner attention. Towards this end, our interests have focused on the role that metal oxidation state plays in the structure, reactivity and spectral properties of organouranium complexes. We report our progress in the synthesis of substituted U{sup V}-imido complexes using various routes: (1) Direct oxidation of U{sup IV}-imido complexes with copper(I) salts; (2) Salt metathesis with U{sup V}-imido halides; (3) Protonolysis and insertion of an U{sup V}-imido alkyl or aryl complex with H-N{double_bond}CPh{sub 2} or N{triple_bond}C-Ph, respectively, to form a U{sup V}-imido ketimide complex. Further, we report and compare the crystallographic, electrochemical, spectroscopic and magnetic characterization of the pentavalent uranium (C{sub 5}Me{sub 5}){sub 2}U({double_bond}N-Ar)(Y) series (Y = OTf, SPh, C{triple_bond}C-Ph, NPh{sub 2}, OPh, N{double_bond}CPh{sub 2}) to further interrogate the molecular, electronic, and magnetic structures of this new class of uranium complexes.

  16. Medicinal Chemistry Projects Requiring Imaginative Structure-Based Drug Design Methods.

    Science.gov (United States)

    Moitessier, Nicolas; Pottel, Joshua; Therrien, Eric; Englebienne, Pablo; Liu, Zhaomin; Tomberg, Anna; Corbeil, Christopher R

    2016-09-20

    Computational methods for docking small molecules to proteins are prominent in drug discovery. There are hundreds, if not thousands, of documented examples-and several pertinent cases within our research program. Fifteen years ago, our first docking-guided drug design project yielded nanomolar metalloproteinase inhibitors and illustrated the potential of structure-based drug design. Subsequent applications of docking programs to the design of integrin antagonists, BACE-1 inhibitors, and aminoglycosides binding to bacterial RNA demonstrated that available docking programs needed significant improvement. At that time, docking programs primarily considered flexible ligands and rigid proteins. We demonstrated that accounting for protein flexibility, employing displaceable water molecules, and using ligand-based pharmacophores improved the docking accuracy of existing methods-enabling the design of bioactive molecules. The success prompted the development of our own program, Fitted, implementing all of these aspects. The primary motivation has always been to respond to the needs of drug design studies; the majority of the concepts behind the evolution of Fitted are rooted in medicinal chemistry projects and collaborations. Several examples follow: (1) Searching for HDAC inhibitors led us to develop methods considering drug-zinc coordination and its effect on the pKa of surrounding residues. (2) Targeting covalent prolyl oligopeptidase (POP) inhibitors prompted an update to Fitted to identify reactive groups and form bonds with a given residue (e.g., a catalytic residue) when the geometry allows it. Fitted-the first fully automated covalent docking program-was successfully applied to the discovery of four new classes of covalent POP inhibitors. As a result, efficient stereoselective syntheses of a few screening hits were prioritized rather than synthesizing large chemical libraries-yielding nanomolar inhibitors. (3) In order to study the metabolism of POP inhibitors by

  17. Cluster-cluster clustering

    International Nuclear Information System (INIS)

    Barnes, J.; Dekel, A.; Efstathiou, G.; Frenk, C.S.; Yale Univ., New Haven, CT; California Univ., Santa Barbara; Cambridge Univ., England; Sussex Univ., Brighton, England)

    1985-01-01

    The cluster correlation function xi sub c(r) is compared with the particle correlation function, xi(r) in cosmological N-body simulations with a wide range of initial conditions. The experiments include scale-free initial conditions, pancake models with a coherence length in the initial density field, and hybrid models. Three N-body techniques and two cluster-finding algorithms are used. In scale-free models with white noise initial conditions, xi sub c and xi are essentially identical. In scale-free models with more power on large scales, it is found that the amplitude of xi sub c increases with cluster richness; in this case the clusters give a biased estimate of the particle correlations. In the pancake and hybrid models (with n = 0 or 1), xi sub c is steeper than xi, but the cluster correlation length exceeds that of the points by less than a factor of 2, independent of cluster richness. Thus the high amplitude of xi sub c found in studies of rich clusters of galaxies is inconsistent with white noise and pancake models and may indicate a primordial fluctuation spectrum with substantial power on large scales. 30 references

  18. Temperature- and field-induced structural transitions in magnetic colloidal clusters

    Science.gov (United States)

    Hernández-Rojas, J.; Calvo, F.

    2018-02-01

    Magnetic colloidal clusters can form chain, ring, and more compact structures depending on their size. In the present investigation we examine the combined effects of temperature and external magnetic field on these configurations by means of extensive Monte Carlo simulations and a dedicated analysis based on inherent structures. Various thermodynamical, geometric, and magnetic properties are calculated and altogether provide evidence for possibly multiple structural transitions at low external magnetic field. Temperature effects are found to overcome the ordering effect of the external field, the melted stated being associated with low magnetization and a greater compactness. Tentative phase diagrams are proposed for selected sizes.

  19. The structure and energetic of AlAsn (n = 1-15) clusters: A first-principles study

    International Nuclear Information System (INIS)

    Guo Ling

    2010-01-01

    Geometric structures of AlAs n (n = 1-15) clusters are reported. The binding energy, dissociation energy, stability of these clusters are studied with the three-parameter hybrid generalized gradient approximation (GGA) due to Becke-Lee-Yang-Parr (B3LYP). Ionization potentials, electron affinities, hardness, and static polarizabilities are calculated for the ground-state structures within the same method. The growth pattern for AlAs n (n = 6-15) clusters is Al-substituted pure As n+1 clusters and it keeps the similar frameworks of the most stable As n+1 clusters (for example AlAs 6 , AlAs 7 , AlAs 9 , AlAs 14 and AlAs 15 clusters) or capping the different sides of the low-lying geometry of As n clusters (for example AlAs 8 , AlAs 10 , AlAs 11 , and AlAs 12 clusters). The Al atom prefer to occupy a peripheral position for n n (n = 1-5, 13) clusters. The odd-even oscillations from AlAs n (n = 5-15) in the dissociation energy, the second-order energy differences, the HOMO-LUMO gaps, the electron affinity, and the hardness are more pronounced. The stability analysis based on the energies clearly shows the AlAs n clusters from n = 5 with an even number of valence electrons are more stable than clusters with odd number of valence electrons.

  20. The Materials Chemistry of Atomic Oxygen with Applications to Anisotropic Etching of Submicron Structures in Microelectronics and the Surface Chemistry Engineering of Porous Solids

    Science.gov (United States)

    Koontz, Steve L.; Leger, Lubert J.; Wu, Corina; Cross, Jon B.; Jurgensen, Charles W.

    1994-01-01

    Neutral atomic oxygen is the most abundant component of the ionospheric plasma in the low Earth orbit environment (LEO; 200 to 700 kilometers altitude) and can produce significant degradation of some spacecraft materials. In order to produce a more complete understanding of the materials chemistry of atomic oxygen, the chemistry and physics of O-atom interactions with materials were determined in three radically different environments: (1) The Space Shuttle cargo bay in low Earth orbit (the EOIM-3 space flight experiment), (2) a high-velocity neutral atom beam system (HVAB) at Los Alamos National Laboratory (LANL), and (3) a microwave-plasma flowing-discharge system at JSC. The Space Shuttle and the high velocity atom beam systems produce atom-surface collision energies ranging from 0.1 to 7 eV (hyperthermal atoms) under high-vacuum conditions, while the flowing discharge system produces a 0.065 eV surface collision energy at a total pressure of 2 Torr. Data obtained in the three different O-atom environments referred to above show that the rate of O-atom reaction with polymeric materials is strongly dependent on atom kinetic energy, obeying a reactive scattering law which suggests that atom kinetic energy is directly available for overcoming activation barriers in the reaction. General relationships between polymer reactivity with O atoms and polymer composition and molecular structure have been determined. In addition, vacuum ultraviolet photochemical effects have been shown to dominate the reaction of O atoms with fluorocarbon polymers. Finally, studies of the materials chemistry of O atoms have produced results which may be of interest to technologists outside the aerospace industry. Atomic oxygen 'spin-off' or 'dual use' technologies in the areas of anisotropic etching in microelectronic materials and device processing, as well as surface chemistry engineering of porous solid materials are described.

  1. Structural Analysis of Lexical Bundles in University Lectures of Politics and Chemistry

    Directory of Open Access Journals (Sweden)

    Hadi Kashiha

    2014-01-01

    Full Text Available Referred to as extended collocations, lexical bundles are considered as a main factor in building fluency in academic discourse; helping to shape meaning and coherence in a text or speech. For decades, lexical bundles have attracted considerable amount of attention in corpus-based research in English for Academic Purposes (EAP. While, the focus of the most of the studies on lexical bundles was to explore the use of these multi-word expressions in academic written registers such as research articles, academic spoken registers such as university lectures have not received that amount of attention from the scholars. In this vein, there is still an open question of how they are structurally different across disciplines. With these concerns in mind, this study aimed to explore how lexical bundles are used structurally in a 50291 words corpus of 8 university lectures across two disciplines: chemistry and politics. To this aim, the most frequent four-word bundles in the corpus were classified according to their grammatical types to see the possible disciplinary variations in their frequency of use as well as the structure involved in their use. Results of the analysis revealed that noun phrase and prepositional phrase fragments were the most common structures in the lectures of the two disciplines, accounting for more than half of the bundles in politics. University lecturers appear to apply a variety of structures in the use of lexical bundles often peculiar to the discipline in order to convey their disciplinary messages.  This would lead to the need to emphasize the instruction of the most common structures in that discipline in a way for the lectures to be as comprehensive as possible for the intended audiences.

  2. Structural vs. intrinsic carriers: contrasting effects of cation chemistry and disorder on ionic conductivity in pyrochlores

    International Nuclear Information System (INIS)

    Perriot, Romain; Uberuaga, Blas P.

    2015-01-01

    We use molecular dynamics simulations to investigate the role of cation disorder on oxygen diffusion in Gd 2 Zr 2 O 7 (GZO) and Gd 2 Ti 2 O 7 (GTO) pyrochlores, a class of complex oxides which contain a structural vacancy relative to the basic fluorite structure. The introduction of disorder has distinct effects depending on the chemistry of the material, increasing the mobility of structural carriers by up to four orders of magnitude in GZO. In contrast, in GTO, there is no mobility at zero or low disorder on the ns timescale, but higher disorder liberates the otherwise immobile carriers, allowing diffusion with rates comparable to GZO for the fully disordered material. Here, we show that the cation disorder enhances the diffusivity by both increasing the concentration of mobile structural carriers and their individual mobility. The disorder also influences the diffusion in materials containing intrinsic carriers, such as additional vacancies VO or oxygen interstitials OI. And while in ordered GZO and GTO the contribution of the intrinsic carriers dominates the overall diffusion of oxygen, OI in GZO contributes along with structural carriers, and the total diffusion rate can be calculated by assuming simple additive contributions from the two sources. Although the disorder in the materials with intrinsic defects usually enhances the diffusivity as in the defect-free case, in low concentrations, cation antisites AB or BA, where A = Gd and B = Zr or Ti, can act as traps for fast intrinsic defects. The trapping results in a lowering of the diffusivity, and causes a non-monotonic behavior of the diffusivity with disorder. Conversely, in the case of slow intrinsic defects, the main effect of the disorder is to liberate the structural carriers, resulting in an increase of the diffusivity regardless of the defect trapping.

  3. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors

  4. Nuclear chemistry

    International Nuclear Information System (INIS)

    Vertes, A.; Kiss, I.

    1987-01-01

    This book is an introduction to the application of nuclear science in modern chemistry. The first group of chapters discuss the basic phenomena and concepts of nuclear physics with emphasis on their relation to chemical problems, including the main properties and the composition of atomic nuclei, nuclear reactions, radioactive decay and interactions of radiation with matter. These chapters provide the basis for understanding the following chapters which encompass the wide scope of nuclear chemistry. The methods of the investigation of chemical structure based on the interaction of nuclear radiation with matter including positronium chemistry and other exotic atoms is elaborated in particular detail. Separate chapters are devoted to the use of radioactive tracers, the chemical consequences of nuclear processes (i.e. hot atom chemistry), radiation chemistry, isotope effects and their applications, and the operation of nuclear reactors. (Auth.)

  5. CHIMERA: Top-down model for hierarchical, overlapping and directed cluster structures in directed and weighted complex networks

    Science.gov (United States)

    Franke, R.

    2016-11-01

    In many networks discovered in biology, medicine, neuroscience and other disciplines special properties like a certain degree distribution and hierarchical cluster structure (also called communities) can be observed as general organizing principles. Detecting the cluster structure of an unknown network promises to identify functional subdivisions, hierarchy and interactions on a mesoscale. It is not trivial choosing an appropriate detection algorithm because there are multiple network, cluster and algorithmic properties to be considered. Edges can be weighted and/or directed, clusters overlap or build a hierarchy in several ways. Algorithms differ not only in runtime, memory requirements but also in allowed network and cluster properties. They are based on a specific definition of what a cluster is, too. On the one hand, a comprehensive network creation model is needed to build a large variety of benchmark networks with different reasonable structures to compare algorithms. On the other hand, if a cluster structure is already known, it is desirable to separate effects of this structure from other network properties. This can be done with null model networks that mimic an observed cluster structure to improve statistics on other network features. A third important application is the general study of properties in networks with different cluster structures, possibly evolving over time. Currently there are good benchmark and creation models available. But what is left is a precise sandbox model to build hierarchical, overlapping and directed clusters for undirected or directed, binary or weighted complex random networks on basis of a sophisticated blueprint. This gap shall be closed by the model CHIMERA (Cluster Hierarchy Interconnection Model for Evaluation, Research and Analysis) which will be introduced and described here for the first time.

  6. Crystal chemistry of Ruddlesden-Popper type structures in high Tc ceramic superconductors

    International Nuclear Information System (INIS)

    Dwivedi, Anurag; Cormack, A.N.

    1991-01-01

    Similar structural patterns have been noticed in the systems La-Cu-O, La-Ni-O and Bi and Tl-containing superconducting oxides. The formation of Ruddlesden-Popper type layers (alternating slabs of rocksalt and perovskite strucutres) is seen in these oxides which is similar in many respects to what is seen in the system Sr-Ti-O. However, there are some significant differences, for example the rocksalt and perovskite blocks in new superconducting compounds are not necessarily electrically neutral, unlike in the Sr-Ti-O system. It, thus, becomes necessary to create oxygen vacancies in the basic perovskite structure of Bi-containing compounds, when the width of the perovskite slab changes on addition of extra Cu-O planes. Results of atomistic simulations suggest that these missing oxygen ions allows the Cu-O planes to buckle in Bi-series of compounds. This is also supported by the absence of buckling in the Sr-Ti-O series of compounds and the first member of Bi-containing compounds in which there are no missing oxygen ions. Additional results on the phase stability of polytypoid structure in la-Cu-O system and defect chemistry of compounds of La N i-O system are presented. (author). 14 re fs., 7 figs., 4 tabs

  7. Anomalous properties of technetium clusters

    International Nuclear Information System (INIS)

    Kryuchkov, S.V.

    1985-01-01

    On the basis of critical evaluation of literature data in the field of chemistry of technetium cluster compounds with ligands of a weak field a conclusion is made on specific, ''anomalous'' properties of technetium cluster complexes which consist in an increased ability of the given element to the formation of a series of binuclear and multinuclear clusters, similar in composition and structure and easily transforming in each other. The majority of technetium clusters unlike similar compounds of other elements are paramagnetic with one unpaired electron on ''metallic'' MO of loosening type. All theoretical conceptions known today on the electronic structure of technetium clusters are considered. It is pointed out, that the best results in the explanation of ''anomalous'' properties of technetium clusters can be obtained in the framework of nonempirical methods of self-consistent field taking into account configuration interactions. It is also shown, that certain properties of technetium clusters can be explained on the basis of qualitative model of Coulomb repulsion of metal atoms in clusters. The conclusion is made, that technetium position in the Periodic table, as well as recently detected technetium property to the decrease of effective charge on its atoms during M-M bond formation promote a high ability of the element to cluster formation both with weak field ligands and with strong field one

  8. Introducing NMR to a General Chemistry Audience: A Structural-Based Instrumental Laboratory Relating Lewis Structures, Molecular Models, and [superscript 13]C NMR Data

    Science.gov (United States)

    Pulliam, Curtis R.; Pfeiffer, William F.; Thomas, Alyssa C.

    2015-01-01

    This paper describes a first-year general chemistry laboratory that uses NMR spectroscopy and model building to emphasize molecular shape and structure. It is appropriate for either a traditional or an atoms-first curriculum. Students learn the basis of structure and the use of NMR data through a cooperative learning hands-on laboratory…

  9. Melodic pattern discovery by structural analysis via wavelets and clustering techniques

    DEFF Research Database (Denmark)

    Velarde, Gissel; Meredith, David

    We present an automatic method to support melodic pattern discovery by structural analysis of symbolic representations by means of wavelet analysis and clustering techniques. In previous work, we used the method to recognize the parent works of melodic segments, or to classify tunes into tune......-means to cluster melodic segments into groups of measured similarity and obtain a raking of the most prototypical melodic segments or patterns and their occurrences. We test the method on the JKU Patterns Development Database and evaluate it based on the ground truth defined by the MIREX 2013 Discovery of Repeated...... Themes & Sections task. We compare the results of our method to the output of geometric approaches. Finally, we discuss about the relevance of our wavelet-based analysis in relation to structure, pattern discovery, similarity and variation, and comment about the considerations of the method when used...

