Understanding the evolution of luminescent gold quantum clusters in protein templates.

PubMed

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

2011-11-22

We show that the time-dependent biomineralization of Au(3+) by native lactoferrin (NLf) and bovine serum albumin (BSA) resulting in near-infrared (NIR) luminescent gold quantum clusters (QCs) occurs through a protein-bound Au(1+) intermediate and subsequent emergence of free protein. The evolution was probed by diverse tools, principally, using matrix-assisted laser desorption ionization mass spectrometry (MALDI MS), X-ray photoelectron spectroscopy (XPS), and photoluminescence spectroscopy (PL). The importance of alkaline pH in the formation of clusters was probed. At neutral pH, a Au(1+)-protein complex was formed (starting from Au(3+)) with the binding of 13-14 gold atoms per protein. When the pH was increased above 12, these bound gold ions were further reduced to Au(0) and nucleation and growth of cluster commenced, which was corroborated by the beginning of emission; at this point, the number of gold atoms per protein was ~25, suggesting the formation of Au(25). During the cluster evolution, at certain time intervals, for specific molar ratios of gold and protein, occurrence of free protein was noticed in the mass spectra, suggesting a mixture of products and gold ion redistribution. By providing gold ions at specific time of the reaction, monodispersed clusters with enhanced luminescence could be obtained, and the available quantity of free protein could be utilized efficiently. Monodispersed clusters would be useful in obtaining single crystals of protein-protected noble metal quantum clusters where homogeneity of the system is of primary concern. © 2011 American Chemical Society

Properties of the gold-sulphur interface: from self-assembled monolayers to clusters

NASA Astrophysics Data System (ADS)

Bürgi, Thomas

2015-09-01

The gold-sulphur interface of self-assembled monolayers (SAMs) was extensively studied some time ago. More recently tremendous progress has been made in the preparation and characterization of thiolate-protected gold clusters. In this feature article we address different properties of the two systems such as their structure, the mobility of the thiolates on the surface and other dynamical aspects, the chirality of the structures and characteristics related to it and their vibrational properties. SAMs and clusters are in the focus of different communities that typically use different experimental approaches to study the respective systems. However, it seems that the nature of the Au-S interfaces in the two cases is quite similar. Recent single crystal X-ray structures of thiolate-protected gold clusters reveal staple motifs characterized by gold ad-atoms sandwiched between two sulphur atoms. This finding contradicts older work on SAMs. However, newer studies on SAMs also reveal ad-atoms. Whether this finding can be generalized remains to be shown. In any case, more and more studies highlight the dynamic nature of the Au-S interface, both on flat surfaces and in clusters. At temperatures slightly above ambient thiolates migrate on the gold surface and on clusters. Evidence for desorption of thiolates at room temperature, at least under certain conditions, has been demonstrated for both systems. The adsorbed thiolate can lead to chirality at different lengths scales, which has been shown both on surfaces and for clusters. Chirality emerges from the organization of the thiolates as well as locally at the molecular level. Chirality can also be transferred from a chiral surface to an adsorbate, as evidenced by vibrational spectroscopy.

Properties of the gold-sulphur interface: from self-assembled monolayers to clusters.

PubMed

Bürgi, Thomas

2015-10-14

The gold-sulphur interface of self-assembled monolayers (SAMs) was extensively studied some time ago. More recently tremendous progress has been made in the preparation and characterization of thiolate-protected gold clusters. In this feature article we address different properties of the two systems such as their structure, the mobility of the thiolates on the surface and other dynamical aspects, the chirality of the structures and characteristics related to it and their vibrational properties. SAMs and clusters are in the focus of different communities that typically use different experimental approaches to study the respective systems. However, it seems that the nature of the Au-S interfaces in the two cases is quite similar. Recent single crystal X-ray structures of thiolate-protected gold clusters reveal staple motifs characterized by gold ad-atoms sandwiched between two sulphur atoms. This finding contradicts older work on SAMs. However, newer studies on SAMs also reveal ad-atoms. Whether this finding can be generalized remains to be shown. In any case, more and more studies highlight the dynamic nature of the Au-S interface, both on flat surfaces and in clusters. At temperatures slightly above ambient thiolates migrate on the gold surface and on clusters. Evidence for desorption of thiolates at room temperature, at least under certain conditions, has been demonstrated for both systems. The adsorbed thiolate can lead to chirality at different lengths scales, which has been shown both on surfaces and for clusters. Chirality emerges from the organization of the thiolates as well as locally at the molecular level. Chirality can also be transferred from a chiral surface to an adsorbate, as evidenced by vibrational spectroscopy.

Cyanide leaching of Au/CeO2: highly active gold clusters for 1,3-butadiene hydrogenation.

PubMed

Guan, Y; Hensen, E J M

2009-11-07

Ceria-supported gold catalysts before and after leaching by NaCN were investigated by X-ray absorption spectroscopy at the Au L(III) edge. After gold leaching, isolated gold cations remain in close interaction with the support. These ions form an ideal precursor to very small clusters of a few gold atoms upon reduction. The resulting gold clusters exhibit a very high intrinsic activity in the hydrogenation of 1,3-butadiene, which is at least one order of magnitude higher than that of the nanometre-sized gold particles in the non-leached parent catalyst. These findings point to a very strong structure sensitivity of the gold-catalyzed hydrogenation of dienes.

Tuning optical properties of magic number cluster (SiO2)4O2H4 by substitutional bonding with gold atoms.

PubMed

Cai, Xiulong; Zhang, Peng; Ma, Liuxue; Zhang, Wenxian; Ning, Xijing; Zhao, Li; Zhuang, Jun

2009-04-30

By bonding gold atoms to the magic number cluster (SiO(2))(4)O(2)H(4), two groups of Au-adsorbed shell-like clusters Au(n)(SiO(2))(4)O(2)H(4-n) (n = 1-4) and Au(n)(SiO(2))(4)O(2) (n = 5-8) were obtained, and their spectral properties were studied. The ground-state structures of these clusters were optimized by density functional theory, and the results show that in despite of the different numbers and types of the adsorbed Au atoms, the cluster core (SiO(2))(4)O(2) of T(d) point-group symmetry keeps almost unchanged. The absorption spectra were obtained by time-dependent density functional theory. From one group to the other, an extension of absorption wavelength from the UV-visible to the NIR region was observed, and in each group the absorption strengths vary linearly with the number of Au atoms. These features indicate their advantages for exploring novel materials with easily controlled tunable optical properties. Furthermore, due to the weak electronic charge transfer between the Au atoms, the clusters containing Au(2) dimers, especially Au(8)(SiO(2))(4)O(2), absorb strongly NIR light at 900 approximately 1200 nm. Such strong absorption suggests potential applications of these shell-like clusters in tumor cells thermal therapy, like the gold-coated silica nanoshells with larger sizes.

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

DTIC Science & Technology

1986-09-23

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

Ligand-free gold atom clusters adsorbed on graphene nano sheets generated by oxidative laser fragmentation in water

NASA Astrophysics Data System (ADS)

Lau, Marcus; Haxhiaj, Ina; Wagener, Philipp; Intartaglia, Romuald; Brandi, Fernando; Nakamura, Junji; Barcikowski, Stephan

2014-08-01

Over three decades after the first synthesis of stabilized Au55-clusters many scientific questions about gold cluster properties are still unsolved and ligand-free colloidal clusters are difficult to fabricate. Here we present a novel route to produce ultra-small gold particles by using a green technique, the laser ablation and fragmentation in water, without using reductive or stabilizing agents at any step of the synthesis. For fabrication only a pulsed laser, a gold-target, pure water, sodium hydroxide and hydrogen peroxide are deployed. The particles are exemplarily hybridized to graphene supports showing that these carbon-free colloidal clusters might serve as versatile building blocks.

Optimum Particle Size for Gold-Catalyzed CO Oxidation

PubMed Central

2018-01-01

The structure sensitivity of gold-catalyzed CO oxidation is presented by analyzing in detail the dependence of CO oxidation rate on particle size. Clusters with less than 14 gold atoms adopt a planar structure, whereas larger ones adopt a three-dimensional structure. The CO and O2 adsorption properties depend strongly on particle structure and size. All of the reaction barriers relevant to CO oxidation display linear scaling relationships with CO and O2 binding strengths as main reactivity descriptors. Planar and three-dimensional gold clusters exhibit different linear scaling relationship due to different surface topologies and different coordination numbers of the surface atoms. On the basis of these linear scaling relationships, first-principles microkinetics simulations were conducted to determine CO oxidation rates and possible rate-determining step of Au particles. Planar Au9 and three-dimensional Au79 clusters present the highest CO oxidation rates for planar and three-dimensional clusters, respectively. The planar Au9 cluster is much more active than the optimum Au79 cluster. A common feature of optimum CO oxidation performance is the intermediate binding strengths of CO and O2, resulting in intermediate coverages of CO, O2, and O. Both these optimum particles present lower performance than maximum Sabatier performance, indicating that there is sufficient room for improvement of gold catalysts for CO oxidation. PMID:29707098

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

NASA Astrophysics Data System (ADS)

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

2006-01-01

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

A grand unified model for liganded gold clusters

NASA Astrophysics Data System (ADS)

Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

2016-12-01

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three `flavours' (namely, bottom, middle and top) to represent three possible valence states. The `composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design.

Gd@Au15: A magic magnetic gold cluster for cancer therapy and bioimaging

NASA Astrophysics Data System (ADS)

Yadav, Brahm Deo; Kumar, Vijay

2010-09-01

We report from ab initio calculations a magic magnetic cage cluster of gold, Gd@Au15, obtained by doping of a Gd atom in gold clusters. It has a highest occupied molecular orbital-lowest unoccupied molecular orbital gap of 1.31 eV within the generalized gradient approximation that makes it a potential candidate for cancer therapy with an additional attractive feature that its large magnetic moment of 7 μB could be beneficial for magnetic resonance imaging.

A comprehensive study of catalytic, morphological and electronic properties of ligand-protected gold nanoclusters using XPS, STM, XAFS, and TPD techniques

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

Wu, Qiyuan; Cen, Jiajie; Zhao, Yue

Ultra-small gold nanoclusters were synthesized via a ligand exchange method and deposited onto different TiO2 supports to study their properties. STM imaging revealed that the as-synthesized gold nanoclusters had 2-D morphology consisting of monolayers of gold atoms. In conclusion, subsequent XPS, XAFS, and CO oxidation TPD results indicated that heat treatments of gold clusters at different temperatures significantly altered their electronic and catalytic properties due to ligand deprotection and cluster agglomeration.

A comprehensive study of catalytic, morphological and electronic properties of ligand-protected gold nanoclusters using XPS, STM, XAFS, and TPD techniques

DOE PAGES

Wu, Qiyuan; Cen, Jiajie; Zhao, Yue; ...

2017-12-08

Ultra-small gold nanoclusters were synthesized via a ligand exchange method and deposited onto different TiO2 supports to study their properties. STM imaging revealed that the as-synthesized gold nanoclusters had 2-D morphology consisting of monolayers of gold atoms. In conclusion, subsequent XPS, XAFS, and CO oxidation TPD results indicated that heat treatments of gold clusters at different temperatures significantly altered their electronic and catalytic properties due to ligand deprotection and cluster agglomeration.

Reactivity and Catalytic Activity of Hydrogen Atom Chemisorbed Silver Clusters.

PubMed

Manzoor, Dar; Pal, Sourav

2015-06-18

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

A grand unified model for liganded gold clusters

PubMed Central

Xu, Wen Wu; Zhu, Beien; Zeng, Xiao Cheng; Gao, Yi

2016-01-01

A grand unified model (GUM) is developed to achieve fundamental understanding of rich structures of all 71 liganded gold clusters reported to date. Inspired by the quark model by which composite particles (for example, protons and neutrons) are formed by combining three quarks (or flavours), here gold atoms are assigned three ‘flavours' (namely, bottom, middle and top) to represent three possible valence states. The ‘composite particles' in GUM are categorized into two groups: variants of triangular elementary block Au3(2e) and tetrahedral elementary block Au4(2e), all satisfying the duet rule (2e) of the valence shell, akin to the octet rule in general chemistry. The elementary blocks, when packed together, form the cores of liganded gold clusters. With the GUM, structures of 71 liganded gold clusters and their growth mechanism can be deciphered altogether. Although GUM is a predictive heuristic and may not be necessarily reflective of the actual electronic structure, several highly stable liganded gold clusters are predicted, thereby offering GUM-guided synthesis of liganded gold clusters by design. PMID:27910848

Density Functional Investigation of the Inclusion of Gold Clusters on a CH 3 S Self-Assembled Lattice on Au(111)

DOE PAGES

Allen, Darnel J.; Archibald, Wayne E.; Harper, John A.; ...

2016-01-01

We employ first-principles density functional theoretical calculations to address the inclusion of gold (Au) clusters in a well-packed CH 3 S self-assembled lattice. We compute CH 3 S adsorption energies to quantify the energetic stability of the self-assembly and gold adsorption and dissolution energies to characterize the structural stability of a series of Au clusters adsorbed at the SAM-Au interface. Our results indicate that the inclusion of Au clusters with less than four Au atoms in the SAM-Au interface enhances the binding of CH 3 S species. In contrast, larger Au clusters destabilize the self-assembly. We attribute this effect tomore » the low-coordinated gold atoms in the cluster. For small clusters, these low-coordinated sites have significantly different electronic properties compared to larger islands, which makes the binding with the self-assembly energetically more favorable. Our results further indicate that Au clusters in the SAM-Au interface are thermodynamically unstable and they will tend to dissolve, producing Au adatoms incorporated in the self-assembly in the form of CH 3 S-Au-SCH 3 species. This is due to the strong S-Au bond which stabilizes single Au adatoms in the self-assembly. Our results provide solid insight into the impact of adatom islands at the CH 3 S-Au interface.« less

Density-functional theory study of the geometries, stabilities, and electronic properties of Au n Rb (n = 1-10) clusters: comparison with pure gold clusters

NASA Astrophysics Data System (ADS)

Hu, Yan-Fei; Jiang, Gang; Meng, Da-Qiao

2012-01-01

The density functional method with the relativistic effective core potential has been employed to investigate systematically the geometric structures, relative stabilities, growth-pattern behavior, and electronic properties of small bimetallic Au n Rb (n = 1-10) and pure gold Au n (n ≤ 11) clusters. For the geometric structures of the Au n Rb (n = 1-10) clusters, the dominant growth pattern is for a Rb-substituted Au n +1 cluster or one Au atom capped on a Au n -1Rb cluster, and the turnover point from a two-dimensional to a three-dimensional structure occurs at n = 4. Moreover, the stability of the ground-state structures of these clusters has been examined via an analysis of the average atomic binding energies, fragmentation energies, and the second-order difference of energies as a function of cluster size. The results exhibit a pronounced even-odd alternation phenomenon. The same pronounced even-odd alternations are found for the HOMO-LUMO gap, VIPs, VEAs, and the chemical hardness. In addition, about one electron charge transfers from the Au n host to the Rb atom in each corresponding Au n Rb cluster.

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

NASA Astrophysics Data System (ADS)

Heard, Christopher J.; Johnston, Roy L.

2013-02-01

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

A DFT study of pure and lithium doped gold clusters

NASA Astrophysics Data System (ADS)

Rani, Babita

2018-05-01

First principles calculations on Aun and Aun-1Li (n=1-6) clusters are performed to understand the effect of size and composition on their structural and energy parameters. It has been found that binding energy increases continuously with increase in the size of pure Aun and doped Aun-1Li clusters and attains its maximum at n=6. Also, Li doping results in the improvement of relative stabilities of pure gold clusters, owing to higher bond strength (i.e. shorter bond length) of Au- Li bond as compared to Au-Au bonds. Moreover, Aun-1Li clusters are found to be more compact. Structural transformations are observed in case of gold clusters doped with Li atom which may affect their application in the field of catalysis.

Far-infrared spectra of yttrium-doped gold clusters Au(n)Y (n=1-9).

PubMed

Lin, Ling; Claes, Pieterjan; Gruene, Philipp; Meijer, Gerard; Fielicke, André; Nguyen, Minh Tho; Lievens, Peter

2010-06-21

The geometric, spectroscopic, and electronic properties of neutral yttrium-doped gold clusters Au(n)Y (n=1-9) are studied by far-infrared multiple photon dissociation (FIR-MPD) spectroscopy and quantum chemical calculations. Comparison of the observed and calculated vibrational spectra allows the structures of the isomers present in the molecular beam to be determined. Most of the isomers for which the IR spectra agree best with experiment are calculated to be the energetically most stable ones. Attachment of xenon to the Au(n)Y cluster can cause changes in the IR spectra, which involve band shifts and band splittings. In some cases symmetry changes, as a result of the attachment of xenon atoms, were also observed. All the Au(n)Y clusters considered prefer a low spin state. In contrast to pure gold clusters, which exhibit exclusively planar lowest-energy structures for small sizes, several of the studied species are three-dimensional. This is particularly the case for Au(4)Y and Au(9)Y, while for some other sizes (n=5, 8) the 3D structures have an energy similar to that of their 2D counterparts. Several of the lowest-energy structures are quasi-2D, that is, slightly distorted from planar shapes. For all the studied species the Y atom prefers high coordination, which is different from other metal dopants in gold clusters.

Formation of bimetallic clusters in superfluid helium nanodroplets analysed by atomic resolution electron tomography

PubMed Central

Haberfehlner, Georg; Thaler, Philipp; Knez, Daniel; Volk, Alexander; Hofer, Ferdinand; Ernst, Wolfgang E.; Kothleitner, Gerald

2015-01-01

Structure, shape and composition are the basic parameters responsible for properties of nanoscale materials, distinguishing them from their bulk counterparts. To reveal these in three dimensions at the nanoscale, electron tomography is a powerful tool. Advancing electron tomography to atomic resolution in an aberration-corrected transmission electron microscope remains challenging and has been demonstrated only a few times using strong constraints or extensive filtering. Here we demonstrate atomic resolution electron tomography on silver/gold core/shell nanoclusters grown in superfluid helium nanodroplets. We reveal morphology and composition of a cluster identifying gold- and silver-rich regions in three dimensions and we estimate atomic positions without using any prior information and with minimal filtering. The ability to get full three-dimensional information down to the atomic scale allows understanding the growth and deposition process of the nanoclusters and demonstrates an approach that may be generally applicable to all types of nanoscale materials. PMID:26508471

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

PubMed Central

Wang, Yang-Gang; Mei, Donghai; Glezakou, Vassiliki-Alexandra; Li, Jun; Rousseau, Roger

2015-01-01

Catalysis by gold supported on reducible oxides has been extensively studied, yet issues such as the nature of the catalytic site and the role of the reducible support remain fiercely debated topics. Here we present ab initio molecular dynamics simulations of an unprecedented dynamic single-atom catalytic mechanism for the oxidation of carbon monoxide by ceria-supported gold clusters. The reported dynamic single-atom catalytic mechanism results from the ability of the gold cation to strongly couple with the redox properties of the ceria in a synergistic manner, thereby lowering the energy of redox reactions. The gold cation can break away from the gold nanoparticle to catalyse carbon monoxide oxidation, adjacent to the metal/oxide interface and subsequently reintegrate back into the nanoparticle after the reaction is completed. Our study highlights the importance of the dynamic creation of active sites under reaction conditions and their essential role in catalysis. PMID:25735407

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

PubMed

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

2007-02-16

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

Nano-jewellery: C5Au12--a gold-plated diamond at molecular level.

PubMed

Naumkin, F

2006-06-07

A mixed carbon-metal cluster is designed by combining the tetrahedral C(5) radical (with a central atom-the skeleton of the C(5)H(12) molecule) and the spherical Au(12) layer (the external atomic shell of the Au(13) cluster). The C(5)Au(12) cluster and its negative and positive ionic derivatives, C(5)Au(12)(+/-), are investigated ab initio (DFT) in terms of optimized structures and relative energies of a few spin-states, for the icosahedral-like and octahedral-like isomers. The cluster is predicted to be generally more stable in its octahedral shape (similar to C(5)H(12)) which prevails for the negative ion and may compete with the icosahedral shape for the neutral system and positive ion. Adiabatic ionization energies (AIE) and electron affinities (AEA) of C(5)Au(12), vertical electron-detachment (VDE) energies of C(5)Au(12)(-), and vertical ionization and electron-attachment energies (VIE, VEA) of C(5)Au(12) are calculated as well, and compared with those for the corresponding isomers of the Au(13) cluster. The AIE and VIE values are found to be close for the two systems, while the AEA and VDE values are significantly reduced for the radical-based species. A simple fragment-based model is proposed for the decomposition of the total interaction into carbon-gold and gold-gold components.

Understanding ligand effects in gold clusters using mass spectrometry

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

Johnson, Grant E.; Laskin, Julia

This review summarizes recent research on the influence of phosphine ligands on the size, stability, and reactivity of gold clusters synthesized in solution. Sub-nanometer clusters exhibit size- and composition-dependent properties that are unique from those of larger nanoparticles. The highly tunable properties of clusters and their high surface-to-volume ratio make them promising candidates for a variety of technological applications. However, because “each-atom-counts” toward defining cluster properties it is critically important to develop robust synthesis methods to efficiently prepare clusters of predetermined size. For decades phosphines have been known to direct the size-selected synthesis of gold clusters. Despite the preparation ofmore » numerous species it is still not understood how different functional groups at phosphine centers affect the size and properties of gold clusters. Using electrospray ionization mass spectrometry (ESI-MS) it is possible to characterize the effect of ligand substitution on the distribution of clusters formed in solution at defined reaction conditions. In addition, ligand exchange reactions on preformed clusters may be monitored using ESI-MS. Collision induced dissociation (CID) may also be employed to obtain qualitative insight into the fragmentation of mixed ligand clusters and the relative binding energies of differently substituted phosphines. Quantitative ligand binding energies and cluster stability may be determined employing surface induced dissociation (SID) in a custom-built Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR-MS). Rice-Ramsperger-Kassel-Marcus (RRKM) based modeling of the SID data allows dissociation energies and entropy values to be extracted that may be compared with the results of high-level theoretical calculations. The charge reduction and reactivity of atomically precise gold clusters, including partially ligated species generated in the gas-phase by in source CID, on well-defined surfaces may be explored using ion soft landing (SL) in a custom-built instrument combined with in situ time of flight secondary ion mass spectrometry (TOF-SIMS). Jointly, this multipronged experimental approach allows characterization of the full spectrum of relevant phenomena including cluster synthesis, ligand exchange, thermochemistry, surface immobilization, and reactivity. The fundamental insights obtained from this work will facilitate the directed synthesis of gold clusters with predetermined size and properties for specific applications.« less

Synthesis, characterization and optical properties of an amino-functionalized gold thiolate cluster: Au10(SPh-pNH2)10.

PubMed

Lavenn, Christophe; Albrieux, Florian; Tuel, Alain; Demessence, Aude

2014-03-15

Research interest in ultra small gold thiolate clusters has been rising in recent years for the challenges they offer to bring together properties of nanoscience and well-defined materials from molecular chemistry. Here, a new atomically well-defined Au10 gold nanocluster surrounded by ten 4-aminothiophenolate ligands is reported. Its synthesis followed the similar conditions reported for the elaboration of Au144(SR)60, but because the reactivity of thiophenol ligands is different from alkanethiol derivates, smaller Au10 clusters were formed. Different techniques, such as ESI-MS, elemental analysis, XRD, TGA, XPS and UV-vis-NIR experiments, have been carried out to determine the Au10(SPh-pNH2)10 formula. Photoemission experiment has been done and reveals that the Au10 clusters are weakly luminescent as opposed to the amino-based ultra-small gold clusters. This observation points out that the emission of gold thiolate clusters is highly dependent on both the structure of the gold core and the type of the ligands at the surface. In addition, ultra-small amino-functionalized clusters offer the opportunity for extended work on self-assembling networks or deposition on substrates for nanotechnologies or catalytic applications. Copyright © 2013 Elsevier Inc. All rights reserved.

Design of Janus nanoparticles with atomic precision: tungsten-doped gold nanostructures.

PubMed

Sun, Qiang; Wang, Qian; Jena, Puru; Kawazoe, Yoshiyuki

2008-02-01

Janus nanoparticles, characterized by their anisotropic structure and interactions, have added a new dimension to nanoscience because of their potential applications in biomedicine, sensors, catalysis, and assembled materials. The technological applications of these nanoparticles, however, have been limited as the current chemical, physical, and biosynthetic methods lack sufficient size and shape selectivity. We report a technique where gold clusters doped with tungsten can serve as a seed that facilitates the natural growth of anisotropic nanostructures whose size and shape can be controlled with atomic precision. Using ab initio simulated annealing and molecular dynamics calculations on AunW (n > 12) clusters, we discovered that the W@Au12 cage cluster forms a very stable core with the remaining Au atoms forming patchy structures on its surface. The anisotropic geometry gives rise to anisotropies in vibrational spectra, charge distributions, electronic structures, and reactivity, thus making it useful to have dual functionalities. In particular, the core-patch structure is shown to possess a hydrophilic head and a hydrophobic tail. The W@Au12 clusters can also be used as building blocks of a nanoring with novel properties.

Metastability of the atomic structures of size-selected gold nanoparticles

NASA Astrophysics Data System (ADS)

Wells, Dawn M.; Rossi, Giulia; Ferrando, Riccardo; Palmer, Richard E.

2015-04-01

All nanostructures are metastable - but some are more metastable than others. Here we employ aberration-corrected electron microscopy and atomistic computer simulations to demonstrate the hierarchy of metastability in deposited, size-selected gold nanoparticles (clusters), an archetypal class of nanomaterials well known for the catalytic activity which only appears on the nanometer-scale. We show that the atomic structures presented by ``magic number'' Au561, Au742 and Au923 clusters are ``locked''. They are in fact determined by the solidification which occurs from the liquid state early in their growth (by assembly from atoms in the gas phase) followed by template growth. It is quite likely that transitions from a locked, metastable configuration to a more stable (but still metastable) structure, as observed here under the electron beam, will occur during catalytic reactions, for example.All nanostructures are metastable - but some are more metastable than others. Here we employ aberration-corrected electron microscopy and atomistic computer simulations to demonstrate the hierarchy of metastability in deposited, size-selected gold nanoparticles (clusters), an archetypal class of nanomaterials well known for the catalytic activity which only appears on the nanometer-scale. We show that the atomic structures presented by ``magic number'' Au561, Au742 and Au923 clusters are ``locked''. They are in fact determined by the solidification which occurs from the liquid state early in their growth (by assembly from atoms in the gas phase) followed by template growth. It is quite likely that transitions from a locked, metastable configuration to a more stable (but still metastable) structure, as observed here under the electron beam, will occur during catalytic reactions, for example. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr05811a

Interaction of benzene thiol and thiolate with small gold clusters.

PubMed

Letardi, Sara; Cleri, Fabrizio

2004-06-01

We studied the interaction between benzene thiol and thiolate molecules, and gold clusters made of 1 to 3 atoms, by means of ab initio density functional theory in the local density approximation. We find that the thiolate is energetically more stable than the thiol, however the process of detachment of H from the thiol appears to be possibly mediated by the intermediate step of H chemisorption on Au. Cleavage of the S-H bond is accompanied by a 90 degrees rotation of the molecule around the S-Au bond, showing a strong steric specificity. Such a rotation is induced by the relative energy shift of the S atom p orbitals with respect to the benzene pi ring and the Au d orbitals. By analyzing the correlation of the bond energy, bond lengths, and HOMO-LUMO gap with the number of S-Au bonds, we find that the thiolate S atom appears to prefer a low-coordination condition on Au clusters. (c) 2004 American Institute of Physics.

Electrochemical oxygen reduction behavior of selectively deposited platinum atoms on gold nanoparticles.

PubMed

Sarkar, A; Kerr, J B; Cairns, E J

2013-07-22

Carbon-supported Pt@Au "core-shell" nanoparticles with varying surface concentration of platinum atoms have been synthesized using a novel redox-mediated synthesis approach. The synthesis technique allows for a selective deposition of platinum atoms on the surface of prefabricated gold nanoparticles. Energy dispersive spectroscopic analyses in a scanning electron microscope reveal that the platinum to gold atomic ratios are close to the nominal values, validating the synthesis scheme. X-ray diffraction data indicate an un-alloyed structure. The platinum to gold surface atomic ratio determined from cyclic voltammetry and copper under-potential deposition experiments reveal good agreement with the calculated values at low platinum concentration. However, there is an increase in non-uniformity in the deposition process upon increasing the platinum concentration. Koutecky-Levich analysis of the samples indicates a transition of the total number of electrons transferred (n) in the electrochemical oxygen reduction reaction from two to four electrons upon increasing the surface concentration of platinum atoms. Furthermore, the data indicate that isolated platinum atoms can reduce molecular oxygen but via a two-electron route. Moreover, successful four-electron reduction of molecular oxygen requires clusters of platinum atoms. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

NASA Astrophysics Data System (ADS)

Liu, Siqi; Xu, Yi-Jun

2016-03-01

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

Self-Assembled Gold Nano-Ripple Formation by Gas Cluster Ion Beam Bombardment.

PubMed

Tilakaratne, Buddhi P; Chen, Quark Y; Chu, Wei-Kan

2017-09-08

In this study, we used a 30 keV argon cluster ion beam bombardment to investigate the dynamic processes during nano-ripple formation on gold surfaces. Atomic force microscope analysis shows that the gold surface has maximum roughness at an incident angle of 60° from the surface normal; moreover, at this angle, and for an applied fluence of 3 × 10 16 clusters/cm², the aspect ratio of the nano-ripple pattern is in the range of ~50%. Rutherford backscattering spectrometry analysis reveals a formation of a surface gradient due to prolonged gas cluster ion bombardment, although the surface roughness remains consistent throughout the bombarded surface area. As a result, significant mass redistribution is triggered by gas cluster ion beam bombardment at room temperature. Where mass redistribution is responsible for nano-ripple formation, the surface erosion process refines the formed nano-ripple structures.

Bottom-up formation of robust gold carbide

PubMed Central

Westenfelder, Benedikt; Biskupek, Johannes; Meyer, Jannik C.; Kurasch, Simon; Lin, Xiaohang; Scholz, Ferdinand; Gross, Axel; Kaiser, Ute

2015-01-01

A new phenomenon of structural reorganization is discovered and characterized for a gold-carbon system by in-situ atomic-resolution imaging at temperatures up to 1300 K. Here, a graphene sheet serves in three ways, as a quasi transparent substrate for aberration-corrected high-resolution transmission electron microscopy, as an in-situ heater, and as carbon supplier. The sheet has been decorated with gold nanoislands beforehand. During electron irradiation at 80 kV and at elevated temperatures, the accumulation of gold atoms has been observed on defective graphene sites or edges as well as at the facets of gold nanocrystals. Both resulted in clustering, forming unusual crystalline structures. Their lattice parameters and surface termination differ significantly from standard gold nanocrystals. The experimental data, supported by electron energy loss spectroscopy and density-functional theory calculations, suggests that isolated gold and carbon atoms form – under conditions of heat and electron irradiation – a novel type of compound crystal, Au-C in zincblende structure. The novel material is metastable, but surprisingly robust, even under annealing condition. PMID:25772348

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

PubMed Central

Liu, Siqi; Xu, Yi-Jun

2016-01-01

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

Ab initio study on the structural and electronic properties of water surrounding a multifunctional nanoprobe

NASA Astrophysics Data System (ADS)

Xia, Xiuli; Shao, Yuanzhi

2018-02-01

We report the magneto-electric behavior of a dual-modality biomedical nanoprobe, a ternary nanosystem consisting of gold and gadolinia clusters and water molecules, with the effect of both nanoclusters on the structural and electronic properties of water. The hydrogen-oxygen bond lengths and angles as well as electronic charges of water molecules surrounding both nanoclusters were calculated using Hubbard U corrected density functional theory aided by molecular dynamics approach. The calculations reveal existence of a magneto-electric interaction between gold and gadolinium oxide nanoclusters, which influences the physical properties of surrounding water remarkably. A broader (narrower) distribution of Hsbnd O bond lengths (Hsbnd Osbnd H bond angles) was observed at the presence of either gold or gadolinia nanoclusters. The presence of Gd6O9 cluster leads to the larger charges of neighbour oxygen atoms. The distribution of oxygen atom charges becomes border when both Gd6O9 and Au13 clusters coexist. Ab initio calculation provides a feasible approach to explore the most essential interactions among functional components of a multimodal nanoprobe applied in aqueous environment.

Exploring the atomic structure of 1.8nm monolayer-protected gold clusters with aberration-corrected STEM.

PubMed

Liu, Jian; Jian, Nan; Ornelas, Isabel; Pattison, Alexander J; Lahtinen, Tanja; Salorinne, Kirsi; Häkkinen, Hannu; Palmer, Richard E

2017-05-01

Monolayer-protected (MP) Au clusters present attractive quantum systems with a range of potential applications e.g. in catalysis. Knowledge of the atomic structure is needed to obtain a full understanding of their intriguing physical and chemical properties. Here we employed aberration-corrected scanning transmission electron microscopy (ac-STEM), combined with multislice simulations, to make a round-robin investigation of the atomic structure of chemically synthesised clusters with nominal composition Au 144 (SCH 2 CH 2 Ph) 60 provided by two different research groups. The MP Au clusters were "weighed" by the atom counting method, based on their integrated intensities in the high angle annular dark field (HAADF) regime and calibrated exponent of the Z dependence. For atomic structure analysis, we compared experimental images of hundreds of clusters, with atomic resolution, against a variety of structural models. Across the size range 123-151 atoms, only 3% of clusters matched the theoretically predicted Au 144 (SR) 60 structure, while a large proportion of the clusters were amorphous (i.e. did not match any model structure). However, a distinct ring-dot feature, characteristic of local icosahedral symmetry, was observed in about 20% of the clusters. Copyright © 2017. Published by Elsevier B.V.

Vibrational properties of gold nanoparticles obtained by green synthesis

NASA Astrophysics Data System (ADS)

Alvarez, Ramón A. B.; Cortez-Valadez, M.; Bueno, L. Oscar Neira; Britto Hurtado, R.; Rocha-Rocha, O.; Delgado-Beleño, Y.; Martinez-Nuñez, C. E.; Serrano-Corrales, Luis Ivan; Arizpe-Chávez, H.; Flores-Acosta, M.

2016-10-01

This study reports the synthesis and characterization of gold nanoparticles through an ecological method to obtain nanostructures from the extract of the plant Opuntia ficus-indica. Colloidal nanoparticles show sizes that vary between 10-20 nm, and present various geometric morphologies. The samples were characterized through optical absorption, Raman Spectroscopy and Transmission Electron Microscopy (TEM). Additionally, low energy metallic clusters of Aun (n=2-20 atoms) were modeled by computational quantum chemistry. The theoretical results were obtained with Density Functional Theory (DFT). The predicted results of Au clusters show a tendency and are correlated with the experimental results concerning the optical absorption bands and Raman spectroscopy in gold nanoparticles.