  10. Structure and stability of M6N8 clusters (M = Si, Ge, Sn, Ti).

    Science.gov (United States)

    Davydova, Elena I; Timoshkin, Alexey Y; Frenking, Gernot

    2010-06-10

    The structures and stabilities of the M(6)N(8) clusters (M = Si, Ge, Sn, Ti) have been theoretically studied at DFT and ab initio levels of theory. Two new isomers have been considered: cage-like molecules and propeller-like molecules. It is shown that only for M = Si are both isomers true minima on the potential energy surface. The thermodynamics of the dissociation process (1/6)M(6)N(8) --> (1/3)M(3)N(4) is discussed. For each M(3)N(4) molecule, four structures with different multiplicity are considered. The thermodynamic analysis shows that independently of the multiplicity of M(3)N(4) nitrides all M(6)N(8) clusters are stable in the gas phase in a wide temperature range and could be potential intermediates in chemical vapor deposition of the nitride materials.

  11. "Just as the Structural Formula Does": Names, Diagrams, and the Structure of Organic Chemistry at the 1892 Geneva Nomenclature Congress.

    Science.gov (United States)

    Hepler-Smith, Evan

    2015-02-01

    At the Geneva Nomenclature Congress of 1892, some of the foremost organic chemists of the late nineteenth century crafted a novel relationship between chemical substances, chemical diagrams, and chemical names that has shaped practices of chemical representation ever since. During the 1880s, the French chemist Charles Friedel organised the nomenclature reform effort that culminated in the Geneva Congress; in the disorderly nomenclature of German synthetic chemistry, Friedel saw an opportunity to advance French national interests and his own pedagogical goals. Friedel and a group of close colleagues reconceived nomenclature as a unified field, in which all chemical names ought to relate clearly to one another and to the structure of the compounds they represented. The German chemist Adolf von Baeyer went a step farther, arguing for names that precisely and uniquely corresponded to the structural formula of each compound, tailored for use in chemical dictionaries and handbooks. Baeyer's vision prevailed at the Geneva Congress, which consequently codified rules for rigorously mapping structural formulas into names, resulting in names that faithfully represented the features of these diagrams but not always the chemical behaviour of the compounds themselves. This approach ultimately limited both the number of chemical compounds that the Geneva rules were able to encompass and the breadth of their application. However, the relationship between diagram and name established at the Geneva Congress became the foundation not only of subsequent systems of chemical nomenclature but of methods of organising information that have supported the modern chemical sciences.

  12. [Clustered regularly interspaced short palindromic repeats: structure, function and application--a review].

    Science.gov (United States)

    Cui, Yujun; Li, Yanjun; Yan, Yanfeng; Yang, Ruifu

    2008-11-01

    CRISPRs (Clustered Regularly Interspaced Short Palindromic Repeats), the basis of spoligotyping technology, can provide prokaryotes with heritable adaptive immunity against phages' invasion. Studies on CRISPR loci and their associated elements, including various CAS (CRISPR-associated) proteins and leader sequences, are still in its infant period. We introduce the brief history', structure, function, bioinformatics research and application of this amazing immunity system in prokaryotic organism for inspiring more scientists to find their interest in this developing topic.

  13. Magnetism, structure and chemical order in small CoPd clusters: A first-principles study

    KAUST Repository

    Mokkath, Junais Habeeb

    2014-01-01

    The structural, electronic and magnetic properties of small ComPdn (N=m+n=8,m=0-N) nanoalloy clusters are studied in the framework of a generalized-gradient approximation to density-functional theory. The optimized cluster structures have a clear tendency to maximize the number of nearest-neighbor CoCo pairs. The magnetic order is found to be ferromagnetic-like (FM) for all the ground-state structures. Antiferromagnetic-like spin arrangements were found in some low-lying isomers. The average magnetic moment per atom μ̄N increases approximately linearly with Co content. A remarkable enhancement of the local Co moments is observed as a result of Pd doping. This is a consequence of the increase in the number of Co d holes, due to CoPd charge transfer, combined with the reduced local coordination. The influence of spin-orbit interactions on the cluster properties is also discussed. © 2013 Elsevier B.V.

  14. Probing the structural and electronic properties of cationic rubidium-gold clusters: [AunRb]+ (n = 1-10)

    Science.gov (United States)

    Zhao, Ya-Ru; Zhang, Hai-Rong; Qian, Yu; Duan, Xu-Chao; Hu, Yan-Fei

    2016-03-01

    Density functional theory has been applied to study the geometric structures, relative stabilities, and electronic properties of cationic [AunRb]+ and Aun + 1+ (n = 1-10) clusters. For the lowest energy structures of [AunRb]+ clusters, the planar to three-dimensional transformation is found to occur at cluster size n = 4 and the Rb atoms prefer being located at the most highly coordinated position. The trends of the averaged atomic binding energies, fragmentation energies, second-order difference of energies, and energy gaps show pronounced even-odd alternations. It indicated that the clusters containing odd number of atoms maintain greater stability than the clusters in the vicinity. In particular, the [Au6Rb]+ clusters are the most stable isomer for [AunRb]+ clusters in the region of n = 1-10. The charges in [AunRb]+ clusters transfer from the Rb atoms to Aun host. Density of states revealed that the Au-5d, Au-5p, and Rb-4p orbitals hardly participated in bonding. In addition, it is found that the most favourable channel of the [AunRb]+ clusters is Rb+ cation ejection. The electronic localisation function (ELF) analysis of the [AunRb]+ clusters shown that strong interactions are not revealed in this study.

  15. The structure of the nuclear stellar cluster of the Milky Way

    International Nuclear Information System (INIS)

    Schoedel, Rainer; Eckart, Andreas

    2006-01-01

    The structure of the nuclear stellar cluster of the Milky Way is of particular interest because it is the densest stellar cluster in our Galaxy, where the theoretical prediction of the formation of a stellar cusp around the central supermassive black hole, Sagittarius A* (Sgr A*) can be examined. We present high-resolution adaptive optics observations with multiple intermediate band liters of the inner ∼20'' around Sgr A*. From the images, stellar number counts and a detailed map of the interstellar extinction toward the central 0.5 pc of the Milky Way were determined. The extinction map is consistent with a putative southwest-northeast aligned outfbw from the central arcseconds. An azimuthally averaged, crowding and extinction corrected stellar density profle presents clear evidence for the existence of a stellar cusp around Sgr A*. We show that the profle of the surface brightness density is dominated by the brightest stars in the central arcseconds and is different from the shape of the stellar cluster as inferred from the number counts. Several density peaks found in the cluster may indicate clumping, possibly related to the last epoch of star formation in the Galactic Center. There is evidence for a common proper motion of the stars in one of these clumps

  16. Towards a unified developments of cluster science

    International Nuclear Information System (INIS)

    Wang Guanghou

    1998-01-01

    In the development of cluster science many concepts and methods have been introduced from nuclear physics, condensed matter physics and quantum chemistry, forming an interdisciplinary field between atomic and molecular physics on the one hand and condensed matter physics on the other hand. Recent achievements in the study of the structures and properties of clusters are reviewed in comparison with those of nuclei and quantum dots

  17. Adaptation of quantum chemistry software for the electronic structure calculations on GPU for solid-state systems

    International Nuclear Information System (INIS)

    Gusakov, V.E.; Bel'ko, V.I.; Dorozhkin, N.N.

    2015-01-01

    We report on adaptation of quantum chemistry software - Quantum Espresso and LASTO - for the electronic structure calculations for the complex solid-state systems on the GeForce series GPUs using the nVIDIA CUDA technology. Specifically, protective covering based on transition metal nitrides are considered. (authors)

  18. Incorporating Modeling and Simulations in Undergraduate Biophysical Chemistry Course to Promote Understanding of Structure-Dynamics-Function Relationships in Proteins

    Science.gov (United States)

    Hati, Sanchita; Bhattacharyya, Sudeep

    2016-01-01

    A project-based biophysical chemistry laboratory course, which is offered to the biochemistry and molecular biology majors in their senior year, is described. In this course, the classroom study of the structure-function of biomolecules is integrated with the discovery-guided laboratory study of these molecules using computer modeling and…

  19. Measurements of local chemistry and structure in Ni(O)-YSZ composites during reduction using energy-filtered environmental TEM

    DEFF Research Database (Denmark)

    Jeangros, Quentin; Hansen, Thomas Willum; Wagner, Jakob Birkedal

    2014-01-01

    Energy-filtered transmission electron microscopy images are acquired during the reduction of a NiO-YSZ composite in H-2 up to 600 degrees C. Temperature-resolved quantitative information about both chemistry and structure is extracted with nm spatial resolution from the data, paving the way...

  20. Exploring the atomic structure of 1.8 nm monolayer-protected gold clusters with aberration-corrected STEM

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Jian; Jian, Nan; Ornelas, Isabel; Pattison, Alexander J. [Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom); Lahtinen, Tanja; Salorinne, Kirsi [Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Häkkinen, Hannu [Department of Chemistry, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Department of Physics, Nanoscience Center, University of Jyväskylä, FI-40014 Jyväskylä (Finland); Palmer, Richard E., E-mail: richardepalmerwork@yahoo.com [Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Birmingham B15 2TT (United Kingdom)

    2017-05-15

    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{sub 144}(SCH{sub 2}CH{sub 2}Ph){sub 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{sub 144}(SR){sub 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. - Highlights: • Chemically synthesised gold clusters were “weighed” by atom counting to get true size. • Image simulations show a few percent of clusters have the predicted atomic structure. • But a specific ring-dot feature indicates local icosahedral order in many clusters.

  1. Structure vs chemistry: friction and wear of Pt-based metallic surfaces.

    Science.gov (United States)

    Caron, A; Louzguine-Luzguin, D V; Bennewitz, R

    2013-11-13

    In comparison of a Pt57.5Cu14.7Ni5.3P22.5 metallic glass with a Pt(111) single crystal we find that wearless friction is determined by chemistry through bond formation alloying, while wear is determined by structure through plasticity mechanisms. In the wearless regime, friction is affected by the chemical composition of the counter body and involves the formation of a liquid-like neck and interfacial alloying. The wear behavior of Pt-based metallic surfaces is determined by their structural properties and corresponding mechanisms for plastic deformation. In the case of Pt(111) wear occurs by dislocation-mediated homogeneous plastic deformation. In contrast the wear of Pt57.5Cu14.7Ni5.3P22.5 metallic glass occurs through localized plastic deformation in shear bands that merge together in a single shear zone above a critical load and corresponds to the shear softening of metallic glasses. These results open a new route in the control of friction and wear of metals and are relevant for the development of self-lubricated and wear-resistant mechanical devices.

  2. Investigation of the cluster structure in aqueous suspensions of nanodiamonds by small-angle neutron scattering

    Directory of Open Access Journals (Sweden)

    L. A. Bulavin

    2015-07-01

    Full Text Available The paper presents the results of the structural study of various types of the water-detonation nanodiamond liquid systems, which are obtained by small-angle scattering of thermal neutrons. It was shown that in the mass fraction range (0.3 - 1.8 % the experimental spectra are well described by a two-level model of unified exponential/power-law approach. The resulting structural parameters allowed us to estimate the aggregation number in the studied systems. Sizes of the nanodiamond particles and their clusters are found as well as the fractal dimension of the latter.

  3. Investigation of the cluster structure in aqueous suspensions of nanodiamonds by small-angle neutron scattering

    International Nuclear Information System (INIS)

    Bulavin, L.A.; Tomchuk, O.V.; Avdeev, M.V.

    2015-01-01

    The paper presents the results of the structural study of various types of the water-detonation nanodiamond liquid systems, which are obtained by small-angle scattering of thermal neutrons. It was shown that in the mass fraction range (0.3/1.8) % the experimental spectra are well described by a two-level model of unified exponential/power-law approach. The resulting structural parameters allowed us to estimate the aggregation number in the studied systems. Sizes of the nanodiamond particles and their clusters are found as well as the fractal dimension of the latter

  4. Influence of a transition metal atom on the geometry and electronic structure of Mg and Mg-H clusters

    International Nuclear Information System (INIS)

    Siretskiy, M.Yu.; Shelyapina, M.G.; Fruchart, D.; Miraglia, S.; Skryabina, N.E.

    2009-01-01

    We report on the study of (MgH 2 ) n + M complexes (M = Ti or Ni) carried out within the framework of the cluster density functional theory (DFT) method. The influence of such transition metal atoms on the cluster geometry and electronic structure is discussed considering the stability of MgH 2 hydride.

  5. Electronic Structure and Bonding Situation in M2O2 (M=Be,Mg,Ca) Rhombic Clusters.

    Czech Academy of Sciences Publication Activity Database

    Li, W.-L.; Lu, J.-B.; Zhao, L.; Ponec, Robert; Cooper, D.L.; Li, J.; Frenking, G.

    Roč. 122, č. 10 ( 2018 ), s. 2816-2822 ISSN 1089-5639 Grant - others:NNSFCH(CN) 21590792; NNSFCH(CN) 21433005; NNSFCH(CN) 21703099; JPY NSF(CN) BK20170964; NTU(CN) 39837123 Institutional support: RVO:67985858 Keywords : electronic structures * M2O2n clustery * theoretical isnights Subject RIV: CF - Physical ; Theoretical Chemistry OBOR OECD: Physical chemistry Impact factor: 2.847, year: 2016

  6. New experimental investigation of cluster structures in 10 Be and 16 C neutron-rich nuclei

    Science.gov (United States)

    Dell'Aquila, L.; Acosta, D.; Auditore, L.; Cardella, G.; De Filippo, E.; De Luca, S.; Francalanza, L.; Gnoffo, B.; Lanzalone, G.; Lombardo, I.; Martorana, N. S.; Norella, S.; Pagano, A.; Pagano, E. V.; Papa, M.; Pirrone, S.; Politi, G.; Quattrocchi, L.; Rizzo, F.; Russotto, P.; Trifirò, A.; Trimarchi, M.; Verde, G.; Vigilante, M.

    2017-11-01

    The existence of cluster structures in ^{10} Be and ^{16} C neutron-rich isotopes is investigated via projectile break-up reactions induced on polyethylene (CH _2 target. We used a fragmentation beam constituted by 55MeV/u ^{10} Be and 49MeV/u ^{16} C beams provided by the FRIBs facility at INFN-LNS. Invariant mass spectra of 4{He}+ 6 He and 6{He} + ^{10} Be breakup fragments are reconstructed by means of the CHIMERA 4π detector to investigate the presence of excited states of projectile nuclei characterized by cluster structure. In the first case, we suggest the presence of a new state in ^{10} Be at 13.5MeV. A non-vanishing yield corresponding to 20.6MeV excitation energy of ^{16} C was observed in the 6{He} + ^{10} Be cluster decay channel. To improve the results of the present analysis, a new experiment has been performed recently, taking advantage of the coupling of CHIMERA and FARCOS. In the paper we describe the data reduction process of the new experiment together with preliminary results.

  7. Structure and gene cluster of the O-antigen of Escherichia coli O54.

    Science.gov (United States)

    Naumenko, Olesya I; Guo, Xi; Senchenkova, Sof'ya N; Geng, Peng; Perepelov, Andrei V; Shashkov, Alexander S; Liu, Bin; Knirel, Yuriy A

    2018-06-15

    Mild acid hydrolysis of the lipopolysaccharide of Escherichia coli O54 afforded an O-polysaccharide, which was studied by sugar analysis, solvolysis with anhydrous trifluoroacetic acid, and 1 H and 13 C NMR spectroscopy. Solvolysis cleaved predominantly the linkage of β-d-Ribf and, to a lesser extent, that of β-d-GlcpNAc, whereas the other linkages, including the linkage of α-l-Rhap, were stable under selected conditions (40 °C, 5 h). The following structure of the O-polysaccharide was established: →4)-α-d-GalpA-(1 → 2)-α-l-Rhap-(1 → 2)-β-d-Ribf-(1 → 4)-β-d-Galp-(1 → 3)-β-d-GlcpNAc-(1→ The O-antigen gene cluster of E. coli O54 was analyzed and found to be consistent in general with the O-polysaccharide structure established but there were two exceptions: i) in the cluster, there were genes for phosphoserine phosphatase and serine transferase, which have no apparent role in the O-polysaccharide synthesis, and ii) no ribofuranosyltransferase gene was present in the cluster. Both uncommon features are shared by some other enteric bacteria. Copyright © 2018 Elsevier Ltd. All rights reserved.

  8. Properties of ammonium ion-water clusters: analyses of structure evolution, noncovalent interactions, and temperature and humidity effects.

    Science.gov (United States)

    Pei, Shi-Tu; Jiang, Shuai; Liu, Yi-Rong; Huang, Teng; Xu, Kang-Ming; Wen, Hui; Zhu, Yu-Peng; Huang, Wei

    2015-03-26

    Although ammonium ion-water clusters are abundant in the biosphere, some information regarding these clusters, such as their growth route, the influence of temperature and humidity, and the concentrations of various hydrated clusters, is lacking. In this study, theoretical calculations are performed on ammonium ion-water clusters. These theoretical calculations are focused on determining the following characteristics: (1) the pattern of cluster growth; (2) the percentages of clusters of the same size at different temperatures and humidities; (3) the distributions of different isomers for the same size clusters at different temperatures; (4) the relative strengths of the noncovalent interactions for clusters of different sizes. The results suggest that the dipole moment may be very significant for the ammonium ion-water system, and some new stable isomers were found. The nucleation of ammonium ions and water molecules is favorable at low temperatures; thus, the clusters observed at high altitudes might not be present at low altitudes. High humidity can contribute to the formation of large ammonium ion-water clusters, whereas the formation of small clusters may be favorable under low-humidity conditions. The potential energy surfaces (PES) of these different sized clusters are complicated and differ according to the distribution of isomers at different temperatures. Some similar structures are observed between NH4(+)(H2O)n and M(H2O)n (where M represents an alkali metal ion or water molecule); when n = 8, the clusters begin to form the closed-cage geometry. As the cluster size increases, these interactions become progressively weaker. The successive binding energy at the DF-MP2-F12/VDZ-F12 level is better than that at the PW91PW91/6-311++G(3df, 3pd) level and is consistent with the experimentally determined values.

  9. The HST/ACS Coma Cluster Survey - VII. Structure and assembly of massive galaxies in the centre of the Coma cluster

    NARCIS (Netherlands)

    Weinzirl, Tim; Jogee, Shardha; Neistein, Eyal; Khochfar, Sadegh; Kormendy, John; Marinova, Irina; Hoyos, Carlos; Balcells, Marc; den Brok, Mark; Hammer, Derek; Peletier, Reynier F.; Kleijn, Gijs Verdoes; Carter, David; Goudfrooij, Paul; Lucey, John R.; Mobasher, Bahram; Trentham, Neil; Erwin, Peter; Puzia, Thomas

    2014-01-01

    We constrain the assembly history of galaxies in the projected central 0.5 Mpc of the Coma cluster by performing structural decomposition on 69 massive (M⋆ ≥ 109 M⊙) galaxies using high-resolution F814W images from the Hubble Space Telescope (HST) Treasury Survey of Coma. Each galaxy is modelled

  10. Structure Identification Using High Resolution Mass Spectrometry Data and the EPAs Chemistry Dashboard (ACS Fall meeting)

    Science.gov (United States)

    The iCSS Chemistry Dashboard is a publicly accessible dashboard provided by the National Center for Computation Toxicology at the US-EPA. It serves a number of purposes, including providing a chemistry database underpinning many of our public-facing projects (e.g. ToxCast and Exp...

  11. C,N-Chelated Organotin(IV) Azides: Synthesis, Structure and Use within the Click Chemistry.

    Czech Academy of Sciences Publication Activity Database

    Švec, P.; Bartoš, K.; Růžičková, Z.; Cuřínová, Petra; Dušek, L.; Turek, J.; de Proft, F.; Růžička, A.

    2016-01-01

    Roč. 40, č. 7 (2016), s. 5808-5817 ISSN 1144-0546 Grant - others:FWO(BE) 12T6615N Institutional support: RVO:67985858 Keywords : organotin(IV)azides * click chemistry * chelation Subject RIV: CC - Organic Chemistry Impact factor: 3.269, year: 2016

  12. PubChemQC Project: A Large-Scale First-Principles Electronic Structure Database for Data-Driven Chemistry.

    Science.gov (United States)

    Nakata, Maho; Shimazaki, Tomomi

    2017-06-26

    Large-scale molecular databases play an essential role in the investigation of various subjects such as the development of organic materials, in silico drug design, and data-driven studies with machine learning. We have developed a large-scale quantum chemistry database based on first-principles methods. Our database currently contains the ground-state electronic structures of 3 million molecules based on density functional theory (DFT) at the B3LYP/6-31G* level, and we successively calculated 10 low-lying excited states of over 2 million molecules via time-dependent DFT with the B3LYP functional and the 6-31+G* basis set. To select the molecules calculated in our project, we referred to the PubChem Project, which was used as the source of the molecular structures in short strings using the InChI and SMILES representations. Accordingly, we have named our quantum chemistry database project "PubChemQC" ( http://pubchemqc.riken.jp/ ) and placed it in the public domain. In this paper, we show the fundamental features of the PubChemQC database and discuss the techniques used to construct the data set for large-scale quantum chemistry calculations. We also present a machine learning approach to predict the electronic structure of molecules as an example to demonstrate the suitability of the large-scale quantum chemistry database.

  13. Chemistry and cosmology.

    Science.gov (United States)

    Black, John H

    2006-01-01

    The simplest elements, hydrogen and helium, offer a remarkably rich chemistry, which has controlled crucial features of the early evolution of the universe. Theoretical models of the origin of structure (stars, galaxies, clusters of galaxies, etc.) now incorporate this chemistry in some detail. In addition to the origin of structure, cosmologists are concerned with observational tests of competing world models. Primordial chemistry may give rise to some of the earliest departures from thermodynamic equilibrium in the universe. These effects may be observable as broad-band spectroscopic distortions of the cosmic background radiation, which otherwise exhibits a nearly perfect blackbody spectrum. The chemical history of the expanding universe is followed through a detailed calculation of the evolution of the abundances of H, H+, H-, H2, H2+, H3+, and other minor species. It is shown that continuous absorption by the small concentration of H- can produce a distortion in the cosmic background spectrum with a maximum at a frequency near nu/c = 9 cm-1 (wavelength 1.1 mm). The predicted effect lies only a factor of 5 below current limits. Its detection would provide an important test of our understanding of the recombination epoch of the universe.

  14. Development of a Genetic Algorithm to Automate Clustering of a Dependency Structure Matrix

    Science.gov (United States)

    Rogers, James L.; Korte, John J.; Bilardo, Vincent J.

    2006-01-01

    Much technology assessment and organization design data exists in Microsoft Excel spreadsheets. Tools are needed to put this data into a form that can be used by design managers to make design decisions. One need is to cluster data that is highly coupled. Tools such as the Dependency Structure Matrix (DSM) and a Genetic Algorithm (GA) can be of great benefit. However, no tool currently combines the DSM and a GA to solve the clustering problem. This paper describes a new software tool that interfaces a GA written as an Excel macro with a DSM in spreadsheet format. The results of several test cases are included to demonstrate how well this new tool works.

  15. Role of the cluster structure of {sup 7}Li in the dynamics of fragment capture

    Energy Technology Data Exchange (ETDEWEB)

    Shrivastava, A., E-mail: aradhana@barc.gov.in [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Navin, A. [GANIL, CEA/DSM - CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); Diaz-Torres, A. [ECT, Villa Tambosi, I-38123 Villazzano, Trento (Italy); Nanal, V. [DNAP, Tata Institute of Fundamental Research, Mumbai 400005 (India); Ramachandran, K. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Rejmund, M. [GANIL, CEA/DSM - CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); Bhattacharyya, S. [Variable Energy Cyclotron Centre, 1/AF Bidhan Nagar, Kolkata 700064 (India); Chatterjee, A.; Kailas, S. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Lemasson, A. [GANIL, CEA/DSM - CNRS/IN2P3, Bd Henri Becquerel, BP 55027, F-14076 Caen Cedex 5 (France); Palit, R. [DNAP, Tata Institute of Fundamental Research, Mumbai 400005 (India); Parkar, V.V. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Pillay, R.G. [DNAP, Tata Institute of Fundamental Research, Mumbai 400005 (India); Rout, P.C. [Nuclear Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Sawant, Y. [DNAP, Tata Institute of Fundamental Research, Mumbai 400005 (India)

    2013-01-08

    Exclusive measurements of prompt {gamma}-rays from the heavy-residues with various light charged particles in the {sup 7}Li + {sup 198}Pt system, at an energy near the Coulomb barrier (E/V{sub b}{approx}1.6) are reported. Recent dynamic classical trajectory calculations, constrained by the measured fusion, {alpha}- and t-capture cross-sections have been used to explain the excitation energy dependence of the residue cross-sections. These calculations distinctly illustrate a two-step process, breakup followed by fusion, in case of the capture of t and {alpha} clusters; whereas for {sup 6}He+p and {sup 5}He+d configurations, massive transfer is inferred to be the dominant mechanism. The present work clearly demonstrates the role played by the cluster structures of {sup 7}Li in understanding the reaction dynamics at energies around the Coulomb barrier.

  16. Surface self-diffusion of adatom on Pt cluster with truncated octahedron structure

    International Nuclear Information System (INIS)

    Yang Jianyu; Hu Wangyu; Chen Shuguang

    2010-01-01

    Surface diffusion of single Pt adatom on Pt cluster with truncated octahedron structure is investigated through a combination of molecular dynamics and nudged elastic band method. Using an embedded atom method to describe the atomic interactions, the minimum energy paths are determined and the energy barriers for adatom diffusion across and along step are evaluated. The diffusion of adatom crossing step edge between {111} and {100} facets has a surprisingly low barrier of 0.03 eV, which is 0.12 eV lower than the barrier for adatom diffusion from {111} to neighboring {111} facet. Owing to the small barrier of adatom diffusion across the step edge between {111} and {100} facets, the diffusion of adatom along the step edge cannot occur. The molecular dynamics simulations at low temperatures also support these results. Our results show that mass transport will prefer step with {100} microfacet and the Pt clusters can have only {111} facets in epitaxial growth.

  17. Structure and binding of molecular clusters of trivalent metal halides in an ionic model

    International Nuclear Information System (INIS)

    Akdeniz, Z.; Pastore, G.; Tosi, M.P.

    1997-10-01

    A model of ionic interactions first proposed for the molecular monomers of alkaline earth dihalides (G. Galli and M. P. Tosi, N. Ciemento D 4,413 (1984)) is used in a systematic study of the structure and binding of monomeric and dimeric units of Al, Fe ad Ga chlorides, bromides and iodides. Ionized states obtained by stripping or adding a halogen ion are considered in addition to neutral states. The main motivation for this work comes from recent studies of liquid structure in several of these systems by neutron and X-ray diffraction and Raman scattering. Main attention is consequently given in the present calculations to (i) bond lengths and bond angles in isolated clusters as precursors of local structures in melts, and (ii) stability of local structures against fluctuations into ionized states. The results are discussed in comparison with the available experimental data as well as with the results from Hartree-Fock and density functional calculations. (author)

  18. Evolving knowledge of sex differences in brain structure, function, and chemistry.

    Science.gov (United States)

    Cosgrove, Kelly P; Mazure, Carolyn M; Staley, Julie K

    2007-10-15

    Clinical and epidemiologic evidence demonstrates sex differences in the prevalence and course of various psychiatric disorders. Understanding sex-specific brain differences in healthy individuals is a critical first step toward understanding sex-specific expression of psychiatric disorders. Here, we evaluate evidence on sex differences in brain structure, chemistry, and function using imaging methodologies, including functional magnetic resonance imaging (fMRI), positron emission tomography (PET), single photon emission computed tomography (SPECT), and structural magnetic resonance imaging (MRI) in mentally healthy individuals. MEDLINE searches of English-language literature (1980-November 2006) using the terms sex, gender, PET, SPECT, MRI, fMRI, morphometry, neurochemistry, and neurotransmission were performed to extract relevant sources. The literature suggests that while there are many similarities in brain structure, function, and neurotransmission in healthy men and women, there are important differences that distinguish the male from the female brain. Overall, brain volume is greater in men than women; yet, when controlling for total volume, women have a higher percentage of gray matter and men a higher percentage of white matter. Regional volume differences are less consistent. Global cerebral blood flow is higher in women than in men. Sex-specific differences in dopaminergic, serotonergic, and gamma-aminobutyric acid (GABA)ergic markers indicate that male and female brains are neurochemically distinct. Insight into the etiology of sex differences in the normal living human brain provides an important foundation to delineate the pathophysiological mechanisms underlying sex differences in neuropsychiatric disorders and to guide the development of sex-specific treatments for these devastating brain disorders.

  19. Structural, electronic, and magnetic properties of 3D metal trioxide and tetraoxide superhalogen cluster-doped monolayer BN

    International Nuclear Information System (INIS)

    Meng, Jingjing; Li, Dan; Niu, Yuan; Zhao, Hongmin; Liang, Chunjun; He, Zhiqun

    2016-01-01

    The structural, electronic, and magnetic properties of monolayer BN doped with 3D metal trioxide and tetraoxide superhalogen clusters are investigated using first-principle calculations. TMO_3_(_4_)-doped monolayer BN exhibits a low negative formation energy, whereas TM atoms embedded in monolayer BN show a high positive formation energy. TMO_3_(_4_) clusters are embedded more easily in monolayer BN than TM atoms. Compared with TMO_3-doped structures, TMO_4-doped structures have a higher structural stability because of their higher binding energies. Given their low negative formation energies, TMO_4-doped structures are more favored for specific applications than TMO_3-doped structures and TM atom-doped structures. Large magnetic moments per supercell and significant ferromagnetic couplings between a TM atom and neighboring B and N atoms on the BN layer were observed in all TMO_4-doped structures, except for TiO_4-doped structures. - Highlights: • TMO_3_(_4_) superhalogen clusters incorporated into monolayer BN were investigated. • TMO_3_(_4_) clusters are embedded more easily in monolayer BN than TM atoms. • TMO_4-doped structures are more favored for specific applications. • Large magnetic moments were observed in TMO_4-doped structures. • The band gap was sensitively dependent on the doped clusters.

  20. A facility for using cluster research to study environmental problems. Workshop proceedings

    Energy Technology Data Exchange (ETDEWEB)

    1991-11-01

    This report begins by describing the general application of cluster based research to environmental chemistry and the development of a Cluster Structure and Dynamics Research Facility (CSDRF). Next, four important areas of cluster research are described in more detail, including how they can impact environmental problems. These are: surface-supported clusters, water and contaminant interactions, time-resolved dynamic studies in clusters, and cluster structures and reactions. These facilities and equipment required for each area of research are then presented. The appendices contain workshop agenda and a listing of the researchers who participated in the workshop discussions that led to this report.

  1. Isolated electrostatic structures observed throughout the Cluster orbit: relationship to magnetic field strength

    Directory of Open Access Journals (Sweden)

    J. S. Pickett

    2004-07-01

    Full Text Available Isolated electrostatic structures are observed throughout much of the 4RE by 19.6RE Cluster orbit. These structures are observed in the Wideband plasma wave instrument's waveform data as bipolar pulses (one positive and one negative peak in the electric field amplitude and tripolar pulses (two positive and one negative peak, or vice versa. These structures are observed at all of the boundary layers, in the solar wind and magnetosheath, and along auroral field lines at 4.5-6.5RE. Using the Wideband waveform data from the various Cluster spacecraft we have carried out a survey of the amplitudes and time durations of these structures and how these quantities vary with the local magnetic field strength. Such a survey has not been carried out before, and it reveals certain characteristics of solitary structures in a finite magnetic field, a topic still inadequately addressed by theories. We find that there is a broad range of electric field amplitudes at any specific magnetic field strength, and there is a general trend for the electric field amplitudes to increase as the strength of the magnetic field increases over a range of 5 to 500nT. We provide a possible explanation for this trend that relates to the structures being Bernstein-Greene-Kruskal mode solitary waves. There is no corresponding dependence of the duration of the structures on the magnetic field strength, although a plot of these two quantities reveals the unexpected result that with the exception of the magnetosheath, all of the time durations for all of the other regions are comparable, whereas the magnetosheath time durations clearly are in a different category of much smaller time duration. We speculate that this implies that the structures are much smaller in size. The distinctly different pulse durations for the magnetosheath pulses indicate the possibility that the pulses are generated by a mechanism which is different from the mechanism operating in other regions.

  2. A DFT study on the structures and electronic states of zinc cluster Znn (n = 2-32)

    International Nuclear Information System (INIS)

    Iokibe, Kei; Tachikawa, Hiroto; Azumi, Kazuhisa

    2007-01-01

    Ab-initio and density functional theory (DFT) calculations have been carried out for zinc clusters Zn n (n = 2-32, n is the number of atoms to form a cluster) to elucidate the structure and electronic charge states of the clusters and the mechanism of clustering. The binding energies of Zn atoms were negligibly small at n = 2-3, whereas the energy increased significantly at n = 4 (the first transition). The second transition occurred at n = 8-16. In the larger clusters (n = 16-32), the binding energy increased slightly with increasing cluster size (n). The cluster size dependence of the binding energy and bond length between zinc atoms agreed well with that of the natural population of electrons in the 4p orbital of the zinc atom. In the larger clusters (n > 20), it was found that the zinc atoms in the surface region of the cluster have a positive charge, whereas those in the interior region have a negative charge with a large population in the 4p orbital. The formation mechanism of zinc clusters was discussed on the basis of the theoretical results

  3. Infrared spectroscopic studies on the cluster size dependence of charge carrier structure in nitrous oxide cluster anions

    International Nuclear Information System (INIS)

    Thompson, Michael C.; Weber, J. Mathias

    2016-01-01

    We report infrared photodissociation spectra of nitrous oxide cluster anions of the form (N 2 O) n O − (n = 1–12) and (N 2 O) n − (n = 7–15) in the region 800–1600 cm −1 . The charge carriers in these ions are NNO 2 − and O − for (N 2 O) n O − clusters with a solvation induced core ion switch, and N 2 O − for (N 2 O) n − clusters. The N–N and N–O stretching vibrations of N 2 O − (solvated by N 2 O) are reported for the first time, and they are found at (1595 ± 3) cm −1 and (894 ± 5) cm −1 , respectively. We interpret our infrared spectra by comparison with the existing photoelectron spectroscopy data and with computational data in the framework of density functional theory.

  4. Pressure-induced chemistry in a nitrogen-hydrogen host-guest structure

    Science.gov (United States)

    Spaulding, Dylan K.; Weck, Gunnar; Loubeyre, Paul; Datchi, Fréderic; Dumas, Paul; Hanfland, Michael

    2014-12-01

    New topochemistry in simple molecular systems can be explored at high pressure. Here we examine the binary nitrogen/hydrogen system using Raman spectroscopy, synchrotron X-ray diffraction, synchrotron infrared microspectroscopy and visual observation. We find a eutectic-type binary phase diagram with two stable high-pressure van der Waals compounds, which we identify as (N2)6(H2)7 and N2(H2)2. The former represents a new type of van der Waals host-guest compound in which hydrogen molecules are contained within channels in a nitrogen lattice. This compound shows evidence for a gradual, pressure-induced change in bonding from van der Waals to ionic interactions near 50 GPa, forming an amorphous dinitrogen network containing ionized ammonia in a room-temperature analogue of the Haber-Bosch process. Hydrazine is recovered on decompression. The nitrogen-hydrogen system demonstrates the potential for new pressure-driven chemistry in high-pressure structures and the promise of tailoring molecular interactions for materials synthesis.

  5. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Science.gov (United States)

    Sych, N. V.; Trofymenko, S. I.; Poddubnaya, O. I.; Tsyba, M. M.; Sapsay, V. I.; Klymchuk, D. O.; Puziy, A. M.