Decoupling of epitaxial graphene via gold intercalation probed by dispersive Raman spectroscopy

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

Pillai, P. B., E-mail: p.pillai@sheffield.ac.uk, E-mail: m.desouza@sheffield.ac.uk; DeSouza, M., E-mail: p.pillai@sheffield.ac.uk, E-mail: m.desouza@sheffield.ac.uk; Narula, R.

Signatures of a superlattice structure composed of a quasi periodic arrangement of atomic gold clusters below an epitaxied graphene (EG) layer are examined using dispersive Raman spectroscopy. The gold-graphene system exhibits a laser excitation energy dependant red shift of the 2D mode as compared to pristine epitaxial graphene. The phonon dispersions in both the systems are mapped using the experimentally observed Raman signatures and a third-nearest neighbour tight binding electronic band structure model. Our results reveal that the observed excitation dependent Raman red shift in gold EG primarily arise from the modifications of the phonon dispersion in gold-graphene and showsmore » that the extent of decoupling of graphene from the underlying SiC substrate can be monitored from the dispersive nature of the Raman 2D modes. The intercalated gold atoms restore the phonon band structure of epitaxial graphene towards free standing graphene.« less

Gold-promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction.

PubMed

Kuttiyiel, Kurian A; Sasaki, Kotaro; Su, Dong; Wu, Lijun; Zhu, Yimei; Adzic, Radoslav R

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here we report on a structurally ordered Au10Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that, at elevated temperatures, palladium cobalt nanoparticles undergo an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets via addition of gold atoms. The superior stability of this catalyst compared with platinum after 10,000 potential cycles in alkaline media is attributed to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matter.

Equilibrium geometries, electronic and magnetic properties of small AunNi- (n = 1-9) clusters

NASA Astrophysics Data System (ADS)

Tang, Cui-Ming; Chen, Xiao-Xu; Yang, Xiang-Dong

2014-05-01

Geometrical, electronic and magnetic properties of small AunNi- (n = 1-9) clusters have been investigated based on density functional theory (DFT) at PW91P86 level. An extensive structural search shows that the relative stable structures of AunNi- (n = 1-9) clusters adopt 2D structure for n = 1-5, 7 and 3D structure for n = 6, 8-9. And the substitution of a Ni atom for an Au atom in the Au-n+1 cluster obviously changes the structure of the host cluster. Moreover, an odd-even alternation phenomenon has been found for HOMO-LUMO energy gaps, indicating that the relative stable structures of the AunNi- clusters with odd-numbered gold atoms have a higher relative stability. Finally, the natural population analysis (NPA) and the vertical detachment energies (VDE) are studied, respectively. The theoretical values of VDE are reported for the first time to our best knowledge.

From clusters to bulk: A relativistic density functional investigation on a series of gold clusters Aun, n=6,…,147

NASA Astrophysics Data System (ADS)

Häberlen, Oliver D.; Chung, Sai-Cheong; Stener, Mauro; Rösch, Notker

1997-03-01

A series of gold clusters spanning the size range from Au6 through Au147 (with diameters from 0.7 to 1.7 nm) in icosahedral, octahedral, and cuboctahedral structure has been theoretically investigated by means of a scalar relativistic all-electron density functional method. One of the main objectives of this work was to analyze the convergence of cluster properties toward the corresponding bulk metal values and to compare the results obtained for the local density approximation (LDA) to those for a generalized gradient approximation (GGA) to the exchange-correlation functional. The average gold-gold distance in the clusters increases with their nuclearity and correlates essentially linearly with the average coordination number in the clusters. An extrapolation to the bulk coordination of 12 yields a gold-gold distance of 289 pm in LDA, very close to the experimental bulk value of 288 pm, while the extrapolated GGA gold-gold distance is 297 pm. The cluster cohesive energy varies linearly with the inverse of the calculated cluster radius, indicating that the surface-to-volume ratio is the primary determinant of the convergence of this quantity toward bulk. The extrapolated LDA binding energy per atom, 4.7 eV, overestimates the experimental bulk value of 3.8 eV, while the GGA value, 3.2 eV, underestimates the experiment by almost the same amount. The calculated ionization potentials and electron affinities of the clusters may be related to the metallic droplet model, although deviations due to the electronic shell structure are noticeable. The GGA extrapolation to bulk values yields 4.8 and 4.9 eV for the ionization potential and the electron affinity, respectively, remarkably close to the experimental polycrystalline work function of bulk gold, 5.1 eV. Gold 4f core level binding energies were calculated for sites with bulk coordination and for different surface sites. The core level shifts for the surface sites are all positive and distinguish among the corner, edge, and face-centered sites; sites in the first subsurface layer show still small positive shifts.

Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study

NASA Astrophysics Data System (ADS)

Helmbrecht, C.; Lützenkirchen-Hecht, D.; Frank, W.

2015-03-01

Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time.Colourless solutions of blue light-emitting, water-soluble gold nanoclusters (AuNC) were synthesized from gold colloids under microwave irradiation using small organic molecules as ligands. Stabilized by 1,3,5-triaza-7-phosphaadamantane (TPA) or l-glutamine (GLU), fluorescence quantum yields up to 5% were obtained. AuNC are considered to be very promising for biological labelling, optoelectronic devices and light-emitting materials but the structure-property relationships have still not been fully clarified. To expand the knowledge about the AuNC apart from their fluorescent properties they were studied by X-ray absorption spectroscopy elucidating the oxidation state of the nanoclusters' gold atoms. Based on curve fitting of the XANES spectra in comparison to several gold references, optically transparent fluorescent AuNC are predicted to be ligand-stabilized Au5+ species. Additionally, their near edge structure compared with analogous results of polynuclear clusters known from the literature discloses an increasing intensity of the feature close to the absorption edge with decreasing cluster size. As a result, a linear relationship between the cluster size and the X-ray absorption coefficient can be established for the first time. Electronic supplementary information (ESI) available: The deconvoluted reference spectra are given in ESI Fig. 1-9. See DOI: 10.1039/c4nr07051h

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

NASA Astrophysics Data System (ADS)

Mishra, Dinesh

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

Structural study of gold clusters.

PubMed

Xiao, Li; Tollberg, Bethany; Hu, Xiankui; Wang, Lichang

2006-03-21

Density functional theory (DFT) calculations were carried out to study gold clusters of up to 55 atoms. Between the linear and zigzag monoatomic Au nanowires, the zigzag nanowires were found to be more stable. Furthermore, the linear Au nanowires of up to 2 nm are formed by slightly stretched Au dimers. These suggest that a substantial Peierls distortion exists in those structures. Planar geometries of Au clusters were found to be the global minima till the cluster size of 13. A quantitative correlation is provided between various properties of Au clusters and the structure and size. The relative stability of selected clusters was also estimated by the Sutton-Chen potential, and the result disagrees with that obtained from the DFT calculations. This suggests that a modification of the Sutton-Chen potential has to be made, such as obtaining new parameters, in order to use it to search the global minima for bigger Au clusters.

Mechanistic Investigations of Branched Macromolecules and Metal Nanocomposites for Nonlinear Optical Applications

DTIC Science & Technology

2009-09-26

gold which show a band gap opening. them with alkyl or aryl thiolates and they are often referred as monolayer protected gold clusters (MPC...workers16-18, as well as Tsukuda and co-workers19 with several thiolate capped MPCs. The PI’s laboratory has observed luminescence mainly in the near...properties for sizes between ~50 and ~1000 atoms is not well understood. Careful analysis of absorption spectra for thiolate stabilized gold MPC

Water-soluble Au13 clusters protected by binary thiolates: Structural accommodation and the use for chemosensing

NASA Astrophysics Data System (ADS)

Ding, Weihua; Huang, Chuanqi; Guan, Lingmei; Liu, Xianhu; Luo, Zhixun; Li, Weixue

2017-05-01

Here we report a successful synthesis of water-soluble 13-atoms gold clusters under the monolayer protection of binary thiolates, glutathione and penicillamine, under a molecular formula of Au13(SG)5(PA)7. This monolayer-protected cluster (MPC) finds decent stability and is demonstrated to possess an icosahedral geometry pertaining to structural accommodation in contrast to a planar bare Au13 of local minima energy. Natural bond orbital (NBO) analysis depicts the interaction patterns between gold and the ligands, enlightening to understand the origin of enhanced stability of the Au13 MPCs. Further, the water-soluble Au13 MPCs are found to be a decent candidate for chemosensing and bioimaging.

Probing the structural and electronic properties of cationic rubidium-gold clusters: [AunRb]+ (n = 1-10)

NASA Astrophysics Data System (ADS)

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.

Gold nanoparticles for cancer detection and treatment: The role of adhesion

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

Oni, Y.; Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, New Jersey 08544; Hao, K.

2014-02-28

This paper presents the results of an experimental study of the effects of adhesion between gold nanoparticles and surfaces that are relevant to the potential applications in cancer detection and treatment. Adhesion is measured using a dip coating/atomic force microscopy (DC/AFM) technique. The adhesion forces are obtained for dip-coated gold nanoparticles that interact with peptide or antibody-based molecular recognition units (MRUs) that attach specifically to breast cancer cells. They include MRUs that attach specifically to receptors on breast cancer cells. Adhesion forces between anti-cancer drugs such as paclitaxel, and the constituents of MRU-conjugated Au nanoparticle clusters, are measured using forcemore » microscopy techniques. The implications of the results are then discussed for the design of robust gold nanoparticle clusters and for potential applications in localized drug delivery and hyperthermia.« less

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

NASA Astrophysics Data System (ADS)

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

2006-09-01

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

Importance of many-body dispersion and temperature effects on gas-phase gold cluster (meta)stability

NASA Astrophysics Data System (ADS)

Goldsmith, Bryan R.; Gruene, Philipp; Lyon, Jonathan T.; Rayner, David M.; Fielicke, André; Scheffler, Matthias; Ghiringhelli, Luca M.

Gold clusters in the gas phase exhibit many structural isomers that are shown to intercovert frequently, even at room temperature. We performed ab initio replica-exchange molecular dynamics (REMD) calculations on gold clusters (of sizes 5-14 atoms) to identify metastable states and their relative populations at finite temperature, as well as to examine the importance of temperature and van der Waals (vdW) on their isomer energetic ordering. Free energies of the gold cluster isomers are optimally estimated using the Multistate Bennett Acceptance Ratio. The distribution of bond coordination numbers and radius of gyration are used to address the challenge of discriminating isomers along their dynamical trajectories. Dispersion effects are important for stabilizing three-dimensional structures relative to planar structures and brings isomer energetic predictions to closer quantitative agreement compared with RPA@PBE calculations. We find that higher temperatures typically stabilize metastable three-dimensional structures relative to planar/quasiplanar structures. Computed IR spectra of low free energy Au9, Au10, and Au12 isomers are in agreement with experimental spectra obtained by far-IR multiple photon dissociation in a molecular beam at 100 K.

Silver enhancement of nanogold and undecagold

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

Hainfield, J.F.; Furuya, F.R.

1995-07-01

A recent advance in immunogold technology has been the use of molecular gold instead of colloidal gold. A number of advantages are realized by this approach, such as stable covalent, site-specific attachment, small probe size and absence of aggregates for improved penetration. Silver enhancement has led to improved and unique results for electron and light microscopy, as well as their use with blots and gels. Most previous work with immunogold silver staining has been done with colloidal gold particles. More recently, large gold compounds (``clusters``) having a definite number of gold atoms and defined organic shell, have been used, frequentlymore » with improved results. These gold dusters, large compared to simple compounds, are, however, at the small end of the colloidal gold scale in size; undecagold is 0.8 nm and Nanogold is 1.4 nm. They may be used in practically all applications where colloidal gold is used (Light and electron microscopy, dot blots, etc.) and in some unique applications, where at least the larger colloidal golds don`t work, such as running gold labeled proteins on gels (which are later detected by silver enhancement). The main differences between gold clusters and colloidal golds are the small size of the dusters and their covalent attachment to antibodies or other molecules.« less

Thin Metallic Films From Solvated Metal Atoms

NASA Astrophysics Data System (ADS)

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

1988-02-01

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

A model for sputtering from solid surfaces bombarded by energetic clusters

NASA Astrophysics Data System (ADS)

Benguerba, Messaoud

2018-04-01

A model is developed to explain and predict the sputtering from solid surfaces bombarded by energetic clusters, on the basis of shock wave generated at the impact of cluster. Under the shock compression the temperature increases causing the vaporization of material that requires an internal energy behind the shock, at least, of about twice the cohesive energy of target. The sputtering is treated as a gas of vaporized particles from a hemispherical volume behind the shock front. The sputter yield per cluster atoms is given as a universal function depending on the ratio of target to cluster atomic density and the ratio of cluster velocity to the velocity calculated on the basis of an internal energy equals about twice cohesive energy. The predictions of the model for self sputter yield of copper, gold, tungsten and of silver bombarded by C60 clusters agree well, with the corresponding data simulated by molecular dynamics.

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

NASA Astrophysics Data System (ADS)

Pettiette, Claire Lynn

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

Self-assembled monolayer and multilayer films of the nanocluster [HxPMo12O40 subsetH4Mo72Fe30(O2CMe)15O254(H2O)68] on gold.

PubMed

Colorado, Ramon; Crouse, Christopher A; Zeigler, Christopher N; Barron, Andrew R

2008-08-19

Films of the molybdenum-iron nanocluster [H x PMo 12O 40 subsetH 4Mo 72Fe 30(O 2CMe) 15O 254(H2O) 68] (FeMoC) were generated on gold via the self-assembly technique using two divergent routes. The first route entails the self-assembly of unfunctionalized FeMoC onto a preprepared carboxyl-terminated SAM on gold. The second route involves the preparation of thiol-terminated functionalized FeMoC clusters, which are then allowed to self-assemble onto bare gold surfaces. Monolayer films of FeMoC clusters are attained via both routes, with the second route requiring shorter immersion times (2 days) than the first route (6 days). Multilayer films of FeMoC are formed via the second route for immersion times longer than 2 days. Characterization of these films using optical ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy confirm the self-assembly of the clusters on the surfaces.

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

PubMed

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

2016-02-01

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

From the Superatom Model to a Diverse Array of Super-Elements: A Systematic Study of Dopant Influence on the Electronic Structure of Thiolate-Protected Gold Clusters.

PubMed

Schacht, Julia; Gaston, Nicola

2016-10-18

The electronic properties of doped thiolate-protected gold clusters are often referred to as tunable, but their study to date, conducted at different levels of theory, does not allow a systematic evaluation of this claim. Here, using density functional theory, the applicability of the superatomic model to these clusters is critically evaluated, and related to the degree of structural distortion and electronic inhomogeneity in the differently doped clusters, with dopant atoms Pd, Pt, Cu, and Ag. The effect of electron number is systematically evaluated by varying the charge on the overall cluster, and the nominal number of delocalized electrons, employed in the superatomic model, is compared to the numbers obtained from Bader analysis of individual atomic charges. We find that the superatomic model is highly applicable to all of these clusters, and is able to predict and explain the changing electronic structure as a function of charge. However, significant perturbations of the model arise due to doping, due to distortions of the core structure of the Au 13 [RS(AuSR) 2 ] 6 - cluster. In addition, analysis of the electronic structure indicates that the superatomic character is distributed further across the ligand shell in the case of the doped clusters, which may have implications for the self-assembly of these clusters into materials. The prediction of appropriate clusters for such superatomic solids relies critically on such quantitative analysis of the tunability of the electronic structure. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gold nanoparticles with different capping systems: an electronic and structural XAS analysis.

PubMed

López-Cartes, C; Rojas, T C; Litrán, R; Martínez-Martínez, D; de la Fuente, J M; Penadés, S; Fernández, A

2005-05-12

Gold nanoparticles (NPs) have been prepared with three different capping systems: a tetralkylammonium salt, an alkanethiol, and a thiol-derivatized neoglycoconjugate. Also gold NPs supported on a porous TiO(2) substrate have been investigated. X-ray absorption spectroscopy (XAS) has been used to determine the electronic behavior of the different capped/supported systems regarding the electron/hole density of d states. Surface and size effects, as well as the role of the microstructure, have been also studied through an exhaustive analysis of the EXAFS (extended X-ray absorption fine structure) data. Very small gold NPs functionalized with thiol-derivatized molecules show an increase in d-hole density at the gold site due to Au-S charge transfer. This effect is overcoming size effects (which lead to a slightly increase of the d-electron density) for high S:Au atomic ratios and core-shell microstructures where an atomically abrupt Au-S interface likely does not exist. It has been also shown that thiol functionalization of very small gold NPs is introducing a strong distortion as compared to fcc order. To the contrary, electron transfer from reduced support oxides to gold NPs can produce a higher increase in d-electron density at the gold site, as compared to naked gold clusters.

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

NASA Astrophysics Data System (ADS)

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

2016-03-01

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

A DFT study on surface-enhanced Raman spectroscopy of aromatic dithiol derivatives adsorbed on gold nanojunctions

NASA Astrophysics Data System (ADS)

You, Tingting; Lang, Xiufeng; Huang, Anping; Yin, Penggang

2018-01-01

A computational study on aromatic dithiol derivatives (HS-Ar-X-Ar-SH, X = O, S, Se, NH, CH2, Ndbnd N, CHdbnd CH, Ctbnd C) interacting with gold cluster(s) was presented to investigate the chemical enhancement mechanism related to surface-enhanced Raman spectroscopy (SERS) for molecular junctions. Density functional theory (DFT) were performed on derivatives molecules as well as their single-end-linked (SEL) or double-end-linked (DEL) complexes for geometric, spectra, electronic and excitation properties, leading to discussions on dominant factor during SERS process. The resulted enhancement factors of SEL and DEL complexes exhibited specific dependency on linking atom or functional group between two phenyls, which was in accordance with the variation of polarizabilities and molecule-cluster transition energy.

Charge transfer interactions in oligomer coated gold nanoclusters

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

Newmai, M. Boazbou; Kumar, Pandian Senthil, E-mail: duplasmonics@gmail.com

Gold nanoclusters were synthesized by a bottom-up synergistic approach of in-situ oligomerization of the monomer, N-vinyl pyrrolidone (NVP) and simultaneous weak reduction of Au-NVP complexes in the absence of any other external energy sources, thereby making these tiny gold clusters as the most elemental building blocks to construct further novel nano/microstructures with application potentials. It is well-known that metal clusters with less than 2 nm size do not show the usual surface plasmon band, because of the presence of a band-gap at the fermi level. Nevertheless, our present oligomer coated gold clusters show a discrete intense band at around 630 nm, whichmore » could very well be attributed to the charge transfer between the oligomer chain and the surface Au atoms. Such kind of sacrificial plasmon induced charge transfer interaction, observed for the very first time to the best of our knowledge, were also strongly corroborated through the enhancement / shifting of specific vibrational / rotational peaks as observed from the FTIR and Raman measurements as a function of the metal oxidation states, thus representing a new prototype for an efficient solar energy conversion probe.« less

Synthesis, Characterization and Application of Water-soluble Gold and Silver Nanoclusters

NASA Astrophysics Data System (ADS)

Kumar, Santosh

The term `nanotechnology' has emerged as a buzzword since the last few decades. It has found widespread applications across disciplines, from medicine to energy. The synthesis of gold and silver nanoclusters has found much excitement, due to their novel material properties. Seminal work by various groups, including ours, has shown that the size of these clusters can be controlled with atomic precision. This control gives access to tuning the optical and electronic properties. The majority of nanoclusters reported thus far are not water soluble, which limit their applications in biology that requires water-solubility. Going from organic to aqueous phase is by no means a simple task, as it is associated with many challenges. Their stability in the presence of oxygen, difficulty in characterization, and separation of pure nanoclusters are some of the major bottlenecks associated with the synthesis of water-soluble gold nanoclusters. Water-soluble gold nanoclusters hold great potential in biological labeling, bio-catalysis and nano-bioconjugates. To overcome this problem, a new ligand with structural rigidity is needed. After considering various possibilities, we chose Captopril as a candidate ligand. In my thesis research, the synthesis of Au25 nanocluster capped with captopril has been reported. Captopril-protected Au25 nanocluster showed significantly higher thermal stability and enhanced chiroptical properties than the Glutathione-capped cluster, which confirms our initial rationale, that the ligand is critical in protecting the nanocluster. The optical absorption properties of these Au25 nanoclusters are studied and compared to the plasmonic nanoparticles. The high thermal stability and solubility of Au25 cluster capped with Captopril motivated us to explore this ligand for the synthesis of other gold clusters. Captopril is a chiral molecule with two chiral centers. The chiral ligand can induce chirality to the overall cluster, even if the core is achiral. Therefore, to obtain Au38 clusters as an enantiomer, the ligand employed should be chiral. The enantioselective synthesis of Au 38 capped with different chiral ligands has been reported and their chiroptical properties have been compared. The synthesis of a series of water-soluble Au nanoclusters has motivated us to study the effect of capping ligands and the core-size on their steady-state and time-resolved fluorescence properties, since the photoluminescence properties are particularly important for bioimaging and biomedical applications of nanoclusters. To gain fundamental insights into the origin of luminescence in nanoclusters, the effect of temperature on the fluorescence properties of these clusters has also been studied. The different sized nanoclusters ranging from a few dozen atoms to hundreds of atoms form a bridge between discrete atoms and the plasmonic nanocrystals; the latter involves essentially collective electron excitation-a phenomenon well explained by classical physics as opposed to quantum physics. The central question is: at what size does this transition from quantum behavior to classical behavior occur? To unravel this, we have successfully synthesized a series of silver nanoclusters. The precise formula assignment and their structural determination are still ongoing. We have successfully demonstrated the application of these water-soluble Au nanoclusters in photodynamic therapy for the treatment of cancer. We have successfully demonstrated that Au nanocluster system can produce singlet oxygen without the presence of any organic photosensitizers. In a collaborative project with Dr. Peteanu's group, the quenching efficiency of organic dyes by these water soluble nanoclusters is studied in different systems. Overall, this thesis outlines the successful synthesis of a family of water-soluble nanoclusters, their optical, chiroptical and fluorescence properties, as well as some applications of these nanoclusters.

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

NASA Astrophysics Data System (ADS)

Šljivančanin, Željko; Belić, Milivoj

2017-09-01

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

Gold and gold-iron oxide magnetic glyconanoparticles: synthesis, characterization and magnetic properties.

PubMed

de la Fuente, Jesús M; Alcántara, David; Eaton, Peter; Crespo, Patricia; Rojas, Teresa C; Fernandez, Asunción; Hernando, Antonio; Penadés, Soledad

2006-07-06

The preparation, characterization and the magnetic properties of gold and gold-iron oxide glyconanoparticles (GNPs) are described. Glyconanoparticles were prepared in a single step procedure in the presence of aqueous solution of thiol functionalized neoglycoconjugates and either gold salts or both gold and iron salts. Neoglycoconjugates of lactose and maltose disaccharides with different linkers were used. Iron-free gold or gold-iron oxide GNPs with controlled gold-iron ratios were obtained. The average core-size diameters are in the range of 1.5-2.5 nm. The GNPs are fully characterized by (1)H NMR spectrometry, transmission electron microscopy (TEM), and UV-vis and X-ray absorption (XAS) spectroscopies. Inductive plasma-atomic emission spectrometry (ICP) and elemental analysis gave the average number of neoglycoconjugates per cluster. The magnetic properties were measured in a SQUID magnetometer. The most remarkable results was the observation of a permanent magnetism up to room temperature in the iron-free gold GNPs, that was not present in the corresponding gold-iron oxide GNPs.

Structural evolution and properties of small-size thiol-protected gold nanoclusters

NASA Astrophysics Data System (ADS)

Ma, Miaomiao; Liu, Liren; Zhu, Hengjiang; Lu, Junzhe; Tan, Guiping

2018-07-01

Ligand-protected gold clusters are widely used in biosensors and catalysis. Understanding the structural evolution of these kinds of nanoclusters is important for experimental synthesis. Herein, based on the particle swarm optimisation algorithm and density functional theory method, we use [Au1(SH)2]n, [Au2(SH)3]n, [Au3(SH)4]n (n = 1-3) as basic units to research the structural evolution relationships from building blocks to the final whole structures. Results show that there is a 'line-ring-core' structural evolution pattern in the growth process of the nanoclusters. The core structures of the ligand-protected gold clusters consist of Au3, Au4, Au6 and Au7 atoms. The electronics and optics analysis reflects that stability and optical properties gradually enhance with increase in size. These results can be used to understand the initial growth stage and design new ligand-protected nanoclusters.

Size-focusing synthesis of gold nanoclusters with p-mercaptobenzoic acid.

PubMed

Tvedte, Laura M; Ackerson, Christopher J

2014-09-18

Etching or size-focusing methods are now widespread for preparation of atomically monodisperse thiolate-protected gold nanoparticles. Size-focusing methods are not widespread, however, in the production of water-soluble gold nanoparticles. Reported here is a new method for size-focusing of large gold nanoparticles utilizing p-mercaptobenzoic acid. We observe preferential formation of three large gold nanoparticles with approximate masses of 23, 51, and 88 kDa. On the basis of the stability of these masses against further etching or growth, they appear to be especially stable sizes. These sizes are not prominent after etching challenges with organosoluble ligands, and the 51 and 88 kDa sizes appear to be novel stable thiolate-protected gold cluster sizes. The overall trend in particle size distribution over time is also unusual, with larger sizes dominating at longer time points.

Density functional study on structure and stability of bimetallic AuNZn (N<=6) clusters and their cations

NASA Astrophysics Data System (ADS)

Tanaka, Hiromasa; Neukermans, Sven; Janssens, Ewald; Silverans, Roger E.; Lievens, Peter

2003-10-01

A systematic study on the structure and stability of zinc doped gold clusters has been performed by density functional theory calculations. All the lowest-energy isomers found have a planar structure and resemble pure gold clusters in shape. Stable isomers tend to equally delocalize valence s electrons of the constituent atoms over the entire structure and maximize the number of Au-Zn bonds in the structure. This is because the Au-Zn bond is stronger than the Au-Au bond and gives an extra σ-bonding interaction by the overlap between vacant Zn 4p and valence Au 6s(5d) orbitals. No three-dimensional isomers were found for Au5Zn+ and Au4Zn clusters containing six delocalized valence electrons. This result reflects that these clusters have a magic number of delocalized electrons for two-dimensional systems. Calculated vertical ionization energies and dissociation energies as a function of the cluster size show odd-even behavior, in agreement with recent mass spectrometric observations [Tanaka et al., J. Am. Chem. Soc. 125, 2862 (2003)].

Gold-superheavy-element interaction in diatomics and cluster adducts: A combined four-component Dirac-Kohn-Sham/charge-displacement study.

PubMed

Rampino, Sergio; Storchi, Loriano; Belpassi, Leonardo

2015-07-14

The chemistry of superheavy elements (Z ≥ 104) is actively investigated in atom-at-a-time experiments of volatility through adsorption on gold surfaces. In this context, common guidelines for interpretation based on group trends in the periodic table should be used cautiously, because relativistic effects play a central role and may cause predictions to fall short. In this paper, we present an all-electron four-component Dirac-Kohn-Sham comparative study of the interaction of gold with Cn (Z = 112), Fl (Z = 114), and Uuo (Z = 118) versus their lighter homologues of the 6th period, Hg, Pb, and Rn plus the noble gas Xe. Calculations were carried out for Au-E (E = Hg, Cn, Pb, Fl, Xe, Rn, Uuo), Au7- and Au20-E (E = Hg, Cn, Pb, Fl, Rn) complexes, where Au7 (planar) and Au20 (pyramidal) are experimentally determined clusters having structures of increasing complexity. Results are analysed both in terms of the energetics of the complexes and of the electron charge rearrangement accompanying their formation. In line with the available experimental data, Cn and more markedly Fl are found to be less reactive than their lighter homologues. On the contrary, Uuo is found to be more reactive than Rn and Xe. Cn forms the weakest bond with the gold atom, compared to Fl and Uuo. The reactivity of Fl decreases with increasing gold-fragment size more rapidly than that of Cn and, as a consequence, the order of the reactivity of these two elements is inverted upon reaching the Au20-cluster adduct. Density difference maps between adducts and fragments reveal similarities in the behaviour of Cn and Xe, and in that of Uuo and the more reactive species Hg and Pb. These findings are given a quantitative ground via charge-displacement analysis.

Hydrogen-Mediated Electron Doping of Gold Clusters As Revealed by In Situ X-ray and UV-vis Absorption Spectroscopy.

PubMed

Ishida, Ryo; Hayashi, Shun; Yamazoe, Seiji; Kato, Kazuo; Tsukuda, Tatsuya

2017-06-01

We previously reported that small (∼1.2 nm) gold clusters stabilized by poly(N-vinyl-2-pyrrolidone) (Au:PVP) exhibited a localized surface plasmon resonance (LSPR) band at ∼520 nm in the presence of NaBH 4 . To reveal the mechanism of this phenomenon, the electronic structure of Au:PVP during the reaction with NaBH 4 in air was examined by means of in situ X-ray absorption spectroscopy at Au L 3 -edge and UV-vis spectroscopy. These measurements indicated that the appearance of the LSPR band is not associated with the growth in size but is ascribed to electron doping to the Au sp band by the adsorbed H atoms.

Gold–promoted structurally ordered intermetallic palladium cobalt nanoparticles for the oxygen reduction reaction

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

Kuttiyiel, Kurian A.; Sasaki, Kotaro; Su, Dong

2014-11-06

Considerable efforts to make palladium and palladium alloys active catalysts and a possible replacement for platinum have had a marginal success. Here, we report on a structurally ordered Au₁₀Pd₄₀Co₅₀ catalyst that exhibits comparable activity to conventional platinum catalysts in both acid and alkaline media. Electron microscopic techniques demonstrate that via addition of gold atoms PdCo nanoparticles undergo at elevated temperatures an atomic structural transition from core-shell to a rare intermetallic ordered structure with twin boundaries forming stable {111}, {110} and {100} facets. The superior stability of this catalyst compared to platinum after 10,000 potential cycles in alkaline media is attributedmore » to the atomic structural order of PdCo nanoparticles along with protective effect of clusters of gold atoms on the surface. This strategy of making ordered palladium intermetallic alloy nanoparticles can be used in diverse heterogeneous catalysis where particle size and structural stability matters.« less

Hydrodynamic fractionation of finite size gold nanoparticle clusters.

PubMed

Tsai, De-Hao; Cho, Tae Joon; DelRio, Frank W; Taurozzi, Julian; Zachariah, Michael R; Hackley, Vincent A

2011-06-15

We demonstrate a high-resolution in situ experimental method for performing simultaneous size classification and characterization of functional gold nanoparticle clusters (GNCs) based on asymmetric-flow field flow fractionation (AFFF). Field emission scanning electron microscopy, atomic force microscopy, multi-angle light scattering (MALS), and in situ ultraviolet-visible optical spectroscopy provide complementary data and imagery confirming the cluster state (e.g., dimer, trimer, tetramer), packing structure, and purity of fractionated populations. An orthogonal analysis of GNC size distributions is obtained using electrospray-differential mobility analysis (ES-DMA). We find a linear correlation between the normalized MALS intensity (measured during AFFF elution) and the corresponding number concentration (measured by ES-DMA), establishing the capacity for AFFF to quantify the absolute number concentration of GNCs. The results and corresponding methodology summarized here provide the proof of concept for general applications involving the formation, isolation, and in situ analysis of both functional and adventitious nanoparticle clusters of finite size. © 2011 American Chemical Society

From atoms to layers: in situ gold cluster growth kinetics during sputter deposition

NASA Astrophysics Data System (ADS)

Schwartzkopf, Matthias; Buffet, Adeline; Körstgens, Volker; Metwalli, Ezzeldin; Schlage, Kai; Benecke, Gunthard; Perlich, Jan; Rawolle, Monika; Rothkirch, André; Heidmann, Berit; Herzog, Gerd; Müller-Buschbaum, Peter; Röhlsberger, Ralf; Gehrke, Rainer; Stribeck, Norbert; Roth, Stephan V.

2013-05-01

The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources.The adjustment of size-dependent catalytic, electrical and optical properties of gold cluster assemblies is a very significant issue in modern applied nanotechnology. We present a real-time investigation of the growth kinetics of gold nanostructures from small nuclei to a complete gold layer during magnetron sputter deposition with high time resolution by means of in situ microbeam grazing incidence small-angle X-ray scattering (μGISAXS). We specify the four-stage growth including their thresholds with sub-monolayer resolution and identify phase transitions monitored in Yoneda intensity as a material-specific characteristic. An innovative and flexible geometrical model enables the extraction of morphological real space parameters, such as cluster size and shape, correlation distance, layer porosity and surface coverage, directly from reciprocal space scattering data. This approach enables a large variety of future investigations of the influence of different process parameters on the thin metal film morphology. Furthermore, our study allows for deducing the wetting behavior of gold cluster films on solid substrates and provides a better understanding of the growth kinetics in general, which is essential for optimization of manufacturing parameters, saving energy and resources. Electronic supplementary information (ESI) available: The full GISAXS image sequence of the experiment, the model-based IsGISAXS-simulation sequence as movie files for comparison and detailed information about sample cleaning, XRR, FESEM, IsGISAXS, comparison μGIWAXS/μGISAXS, and sampling statistics. See DOI: 10.1039/c3nr34216f

Peptide protected gold clusters: chemical synthesis and biomedical applications

NASA Astrophysics Data System (ADS)

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

2016-06-01

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

Gold atoms and clusters on MgO(100) films; an EPR and IRAS study

NASA Astrophysics Data System (ADS)

Yulikov, M.; Sterrer, M.; Risse, T.; Freund, H.-J.

2009-06-01

Single gold atoms deposited on single crystalline MgO(1 0 0) films grown on Mo(1 0 0) are characterized by electron paramagnetic resonance spectroscopy as well as IR spectroscopy using CO as probe molecules. In this article we describe the first angular dependent measurements to determine the principal hyperfine components of a secondary hyperfine interaction, namely, with 17O of the MgO. The values determined here are in perfect agreement with theoretical expectations and corroborate the previously reported binding mechanism of Au atoms on the oxygen anions of the MgO terrace. The temperature dependent EPR data reveal an onset of Au atom mobility at about 80 K while the formation of Au particles occurs only above 125 K. By an analysis of the EPR line width in combination with STM measurements it is possible to deduce an increase of the interatomic distance above 80 K. The Au/CO complexes show a somewhat smaller temperature stability as compared to the Au atoms. The observed thermal stability is in perfect agreement with theoretical predictions for CO desorption.