    2012-11-01

    Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (SBET = 2081 m2/g, Vtot = 1.1 cm3/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  6. The control of stoichiometry in Epitaxial semiconductor structures. Interfacial Chemistry: Property relations. A workshop review

    Science.gov (United States)

    Bachmann, Klaus J.

    1995-01-01

    A workshop on the control of stoichiometry in epitaxial semiconductor structures was held on August 21-26, 1995 in the hotel Stutenhaus at Vesser in Germany. The secluded location of the workshop in the forest of Thuringia and its informal style stimulated extensive private discussions among the participants and promoted new contacts between young scientists from Eastern and Western Europe and the USA. Topics addressed by the presentations were interactions of precursors to heteroepitaxy and doping with the substrate surface, the control of interfacial properties under the conditions of heteroepitaxy for selected materials systems, methods of characterization of interfaces and native point defects in semiconductor heterostructures and an in depth evaluation of the present status of the control and characterization of the point defect chemistry for one specific semiconductor (ZnGeP2), including studies of both heterostructures and bulk single crystals. The selected examples of presentations and comments given here represent individual choices - made by the author to highlight major points of the discussions.

  7. GEMINI/GeMS Observations Unveil the Structure of the Heavily Obscured Globular Cluster Liller 1.

    Science.gov (United States)

    Saracino, S.; Dalessandro, E.; Ferraro, F. R.; Lanzoni, B.; Geisler, D.; Mauro, F.; Villanova, S.; Moni Bidin, C.; Miocchi, P.; Massari, D.

    2015-06-01

    By exploiting the exceptional high-resolution capabilities of the near-IR camera GSAOI combined with the Gemini Multi-Conjugate Adaptive System at the GEMINI South Telescope, we investigated the structural and physical properties of the heavily obscured globular cluster Liller 1 in the Galactic bulge. We have obtained the deepest and most accurate color-magnitude diagram published so far for this cluster, reaching {{K}s}˜ 19 (below the main-sequence turnoff level). We used these data to redetermine the center of gravity of the system, finding that it is located about 2.″2 southeast from the literature value. We also built new star density and surface brightness profiles for the cluster and rederived its main structural and physical parameters (scale radii, concentration parameter, central mass density, total mass). We find that Liller 1 is significantly less concentrated (concentration parameter c=1.74) and less extended (tidal radius {{r}t}=298\\prime\\prime and core radius {{r}c}=5\\buildrel{\\prime\\prime}\\over{.} 39) than previously thought. By using these newly determined structural parameters, we estimated the mass of Liller 1 to be {{M}tot}=2.3+0.3-0.1× {{10}6} {{M}⊙ } ({{M}tot}=1.5+0.2-0.1× {{10}6} {{M}⊙ } for a Kroupa initial mass function), which is comparable to that of the most massive clusters in the Galaxy (ω Centari and Terzan 5). Also, Liller 1 has the second-highest collision rate (after Terzan 5) among all star clusters in the Galaxy, thus confirming that it is an ideal environment for the formation of collisional objects (such as millisecond pulsars). Based on observations obtained at the Gemini Observatory, which is operated by the Association of Universities for Research in Astronomy, Inc., under a cooperative agreement with the NSF on behalf of the Gemini partnership: the National Science Foundation (United States), the National Research Council (Canada), CONICYT (Chile), the Australian Research Council (Australia), Ministério da

  8. Symmetry and topology code of the cluster self-assembly of framework MT structures of alumophosphates AlPO4(H2O)2 (metavariscite and variscite) and Al2(PO4)2(H2O)3 (APC)

    Science.gov (United States)

    Ilyushin, G. D.; Blatov, V. A.

    2017-03-01

    The supramolecular chemistry of alumophosphates, which form framework 3D MT structures from polyhedral AlO4(H2O)2 clusters with octahedral O coordination (of M polyhedra) and PO4 and AlO4 with tetrahedral O coordination (of T polyhedra), is considered. A combinatorial-topological modeling of the formation of possible types of linear (six types) and ring (two types) tetrapolyhedral cluster precursors M2T2 from MT monomers is carried out. Different versions of chain formation from linked (MT)2 rings (six types) are considered. The model, which has a universal character, has been used to simulate the cluster selfassembly of the crystal structure of AlPO4(H2O)2 minerals (metavariscite, m-VAR, and variscite, VAR) and zeolite [Al2(PO4)2(H2O)2] · H2O (APC). A tetrapolyhedral linear precursor is established for m-VAR and a ring precursor (MT)2 is established for VAR and APC. The symmetry and topology code of the processes of crystal structure self-assembly from cluster precursors is completely reconstructed. The functional role of the O-H···O hydrogen bonds is considered for the first time. The cluster self-assembly model explains the specific features of the morphogenesis of single crystals: m-VAR prisms, flattened VAR octahedra, and needleshaped APC square-base prisms.

  9. A qualitative inquiry into the effects of visualization on high school chemistry students' learning process of molecular structure

    Science.gov (United States)

    Deratzou, Susan

    This research studies the process of high school chemistry students visualizing chemical structures and its role in learning chemical bonding and molecular structure. Minimal research exists with high school chemistry students and more research is necessary (Gabel & Sherwood, 1980; Seddon & Moore, 1986; Seddon, Tariq, & Dos Santos Veiga, 1984). Using visualization tests (Ekstrom, French, Harman, & Dermen, 1990a), a learning style inventory (Brown & Cooper, 1999), and observations through a case study design, this study found visual learners performed better, but needed more practice and training. Statistically, all five pre- and post-test visualization test comparisons were highly significant in the two-tailed t-test (p > .01). The research findings are: (1) Students who tested high in the Visual (Language and/or Numerical) and Tactile Learning Styles (and Social Learning) had an advantage. Students who learned the chemistry concepts more effectively were better at visualizing structures and using molecular models to enhance their knowledge. (2) Students showed improvement in learning after visualization practice. Training in visualization would improve students' visualization abilities and provide them with a way to think about these concepts. (3) Conceptualization of concepts indicated that visualizing ability was critical and that it could be acquired. Support for this finding was provided by pre- and post-Visualization Test data with a highly significant t-test. (4) Various molecular animation programs and websites were found to be effective. (5) Visualization and modeling of structures encompassed both two- and three-dimensional space. The Visualization Test findings suggested that the students performed better with basic rotation of structures as compared to two- and three-dimensional objects. (6) Data from observations suggest that teaching style was an important factor in student learning of molecular structure. (7) Students did learn the chemistry concepts

  10. Structural and electronic properties of V{sub 2}B{sub n} (n = 1–10) clusters

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Li-Nan; Jia, Jianfeng, E-mail: jiajf@dns.sxnu.edu.cn; Wu, Hai-Shun, E-mail: wuhs@mail.sxnu.edu.cn

    2015-09-28

    Highlights: • Ground state isomers of V{sub 2}B{sub n} clusters are presented. • The growth pattern of V{sub 2}B{sub n} clusters is discussed. • V{sub 2}B{sub 6} is found to be the magically stable cluster. • The different ground state structure of V{sub 2}B{sub n} from that of Ta{sub 2}B{sub n} is caused by the small atomic radius of V atom. - Abstract: Inspired by the discovery of a series of Ta{sub 2}B{sub n} clusters, the geometric structures, stabilities, and electronic properties of V{sub 2}B{sub n} clusters up to n = 10 have been systematically investigated based on the density-functional B3LYP method and the CCSD(T) method. Among the small size clusters, the V{sub 2}B{sub 5} cluster was observed to have different geometric motif than Sc{sub 2}B{sub 5}, Ti{sub 2}B{sub 5} and Ta{sub 2}B{sub 5}. For V{sub 2}B{sub n} clusters with an n ⩾ 6, the bipyramidal structure is energetically favored, as for Sc{sub 2}B{sub n} and Ti{sub 2}B{sub n}. The second-order difference of energies, binding energies, dissociation energies, vertical ionization potentials, vertical electron affinities and chemical hardness of the V{sub 2}B{sub n} clusters were calculated and analyzed. The V{sub 2}B{sub 6} cluster was determined to be stable thermodynamically and might be observed in a future experiment. To understand the stability of the V{sub 2}B{sub 6} cluster, a detailed inspection of its occupied valence orbitals was performed.

  11. Materials Chemistry

    CERN Document Server

    Fahlman, Bradley D

    2011-01-01

    The 2nd edition of Materials Chemistry builds on the strengths that were recognized by a 2008 Textbook Excellence Award from the Text and Academic Authors Association (TAA). Materials Chemistry addresses inorganic-, organic-, and nano-based materials from a structure vs. property treatment, providing a suitable breadth and depth coverage of the rapidly evolving materials field. The 2nd edition continues to offer innovative coverage and practical perspective throughout. After briefly defining materials chemistry and its history, seven chapters discuss solid-state chemistry, metals, semiconducting materials, organic "soft" materials, nanomaterials, and materials characterization. All chapters have been thoroughly updated and expanded with, for example, new sections on ‘soft lithographic’ patterning, ‘click chemistry’ polymerization, nanotoxicity, graphene, as well as many biomaterials applications. The polymer and ‘soft’ materials chapter represents the largest expansion for the 2nd edition. Each ch...

  12. Cluster Headache

    OpenAIRE

    Pearce, Iris

    1985-01-01

    Cluster headache is the most severe primary headache with recurrent pain attacks described as worse than giving birth. The aim of this paper was to make an overview of current knowledge on cluster headache with a focus on pathophysiology and treatment. This paper presents hypotheses of cluster headache pathophysiology, current treatment options and possible future therapy approaches. For years, the hypothalamus was regarded as the key structure in cluster headache, but is now thought to be pa...

  13. Electron spin interactions in chemistry and biology fundamentals, methods, reactions mechanisms, magnetic phenomena, structure investigation

    CERN Document Server

    Likhtenshtein, Gertz

    2016-01-01

    This book presents the versatile and pivotal role of electron spin interactions in nature. It provides the background, methodologies and tools for basic areas related to spin interactions, such as spin chemistry and biology, electron transfer, light energy conversion, photochemistry, radical reactions, magneto-chemistry and magneto-biology. The book also includes an overview of designing advanced magnetic materials, optical and spintronic devices and photo catalysts. This monograph appeals to scientists and graduate students working in the areas related to spin interactions physics, biophysics, chemistry and chemical engineering.

  14. Factor Structure of the PTSD Checklist for DSM-5: Relationships Among Symptom Clusters, Anger, and Impulsivity.

    Science.gov (United States)

    Armour, Cherie; Contractor, Ateka; Shea, Tracie; Elhai, Jon D; Pietrzak, Robert H

    2016-02-01

    Scarce data are available regarding the dimensional structure of Diagnostic and Statistical Manual of Mental Disorders, 5th Edition (DSM-5) posttraumatic stress disorder (PTSD) symptoms and how factors relate to external constructs. We evaluated six competing models of DSM-5 PTSD symptoms, including Anhedonia, Externalizing Behaviors, and Hybrid models, using confirmatory factor analyses in a sample of 412 trauma-exposed college students. We then examined whether PTSD symptom clusters were differentially related to measures of anger and impulsivity using Wald chi-square tests. The seven-factor Hybrid model was deemed optimal compared with the alternatives. All symptom clusters were associated with anger; the strongest association was between externalizing behaviors and anger (r = 0.54). All symptom clusters, except re-experiencing and avoidance, were associated with impulsivity, with the strongest association between externalizing behaviors and impulsivity (r = 0.49). A seven-factor Hybrid model provides superior fit to DSM-5 PTSD symptom data, with the externalizing behaviors factor being most strongly related to anger and impulsivity.

  15. Proper Motions and Structural Parameters of the Galactic Globular Cluster M71

    Energy Technology Data Exchange (ETDEWEB)

    Cadelano, M.; Dalessandro, E.; Ferraro, F. R.; Miocchi, P.; Lanzoni, B.; Pallanca, C. [Dipartimento di Fisica e Astronomia, Università di Bologna, Viale Berti Pichat 6/2, I-40127 Bologna (Italy); Massari, D. [INAF—Osservatorio Astronomico di Bologna, Via Ranzani 1, I-40127 Bologna (Italy)

    2017-02-20

    By exploiting two ACS/ HST data sets separated by a temporal baseline of ∼7 years, we have determined the relative stellar proper motions (PMs; providing membership) and the absolute PM of the Galactic globular cluster M71. The absolute PM has been used to reconstruct the cluster orbit within a Galactic, three-component, axisymmetric potential. M71 turns out to be in a low-latitude disk-like orbit inside the Galactic disk, further supporting the scenario in which it lost a significant fraction of its initial mass. Since large differential reddening is known to affect this system, we took advantage of near-infrared, ground-based observations to re-determine the cluster center and density profile from direct star counts. The new structural parameters turn out to be significantly different from the ones quoted in the literature. In particular, M71 has a core and a half-mass radii almost 50% larger than previously thought. Finally, we estimate that the initial mass of M71 was likely one order of magnitude larger than its current value, thus helping to solve the discrepancy with the observed number of X-ray sources.

  16. Identification of alterations associated with age in the clustering structure of functional brain networks.

    Science.gov (United States)

    Guzman, Grover E C; Sato, Joao R; Vidal, Maciel C; Fujita, Andre

    2018-01-01

    Initial studies using resting-state functional magnetic resonance imaging on the trajectories of the brain network from childhood to adulthood found evidence of functional integration and segregation over time. The comprehension of how healthy individuals' functional integration and segregation occur is crucial to enhance our understanding of possible deviations that may lead to brain disorders. Recent approaches have focused on the framework wherein the functional brain network is organized into spatially distributed modules that have been associated with specific cognitive functions. Here, we tested the hypothesis that the clustering structure of brain networks evolves during development. To address this hypothesis, we defined a measure of how well a brain region is clustered (network fitness index), and developed a method to evaluate its association with age. Then, we applied this method to a functional magnetic resonance imaging data set composed of 397 males under 31 years of age collected as part of the Autism Brain Imaging Data Exchange Consortium. As results, we identified two brain regions for which the clustering change over time, namely, the left middle temporal gyrus and the left putamen. Since the network fitness index is associated with both integration and segregation, our finding suggests that the identified brain region plays a role in the development of brain systems.

  17. Formation Mechanism and Binding Energy for Body-Centred Regular Icosahedral Structure of Li13 Cluster

    International Nuclear Information System (INIS)

    Liu Weina; Li Ping; Gou Qingquan; Zhao Yanping

    2008-01-01

    The formation mechanism for the body-centred regular icosahedral structure of Li 13 cluster is proposed. The curve of the total energy versus the separation R between the nucleus at the centre and nuclei at the apexes for this structure of Li 13 has been calculated by using the method of Gou's modified arrangement channel quantum mechanics (MACQM). The result shows that the curve has a minimal energy of -96.951 39 a.u. at R = 5.46a 0 . When R approaches to infinity, the total energy of thirteen lithium atoms has the value of -96.564 38 a.u. So the binding energy of Li 13 with respect to thirteen lithium atoms is 0.387 01 a.u. Therefore the binding energy per atom for Li 13 is 0.029 77 a.u. or 0.810 eV, which is greater than the binding energy per atom of 0.453 eV for Li 2 , 0.494 eV for Li 3 , 0.7878 eV for Li 4 , 0.632 eV for Li 5 , and 0.674 eV for Li 7 calculated by us previously. This means that the Li 13 cluster may be formed stably in a body-centred regular icosahedral structure with a greater binding energy

  18. In-situ small/wide-angle neutron scattering studies of the cluster structure in polyelectrolyte membrane for fuel cells

    International Nuclear Information System (INIS)

    Nakano, Tomohiro; Kaneko, Michiyo; Otomo, Toshiya; Kamiyama, Takashi; Sugiyama, Masaaki; Fukunaga, Toshiharu; Kanno, Ryoji; Yamamoto, Satoru; Hyodo, Shiaki

    2007-01-01

    Proton conductivity of Nafion membrane is varied by humidity and it has been thought to be affected by the cluster structure of the membrane. We applied Small-Angle Scattering technique under humidity-controlled atmosphere with X-ray (SAXS) and neutron (SANS) to clarify the relationship between the cluster structure and molecular structure in two types of Nafion membrane, N115 and NE151F, which have different equivalent weight (EW). The proton conductivity of N115 is higher than that of NE151F. By these two measurements, three different sized periodic structures were observed in the Nafion membrane. Contrast variation method (D/H=60/40, 75/25, 80/20, 90/10) was also applied in SANS experiments and it was suggested that two of three peaks are originated from two different sizes of water clusters. A distinguishing peak at q=0.2[A -1 ], which shifts to lower q region by humidity increase, was reproduced by a simulation of Dissipative Particle Dynamics (DPD): the shifts of the peak was interpreted as the swelling of cluster structure. The size of the cluster calculated from the peak position is positively correlated with the proton conductivity. Finally, the effect of EW on the proton conductivity of Nafion membrane was briefly discussed from the point of its cluster structure. (author)

  19. Structure and Magnetic Properties of a Dodecanuclear Twisted-Ring Iron(III) Cluster.

    Science.gov (United States)

    Caneschi, Andrea; Cornia, Andrea; Fabretti, Antonio C; Gatteschi, Dante

    1999-05-03

    An unprecedented nonplanar structure characterizes the complex [Fe(OCH 3 ) 2 (dbm)] 12 (on the left in the picture), which contains the largest cyclic ferric cluster yet reported with chemically equivalent bridging units. It is made up of twelve high-spin, antiferromagnetically coupled iron(III) centers and neatly reacts with Na I or Li I templates in organic solution to give hexairon(III) coronates (right). Fe=•, O=○, NaI or LiI=• Hdbm=dibenzoylmethane. © 1999 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

  20. Structural oxidation state studies of the manganese cluster in the oxygen evolving complex of photosystem II

    Energy Technology Data Exchange (ETDEWEB)

    Liang, Wenchuan [Univ. of California, Berkeley, CA (United States)

    1994-11-01

    X-ray absorption spectroscopy (XAS) was performed on Photosystem II (PSII)-enriched membranes prepared from spinach to explore: (1) the correlation between structure and magnetic spin state of the Mn cluster in the oxygen evolving complex (OEC) in the S2 state; and (2) the oxidation state changes of the Mn cluster in the flash-induced S-states. The structure of the Mn cluster in the S2 state with the g~4 electron paramagnetic resonance (EPR) signal (S2-g4 state) was compared with that in the S2 state with multiline signal (S2-MLS state) and the S1 state. The S2-g4 state has a higher XAS inflection point energy than that of the S1 state, indicating the oxidation of Mn in the advance from the S1 to the S2-g4 state. Differences in the edge shape and in the extended X-ray absorption fine structure (EXAFS) show that the structure of the Mn cluster in the S2-g4 state is different from that in the S2-MLS or the S1 state. In the S2-g4 state, the second shell of backscatterers from the Mn absorber contains two Mn-Mn distances of 2.73 Å and 2.85 Å. Very little distance disorder exists in the second shell of the S1 or S2-MLS states. The third shell of the S2-g4 state at about 3.3 Å also contains increased heterogeneity relative to that of the S2-MLS or the S1 state. Various S-states were prepared at room-temperature by saturating, single-turnover flashes. The flash-dependent oscillation in the amplitude of the MLS was used to characterize the S-state composition and to construct "pure" S-state Mn K-edge spectra. The edge position shifts to higher energy by 1.8 eV upon the S1 → S2 transition.

  1. General chemistry

    International Nuclear Information System (INIS)

    Kwon, Yeong Sik; Lee, Dong Seop; Ryu, Haung Ryong; Jang, Cheol Hyeon; Choi, Bong Jong; Choi, Sang Won

    1993-07-01

    The book concentrates on the latest general chemistry, which is divided int twenty-three chapters. It deals with basic conception and stoichiometry, nature of gas, structure of atoms, quantum mechanics, symbol and structure of an electron of ion and molecule, chemical thermodynamics, nature of solid, change of state and liquid, properties of solution, chemical equilibrium, solution and acid-base, equilibrium of aqueous solution, electrochemistry, chemical reaction speed, molecule spectroscopy, hydrogen, oxygen and water, metallic atom; 1A, IIA, IIIA, carbon and atom IVA, nonmetal atom and an inert gas, transition metals, lanthanons, and actinoids, nuclear properties and radioactivity, biochemistry and environment chemistry.

  2. Cluster management.

    Science.gov (United States)

    Katz, R

    1992-11-01

    Cluster management is a management model that fosters decentralization of management, develops leadership potential of staff, and creates ownership of unit-based goals. Unlike shared governance models, there is no formal structure created by committees and it is less threatening for managers. There are two parts to the cluster management model. One is the formation of cluster groups, consisting of all staff and facilitated by a cluster leader. The cluster groups function for communication and problem-solving. The second part of the cluster management model is the creation of task forces. These task forces are designed to work on short-term goals, usually in response to solving one of the unit's goals. Sometimes the task forces are used for quality improvement or system problems. Clusters are groups of not more than five or six staff members, facilitated by a cluster leader. A cluster is made up of individuals who work the same shift. For example, people with job titles who work days would be in a cluster. There would be registered nurses, licensed practical nurses, nursing assistants, and unit clerks in the cluster. The cluster leader is chosen by the manager based on certain criteria and is trained for this specialized role. The concept of cluster management, criteria for choosing leaders, training for leaders, using cluster groups to solve quality improvement issues, and the learning process necessary for manager support are described.

  3. Impact of the Fused Deposition (FDM) Printing Process on Polylactic Acid (PLA) Chemistry and Structure

    OpenAIRE

    Michael Arthur Cuiffo; Jeffrey Snyder; Alicia M. Elliott; Nicholas Romero; Sandhiya Kannan; Gary P. Halada

    2017-01-01

    Polylactic acid (PLA) is an organic polymer commonly used in fused deposition (FDM) printing and biomedical scaffolding that is biocompatible and immunologically inert. However, variations in source material quality and chemistry make it necessary to characterize the filament and determine potential changes in chemistry occurring as a result of the FDM process. We used several spectroscopic techniques, including laser confocal microscopy, Fourier transform infrared (FTIR) spectroscopy and pho...

  4. Structural, electronic, and magnetic properties of Y(n)O (n=2-14) clusters: Density functional study.

    Science.gov (United States)

    Yang, Zhi; Xiong, Shi-Jie

    2008-09-28

    The geometries stability, electronic properties, and magnetism of Y(n)O clusters up to n=14 are systematically studied with density functional theory. In the lowest-energy structures of Y(n)O clusters, the equilibrium site of the oxygen atom gradually moves from an outer site of the cluster, via a surface site, and finally, to an interior site as the number of the Y atoms increases from 2 to 14. Starting from n=12, the O atom falls into the center of the cluster with the Y atoms forming the outer frame. The results show that clusters with n=2, 4, 8, and 12 are more stable than their respective neighbors, and that the total magnetic moments of Y(n)O clusters are all quite small except Y(12)O cluster. The lowest-energy structure of Y(12)O cluster is a perfect icosahedron with a large magnetic moment 6mu(B). In addition, we find that the total magnetic moments are quenched for n=2, 6, and 8 due to the closed-shell electronic configuration. The calculated ionization potentials and electron affinities are in good agreement with the experimental results, which imply that the present theoretical treatments are satisfactory.

  5. The latest general chemistry

    International Nuclear Information System (INIS)

    Ryu, Geun Bae; Choi, Se Yeong; Kim, Chin Yeong; Yoon, Gil Jung; Lee, Eun Seok; Seo, Moon Gyu

    1995-02-01

    This book deals with the latest general chemistry, which is comprised of twenty-three chapters, the contents of this book are introduction, theory of atoms and molecule, chemical formula and a chemical reaction formula, structure of atoms, nature of atoms and the periodic table, structure of molecule and spectrum, gas, solution, solid, chemical combination, chemical reaction speed, chemical equilibrium, thermal chemistry, oxidation-reduction, electrochemistry, acid-base, complex, aquatic chemistry, air chemistry, nuclear chemistry, metal and nonmetal, organic chemistry and biochemistry. It has exercise in the end of each chapter.

  6. Application of digital image processing methods on the cluster structure at the wall of a circulating fluidized bed

    Energy Technology Data Exchange (ETDEWEB)

    Li, Hai-guang; Zhao, Zeng-wu; Li, Bao-wei; Wu, Wen-fei [Inner Mongolia Univ. of Science and Technology, Baotou (China). School of Environment and Energy

    2013-07-01

    This paper describes experiments to investigate the cluster structure of gas-particle flow at the wall region of a circulating fluidized bed (CFB). The setup is in a cold scale-model circulating fluidized bed with a riser that has a 0.30 m 0.28 m cross-section and is 2.9 m tall. A video camera was utilized to visualize the cluster structure through a transparent Plexiglas wall. An image processing system was used to analyze images, which were obtained under different superficial gas velocities and solid circulating rates. The results show that distinctly different cluster structures exist in the different operating conditions, which the number, shape and size of the clusters are affected by main air flow.

  7. Electrostatics in Chemistry

    Indian Academy of Sciences (India)

    fundamental concepts of electrostatics as applied to atoms and molecules. The electric ... chemistry, the chemistry of the covalent bond, deals with the structures ..... the position of an asteroid named Ceres ... World Scientific. Singapore, 1992.

  8. Surface chemistry and electronic structure of nonpolar and polar GaN films

    Energy Technology Data Exchange (ETDEWEB)

    Mishra, Monu; Krishna, T.C. Shibin; Aggarwal, Neha; Gupta, Govind, E-mail: govind@nplindia.org

    2015-08-01

    Highlights: • Surface chemistry and electronic structure of polar and nonpolar GaN is reported. • Influence of polarization on electron affinity of p & np GaN films is investigated. • Correlation between surface morphology and polarity has been deduced. - Abstract: Photoemission and microscopic analysis of nonpolar (a-GaN/r-Sapphire) and polar (c-GaN/c-Sapphire) epitaxial gallium nitride (GaN) films grown via RF-Molecular Beam Epitaxy is reported. The effect of polarization on surface properties like surface states, electronic structure, chemical bonding and morphology has been investigated and correlated. It was observed that polarization lead to shifts in core level (CL) as well as valence band (VB) spectra. Angle dependent X-ray Photoelectron Spectroscopic analysis revealed higher surface oxide in polar GaN film compared to nonpolar GaN film. On varying the take off angle (TOA) from 0° to 60°, the Ga−O/Ga−N ratio varied from 0.11–0.23 for nonpolar and 0.17–0.36 for polar GaN film. The nonpolar film exhibited N-face polarity while Ga-face polarity was perceived in polar GaN film due to the inherent polarization effect. Polarization charge compensated surface states were observed on the polar GaN film and resulted in downward band bending. Ultraviolet photoelectron spectroscopic measurements revealed electron affinity and ionization energy of 3.4 ± 0.1 eV and 6.8 ± 0.1 eV for nonpolar GaN film and 3.8 ± 0.1 eV and 7.2 ± 0.1 eV for polar GaN film respectively. Field Emission Scanning Electron Microscopy measurements divulged smooth morphology with pits on polar GaN film. The nonpolar film on the other hand showed pyramidal structures having facets all over the surface.

  9. Structural stabilities and electronic properties of Mg28-nAln clusters: A first-principles study

    Directory of Open Access Journals (Sweden)

    Bao-Juan Lu

    2017-09-01

    Full Text Available In this paper, we have constructed the alloy configurations of Mg28-nAln by replacing atoms at various possible positions, starting from the stable structures of Mg28 and Al28 clusters. According to the symmetry of the cluster structure, the isomers of these initial structures have been screened with the congruence check, which would reduce computational hours and improve efficiency. Using the first-principles method, the structural evolution, mixing behavior and electronic properties of Mg28-nAln clusters are investigated for all compositions. We conclude that Al atoms prefer to reside in the central positions of Mg−Al clusters and Mg atoms tend to occupy the peripheral location. The negative mixing enthalpies imply the stabilities of these Mg-Al clusters and thus possible applications in catalysis and hydrogen storage materials. Among Mg28-nAln clusters, Mg24Al4, Mg21Al7, Mg14Al14, Mg26Al2 and Mg27Al1 present relatively high thermodynamic stabilities, and the electronic properties of these stable structures are discussed with the charge distributions around the Fermi level.

  10. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    International Nuclear Information System (INIS)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M.; Sapsay, V.I.; Klymchuk, D.O.; Puziy, A.M.

    2012-01-01

    Highlights: ► Phosphoric acid activation results in formation of carbons with acidic surface groups. ► Maximum amount of surface groups is introduced at impregnation ratio 1.25. ► Phosphoric acid activated carbons show high capacity to copper. ► Phosphoric acid activated carbons are predominantly microporous. ► Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 °C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S BET = 2081 m 2 /g, V tot = 1.1 cm 3 /g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0–2.6), weakly acidic carboxylic (pK = 4.7–5.0), enol/lactone (pK = 6.7–7.4; 8.8–9.4) and phenol (pK = 10.1–10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

  11. Secondary Structures in Phe-Containing Isolated Dipeptide Chains: Laser Spectroscopy vs Quantum Chemistry.

    Science.gov (United States)

    Loquais, Yohan; Gloaguen, Eric; Habka, Sana; Vaquero-Vara, Vanesa; Brenner, Valérie; Tardivel, Benjamin; Mons, Michel

    2015-06-11

    The intrinsic conformational landscape of two phenylalanine-containing protein chain models (-Gly-Phe- and -Ala-Phe- sequences) has been investigated theoretically and experimentally in the gas phase. The near UV spectroscopy (first ππ* transition of the Phe ring) is obtained experimentally under jet conditions where the conformational features can be resolved. Single-conformation IR spectroscopy in the NH stretch region is then obtained by IR/UV double resonance in the ground state, leading to resolved vibrational spectra that are assigned in terms of conformation and H-bonding content from comparison with quantum chemistry calculations. For the main conformer, whose UV spectrum exhibits a significant Franck-Condon activity in low frequency modes involving peptide backbone motions relative to the Phe chromophore, excited state IR spectroscopy has also been recorded in a UV/IR/UV experiment. The NH stretch spectral changes observed in such a ππ* labeling experiment enable us to determine those NH bonds that are coupled to the phenyl ring; they are compared to CC2 excited state calculations to quantify the geometry change upon ππ* excitation. The complete and consistent series of data obtained enable us to propose an unambiguous assignment for the gallery of conformers observed and to demonstrate that, in these two sequences, three conceptually important local structural motifs of proteins (β-strands, 27 ribbons, and β-turns) are represented. The satisfactory agreement between the experimental conformational distribution and the predicted landscape anticipated from the DFT-D approach demonstrates the capabilities of a theoretical method that accounts for dispersive interactions. It also shows that the flaws, inherent to a resonant two-photon ionization detection scheme, often evoked for aromatic chromophores, do not seem to be significant in the case of Phe.

  12. Porous structure and surface chemistry of phosphoric acid activated carbon from corncob

    Energy Technology Data Exchange (ETDEWEB)

    Sych, N.V.; Trofymenko, S.I.; Poddubnaya, O.I.; Tsyba, M.M. [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine); Sapsay, V.I.; Klymchuk, D.O. [M.G. Kholodny Institute of Botany, National Academy of Sciences of Ukraine, 2 Tereshchenkivska St., 01601 Kyiv (Ukraine); Puziy, A.M., E-mail: alexander.puziy@ispe.kiev.ua [Institute for Sorption and Endoecology Problems, National Academy of Sciences of Ukraine, 13 General Naumov St., 03164 Kyiv (Ukraine)

    2012-11-15

    Highlights: Black-Right-Pointing-Pointer Phosphoric acid activation results in formation of carbons with acidic surface groups. Black-Right-Pointing-Pointer Maximum amount of surface groups is introduced at impregnation ratio 1.25. Black-Right-Pointing-Pointer Phosphoric acid activated carbons show high capacity to copper. Black-Right-Pointing-Pointer Phosphoric acid activated carbons are predominantly microporous. Black-Right-Pointing-Pointer Maximum surface area and pore volume achieved at impregnation ratio 1.0. - Abstract: Active carbons have been prepared from corncob using chemical activation with phosphoric acid at 400 Degree-Sign C using varied ratio of impregnation (RI). Porous structure of carbons was characterized by nitrogen adsorption and scanning electron microscopy. Surface chemistry was studied by IR and potentiometric titration method. It has been shown that porosity development was peaked at RI = 1.0 (S{sub BET} = 2081 m{sup 2}/g, V{sub tot} = 1.1 cm{sup 3}/g), while maximum amount of acid surface groups was observed at RI = 1.25. Acid surface groups of phosphoric acid activated carbons from corncob includes phosphate and strongly acidic carboxylic (pK = 2.0-2.6), weakly acidic carboxylic (pK = 4.7-5.0), enol/lactone (pK = 6.7-7.4; 8.8-9.4) and phenol (pK = 10.1-10.7). Corncob derived carbons showed high adsorption capacity to copper, especially at low pH. Maximum adsorption of methylene blue and iodine was observed for carbon with most developed porosity (RI = 1.0).

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

    Science.gov (United States)

    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.

  14. The Centaurus cluster of galaxies. II. The bimodal-velocity structure

    International Nuclear Information System (INIS)

    Lucey, J.R.; Currie, M.J.; Dickens, R.J.

    1985-09-01

    This is the second paper in a series that describes an extensive study of the Centaurus cluster of galaxies. The paper concerns the bimodal velocity distribution of the galaxies in the cluster. The likely location of the two main cluster components is discussed. The data strongly favours the hypothesis that the two components lie within the same cluster. (UK)

  15. Crystal structures and luminescence of two cadmium-carboxylate cluster-based compounds with mixed ligands

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Hui-Fang; Lei, Qian; Wang, Yu-Ling; Yin, Shun-Gao; Liu, Qing-Yan [College of Chemistry and Chemical Engineering and Key Lab. of Functional Small Organic Molecule of Ministry of Education, Jiangxi Normal Univ., Nanchang (China)

    2017-04-04

    Reactions of Cd(NO{sub 3}){sub 2}.4H{sub 2}O with 2-quinolinecarboxylic acid (H-QLC) in the presence of 1,4-benzenedicarboxylic acid (H{sub 2}-BDC) or 1,3,5-benzenetricarboxylic acid (H-BTC) in DMF/H{sub 2}O solvent afforded two compounds, namely, [Cd(QLC)(BDC){sub 1/2}(H{sub 2}O)]{sub n} (1) and [Cd(QLC)(BTC){sub 1/3}]{sub n} (2). Both compounds are two-dimensional (2D) frameworks but feature different cadmium-carboxylate clusters as a result of the presence of the polycarboxylate ligands with different geometries and coordination preference. The dinuclear Cd{sub 2}(QLC){sub 2} units in 1 are bridged by the pairs of bridging water ligands to give a one-dimensional (1D) chain, which is further linked by the second ligand of BDC{sup 2-} to form a 2D structure. Compound 2 is constructed from unique hexanuclear macrometallacyclic Cd{sub 6}(QLC){sub 6} clusters, which are linked by the surrounding BTC{sup 3-} ligands to generate a 2D structure. Photoluminescence studies showed both compounds exhibit ligand-centered luminescent emissions with emission maxima at 405 and 401 nm, respectively. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  16. Crystal structure of the FeS cluster-containing nucleotide excision repair helicase XPD.