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

PubMed

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

2016-04-07

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

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

DOE PAGES

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

2016-02-29

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

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

DTIC Science & Technology

2015-07-21

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

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

PubMed

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

2014-09-18

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

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

PubMed

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

Magnetic Ordering in Gold Nanoclusters

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

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Magnetic Ordering in Gold Nanoclusters

DOE PAGES

Agrachev, Mikhail; Antonello, Sabrina; Dainese, Tiziano; ...

2017-06-12

Here, several research groups have observed magnetism in monolayer-protected gold-cluster samples, but the results were often contradictory and thus a clear understanding of this phenomenon is still missing. We used Au 25(SCH 2CH 2Ph) 18 0, which is a paramagnetic cluster that can be prepared with atomic precision and whose structure is known precisely. Previous magnetometry studies only detected paramagnetism. We used samples representing a range of crystallographic orders and studied their magnetic behaviors by electron paramagnetic resonance (EPR). As a film, Au 25(SCH 2CH 2Ph) 18 0 displays paramagnetic behavior but, at low temperature, ferromagnetic interactions are detectable. Onemore » or few single crystals undergo physical reorientation with the applied field and display ferromagnetism, as detected through hysteresis experiments. A large collection of microcrystals is magnetic even at room temperature and shows distinct paramagnetic, superparamagnetic, and ferromagnetic behaviors. Simulation of the EPR spectra shows that both spin-orbit coupling and crystal distortion are important to determine the observed magnetic behaviors. DFT calculations carried out on single cluster and periodic models predict values of spin6orbit coupling and crystal6splitting effects in agreement with the EPR derived quantities. Magnetism in gold nanoclusters is thus demonstrated to be the outcome of a very delicate balance of factors. To obtain reproducible results, the samples must be (i) controlled for composition and thus be monodispersed with atomic precision, (ii) of known charge state, and (iii) well defined also in terms of crystallinity and experimental conditions. This study highlights the efficacy of EPR spectroscopy to provide a molecular understanding of these phenomena« less

Remarkable Second-Order Optical Nonlinearity of Nano-Sized Au Cluster: A TDDFT Study

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

Wu, Kechen; Li, Jun; Lin, Chensheng

2004-04-21

The dipole polarizability, static first hyperpolarizability, and UV-vis spectrum of the recently identified nano-sized tetrahedral cluster of Au have been investigated by using time-dependent density functional response theory. We have discovered that the Au cluster possesses remarkably large molecular second-order optical nonlinearity with the first hyperpolarizabilty (xyz) calculated to be 14.3 x 10 electrostatic unit (esu). The analysis of the low-energy absorption band suggests that the charge transfer from the edged gold atoms to the vertex ones plays the key role in nonlinear optical (NLO) response of Au.

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

PubMed

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

2017-05-01

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

Novel Catalysis by Gold: A Modern Alchemy

NASA Astrophysics Data System (ADS)

Haruta, Masatake

Gold has long been neglected as a catalyst because of its chemical inertness. However, when gold is deposited as nanoparticles on carbon and polymer materials as well as on base metal oxides and hydroxides, it exhibits unique catalytic properties for many reactions such as CO oxidation at a temperature as low as 200 K, gas phase direct epoxidation of propylene, and aerobic oxidation of glucose to gluconic acid. The structure-catalytic activity correlations are discussed with emphasis on the contact structure, support selection, and the size control of gold particles. Gold clusters with diameters smaller than 2 nm are expected to exhibit novel properties in catalysis, optics, and electronics depending on the size (number of atoms), shape, and the electronic and chemical interaction with the support materials. The above achievements and attempts can be regarded as a modern alchemy that creates valuables by means of the noblest element with little practical use.

Atomically Precise Metal Nanoclusters for Catalytic Application

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

Jin, Rongchao

2016-11-18

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

Dual effects of water vapor on ceria-supported gold clusters.

PubMed

Li, Zhimin; Li, Weili; Abroshan, Hadi; Ge, Qingjie; Li, Gao; Jin, Rongchao

2018-04-05

Atomically precise nanocatalysts are currently being intensely pursued in catalysis research. Such nanocatalysts can serve as model catalysts for gaining fundamental insights into catalytic processes. In this work we report a discovery that water vapor provokes the mild removal of surface long-chain ligands on 25-atom Au25(SC12H25)18 nanoclusters in a controlled manner. Using the resultant Au25(SC12H25)18-x/CeO2 catalyst and CO oxidation as a probe reaction, we found that the catalytic activity of cluster/CeO2 is enhanced from nearly zero conversion of CO (in the absence of water) to 96.2% (in the presence of 2.3 vol% H2O) at the same temperature (100 °C). The cluster catalysts exhibit high stability during the CO oxidation process under moisture conditions (up to 20 vol% water vapor). Water vapor plays a dual role in gold cluster-catalyzed CO oxidation. FT-IR and XPS analyses in combination with density functional theory (DFT) simulations suggest that the "-SC12H25" ligands are easier to be removed under a water vapor atmosphere, thus generating highly active sites. Moreover, the O22- peroxide species constitutes the active oxygen species in CO oxidation, evidenced by Raman spectroscopy analysis and isotope experiments on the CeO2 and cluster/CeO2. The results also indicate the perimeter sites of the interface of Au25(SC12H25)18-x/CeO2 to be active sites for catalytic CO oxidation. The controlled exposure of active sites under mild conditions is of critical importance for the utilization of clusters in catalysis.

Smallest fullerene-like clusters in two-probe device junctions: first principle study

NASA Astrophysics Data System (ADS)

Kaur, Milanpreet; Sawhney, Ravinder Singh; Engles, Derick

2017-07-01

First principle calculations based on density functional theory are realised to investigate the electron transport of the smallest fullerene-like clusters as two-probe junction devices. The junction devices are constructed by mechanically controlled break junction techniques to ensure the maximum stability of the Be20, B20 and N20 cluster molecular junctions. We investigate the density of states, transmission spectrum, molecular orbitals, current and differential conductance characteristics at discrete bias voltages to gain insight about the various transport phenomena occurring in these nano-junctions. The results show that B20 molecule when stringed to gold electrodes works as an ideal nano-device similar to the pure C20 device and is more symmetric in its characteristic nature. However, in N20 molecular device, the conduction is negligible due to the higher atomic interactions within N20 molecule, despite the fact that it is constructed with penta-valent atoms.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan , Pellin, Michael J.; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-04-03

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan [Lisle, IL; Pellin, Michael J [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-03-27

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Gold as hydrogen: Structural and electronic properties and chemical bonding in Si3Au3+/0/- and comparisons to Si3H3+/0/-

NASA Astrophysics Data System (ADS)

Kiran, Boggavarapu; Li, Xi; Zhai, Hua-Jin; Wang, Lai-Sheng

2006-10-01

A single Au atom has been shown to behave like H in its bonding to Si in several mono- and disilicon gold clusters. In the current work, we investigate the Au /H analogy in trisilicon gold clusters, Si3Au3+/0/-. Photoelectron spectroscopy and density functional calculations are combined to examine the geometric and electronic structure of Si3Au3-. We find that there are three isomers competing for the ground state of Si3Au3- as is the case for Si3H3-. Extensive structural searches show that the potential energy surfaces of the trisilicon gold clusters (Si3Au3-, Si3Au3, and Si3Au3+) are similar to those of the corresponding silicon hydrides. The lowest energy isomers for Si3Au3- and Si3Au3 are structurally similar to a Si3Au four-membered ring serving as a common structural motif. For Si3Au3+, the 2π aromatic cyclotrisilenylium auride ion, analogous to the aromatic cyclotrisilenylium ion (Si3H3+), is the most stable species. Comparison of the structures and chemical bonding between Si3Au3+/0/- and the corresponding silicon hydrides further extends the isolobal analogy between Au and H.

Gold–superheavy-element interaction in diatomics and cluster adducts: A combined four-component Dirac-Kohn-Sham/charge-displacement study

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

Rampino, Sergio, E-mail: srampino@thch.unipg.it; Belpassi, Leonardo, E-mail: leonardo.belpassi@cnr.it; Storchi, Loriano

The chemistry of superheavy elements (Z ≥ 104) is actively investigated in atom-at-a-time experiments of volatility through adsorption on gold surfaces. In this context, common guidelines for interpretation based on group trends in the periodic table should be used cautiously, because relativistic effects play a central role and may cause predictions to fall short. In this paper, we present an all-electron four-component Dirac-Kohn-Sham comparative study of the interaction of gold with Cn (Z = 112), Fl (Z = 114), and Uuo (Z = 118) versus their lighter homologues of the 6th period, Hg, Pb, and Rn plus the noble gasmore » Xe. Calculations were carried out for Au–E (E = Hg, Cn, Pb, Fl, Xe, Rn, Uuo), Au{sub 7}– and Au{sub 20}–E (E = Hg, Cn, Pb, Fl, Rn) complexes, where Au{sub 7} (planar) and Au{sub 20} (pyramidal) are experimentally determined clusters having structures of increasing complexity. Results are analysed both in terms of the energetics of the complexes and of the electron charge rearrangement accompanying their formation. In line with the available experimental data, Cn and more markedly Fl are found to be less reactive than their lighter homologues. On the contrary, Uuo is found to be more reactive than Rn and Xe. Cn forms the weakest bond with the gold atom, compared to Fl and Uuo. The reactivity of Fl decreases with increasing gold-fragment size more rapidly than that of Cn and, as a consequence, the order of the reactivity of these two elements is inverted upon reaching the Au{sub 20}-cluster adduct. Density difference maps between adducts and fragments reveal similarities in the behaviour of Cn and Xe, and in that of Uuo and the more reactive species Hg and Pb. These findings are given a quantitative ground via charge-displacement analysis.« less

Slider thickness promotes lubricity: from 2D islands to 3D clusters

NASA Astrophysics Data System (ADS)

Guerra, Roberto; Tosatti, Erio; Vanossi, Andrea

2016-05-01

The sliding of three-dimensional clusters and two-dimensional islands adsorbed on crystal surfaces represents an important test case to understand friction. Even for the same material, monoatomic islands and thick clusters will not as a rule exhibit the same friction, but specific differences have not been explored. Through realistic molecular dynamics simulations of the static friction of gold on graphite, an experimentally relevant system, we uncover as a function of gold thickness a progressive drop of static friction from monolayer islands, that are easily pinned, towards clusters, that slide more readily. The main ingredient contributing to this thickness-induced lubricity appears to be the increased effective rigidity of the atomic contact, acting to reduce the cluster interdigitation with the substrate. A second element which plays a role is the lateral contact size, which can accommodate the solitons typical of the incommensurate interface only above a critical contact diameter, which is larger for monolayer islands than for thick clusters. The two effects concur to make clusters more lubric than islands, and large sizes more lubric than smaller ones. These conclusions are expected to be of broader applicability in diverse nanotribological systems, where the role played by static, and dynamic, friction is generally quite important.

Slider thickness promotes lubricity: from 2D islands to 3D clusters.

PubMed

Guerra, Roberto; Tosatti, Erio; Vanossi, Andrea

2016-06-07

The sliding of three-dimensional clusters and two-dimensional islands adsorbed on crystal surfaces represents an important test case to understand friction. Even for the same material, monoatomic islands and thick clusters will not as a rule exhibit the same friction, but specific differences have not been explored. Through realistic molecular dynamics simulations of the static friction of gold on graphite, an experimentally relevant system, we uncover as a function of gold thickness a progressive drop of static friction from monolayer islands, that are easily pinned, towards clusters, that slide more readily. The main ingredient contributing to this thickness-induced lubricity appears to be the increased effective rigidity of the atomic contact, acting to reduce the cluster interdigitation with the substrate. A second element which plays a role is the lateral contact size, which can accommodate the solitons typical of the incommensurate interface only above a critical contact diameter, which is larger for monolayer islands than for thick clusters. The two effects concur to make clusters more lubric than islands, and large sizes more lubric than smaller ones. These conclusions are expected to be of broader applicability in diverse nanotribological systems, where the role played by static, and dynamic, friction is generally quite important.

Water-Soluble Phosphine-Protected Au₁₁ Clusters: Synthesis, Electronic Structure, and Chiral Phase Transfer in a Synergistic Fashion.

PubMed

Yao, Hiroshi; Iwatsu, Mana

2016-04-05

Synthesis of atomically precise, water-soluble phosphine-protected gold clusters is still currently limited probably due to a stability issue. We here present the synthesis, magic-number isolation, and exploration of the electronic structures as well as the asymmetric conversion of triphenylphosphine monosulfonate (TPPS)-protected gold clusters. Electrospray ionization mass spectrometry and elemental analysis result in the primary formation of Au11(TPPS)9Cl undecagold cluster compound. Magnetic circular dichroism (MCD) spectroscopy clarifies that extremely weak transitions are present in the low-energy region unresolved in the UV-vis absorption, which can be due to the Faraday B-terms based on the magnetically allowed transitions in the cluster. Asymmetric conversion without changing the nuclearity is remarkable by the chiral phase transfer in a synergistic fashion, which yields a rather small anisotropy factor (g-factor) of at most (2.5-7.0) × 10(-5). Quantum chemical calculations for model undecagold cluster compounds are then used to evaluate the optical and chiroptical responses induced by the chiral phase transfer. On this basis, we find that the Au core distortion is ignorable, and the chiral ion-pairing causes a slight increase in the CD response of the Au11 cluster.

A comparative DFT study of interactions of Au and small gold clusters Aun (n = 2-4) with CH3S and CH2 radicals

NASA Astrophysics Data System (ADS)

Blaško, Martin; Rajský, Tomáš; Urban, Miroslav

2017-03-01

We compare DFT binding energies (BEs) of Au and small gold clusters interacting with CH3S and CH2 ligands (Aun-L complexes, n = 1-4). The spin state and the binding mechanism in Aun-L varies with the participation of singly occupied non-bonding orbitals or doubly occupied lone-pair orbitals of a ligand and on the number of atoms (even or odd) of Aun. The highest BE, 354 kJ/mol, exhibits the Au3-CH2 complex with the covalent bond in which participate two singly occupied orbitals of the triplet state of CH2. With CH3S the highest BE (277 kJ/mol) is calculated for Au3-SCH3 with the single Au-S bond.

Structural evolution study of 1-2 nm gold clusters

NASA Astrophysics Data System (ADS)

Beltrán, M. R.; Suárez Raspopov, R.; González, G.

2011-12-01

We have explored lowest energy minima structures of gold atom clusters both, charged and neutral (Aun^{ν}νn with n = 20, 28, 34, 38, 55, 75, 101, 146, 147, 192, 212 atoms and ν = 0, ±1). The structures have been obtained from first principles generalized gradient approximation, density functional theory (DFT) calculations based on norm-conserving pseudopotentials and numerical atomic basis sets. We have found two new disordered or defective isomers lower in energy than their ordered counterparts for n = 101, 147. The purpose of this work is to systematically study the difference between the electronic properties of the two lowest ordered and disordered isomers for each size. Our results agree with previous first principle calculations and with some recent experimental results (Au20 and Au101). For each case we report total energies, binding energies, ionization potentials, electron affinities, density of states, highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gaps, Housdorff chirality measure index and their simulated image in a high resolution transmission electron microscopy (HRTEM). The calculated properties of the two low lying (ordered and disordered) isomers show clear differences as to be singled out in a suitable experimental setting. An extensive discussion on the evolution with size of the cohesive energy, the ionization potentials, the electron affinities, the HOMO-LUMO gaps and their index of chirality to determine the crossover between them is given.

Bimetallic cages

NASA Astrophysics Data System (ADS)

Fournier, René; Afzal-Hussain, Sabeen

2013-02-01

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

Laser ablation synthesis of new gold phosphides using red phosphorus and nanogold as precursors. Laser desorption ionisation time-of-flight mass spectrometry.

PubMed

Panyala, Nagender Reddy; Peña-Méndez, Eladia María; Havel, Josef

2012-05-15

Gold phosphides show unique optical or semiconductor properties and there are extensive high technology applications, e.g. in laser diodes, etc. In spite of the various AuP structures known, the search for new materials is wide. Laser ablation synthesis is a promising screening and synthetic method. Generation of gold phosphides via laser ablation of red phosphorus and nanogold mixtures was studied using laser desorption ionisation time-of-flight mass spectrometry (LDI TOFMS). Gold clusters Au(m)(+) (m = 1 to ~35) were observed with a difference of one gold atom and their intensities were in decreasing order with respect to m. For P(n)(+) (n = 2 to ~111) clusters, the intensities of odd-numbered phosphorus clusters are much higher than those for even-numbered phosphorus clusters. During ablation of P-nanogold mixtures, clusters Au(m)(+) (m = 1-12), P(n)(+) (n = 2-7, 9, 11, 13-33, 35-95 (odd numbers)), AuP(n)(+) (n = 1, 2-88 (even numbers)), Au(2)P(n)(+) (n = 1-7, 14-16, 21-51 (odd numbers)), Au(3)P(n)(+) (n = 1-6, 8, 9, 14), Au(4)P(n)(+) (n = 1-9, 14-16), Au(5)P(n)(+) (n = 1-6, 14, 16), Au(6)P(n)(+) (n = 1-6), Au(7)P(n)(+) (n = 1-7), Au(8)P(n)(+) (n = 1-6, 8), Au(9)P(n)(+) (n = 1-10), Au(10)P(n)(+) (n = 1-8, 15), Au(11)P(n)(+) (n = 1-6), and Au(12)P(n)(+) (n = 1, 2, 4) were detected in positive ion mode. In negative ion mode, Au(m)(-) (m = 1-5), P(n)(-) (n = 2, 3, 5-11, 13-19, 21-35, 39, 41, 47, 49, 55 (odd numbers)), AuP(n)(-) (n = 4-6, 8-26, 30-36 (even numbers), 48), Au(2)P(n)(-) (n = 2-5, 8, 11, 13, 15, 17), A(3) P(n)(-) (n = 6-11, 32), Au(4)P(n)(-) (n = 1, 2, 4, 6, 10), Au(6)P(5)(-), and Au(7)P(8)(-) clusters were observed. In both modes, phosphorus-rich Au(m)P(n) clusters prevailed. The first experimental evidence for formation of AuP(60) and gold-covered phosphorus Au(12)P(n) (n = 1, 2, 4) clusters is given. The new gold phosphides generated might inspire synthesis of new Au-P materials with specific properties. Copyright © 2012 John Wiley & Sons, Ltd.

Active sites of ligand-protected Au{sub 25} nanoparticle catalysts for CO{sub 2} electroreduction to CO

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

Alfonso, Dominic R., E-mail: alfonso@netl.doe.gov; Kauffman, Douglas; Matranga, Christopher

2016-05-14

Recent experimental studies have reported the electrochemical reduction of carbon dioxide (CO{sub 2}) into CO at atomically precise negatively charged Au{sub 25}{sup −} nanoclusters. The studies showed CO{sub 2} conversion at remarkably low overpotentials, but the exact mechanisms and nature of the active sites remain unclear. We used first-principles density functional theory and continuum solvation models to examine the role of the cluster during electrochemical CO{sub 2} reduction and analyze the free energies of proposed intermediate species. Contrary to previous assumptions, our results show that the fully ligand protected cluster is not an active CO{sub 2} reduction catalyst because formationmore » of the crucial carboxyl intermediate required very high electrochemical potentials. Instead, our calculations suggest that the reduction process likely occurs on a dethiolated gold site, and adsorbed carboxyl intermediate formation was significantly stabilized at dethiolated gold sites. These findings point to the crucial role of exposed metal sites during electrochemical CO{sub 2} reduction at gold nanocluster catalysts.« less

Origin of the transition voltage in gold-vacuum-gold atomic junctions.

PubMed

Wu, Kunlin; Bai, Meilin; Sanvito, Stefano; Hou, Shimin

2013-01-18

The origin and the distance dependence of the transition voltage of gold-vacuum-gold junctions are investigated by employing first-principles quantum transport simulations. Our calculations show that atomic protrusions always exist on the electrode surface of gold-vacuum-gold junctions fabricated using the mechanically controllable break junction (MCBJ) method. The transition voltage of these gold-vacuum-gold junctions with atomically sharp electrodes is determined by the local density of states (LDOS) of the apex gold atom on the electrode surface rather than by the vacuum barrier shape. More specifically, the absolute value of the transition voltage roughly equals the rising edge of the LDOS peak contributed by the 6p atomic orbitals of the gold atoms protruding from the electrode surface, whose local Fermi level is shifted downwards when a bias voltage is applied. Since the LDOS of the apex gold atom depends strongly on the exact shape of the electrode, the transition voltage is sensitive to the variation of the atomic configuration of the junction. For asymmetric junctions, the transition voltage may also change significantly depending on the bias polarity. Considering that the occurrence of the transition voltage requires the electrode distance to be larger than a critical value, the interaction between the two electrodes is actually rather weak. Consequently, the LDOS of the apex gold atom is mainly determined by its local atomic configuration and the transition voltage only depends weakly on the electrode distance as observed in the MCBJ experiments.

Why can a gold salt react as a base?

PubMed

Anania, Mariarosa; Jašíková, Lucie; Jašík, Juraj; Roithová, Jana

2017-09-26

This study shows that gold salts [(L)AuX] (L = PMe 3 , PPh 3 , JohnPhos, IPr; X = SbF 6 , PF 6 , BF 4 , TfO, Tf 2 N) act as bases in aqueous solutions and can transform acetone to digold acetonyl complexes [(L) 2 Au 2 (CH 2 COCH 3 )] + without any additional base present in solution. The key step is the formation of digold hydroxide complexes [(L) 2 Au 2 (OH)] + . The kinetics of the formation of the digold complexes and their mutual transformation is studied by electrospray ionization mass spectrometry and the delayed reactant labelling method. We show that the formation of digold hydroxide is the essential first step towards the formation of the digold acetonyl complex, the reaction is favoured by more polar solvents, and the effect of counter ions is negligible. DFT calculations suggest that digold hydroxide and digold acetonyl complexes can exist in solution only due to the stabilization by the interaction with two gold atoms. The reaction between the digold hydroxide and acetone proceeds towards the dimer {[(L)Au(OH)]·[(L)Au(CH 3 COCH 3 )] + }. The monomeric units interact at the gold atoms in the perpendicular arrangement typical of the gold clusters bound by the aurophilic interaction. The hydrogen is transferred within the dimer and the reaction continues towards the digold acetonyl complex and water.

Energetic stabilities of thiolated pyrimidines on gold nanoparticles investigated by Raman spectroscopy and density functional theory calculations.

PubMed

Ganbold, Erdene-Ochir; Yoon, Jinha; Cho, Kwang-Hwi; Joo, Sang-Woo

2015-01-01

The adsorption structures of 2-thiocytosine (2TC) on gold surfaces were examined by means of vibrational Raman spectroscopy and quantum mechanical density functional theory calculations. The 1H-thione-amino form was calculated to be most stable among the six examined tautomers. The three plausible binding geometries of sulfur, pyrimidine nitrogen, and amino group binding modes were calculated to estimate the binding energies of the 1H-thione-amino form with six gold cluster atoms. Thiouracils including 2-thiouracil (2TU), 4-thiouracil (4TU), and 6-methyl-2-thiouracil (6M2TU) were also studied to compare their relative binding energies on gold atoms. The intracellular localization of a DNA base analog of 2TC on gold nanoparticles (AuNPs) in HeLa cells was identified by means of surface-enhanced Raman scattering. AuNPs were modified with 2TC by self-assembly. Our dark-field microscopy and z-depth-dependent confocal Raman spectroscopy indicated that 2TC-assembled AuNPs could be found inside cancer cells. On the other hand, we did not observe noticeably strong Raman peaks in the cases of thiouracils including 2TU, 4TU, and 6M2TU. This may be due to the additional amino group of 2TC, which can lead to a stronger binding of adsorbates on AuNPs. Copyright © 2015. Published by Elsevier B.V.

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

DOE PAGES

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

2015-03-04

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

Adsorption of the astatine species on a gold surface: A relativistic density functional theory study

NASA Astrophysics Data System (ADS)

Demidov, Yuriy; Zaitsevskii, Andréi

2018-01-01

We report first-principle based studies of the adsorption interaction of astatine species on a gold surface. These studies are aimed primarily at the support and interpretation of gas chromatographic experiments with superheavy elements, tennessine (Ts, Z = 117), a heavier homologue of At, and possibly its pseudo-homologue nihonium (Nh, Z = 113). We use gold clusters with up to 69 atoms to simulate the adsorption sites and estimate the desorption energies of At & AtOH from a stable gold (1 1 1) surface. To describe the electronic structure of At -Aun and AtOH -Aun complexes, we combine accurate shape-consistent relativistic pseudopotentials and non-collinear two-component relativistic density functional theory. The predicted desorption energies of At and AtOH on gold are 130 ± 10 kJ/mol and 90 ± 10 kJ/mol, respectively. These results confirm the validity of the estimates derived from chromatographic data (147 ± 15 kJ/mol for At, and 100-10+20 kJ/mol for AtOH).

Determination of gold in geologic materials by solvent extraction and atomic-absorption spectrometry

USGS Publications Warehouse

Huffman, Claude; Mensik, J.D.; Riley, L.B.

1967-01-01

The two methods presented for the determination of traces of gold in geologic materials are the cyanide atomic-absorption method and the fire-assay atomic-absorption method. In the cyanide method gold is leached with a sodium-cyanide solution. The monovalent gold is then oxidized to the trivalent state and concentrated by extracting into methyl isobutyl ketone prior to estimation by atomic absorption. In the fire-assay atomic-absorption method, the gold-silver bead obtained from fire assay is dissolved in nitric and hydrochloric acids. Gold is then concentrated by extracting into methyl isobutyl ketone prior to determination by atomic absorption. By either method concentrations as low as 50 parts per billion of gold can be determined in a 15-gram sample.

Thermodynamic Behavior of Nano-sized Gold Clusters on the (001) Surface

NASA Technical Reports Server (NTRS)

Paik, Sun M.; Yoo, Sung M.; Namkung, Min; Wincheski, Russell A.; Bushnell, Dennis M. (Technical Monitor)

2001-01-01

We have studied thermal expansion of the surface layers of the hexagonally reconstructed Au (001) surface using a classical Molecular Dynamics (MD) simulation technique with an Embedded Atomic Method (EAM) type many-body potential. We find that the top-most hexagonal layer contracts as temperature increases, whereas the second layer expands or contracts depending on the system size. The magnitude of expansion coefficient of the top layer is much larger than that of the other layers. The calculated thermal expansion coefficients of the top-most layer are about -4.93 x 10(exp -5)Angstroms/Kelvin for the (262 x 227)Angstrom cluster and -3.05 x 10(exp -5)Angstroms/Kelvin for (101 x 87)Angstrom cluster. The Fast Fourier Transform (FFT) image of the atomic density shows that there exists a rotated domain of the top-most hexagonal cluster with rotation angle close to 1 degree at temperature T less than 1000Kelvin. As the temperature increases this domain undergoes a surface orientational phase transition. These predictions are in good agreement with previous phenomenological theories and experimental studies.

Structural and dynamical characterization of water on the Au (100) and graphene surfaces: A molecular dynamics simulation approach

NASA Astrophysics Data System (ADS)

Foroutan, Masumeh; Darvishi, Mehdi; Fatemi, S. Mahmood

2017-09-01

The positioning, adsorption, and movement of water on substrates is dependent upon the chemical nature and arrangement of the atoms of the surface. Therefore the behavior of water molecules on a substrate is a reflection of properties of the surface. Based on this premise, graphene and gold substrates were chosen to study this subject from a molecular perspective. In this work, the structural and dynamical behaviors of a water nanodroplet on Au (100) and the graphene interfaces have been studied by molecular dynamics simulation. The results have shown how the structural and dynamical behaviors of water molecules at the interface reflect the characteristics of these surfaces. The results have demonstrated that residence time and hydrogen bonds' lifetime at the water-Au (100) interface are bigger than at the water-graphene interface. Energy contour map analysis indicates a more uniform surface energy on graphene than on the gold surface. The obtained results illustrate that water clusters on gold and graphene form tetramer and hexamer structures, respectively. Furthermore, the water molecules are more ordered on the gold surface than on graphene. The study of hydrogen bonds showed that the order, stability, and the number of hydrogen bonds is higher on the gold surface. The positioning pattern of water molecules is also similar to the arrangement of gold atoms while no regularity was observed on graphene. The study of dynamical behavior of water molecules revealed that the movement of water on gold is much less than on graphene which is in agreement with the strong water-gold interaction in comparison to the water-graphene interaction.

Dual structural transition in small nanoparticles of Cu-Au alloy

NASA Astrophysics Data System (ADS)

Gafner, Yuri; Gafner, Svetlana; Redel, Larisa; Zamulin, Ivan

2018-02-01

Cu-Au alloy nanoparticles are known to be widely used in the catalysis of various chemical reactions as it was experimentally defined that in many cases the partial substitution of copper with gold increases catalytic activity. However, providing the reaction capacity of alloy nanoparticles the surface electronic structure strongly depends on their atomic ordering. Therefore, to theoretically determine catalytic properties, one needs to use a most real structural model complying with Cu-Au nanoparticles under various external influences. So, thermal stability limits were studied for the initial L12 phase in Cu3Au nanoalloy clusters up to 8.0 nm and Cu-Au clusters up to 3.0 nm at various degrees of Au atom concentration, with molecular dynamics method using a modified tight-binding TB-SMA potential. Dual structural transition L12 → FCC and further FCC → Ih is shown to be possible under the thermal factor in Cu3Au and Cu-Au clusters with the diameter up to 3.0 nm. The temperature of the structural transition FCC → Ih is established to decrease for small particles of Cu-Au alloy under the increase of Au atom concentration. For clusters with this structural transition, the melting point is found to be a linear increasing function of concentration, and for clusters without FCC → Ih structural transition, the melting point is a linear decreasing function of Au content. Thus, the article shows that doping Cu nanoclusters with Au atoms allows to control the forming structure as well as the melting point.

Martensitic transformations in Ag-Au bimetallic core-shell nanoalloys

NASA Astrophysics Data System (ADS)

Chen, Fuyi; Johnston, Roy L.

2008-01-01

Combining the Gupta potential and bond order analysis in a molecular dynamics simulation, a martensitic transformation is observed in the 147-atom AucoreAgshell nanostructure at 328K. The response time for this transformation is about 7ps at 350K. In pure gold clusters, it was previously thought that a similar solid-to-solid transformation is a prelude to melting transitions. In the present case, atomic pathway snapshots show that the heating energy is used to overcome the energy barrier for initiating the spontaneous process. The subsequent twist-deformation propagation and termination are clearly observed.

Bonding properties of FCC-like Au 44 (SR) 28 clusters from X-ray absorption spectroscopy

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

Yang, Rui; Chevrier, Daniel M.; Zeng, Chenjie

Thiolate-protected gold clusters with precisely controlled atomic composition have recently emerged as promising candidates for a variety of applications because of their unique optical, electronic, and catalytic properties. The recent discovery of the Au44(SR)28 total structure is considered as an interesting finding in terms of the face-centered cubic (FCC)-like core structure in small gold-thiolate clusters. Herein, the unique bonding properties of Au44(SR)28 is analyzed using temperature-dependent X-ray absorption spectroscopy (XAS) measurements at the Au L3-edge and compared with other FCC-like clusters such as Au36(SR)24 and Au28(SR)20. A negative thermal expansion was detected for the Au–Au bonds of the metal coremore » (the first Au–Au shell) and was interpreted based on the unique Au core structure consisting of the Au4 units. EXAFS fitting results from Au28(SR)20, Au36(SR)24, and Au44(SR)28 show a size-dependent negative thermal expansion behavior in the first Au–Au shell, further highlighting the importance of the Au4 units in determining the Au core bonding properties and shedding light on the growth mechanism of these FCC-like Au clusters.« less

Assessment of interaction-strength interpolation formulas for gold and silver clusters

NASA Astrophysics Data System (ADS)

Giarrusso, Sara; Gori-Giorgi, Paola; Della Sala, Fabio; Fabiano, Eduardo

2018-04-01

The performance of functionals based on the idea of interpolating between the weak- and the strong-interaction limits the global adiabatic-connection integrand is carefully studied for the challenging case of noble-metal clusters. Different interpolation formulas are considered and various features of this approach are analyzed. It is found that these functionals, when used as a correlation correction to Hartree-Fock, are quite robust for the description of atomization energies, while performing less well for ionization potentials. Future directions that can be envisaged from this study and a previous one on main group chemistry are discussed.

Clustering of gold particles in Au implanted CrN thin films: The effect on the SPR peak position

NASA Astrophysics Data System (ADS)

Novaković, M.; Popović, M.; Schmidt, E.; Mitrić, M.; Bibić, N.; Rakočević, Z.; Ronning, C.

2017-12-01

We report on the formation of gold particles in 280 nm thin polycrystalline CrN layers caused by Au+ ion implantation. The CrN layers were deposited at 150 °C by d.c. reactive sputtering on Si(100) wafers and then implanted at room temperature with 150 keV Au+ ions to fluences of 2 × 1016 cm-2 to 4.1 × 1016 cm-2. The implanted layers were analysed by the means of Rutherford backscattering spectrometry, X-ray diffraction, atomic force microscopy and spectroscopic ellipsometry measurements. The results revealed that the Au atoms are situated in the near-surface region of the implanted CrN layers. At the fluence of 2 × 1016 cm-2 the formation of Au particles of ∼200 nm in diameter has been observed. With increasing Au ion fluence the particles coalesce into clusters with dimensions of ∼1.7 μm. The synthesized particles show a strong absorption peak associated with the excitation of surface plasmon resonances (SPR). The position of the SPR peak shifted in the range of 426.8-690.5 nm when the Au+ ion fluence was varied from 2 × 1016 cm-2 to 4.1 × 1016 cm-2. A correlation of the shift in the peak wavelength caused by the change in the particles size and clustering has been revealed, suggesting that the interaction between Au particles dominate the surface plasmon resonance effect.

Ejection of nanoclusters from gold nanoislet layers by 38 keV Au ions in the elastic stopping mode.

PubMed

Baranov, I A; Della-Negra, S; Domaratsky, V P; Chemezov, A V; Kirillov, S N; Novikov, A C; Obnorsky, V V; Pautrat, M; Urbassek, H M; Wien, K; Yarmiychuk, S V; Zhurkin, E E

2009-07-01

Total absolute yields of the ejected gold were obtained regardless of the type of the particles are--atoms, clusters, nanoclusters,--as well as absolute yields of gold nanoclusters, from nanoislet gold targets under bombardment by monoatomic gold ions at 45 degrees to the target surface with the energy 38 keV, i.e., in the "purely" elastic stopping mode -6 keV/nm up to the fluence of 4 x 10(12) cm2. Three targets had gold nanoislets on the substrate surface: 2-12 nm; -18 nm; -35 nm, the most probable sizes being 7.1; 9.4; 17.5 nm respectively. The part of the surface area covered with gold was known. Total transfer of gold was determined by means of the neutron-activation analysis and decreased from 450 to 20 at/ion. The number of the ejected gold nanoclusters was determined using TEM and decreased from approximately 0.06 to < 0.01 per one 38 keV Au ion with the increase of the most probable sizes of the nanoislets on the target from 7.1 to 17.5 nm. The yields appeared to be surprisingly high, which is of scientific and practical importance. Tentative estimations were made using molecular dynamics simulations.

Monte Carlo investigation of the increased radiation deposition due to gold nanoparticles using kilovoltage and megavoltage photons in a 3D randomized cell model.

PubMed

Douglass, Michael; Bezak, Eva; Penfold, Scott

2013-07-01

Investigation of increased radiation dose deposition due to gold nanoparticles (GNPs) using a 3D computational cell model during x-ray radiotherapy. Two GNP simulation scenarios were set up in Geant4; a single 400 nm diameter gold cluster randomly positioned in the cytoplasm and a 300 nm gold layer around the nucleus of the cell. Using an 80 kVp photon beam, the effect of GNP on the dose deposition in five modeled regions of the cell including cytoplasm, membrane, and nucleus was simulated. Two Geant4 physics lists were tested: the default Livermore and custom built Livermore/DNA hybrid physics list. 10(6) particles were simulated at 840 cells in the simulation. Each cell was randomly placed with random orientation and a diameter varying between 9 and 13 μm. A mathematical algorithm was used to ensure that none of the 840 cells overlapped. The energy dependence of the GNP physical dose enhancement effect was calculated by simulating the dose deposition in the cells with two energy spectra of 80 kVp and 6 MV. The contribution from Auger electrons was investigated by comparing the two GNP simulation scenarios while activating and deactivating atomic de-excitation processes in Geant4. The physical dose enhancement ratio (DER) of GNP was calculated using the Monte Carlo model. The model has demonstrated that the DER depends on the amount of gold and the position of the gold cluster within the cell. Individual cell regions experienced statistically significant (p < 0.05) change in absorbed dose (DER between 1 and 10) depending on the type of gold geometry used. The DER resulting from gold clusters attached to the cell nucleus had the more significant effect of the two cases (DER ≈ 55). The DER value calculated at 6 MV was shown to be at least an order of magnitude smaller than the DER values calculated for the 80 kVp spectrum. Based on simulations, when 80 kVp photons are used, Auger electrons have a statistically insignificant (p < 0.05) effect on the overall dose increase in the cell. The low energy of the Auger electrons produced prevents them from propagating more than 250-500 nm from the gold cluster and, therefore, has a negligible effect on the overall dose increase due to GNP. The results presented in the current work show that the primary dose enhancement is due to the production of additional photoelectrons.

Towards Effective Photothermal/Photodynamic Treatment Using Plasmonic Gold Nanoparticles

PubMed Central

Bucharskaya, Alla; Maslyakova, Galina; Terentyuk, Georgy; Yakunin, Alexander; Avetisyan, Yuri; Bibikova, Olga; Tuchina, Elena; Khlebtsov, Boris; Khlebtsov, Nikolai; Tuchin, Valery

2016-01-01

Gold nanoparticles (AuNPs) of different size and shape are widely used as photosensitizers for cancer diagnostics and plasmonic photothermal (PPT)/photodynamic (PDT) therapy, as nanocarriers for drug delivery and laser-mediated pathogen killing, even the underlying mechanisms of treatment effects remain poorly understood. There is a need in analyzing and improving the ways to increase accumulation of AuNP in tumors and other crucial steps in interaction of AuNPs with laser light and tissues. In this review, we summarize our recent theoretical, experimental, and pre-clinical results on light activated interaction of AuNPs with tissues and cells. Specifically, we discuss a combined PPT/PDT treatment of tumors and killing of pathogen bacteria with gold-based nanocomposites and atomic clusters, cell optoporation, and theoretical simulations of nanoparticle-mediated laser heating of tissues and cells. PMID:27517913

Site-specific biomolecule labeling with gold clusters.

PubMed

Ackerson, Christopher J; Powell, Richard D; Hainfeld, James F

2010-01-01

Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: linker-mediated bioconjugation, direct gold-biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (His)-tagged proteins. Copyright © 2010 Elsevier Inc. All rights reserved.

Interaction between benzenedithiolate and gold: Classical force field for chemical bonding

NASA Astrophysics Data System (ADS)

Leng, Yongsheng; Krstić, Predrag S.; Wells, Jack C.; Cummings, Peter T.; Dean, David J.

2005-06-01

We have constructed a group of classical potentials based on ab initio density-functional theory (DFT) calculations to describe the chemical bonding between benzenedithiolate (BDT) molecule and gold atoms, including bond stretching, bond angle bending, and dihedral angle torsion involved at the interface between the molecule and gold clusters. Three DFT functionals, local-density approximation (LDA), PBE0, and X3LYP, have been implemented to calculate single point energies (SPE) for a large number of molecular configurations of BDT-1, 2 Au complexes. The three DFT methods yield similar bonding curves. The variations of atomic charges from Mulliken population analysis within the molecule/metal complex versus different molecular configurations have been investigated in detail. We found that, except for bonded atoms in BDT-1, 2 Au complexes, the Mulliken partial charges of other atoms in BDT are quite stable, which significantly reduces the uncertainty in partial charge selections in classical molecular simulations. Molecular-dynamics (MD) simulations are performed to investigate the structure of BDT self-assembled monolayer (SAM) and the adsorption geometry of S adatoms on Au (111) surface. We found that the bond-stretching potential is the most dominant part in chemical bonding. Whereas the local bonding geometry of BDT molecular configuration may depend on the DFT functional used, the global packing structure of BDT SAM is quite independent of DFT functional, even though the uncertainty of some force-field parameters for chemical bonding can be as large as ˜100%. This indicates that the intermolecular interactions play a dominant role in determining the BDT SAMs global packing structure.

Interaction between benzenedithiolate and gold: classical force field for chemical bonding.

PubMed

Leng, Yongsheng; Krstić, Predrag S; Wells, Jack C; Cummings, Peter T; Dean, David J

2005-06-22

We have constructed a group of classical potentials based on ab initio density-functional theory (DFT) calculations to describe the chemical bonding between benzenedithiolate (BDT) molecule and gold atoms, including bond stretching, bond angle bending, and dihedral angle torsion involved at the interface between the molecule and gold clusters. Three DFT functionals, local-density approximation (LDA), PBE0, and X3LYP, have been implemented to calculate single point energies (SPE) for a large number of molecular configurations of BDT-1, 2 Au complexes. The three DFT methods yield similar bonding curves. The variations of atomic charges from Mulliken population analysis within the molecule/metal complex versus different molecular configurations have been investigated in detail. We found that, except for bonded atoms in BDT-1, 2 Au complexes, the Mulliken partial charges of other atoms in BDT are quite stable, which significantly reduces the uncertainty in partial charge selections in classical molecular simulations. Molecular-dynamics (MD) simulations are performed to investigate the structure of BDT self-assembled monolayer (SAM) and the adsorption geometry of S adatoms on Au (111) surface. We found that the bond-stretching potential is the most dominant part in chemical bonding. Whereas the local bonding geometry of BDT molecular configuration may depend on the DFT functional used, the global packing structure of BDT SAM is quite independent of DFT functional, even though the uncertainty of some force-field parameters for chemical bonding can be as large as approximately 100%. This indicates that the intermolecular interactions play a dominant role in determining the BDT SAMs global packing structure.

Site-Specific Biomolecule Labeling with Gold Clusters

PubMed Central

Ackerson, Christopher J.; Powell, Richard D.; Hainfeld, James F.

2013-01-01

Site-specific labeling of biomolecules in vitro with gold clusters can enhance the information content of electron cryomicroscopy experiments. This chapter provides a practical overview of well-established techniques for forming biomolecule/gold cluster conjugates. Three bioconjugation chemistries are covered: Linker-mediated bioconjugation, direct gold–biomolecule bonding, and coordination-mediated bonding of nickel(II) nitrilotriacetic acid (NTA)-derivatized gold clusters to polyhistidine (His)-tagged proteins. PMID:20887859

Studies of cluster-assembled materials: From gas phase to condensed phase

NASA Astrophysics Data System (ADS)

Gao, Lin

Clusters, defined as "a number of similar things that occur together" in Webster's dictionary, has different meanings depending on the given subject. To physicists and chemists, the word cluster means "a group of atoms or molecules formed by interactions ranging from very weak van der Waals interactions to strong ionic bonds." Unlike molecules, which are made by nature and are stable under ambient conditions, clusters discovered in a laboratory are often metastable. Molecules have specific stoichiometry, whereas the cluster's composition can usually be altered atom by atom. Thus, clusters can be taken as intrinsically "artificial molecules" with considerably more tunabilities in their properties. Research into the relative stability and instability of clusters has in recent years become a very active research area, especially following the study by Khanna and Castleman that first suggested that by varying size and composition, clusters can expand the periodic table to the 3 rd-dimension; that is, clusters can mimic the chemistry of atoms and may, therefore, be used as the building blocks of new materials. The discovery of Met-Cars has drawn worldwide interests and has been actively investigated by researchers from a variety of fields, including physics, chemistry and material science. However, the unsuccessful search for a solvent capable of isolating Met-Cars has impeded progress in characterizing the material in the condensed state and, hence, limited its potential applications as a novel nanoscale material. An alternative method involving the deposition of mass-gated species and the subsequent structural investigation via Transmission Electron Microscopy (TEM) has been employed. With particularly interesting results, soft-landed deposits of zirconium Met-Cars were found to form a face-centered-cubic (FCC) structure with a lattice parameter ˜ 15A. The production of Met-Cars is conducted with the direct laser vaporization (DLV) of metal/graphite composite pellets. After being mass gated in a reflectron equipped time-of-flight mass spectrometer (TOF-MS) and deposited onto TEM grids, the resultant specimens can be loaded onto high-resolution TEM investigation via electron diffraction. In conclusion, soft-landing of mass selected clusters has been shown to be a successful approach to obtain structural information on Zr-Met-Car cluster-assembled materials collected from the gas phase. TEM images indicate the richness of the morphologies associated with these cluster crystals. However, passivation methods are expected to be examined further to overcome the limited stabilities of these novel clusters. From this initial study, it's shown the promising opportunity to study other Met-Cars species and more cluster-based materials. Experimental results of reactions run with a solvothermal synthesis method obtained while searching for new Zr-C cluster assembled materials, are reported. One unexpected product in single crystal form was isolated and tentatively identified by X-ray diffraction to be [Zr6i O(OH)O12·2(Bu)4], with space group P2 1/n and lattice parameters of a = 12.44 A, b = 22.06 A, c = 18.40 A, alpha = 90°, beta = 105°, gamma = 90°, V = 4875 A3 and R 1 = 3.15% for the total observed data (I ≥ 2 sigma I) and oR2 = 2.82%. This novel hexanuclear Zr(IV)-oxo-hydroxide cluster anion may be the first member in polyoxometalates class with metal atoms from the IVB group and having Oh symmetry. Alternatively, it may be the first member in {[(Zr6Z)X 12]X6}m- class with halides replaced by oxo- and hydroxyl groups and with an increased oxidation state of Zr. It is predicted to bear application potentials directed by both families. This work could suggest a direction in which the preparation of Zr-C cluster-assembled materials in a liquid environment may be eventually fulfilled. 1,3-Bis(diethylphosphino)propane (depp) protected small gold clusters are studied via multiple techniques, including Electrospray Ionization Mass Spectrometry (ESI-MS), Ultraviolet-Visible Spectroscopy (Uv-Vis), Nuclear Magnetic Resonance (NMR) for solution phase and Transmission Electron Microscopy (TEM) for the condensed phase. In particular, undeca-, dodeca- and trideca-gold clusters protected by depp and halogen ligands, i.e. [Au11-13(depp) 4Cl2-4]+, are found to be all predominant and persist in solution for months, while they gradually and spontaneously grow into a monomial trideca-gold clusters series. The unique preferred ligand combination, depp along with Cl, is discussed in terms of the ligand-core interaction and the closed-shell electronic configurations of the Au n (n = 11-13) cores, which enables them to serve as building units for larger cluster-assembled nanoparticles and form Self-Assembled Arrays (SAAs), as discovered by TEM measurements. Such spontaneous-growth behavior and the resultant SAAs observations are correlated by icosahedra-close-packing modes of clusters, following "magic numbers" rules. ˜7 shells of such cluster packing are proposed to be in the SAAs.

Charge transfer and formation of reduced Ce3+ upon adsorption of metal atoms at the ceria (110) surface.

PubMed

Nolan, Michael

2012-04-07

The modification of cerium dioxide with nanoscale metal clusters is intensely researched for catalysis applications, with gold, silver, and copper having been particularly well studied. The interaction of the metal cluster with ceria is driven principally by a localised interaction between a small number of metal atoms (as small as one) and the surface and understanding the fundamentals of the interaction of metal atoms with ceria surfaces is therefore of great interest. Much attention has been focused on the interaction of metals with the (111) surface of ceria, since this is the most stable surface and can be grown as films, which are probed experimentally. However, nanostructures exposing other surfaces such as (110) show high activity for reactions including CO oxidation and require further study; these nanostructures could be modified by deposition of metal atoms or small clusters, but there is no information to date on the atomic level details of metal-ceria interactions involving the (110) surface. This paper presents the results of density functional theory (DFT) corrected for on-site Coulomb interactions (DFT+U) calculations of the adsorption of a number of different metal atoms at an extended ceria (110) surface; the metals are Au, Ag, Cu, Al, Ga, In, La, Ce, V, Cr, and Fe. Upon adsorption all metals are oxidised, transferring electron(s) to the surface, resulting in localised surface distortions. The precise details depend on the identity of the metal atom. Au, Ag, Cu each transfer one electron to the surface, reducing one Ce ion to Ce(3+), while of the trivalent metals, Al and La are fully oxidised, but Ga and In are only partially oxidised. Ce and the transition metals are also partially oxidised, with the number of reduced Ce ions possible in this surface no more than three per adsorbed metal atom. The predicted oxidation states of the adsorbed metal atoms should be testable in experiments on ceria nanostructures modified with metal atoms.

A phosphorescent silver(I)-gold (I) cluster complex that specifically lights up the nucleolus of living cells with FLIM imaging.

PubMed

Chen, Min; Lei, Zhen; Feng, Wei; Li, Chunyan; Wang, Quan-Ming; Li, Fuyou

2013-06-01

The phosphorescent silver(I)-gold(I) cluster complex [CAu6Ag2(dppy)6](BF4)4 (N1) selectively stains the nucleolus, with a much lower uptake in the nucleus and cytoplasm, and exhibits excellent photostability. This Ag-Au cluster, which has a photoluminescent lifetime of microseconds, is particularly attractive as a probe in applications of time-gated microscopy. Investigation of the pathway of cellular entry indicated that N1 permeates the outer membrane and nuclear membrane of living cells through an energy-dependent and non-endocytic route within 10 min. High concentrations of N1 in the nucleolus have been quantified by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and transmission electron microscopy coupled with an energy dispersive X-ray analysis (TEM-EDXA), which also helped to elucidate the mechanism of the specific staining. Intracellular selective staining may be correlated with the microenvironment of the nucleolus, which is consistent with experiments conducted at different phases of the cell cycle. These results prove that N1 is a very attractive phosphorescent staining reagent for visualizing the nucleolus of living cells. Copyright © 2013 Elsevier Ltd. All rights reserved.

Three-dimensional atom probe tomography of oxide, anion, and alkanethiolate coatings on gold.

PubMed

Zhang, Yi; Hillier, Andrew C

2010-07-15

We have used three-dimensional atom probe tomography to analyze several nanometer-thick and monomolecular films on gold surfaces. High-purity gold wire was etched by electropolishing to create a sharp tip suitable for field evaporation with a radius of curvature of <100 nm. The near-surface region of a freshly etched gold tip was examined with the atom probe at subnanometer spatial resolution and with atom-level composition accuracy. A thin contaminant layer, primarily consisting of water and atmospheric gases, was observed on a fresh tip. This sample exhibited crystalline lattice spacings consistent with the interlayer spacing of {200} lattice planes of bulk gold. A thin oxide layer was created on the gold surface via plasma oxidation, and the thickness and composition of this layer was measured. Clear evidence of a nanometer-thick oxide layer was seen coating the gold tip, and the atomic composition of the oxide layer was consistent with the expected stoichiometry for gold oxide. Monomolecular anions layers of Br(-) and I(-) were created via adsorption from aqueous solutions onto the gold. Atom probe data verified the presence of the monomolecular anion layers on the gold surface, with ion density values consistent with literature values. A hexanethiolate monolayer was coated onto the gold tip, and atom probe analysis revealed a thin film whose ion fragments were consistent with the molecular composition of the monolayer and a surface coverage similar to that expected from literature. Details of the various coating compositions and structures are presented, along with discussion of the reconstruction issues associated with properly analyzing these thin-film systems.

Perspectives on the energy landscape of Au-Cl binary systems from the structural phase diagram of AuxCly (x + y = 20).

PubMed

Tian, Zhimei; Cheng, Longjiu

2015-05-28

Ligand-protected gold (Au-L) nanoclusters have attracted much attention, where the reported electronic and geometric structures show great diversity. To give a direct and overall view of the energy landscape of Au-L binary systems, the AuxCly (x + y = 20) system is taken as a test case. By intensive global search of the potential energy surface at the level of density functional theory, a diverse set of global minima and low-lying isomers are found at each composition, and the structural phase diagram is obtained. The unbiased global search is carried out using the method combining the genetic algorithm with the TPSS functional. At x = 10 with the stoichiometric ratio of Au and Cl (1 : 1), the cluster presents a catenane structure. When x is in the range of 11-20, the clusters are Au-rich, and the Au-Cl system can be viewed as Cl-protected gold nanoclusters, where the gold cores consist of superatoms, superatom networks, or superatomic molecules in electronic structures. At x = 11-15, the gold cores consist of Au3, Au4 and Au5 2e-superatoms protected by staple motifs. At x = 16-20, the clusters are pyramidal superatomic molecules with one Au16 superatom core bonding with the four vertical atoms (Au or Cl). When x is in the scope of 9-5, the clusters are Cl-rich, and the 5d electrons of Au participate in bonding, resulting in high multiplicities. The Au-Cl binary system shows great diversity and flexibility in electronic and geometric structures, and there are corresponding structures to most of the experimentally produced Au-L nanoclusters in our structural phase diagram. We believe that the structural phase diagram gives an overall perspective on the universe of Au-L nanoclusters.

Real-time visualization of clustering and intracellular transport of gold nanoparticles by correlative imaging

NASA Astrophysics Data System (ADS)

Liu, Mengmeng; Li, Qian; Liang, Le; Li, Jiang; Wang, Kun; Li, Jiajun; Lv, Min; Chen, Nan; Song, Haiyun; Lee, Joon; Shi, Jiye; Wang, Lihua; Lal, Ratnesh; Fan, Chunhai

2017-05-01

Mechanistic understanding of the endocytosis and intracellular trafficking of nanoparticles is essential for designing smart theranostic carriers. Physico-chemical properties, including size, clustering and surface chemistry of nanoparticles regulate their cellular uptake and transport. Significantly, even single nanoparticles could cluster intracellularly, yet their clustering state and subsequent trafficking are not well understood. Here, we used DNA-decorated gold (fPlas-gold) nanoparticles as a dually emissive fluorescent and plasmonic probe to examine their clustering states and intracellular transport. Evidence from correlative fluorescence and plasmonic imaging shows that endocytosis of fPlas-gold follows multiple pathways. In the early stages of endocytosis, fPlas-gold nanoparticles appear mostly as single particles and they cluster during the vesicular transport and maturation. The speed of encapsulated fPlas-gold transport was critically dependent on the size of clusters but not on the types of organelle such as endosomes and lysosomes. Our results provide key strategies for engineering theranostic nanocarriers for efficient health management.

Origin of the periodic structure in the conductance curve of gold nanojunctions in hydrogen environment

NASA Astrophysics Data System (ADS)

Jiang, Zhuoling; Wang, Hao; Sanvito, Stefano; Hou, Shimin

2016-03-01

The evolution of the atomic structure and the vibrational and electronic transport properties of gold atomic junctions incorporating molecular and atomic hydrogen upon elongation have been investigated with the nonequilibrium Green's function formalism combined with density functional theory. Our calculations show that for the case of gold junctions doped with a single H2 molecule the low-bias conductance drops rapidly with the electrodes' separation, while it remains almost constant if a single H atom replaces the molecule. In contrast, when one considers two H atoms adsorbed on a gold monatomic chain forming an Au-H-Au-H-Au double-bridge structure, the low-bias conductance increases first and then shows a plateau upon stretching the junction, in perfect agreement with experiments on gold nanocontacts in hydrogen environment. Furthermore, also the distribution of the calculated vibrational energies of the two H atoms is consistent with the experimental result in the low-conductance region, demonstrating clear evidence that hydrogen molecules can dissociate on stretched gold monatomic chains. These findings are helpful to improve our understanding of the structure-property relation of gold nanocontacts and also provide a new prospect for gold nanowires being used as chemical sensors and catalysts.

Adhesion and Atomic Structures of Gold on Ceria Nanostructures:The Role of Surface Structure and Oxidation State of Ceria Supports

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

Lin, Yuyuan; Wu, Zili; Wen, Jianguo

2015-01-01

Recent advances in heterogeneous catalysis have demonstrated that oxides supports with the same material but different shapes can result in metal catalysts with distinct catalytic properties. The shape-dependent catalysis was not well-understood owing to the lack of direct visualization of the atomic structures at metal-oxide interface. Herein, we utilized aberration-corrected electron microscopy and revealed the atomic structures of gold particles deposited on ceria nanocubes and nanorods with {100} or {111} facets exposed. For the ceria nanocube support, gold nanoparticles have extended atom layers at the metal-support interface. In contrast, regular gold nanoparticles and rafts are present on the ceria nanorodmore » support. After hours of water gas shift reaction, the extended gold atom layers and rafts vanish, which is associated with the decrease of the catalytic activities. By understanding the atomic structures of the support surfaces, metal-support interfaces, and morphologies of the gold particles, a direct structure-property relationship is established.« less

A unique ore-placer cluster with high-Hg gold mineralization in the Amur region (Russia)

NASA Astrophysics Data System (ADS)

Stepanov, V. A.; Moyseenko, V. G.; Melnikov, A. V.

2017-02-01

This work presents the geological structure and a description of gold-ore manifestations and gold placers in the Un'ya-Bom ore-placer cluster of the Amur gold-bearing province. The host rocks are Late Paleozoic and Mesozoic black-shale formations. Intrusive formations are rare. The sublatitudinal Un'ya thrust fault, along which Paleozoic sandstones overlap Mesozoic flyschoid deposits, is regarded as an orecontrolling structure. Gold-quartz and low-sulfide ores are confined to quartz-vein zones. Ore minerals are arsenopyrite, scheelite, ferberite, galena, and native gold. Gold-ore manifestations and placers contain high-Hg native gold. The high Hg content in native gold is explained by the occurrence of the eroded frontal part of the gold-ore pipe in the ore cluster, a source of native gold.

Local density variation of gold nanoparticles in aquatic environments

NASA Astrophysics Data System (ADS)

Hosseinzadeh, F.; Shirazian, F.; Shahsavari, R.; Khoei, A. R.

2016-10-01

Gold (Au) nanoparticles are widely used in diagnosing cancer, imaging, and identification of therapeutic methods due to their particular quantum characteristics. This research presents different types of aqueous models and potentials used in TIP3P, to study the effect of the particle size and density of Au clusters in aquatic environments; so it can be useful to facilitate future investigation of the interaction of proteins with Au nanoparticles. The EAM potential is used to model the structure of gold clusters. It is observed that in the systems with identical gold/water density and different cluster radii, gold particles are distributed in aqueous environment almost identically. Thus, Au particles have identical local densities, and the root mean square displacement (RMSD) increases with a constant slope. However in systems with constant cluster radii and different gold/water densities, Au particle dispersion increases with density; as a result, the local density decreases and the RMSD increases with a larger slope. In such systems, the larger densities result in more blunted second peaks in gold-gold radial distribution functions, owing to more intermixing of the clusters and less FCC crystalline features at longer range, a mechanism that is mediated by the competing effects of gold-water and gold-gold interactions.

Structural and optical properties of gold-incorporated diamond-like carbon thin films deposited by RF magnetron sputtering

NASA Astrophysics Data System (ADS)

Majeed, Shahbaz; Siraj, K.; Naseem, S.; Khan, Muhammad F.; Irshad, M.; Faiz, H.; Mahmood, A.

2017-07-01

Pure and gold-doped diamond-like carbon (Au-DLC) thin films are deposited at room temperature by using RF magnetron sputtering in an argon gas-filled chamber with a constant flow rate of 100 sccm and sputtering time of 30 min for all DLC thin films. Single-crystal silicon (1 0 0) substrates are used for the deposition of pristine and Au-DLC thin films. Graphite (99.99%) and gold (99.99%) are used as co-sputtering targets in the sputtering chamber. The optical properties and structure of Au-DLC thin films are studied with the variation of gold concentration from 1%-5%. Raman spectroscopy, atomic force microscopy (AFM), Vickers hardness measurement (VHM), and spectroscopic ellipsometry are used to analyze these thin films. Raman spectroscopy indicates increased graphitic behavior and reduction in the internal stresses of Au-DLC thin films as the function of increasing gold doping. AFM is used for surface topography, which shows that spherical-like particles are formed on the surface, which agglomerate and form larger clusters on the surface by increasing the gold content. Spectroscopy ellipsometry analysis elucidates that the refractive index and extinction coefficient are inversely related and the optical bandgap energy is decreased with increasing gold content. VHM shows that gold doping reduces the hardness of thin films, which is attributed to the increase in sp2-hybridization.

Platinum atomic wire encapsulated in gold nanotubes: A first principle study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib; Sahoo, Suman K.

2014-04-24

The nanotubes of gold incorporated with platinum atomic wire have been investigated by means of firstprinciples density functional theory with plane wave pseudopotential approximation. The structure with zig-zag chain of Pt atoms in side gold is found to be 0.73 eV lower in energy in comparison to straight chain of platinum atoms. The Fermi level of the composite tube was consisting of d-orbitals of Pt atoms. Further interaction of oxygen with these tubes reveals that while tube with zig-zag Pt prefers dissociative adsorption of oxygen molecule, the gold tube with linear Pt wire favors molecular adsorption.

Atomically dispersed Au-(OH)x species bound on titania catalyze the low-temperature water-gas shift reaction.

PubMed

Yang, Ming; Allard, Lawrence F; Flytzani-Stephanopoulos, Maria

2013-03-13

We report a new method for stabilizing appreciable loadings (~1 wt %) of isolated gold atoms on titania and show that these catalyze the low-temperature water-gas shift reaction. The method combines a typical gold deposition/precipitation method with UV irradiation of the titania support suspended in ethanol. Dissociation of H2O on the thus-created Au-O-TiO(x) sites is facile. At higher gold loadings, nanoparticles are formed, but they were shown to add no further activity to the atomically bound gold on titania. Removal of this "excess" gold by sodium cyanide leaching leaves the activity intact and the atomically dispersed gold still bound on titania. The new materials may catalyze a number of other reactions that require oxidized active metal sites.

Measurements of stretch lengths of gold mono-atomic wires covered with 1,6-hexanedithiol in 0.1 M NaClO4 with an electrochemical scanning tunneling microscope.

PubMed

Sun, Jian; Akiba, Uichi; Fujihira, Masamichi

2008-09-01

Stretch lengths of pure gold mono-atomic wires have been studied recently with an electrochemical scanning tunneling microscope (STM). Here, we will report a study of stretch lengths of gold mono-atomic wires with and without 1,6-hexanedithiol (HDT) using the STM break-junction method. First, the stretch length was measured as a function of electrode potentials of a bare Au(111) substrate and a gold STM tip in a 0.1 M NaClO4 aqueous solution. Second, a self-assembled monolayer (SAM) was fabricated on an Au(111) substrate by dipping the substrate into a 1 mM HDT ethanol solution. At last, we measured the stretch length of gold mono-atomic wires on a substrate covered with the SAM in place of the bare Au(111) substrate. We compared the electrode potential dependence of the stretch lengths of gold mono-atomic wires covered with and without HDT. We will discuss the effect of the electrode potential on the stretch lengths by taking account of electrocapillarity of gold mono-atomic wires.

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

DOE PAGES

Grinter, D. C.; Park, J. B.; Agnoli, S.; ...

2016-08-01

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

Water–gas shift reaction over gold nanoparticles dispersed on nanostructured CeO x–TiO 2(110) surfaces: Effects of high ceria coverage

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

Grinter, D. C.; Park, J. B.; Agnoli, S.

We used scanning tunnelling microscopy to study the morphology of an overlayer of ceria in contact with a TiO 2(110) substrate. Two types of domains were observed after ceria deposition. An ordered ceria film covered half of the surface and high-resolution imaging suggested a near-c(6 × 2) relationship to the underlying TiO 2(110)-(1 × 1). For the other half of the surface, it comprised CeO x nanoparticles and reconstructed TiOx supported on TiO 2(110)-(1 × 1). Exposure to a small amount of gold resulted in the formation of isolated gold atoms and small clusters on the ordered ceria film andmore » TiO 2(110)-(1 × 1) areas, which exhibited significant sintering at 500 K and showed strong interaction between the sintered gold clusters and the domain boundaries of the ceria film. The Au/CeO x/TiO 2(110) model system proved to be a good catalyst for the water–gas shift (WGS) exhibiting much higher turnover frequencies (TOFs) than Cu(111) and Pt(111) benchmarks, or the individual Au/TiO 2(110) and Au/CeO 2(111) systems. Finally, for Au/CeO x/TiO 2(110) catalysts, there was a decrease in catalytic activity with increasing ceria coverage that correlates with a reduction in the concentration of Ce 3 + formed during WGS reaction conditions.« less

A Flexible Method for Production of Stable Atomic Clusters with Variable Size for Chemical and Catalytic Activity Studies

DTIC Science & Technology

2011-12-01

Figure 2. Picture of the spark discharge with Ga electrodes. dgap superconducting transition temperature would cause a jump in the AEM current ...failing to comply with a collection of information if it does not display a currently valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE...materials such as gold, sodium, and aluminum will not form a sufficiently concentrated vapor cloud from a current -carrying wire to form aerosol

Advances in single-molecule magnet surface patterning through microcontact printing.

PubMed

Mannini, Matteo; Bonacchi, Daniele; Zobbi, Laura; Piras, Federica M; Speets, Emiel A; Caneschi, Andrea; Cornia, Andrea; Magnani, Agnese; Ravoo, Bart Jan; Reinhoudt, David N; Sessoli, Roberta; Gatteschi, Dante

2005-07-01

We present an implementation of strategies to deposit single-molecule magnets (SMMs) using microcontact printing microCP). We describe different approaches of microCP to print stripes of a sulfur-functionalized dodecamanganese (III, IV) cluster on gold surfaces. Comparison by atomic force microscopy profile analysis of the patterned structures confirms the formation of a chemically stable single layer of SMMs. Images based on chemical contrast, obtained by time-of-flight secondary ion mass spectrometry, confirm the patterned structure.

Determining the composition of gold nanoparticles: a compilation of shapes, sizes, and calculations using geometric considerations.

PubMed

Mori, Taizo; Hegmann, Torsten

2016-01-01

Size, shape, overall composition, and surface functionality largely determine the properties and applications of metal nanoparticles. Aside from well-defined metal clusters, their composition is often estimated assuming a quasi-spherical shape of the nanoparticle core. With decreasing diameter of the assumed circumscribed sphere, particularly in the range of only a few nanometers, the estimated nanoparticle composition increasingly deviates from the real composition, leading to significant discrepancies between anticipated and experimentally observed composition, properties, and characteristics. We here assembled a compendium of tables, models, and equations for thiol-protected gold nanoparticles that will allow experimental scientists to more accurately estimate the composition of their gold nanoparticles using TEM image analysis data. The estimates obtained from following the routines described here will then serve as a guide for further analytical characterization of as-synthesized gold nanoparticles by other bulk (thermal, structural, chemical, and compositional) and surface characterization techniques. While the tables, models, and equations are dedicated to gold nanoparticles, the composition of other metal nanoparticle cores with face-centered cubic lattices can easily be estimated simply by substituting the value for the radius of the metal atom of interest.

Nonlinear effects in defect production by atomic and molecular ion implantation

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

David, C., E-mail: david@igcar.gov.in; Dholakia, Manan; Chandra, Sharat

This report deals with studies concerning vacancy related defects created in silicon due to implantation of 200 keV per atom aluminium and its molecular ions up to a plurality of 4. The depth profiles of vacancy defects in samples in their as implanted condition are carried out by Doppler broadening spectroscopy using low energy positron beams. In contrast to studies in the literature reporting a progressive increase in damage with plurality, implantation of aluminium atomic and molecular ions up to Al{sub 3}, resulted in production of similar concentration of vacancy defects. However, a drastic increase in vacancy defects is observed duemore » to Al{sub 4} implantation. The observed behavioural trend with respect to plurality has even translated to the number of vacancies locked in vacancy clusters, as determined through gold labelling experiments. The impact of aluminium atomic and molecular ions simulated using MD showed a monotonic increase in production of vacancy defects for cluster sizes up to 4. The trend in damage production with plurality has been explained on the basis of a defect evolution scheme in which for medium defect concentrations, there is a saturation of the as-implanted damage and an increase for higher defect concentrations.« less

Global hybrids from the semiclassical atom theory satisfying the local density linear response.

PubMed

Fabiano, Eduardo; Constantin, Lucian A; Cortona, Pietro; Della Sala, Fabio

2015-01-13

We propose global hybrid approximations of the exchange-correlation (XC) energy functional which reproduce well the modified fourth-order gradient expansion of the exchange energy in the semiclassical limit of many-electron neutral atoms and recover the full local density approximation (LDA) linear response. These XC functionals represent the hybrid versions of the APBE functional [Phys. Rev. Lett. 2011, 106, 186406] yet employing an additional correlation functional which uses the localization concept of the correlation energy density to improve the compatibility with the Hartree-Fock exchange as well as the coupling-constant-resolved XC potential energy. Broad energetic and structural testing, including thermochemistry and geometry, transition metal complexes, noncovalent interactions, gold clusters and small gold-molecule interfaces, as well as an analysis of the hybrid parameters, show that our construction is quite robust. In particular, our testing shows that the resulting hybrid, including 20% of Hartree-Fock exchange and named hAPBE, performs remarkably well for a broad palette of systems and properties, being generally better than popular hybrids (PBE0 and B3LYP). Semiempirical dispersion corrections are also provided.