    Directory of Open Access Journals (Sweden)

    Stefanie C Wolski

    2008-06-01

    Full Text Available DNA damage recognition by the nucleotide excision repair pathway requires an initial step identifying helical distortions in the DNA and a proofreading step verifying the presence of a lesion. This proofreading step is accomplished in eukaryotes by the TFIIH complex. The critical damage recognition component of TFIIH is the XPD protein, a DNA helicase that unwinds DNA and identifies the damage. Here, we describe the crystal structure of an archaeal XPD protein with high sequence identity to the human XPD protein that reveals how the structural helicase framework is combined with additional elements for strand separation and DNA scanning. Two RecA-like helicase domains are complemented by a 4Fe4S cluster domain, which has been implicated in damage recognition, and an alpha-helical domain. The first helicase domain together with the helical and 4Fe4S-cluster-containing domains form a central hole with a diameter sufficient in size to allow passage of a single stranded DNA. Based on our results, we suggest a model of how DNA is bound to the XPD protein, and can rationalize several of the mutations in the human XPD gene that lead to one of three severe diseases, xeroderma pigmentosum, Cockayne syndrome, and trichothiodystrophy.

  17. 2nd International Symposium "Atomic Cluster Collisions : Structure and Dynamics from the Nuclear to the Biological Scale"

    CERN Document Server

    Solov'yov, Andrey; ISACC 2007; Latest advances in atomic cluster collisions

    2008-01-01

    This book presents a 'snapshot' of the most recent and significant advances in the field of cluster physics. It is a comprehensive review based on contributions by the participants of the 2nd International Symposium on Atomic Cluster Collisions (ISACC 2007) held in July 19-23, 2007 at GSI, Darmstadt, Germany. The purpose of the Symposium is to promote the growth and exchange of scientific information on the structure and properties of nuclear, atomic, molecular, biological and complex cluster systems studied by means of photonic, electronic, heavy particle and atomic collisions. Particular attention is devoted to dynamic phenomena, many-body effects taking place in cluster systems of a different nature - these include problems of fusion and fission, fragmentation, collective electron excitations, phase transitions, etc.Both the experimental and theoretical aspects of cluster physics, uniquely placed between nuclear physics on the one hand and atomic, molecular and solid state physics on the other, are discuss...

  18. Structural calculations and experimental detection of small Ga mS n clusters using time-of-flight mass spectrometry

    Science.gov (United States)

    BelBruno, J. J.; Sanville, E.; Burnin, A.; Muhangi, A. K.; Malyutin, A.

    2009-08-01

    Ga mS n clusters were generated by laser ablation of a solid sample of Ga 2S 3. The resulting molecules were analyzed in a time-of-flight mass spectrometer. In addition to atomic species, the spectra exhibited evidence for the existence of GaS3+, GaS4+, GaS5+, and GaS6+ clusters. The potential neutral and cationic structures of the observed Ga mS n clusters were computationally investigated using a density-functional approach. Reference is made to the kinetic pathways required for production of clusters from the starting point of the stoichiometric molecule or molecular ion. Cluster atomization enthalpies are compared with bulk values from the literature.

  19. Consumers' Kansei Needs Clustering Method for Product Emotional Design Based on Numerical Design Structure Matrix and Genetic Algorithms.

    Science.gov (United States)

    Yang, Yan-Pu; Chen, Deng-Kai; Gu, Rong; Gu, Yu-Feng; Yu, Sui-Huai

    2016-01-01

    Consumers' Kansei needs reflect their perception about a product and always consist of a large number of adjectives. Reducing the dimension complexity of these needs to extract primary words not only enables the target product to be explicitly positioned, but also provides a convenient design basis for designers engaging in design work. Accordingly, this study employs a numerical design structure matrix (NDSM) by parameterizing a conventional DSM and integrating genetic algorithms to find optimum Kansei clusters. A four-point scale method is applied to assign link weights of every two Kansei adjectives as values of cells when constructing an NDSM. Genetic algorithms are used to cluster the Kansei NDSM and find optimum clusters. Furthermore, the process of the proposed method is presented. The details of the proposed approach are illustrated using an example of electronic scooter for Kansei needs clustering. The case study reveals that the proposed method is promising for clustering Kansei needs adjectives in product emotional design.

  20. Diffusion and growth of aluminum adatoms on magnesium clusters with hexahedral structure

    International Nuclear Information System (INIS)

    Dai, Xiongying; Hu, Wangyu; Yang, Jianyu; Chen, Chuanpin

    2015-01-01

    The surface diffusion and growth of Al atoms on Mg clusters with hexahedral structure was investigated using molecular dynamics simulations. The diffusion pathways and the corresponding energy barriers were determined via the nudged elastic band method. Two diffusion paths from a (0001) facet to a neighboring (11 ¯ 01) facet and between two adjacent (11 ¯ 01) facets were considered. The energy barriers on the (11 ¯ 01) facets and between the two (11 ¯ 01) facets were remarkably increased. As such, the adatom's mobility became limited at low temperatures. The growth of small Al–Mg nanoclusters was modeled via the one-by-one atom deposition technique to form an anomalous core–shell structure. The Mg atoms with lower surface energy and larger atomic radius occupied the core and the Al atoms with higher surface energy and smaller atomic radius occupied the shell

  1. First Cluster results of the magnetic field structure of the mid- and high-altitude cusps

    Directory of Open Access Journals (Sweden)

    P. J. Cargill

    Full Text Available Magnetic field measurements from the four Cluster spacecraft from the mid- and high-altitude cusp are presented. Cluster underwent two encounters with the mid-altitude cusp during its commissioning phase (24 August 2000. Evidence for field-aligned currents (FACs was seen in the data from all three operating spacecraft from northern and southern cusps. The extent of the FACs was of the order of 1 RE in the X-direction, and at least 300 km in the Y-direction. However, fine-scale field structures with scales of the order of the spacecraft separation (300 km were observed within the FACs. In the northern crossing, two of the spacecraft appeared to lie along the same magnetic field line, and observed very well matched signals. However, the third spacecraft showed evidence for structuring transverse to the field on scales of a few hundred km. A crossing of the high-altitude cusp from 13 February 2001 is presented. It is revealed to be a highly dynamic structure with the boundaries moving with velocities ranging from a few km/s to tens of km/s, and having structure on timescales ranging from less than one minute up to several minutes. The cusp proper is associated with the presence of a very disordered magnetic field, which is entirely different from the magnetosheath turbulence.

    Key words. Magnetospheric physics (current systems; magnetopause, cusp, and boundary layers – Space plasma physics (discontinuities

  2. Titanium embedded cage structure formation in Al{sub n}Ti{sup +} clusters and their interaction with Ar

    Energy Technology Data Exchange (ETDEWEB)

    Torres, M. B., E-mail: begonia@ubu.es [Departamento de Matemáticas y Computación, Universidad de Burgos, 09006 Burgos (Spain); Vega, A.; Balbás, L. C. [Departamento de Física Teórica, Universidad de Valladolid, 47011 Valladolid (Spain); Aguilera-Granja, F. [Instituto de Física, Universidad de San Luis Potosí, 78000 San Luis de Potosí (Mexico)

    2014-05-07

    Recently, Ar physisorption was used as a structural probe for the location of the Ti dopant atom in aluminium cluster cations, Al{sub n}Ti{sup +} [Lang et al., J. Am. Soc. Mass Spectrom. 22, 1508 (2011)]. As an experiment result, the lack of Ar complexes for n > n{sub c} determines the cluster size for which the Ti atom is located inside of an Al cage. To elucidate the decisive factors for the formation of endohedrally Al{sub n}Ti{sup +}, experimentalists proposed detailed computational studies as indispensable. In this work, we investigated, using the density functional theory, the structural and electronic properties of singly titanium doped cationic clusters, Al{sub n}Ti{sup +} (n = 16–21) as well as the adsorption of an Ar atom on them. The first endohedral doped cluster, with Ti encapsulated in a fcc-like cage skeleton, appears at n{sub c} = 21, which is the critical number consistent with the exohedral-endohedral transition experimentally observed. At this critical size the non-crystalline icosahedral growth pattern, related to the pure aluminium clusters, with the Ti atom in the surface, changes into a endohedral fcc-like pattern. The map of structural isomers, relative energy differences, second energy differences, and structural parameters were determined and analyzed. Moreover, we show the critical size depends on the net charge of the cluster, being different for the cationic clusters (n{sub c} = 21) and their neutral counterparts (n{sub c} = 20). For the Al {sub n} Ti {sup +} · Ar complexes, and for n < 21, the preferred Ar adsorption site is on top of the exohedral Ti atom, with adsorption energy in very good agreement with the experimental value. Instead, for n = 21, the Ar adsorption occurs on the top an Al atom with very low absorption energy. For all sizes the geometry of the Al{sub n}Ti{sup +} clusters keeps unaltered in the Ar-cluster complexes. This fact indicates that Ar adsorption does not influence the cluster structure, providing support

  3. Effect of charge state and stoichiometry on the structure and reactivity of nickel oxide clusters with CO

    Science.gov (United States)

    Johnson, Grant E.; Reilly, Nelly M.; Castleman, A. W., Jr.

    2009-02-01

    The collision induced fragmentation and reactivity of cationic and anionic nickel oxide clusters with carbon monoxide were studied experimentally using guided-ion-beam mass spectrometry. Anionic clusters with a stoichiometry containing one more oxygen atom than nickel atom (NiO2-, Ni2O3-, Ni3O4- and Ni4O5-) were found to exhibit dominant products resulting from the transfer of a single oxygen atom to CO, suggesting the formation of CO2. Of these four species, Ni2O3- and Ni4O5- were observed to be the most reactive having oxygen transfer products accounting for approximately 5% and 10% of the total ion intensity at a maximum pressure of 15 mTorr of CO. Our findings, therefore, indicate that anionic nickel oxide clusters containing an even number of nickel atoms and an odd number of oxygen atoms are more reactive than those with an odd number of nickel atoms and an even number of oxygen atoms. The majority of cationic nickel oxides, in contrast to anionic species, reacted preferentially through the adsorption of CO onto the cluster accompanied by the loss of either molecular O2 or nickel oxide units. The adsorption of CO onto positively charged nickel oxides, therefore, is exothermic enough to break apart the gas-phase clusters. Collision induced dissociation experiments, employing inert xenon gas, were also conducted to gain insight into the structural properties of nickel oxide clusters. The fragmentation products were found to vary considerably with size and stoichiometry as well as ionic charge state. In general, cationic clusters favored the collisional loss of molecular O2 while anionic clusters fragmented through the loss of both atomic oxygen and nickel oxide units. Our results provide insight into the effect of ionic charge state on the structure of nickel oxide clusters. Furthermore, we establish how the size and stoichiometry of nickel oxide clusters influences their ability to oxidize CO, an important reaction for environmental pollution abatement.

  4. Isolated electrostatic structures observed throughout the Cluster orbit: relationship to magnetic field strength

    Directory of Open Access Journals (Sweden)

    J. S. Pickett

    2004-07-01

    Full Text Available Isolated electrostatic structures are observed throughout much of the 4RE by 19.6RE Cluster orbit. These structures are observed in the Wideband plasma wave instrument's waveform data as bipolar pulses (one positive and one negative peak in the electric field amplitude and tripolar pulses (two positive and one negative peak, or vice versa. These structures are observed at all of the boundary layers, in the solar wind and magnetosheath, and along auroral field lines at 4.5-6.5RE. Using the Wideband waveform data from the various Cluster spacecraft we have carried out a survey of the amplitudes and time durations of these structures and how these quantities vary with the local magnetic field strength. Such a survey has not been carried out before, and it reveals certain characteristics of solitary structures in a finite magnetic field, a topic still inadequately addressed by theories. We find that there is a broad range of electric field amplitudes at any specific magnetic field strength, and there is a general trend for the electric field amplitudes to increase as the strength of the magnetic field increases over a range of 5 to 500nT. We provide a possible explanation for this trend that relates to the structures being Bernstein-Greene-Kruskal mode solitary waves. There is no corresponding dependence of the duration of the structures on the magnetic field strength, although a plot of these two quantities reveals the unexpected result that with the exception of the magnetosheath, all of the time durations for all of the other regions are comparable, whereas the magnetosheath time durations clearly are in a different category of much smaller time duration. We speculate that this implies that the structures are much smaller in size. The distinctly different pulse durations for the magnetosheath pulses indicate the possibility that the pulses are generated by a mechanism which is different

  5. Structures, stability, magnetic moments and growth strategies of the Fe_nN (n = 1–7) clusters: All-electron density functional theory calculations

    International Nuclear Information System (INIS)

    Li, Zhi; Zhao, Zhen

    2017-01-01

    The geometries, electronic properties, magnetic moments and growth strategies of the Fe_nN (n = 1–7) clusters are investigated using all-electron density functional theory. The results show that N doping significantly distorts the Fe_n clusters. Fe_4N and Fe_6N clusters are more stable structures than other considered Fe_nN clusters. Local peaks of HOMO-LUMO gap curve are found at n = 3, 7, implying that the chemical stability of the Fe_3N and Fe_7N clusters is higher. Fe_2N, Fe_4N and Fe_6N clusters have larger magnetic moments compared to other considered Fe_nN (n = 1–7) clusters. It can be seen that the Fe_5 clusters are easier to adsorb a Fe atom while the Fe_4 clusters are easier to adsorb a N atom. The considered Fe_mN clusters prefer to adsorb a Fe atom and larger Fe_mN clusters are easier to grow. - Highlights: • The structural stability of the Fe_4N and Fe_6N clusters is higher. • The chemical stability of the Fe_3N and Fe_7N clusters is higher. • Fe_5 clusters are easier to adsorb a Fe atom while Fe_4 clusters are easier to adsorb a N atom. • Fe_nN clusters prefer to adsorb a Fe atom.

  6. Physical Chemistry '98: Fourth International Conference on Fundamental and Applied Aspects of Physical Chemistry - Papers

    International Nuclear Information System (INIS)

    Ribnikar, S.; Anic, S.

    1998-01-01

    The proceedings has following chapters: Plenary lectures; Chemical Thermodynamics; Spectroscopy, Molecular Structures, Physical Chemistry of Plasma; Kinetics, Catalysis, Nonlinear Dynamics; Electrochemistry; Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry; Solid State Physical Chemistry, Material Science; Macromolecular Physical Chemistry; Environmental Protection; Phase Boundaries; Complex Compounds; General Physical Chemistry. A separated abstract was prepared for each of the 20 papers selected from the three chapters: Biophysical Chemistry, Photochemistry, Radiation Chemistry; Radiochemistry, Nuclear Chemistry. and Environmental Protection. Refs and figs

  7. A critical size for emergence of nonbulk electronic and geometric structures in dodecanethiolate-protected Au clusters.

    Science.gov (United States)

    Negishi, Yuichi; Nakazaki, Tafu; Malola, Sami; Takano, Shinjiro; Niihori, Yoshiki; Kurashige, Wataru; Yamazoe, Seiji; Tsukuda, Tatsuya; Häkkinen, Hannu

    2015-01-28

    We report on how the transition from the bulk structure to the cluster-specific structure occurs in n-dodecanethiolate-protected gold clusters, Au(n)(SC12)m. To elucidate this transition, we isolated a series of Au(n)(SC12)m in the n range from 38 to ∼520, containing five newly identified or newly isolated clusters, Au104(SC12)45, Au(∼226)(SC12)(∼76), Au(∼253)(SC12)(∼90), Au(∼356)(SC12)(∼112), and Au(∼520)(SC12)(∼130), using reverse-phase high-performance liquid chromatography. Low-temperature optical absorption spectroscopy, powder X-ray diffractometry, and density functional theory (DFT) calculations revealed that the Au cores of Au144(SC12)60 and smaller clusters have molecular-like electronic structures and non-fcc geometric structures, whereas the structures of the Au cores of larger clusters resemble those of the bulk gold. A new structure model is proposed for Au104(SC12)45 based on combined approach between experiments and DFT calculations.

  8. Structures, electronic properties and magnetisms of FeBN (N ≤ 15) clusters: density functional theory investigations

    International Nuclear Information System (INIS)

    Liu Huoyan; Lel Xueling; Chen Hang; Liu Zhifeng; Liu Liren; Zhu Hengjiang

    2011-01-01

    The equilibrium structures, electronic properties and magnetisms of FeB N (N ≤ 15) clusters have been investigated by generalized gradient approximation (GGA) of density functional theory at different spin multiplicities. The average atomic binding energies, second-order energy differences and gaps of ground-state structures are calculated and discussed. The results show that FeB 3 , FeB 8 , FeB 12 and FeB 14 possess relatively higher stabilities. Moreover, there is a distinct hybridization between the d orbital of Fe and the p orbital of B for the ground-state cluster. The total magnetic moment for groundstate cluster is mainly provided by 3 d orbital of Fe atom, and exhibits the odd-even oscillation tendency with the increasing of cluster size. (authors)

  9. Determination of spectral, structural and energetic properties of small lithium clusters, within the density functional theory formalism

    International Nuclear Information System (INIS)

    Gardet, G.