Charge Retention by Monodisperse Gold Clusters on Surfaces Prepared Using Soft Landing of Mass Selected Ions

NASA Astrophysics Data System (ADS)

Johnson, Grant; Priest, Thomas; Laskin, Julia

2012-02-01

Monodisperse gold clusters have been prepared on surfaces in different charge states through soft landing of mass-selected ions. Gold clusters were synthesized in methanol solution by reduction of a gold precursor with a weak reducing agent in the presence of a diphosphine capping ligand. Electrospray ionization was used to introduce the clusters into the gas-phase and mass-selection was employed to isolate a single ionic cluster species which was delivered to surfaces at well controlled kinetic energies. Using in-situ time of flight secondary ion mass spectrometry (SIMS) it is demonstrated that the cluster retains its 3+ charge state when soft landed onto the surface of a fluorinated self assembled monolayer on gold. In contrast, when deposited onto carboxylic acid terminated and conventional alkyl thiol surfaces on gold the clusters exhibit larger relative abundances of the 2+ and 1+ charge states, respectively. The kinetics of charge reduction on the surface have been investigated using in-situ Fourier Transform Ion Cyclotron Resonance SIMS. It is shown that an extremely slow interfacial charge reduction occurs on the fluorinated monolayer surface while an almost instantaneous neutralization takes place on the surface of the alkyl thiol monolayer. Our results demonstrate that the size and charge state of small gold clusters on surfaces, both of which exert a dramatic influence on their chemical and physical properties, may be tuned through soft landing of mass-selected ions onto selected substrates.

Phase transitions and kinetic properties of gold nanoparticles confined between two-layer graphene nanosheets

NASA Astrophysics Data System (ADS)

Wang, Gang; Wu, Nanhua; Chen, Jionghua; Wang, Jinjian; Shao, Jingling; Zhu, Xiaolei; Lu, Xiaohua; Guo, Lucun

2016-11-01

The thermodynamic and kinetic behaviors of gold nanoparticles confined between two-layer graphene nanosheets (two-layer-GNSs) are examined and investigated during heating and cooling processes via molecular dynamics (MD) simulation technique. An EAM potential is applied to represent the gold-gold interactions while a Lennard-Jones (L-J) potential is used to describe the gold-GNS interactions. The MD melting temperature of 1345 K for bulk gold is close to the experimental value (1337 K), confirming that the EAM potential used to describe gold-gold interactions is reliable. On the other hand, the melting temperatures of gold clusters supported on graphite bilayer are corrected to the corresponding experimental values by adjusting the εAu-C value. Therefore, the subsequent results from current work are reliable. The gold nanoparticles confined within two-layer GNSs exhibit face center cubic structures, which is similar to those of free gold clusters and bulk gold. The melting points, heats of fusion, and heat capacities of the confined gold nanoparticles are predicted based on the plots of total energies against temperature. The density distribution perpendicular to GNS suggests that the freezing of confined gold nanoparticles starts from outermost layers. The confined gold clusters exhibit layering phenomenon even in liquid state. The transition of order-disorder in each layer is an essential characteristic in structure for the freezing phase transition of the confined gold clusters. Additionally, some vital kinetic data are obtained in terms of classical nucleation theory.

Optical amplification of photothermal therapy with gold nanoparticles and nanoclusters

NASA Astrophysics Data System (ADS)

Khlebtsov, Boris; Zharov, Vladimir; Melnikov, Andrei; Tuchin, Valery; Khlebtsov, Nikolai

2006-10-01

Recently, several groups (Anderson, Halas, Zharov, and their co-workers, 2003; El-Sayed and co-workers, 2006) demonstrated, through pioneering results, the great potential of photothermal (PT) therapy for the selective treatment of cancer cells, bacteria, viruses, and DNA targeted with gold nanospheres, nanoshells, nanorods, and nanosphere clusters. However, the current understanding of the relationship between the nanoparticle/cluster parameters (size, shape, particle/cluster structure, etc) and the efficiency of PT therapy is limited. Here, we report theoretical simulations aimed at finding the optimal single-particle and cluster structures to achieve its maximal absorption, which is crucial for PT therapeutic effects. To characterize the optical amplification in laser-induced thermal effects, we introduce relevant parameters such as the ratio of the absorption cross section to the gold mass of a single-particle structure and absorption amplification, defined as the ratio of cluster absorption to the total absorption of non-interacting particles. We consider the absorption efficiency of single nanoparticles (gold spheres, rods, and silica/gold nanoshells), linear chains, 2D lattice arrays, 3D random volume clusters, and the random aggregated N-particle ensembles on the outer surface of a larger dielectric sphere, which mimic aggregation of nanosphere bioconjugates on or within cancer cells. The cluster particles are bare or biopolymer-coated gold nanospheres. The light absorption of cluster structures is studied by using the generalized multiparticle Mie solution and the T-matrix method. The gold nanoshells with (silica core diameter)/(gold shell thickness) parameters of (50-100)/(3-8) nm and nanorods with minor/major sizes of (15-20)/(50-70) nm are shown to be more efficient PT labels and sensitizers than the equivolume solid single gold spheres. In the case of nanosphere clusters, the interparticle separations and the short linear-chain fragments are the main structural parameters determining the absorption efficiency and its spectral shifting to the red. Although we have not found a noticeable dependence of absorption amplification on the cluster sphere size, 20-40 nm particles are found to be most effective, in accordance with our experimental observations. The long-wavelength absorption efficiency of random clusters increases with the cluster particle number N at small N and reveals a saturation behaviour at N>20.

Efficient electrocatalytic conversion of CO.sub.2 to CO using ligand-protected Au.sub.25 clusters

DOEpatents

Kauffman, Douglas; Matranga, Christopher; Qian, Huifeng; Jin, Rongchao; Alfonso, Dominic R.

2015-09-22

An apparatus and method for CO.sub.2 reduction using an Au.sub.25 electrode. The Au.sub.25 electrode is comprised of ligand-protected Au.sub.25 having a structure comprising an icosahedral core of 13 atoms surrounded by a shell of six semi-ring structures bonded to the core of 13 atoms, where each semi-ring structure is typically --SR--Au--SR--Au--SR or --SeR--Au--SeR--Au--SeR. The 12 semi-ring gold atoms within the six semi-ring structures are stellated on 12 of the 20 faces of the icosahedron of the Au.sub.13 core, and organic ligand --SR or --SeR groups are bonded to the Au.sub.13 core with sulfur or selenium atoms. The Au.sub.25 electrode and a counter-electrode are in contact with an electrolyte comprising CO.sub.2 and H+, and a potential of at least -0.1 volts is applied from the Au.sub.25 electrode to the counter-electrode.

Adsorption of carbon monoxide on smaller gold-cluster anions in an atmospheric-pressure flow-reactor: temperature and humidity dependence.

PubMed

Wallace, William T; Wyrwas, Richard B; Leavitt, Andrew J; Whetten, Robert L

2005-03-07

In the absence of moisture and at room temperature, the activity and saturation of CO on gold cluster anions, Au(N)-, are known to be highly dependent on the size of the cluster. Small Au(N)- clusters (N = 2,3) showed no adsorption activity, and the saturation CO adsorption values did not increase proportionately to cluster size or area. Here, we report on the effects of water vapor and temperature on the ability of Au(N)- clusters to adsorb CO in a high-pressure, fast-flow reactor. In contrast to all earlier reports, our results using this method show that smaller gold-cluster anions bind single and multiple CO groups at ambient temperature and above. In particular, species previously unseen at room temperature, corresponding to Au2(CO)-, Au3(CO) and Au4(CO)2, have been observed. Apparently, the presence of water vapor facilitates the adsorption of CO on the smaller clusters, possibly by aiding in the release of adsorption energy. As the number of studies concerning gold catalysis has continually increased over the past decade, these results provide important new information on the possible role of moisture in gold catalysis.

Nanoscale Decoration of Electrode Surfaces with an STM

DTIC Science & Technology

1999-05-30

covered gold electrode surfaces at predetermined positions. First, metal is deposited electrochemically onto the STM tip, then the clusters are formed by a...onto the tip, the jump-to-contact occurs in the opposite direction leaving holes in the gold surface. The stability of the metal clusters against anodic...deposition, clusters, a surprisingly high stability of the small Ag Hg/HgSO4 for Ag deposition and a Pt wire for Ni clusters on gold against anodic

Precipitation of lamellar gold nanocrystals in molten polymers

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

Palomba, M.; Carotenuto, G., E-mail: giancaro@unina.it

Non-aggregated lamellar gold crystals with regular shape (triangles, squares, pentagons, etc.) have been produced by thermal decomposition of gold chloride (AuCl) molecules in molten amorphous polymers (polystyrene and poly(methyl methacrylate)). Such covalent inorganic gold salt is high soluble into non-polar polymers and it thermally decomposes at temperatures compatible with the polymer thermal stability, producing gold atoms and chlorine radicals. At the end of the gold precipitation process, the polymer matrix resulted chemically modified because of the partial cross-linking process due to the gold atom formation reaction.

Electron localization in rod-shaped triicosahedral gold nanocluster

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

Zhou, Meng; Jin, Renxi; Sfeir, Matthew Y.

Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. There is little known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. We reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons tomore » one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm -1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The electron localization phenomenon we observed provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.« less

Electron localization in rod-shaped triicosahedral gold nanocluster

DOE PAGES

Zhou, Meng; Jin, Renxi; Sfeir, Matthew Y.; ...

2017-05-30

Atomically precise gold nanocluster based on linear assembly of repeating icosahedrons (clusters of clusters) is a unique type of linear nanostructure, which exhibits strong near-infrared absorption as their free electrons are confined in a one-dimensional quantum box. There is little known about the carrier dynamics in these nanoclusters, which limit their energy-related applications. We reported the observation of exciton localization in triicosahedral Au37 nanoclusters (0.5 nm in diameter and 1.6 nm in length) by measuring femtosecond and nanosecond carrier dynamics. Upon photoexcitation to S1 electronic state, electrons in Au37 undergo ~100-ps localization from the two vertexes of three icosahedrons tomore » one vertex, forming a long-lived S1* state. Such phenomenon is not observed in Au25 (dimer) and Au13 (monomer) consisting of two and one icosahedrons, respectively. We have further observed temperature dependence on the localization process, which proves it is thermally driven. Two excited-state vibration modes with frequencies of 20 and 70 cm -1 observed in the kinetic traces are assigned to the axial and radial breathing modes, respectively. The electron localization is ascribed to the structural distortion of Au37 in the excited state induced by the strong coherent vibrations. The electron localization phenomenon we observed provides unique physical insight into one-dimensional gold nanoclusters and other nanostructures, which will advance their applications in solar-energy storage and conversion.« less

Approximate treatment of semicore states in GW calculations with application to Au clusters.

PubMed

Xian, Jiawei; Baroni, Stefano; Umari, P

2014-03-28

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G0W0 level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore states are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au20 and Au32, that would be otherwise very difficult to deal with.

Approximate treatment of semicore states in GW calculations with application to Au clusters

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

Xian, Jiawei; Baroni, Stefano; CNR-IOM Democritos, Theory-Elettra group, Trieste

We address the treatment of transition metal atoms in GW electronic-structure calculations within the plane-wave pseudo-potential formalism. The contributions of s and p semi-core electrons to the self-energy, which are essential to grant an acceptable accuracy, are dealt with using a recently proposed scheme whereby the exchange components are treated exactly at the G{sub 0}W{sub 0} level, whereas a suitable approximation to the correlation components is devised. This scheme is benchmarked for small gold nano-clusters, resulting in ionization potentials, electron affinities, and density of states in very good agreement with those obtained from calculations where s and p semicore statesmore » are treated as valence orbitals, and allowing us to apply this same scheme to clusters of intermediate size, Au{sub 20} and Au{sub 32}, that would be otherwise very difficult to deal with.« less

Flameless atomic-absorption determination of gold in geological materials

USGS Publications Warehouse

Meier, A.L.

1980-01-01

Gold in geologic material is dissolved using a solution of hydrobromic acid and bromine, extracted with methyl isobutyl ketone, and determined using an atomic-absorption spectrophotometer equipped with a graphite furnace atomizer. A comparison of results obtained by this flameless atomic-absorption method on U.S. Geological Survey reference rocks and geochemical samples with reported values and with results obtained by flame atomic-absorption shows that reasonable accuracy is achieved with improved precision. The sensitivity, accuracy, and precision of the method allows acquisition of data on the distribution of gold at or below its crustal abundance. ?? 1980.

Alloy-assisted deposition of three-dimensional arrays of atomic gold catalyst for crystal growth studies

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

Fang, Yin; Jiang, Yuanwen; Cherukara, Mathew J.

Large-scale assembly of individual atoms over smooth surfaces is difficult to achieve. A configuration of an atom reservoir, in which individual atoms can be readily extracted, may successfully address this challenge. In this work, we demonstrate that a liquid gold-silicon alloy established in classical vapor-liquid-solid growth can deposit ordered and three-dimensional rings of isolated gold atoms over silicon nanowire sidewalls. Here, we perform ab initio molecular dynamics simulation and unveil a surprising single atomic gold-catalyzed chemical etching of silicon. Experimental verification of this catalytic process in silicon nanowires yields dopant-dependent, massive and ordered 3D grooves with spacing down to similarmore » to 5 nm. Finally, we use these grooves as self-labeled and ex situ markers to resolve several complex silicon growths, including the formation of nodes, kinks, scale-like interfaces, and curved backbones.« less

Alloy-assisted deposition of three-dimensional arrays of atomic gold catalyst for crystal growth studies

DOE PAGES

Fang, Yin; Jiang, Yuanwen; Cherukara, Mathew J.; ...

2017-12-08

Large-scale assembly of individual atoms over smooth surfaces is difficult to achieve. A configuration of an atom reservoir, in which individual atoms can be readily extracted, may successfully address this challenge. In this work, we demonstrate that a liquid gold-silicon alloy established in classical vapor-liquid-solid growth can deposit ordered and three-dimensional rings of isolated gold atoms over silicon nanowire sidewalls. Here, we perform ab initio molecular dynamics simulation and unveil a surprising single atomic gold-catalyzed chemical etching of silicon. Experimental verification of this catalytic process in silicon nanowires yields dopant-dependent, massive and ordered 3D grooves with spacing down to similarmore » to 5 nm. Finally, we use these grooves as self-labeled and ex situ markers to resolve several complex silicon growths, including the formation of nodes, kinks, scale-like interfaces, and curved backbones.« less

Scanning the potential energy surface for synthesis of dendrimer-wrapped gold clusters: design rules for true single-molecule nanostructures.

PubMed

Thompson, Damien; Hermes, Jens P; Quinn, Aidan J; Mayor, Marcel

2012-04-24

The formation of true single-molecule complexes between organic ligands and nanoparticles is challenging and requires careful design of molecules with size, shape, and chemical properties tailored for the specific nanoparticle. Here we use computer simulations to describe the atomic-scale structure, dynamics, and energetics of ligand-mediated synthesis and interlinking of 1 nm gold clusters. The models help explain recent experimental results and provide insight into how multidentate thioether dendrimers can be employed for synthesis of true single-ligand-nanoparticle complexes and also nanoparticle-molecule-nanoparticle "dumbbell" nanostructures. Electronic structure calculations reveal the individually weak thioether-gold bonds (325 ± 36 meV), which act collectively through the multivalent (multisite) anchoring to stabilize the ligand-nanoparticle complex (∼7 eV total binding energy) and offset the conformational and solvation penalties involved in this "wrapping" process. Molecular dynamics simulations show that the dendrimer is sufficiently flexible to tolerate the strained conformations and desolvation penalties involved in fully wrapping the particle, quantifying the subtle balance between covalent anchoring and noncovalent wrapping in the assembly of ligand-nanoparticle complexes. The computed preference for binding of a single dendrimer to the cluster reveals the prohibitively high dendrimer desolvation barrier (1.5 ± 0.5 eV) to form the alternative double-dendrimer structure. Finally, the models show formation of an additional electron transfer channel between nitrogen and gold for ligands with a central pyridine unit, which gives a stiff binding orientation and explains the recently measured larger interparticle distances for particles synthesized and interlinked using linear ligands with a central pyridine rather than a benzene moiety. The findings stress the importance of organic-inorganic interactions, the control of which is central to the rational engineering and eventual large-scale production of functional building blocks for nano(bio)electronics.

MICROSCOPIC USES OF NANOGOLD.

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

HAINFELD,J.F.POWELL,R.D.FURUYA,F.R.

2003-04-17

Gold has been used for immunocytochemistry since 1971 when Faulk and Taylor discovered adsorption of antibodies to colloidal gold. It is an ideal label for electron microscopy (EM) due to its high atomic number, which scatters electrons efficiently, and the fact that preparative methods have been developed to make uniform particles in the appropriate size range of 5 to 30 nm. Use in light microscopy (LM) generally requires silver enhancement (autometallography; AMG) of these small gold particles. Significant advances in this field since that time have included a better understanding of the conditions for best antibody adsorption, more regular goldmore » size production, adsorption of other useful molecules, like protein A, and advances in silver enhancement. Many studies have also been accomplished showing the usefulness of these techniques to cell biology and biomedical research. A further advance in this field was the development of Nanogold{trademark}, a 1.4 nm gold cluster. A significant difference from colloidal gold is that Nanogold is actually a coordination compound containing a gold core covalently linked to surface organic groups. These in turn may be covalently attached to antibodies. This approach to immunolabeling has several advantages compared to colloidal gold such as vastly better penetration into tissues, generally greater sensitivity, and higher density of labeling. Since Nanogold is covalently coupled to antibodies, it may also be directly coupled to almost any protein, peptide, carbohydrate, or molecule of interest, including molecules which do not adsorb to colloidal gold. This increases the range of probes possible, and expands the applications of gold labeling.« less

Molecular vibrations in metal-single-molecule-metal junctions

NASA Astrophysics Data System (ADS)

Yokota, Kazumichi; Taniguchi, Masateru; Kawai, Tomoji

2010-03-01

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

Inelastic fingerprints of hydrogen contamination in atomic gold wire systems

NASA Astrophysics Data System (ADS)

Frederiksen, Thomas; Paulsson, Magnus; Brandbyge, Mads

2007-03-01

We present series of first-principles calculations for both pure and hydrogen contaminated gold wire systems in order to investigate how such impurities can be detected. We show how a single H atom or a single H2 molecule in an atomic gold wire will affect forces and Au-Au atom distances under elongation. We further determine the corresponding evolution of the low-bias conductance as well as the inelastic contributions from vibrations. Our results indicate that the conductance of gold wires is only slightly reduced from the conductance quantum G0 = 2e2/h by the presence of a single hydrogen impurity, hence making it difficult to use the conductance itself to distinguish between various configurations. On the other hand, our calculations of the inelastic signals predict significant differences between pure and hydrogen contaminated wires, and, importantly, between atomic and molecular forms of the impurity. A detailed characterization of gold wires with a hydrogen impurity should therefore be possible from the strain dependence of the inelastic signals in the conductance.

Symmetry and electronic structure of noble-metal nanoparticles and the role of relativity.

PubMed

Häkkinen, Hannu; Moseler, Michael; Kostko, Oleg; Morgner, Nina; Hoffmann, Margarita Astruc; von Issendorff, Bernd

2004-08-27

We present high resolution UV-photoelectron spectra of cold mass selected Cun-, Agn-, and Aun- with n=53-58. The observed electron density of states is not the expected simple electron shell structure, but is strongly influenced by electron-lattice interactions. Only Cu55- and Ag55- exhibit highly degenerate states. This is a direct consequence of their icosahedral symmetry, as is confirmed by density functional theory calculations. Neighboring sizes exhibit perturbed electronic structures, as they are formed by removal or addition of atoms to the icosahedron and therefore have lower symmetries. Gold clusters in the same size range show completely different spectra with almost no degeneracy, which indicates that they have structures of much lower symmetry. This behavior is related to strong relativistic bonding effects in gold, as demonstrated by ab initio calculations for Au55-.

Clusters of Monoisotopic Elements for Calibration in (TOF) Mass Spectrometry

NASA Astrophysics Data System (ADS)

Kolářová, Lenka; Prokeš, Lubomír; Kučera, Lukáš; Hampl, Aleš; Peňa-Méndez, Eladia; Vaňhara, Petr; Havel, Josef

2017-03-01

Precise calibration in TOF MS requires suitable and reliable standards, which are not always available for high masses. We evaluated inorganic clusters of the monoisotopic elements gold and phosphorus (Au n +/Au n - and P n +/P n -) as an alternative to peptides or proteins for the external and internal calibration of mass spectra in various experimental and instrumental scenarios. Monoisotopic gold or phosphorus clusters can be easily generated in situ from suitable precursors by laser desorption/ionization (LDI) or matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). Their use offers numerous advantages, including simplicity of preparation, biological inertness, and exact mass determination even at lower mass resolution. We used citrate-stabilized gold nanoparticles to generate gold calibration clusters, and red phosphorus powder to generate phosphorus clusters. Both elements can be added to samples to perform internal calibration up to mass-to-charge ( m/z) 10-15,000 without significantly interfering with the analyte. We demonstrated the use of the gold and phosphorous clusters in the MS analysis of complex biological samples, including microbial standards and total extracts of mouse embryonic fibroblasts. We believe that clusters of monoisotopic elements could be used as generally applicable calibrants for complex biological samples.

High-mass heterogeneous cluster formation by ion bombardment of the ternary alloy Au 7Cu 5Al 4

DOE PAGES

Zinovev, Alexander V.; King, Bruce V.; Veryovkin, Igor V.; ...

2016-02-04

The ternary alloy Au 7Cu 5Al 4 was irradiated with 0.1–10 keV Ar + and the surface composition analyzed using laser sputter neutral mass spectrometry. Ejected clusters containing up to seven atoms, with masses up to 2000 amu, were observed. By monitoring the signals from sputtered clusters, the surface composition of the alloy was seen to change with 100 eV Ar + dose, reaching equilibrium after 10 nm of the surface was eroded, in agreement with TRIDYN simulation and indicating that the changes were due to preferential sputtering of Al and Cu. Ejected gold containing clusters were found to increasemore » markedly in intensity while aluminum containing clusters decreased in intensity as a result of Ar sputtering. Such an effect was most pronounced for low energy (<1 keV) Ar + sputtering and was consistent with TRIDYN simulations of the depth profiling. As a result, the component sputter yields from the ternary alloy were consistent with previous binary alloy measurements but showed greater Cu surface concentrations than expected from TRIDYN simulations.« less

Time-resolved in situ XAS study of the preparation of supported gold clusters.

PubMed

Bus, Eveline; Prins, Roel; van Bokhoven, Jeroen A

2007-07-07

Incipient-wetness impregnation of gamma-Al(2)O(3) with HAuCl(4) and subsequent removal of chlorine with NaOH, and deposition-precipitation of HAuCl(4) on TiO(2) at pH 7 resulted in supported Au(3+) species. Time-resolved in situ XAS at the Au L(3) edge showed that the Al(2)O(3)-supported oxidic or hydroxidic species were reduced in hydrogen at 440 K to yield small metallic gold clusters. The Au(3+) precursor decomposed to metallic gold in inert atmosphere at 573 K and in oxidizing atmosphere above 623 K. In all atmospheres, initially small clusters were formed that gradually grew with increasing temperature. The TiO(2)-supported species were considerably less stable. In hydrogen and carbon monoxide, Au(0) clusters of 1 to 1.5 nm were formed at room temperature, which was the lowest temperature studied. In inert and oxidizing atmosphere, the Au(3+) precursor decomposed fully to metallic gold at 530 K, as shown by XAS and temperature-programmed experiments. Large clusters were obtained already in the initial stage of reduction. Residual chlorine inhibited the reduction and led to sintering of the gold clusters. Exposure of the TiO(2)-supported catalyst precursor to light or the X-ray beam led to partial reduction, and STEM showed that storage of the reduced gold clusters under ambient conditions led to agglomeration and bimodal cluster-size distributions.

Coverage Dependent Charge Reduction of Cationic Gold Clusters on Surfaces Prepared Using Soft Landing of Mass-selected Ions

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

Johnson, Grant E.; Priest, Thomas A.; Laskin, Julia

2012-11-29

The ionic charge state of monodisperse cationic gold clusters on surfaces may be controlled by selecting the coverage of mass-selected ions soft landed onto a substrate. Polydisperse diphosphine-capped gold clusters were synthesized in solution by reduction of chloro(triphenylphosphine)gold(I) with borane tert-butylamine in the presence of 1,3-bis(diphenylphosphino)propane. The polydisperse gold clusters were introduced into the gas phase by electrospray ionization and mass selection was employed to select a multiply charged cationic cluster species (Au11L53+, m/z = 1409, L = 1,3-bis(diphenylphosphino)propane) which was delivered to the surfaces of four different self-assembled monolayers on gold (SAMs) at coverages of 1011 and 1012 clusters/mm2.more » Employing the spatial profiling capabilities of in-situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) it is shown that, in addition to the chemical functionality of the monolayer (as demonstrated previously: ACS Nano, 2012, 6, 573) the coverage of cationic gold clusters on the surface may be used to control the distribution of ionic charge states of the soft-landed multiply charged clusters. In the case of a 1H,1H,2H,2H-perfluorodecanethiol SAM (FSAM) almost complete retention of charge by the deposited Au11L53+ clusters was observed at a lower coverage of 1011 clusters/mm2. In contrast, at a higher coverage of 1012 clusters/mm2, pronounced reduction of charge to Au11L52+ and Au11L5+ was observed on the FSAM. When soft landed onto 16- and 11-mercaptohexadecanoic acid surfaces on gold (16,11-COOH-SAMs), the mass-selected Au11L53+ clusters exhibited partial reduction of charge to Au11L52+ at lower coverage and additional reduction of charge to both Au11L52+ and Au11L5+ at higher coverage. The reduction of charge was found to be more pronounced on the surface of the shorter (thinner) C11 than the longer (thicker) C16-COOH-SAM. On the surface of the 1-dodecanethiol (HSAM) monolayer, the most abundant charge state was found to be Au11L52+ at lower coverage and Au11L5+ at higher coverage, respectively. A coverage-dependent electron tunneling mechanism is proposed to account for the observed reduction of charge of mass-selected multiply charged gold clusters soft landed on SAMs. The results demonstrate that one of the critical parameters that influence the chemical and physical properties of supported metal clusters, ionic charge state, may be controlled by selecting the coverage of charged species soft landed onto surfaces.« less

Transformation of Au144(SCH2CH2Ph)60 to Au133(SPh-tBu)52 Nanomolecules: Theoretical and Experimental Study.

PubMed

Nimmala, Praneeth Reddy; Theivendran, Shevanuja; Barcaro, Giovanni; Sementa, Luca; Kumara, Chanaka; Jupally, Vijay Reddy; Apra, Edoardo; Stener, Mauro; Fortunelli, Alessandro; Dass, Amala

2015-06-04

Ultrastable gold nanomolecule Au144(SCH2CH2Ph)60 upon etching with excess tert-butylbenzenethiol undergoes a core-size conversion and compositional change to form an entirely new core of Au133(SPh-tBu)52. This conversion was studied using high-resolution electrospray mass spectrometry which shows that the core size conversion is initiated after 22 ligand exchanges, suggesting a relatively high stability of the Au144(SCH2CH2Ph)38(SPh-tBu)22 intermediate. The Au144 → Au133 core size conversion is surprisingly different from the Au144 → Au99 core conversion reported in the case of thiophenol, -SPh. Theoretical analysis and ab initio molecular dynamics simulations show that rigid p-tBu groups play a crucial role by reducing the cluster structural freedom, and protecting the cluster from adsorption of exogenous and reactive species, thus rationalizing the kinetic factors that stabilize the Au133 core size. This 144-atom to 133-atom nanomolecule's compositional change is reflected in optical spectroscopy and electrochemistry.

Formation of small gold clusters in solution by laser excitation of interband transition

NASA Astrophysics Data System (ADS)

Mafuné, Fumitaka; Kondow, Tamotsu

2003-04-01

Gold nanoparticles with ˜10 nm in average diameter were prepared by laser ablation of a gold metal plate in an aqueous solution of sodium dodecyl sulfate (SDS) and were fragmented by excitation of an interband transition of gold nanoparticles under irradiation of an intense 355-nm pulsed laser. Fragmentation dynamics was investigated by comparing the fragmentation by excitation of a surface plasmon band of gold nanoparticles by a 532-nm laser. It is found that gold nanoparticles with 1.5-nm average diameter are produced together with small gold clusters by properly optimizing the surfactant concentration.

Mapping atomic contact between pentacene and a Au surface using scanning tunneling spectroscopy.

PubMed

Song, Young Jae; Lee, Kyuho; Kim, Seong Heon; Choi, Byoung-Young; Yu, Jaejun; Kuk, Young

2010-03-10

We mapped spatially varying intramolecular electronic structures on a pentacene-gold interface using scanning tunneling spectroscopy. Along with ab initio calculations based on density functional theory, we found that the directional nature of the d orbitals of Au atoms plays an important role in the interaction at the pentacene-gold contact. The gold-induced interface states are broadened and shifted by various pentacene-gold distances determined by the various registries of a pentacene molecule on a gold substrate.

Substrate doping: A strategy for enhancing reactivity on gold nanocatalysts by tuning sp bands

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

Mammen, Nisha; Narasimhan, Shobhana; Gironcoli, Stefano de

2015-10-14

We suggest that the reactivity of Au nanocatalysts can be greatly increased by doping the oxide substrate on which they are placed with an electron donor. To demonstrate this, we perform density functional theory calculations on a model system consisting of a 20-atom gold cluster placed on a MgO substrate doped with Al atoms. We show that not only does such substrate doping switch the morphology of the nanoparticles from the three-dimensional tetrahedral form to the two-dimensional planar form, but it also significantly lowers the barrier for oxygen dissociation by an amount proportional to the dopant concentration. At a dopingmore » level of 2.78%, the dissociation barrier is reduced by more than half, which corresponds to a speeding up of the oxygen dissociation rate by five orders of magnitude at room temperature. This arises from a lowering in energy of the s and p states of Au. The d states are also lowered in energy, however, this by itself would have tended to reduce reactivity. We propose that a suitable measure of the reactivity of Au nanoparticles is the difference in energy of sp and d states.« less

Influence of the size and charge of gold nanoclusters on complexation with siRNA: a molecular dynamics simulation study.

PubMed

Mudedla, Sathish Kumar; Azhagiya Singam, Ettayapuram Ramaprasad; Balamurugan, Kanagasabai; Subramanian, Venkatesan

2015-11-11

The complexation of small interfering RNA (siRNA) with positively charged gold nanoclusters has been studied in the present investigation with the help of classical molecular dynamics and steered molecular dynamics simulations accompanied by free energy calculations. The results show that gold nanoclusters form a stable complex with siRNA. The wrapping of siRNA around the gold nanocluster depends on the size and charge on the surface of the gold cluster. The binding pattern of the gold nanocluster with siRNA is also influenced by the presence of another cluster. The interaction between the positively charged amines in the gold nanocluster and the negatively charged phosphate group in the siRNA is responsible for the formation of complexes. The binding free energy value increases with the size of the gold cluster and the number of positive charges present on the surface of the gold nanocluster. The results reveal that the binding energy of small gold nanoclusters increases in the presence of another gold nanocluster while the binding of large gold nanoclusters decreases due to the introduction of another gold nanocluster. Overall, the findings have clearly demonstrated the effect of size and charge of gold nanoclusters on their interaction pattern with siRNA.

A hexanuclear gold carbonyl cluster† †Dedicated to Prof. Dr Pablo Espinet on the occasion of his 65th birthday. Abbreviations are defined prior to the Acknowledgements section. As defined in ref. 1, “clusters are molecular units which may contain small or large numbers of similar atoms where there are several short internuclear distances between atom pairs.” This definition is fully compatible with that originally given by F. A. Cotton (ref. 2). ‡ ‡Electronic supplementary information (ESI) available: Experimental procedures, comments on the X-ray structure determinations and 3D Hirschfeld surfaces for the ions constituting the crystal of 4. CCDC 1049919–1049921. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01578b Click here for additional data file. Click here for additional data file.

PubMed Central

Martínez-Salvador, Sonia; Falvello, Larry R.; Martín, Antonio

2015-01-01

The hexanuclear gold carbonyl cluster [PPh4]2[Au6(CF3)6Br2(CO)2] (4) has been obtained by spontaneous self-assembly of the following independent units: CF3AuCO (1) and [PPh4][Br(AuCF3)2] (3). The cyclo-Au6 aggregate 4, in which the components are held together by unassisted, fairly strong aurophilic interactions (Au···Au ∼310 pm), exhibits a cyclohexane-like arrangement with chair conformation. These aurophilic interactions also result in significant ν(CO) lowering: from 2194 cm–1 in the separate component 1 to 2171 cm–1 in the mixed aggregate 4. Procedures to prepare the single-bridged dinuclear component 3 as well as the mononuclear derivative [PPh4][CF3AuBr] (2) are also reported. PMID:28717445

DFT calculations for Au adsorption onto a reduced TiO2 (110) surface with the coexistence of Cl

NASA Astrophysics Data System (ADS)

Tada, Kohei; Sakata, Kohei; Yamada, Satoru; Okazaki, Kazuyuki; Kitagawa, Yasutaka; Kawakami, Takashi; Yamanaka, Shusuke; Okumura, Mitsutaka

2014-02-01

Residual chlorines, which originate from HAuCl4, enhance the aggregation of gold (Au) nanoparticles and clusters, preventing the generation of highly active supported Au catalysts. However, the detailed mechanism of residual-chlorine-promoted aggregation of Au is unknown. Herein to investigate this mechanism, density functional theory (DFT) calculations of Au and Cl adsorption onto a reduced rutile TiO2 (110) surface were performed using a generalised gradient approximation Perdew, Burke, and Ernzerhof formula (GGA-PBE) functional and plane-wave basis. Although both Au and Cl atoms prefer to mono-absorb onto oxygen defect sites, Cl atoms have a stronger absorption onto a reduced TiO2 (110) surface, abbreviated as rTiO2 (110) in the following, than Au atoms. Additionally, co-adsorption of a Cl atom and a Au atom or Au nanorod onto a rTiO2 surface was investigated; Cl adsorption onto an oxygen defect site weakens the interaction between a Au atom or Au nanorod and rTiO2 (110) surface. The calculation results suggest that the depletion of interaction between Au and rTiO2 surface is due to strong interaction between Cl atoms at oxygen defect sites and neighbouring bridging oxygen (OB) atoms.

PHENOTYPIC AND GENETIC HETEROGENEITY AMONG SUBJECTS WITH MILD AIRFLOW OBSTRUCTION IN COPDGENE

PubMed Central

Lee, Jin Hwa; Cho, Michael H.; McDonald, Merry-Lynn N.; Hersh, Craig P.; Castaldi, Peter J.; Crapo, James D.; Wan, Emily S.; Dy, Jennifer G.; Chang, Yale; Regan, Elizabeth A.; Hardin, Megan; DeMeo, Dawn L.; Silverman, Edwin K.

2014-01-01

Background Chronic obstructive pulmonary disease (COPD) is characterized by marked phenotypic heterogeneity. Most previous studies have focused on COPD subjects with FEV1 < 80% predicted. We investigated the clinical and genetic heterogeneity in subjects with mild airflow limitation in spirometry grade 1 defined by the Global Initiative for chronic Obstructive Lung Disease (GOLD 1). Methods Data from current and former smokers participating in the COPDGene Study (NCT00608764) were analyzed. K-means clustering was performed to explore subtypes within 794 GOLD 1 subjects. For all subjects with GOLD 1 and with each cluster, a genome-wide association study and candidate gene testing were performed using smokers with normal lung function as a control group. Combinations of COPD genome-wide significant single nucleotide polymorphisms (SNPs) were tested for association with FEV1 (% predicted) in GOLD 1 and in a combined group of GOLD1 and smoking control subjects. Results K-means clustering of GOLD 1 subjects identified putative “near-normal”, “airway-predominant”, “emphysema-predominant” and “lowest FEV1 % predicted” subtypes. In non-Hispanic whites, the only SNP nominally associated with GOLD 1 status relative to smoking controls was rs7671167 (FAM13A) in logistic regression models with adjustment for age, sex, pack-years of smoking, and genetic ancestry. The emphysema-predominant GOLD 1 cluster was nominally associated with rs7671167 (FAM13A) and rs161976 (BICD1). The lowest FEV1 % predicted cluster was nominally associated with rs1980057 (HHIP) and rs1051730 (CHRNA3). Combinations of COPD genome-wide significant SNPs were associated with FEV1 (% predicted) in a combined group of GOLD 1 and smoking control subjects. Conclusions Our results indicate that GOLD 1 subjects show substantial clinical heterogeneity, which is at least partially related to genetic heterogeneity. PMID:25154699

Phenotypic and genetic heterogeneity among subjects with mild airflow obstruction in COPDGene.

PubMed

Lee, Jin Hwa; Cho, Michael H; McDonald, Merry-Lynn N; Hersh, Craig P; Castaldi, Peter J; Crapo, James D; Wan, Emily S; Dy, Jennifer G; Chang, Yale; Regan, Elizabeth A; Hardin, Megan; DeMeo, Dawn L; Silverman, Edwin K

2014-10-01

Chronic obstructive pulmonary disease (COPD) is characterized by marked phenotypic heterogeneity. Most previous studies have focused on COPD subjects with FEV1 < 80% predicted. We investigated the clinical and genetic heterogeneity in subjects with mild airflow limitation in spirometry grade 1 defined by the Global Initiative for chronic Obstructive Lung Disease (GOLD 1). Data from current and former smokers participating in the COPDGene Study (NCT00608764) were analyzed. K-means clustering was performed to explore subtypes within 794 GOLD 1 subjects. For all subjects with GOLD 1 and with each cluster, a genome-wide association study and candidate gene testing were performed using smokers with normal lung function as a control group. Combinations of COPD genome-wide significant single nucleotide polymorphisms (SNPs) were tested for association with FEV1 (% predicted) in GOLD 1 and in a combined group of GOLD 1 and smoking control subjects. K-means clustering of GOLD 1 subjects identified putative "near-normal", "airway-predominant", "emphysema-predominant" and "lowest FEV1% predicted" subtypes. In non-Hispanic whites, the only SNP nominally associated with GOLD 1 status relative to smoking controls was rs7671167 (FAM13A) in logistic regression models with adjustment for age, sex, pack-years of smoking, and genetic ancestry. The emphysema-predominant GOLD 1 cluster was nominally associated with rs7671167 (FAM13A) and rs161976 (BICD1). The lowest FEV1% predicted cluster was nominally associated with rs1980057 (HHIP) and rs1051730 (CHRNA3). Combinations of COPD genome-wide significant SNPs were associated with FEV1 (% predicted) in a combined group of GOLD 1 and smoking control subjects. Our results indicate that GOLD 1 subjects show substantial clinical heterogeneity, which is at least partially related to genetic heterogeneity. Copyright © 2014 Elsevier Ltd. All rights reserved.

Study on the coloration response of a radiochromic film to MeV cluster ion beams

NASA Astrophysics Data System (ADS)

Yuri, Yosuke; Narumi, Kazumasa; Chiba, Atsuya; Hirano, Yoshimi; Saitoh, Yuichi

2017-11-01

A radiochromic film, Gafchromic HD-V2, is applied to a possible method of measuring a two-dimensional (2D) spatial profile of MeV cluster ion beams. The coloration responses of the HD-V2 film to MeV carbon and gold cluster ion beams are experimentally investigated since some cluster effect may appear. The degree of the film coloration is quantified as a change in optical density (OD) by reading the films with an image scanner for high-resolution measurement of the 2D beam profile. The OD response of HD-V2 is characterized as a function of the ion and atom fluence for comparison. The dependences of the OD response on the cluster size, kinetic energy, and ion species are discussed. It is found that the sensitivity of the OD change is reduced when the cluster size is large. The beam profile of MeV cluster ion beams delivered from the tandem accelerator in TIARA is characterized from the measurement result using HD-V2 films. The present results show that the use of the Gafchromic HD-V2 film is suitable for the detail beam profile measurement of MeV cluster ions, especially C60 ions, whose available intensity is rather low in comparison with that of monatomic ion beams.

Quantum sized gold nanoclusters with atomic precision.

PubMed

Qian, Huifeng; Zhu, Manzhou; Wu, Zhikun; Jin, Rongchao

2012-09-18

Gold nanoparticles typically have a metallic core, and the electronic conduction band consists of quasicontinuous energy levels (i.e. spacing δ ≪ k(B)T, where k(B)T is the thermal energy at temperature T (typically room temperature) and k(B) is the Boltzmann constant). Electrons in the conduction band roam throughout the metal core, and light can collectively excite these electrons to give rise to plasmonic responses. This plasmon resonance accounts for the beautiful ruby-red color of colloidal gold first observed by Faraday back in 1857. On the other hand, when gold nanoparticles become extremely small (<2 nm in diameter), significant quantization occurs to the conduction band. These quantum-sized nanoparticles constitute a new class of nanomaterial and have received much attention in recent years. To differentiate quantum-sized nanoparticles from conventional plasmonic gold nanoparticles, researchers often refer to the ultrasmall nanoparticles as nanoclusters. In this Account, we chose several typical sizes of gold nanoclusters, including Au(25)(SR)(18), Au(38)(SR)(24), Au(102)(SR)(44), and Au(144)(SR)(60), to illustrate the novel properties of metal nanoclusters imparted by quantum size effects. In the nanocluster size regime, many of the physical and chemical properties of gold nanoparticles are fundamentally altered. Gold nanoclusters have discrete electronic energy levels as opposed to the continuous band in plasmonic nanoparticles. Quantum-sized nanoparticles also show multiple optical absorption peaks in the optical spectrum versus a single surface plasmon resonance (SPR) peak at 520 nm for spherical gold nanocrystals. Although larger nanocrystals show an fcc structure, nanoclusters often have non-fcc atomic packing structures. Nanoclusters also have unique fluorescent, chiral, and magnetic properties. Due to the strong quantum confinement effect, adding or removing one gold atom significantly changes the structure and the electronic and optical properties of the nanocluster. Therefore, precise atomic control of nanoclusters is critically important: the nanometer precision typical of conventional nanoparticles is not sufficient. Atomically precise nanoclusters are represented by molecular formulas (e.g. Au(n)(SR)(m) for thiolate-protected ones, where n and m denote the respective number of gold atoms and ligands). Recently, major advances in the synthesis and structural characterization of molecular purity gold nanoclusters have made in-depth investigations of the size evolution of metal nanoclusters possible. Metal nanoclusters lie in the intermediate regime between localized atomic states and delocalized band structure in terms of electronic properties. We anticipate that future research on quantum-sized nanoclusters will stimulate broad scientific and technological interests in this special type of metal nanomaterial.

Cluster-to-cluster transformation among Au6, Au8 and Au11 nanoclusters.

PubMed

Ren, Xiuqing; Fu, Junhong; Lin, Xinzhang; Fu, Xuemei; Yan, Jinghui; Wu, Ren'an; Liu, Chao; Huang, Jiahui

2018-05-22

We present the cluster-to-cluster transformations among three gold nanoclusters, [Au6(dppp)4]2+ (Au6), [Au8(dppp)4Cl2]2+ (Au8) and [Au11(dppp)5]3+ (Au11). The conversion process follows a rule that states that the transformation of a small cluster to a large cluster is achieved through an oxidation process with an oxidizing agent (H2O2) or with heating, while the conversion of a large cluster to a small one occurs through a reduction process with a reducing agent (NaBH4). All the reactions were monitored using UV-Vis spectroscopy and ESI-MS. This work may provide an alternative approach to the synthesis of novel gold nanoclusters and a further understanding of the structural transformation relationship of gold nanoclusters.

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

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

Ligare, Marshall R.; Baker, Erin S.; Laskin, Julia

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.

Solvent-driven reductive activation of carbon dioxide by gold anions.

PubMed

Knurr, Benjamin J; Weber, J Mathias

2012-11-14

Catalytic activation and electrochemical reduction of CO(2) for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle. The role of solvent molecules in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass-selected Au(CO(2))(n)(-) cluster ions to probe the solvation of AuCO(2)(-) as a model for a reactive intermediate in the reductive activation of a CO(2) ligand by a single-atom catalyst. For the first few solvent molecules, solvation of the complex preferentially occurs at the CO(2) moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional solvent molecules with the Au atom diminishes reduction. The results show how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single-atom catalyst engineering.

Probing the Sulfur-Modified Capping Layer of Gold Nanoparticles Using Surface Enhanced Raman Spectroscopy (SERS) Effects.

PubMed

Prado, Adilson R; Souza, Danilo Oliveira de; Oliveira, Jairo P; Pereira, Rayssa H A; Guimarães, Marco C C; Nogueira, Breno V; Dixini, Pedro V; Ribeiro, Moisés R N; Pontes, Maria J

2017-12-01

Gold nanoparticles (AuNP) exhibit particular plasmonic properties when stimulated by visible light, which makes them a promising tool to many applications in sensor technology and biomedical applications, especially when associated to sulfur-based compounds. Sulfur species form a great variety of self-assembled structures that cap AuNP and this interaction rules the optical and plasmonic properties of the system. Here, we report the behavior of citrate-stabilized gold nanospheres in two distinct sulfur colloidal solutions, namely, thiocyanate and sulfide ionic solutions. Citrate-capped gold nanospheres were characterized using ultraviolet-visible (UV-Vis) absorption, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and atomic force microscopy (AFM). In the presence of sulfur species, we have observed the formation of NP clusters and chain-like structures, giving rise to surface-enhanced effects. Surface-enhanced Raman spectroscopy (SERS) pointed to a modification in citrate vibrational modes, which suggests substitution of citrate by either thiocyanate or sulfide ions with distinct dynamics, as showed by in situ fluorescence. Moreover, we report the emergence of surface-enhanced infrared absorption (SEIRA) effect, which corroborates SERS conclusions. Further, SEIRA shows a great potential as a tool for specification of sulfur compounds in colloidal solutions, which is particularly useful when dealing with sensor technology.

Charge-Dependent Atomic-Scale Structures of High-Index and (110) Gold Electrode Surfaces as Revealed by Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

known gold atomic diameter of 2.89 A. Within a given domain, featuring adjacent terrace strings separated by monoatomic steps, the measured unit-cell...to utilize high-index gold faces in exploring the influence of monoatomic steps and related structural features on surface electrochemical phenomena...110) Gold Electrode Surfaces D1 T IC as Revealed by Scanning Tunneling Microscopy FLECTE MAR 10 19941 by E Xiaoping Gao, Gregory J. Edens, Antoinette

Determination of gold in copper-bearing sulphide ores and metallurgical flotation products by atomic-absorption spectrometry.

PubMed

Strong, B; Murray-Smith, R

1974-12-01

A method is described which is specific for the determination of gold in sulphide copper ores and concentrates. Direct decomposition with aqua regia was found to be incomplete. A carefully controlled roasting stage followed by treatment with hydrochloric acid and then aqua regia was effective for dissolving all the gold. The gold is extracted into 4-methylpentan-2-one (methyli-sobutylketone) then aspirated into a very lean air-acetylene flame and the gold determined by atomic-absorption spectrometry. No interferences were observed from large concentrations of copper, iron or nickel.

Kinetic Assembly of Near-IR Active Gold Nanoclusters using Weakly Adsorbing Polymers to Control Size

PubMed Central

Tam, Jasmine M.; Murthy, Avinash K.; Ingram, Davis R.; Nguyen, Robin; Sokolov, Konstantin V.; Johnston, Keith P.

2013-01-01

Clusters of metal nanoparticles with an overall size less than 100 nm and high metal loadings for strong optical functionality, are of interest in various fields including microelectronics, sensors, optoelectronics and biomedical imaging and therapeutics. Herein we assemble ~5 nm gold particles into clusters with controlled size, as small as 30 nm and up to 100 nm, which contain only small amounts of polymeric stabilizers. The assembly is kinetically controlled with weakly adsorbing polymers, PLA(2K)-b-PEG(10K)-b-PLA(2K) or PEG (MW = 3350), by manipulating electrostatic, van der Waals (VDW), steric, and depletion forces. The cluster size and optical properties are tuned as a function of particle volume fractions and polymer/gold ratios to modulate the interparticle interactions. The close spacing between the constituent gold nanoparticles and high gold loadings (80–85% w/w gold) produce a strong absorbance cross section of ~9×10−15 m2 in the NIR at 700 nm. This morphology results from VDW and depletion attractive interactions that exclude the weakly adsorbed polymeric stabilizer from the cluster interior. The generality of this kinetic assembly platform is demonstrated for gold nanoparticles with a range of surface charges from highly negative to neutral, with the two different polymers. PMID:20361735

Unimolecular Logic Gate with Classical Input by Single Gold Atoms.

PubMed

Skidin, Dmitry; Faizy, Omid; Krüger, Justus; Eisenhut, Frank; Jancarik, Andrej; Nguyen, Khanh-Hung; Cuniberti, Gianaurelio; Gourdon, Andre; Moresco, Francesca; Joachim, Christian

2018-02-27

By a combination of solution and on-surface chemistry, we synthesized an asymmetric starphene molecule with two long anthracenyl input branches and a short naphthyl output branch on the Au(111) surface. Starting from this molecule, we could demonstrate the working principle of a single molecule NAND logic gate by selectively contacting single gold atoms by atomic manipulation to the longer branches of the molecule. The logical input "1" ("0") is defined by the interaction (noninteraction) of a gold atom with one of the input branches. The output is measured by scanning tunneling spectroscopy following the shift in energy of the electronic tunneling resonances at the end of the short branch of the molecule.

Gold in natural water: A method of determination by solvent extraction and electrothermal atomization

USGS Publications Warehouse

McHugh, J.B.

1984-01-01

A method has been developed using electrothermal atomization to effectively determine the amount of gold in natural water within the nanogram range. The method has four basic steps: (1) evaporating a 1-L sample; (2) putting it in hydrobromic acid-bromine solution; (3) extracting the sample with methyl-isobutyl-ketone; and (4) determining the amount of gold using an atomic absorption spectrophotometer. The limit of detection is 0.001 ??g gold per liter. Results from three studies indicate, respectively, that the method is precise, effective, and free of interference. Specifically, a precision study indicates that the method has a relative standard deviation of 16-18%; a recovery study indicates that the method recovers gold at an average of 93%; and an interference study indicates that the interference effects are eliminated with solvent extraction and background correction techniques. Application of the method to water samples collected from 41 sites throughout the Western United States and Alaska shows a gold concentration range of < 0.001 to 0.036 ??g gold per liter, with an average of 0.005 ??g/L. ?? 1984.

Real-Time Plasmonic Monitoring of Single Gold Amalgam Nanoalloy Electrochemical Formation and Stripping.

PubMed

Wang, Jun-Gang; Fossey, John S; Li, Meng; Xie, Tao; Long, Yi-Tao

2016-03-01

Direct electrodeposition of mercury onto gold nanorods on an ITO substrate, without reducing agents, is reported. The growth of single gold amalgam nanoalloy particles and subsequent stripping was monitored in real-time monitoring by plasmonic effects and single-nanoparticle dark-field spectroelectrochemistry techniques. Time-dependent scattering spectral information conferred insight into the growth and stripping mechanism of a single nanoalloy particle. Four critical stages were observed: First, rapid deposition of Hg atoms onto Au nanorods; second, slow diffusion of Hg atoms into Au nanorods; third, prompt stripping of Hg atoms from Au nanorods; fourth, moderate diffusion from the inner core of Au nanorods. Under high Hg(2+) concentrations, homogeneous spherical gold amalgam nanoalloys were obtained. These results demonstrate that the morphology and composition of individual gold amalgam nanoalloys can be precisely regulated electrochemically. Moreover, gold amalgam nanoalloys with intriguing optical properties, such as modulated plasmonic lifetimes and quality factor Q, could be obtained. This may offer opportunities to extend applications in photovoltaic energy conversion and chemical sensing.

A unique ore-placer area of the Amur region with high-Hg gold

NASA Astrophysics Data System (ADS)

Melnikov, A. V.; Stepanov, V. A.; Moiseenko, V. G.

2017-10-01

This work presents the geological structure and a description of the gold-ore occurrences and gold placers of the Un'ya-Bom ore-placer cluster of the Amur gold-bearing province. The host rocks are Late Paleozoic and Mesozoic black shales. Intrusive formations occur rarely. The sublatitudinal Un'ya Thrust is the principal ore-controlling structure. Paleozoic sandstones are thrust over Mesozoic flysch deposits along the Un'ya Thrust. The gold-ore occurrences are represented by quartz-vein zones. The ores are gold-quartz, low-sulfide. Ore minerals are arsenopyrite, scheelite, ferberite, galena, and native gold. High-Hg native gold was revealed in the ore occurrences and placers. The high Hg content in native gold is explained by the presence of the frontal part of the gold-bearing column located within the cluster; the rich placers were formed due to crushing of this column.

Computing and Applying Atomic Regulons to Understand Gene Expression and Regulation

PubMed Central

Faria, José P.; Davis, James J.; Edirisinghe, Janaka N.; Taylor, Ronald C.; Weisenhorn, Pamela; Olson, Robert D.; Stevens, Rick L.; Rocha, Miguel; Rocha, Isabel; Best, Aaron A.; DeJongh, Matthew; Tintle, Nathan L.; Parrello, Bruce; Overbeek, Ross; Henry, Christopher S.

2016-01-01

Understanding gene function and regulation is essential for the interpretation, prediction, and ultimate design of cell responses to changes in the environment. An important step toward meeting the challenge of understanding gene function and regulation is the identification of sets of genes that are always co-expressed. These gene sets, Atomic Regulons (ARs), represent fundamental units of function within a cell and could be used to associate genes of unknown function with cellular processes and to enable rational genetic engineering of cellular systems. Here, we describe an approach for inferring ARs that leverages large-scale expression data sets, gene context, and functional relationships among genes. We computed ARs for Escherichia coli based on 907 gene expression experiments and compared our results with gene clusters produced by two prevalent data-driven methods: Hierarchical clustering and k-means clustering. We compared ARs and purely data-driven gene clusters to the curated set of regulatory interactions for E. coli found in RegulonDB, showing that ARs are more consistent with gold standard regulons than are data-driven gene clusters. We further examined the consistency of ARs and data-driven gene clusters in the context of gene interactions predicted by Context Likelihood of Relatedness (CLR) analysis, finding that the ARs show better agreement with CLR predicted interactions. We determined the impact of increasing amounts of expression data on AR construction and find that while more data improve ARs, it is not necessary to use the full set of gene expression experiments available for E. coli to produce high quality ARs. In order to explore the conservation of co-regulated gene sets across different organisms, we computed ARs for Shewanella oneidensis, Pseudomonas aeruginosa, Thermus thermophilus, and Staphylococcus aureus, each of which represents increasing degrees of phylogenetic distance from E. coli. Comparison of the organism-specific ARs showed that the consistency of AR gene membership correlates with phylogenetic distance, but there is clear variability in the regulatory networks of closely related organisms. As large scale expression data sets become increasingly common for model and non-model organisms, comparative analyses of atomic regulons will provide valuable insights into fundamental regulatory modules used across the bacterial domain. PMID:27933038

Fabricating Atom-Sized Gaps by Field-Aided Atom Migration in Nanoscale Junctions

NASA Astrophysics Data System (ADS)

Liu, Ran; Bi, Jun-Jie; Xie, Zhen; Yin, Kaikai; Wang, Dunyou; Zhang, Guang-Ping; Xiang, Dong; Wang, Chuan-Kui; Li, Zong-Liang

2018-05-01

The gap sizes between electrodes generated by typical methods are generally much larger than the dimension of a common molecule when fabricating a single-molecule junction, which dramatically suppresses the yield of single-molecule junctions. Based on the ab initio calculations, we develop a strategy named the field-aided method to accurately fabricate an atomic-sized gap between gold nanoelectrodes. To understand the mechanism of this strategy, configuration evolutions of gold nanojunction in stretching and compressing processes are calculated. The numerical results show that, in the stretching process, the gold atoms bridged between two electrodes are likely to form atomic chains. More significantly, lattice vacant positions can be easily generated in stretching and compressing processes, which make field-aided gap generation possible. In field-aided atom migration (FAAM), the external field can exert driving force, enhance the initial energy of the system, and decrease the barrier in the migration path, which makes the atom migration feasible. Conductance and stretching and compressing forces, as measurable variables in stretching and compressing processes, present very useful signals for determining the time to perform FAAM. Following this desirable strategy, we successfully fabricate gold nanogaps with a dimension of 0.38 ±0.05 nm in the experiment, as our calculation simulates.

Theoretical study of the electronic and optical properties of photochromic dithienylethene derivatives connected to small gold clusters.

PubMed

Perrier, Aurélie; Maurel, François; Aubard, Jean

2007-10-04

In the course of developing electronic devices on a molecular scale, dithienylethenes photochromic molecules constitute promising candidates for optoelectronic applications such as memories and switches. There is thus a great interest to understand and control the switching behavior of photochromic compounds deposited on metallic surfaces or nanoparticles. Within the framework of the density functional theory, we studied the effect of small gold clusters (Au3 and Au9) on the electronic structure and absorption spectrum of a model dithienylethene molecule. The molecular orbital interactions between the photochromic molecule and the gold cluster made it possible to rationalize some experimental findings (Dulic, D.; van der Molen, S. J.; Kudernac, T.; Jonkman, H. T.; de Jong, J. J. D.; Bowden, T. N.; van Esch, J.; Feringa, B. L.; van Wees, B. J. Phys. Rev. Lett. 2003, 91, 207402). For the closed-ring isomer, grafting a photochromic molecule on a small gold cluster does not change the characteristics of the electronic transition involved in the ring-opening reaction. On the opposite, the absorption spectrum of the photochromic open-ring isomer is strongly modified by the inclusion of the metallic cluster. In agreement with experimental results, our study thus showed that the cycloreversion reaction which involves the closed-ring isomer should be still possible, whereas the ring-closure reaction which involves the open-ring isomer should be inhibited. Connecting a dithienylethene molecule to a small gold cluster hence provides a qualitative comprehension of the photochromic activities of dithienylethenes connected to a gold surface.

Determining gold in water by anion-exchange batch extraction

USGS Publications Warehouse

McHugh, J.B.

1986-01-01

This paper describes a batch procedure for determining gold in natural waters. It is completely adaptable to field operations. The water samples are filtered and acidified before they are equilibrated with an anion-exchange resin by shaking. The gold is then eluted with acetone-nitric acid solution, and the eluate evaporated to dryness. The residue is taken up in hydrobromic acid-bromine solution and the gold is extracted with methyl isobutyl ketone. The extract is electrothermally atomized in an atomic-absorption spectrophotometer. The limit of determination is 1 ng 1. ?? 1986.

Cationic Gold Clusters Ligated with Differently Substituted Phosphines: Effect of Substitution on Ligand Reactivity and Binding

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

Johnson, Grant E.; Olivares, Astrid M.; Hill, David E.

2015-01-01

We present a systematic study of the effect of the number of methyl (Me) and cyclohexyl (Cy) functional groups in monodentate phosphine ligands on the solution-phase synthesis of ligated sub-nanometer gold clusters and their gas-phase fragmentation pathways. Small mixed ligand cationic gold clusters were synthesized using ligand exchange reactions between pre-formed triphenylphosphine ligated (PPh3) gold clusters and monodentate Me- and Cy-substituted ligands in solution and characterized using electrospray ionization mass spectrometry (ESI-MS) and collision-induced dissociation (CID) experiments. Under the same experimental conditions, larger gold-PPh3 clusters undergo efficient exchange of unsubstituted PPh3 ligands for singly Me- and Cy-substituted PPh2Me and PPh2Cymore » ligands. The efficiency of ligand exchange decreases with an increasing number of Me or Cy groups in the substituted phosphine ligands. CID experiments performed for a series of ligand-exchanged gold clusters indicate that loss of a neutral Me-substituted ligand is preferred over loss of a neutral PPh¬3 ligand while the opposite trend is observed for Cy-substituted ligands. The branching ratio of the competing ligand loss channels is strongly correlated with the electron donating ability of the phosphorous lone pair as determined by the relative proton affinity of the ligand. The results indicate that the relative ligand binding energies increase in the order PMe3 < PPhMe2 < PPh2Me < PPh3< PPh2Cy < PPhCy2< PCy3. Furthermore, the difference in relative ligand binding energies increases with the number of substituted PPh3-mMem or PPh3-mCym ligands (L) exchanged onto each cluster. This study provides the first experimental determination of the relative binding energies of ligated gold clusters containing differently substituted monophosphine ligands, which are important to controlling their synthesis and reactivity in solution. The results also indicate that ligand substitution is an important parameter that must be considered in theoretical modeling of these complex systems« less

Ultrafast, 2 min synthesis of monolayer-protected gold nanoclusters (d < 2 nm)

NASA Astrophysics Data System (ADS)

Martin, Matthew N.; Li, Dawei; Dass, Amala; Eah, Sang-Kee

2012-06-01

An ultrafast synthesis method is presented for hexanethiolate-coated gold nanoclusters (d < 2 nm, <250 atoms per nanocluster), which takes only 2 min and can be easily reproduced. With two immiscible solvents, gold nanoclusters are separated from the reaction byproducts fast and easily without any need for post-synthesis cleaning.An ultrafast synthesis method is presented for hexanethiolate-coated gold nanoclusters (d < 2 nm, <250 atoms per nanocluster), which takes only 2 min and can be easily reproduced. With two immiscible solvents, gold nanoclusters are separated from the reaction byproducts fast and easily without any need for post-synthesis cleaning. Electronic supplementary information (ESI) available: Experimental details of gold nanocluster synthesis and mass-spectrometry. See DOI: 10.1039/c2nr30890h

Reversing an S-kink effect caused by interface degradation in organic solar cells through gold ion implantation in the PEDOT:PSS layer

NASA Astrophysics Data System (ADS)

Brenes-Badilla, D.; Coutinho, D. J.; Amorim, D. R. B.; Faria, R. M.; Salvadori, M. C.

2018-04-01

In this work, we performed a study on the recovery of the photovoltaic performance of an ITO/PEDOT:PSS/P3HT:PCBM/Ca/Al solar cell after the hole transport layer (PEDOT:PSS) had been degraded by contact with the environment. A device that was fully built in an inert environment exhibited a fill factor (FF) of 0.64, while the device whose hole transport layer was exposed to air presented a FF equal to 0.2. In addition, the J-V characteristic curve of the degraded device did not follow the photovoltaic pattern exhibiting the degenerate S shape. However, the elimination of the deleterious effect was achieved by bombarding gold ions on the contaminated surface of PEDOT:PSS by means of the Metal Plasma Immersion Ion Implantation technique. Due to the low energy of the ionic beam of gold, the implanted gold atoms were located at few nanometers off the surface, forming nanometric clusters, that is, gold nanoparticles. Most probably, the degradation of the J-V photovoltaic curve, represented by the S-kink effect, was caused by the appearance of a potential barrier at PEDOT:PSS/P3HT:PCBM interface, which was demolished by the gold nanoparticles that have work function close to HOMO of P3HT. This S-kink effect was also simulated by using an equivalent circuit model constituted by a two-diode circuit, one of which plays the role of the undesirable potential barrier formed at the PEDOT:PSS/P3HT:PCBM interface. Our analysis shows that deposition of gold nanoparticles next to the interface recovers the good hole injection condition from the PEDOT:PSS into the active layer, restoring the fill factor and the device efficiency.

Solving local structure around dopants in metal nanoparticles with ab initio modeling of X-ray absorption near edge structure

DOE PAGES

Timoshenko, J.; Shivhare, A.; Scott, R. W.; ...

2016-06-30

We adopted ab-initio X-ray Absorption Near Edge Structure (XANES) modelling for structural refinement of local environments around metal impurities in a large variety of materials. Our method enables both direct modelling, where the candidate structures are known, and the inverse modelling, where the unknown structural motifs are deciphered from the experimental spectra. We present also estimates of systematic errors, and their influence on the stability and accuracy of the obtained results. We illustrate our approach by following the evolution of local environment of palladium atoms in palladium-doped gold thiolate clusters upon chemical and thermal treatments.

Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction

DOE PAGES

Yao, Siyu; Zhang, Xiao; Zhou, Wu; ...

2017-06-22

Here, the water-gas shift (WGS) reaction (where carbon monoxide plus water yields dihydrogen and carbon dioxide) is an essential process for hydrogen generation and carbon monoxide removal in various energy-related chemical operations. This equilibrium-limited reaction is favored at a low working temperature. Potential application in fuel cells also requires a WGS catalyst to be highly active, stable, and energy-efficient and to match the working temperature of on-site hydrogen generation and consumption units. We synthesized layered gold (Au) clusters on a molybdenum carbide (α-MoC) substrate to create an interfacial catalyst system for the ultralow-temperature WGS reaction. Water was activated over α-MoCmore » at 303 kelvin, whereas carbon monoxide adsorbed on adjacent Au sites was apt to react with surface hydroxyl groups formed from water splitting, leading to a high WGS activity at low temperatures.« less

Effects of dissolucytotic gold ions on recovering brain lesions.

PubMed

Danscher, Gorm; Larsen, Agnete

2010-04-01

Recent experimental research has shown that metallic gold releases charged gold atoms when placed intracerebrally and that the liberated gold ions affect inflammation in the brain. The observations suggest that metallic gold can be used as a safe suppressor of inflammation in the central nervous system.

DETERMINATION OF TOTAL MERCURY IN FISH TISSUES USING PYROLYSIS ATOMIC ABSORPTION SPECTROMETRY WITH GOLD AMALGAMATION

EPA Science Inventory

A simple and rapid procedure for measuring total mercury in fish tissues is evaluated and
compared with conventional techniques. Using an automated instrument incorporating combustion, preconcentration by amalgamation with gold, and atomic absorption spectrometry (AAS), mill...

Electron transport in stretched monoatomic gold wires.

PubMed

Grigoriev, A; Skorodumova, N V; Simak, S I; Wendin, G; Johansson, B; Ahuja, R

2006-12-08

The conductance of monoatomic gold wires containing 3-7 gold atoms has been obtained from ab initio calculations. The transmission is found to vary significantly depending on the wire stretching and the number of incorporated atoms. Such oscillations are determined by the electronic structure of the one-dimensional (1D) part of the wire between the contacts. Our results indicate that the conductivity of 1D wires can be suppressed without breaking the contact.

An atomic-absorption method for the determination of gold in large samples of geologic materials

USGS Publications Warehouse

VanSickle, Gordon H.; Lakin, Hubert William

1968-01-01

A laboratory method for the determination of gold in large (100-gram) samples has been developed for use in the study of the gold content of placer deposits and of trace amounts of gold in other geologic materials. In this method the sample is digested with bromine and ethyl ether, the gold is extracted into methyl isobutyl ketone, and the determination is made by atomicabsorption spectrophotometry. The lower limit of detection is 0.005 part per million in the sample. The few data obtained so far by this method agree favorably with those obtained by assay and by other atomic-absorption methods. About 25 determinations can be made per man-day.

Effect of nanoscale size and medium on metal work function in oleylamine-capped gold nanocrystals

NASA Astrophysics Data System (ADS)

Abdellatif, M. H.; Ghosh, S.; Liakos, I.; Scarpellini, A.; Marras, S.; Diaspro, A.; Salerno, M.

2016-02-01

The work function is an important material property with several applications in photonics and optoelectronics. We aimed to characterize the work function of clusters resulting from gold nanocrystals capped with oleylamine surfactant and drop-casted onto gold substrate. We used scanning Kelvin probe microscopy to investigate the work function, and complemented our study mainly with X-ray diffraction and X-ray photoelectron spectroscopy. The oleylamine works as an electron blocking layer through which the electrical conduction takes place by tunneling effect. The surface potential appears to depend on the size of the clusters, which can be ascribed to their difference in effective work function with the substrate. The charge state of gold clusters is discussed in comparison with theory, and their capacitance is calculated from a semi-analytical equation. The results suggest that at the nanoscale the work function is not an intrinsic property of a material but rather depends on the size and morphology of the clusters, including also effects of the surrounding materials.