    1995-01-01

    A systematic study of small lithium clusters (with size less than 19), within the Density Functional Theory (DFT) formalism is presented. We examine structural properties of the so called local level of approximation. For clusters with size smaller than 8, the conformations are well known from ab initio calculations and are found here at much lower computational cost, with only small differences. For bigger clusters, two growth pattern have been used, based upon the increase of the number of pentagonal subunits in the clusters by absorption of one or two Li atoms. Several new stable structures are proposed. Then DFT gradient-corrected functionals have been used for relative stability determination of these clusters. Ionisation potentials and binding energies are also investigated in regard to clusters size and geometry. Calculations of excited states of lithium clusters (with size less than 9) have been performed within two different approaches. Using a set of Kohn-Sham orbitals to construct wave functions, oscillator strengths calculation of the electric dipole transitions is performed. Transition energies, oscillator strengths and optical absorption presented here are generally in reasonable agreement with the experimental data and the Configuration Interaction calculations. (author)

  10. Time-of-flight secondary ion mass spectrometry with energetic cluster ion impact ionization for highly sensitive chemical structure characterization

    Energy Technology Data Exchange (ETDEWEB)

    Hirata, K., E-mail: k.hirata@aist.go.jp [National Metrology Institute of Japan, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565 (Japan); Saitoh, Y.; Chiba, A.; Yamada, K.; Narumi, K. [Takasaki Advanced Radiation Research Institute (TARRI), Japan Atomic Energy Agency (JAEA), Takasaki, Gumma 370-1292 (Japan)

    2013-11-01

    Energetic cluster ions with energies of the order of sub MeV or greater were applied to time-of-flight (TOF) secondary ion (SI) mass spectrometry. This gave various advantages including enhancement of SIs required for chemical structure characterization and prevention of charging effects in SI mass spectra for organic targets. We report some characteristic features of TOF SI mass spectrometry using energetic cluster ion impact ionization and discuss two future applications of it.

  11. Structures and energetics of hydrated deprotonated cis-pinonic acid anion clusters and their atmospheric relevance

    Energy Technology Data Exchange (ETDEWEB)

    Hou, Gao-Lei; Zhang, Jun; Valiev, Marat; Wang, Xue-Bin

    2017-01-01

    Pinonic acid, a C10-monocarboxylic acid with a hydrophilic –CO2H group and a hydrophobic hydrocarbon backbone, is a key intermediate oxidation product of α-pinene – an important monoterpene compound in biogenic emission processes that influences the atmosphere. Molecular interaction between cis-pinonic acid and water is essential for understanding its role in the formation and growth of pinene-derived secondary organic aerosols. In this work, we studied the structures, energetics, and optical properties of hydrated clusters of cis-pinonate anion (cPA–), the deprotonated form of cis-pinonic acid, by negative ion photoelectron spectroscopy and ab initio theoretical calculations. Our results show that cPA– can adopt two different structural configurations – open and folded. In the absence of waters, the open configuration has the lowest energy and provides the best agreement with the experiment. The addition waters, which mainly interact with the negatively charged -CO2– group, gradually stabilize the folded configuration and lower its energy difference relative to the most stable open-configured structure. Thermochemical and equilibrium hydrate distribution analysis suggests that the mono- and di- hydrates are likely to exist in humid atmospheric environment with high populations. The detailed molecular description of cPA– hydrated clusters unraveled in this study provides a valuable reference for understanding the initial nucleation process and aerosol formation involving organics containing both hydrophilic and hydrophobic groups, as well as for analyzing the optical properties of those organic aerosols.

  12. Structural integrity of rod cluster control assembly of Chashma Nuclear Power Plant -1

    International Nuclear Information System (INIS)

    Siddiqui, A.; Zafar, F.; Murtaza, G.

    2008-01-01

    This study has been made in an attempt to verify the structural integrity of Rod Cluster Control Assembly (RCCA) of Chashma Nuclear Power Plant-1(CHASNUPP-1) using ANSYS computer code. The CHASNUPP-1 (PWR type, 300 MWe capacity, unit 1) was built by China at Chashma (District Mianwali), Pakistan. The plant is successfully operating since 2000. The rod cluster control assemblies (RCCA) are used to control fast reactivity changes in PWR type reactors during the normal operation and accident conditions. To fulfill this function the RCCA is stepped upwards or downwards by control rod drive mechanism (CRDM). The stepping action produces a large amount of acceleration. The load produced during stepping is normally considered as limiting one. In this work we have considered the experimental results of a test conducted in China. The test was performed to measure the acceleration produced in upward and downward stepping by CRDM on RCCA, at room temperatures, both in air and static water. The test results showed acceleration (g, m/s 2 ) values, 10.8 - 51.0 and 46.4 - 78.0, in air and static water environments, respectively. Making the analysis on conservative side we selected the highest value of acceleration, 78 g, for our study. To ensure the structural strength, a finite element model of CHASNUPP-1 RCCA has been developed simulating the loading conditions prevailing during reactor operation. This model has been analyzed using the Finite Element Code. The Maximum Stress intensity obtained through this analysis, 186 MPa, is less than the yield stress of RCCA material (∼SS 321), 205 MPa, thus fulfills its structural integrity criteria. (authors)

  13. Radiation chemistry

    International Nuclear Information System (INIS)

    Rodgers, F.; Rodgers, M.A.

    1987-01-01

    The contents of this book include: Interaction of ionizing radiation with matter; Primary products in radiation chemistry; Theoretical aspects of radiation chemistry; Theories of the solvated electron; The radiation chemistry of gases; Radiation chemistry of colloidal aggregates; Radiation chemistry of the alkali halides; Radiation chemistry of polymers; Radiation chemistry of biopolymers; Radiation processing and sterilization; and Compound index

  14. Coherent structures at ion scales in fast and slow solar wind: Cluster observations

    Science.gov (United States)

    Perrone, D.; Alexandrova, O.; Zouganelis, Y.; Roberts, O.; Lion, S.; Escoubet, C. P.; Walsh, A. P.; Maksimovic, M.; Lacombe, C.

    2017-12-01

    Spacecraft measurements generally reveal that solar wind electromagnetic fluctuations are in a state of fully-developed turbulence. Turbulence represents a very complex problem in plasmas since cross-scale coupling and kinetic effects are present. Moreover, the intermittency phenomenon, i.e. the manifestation of the non-uniform and inhomogeneous energy transfer and dissipation in a turbulent system, represents a very important aspect of the solar wind turbulent cascade. Here, we study coherent structures responsible for solar wind intermittency around ion characteristic scales. We find that, in fast solar wind, intermittency is due to Alfvén vortex-like structures and current sheets. In slow solar wind, we observe as well compressive structures like magnetic solitons, holes and shocks. By using high-time resolution magnetic field data of multi-point measurements of Cluster spacecraft, we characterize the observed coherent structures in terms of topology and propagation speed. We show that all structures around ion characteristic scales, both in fast and slow solar wind, are characterized by a strong wave-vector anisotropy in the perpendicular direction with respect to the local magnetic field. Moreover, some of them propagate in the plasma rest frame in the direction perpendicular to the local field. Finally, a further analysis on the electron and ion velocity distributions shows a high variability; in particular, close to coherent structures the electron and ion distribution functions appear strongly deformed and far from the thermodynamic equilibrium. Possible interpretations of the observed structures and their role in the heating process of the plasma are also discussed.

  15. Spin-driven structural effects in alkali doped (4)He clusters from quantum calculations.

    Science.gov (United States)

    Bovino, S; Coccia, E; Bodo, E; Lopez-Durán, D; Gianturco, F A

    2009-06-14

    In this paper, we carry out variational Monte Carlo and diffusion Monte Carlo (DMC) calculations for Li(2)((1)Sigma(g) (+))((4)He)(N) and Li(2)((3)Sigma(u) (+))((4)He)(N) with N up to 30 and discuss in detail the results of our computations. After a comparison between our DMC energies with the "exact" discrete variable representation values for the species with one (4)He, in order to test the quality of our computations at 0 K, we analyze the structural features of the whole range of doped clusters. We find that both species reside on the droplet surface, but that their orientation is spin driven, i.e., the singlet molecule is perpendicular and the triplet one is parallel to the droplet's surface. We have also computed quantum vibrational relaxation rates for both dimers in collision with a single (4)He and we find them to differ by orders of magnitude at the estimated surface temperature. Our results therefore confirm the findings from a great number of experimental data present in the current literature and provide one of the first attempts at giving an accurate, fully quantum picture for the nanoscopic properties of alkali dimers in (4)He clusters.

  16. Fermi liquid, clustering, and structure factor in dilute warm nuclear matter

    Science.gov (United States)

    Röpke, G.; Voskresensky, D. N.; Kryukov, I. A.; Blaschke, D.

    2018-02-01

    Properties of nuclear systems at subsaturation densities can be obtained from different approaches. We demonstrate the use of the density autocorrelation function which is related to the isothermal compressibility and, after integration, to the equation of state. This way we connect the Landau Fermi liquid theory well elaborated in nuclear physics with the approaches to dilute nuclear matter describing cluster formation. A quantum statistical approach is presented, based on the cluster decomposition of the polarization function. The fundamental quantity to be calculated is the dynamic structure factor. Comparing with the Landau Fermi liquid theory which is reproduced in lowest approximation, the account of bound state formation and continuum correlations gives the correct low-density result as described by the second virial coefficient and by the mass action law (nuclear statistical equilibrium). Going to higher densities, the inclusion of medium effects is more involved compared with other quantum statistical approaches, but the relation to the Landau Fermi liquid theory gives a promising approach to describe not only thermodynamic but also collective excitations and non-equilibrium properties of nuclear systems in a wide region of the phase diagram.

  17. Characterization of Radiation-Induced Clustering using Atom Probe Tomography in Nuclear Structural Materials

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Gyeong Geun; Lim, Sang Yeob; Chang, Kun Ok; Ha, Jin Hyung; Kwon, Jun Hyun [KAERI, Daejeon (Korea, Republic of)

    2016-05-15

    The degradations include the change in mechanical properties, which are related to the microstructure evolution caused by irradiation. The most widely used tool for the imaging irradiated microstructure is transmission electron microscopy (TEM). The composition of irradiation defects can be analyzed using X-ray spectroscopy (EDS) equipped in the TEM. However, composition characterization of the nano-sized irradiation defects in the matrix is limited due to the beam broadening of TEM and the overlapping of the probed volume during EDS analysis. Recently, Atom probe tomography (APT) has been introduced to the characterization of irradiation defects. APT provides sub-nano scale position of atoms and the chemical composition of a selected volume. SS316 irradiated with Fe ions at above 300 .deg. C caused significant clustering and segregation of Si and Ni at defect sinks. The neutron irradiated low alloy steel showed similar clustering of Ni and Si. The approach of using APT was demonstrated to be well suited for discovering the structure of irradiation defects and performing quantitative analysis in nuclear materials irradiated at high temperature.

  18. Surface self-diffusion of adatom on Pt cluster with truncated octahedron structure

    Energy Technology Data Exchange (ETDEWEB)

    Yang Jianyu, E-mail: wuliyangjianyu@yahoo.com.c [Department of Maths and Physics, Hunan Institute of Engineering, Xiangtan 411104 (China); Hu Wangyu, E-mail: wangyuhu2001@yahoo.com.c [Department of Applied Physics, Hunan University, Changsha 410082 (China); Chen Shuguang [Department of Applied Physics, Hunan University, Changsha 410082 (China)

    2010-05-03

    Surface diffusion of single Pt adatom on Pt cluster with truncated octahedron structure is investigated through a combination of molecular dynamics and nudged elastic band method. Using an embedded atom method to describe the atomic interactions, the minimum energy paths are determined and the energy barriers for adatom diffusion across and along step are evaluated. The diffusion of adatom crossing step edge between {l_brace}111{r_brace} and {l_brace}100{r_brace} facets has a surprisingly low barrier of 0.03 eV, which is 0.12 eV lower than the barrier for adatom diffusion from {l_brace}111{r_brace} to neighboring {l_brace}111{r_brace} facet. Owing to the small barrier of adatom diffusion across the step edge between {l_brace}111{r_brace} and {l_brace}100{r_brace} facets, the diffusion of adatom along the step edge cannot occur. The molecular dynamics simulations at low temperatures also support these results. Our results show that mass transport will prefer step with {l_brace}100{r_brace} microfacet and the Pt clusters can have only {l_brace}111{r_brace} facets in epitaxial growth.

  19. The multi-scattering-Xα method for analysis of the electronic structure of atomic clusters

    International Nuclear Information System (INIS)

    Bahurmuz, A.A.; Woo, C.H.

    1984-12-01

    A computer program, MSXALPHA, has been developed to carry out a quantum-mechanical analysis of the electronic structure of molecules and atomic clusters using the Multi-Scattering-Xα (MSXα) method. The MSXALPHA program is based on a code obtained from the University of Alberta; several improvements and new features were incorporated to increase generality and efficiency. The major ones are: (1) minimization of core memory usage, (2) reduction of execution time, (3) introduction of a dynamic core allocation scheme for a large number of arrays, (4) incorporation of an atomic program to generate numerical orbitals used to construct the initial molecular potential, and (5) inclusion of a routine to evaluate total energy. This report is divided into three parts. The first discusses the theory of the MSXα method. The second gives a detailed description of the program, MSXALPHA. The third discusses the results of calculations carried out for the methane molecule (CH 4 ) and a four-atom zirconium cluster (Zr 4 )

  20. Cluster Interaction of Enterprise Structures in Housing Sector of Municipalities in Ensuring Improvement of Territories

    Directory of Open Access Journals (Sweden)

    Nedelin Mikhail, D.

    2016-03-01

    Full Text Available The process of modernization and greening of business activity is considered in the paper. This process requires in terms of the development dynamics of Russian regions, the implementation of directed towards the modern transformation of the municipal infrastructure in the region, which allows to transform the reform processes on different objects to achieve well-being in the Russian regions from the perspective of state interests, business and civil society. The effective direction for the modernization of the system to ensure the regional social-economic development is the creation of our proposed mechanism of cluster interaction of state and business structures in the sphere of housing and communal services of municipalities. Therefore, in this study, an analysis of the directions of state support for the development of cluster cooperation in the sphere of housing and communal services of municipalities, aimed at achieving a multiplier effect, in the exercise of entrepreneurial activity in the region socially significant areas, in particular - in the landscaping and planting areas is carried out.

  1. Mirror structures above and below the linear instability threshold: Cluster observations, fluid model and hybrid simulations

    Directory of Open Access Journals (Sweden)

    V. Génot

    2009-02-01

    Full Text Available Using 5 years of Cluster data, we present a detailed statistical analysis of magnetic fluctuations associated with mirror structures in the magnetosheath. We especially focus on the shape of these fluctuations which, in addition to quasi-sinusoidal forms, also display deep holes and high peaks. The occurrence frequency and the most probable location of the various types of structures is discussed, together with their relation to local plasma parameters. While these properties have previously been correlated to the β of the plasma, we emphasize here the influence of the distance to the linear mirror instability threshold. This enables us to interpret the observations of mirror structures in a stable plasma in terms of bistability and subcritical bifurcation. The data analysis is supplemented by the prediction of a quasi-static anisotropic MHD model and hybrid numerical simulations in an expanding box aimed at mimicking the magnetosheath plasma. This leads us to suggest a scenario for the formation and evolution of mirror structures.

  2. Cluster magnetic field observations in the magnetosheath: four-point measurements of mirror structures

    Directory of Open Access Journals (Sweden)

    E. A. Lucek

    2001-09-01

    Full Text Available The Cluster spacecraft have returned the first simultaneous four-point measurements of the magnetosheath. We present an analysis of data recorded on 10 November 2000, when the four spacecrafts observed an interval of strong mirrorlike activity. Correlation analysis between spacecraft pairs is used to examine the scale size of the mirror structures in three dimensions. Two examples are presented which suggest that the scale size of mirror structures is ~ 1500–3000 km along the flow direction, and shortest along the magnetopause normal (< 600 km, which, in this case, is approximately perpendicular to both the mean magnetic field and the magnetosheath flow vector. Variations on scales of ~ 750–1000 km are found along the maximum variance direction. The level of correlation in this direction, however, and the time lag observed, are found to be variable. These first results suggest that variations occur on scales of the order of the spacecraft separation ( ~ 1000 km in at least two directions, but analysis of further examples and a statistical survey of structures observed with different magnetic field orientations and tetrahedral configurations will enable us to describe more fully the size and orientation of mirror structures.Key words. Magnetosphenic physics (magnetosheath; plasma waves and instabilities

  3. Cluster magnetic field observations in the magnetosheath: four-point measurements of mirror structures

    Directory of Open Access Journals (Sweden)

    E. A. Lucek

    Full Text Available The Cluster spacecraft have returned the first simultaneous four-point measurements of the magnetosheath. We present an analysis of data recorded on 10 November 2000, when the four spacecrafts observed an interval of strong mirrorlike activity. Correlation analysis between spacecraft pairs is used to examine the scale size of the mirror structures in three dimensions. Two examples are presented which suggest that the scale size of mirror structures is ~ 1500–3000 km along the flow direction, and shortest along the magnetopause normal (< 600 km, which, in this case, is approximately perpendicular to both the mean magnetic field and the magnetosheath flow vector. Variations on scales of ~ 750–1000 km are found along the maximum variance direction. The level of correlation in this direction, however, and the time lag observed, are found to be variable. These first results suggest that variations occur on scales of the order of the spacecraft separation ( ~ 1000 km in at least two directions, but analysis of further examples and a statistical survey of structures observed with different magnetic field orientations and tetrahedral configurations will enable us to describe more fully the size and orientation of mirror structures.

    Key words. Magnetosphenic physics (magnetosheath; plasma waves and instabilities

  4. Multistep continuous-flow synthesis in medicinal chemistry: discovery and preliminary structure-activity relationships of CCR8 ligands.