Probing Electrochemical Adsorbate Structure and Reactions with In-Situ Atomic-Resolution Scanning Microscopy: Some Progress and Prospects

DTIC Science & Technology

1992-10-01

organized into hexagonal patterns, but unlike the monoatomic iodine adlayers noted above the close-packed atomic strings tend to lie along the gold ...adsorbate systems. Illustrative results of the former type are presented for the potential-dependent adsorption of iodide at low-index gold electrodes. The...presented for the potential-dependent adsorption of iodide at low-index gold electrodes. The virtues of acquiring "composite-domain" STM images, where

Growth of fluorescence gold clusters using photo-chemically activated ligands

NASA Astrophysics Data System (ADS)

Mishra, Dinesh; Aldeek, Fadi; Michael, Serge; Palui, Goutam; Mattoussi, Hedi

2016-03-01

Ligands made of lipoic acid (LA) appended with a polyethylene glycol (PEG) chain have been used in the aqueous phase growth of luminescent gold clusters with distinct emission from yellow to near-IR, using two different routes. In the first route, the gold-ligand complex was chemically reduced using sodium borohydride in alkaline medium, which gave near- IR luminescent gold clusters with maximum emission around 745 nm. In the second method, LA-PEG ligand was photochemically modified to a mixture of thiols, oligomers and oxygenated species under UV-irradiation, which was then used as both reducing agent and stabilizing ligand. By adjusting the pH, temperature, and time of the reaction, we were able to obtain clusters with two distinct emission properties. Refluxing the gold-ligand complex in alkaline medium in the presence of excess ligand gave yellow emission within the first two hours and the emission shifted to red after overnight reaction. Mass spectrometry and chemical assay were used to understand the photo-chemical transformation of Lipoic Acid (LA). Mass spectroscopic studies showed the photo-irradiated product contains thiols, oligomers (dimers, trimers and tetramers) as well as oxygenated species. The amount of thiol formed under different conditions of irradiation was estimated using Ellman's assay.

Enhanced Mechanical Stability of Gold Nanotips through Carbon Nanocone Encapsulation

PubMed Central

Cano-Marquez, Abraham G.; Schmidt, Wesller G.; Ribeiro-Soares, Jenaina; Gustavo Cançado, Luiz; Rodrigues, Wagner N.; Santos, Adelina P.; Furtado, Clascidia A.; Autreto, Pedro A.S.; Paupitz, Ricardo; Galvão, Douglas S.; Jorio, Ado

2015-01-01

Gold is a noble metal that, in comparison with silver and copper, has the advantage of corrosion resistance. Despite its high conductivity, chemical stability and biocompatibility, gold exhibits high plasticity, which limits its applications in some nanodevices. Here, we report an experimental and theoretical study on how to attain enhanced mechanical stability of gold nanotips. The gold tips were fabricated by chemical etching and further encapsulated with carbon nanocones via nanomanipulation. Atomic force microscopy experiments were carried out to test their mechanical stability. Molecular dynamics simulations show that the encapsulated nanocone changes the strain release mechanisms at the nanoscale by blocking gold atomic sliding, redistributing the strain along the whole nanostructure. The carbon nanocones are conducting and can induce magnetism, thus opening new avenues on the exploitation of transport, mechanical and magnetic properties of gold covered by sp2 carbon at the nanoscale. PMID:26083864

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

NASA Astrophysics Data System (ADS)

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

2010-02-01

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

Complexes of DNA bases and Watson-Crick base pairs with small neutral gold clusters.

PubMed

Kryachko, E S; Remacle, F

2005-12-08

The nature of the DNA-gold interaction determines and differentiates the affinity of the nucleobases (adenine, thymine, guanine, and cytosine) to gold. Our preliminary computational study [Kryachko, E. S.; Remacle, F. Nano Lett. 2005, 5, 735] demonstrates that two major bonding factors govern this interaction: the anchoring, either of the Au-N or Au-O type, and the nonconventional N-H...Au hydrogen bonding. In this paper, we offer insight into the nature of nucleobase-gold interactions and provide a detailed characterization of their different facets, i.e., geometrical, energetic, and spectroscopic aspects; the gold cluster size and gold coordination effects; proton affinity; and deprotonation energy. We then investigate how the Watson-Crick DNA pairing patterns are modulated by the nucleobase-gold interaction. We do so in terms of the proton affinities and deprotonation energies of those proton acceptors and proton donors which are involved in the interbase hydrogen bondings. A variety of properties of the most stable Watson-Crick [A x T]-Au3 and [G x C]-Au3 hybridized complexes are described and compared with the isolated Watson-Crick A x T and G x C ones. It is shown that enlarging the gold cluster size to Au6 results in a rather short gold-gold bond in the Watson-Crick interbase region of the [G x C]-Au6 complex that bridges the G x C pair and thus leads to a significant strengthening of G x C pairing.

Synthesis, Structure, Stability and Redispersion of Gold-based Nanoparticles

NASA Astrophysics Data System (ADS)

Tiruvalam, Ram Chandra

Nanoscale gold has been shown to possess an intriguing combination of unexpected optical, photochemical and catalytic properties. The ability to control the size, shape, morphology, composition and dispersion of gold-based nanostructures is key to optimizing their performance for nanotechnology applications. The advanced electron microscopy studies described in this thesis analyze three important aspects of gold and gold-palladium alloy nanoparticles: namely, (i) the ability to synthesize gold nanoparticles of controlled size and shape in an aqueous medium; (ii) the colloidal preparation of designer gold-palladium alloys for selective oxidation catalysis; and (iii) the ability to disperse gold as finely and homogeneously as possible on a metal oxide or carbon support. The ability to exploit the nanoscale properties of gold for various engineering applications often depends on our ability to control size and shape of the nanoscale entity by careful manipulation of the synthesis parameters. We have explored an aqueous based synthesis route, using oleylamine as both a reductant and surfactant, for preparing gold nanostructures. By systematically varying synthesis parameters such as oleylamine concentration, reaction temperature, and aging time it is possible to identify processing regimens that generate Au nanostructures having either pseudo-spherical, faceted polyhedral, nanostar or wire shaped morphologies. Furthermore, by quenching the reaction partway through it is possible to create a class of metastable Au-containing structures such as nanocubes, nanoboxes and nanowires. Possible formation mechanisms for these gold based nano-objects are discussed. There is a growing interest in using supported bimetallic AuPd alloy nanoparticles for selective oxidation reactions. In this study, a systematic series of size controlled AuPd bimetallic particles have been prepared by colloidal synthesis methods. Particles having random alloy structures, as well as `designer' particles with Pd-shell/Au-core and Au-shell/Pd-core morphologies, have been prepared and immobilized on both activated carbon and TiO2 supports. These have subsequently been compared as catalysts for the direct production of H2O2 and for benzyl alcohol oxidation in an attempt to elucidate the optimum particle morphology/support combination for both these reactions. Aberration corrected analytical electron microscopy has been used extensively to characterize these sol-immobilized materials. In particular, the STEM -HAADF technique has provided invaluable new (and often unexpected) information on the atomic structure, elemental distribution within particles, and compositional variations between particles for these controlled catalyst preparations. In addition, we have been able to compare their differing thermal stability and sintering behaviors, and to demonstrate that they have quite varying wetting interactions with activated carbon and TiO2 supports. Over the course of their lifetime, many supported metal catalysts exposed to elevated temperatures tend to de-activate by nanoparticle sintering, which decreases the overall exposed metal surface area and the number of active sites available for catalysis. It is sometimes desirable to devise chemical re-dispersion treatments whereby the mean size of the particles is reduced and the catalytic activity regenerated. In this work, the possibility of re-dispersing gold nanoparticles by a simple low temperature methyl iodide (CH3 I) treatment has been investigated. A variety of characterization techniques, including EXAFS, XRD, XPS, UV-DRS and STEM-HAADF imaging has been applied to samples before and after CH3 I treatment, in an attempt to determine the efficacy of the re-dispersion method. It is shown that re-dispersion of Au nanoparticles on activated carbon, graphite, Al2 O3 and TiO2 substrates is possible to varying degrees. A complete re-dispersion of `bulk' gold nanoparticles down to the atomic scale has been achieved on activated carbon and graphite substrates, with the exclusive formation of isolated gold atoms, dimeric species, and sub-nm clusters.

The Next Generation Virgo Cluster Survey. XX. RedGOLD Background Galaxy Cluster Detections

NASA Astrophysics Data System (ADS)

Licitra, Rossella; Mei, Simona; Raichoor, Anand; Erben, Thomas; Hildebrandt, Hendrik; Muñoz, Roberto P.; Van Waerbeke, Ludovic; Côté, Patrick; Cuillandre, Jean-Charles; Duc, Pierre-Alain; Ferrarese, Laura; Gwyn, Stephen D. J.; Huertas-Company, Marc; Lançon, Ariane; Parroni, Carolina; Puzia, Thomas H.

2016-09-01

We build a background cluster candidate catalog from the Next Generation Virgo Cluster Survey (NGVS) using our detection algorithm RedGOLD. The NGVS covers 104 deg2 of the Virgo cluster in the {u}* ,g,r,I,z-bandpasses to a depth of g ˜ 25.7 mag (5σ). Part of the survey was not covered or has shallow observations in the r band. We build two cluster catalogs: one using all bandpasses, for the fields with deep r-band observations (˜20 deg2), and the other using four bandpasses ({u}* ,g,I,z) for the entire NGVS area. Based on our previous Canada-France-Hawaii Telescope Legacy Survey W1 studies, we estimate that both of our catalogs are ˜100% (˜70%) complete and ˜80% pure, at z ≤ 0.6 (z ≲ 1), for galaxy clusters with masses of M ≳ 1014 M ⊙. We show that when using four bandpasses, though the photometric redshift accuracy is lower, RedGOLD detects massive galaxy clusters up to z ˜ 1 with completeness and purity similar to the five-band case. This is achieved when taking into account the bias in the richness estimation, which is ˜40% lower at 0.5 ≤ z < 0.6 and ˜20% higher at 0.6 < z < 0.8, with respect to the five-band case. RedGOLD recovers all the X-ray clusters in the area with mass M 500 > 1.4 × 1014 M ⊙ and 0.08 < z < 0.5. Because of our different cluster richness limits and the NGVS depth, our catalogs reach lower masses than the published redMaPPer cluster catalog over the area, and we recover ˜90%-100% of its detections.

Collective photonic-plasmonic resonances in noble metal - dielectric nanoparticle hybrid arrays

DOE PAGES

Hong, Yan; Reinhard, Björn M.

2014-10-27

Coherent scattering of gold and silver nanoparticles (NPs) in regular arrays can generate Surface Lattice Resonances (SLRs) with characteristically sharp spectral features. Herein, we investigate collective resonances in compositionally more complex arrays comprising NP clusters and NPs with different chemical compositions at pre-defined lattice sites. We first characterize the impact of NP clustering by exchanging individual gold NPs in the array through dimers of electromagnetically strongly coupled gold NPs. Then, we analyze hybrid arrays that contain both gold metal NP dimers and high refractive index dielectric NPs as building blocks. We demonstrate that the integration of gold NP clusters andmore » dielectric NPs into one array enhances E-field intensities not only in the vicinity of the NPs but also in the ambient medium of the entire array. In addition, this work shows that the ability to integrate multiple building blocks with different resonance conditions in one array provides new degrees of freedom for engineering optical fields in the array plane with variable amplitude and phase.« less

Surface anisotropy of iron oxide nanoparticles and slabs from first principles: Influence of coatings and ligands as a test of the Heisenberg model

NASA Astrophysics Data System (ADS)

Brymora, Katarzyna; Calvayrac, Florent

2017-07-01

We performed ab initio computations of the magnetic properties of simple iron oxide clusters and slabs. We considered an iron oxide cluster functionalized by a molecule or glued to a gold cluster of the same size. We also considered a magnetite slab coated by cobalt oxide or a mixture of iron oxide and cobalt oxide. The changes in magnetic behavior were explored using constrained magnetic calculations. A possible value for the surface anisotropy was estimated from the fit of a classical Heisenberg model on ab initio results. The value was found to be compatible with estimations obtained by other means, or inferred from experimental results. The addition of a ligand, coating, or of a metallic nanoparticle to the systems degraded the quality of the description by the Heisenberg Hamiltonian. Proposing a change in the anisotropies allowing for the proportion of each transition atom we could get a much better description of the magnetism of series of hybrid cobalt and iron oxide systems.

Soft Landing of Mass-Selected Gold Clusters: Influence of Ion and Ligand on Charge Retention and Reactivity

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

Johnson, Grant E.; Laskin, Julia

Herein, we employ a combination of reduction synthesis in solution, soft landing of mass-selected precursor and product ions, and in situ time-of-flight secondary ion mass spectrometry (TOF-SIMS) to examine the influence of ion and the length of diphosphine ligands on the charge retention and reactivity of ligated gold clusters deposited onto self-assembled monolayer surfaces (SAMs). Product ions (Au10L42+, (10,4)2+, L = 1,3-bis(diphenyl-phosphino)propane, DPPP) were prepared through in-source collision induced dissociation (CID) and precursor ions [(8,4)2+, L = 1,6-bis(diphenylphosphino)hexane, DPPH] were synthesized in solution for comparison to (11,5)3+ precursor ions ligated with DPPP investigated previously (ACS Nano 2012, 6, 573 andmore » J. Phys. Chem. C. 2012, 116, 24977). Similar to (11,5)3+ precursor ions, the (10,4)2+ product ions are shown to retain charge on 1H,1H,2H,2H-perfluorodecanethiol monolayers (FSAMs). Additional abundant peaks at higher m/z indicative of reactivity are observed in the TOF-SIMS spectrum of (10,4)2+ product ions that are not seen for (11,5)3+ precursor ions. The abundance of (10,4)2+ on 16-mercaptohexadecanoic acid (COOH-SAMs) is demonstrated to be lower than on FSAMs, consistent with partial reduction of charge. The (10,4)2+ product ion on 1-dodecanethiol (HSAMs) exhibits peaks similar to those seen on the COOH-SAM. On the HSAM, higher m/z peaks indicative of reactivity are observed similar to those on the FSAM. The (8,4)2+ DPPH precursor ions are shown to retain charge on FSAMs similar to (11,5)3+ precursor ions prepared with DPPP. An additional peak corresponding to attachment of one gold atom to (8,4)2+ is observed at higher m/z for DPPH-ligated clusters. On the COOH-SAM, (8,4)2+ is less abundant than on the FSAM consistent with partial neutralization. The results indicate that although retention of charge by product ions generated by CID is similar to precursor ions their reactivity during analysis with SIMS is different resulting in the formation of peaks corresponding to reaction products. The length of the ligand exerts only a minor influence on the charge retention and reactivity of gold clusters. Based on the observed reactivity of (10,4)2+ it is anticipated that in-source CID will be increasingly applied for the preparation of a distribution of product ions, including undercoordinated and reactive species, for soft landing onto surfaces.« less

Observing the real time formation of phosphine-ligated gold clusters by electrospray ionization mass spectrometry

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

Ligare, Marshall R.; Johnson, Grant E.; Laskin, Julia

Early stages of the reduction and nucleation of solution-phase gold clusters are largely unknown. This is due, in part, to the high reaction rates and the complexity of the cluster synthesis process. Through the addition of a diphosphine ligand, 1-4,Bis(diphenylphosphino)butane (L4) to the gold precursor, chloro(triphenylphosphine) gold(I) (Au(PPh3)Cl), in methanol organometallic complexes of the type, [Au(L4)x(L4O)y(PPh3)z]+, are formed. These complexes lower the rate of reduction so that the reaction can be directly monitored from 1 min to over an hour using on-line electrospray ionization mass spectrometry (ESI-MS). Our results indicate that the formation of Au8(L4)42+, Au9(L4)4H2+ and Au10(L4)52+ cationic clustersmore » occurs through different reaction pathways that may be kinetically controlled either through the reducing agent concentration or the extent of oxidation of L4. Through comparison of selected ion chronograms our results indicate that Au2(L4)2H+ may be an intermediate in the formation of Au8(L4)42+and Au10(L4)52+ while a variety of chlorinated clusters are involved in the formation of Au9(L4)4H2+. Additionally, high-resolution mass spectrometry was employed to identify 53 gold containing species produced under highly oxidative conditions. New intermediate species are identified which help understand how different gold cluster nuclearities can be stabilized during the growth process.« less

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

Takai, Yoshizo; Kawasaki, Tadahiro; Kimura, Yoshihide

A single-atom-sized gold wire was successfully observed in real time by a newly developed defocus-image modulation processing electron microscope. Because of phase retrieval processing with spherical aberration correction, the single-atom strand wire was observed with high contrast and without contrast blurring. By carefully looking at the atomic distance, the contrast, and the dynamic behavior of the wire, we recognized that there are two stages of the wire. In the first stage the wire maintained the atomic distance in the bulk crystal, but in the second stage the wire showed the atomic distance of the nearest-neighbor atoms with weaker contrast. Themore » gold wire was rather stable for a few seconds under strong electron beam illumination.« less

Diphosphine-protected ultrasmall gold nanoclusters: opened icosahedral Au 13 and heart-shaped Au 8 clusters

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

Zhang, Shan-Shan; Feng, Lei; Senanayake, Ravithree D.

Two ultrasmall gold clusters, Au 13 and Au 8 , were identified as a distorted I h icosahedral Au 13 and edge-shared “core + 4 exo ” structure Au 8 S 2 cores, respectively. They showed interesting luminescence and electrochemical properties.

Diphosphine-protected ultrasmall gold nanoclusters: opened icosahedral Au 13 and heart-shaped Au 8 clusters

DOE PAGES

Zhang, Shan-Shan; Feng, Lei; Senanayake, Ravithree D.; ...

2018-01-01

Two ultrasmall gold clusters, Au 13 and Au 8 , were identified as a distorted I h icosahedral Au 13 and edge-shared “core + 4 exo ” structure Au 8 S 2 cores, respectively. They showed interesting luminescence and electrochemical properties.

Effect of gold nanoparticles on structure and dynamics of binary Lennard-Jones liquid: Wave-vector space analysis

NASA Astrophysics Data System (ADS)

Separdar, L.; Davatolhagh, S.

2016-12-01

Molecular dynamics simulations at constant (N , V , T) are used to study the mutual effects of gold nanoparticles on the structure and dynamics of Kob-Andersen binary Lennard-Jones (BLJ) liquid within the framework of mode coupling theory of dynamic glass transition in the reciprocal space. The results show the 'softening' effect of the gold nanoparticles on the liquid dynamics in terms of (i) reducing the mode coupling crossover temperature Tc with respect to that of the bulk BLJ (i.e. BLJ without nanoparticles), (ii) decreasing the time interval of β-relaxation, and (iii) decreasing the exponent γ characterizing the power-law behavior of the α-relaxation time. This softening effect is explained in terms of the van der Waals attraction between the gold atoms comprising the nanoparticle and the BLJ host atoms, such that adsorption of host atoms onto the nanoparticle surface creates more space or free-volume for the other atoms to diffuse. By the same token interactions of purely excluded-volume-type are expected to result in the opposite effect. It is also noted that, much unlike BLJ host particles, the dynamics of gold nanoparticles is much less dependent on the wave-vector and that it exhibits a nearly exponential behavior in the α-relaxation regime.

The mystery of gold's chemical activity: local bonding, morphology and reactivity of atomic oxygen.

PubMed

Baker, Thomas A; Liu, Xiaoying; Friend, Cynthia M

2011-01-07

Recently, gold has been intensely studied as a catalyst for key synthetic reactions. Gold is an attractive catalyst because, surprisingly, it is highly active and very selective for partial oxidation processes suggesting promise for energy-efficient "green" chemistry. The underlying origin of the high activity of Au is a controversial subject since metallic gold is commonly thought to be inert. Herein, we establish that one origin of the high activity for gold catalysis is the extremely reactive nature of atomic oxygen bound in 3-fold coordination sites on metallic gold. This is the predominant form of O at low concentrations on the surface, which is a strong indication that it is most relevant to catalytic conditions. Atomic oxygen bound to metallic Au in 3-fold sites has high activity for CO oxidation, oxidation of olefins, and oxidative transformations of alcohols and amines. Among the factors identified as important in Au-O interaction are the morphology of the surface, the local binding site of oxygen, and the degree of order of the oxygen overlayer. In this Perspective, we present an overview of both theory and experiments that identify the reactive forms of O and their associated charge density distributions and bond strengths. We also analyze and model the release of Au atoms induced by O binding to the surface. This rough surface also has the potential for O(2) dissociation, which is a critical step if Au is to be activated catalytically. We further show the strong parallels between product distributions and reactivity for O-covered Au at low pressure (ultrahigh vacuum) and for nanoporous Au catalysts operating at atmospheric pressure as evidence that atomic O is the active species under working catalytic conditions when metallic Au is present. We briefly discuss the possible contributions of oxidants that may contain intact O-O bonds and of the Au-metal oxide support interface in Au catalysis. Finally, the challenges and future directions for fully understanding the activity of gold are considered.

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

PubMed

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

2016-07-11

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

Stability chart of small mixed 4He-3He clusters

NASA Astrophysics Data System (ADS)

Guardiola, R.; Navarro, J.

2003-11-01

A stability chart of mixed 4He and 3He clusters has been obtained by means of the diffusion Monte Carlo method, using both the Aziz HFD-B and the Tang-Toennies-Yiu atom-atom interaction. The investigated clusters contain up to eight 4He atoms and up to 20 3He atoms. One single 4He binds 20 3He atoms, and two 4He bind 1, 2, 8, and more than 14 3He atoms. All clusters with three or more 4He atoms are bound, although the combinations 4He33He9,10,11 and 4He34He9 are metastable. Clusters with 2, 8, and 20 3He atoms are particularly stable and define magic 3He numbers.

Platinum clusters with precise numbers of atoms for preparative-scale catalysis.

PubMed

Imaoka, Takane; Akanuma, Yuki; Haruta, Naoki; Tsuchiya, Shogo; Ishihara, Kentaro; Okayasu, Takeshi; Chun, Wang-Jae; Takahashi, Masaki; Yamamoto, Kimihisa

2017-09-25

Subnanometer noble metal clusters have enormous potential, mainly for catalytic applications. Because a difference of only one atom may cause significant changes in their reactivity, a preparation method with atomic-level precision is essential. Although such a precision with enough scalability has been achieved by gas-phase synthesis, large-scale preparation is still at the frontier, hampering practical applications. We now show the atom-precise and fully scalable synthesis of platinum clusters on a milligram scale from tiara-like platinum complexes with various ring numbers (n = 5-13). Low-temperature calcination of the complexes on a carbon support under hydrogen stream affords monodispersed platinum clusters, whose atomicity is equivalent to that of the precursor complex. One of the clusters (Pt 10 ) exhibits high catalytic activity in the hydrogenation of styrene compared to that of the other clusters. This method opens an avenue for the application of these clusters to preparative-scale catalysis.The catalytic activity of a noble metal nanocluster is tied to its atomicity. Here, the authors report an atom-precise, fully scalable synthesis of platinum clusters from molecular ring precursors, and show that a variation of only one atom can dramatically change a cluster's reactivity.

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

DOE PAGES

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

2018-04-24

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

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

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

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

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

X-ray spectroscopy study of electronic structure of laser-irradiated Au nanoparticles in a silica film

NASA Astrophysics Data System (ADS)

Jonnard, P.; Bercegol, H.; Lamaignère, L.; Morreeuw, J.-P.; Rullier, J.-L.; Cottancin, E.; Pellarin, M.

2005-03-01

The electronic structure of gold nanoparticles embedded in a silica film is studied, both before and after irradiation at 355nm by a laser. The Au 5d occupied valence states are observed by x-ray emission spectroscopy. They show that before irradiation the gold atoms are in metallic states within the nanoparticles. After irradiation with a fluence of 0.5J/cm2, it is found that gold valence states are close to those of a metal-poor gold silicide; thanks to a comparison of the experimental Au 5d states with the calculated ones for gold silicides using the density-functional theory. The formation of such a compound is driven by the diffusion of the gold atoms into the silica film upon the laser irradiation. At higher fluence, 1J/cm2, we find a higher percentage of metallic gold that could be attributed to annealing in the silica matrix.

An investigation into the interactions of gold nanoparticles and anti-arthritic drugs with macrophages, and their reactivity towards thioredoxin reductase

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

James, Lloyd R.A.; Xu, Zhi-Qiang; Sluyter, Ronald

Gold(I) complexes are an important tool in the arsenal of established approaches for treating rheumatoid arthritis (RA), while some recent studies have suggested that gold nanoparticles (Au NPs) may also be therapeutically efficacious. These observations prompted the current biological studies involving gold(I) anti-RA agents and Au NPs, which are aimed towards improving our knowledge of how they work. The cytotoxicity of auranofin, aurothiomalate, aurothiosulfate and Au NPs towards RAW264.7 macrophages was evaluated using the MTT assay, with the former compound proving to be the most toxic. The extent of cellular uptake of the various gold agents was determined using graphitemore » furnace atomic absorption spectrometry, while their distribution within macrophages was examined using microprobe synchrotron radiation X-ray fluorescence spectroscopy. The latter technique showed accumulation of gold in discrete regions of the cell, and co-localisation with sulfur in the case of cells treated with aurothiomalate or auranofin. Electrospray ionization mass spectrometry was used to characterize thioredoxin reductase (TrxR) in which the penultimate selenocysteine residue was replaced by cysteine. Mass spectra of solutions of TrxR and aurothiomalate, aurothiosulfate or auranofin showed complexes containing bare gold atoms bound to the protein, or protein adducts containing gold atoms retaining some of their initial ligands. These results support TrxR being an important target of gold(I) drugs used to treat RA, while the finding that Au NPs are incorporated into macrophages, but elicit little toxicity, indicates further exploration of their potential for treatment of RA is warranted.« less

A New-Type of Long-Range Restructuring of Ordered Metal Surfaces Induced by Lateral Adsorbate Interactions: Iodide on AU(110) Electrodes

DTIC Science & Technology

1994-02-01

separated by monoatomic steps. The direction of the (110) gold rows is evident in the atomic- resolution image of a uniform terrace, shown in Fig. 2A...distinguish between the average surface energy of a gold atom within a (110) terrace and at a monoatomic step (edge) site. The difference between these...having (3 x 2) symmetry (coverage - 0.67), is imaged instead of the substrate, with the iodide arranged in parallel close-packed rows in between the gold

Single step synthesis of gold-amino acid composite, with the evidence of the catalytic hydrogen atom transfer (HAT) reaction, for the electrochemical recognition of Serotonin

NASA Astrophysics Data System (ADS)

Choudhary, Meenakshi; Siwal, Samarjeet; Nandi, Debkumar; Mallick, Kaushik

2016-03-01

A composite architecture of amino acid and gold nanoparticles has been synthesized using a generic route of 'in-situ polymerization and composite formation (IPCF)' [1,2]. The formation mechanism of the composite has been supported by a model hydrogen atom (H•≡H++e-) transfer (HAT) type of reaction which belongs to the proton coupled electron transfer (PCET) mechanism. The 'gold-amino acid composite' was used as a catalyst for the electrochemical recognition of Serotonin.

Stretching of short monatomic gold chains-some model calculations

NASA Astrophysics Data System (ADS)

Sumali, Priyanka, Verma, Veena; Dharamvir, Keya

2012-06-01

The Mechanical properties of zig-zag monatomic gold chains containing 5 and 7 atoms were studied using the Siesta Code (SC), which works within the framework of DFT formalism and Gupta Potential (GP), which is an effective atom-atom potential. The zig-zag chains were stretched by keeping the end atoms fixed while rest of the atoms were relaxed till minimum energy is obtained. Energy, Force and Young's Modulus found using GP and SC were plotted as functions of total length. It is found that the breaking force in case of GP is of order of 1.6nN while for SIESTA is of the order of 2.9nN for both the chains.

Origin of selenium–gold interaction in F{sub 2}CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH{sub 3}): Synergistic effects

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

Guo, Xin; Yang, Yu-Ping; Li, Qing-Zhong, E-mail: liqingzhong1990@sina.com, E-mail: lihaibei@sdu.edu.cn

Selenium–gold interaction plays an important role in crystal materials, molecular self-assembly, and pharmacochemistry involving gold. In this paper, we unveiled the mechanism and nature of selenium–gold interaction by studying complexes F{sub 2}CSe⋯AuY (Y = CN, F, Cl, Br, OH, and CH{sub 3}). The results showed that the formation of selenium–gold interaction is mainly attributed to the charge transfer from the lone pair of Se atom to the Au—Y anti-bonding orbital. Energy decomposition analysis indicated that the polarization energy is nearly equivalent to or exceeds the electrostatic term in the selenium–gold interaction. Interestingly, the chalcogen–gold interaction becomes stronger with the increasemore » of chalcogen atomic mass in F{sub 2}CX⋯AuCN (X = O, S, Se, and Te). The cyclic ternary complexes are formed with the introduction of NH{sub 3} into F{sub 2}CSe⋯AuY, in which selenium–gold interaction is weakened and selenium–nitrogen interaction is strengthened due to the synergistic effects.« less

Structures of small Pd Pt bimetallic clusters by Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Cheng, Daojian; Huang, Shiping; Wang, Wenchuan

2006-11-01

Segregation phenomena of Pd-Pt bimetallic clusters with icosahedral and decahedral structures are investigated by using Monte Carlo method based on the second-moment approximation of the tight-binding (TB-SMA) potentials. The simulation results indicate that the Pd atoms generally lie on the surface of the smaller clusters. The three-shell onion-like structures are observed in 55-atom Pd-Pt bimetallic clusters, in which a single Pd atom is located in the center, and the Pt atoms are in the middle shell, while the Pd atoms are enriched on the surface. With the increase of Pd mole fraction in 55-atom Pd-Pt bimetallic clusters, the Pd atoms occupy the vertices of clusters first, then edge and center sites, and finally the interior shell. It is noticed that some decahedral structures can be transformed into the icosahedron-like structure at 300 and 500 K. Comparisons are made with previous experiments and theoretical studies of Pd-Pt bimetallic clusters.

Characteristics of pulse gold vapor laser outlined

NASA Astrophysics Data System (ADS)

1981-09-01

Several dozen laser oscillating spectra lines were found within the very broad spectral wavelengths from infrared to ultraviolet. Laser studies of gold vapor were carried out and a pulsed laser of gold atoms of an operating wavelength of 6278 angstroms was obtained.

Mechanical gate control for atom-by-atom cluster assembly with scanning probe microscopy.

PubMed

Sugimoto, Yoshiaki; Yurtsever, Ayhan; Hirayama, Naoki; Abe, Masayuki; Morita, Seizo

2014-07-11

Nanoclusters supported on substrates are of great importance in physics and chemistry as well as in technical applications, such as single-electron transistors and nanocatalysts. The properties of nanoclusters differ significantly from those of either the constituent atoms or the bulk solid, and are highly sensitive to size and chemical composition. Here we propose a novel atom gating technique to assemble various atom clusters composed of a defined number of atoms at room temperature. The present gating operation is based on the transfer of single diffusing atoms among nanospaces governed by gates, which can be opened in response to the chemical interaction force with a scanning probe microscope tip. This method provides an alternative way to create pre-designed atom clusters with different chemical compositions and to evaluate their chemical stabilities, thus enabling investigation into the influence that a single dopant atom incorporated into the host clusters has on a given cluster stability.

Effects of Burning Conditions to the Formation of Gold Layer Photograph and Gold Layer Hologram

NASA Astrophysics Data System (ADS)

Kuge, Ken'ichi; Takahashi, Ataru; Harada, Takahito; Doi, Keiji; Sakai, Tomoko

Burning stage from gold nanoparticles to gold layer in the formation process of gold-layer photograph using gold deposition development was investigated. The gelatin layer holding gold nanoparticles is carbonized at about 400°C and burned out until about 500°C. Because gold nanoparticles would be compressed only to vertical direction and then melt to form the gold layer, the gold-layer photograph still holds the high resolution. Gold nanoparaticles do not melt completely even at 900°C, and form continuous clusters of several hundred nm.

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

PubMed

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

2018-04-28

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

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Evaluation of Functional SiO₂ Nanoparticles Toxicity by a 3D Culture Model.

PubMed

Pellen-Mussi, Pascal; Tricot-Doleux, Sylvie; Neaime, Chrystelle; Nerambourg, Nicolas; Cabello-Hurtado, Francisco; Cordier, Stéphane; Grasset, Fabien; Jeanne, Sylvie

2018-05-01

as a kind of non-metal oxide SiO2 NPs have been extensively used in biomedicine, pharmaceuticals and other industrial manufacturing fields, such as DNA delivery, cancer therapy… Our group had developed a method based on microemulsion process to prepare SiO2 NPs incorporating photonic or magnetic nanocrystals and luminescent nanosized inorganic metal atom clusters. However, the toxicity of nanoparticles is known to be closely related to their physico-chemical characteristics and chemical composition. it is therefore of interest to investigate the toxicity of these novel SiO2 NPs to the cells that may come in contact. the potential toxic effect of the functional @SiO2 NPs containing Mo6 clusters with or without gold nanoparticles was investigated, at concentrations 1 μg/mL, 10 μg/mL and 100 μg/mL each, on three different cell lines. Cell viability was measured by the MTT test in monolayer's culture whereas the cytotoxicity in spheroid model was examined by the APH assay. In a second time, oxidative-stress-induced cytotoxicity was investigated through glutathione levels dosages. the results indicated that both A549 and L929 cell lines did not exhibit susceptibility to functional @SiO2 NPs-induced oxidative stress unlike KB cells. SiO2 NPs containing CMB may become toxic to cultured cells but only at a very high dosage level. Therefore, this toxicity depends on cell lines and more, on the model of cell cultures. The selection of appropriate cell line remains a critical component in nanotoxicology. these results are relevant to future applications of SiO2 gold-cluster NPs in controlled release applications.

Quantized thermal transport in single-atom junctions

NASA Astrophysics Data System (ADS)

Cui, Longji; Jeong, Wonho; Hur, Sunghoon; Matt, Manuel; Klöckner, Jan C.; Pauly, Fabian; Nielaba, Peter; Cuevas, Juan Carlos; Meyhofer, Edgar; Reddy, Pramod

2017-03-01

Thermal transport in individual atomic junctions and chains is of great fundamental interest because of the distinctive quantum effects expected to arise in them. By using novel, custom-fabricated, picowatt-resolution calorimetric scanning probes, we measured the thermal conductance of gold and platinum metallic wires down to single-atom junctions. Our work reveals that the thermal conductance of gold single-atom junctions is quantized at room temperature and shows that the Wiedemann-Franz law relating thermal and electrical conductance is satisfied even in single-atom contacts. Furthermore, we quantitatively explain our experimental results within the Landauer framework for quantum thermal transport. The experimental techniques reported here will enable thermal transport studies in atomic and molecular chains, which will be key to investigating numerous fundamental issues that thus far have remained experimentally inaccessible.

First principles absorption spectra of Cu{sub n} (n = 2 - 20) clusters.

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

Baishya, K.; Idrobo, J. C.; Ogut, S.