    Science.gov (United States)

    Petersen, Trine P; Mirsharghi, Sahar; Rummel, Pia C; Thiele, Stefanie; Rosenkilde, Mette M; Ritzén, Andreas; Ulven, Trond

    2013-07-08

    A three-step continuous-flow synthesis system and its application to the assembly of a new series of chemokine receptor ligands directly from commercial building blocks is reported. No scavenger columns or solvent switches are necessary to recover the desired test compounds, which were obtained in overall yields of 49-94%. The system is modular and flexible, and the individual steps of the sequence can be interchanged with similar outcome, extending the scope of the chemistry. Biological evaluation confirmed activity on the chemokine CCR8 receptor and provided initial structure-activity-relationship (SAR) information for this new ligand series, with the most potent member displaying full agonist activity with single-digit nanomolar potency. To the best of our knowledge, this represents the first published example of efficient use of multistep flow synthesis combined with biological testing and SAR studies in medicinal chemistry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  5. Study of Chemistry and Structure-Property Relationship on Tunable Plasmonic Nanostructures

    Science.gov (United States)

    Jing, Hao

    In this dissertation, the rational design and controllable fabrication of an array of novel plasmonic nanostructures with geometrically tunable optical properties are demonstrated, including metal-semiconductor hybrid hetero-nanoparticles, bimetallic noble metal nanoparticles and hollow nanostructures (nanobox and nanocage). Firstly, I have developed a robust wet chemistry approach to the geometry control of Ag-Cu2O core-shell nanoparticles through epitaxial growth of Cu2O nanoshells on the surfaces of various Ag nanostructures, such as quasi-spherical nanoparticles, nanocubes, and nanocuboids. Precise control over the core and the shell geometries enables me to develop detailed, quantitative understanding of how the Cu2O nanoshells introduce interesting modifications to the resonance frequencies and the extinction spectral line shapes of multiple plasmon modes of the Ag cores. Secondly, I present a detailed and systematic study of the controlled overgrowth of Pd on Au nanorods. The overgrowth of Pd nanoshells with fine-controlled dimensions and architectures on single-crystalline Au nanorods through seed-mediated growth protocol in the presence of various surfactants is investigated. Thirdly, I have demonstrated that creation of high-index facets on subwavelength metallic nanoparticles provides a unique approach to the integration of desired plasmonic and catalytic properties on the same nanoparticle. Through site-selective surface etching of metallic nanocuboids whose surfaces are dominated by low-index facets, I have controllably fabricated nanorice and nanodumbbell particles, which exhibit drastically enhanced catalytic activities arising from the catalytically active high index facets abundant on the particle surfaces. And the nanorice and nanodumbbell particles also possess appealing tunable plasmonic properties that allow us to gain quantitative insights into nanoparticle-catalyzed reactions with unprecedented sensitivity and detail through time

  6. Synthesis and structure of bivalent ytterbocenes and their coordination chemistry with pi-acceptor ligands

    Energy Technology Data Exchange (ETDEWEB)

    Schultz, Madeleine [Univ. of California, Berkeley, CA (United States)

    2000-05-01

    The bivalent lanthanide metallocenes [1,3-(Me3C)2C5H3]2Yb and (Me4C5H)2Yb have been synthesized and their structures have been determined by X-ray crystallography. Comparison with the known structures of (Me5C5)2Yb and [1,3 -(Me3Si)2C5H3]2Yb leads to an understanding of the role of intermolecular contacts in stabilizing these coordinatively unsaturated molecules. The optical spectra of the base-free ytterbocenes and their Lewis-base adducts have been measured; the position of the HOMO - LUMO transition can be correlated with the degree of bending of the complexes in solution according to a molecular orbital model. Electron - electron repulsion, resulting from additional σ-donor ligands, also affects the HOMO - LUMO transition by increasing the energy of the filled f-orbitals. The base-free metallocene (Me5C5)2Yb coordinates carbon monoxide, resulting in a decrease in Vco relative to that of fi-ee carbon monoxide. This behavior is reminiscent of d-transition metallocene chemistry. Other base-free ytterbocenes also coordinate carbon monoxide and the degree of back-donation is related to the substituents on the cyclopentadienide rings. Isocyanides are coordinated in a 1:2 ratio by the ytterbocenes, giving complexes having vcN higher than those of the free isocyanides. An electrostatic bonding model has been used to explain the changes in CN stretching frequencies. The optical spectra of the carbonyl and isocyanide complexes are consistent with the molecular orbital model of the variation in the HOMO - LUMO gap upon bending, and the increase in electron - electron repulsion due to the additional ligands. The complex (Me5C5)2Yb(bipy) exhibits optical, infrared and NMIZ spectroscopy and an X-ray crystal

  7. The Effects of Cognitive Structure Variables on Achievement in College Chemistry

    Science.gov (United States)

    Ring, Donald G.; Novak, Joseph D.

    1971-01-01

    College freshmen chemistry students who performed best on the course examinations possessed both relevant facts and relevant subsuming concepts. This conclusion supports Ausubel's theory of learning. The presence of facts unorganized by subsumers had little facilitating effect on learning of new materials. (AL)

  8. Leg tendon glands in male bumblebees (Bombus terrestris): structure, secretion chemistry, and possible functions

    Czech Academy of Sciences Publication Activity Database

    Jarau, S.; Žáček, Petr; Šobotník, Jan; Vrkoslav, Vladimír; Hadravová, Romana; Coppée, Audrey; Vašíčková, Soňa; Jiroš, Pavel; Valterová, Irena

    2012-01-01

    Roč. 99, č. 12 (2012), s. 1039-1049 ISSN 0028-1042 R&D Projects: GA TA ČR TA01020969 Institutional support: RVO:61388963 Keywords : bumblebee * hydrocarbons * leg tendon glands * sex specific secretion * wax esters Subject RIV: CC - Organic Chemistry Impact factor: 2.144, year: 2012

  9. Constraints on a possible variation of the fine structure constant from galaxy cluster data

    Energy Technology Data Exchange (ETDEWEB)

    Holanda, R.F.L. [Departamento de Física, Universidade Estadual da Paraíba, 58429-500, Campina Grande – PB (Brazil); Landau, S.J.; Sánchez G, I.E. [Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, and IFIBA, CONICET, Ciudad Universitaria – PabI, Buenos Aires 1428 (Argentina); Alcaniz, J.S. [Departamento de Astronomia, Observatório Nacional, 20921-400, Rio de Janeiro – RJ (Brazil); Busti, V.C., E-mail: holanda@uepb.edu.br, E-mail: slandau@df.uba.ar, E-mail: alcaniz@on.br, E-mail: isg.cos@gmail.com, E-mail: vinicius.busti@astro.iag.usp.br [Departamento de Física Matemática, Instituto de Física, Universidade de São Paulo, CP 66318, 05508-090, São Paulo – SP (Brazil)

    2016-05-01

    We propose a new method to probe a possible time evolution of the fine structure constant α from X-ray and Sunyaev-Zel'dovich measurements of the gas mass fraction ( f {sub gas}) in galaxy clusters. Taking into account a direct relation between variations of α and violations of the distance-duality relation, we discuss constraints on α for a class of dilaton runaway models. Although not yet competitive with bounds from high- z quasar absorption systems, our constraints, considering a sample of 29 measurements of f {sub gas}, in the redshift interval 0.14 < z < 0.89, provide an independent estimate of α variation at low and intermediate redshifts. Furthermore, current and planned surveys will provide a larger amount of data and thus allow to improve the limits on α variation obtained in the present analysis.

  10. A Novel Coordination Polymer Based on Trinuclear Cobalt Building Blocks Cluster: Synthesis, Crystal Structure, and Properties

    Science.gov (United States)

    Lu, J. F.; Tang, Z. H.; Shi, J.; Ge, H. G.; Jiang, M.; Song, J.; Jin, L. X.

    2017-12-01

    The title compound {[Co3(μ3-OH)(μ2-H2O)2(H2O)5(BTC)2] · 6H2O} n (H3BTC is a 1,3,5-benzenetricarboxylic acid) was prepared and characterized by single crystal and powder X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric and elemental analyses. The single crystal X-ray diffraction reveals that the title compound consists of 1D infinite zigzag chains which were constructed by trinuclear cobalt cluster and BTC3- ligand. Neighbouring above-mentioned 1D infinite zigzag chains are further linked by intermolecular hydrogen bonding to form a 3D supermolecular structure. In addition, the luminescent properties of the title compound were investigated.

  11. Electric potential structures of auroral acceleration region border from multi-spacecraft Cluster data

    Science.gov (United States)

    Sadeghi, S.; Emami, M. R.

    2018-04-01

    This paper studies an auroral event using data from three spacecraft of the Cluster mission, one inside and two at the poleward edge of the bottom of the Auroral Acceleration Region (AAR). The study reveals the three-dimensional profile of the region's poleward boundary, showing spatial segmentation of the electric potential structures and their decay in time. It also depicts localized magnetic field variations and field-aligned currents that appear to have remained stable for at least 80 s. Such observations became possible due to the fortuitous motion of the three spacecraft nearly parallel to each other and tangential to the AAR edge, so that the differences and variations can be seen when the spacecraft enter and exit the segmentations, hence revealing their position with respect to the AAR.

  12. Structure and properties of molecular and ionic clusters in vapour over caesium fluoride

    Science.gov (United States)

    Mwanga, Stanley F.; Pogrebnaya, Tatiana P.; Pogrebnoi, Alexander M.

    2015-06-01

    The properties of neutral molecules Cs2F2, Cs3F3, and Cs4F4, and positive and negative cluster ions Cs2F+, CsF2-, Cs3F2+, Cs2F3-, Cs4F3+, and Cs5F4+ were studied by several of quantum chemical methods implementing density function theory and Möller-Plesset perturbation theory of second and fourth orders. For all species, the equilibrium geometrical structure and vibrational spectra were determined. Different isomers have been revealed for the trimer neutral molecule Cs3F3; pentaatomic, both positive and negative, Cs3F2+, Cs2F3-; and heptaatomic Cs4F3+ ions. The most abundant isomers in the saturated vapour were determined. Enthalpies of dissociation reactions and enthalpies of formation of the species were obtained.

  13. Dynamics of fragment capture for cluster structures of weakly bound 7Li

    Directory of Open Access Journals (Sweden)

    Shrivastava A.

    2013-12-01

    Full Text Available Role of cluster structures of 7Li on reaction dynamics have been studied by performing exclusive measurements of prompt-γ rays from residues with scattered particles at energy, E/Vb = 1.6, with 198Pt target. Yields of the residues resulting after capture of t and 4,5,6He, corresponding to different excitation energies of the composite system were estimated. The results were compared with three body classical-dynamical model for breakup fusion, constrained by the measured fusion, α and t capture cross-sections. The cross-section of residues from capture of α and t agreed well with the prediction of the model showing dominance of the two step process - breakup fusion, while those from tightly bound 6He showed massive transfer to be the dominant mechanism.

  14. Electron-Poor Polar Intermetallics: Complex Structures, Novel Clusters, and Intriguing Bonding with Pronounced Electron Delocalization.

    Science.gov (United States)

    Lin, Qisheng; Miller, Gordon J

    2018-01-16

    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.

  15. THE GEMINI/HST CLUSTER PROJECT: STRUCTURAL AND PHOTOMETRIC PROPERTIES OF GALAXIES IN THREE z = 0.28-0.89 CLUSTERS

    International Nuclear Information System (INIS)

    Chiboucas, Kristin; Joergensen, Inger; Barr, Jordi; Collobert, Maela; Davies, Roger; Flint, Kathleen

    2009-01-01

    We present the data processing and analysis techniques we are using to determine the structural and photometric properties of galaxies in our Gemini/HST Galaxy Cluster Project sample. The goal of this study is to understand cluster galaxy evolution in terms of scaling relations and structural properties of cluster galaxies at redshifts 0.15 1/4 law and Sersic function two-dimensional surface brightness profiles to each of the galaxies in our sample. Using simulated galaxies, we test how the assumed profile affects the derived parameters and how the uncertainties affect our Fundamental Plane results. We find that while fitting galaxies that have Sersic index n 1/4 law profiles systematically overestimates the galaxy radius and flux, the combination of profile parameters that enter the Fundamental Plane has uncertainties that are small. Average systematic offsets and associated random uncertainties in magnitude and log r e for n>2 galaxies fitted with r 1/4 law profiles are -0.1 ± 0.3 and 0.1 ± 0.2, respectively. The combination of effective radius and surface brightness, log r e - βlog (I) e , that enters the Fundamental Plane produces offsets smaller than -0.02 ± 0.10. This systematic error is insignificant and independent of galaxy magnitude or size. A catalog of photometry and surface brightness profile parameters is presented for three of the clusters in our sample, RX J0142.0+2131, RX J0152.7-1357, and RX J1226.9+3332 at redshifts 0.28, 0.83, and 0.89, respectively.

  16. NUCORE - A system for nuclear structure calculations with cluster-core models

    International Nuclear Information System (INIS)

    Heras, C.A.; Abecasis, S.M.

    1982-01-01

    Calculation of nuclear energy levels and their electromagnetic properties, modelling the nucleus as a cluster of a few particles and/or holes interacting with a core which in turn is modelled as a quadrupole vibrator (cluster-phonon model). The members of the cluster interact via quadrupole-quadrupole and pairing forces. (orig.)

  17. Structures, energetics and magnetic properties of (NiSn) n clusters ...

    Indian Academy of Sciences (India)

    The preference for tetrahedron unit of Ni3 Sn is seen in the lowest-energy configuration of these clusters. The multi-centre bonding between Ni atoms play an important role in stabilizing the stoichiometric Ni–Sn clusters. Doping of Sn atoms enhances the binding energy and reduces the ionization potential of nickel clusters.

  18. Where Water is Oxidized to Dioxygen: Structure of the Photosynthetic Mn4Ca Cluster from X-ray Spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Yano, Junko; Yano, Junko; Yachandra, Vittal K.

    2007-10-24

    Light-driven oxidation of water to dioxygen in plants, algae and cyanobacteria iscatalyzed within photosystem II (PS II) by a Mn4Ca cluster. Although the cluster has been studied by many different methods, the structure and the mechanism have remained elusive. X-ray absorption and emission spectroscopy and EXAFS studies have been particularly useful in probing the electronic and geometric structure, and the mechanism of the water oxidation reaction. Recent progress, reviewed here, includes polarized X-ray absorption spectroscopy measurements of PS II single crystals. Analysis of those results has constrained the Mn4Ca cluster geometry to a setof three similar high-resolution structures. The structure of the cluster from the present study is unlike either the 3.0 or 3.5 Angstrom-resolution X-ray structures or other previously proposed models. The differences between the models derived from X-rayspectroscopy and crystallography are predominantly because of damage to the Mn4Ca cluster by X-rays under the conditions used for structure determination by X-ray crystallography. X-ray spectroscopy studies are also used for studying the changes in the structure of the Mn4Ca catalytic center as it cycles through the five intermediate states known as the Si-states (i=0-4). The electronic structure of the Mn4Ca cluster has been studied more recently using resonant inelastic X-ray scattering spectroscopy (RIXS), in addition to the earlier X-ray absorption and emission spectroscopy methods. These studies are revealing that the assignment of formaloxidation states is overly simplistic. A more accurate description should consider the charge density on the Mn atoms that includes the covalency of the bonds and delocalization of the charge over the cluster. The geometric and electronic structure of the Mn4Ca cluster in the S-states derived from X-ray spectroscopy are leading to a detailed understanding of the mechanism of the O-O bond formation during the photosynthetic water

  19. Catastrophe Bonds. From Structure to Strategy – A Cluster Analysis at European Level

    Directory of Open Access Journals (Sweden)

    Laura-Gabriela CONSTANTIN

    2014-12-01

    Full Text Available As a core activity and discipline of corporate management and corporate governance, risk management is, especially nowadays, a central part in pursuing the sustainable development desiderates, both from the perspective of the firm and of the society as a whole.Considering the negative impact natural catastrophes have on the companies’ and countries’ competitiveness, the development of sustainable financial products that make a contribution to transferring the risk and allocating the capital in case of disasters stands for a continual preoccupation, especially for the (reinsurance industry, while the study of catastrophe bonds – insurance-linked securities – is of interest in the specialized literature. In this context, the scope of the present research is to expand the empirical studies within this field while examining the link between the structure of the catastrophe bonds and the risk management approach employed while accessing the capital markets through this transactions.The methodology entailed clustering a selection of transactions developed by European cedents based on the size of each issue and correlating the results with an innovative score, developed to encompass several important catastrophe bonds structural components.The findings reflect that the general structural elements of the financial transactions reflect closely the corporate approach regarding the innovative risk intermediation instruments for the examined catastrophe bonds deals. The outcomes also emphasize, as expected, that companies with a stronger presence on this market seem to have a more sophisticated risk management approach.

  20. Structural studies of the Enterococcus faecalis SufU [Fe-S] cluster protein

    Directory of Open Access Journals (Sweden)

    Frazzon Jeverson

    2009-02-01

    Full Text Available Abstract Background Iron-sulfur clusters are ubiquitous and evolutionarily ancient inorganic prosthetic groups, the biosynthesis of which depends on complex protein machineries. Three distinct assembly systems involved in the maturation of cellular Fe-S proteins have been determined, designated the NIF, ISC and SUF systems. Although well described in several organisms, these machineries are poorly understood in Gram-positive bacteria. Within the Firmicutes phylum, the Enterococcus spp. genus have recently assumed importance in clinical microbiology being considered as emerging pathogens for humans, wherein Enterococcus faecalis represents the major species associated with nosocomial infections. The aim of this study was to carry out a phylogenetic analysis in Enterococcus faecalis V583 and a structural and conformational characterisation of it SufU protein. Results BLAST searches of the Enterococcus genome revealed a series of genes with sequence similarity to the Escherichia coli SUF machinery of [Fe-S] cluster biosynthesis, namely sufB, sufC, sufD and SufS. In addition, the E. coli IscU ortholog SufU was found to be the scaffold protein of Enterococcus spp., containing all features considered essential for its biological activity, including conserved amino acid residues involved in substrate and/or co-factor binding (Cys50,76,138 and Asp52 and, phylogenetic analyses showed a close relationship with orthologues from other Gram-positive bacteria. Molecular dynamics for structural determinations and molecular modeling using E. faecalis SufU primary sequence protein over the PDB:1su0 crystallographic model from Streptococcus pyogenes were carried out with a subsequent 50 ns molecular dynamic trajectory. This presented a stable model, showing secondary structure modifications near the active site and conserved cysteine residues. Molecular modeling using Haemophilus influenzae IscU primary sequence over the PDB:1su0 crystal followed by a MD