2011-06-17

Optical absorption spectra for the computed ground state structures of copper clusters (Cu{sub n}, n = 2-20) are investigated from first principles using time-dependent density functional theory in the adiabatic local density approximation (TDLDA). The results are compared with available experimental data, existing calculations, and with results from our previous computations on silver and gold clusters. The main effects of d electrons on the absorption spectra, quenching the oscillator strengths, and getting directly involved in low-energy excitations increase in going from Ag{sub n} to Au{sub n} to Cu{sub n} due to the increase in the hybridization of the occupied, yetmore » shallow, d orbitals and the partially occupied s orbitals. We predict that while Cu nanoparticles of spherical or moderately ellipsoidal shape do not exhibit Mie (surface plasmon) resonances, unlike the case for Ag and Au, extremely prolate or oblate Cu nanoparticles with eccentricities near unity should give rise to Mie resonances in the lower end of the visible range and in the infrared. This tunable resonance predicted by the classical Mie-Gans theory is reproduced with remarkable accuracy by our TDLDA computations on hypothetical Cu clusters in the form of zigzag chains with as few as 6 to 20 atoms.« less

Theoretical characterization on the size-dependent electron and hole trapping activity of chloride-passivated CdSe nanoclusters

NASA Astrophysics Data System (ADS)

Cui, Yingqi; Cui, Xianhui; Zhang, Li; Xie, Yujuan; Yang, Mingli

2018-04-01

Ligand passivation is often used to suppress the surface trap states of semiconductor quantum dots (QDs) for their continuous photoluminescence output. The suppression process is related to the electrophilic/nucleophilic activity of surface atoms that varies with the structure and size of QD and the electron donating/accepting nature of ligand. Based on first-principles-based descriptors and cluster models, the electrophilic/nucleophilic activities of bare and chloride-coated CdSe clusters were studied to reveal the suppression mechanism of Cl-passivated QDs and compared to experimental observations. The surface atoms of bare clusters have higher activity than inner atoms and their activity decreases with cluster size. In the ligand-coated clusters, the Cd atom remains as the electrophilic site, while the nucleophilic site of Se atoms is replaced by Cl atoms. The activities of Cd and Cl atoms in the coated clusters are, however, remarkably weaker than those in bare clusters. Cluster size, dangling atoms, ligand coverage, electronegativity of ligand atoms, and solvent (water) were found to have considerable influence on the activity of surface atoms. The suppression of surface trap states in Cl-passivated QDs was attributed to the reduction of electrophilic/nucleophilic activity of Cd/Se/Cl atoms. Both saturation to under-coordinated surface atoms and proper selection for the electron donating/accepting strength of ligands are crucial for eliminating the charge carrier traps. Our calculations predicted a similar suppressing effect of chloride ligands with experiments and provided a simple but effective approach to assess the charge carrier trapping behaviors of semiconductor QDs.

Determination of gold, indium, tellurium and thallium in the same sample digest of geological materials by atomic-absorption spectroscopy and two-step solvent extraction

USGS Publications Warehouse

Hubert, A.E.; Chao, T.T.

1985-01-01

A rock, soil, or stream-sediment sample is decomposed with hydrofluoric acid, aqua regia, and hydrobromic acid-bromine solution. Gold, thallium, indium and tellurium are separated and concentrated from the sample digest by a two-step MIBK extraction at two concentrations of hydrobromic add. Gold and thallium are first extracted from 0.1M hydrobromic acid medium, then indium and tellurium are extracted from 3M hydrobromic acid in the presence of ascorbic acid to eliminate iron interference. The elements are then determined by flame atomic-absorption spectrophotometry. The two-step solvent extraction can also be used in conjunction with electrothermal atomic-absorption methods to lower the detection limits for all four metals in geological materials. ?? 1985.

Simulating the Effect of Contact Atomic Structure on the Spin-Dependent Transport Properties of Gold Nanowires

NASA Astrophysics Data System (ADS)

Ansarino, Masoud; Ravan, Bahram Abedi

Some experimental research works report on the superb magnetoresistance properties of magnetically contacted gold nanowires. With the intention of trying to understand the spin-dependent transport mechanism of these structures, in this work we have used first-principles density functional theory methods to investigate effects of interface structure on the spintronic characteristics of Au nanowires. Monatomic chains of gold are sandwiched between two ferromagnetic electrodes of Fe and by substituting the interfacial Fe atoms with some other transition metal elements (including Cr, Mn, Co and Ni) the occurrence of possible enhancement in the electronic conductance and magnetoresistance characteristics of the device are investigated. It is observed that replacing the interfacial atoms with Ni raises the junction’s magnetoresistance ratio to as high as 2000%.

The Origin of the Elements

ScienceCinema

Murphy, Edward

2018-01-23

The world around us is made of atoms. Did you ever wonder where these atoms came from? How was the gold in our jewelry, the carbon in our bodies, and the iron in our cars made? In this lecture, we will trace the origin of a gold atom from the Big Bang to the present day, and beyond. You will learn how the elements were forged in the nuclear furnaces inside stars, and how, when they die, these massive stars spread the elements into space. You will learn about the origin of the building blocks of matter in the Big Bang, and we will speculate on the future of the atoms around us today.

Investigation of atomic oxygen-surface interactions related to measurements with dual air density explorer satellites

NASA Technical Reports Server (NTRS)

Wood, B. J.; Ablow, C. M.; Wise, H.

1973-01-01

For a number of candidate materials of construction for the dual air density explorer satellites the rate of oxygen atom loss by adsorption, surface reaction, and recombination was determined as a function of surface and temperature. Plain aluminum and anodized aluminum surfaces exhibit a collisional atom loss probability alpha .01 in the temperature range 140 - 360 K, and an initial sticking probability. For SiO coated aluminum in the same temperature range, alpha .001 and So .001. Atom-loss on gold is relatively rapid alpha .01. The So for gold varies between 0.25 and unity in the temperature range 360 - 140 K.

Melting of size-selected gallium clusters with 60-183 atoms.

PubMed

Pyfer, Katheryne L; Kafader, Jared O; Yalamanchali, Anirudh; Jarrold, Martin F

2014-07-10

Heat capacities have been measured as a function of temperature for size-selected gallium cluster cations with between 60 and 183 atoms. Almost all clusters studied show a single peak in the heat capacity that is attributed to a melting transition. The peaks can be fit by a two-state model incorporating only fully solid-like and fully liquid-like species, and hence no partially melted intermediates. The exceptions are Ga90(+), which does not show a peak, and Ga80(+) and Ga81(+), which show two peaks. For the clusters with two peaks, the lower temperature peak is attributed to a structural transition. The melting temperatures for clusters with less than 50 atoms have previously been shown to be hundreds of degrees above the bulk melting point. For clusters with more than 60 atoms the melting temperatures decrease, approaching the bulk value (303 K) at around 95 atoms, and then show several small upward excursions with increasing cluster size. A plot of the latent heat against the entropy change for melting reveals two groups of clusters: the latent heats and entropy changes for clusters with less than 94 atoms are distinct from those for clusters with more than 93 atoms. This observation suggests that a significant change in the nature of the bonding or the structure of the clusters occurs at 93-94 atoms. Even though the melting temperatures are close to the bulk value for the larger clusters studied here, the latent heats and entropies of melting are still far from the bulk values.

Reactivity Control of Rhodium Cluster Ions by Alloying with Tantalum Atoms.

PubMed

Mafuné, Fumitaka; Tawaraya, Yuki; Kudoh, Satoshi

2016-02-18

Gas phase, bielement rhodium and tantalum clusters, RhnTam(+) (n + m = 6), were prepared by the double laser ablation of Rh and Ta rods in He carrier gas. The clusters were introduced into a reaction gas cell filled with nitric oxide (NO) diluted with He and were subjected to collisions with NO and He at room temperature. The product species were observed by mass spectrometry, demonstrating that the NO molecules were sequentially adsorbed on the RhnTam(+) clusters to form RhnTam(+)NxOx (x = 1, 2, 3, ...) species. In addition, oxide clusters, RhnTam(+)O2, were also observed, suggesting that the NO molecules were dissociatively adsorbed on the cluster, the N atoms migrated on the surface to form N2, and the N2 molecules were released from RhnTam(+)N2O2. The reactivity, leading to oxide formation, was composition dependent: oxide clusters were dominantly formed for the bielement clusters containing both Rh and Ta atoms, whereas such clusters were hardly formed for the single-element Rhn(+) and Tam(+) clusters. DFT calculations indicated that the Ta atoms induce dissociation of NO on the clusters by lowering the dissociation energy, whereas the Rh atoms enable release of N2 by lowering the binding energy of the N atoms on the clusters.

Self-diffusion and microscopic dynamics in a gold-silicon liquid investigated with quasielastic neutron scattering

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

Evenson, Zach, E-mail: Zachary.Evenson@frm2.tum.de; Institut für Materialphysik im Weltraum, Deutsches Zentrum für Luft- und Raumfahrt; Yang, Fan

2016-03-21

We use incoherent quasielastic neutron scattering to study the atomic dynamics of gold in a eutectic Au{sub 81}Si{sub 19} melt. Despite the glass-forming nature of this system, the gold self-diffusivity displays an Arrhenius behavior with a low activation energy characteristic of simple liquids. At high temperatures, long-range transport of gold atoms is well described by hydrodynamic theory with a simple exponential decay of the self-correlation function. On cooling towards the melting temperature, structural relaxation crosses over to a highly stretched exponential behavior. This suggests the onset of a heterogeneous dynamics, even in the equilibrium melt, and is indicative of amore » very fragile liquid.« less

Mass spectrometric identification of Au68(SR)34 molecular gold nanoclusters with 34-electron shell closing.

PubMed

Dass, Amala

2009-08-26

The molecular formula Au(68)(SCH(2)CH(2)Ph)(34) has been assigned to the 14 kDa nanocluster using MALDI-TOF mass spectrometry. The 34-electron shell closing in a macroscopically obtained thiolated gold nanocluster is demonstrated. The Au(68) nanocluster is predicted to have a 49 atom Marks decahedral core with 19 inner core atoms and 30 outer atoms chelating with the staple motifs. The nanoclusters' predicted formulation is [Au](19+30) [Au(SR)(2)](11) [Au(2)(SR)(3)](4).

Electrocatalysts having platium monolayers on palladium, palladium alloy, and gold alloy core-shell nanoparticles, and uses thereof

DOEpatents

Adzic, Radoslav; Mo, Yibo; Vukmirovic, Miomir; Zhang, Junliang

2010-12-21

The invention relates to platinum-coated particles useful as fuel cell electrocatalysts. The particles are composed of a noble metal or metal alloy core at least partially encapsulated by an atomically thin surface layer of platinum atoms. The invention particularly relates to such particles having a palladium, palladium alloy, gold alloy, or rhenium alloy core encapsulated by an atomic monolayer of platinum. In other embodiments, the invention relates to fuel cells containing these electrocatalysts and methods for generating electrical energy therefrom.

Modeling the self-assembly of functionalized fullerenes on solid surfaces using Monte Carlo simulations

NASA Astrophysics Data System (ADS)

Bubnis, Gregory J.

Since their discovery 25 years ago, carbon fullerenes have been widely studied for their unique physicochemical properties and for applications including organic electronics and photovoltaics. For these applications it is highly desirable for crystalline fullerene thin films to spontaneously self-assemble on surfaces. Accordingly, many studies have functionalized fullerenes with the aim of tailoring their intermolecular interactions and controlling interactions with the solid substrate. The success of these rational design approaches hinges on the subtle interplay of intermolecular forces and molecule-substrate interactions. Molecular modeling is well-suited to studying these interactions by directly simulating self-assembly. In this work, we consider three different fullerene functionalization approaches and for each approach we carry out Monte Carlo simulations of the self-assembly process. In all cases, we use a "coarse-grained" molecular representation that preserves the dominant physical interactions between molecules and maximizes computational efficiency. The first approach we consider is the traditional gold-thiolate SAM (self-assembled monolayer) strategy which tethers molecules to a gold substrate via covalent sulfur-gold bonds. For this we study an asymmetric fullerene thiolate bridged by a phenyl group. Clusters of 40 molecules are simulated on the Au(111) substrate at different temperatures and surface coverage densities. Fullerenes and S atoms are found to compete for Au(111) surface sites, and this competition prevents self-assembly of highly ordered monolayers. Next, we investigate self-assembled monolayers formed by fullerenes with hydrogen-bonding carboxylic acid substituents. We consider five molecules with different dimensions and symmetries. Monte Carlo cooling simulations are used to find the most stable solid structures of clusters adsorbed to Au(111). The results show cases where fullerene-Au(111) attraction, fullerene close-packing, and hydrogen-bonding interactions can cooperate to guide self-assembly or compete to hinder it. Finally, we consider three bis-fullerene molecules, each with a different "bridging group" covalently joining two fullerenes. To effectively study the competing "standing-up" and "lying-down" morphologies, we use Monte Carlo simulations in conjunction with replica exchange and force field biasing methods. For clusters adsorbed to smooth model surfaces, we determine free energy landscapes and demonstrate their utility for rationalizing and predicting self-assembly.

Biodegradation mechanisms of iron oxide monocrystalline nanoflowers and tunable shield effect of gold coating.

PubMed

Javed, Yasir; Lartigue, Lénaic; Hugounenq, Pierre; Vuong, Quoc Lam; Gossuin, Yves; Bazzi, Rana; Wilhelm, Claire; Ricolleau, Christian; Gazeau, Florence; Alloyeau, Damien

2014-08-27

Understanding the relation between the structure and the reactivity of nanomaterials in the organism is a crucial step towards efficient and safe biomedical applications. The multi-scale approach reported here, allows following the magnetic and structural transformations of multicore maghemite nanoflowers in a medium mimicking intracellular lysosomal environment. By confronting atomic-scale and macroscopic information on the biodegradation of these complex nanostuctures, we can unravel the mechanisms involved in the critical alterations of their hyperthermic power and their Magnetic Resonance imaging T1 and T2 contrast effect. This transformation of multicore nanoparticles with outstanding magnetic properties into poorly magnetic single core clusters highlights the harmful influence of cellular medium on the therapeutic and diagnosis effectiveness of iron oxide-based nanomaterials. As biodegradation occurs through surface reactivity mechanism, we demonstrate that the inert activity of gold nanoshells can be exploited to protect iron oxide nanostructures. Such inorganic nanoshields could be a relevant strategy to modulate the degradability and ultimately the long term fate of nanomaterials in the organism. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Single molecule magnets with protective ligand shells on gold and titanium dioxide surfaces: In situ electrospray deposition and x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Handrup, Karsten; Richards, Victoria J.; Weston, Matthew; Champness, Neil R.; O'Shea, James N.

2013-10-01

Two single molecule magnets based on the dodecamanganese (III, IV) cluster with either benzoate or terphenyl-4-carboxylate ligands, have been studied on the Au(111) and rutile TiO2(110) surfaces. We have used in situ electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. X-ray absorption spectroscopy measured at the Mn L-edge (Mn 2p) has been used to study the effect of adsorption on the oxidation states of the manganese atoms in the core. In the case of the benzoate-functionalised complex reduction of the manganese metal centres is observed due to the interaction of the manganese core with the underlying surface. In the case of terphenyl-4-carboxylate, the presence of this much larger ligand prevents the magnetic core from interacting with either the gold or the titanium dioxide surfaces and the characteristic Mn3+ and Mn4+ oxidation states necessary for magnetic behaviour are preserved.

Optical trapping of metal-dielectric nanoparticle clusters near photonic crystal microcavities.

PubMed

Mejia, Camilo A; Huang, Ningfeng; Povinelli, Michelle L

2012-09-01

We predict the formation of optically trapped, metal-dielectric nanoparticle clusters above photonic crystal microcavities. We determine the conditions on particle size and position for a gold particle to be trapped above the microcavity. We then show that strong field redistribution and enhancement near the trapped gold nanoparticle results in secondary trapping sites for a pair of dielectric nanoparticles.

Hund’s rule in superatoms with transition metal impurities

PubMed Central

Medel, Victor M.; Reveles, Jose Ulises; Khanna, Shiv N.; Chauhan, Vikas; Sen, Prasenjit; Castleman, A. Welford

2011-01-01

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund’s rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMgn clusters where TM is a 3d atom. The clusters exhibit Hund’s filling, opening the pathway to superatoms with magnetic shells. PMID:21646542

Hund's rule in superatoms with transition metal impurities.

PubMed

Medel, Victor M; Reveles, Jose Ulises; Khanna, Shiv N; Chauhan, Vikas; Sen, Prasenjit; Castleman, A Welford

2011-06-21

The quantum states in metal clusters bunch into supershells with associated orbitals having shapes resembling those in atoms, giving rise to the concept that selected clusters could mimic the characteristics of atoms and be classified as superatoms. Unlike atoms, the superatom orbitals span over multiple atoms and the filling of orbitals does not usually exhibit Hund's rule seen in atoms. Here, we demonstrate the possibility of enhancing exchange splitting in superatom shells via a composite cluster of a central transition metal and surrounding nearly free electron metal atoms. The transition metal d states hybridize with superatom D states and result in enhanced splitting between the majority and minority sets where the moment and the splitting can be controlled by the nature of the central atom. We demonstrate these findings through studies on TMMg(n) clusters where TM is a 3d atom. The clusters exhibit Hund's filling, opening the pathway to superatoms with magnetic shells.

Gold Nanoparticle Quantitation by Whole Cell Tomography.

PubMed

Sanders, Aric W; Jeerage, Kavita M; Schwartz, Cindi L; Curtin, Alexandra E; Chiaramonti, Ann N

2015-12-22

Many proposed biomedical applications for engineered gold nanoparticles require their incorporation by mammalian cells in specific numbers and locations. Here, the number of gold nanoparticles inside of individual mammalian stem cells was characterized using fast focused ion beam-scanning electron microscopy based tomography. Enhanced optical microscopy was used to provide a multiscale map of the in vitro sample, which allows cells of interest to be identified within their local environment. Cells were then serially sectioned using a gallium ion beam and imaged using a scanning electron beam. To confirm the accuracy of single cross sections, nanoparticles in similar cross sections were imaged using transmission electron microscopy and scanning helium ion microscopy. Complete tomographic series were then used to count the nanoparticles inside of each cell and measure their spatial distribution. We investigated the influence of slice thickness on counting single particles and clusters as well as nanoparticle packing within clusters. For 60 nm citrate stabilized particles, the nanoparticle cluster packing volume is 2.15 ± 0.20 times the volume of the bare gold nanoparticles.

DFT Modeling of Cross-Linked Polyethylene: Role of Gold Atoms and Dispersion Interactions.

PubMed

Blaško, Martin; Mach, Pavel; Antušek, Andrej; Urban, Miroslav

2018-02-08

Using DFT modeling, we analyze the concerted action of gold atoms and dispersion interactions in cross-linked polyethylene. Our model consists of two oligomer chains (PEn) with 7, 11, 15, 19, or 23 carbon atoms in each oligomer cross-linked with one to three Au atoms through C-Au-C bonds. In structures with a single gold atom the C-Au-C bond is located in the central position of the oligomer. Binding energies (BEs) with respect to two oligomer radical fragments and Au are as high as 362-489 kJ/mol depending on the length of the oligomer chain. When the dispersion contribution in PEn-Au-PEn oligomers is omitted, BE is almost independent of the number of carbon atoms, lying between 293 and 296 kJ/mol. The dispersion energy contributions to BEs in PEn-Au-PEn rise nearly linearly with the number of carbon atoms in the PEn chain. The carbon-carbon distance in the C-Au-C moiety is around 4.1 Å, similar to the bond distance between saturated closed shell chains in the polyethylene crystal. BEs of pure saturated closed shell PEn-PEn oligomers are 51-187 kJ/mol. Both Au atoms and dispersion interactions contribute considerably to the creation of nearly parallel chains of oligomers with reasonably high binding energies.

Electron microscopy study of gold nanoparticles deposited on transition metal oxides.

PubMed

Akita, Tomoki; Kohyama, Masanori; Haruta, Masatake

2013-08-20

Many researchers have investigated the catalytic performance of gold nanoparticles (GNPs) supported on metal oxides for various catalytic reactions of industrial importance. These studies have consistently shown that the catalytic activity and selectivity depend on the size of GNPs, the kind of metal oxide supports, and the gold/metal oxide interface structure. Although researchers have proposed several structural models for the catalytically active sites and have identified the specific electronic structures of GNPs induced by the quantum effect, recent experimental and theoretical studies indicate that the perimeter around GNPs in contact with the metal oxide supports acts as an active site in many reactions. Thus, it is of immense importance to investigate the detailed structures of the perimeters and the contact interfaces of gold/metal oxide systems by using electron microscopy at an atomic scale. This Account describes our investigation, at the atomic scale using electron microscopy, of GNPs deposited on metal oxides. In particular, high-resolution transmission electron microscopy (HRTEM) and high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) are valuable tools to observe local atomic structures, as has been successfully demonstrated for various nanoparticles, surfaces, and material interfaces. TEM can be applied to real powder catalysts as received without making special specimens, in contrast to what is typically necessary to observe bulk materials. For precise structure analyses at an atomic scale, model catalysts prepared by using well-defined single-crystalline substrates are also adopted for TEM observations. Moreover, aberration-corrected TEM, which has high spatial resolution under 0.1 nm, is a promising tool to observe the interface structure between GNPs and metal oxide supports including oxygen atoms at the interfaces. The oxygen atoms in particular play an important role in the behavior of gold/metal oxide interfaces, because they may participate in catalytic reaction steps. Detailed information about the interfacial structures between GNPs and metal oxides provides valuable structure models for theoretical calculations which can elucidate the local electronic structure effective for activating a reactant molecule. Based on our observations with HRTEM and HAADF-STEM, we report the detailed structure of gold/metal oxide interfaces.

Au13(8e): A secondary block for describing a special group of liganded gold clusters containing icosahedral Au13 motifs

NASA Astrophysics Data System (ADS)

Xu, Wen Wu; Zeng, Xiao Cheng; Gao, Yi

2017-05-01

A grand unified model (GUM) has been proposed recently to understand structure anatomy and evolution of liganded gold clusters. In this work, besides the two types of elementary blocks (triangular Au3(2e) and tetrahedral Au4(2e)), we introduce a secondary block, namely, the icosahedral Au13 with 8e valence electrons, noted as Au13(8e). Using this secondary block, structural anatomy and evolution of a special group of liganded gold nanoclusters containing icosahedral Au13 motifs can be conveniently analyzed. In addition, a new ligand-protected cluster Au49(PR3)10(SR)15Cl2 is predicted to exhibit high chemical and thermal stability, suggesting likelihood of its synthesis in the laboratory.

Gold Glyconanoparticles as Water-Soluble Polyvalent Models To Study Carbohydrate Interactions.

PubMed

de la Fuente, Jesús M; Barrientos, Africa G; Rojas, Teresa C; Rojo, Javier; Cañada, Javier; Fernández, Asunción; Penadés, Soledad

2001-06-18

Glycosphingolipid clustering and interactions at the cell membrane can be modeled by gold glyconanoparticles prepared with biologically significant oligosaccharides. Such water-soluble gold glyconanoparticles with highly polyvalent carbohydrate displays (see picture, gray hemisphere: gold nanoparticle) have been obtained by a simple and versatile strategy. © 2001 WILEY-VCH Verlag GmbH, Weinheim, Fed. Rep. of Germany.

Photoionization of rare gas clusters

NASA Astrophysics Data System (ADS)

Zhang, Huaizhen

This thesis concentrates on the study of photoionization of van der Waals clusters with different cluster sizes. The goal of the experimental investigation is to understand the electronic structure of van der Waals clusters and the electronic dynamics. These studies are fundamental to understand the interaction between UV-X rays and clusters. The experiments were performed at the Advanced Light Source at Lawrence Berkeley National Laboratory. The experimental method employs angle-resolved time-of-flight photoelectron spectrometry, one of the most powerful methods for probing the electronic structure of atoms, molecules, clusters and solids. The van der Waals cluster photoionization studies are focused on probing the evolution of the photoelectron angular distribution parameter as a function of photon energy and cluster size. The angular distribution has been known to be a sensitive probe of the electronic structure in atoms and molecules. However, it has not been used in the case of van der Waals clusters. We carried out outer-valence levels, inner-valence levels and core-levels cluster photoionization experiments. Specifically, this work reports on the first quantitative measurements of the angular distribution parameters of rare gas clusters as a function of average cluster sizes. Our findings for xenon clusters is that the overall photon-energy-dependent behavior of the photoelectrons from the clusters is very similar to that of the corresponding free atoms. However, distinct differences in the angular distribution point at cluster-size-dependent effects were found. For krypton clusters, in the photon energy range where atomic photoelectrons have a high angular anisotropy, our measurements show considerably more isotropic angular distributions for the cluster photoelectrons, especially right above the 3d and 4p thresholds. For the valence electrons, a surprising difference between the two spin-orbit components was found. For argon clusters, we found that the angular distribution parameter values of the two-spin-orbit components from Ar 2p clusters are slightly different. When comparing the beta values for Ar between atoms and clusters, we found different results between Ar 3s atoms and clusters, and between Ar 3p atoms and clusters. Argon cluster resonance from surface and bulk were also measured. Furthermore, the angular distribution parameters of Ar cluster photoelectrons and Ar atom photoelectrons in the 3s → np ionization region were obtained.

Atomically precise cluster catalysis towards quantum controlled catalysts

PubMed Central

Watanabe, Yoshihide

2014-01-01

Catalysis of atomically precise clusters supported on a substrate is reviewed in relation to the type of reactions. The catalytic activity of supported clusters has generally been discussed in terms of electronic structure. Several lines of evidence have indicated that the electronic structure of clusters and the geometry of clusters on a support, including the accompanying cluster-support interaction, are strongly correlated with catalytic activity. The electronic states of small clusters would be easily affected by cluster–support interactions. Several studies have suggested that it is possible to tune the electronic structure through atomic control of the cluster size. It is promising to tune not only the number of cluster atoms, but also the hybridization between the electronic states of the adsorbed reactant molecules and clusters in order to realize a quantum-controlled catalyst. PMID:27877723

Central Doping of a Foreign Atom into the Silver Cluster for Catalytic Conversion of CO2 toward C-C Bond Formation.

PubMed

Liu, Yuanyuan; Chai, Xiaoqi; Cai, Xiao; Chen, Mingyang; Jin, Rongchao; Ding, Weiping; Zhu, Yan

2018-06-19

Clusters with an exact number of atoms are of particular research interest in catalysis. Their catalytic behaviors can be potentially altered with the addition or removal of a single atom. Herein we explore the effects of the single-foreign-atom (Au, Pd and Pt) doping into the core of an Ag cluster with 25-atoms on the catalytic properties, where the foreign atom is protected by 24 Ag atoms (i.e., Au@Ag24, Pd@Ag24, and Pt@Ag24). The central doping of a single atom into the Ag25 cluster is found to have a substantial influence on the catalytic performance in the carboxylation reaction of CO2 with terminal alkyne through C-C bond formation to produce propiolic acid. Our studies reveal that the catalytic properties of the cluster catalysts can be dramatically changed with the subtle alteration by a single atom away from the active sites. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multiple valence superatoms.

PubMed

Reveles, J U; Khanna, S N; Roach, P J; Castleman, A W

2006-12-05

We recently demonstrated that, in gas phase clusters containing aluminum and iodine atoms, an Al(13) cluster behaves like a halogen atom, whereas an Al(14) cluster exhibits properties analogous to an alkaline earth atom. These observations, together with our findings that Al(13)(-) is inert like a rare gas atom, have reinforced the idea that chosen clusters can exhibit chemical behaviors reminiscent of atoms in the periodic table, offering the exciting prospect of a new dimension of the periodic table formed by cluster elements, called superatoms. As the behavior of clusters can be controlled by size and composition, the superatoms offer the potential to create unique compounds with tailored properties. In this article, we provide evidence of an additional class of superatoms, namely Al(7)(-), that exhibit multiple valences, like some of the elements in the periodic table, and hence have the potential to form stable compounds when combined with other atoms. These findings support the contention that there should be no limitation in finding clusters, which mimic virtually all members of the periodic table.

Catalytic behavior of ‘Pt-atomic chain encapsulated gold nanotube’: A density functional study

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

Nigam, Sandeep, E-mail: snigam@barc.gov.in; Majumder, Chiranjib

2016-05-23

With an aim to design novel material and explore its catalytic performance towards CO oxidation, Pt atomic chain was introduced inside gold nanotube (Au-NT). Theoretical calculations at the level of first principles formalism was carried out to investigate the atomic and electronic properties of the composite. Geometrically Pt atoms prefer to align in zig-zag fashion. Significant electronic charge transfer from inside Pt atoms to the outer wall Au atoms is observed. Interaction of O{sub 2} with Au-NT wall follows by injection of additional electronic charge in the anti-bonding orbital of oxygen molecule leading to activation of the O-O bond. Furthermore » interaction of CO molecule with the activated oxygen molecule leads to spontaneous oxidation reaction and formation of CO{sub 2}.« less

Anticancer Agents: Does a Phosphonium Behave Like a Gold(I) Phosphine Complex? Let a "Smart" Probe Answer!

PubMed

Ali, Moussa; Dondaine, Lucile; Adolle, Anais; Sampaio, Carla; Chotard, Florian; Richard, Philippe; Denat, Franck; Bettaieb, Ali; Le Gendre, Pierre; Laurens, Véronique; Goze, Christine; Paul, Catherine; Bodio, Ewen

2015-06-11

Gold phosphine complexes, such as auranofin, have been recognized for decades as antirheumatic agents. Clinical trials are now underway to validate their use in anticancer or anti-HIV treatments. However, their mechanisms of action remain unclear. A challenging question is whether the gold phosphine complex is a prodrug that is administered in an inactive precursor form or rather that the gold atom remains attached to the phosphine ligand during treatment. In this study, we present two novel gold complexes, which we compared to auranofin and to their phosphonium analogue. The chosen ligand is a phosphine-based smart probe, whose strong fluorescence depends on the presence of the gold atom. The in vitro biological action of the gold complexes and the phosphonium derivative were investigated, and a preliminary in vivo study in healthy zebrafish larvae allowed us to evaluate gold complex biodistribution and toxicity. The different analyses carried out showed that these gold complexes were stable and behaved differently from phosphonium and auranofin, both in vitro and in vivo. Two-photon microscopy experiments demonstrated that the cellular targets of these gold complexes are not the same as those of the phosphonium analogue. Moreover, despite similar IC50 values in some cancer cell lines, gold complexes displayed a low toxicity in vivo, in contrast to the phosphonium salt. They are therefore suitable for future in vivo investigations.

Photoelectron velocity-map imaging spectroscopic and theoretical study on the reactivity of the gold atom toward CH3SH, CH3OH, and H2O.

PubMed

Qin, Zhengbo; Cong, Ran; Wu, Xia; Liu, Zhiling; Xie, Hua; Tang, Zichao; Jiang, Ling; Fan, Hongjun

2013-07-21

Photoelectron velocity-map imaging spectroscopy has been used to study the reaction of the anionic gold atom with the HR (R = SCH3, OCH3, OH) molecules. The solvated [Au···HR](-) and inserted [HAuR](-) products have been experimentally observed for R = SCH3, whereas only solvated [Au⋯HR](-) products were found for R = OCH3 and OH. This significant difference in the photoelectron spectra suggests the different reactivity of the Au(-) toward the CH3SH, CH3OH, and H2O molecules. Second order Møller-Plesset perturbation theory and coupled-cluster single double triple excitation calculations have been performed to aid the structural assignment of the spectra and to explore the reaction mechanism. Activation energies for the isomerizations of the solvated structures to the inserted ones in the Au(-)∕Au + HR reactions (R = OCH3 and OH) are predicted to be much higher than those for the Au(-)∕Au + CH3SH reactions, supporting the experimental observation. Theoretical calculations provide the evidence that the intriguing [HAuSCH3](-) product may be formed by the attachment of the electron onto the neutral HAuSCH3 species or the isomerization from the anionic [Au···HSCH3](-) one. These findings should be helpful for understanding the feature that the thiols are able to form the staple motifs, whereas CH3OH and H2O are not.

Meta-atom cluster acoustic metamaterial with broadband negative effective mass density

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

Chen, Huaijun; Zhai, Shilong; Ding, Changlin

2014-02-07

We design a resonant meta-atom cluster, via which a two-dimensional (2D) acoustic metamaterial (AM) with broadband negative effective mass density from 1560 Hz to 5580 Hz is fabricated. Experimental results confirm that there is only weak interaction among the meta-atoms in the cluster. And then the meta-atoms in the cluster independently resonate, resulting in the cluster becoming equivalent to a broadband resonance unit. Extracted effective refractive indices from reflection and transmission measurements of the 2D AM appear to be negative from 1500 Hz to 5480 Hz. The broadband negative refraction has also been demonstrated by our further experiments. We expectmore » that this meta-atom cluster AM will significantly contribute to the design of broadband negative effective mass density AM.« less

A new route to gold nanoflowers

NASA Astrophysics Data System (ADS)

Liebig, Ferenc; Henning, Ricky; Sarhan, Radwan M.; Prietzel, Claudia; Bargheer, Matias; Koetz, Joachim

2018-05-01

Catanionic vesicles spontaneously formed by mixing the anionic surfactant bis(2-ethylhexyl) sulfosuccinate sodium salt with the cationic surfactant cetyltrimethylammonium bromide were used as a reducing medium to produce gold clusters, which are embedded and well-ordered into the template phase. The gold clusters can be used as seeds in the growth process that follows by adding ascorbic acid as a mild reducing component. When the ascorbic acid was added very slowly in an ice bath round-edged gold nanoflowers were produced. When the same experiments were performed at room temperature in the presence of Ag+ ions, sharp-edged nanoflowers could be synthesized. The mechanism of nanoparticle formation can be understood to be a non-diffusion-limited Ostwald ripening process of preordered gold nanoparticles embedded in catanionic vesicle fragments. Surface-enhanced Raman scattering experiments show an excellent enhancement factor of 1.7 · 105 for the nanoflowers deposited on a silicon wafer.

Fungus-mediated biological synthesis of gold nanoparticles: potential in detection of liver cancer

PubMed Central

Chauhan, Arun; Zubair, Swaleha; Tufail, Saba; Sherwani, Asif; Sajid, Mohammad; Raman, Suri C; Azam, Amir; Owais, Mohammad

2011-01-01

Background Nanomaterials are considered to be the pre-eminent component of the rapidly advancing field of nanotechnology. However, developments in the biologically inspired synthesis of nanoparticles are still in their infancy and consequently attracting the attention of material scientists throughout the world. Keeping in mind the fact that microorganism-assisted synthesis of nanoparticles is a safe and economically viable prospect, in the current study we report Candida albicans-mediated biological synthesis of gold nanoparticles. Methods and results Transmission electron microscopy, atomic force microscopy, and various spectrophotometric analyses were performed to characterize the gold nanoparticles. The morphology of the synthesized gold particles depended on the abundance of C. albicans cytosolic extract. Transmission electron microscopy, nanophox particle analysis, and atomic force microscopy revealed the size of spherical gold nanoparticles to be in the range of 20–40 nm and nonspherical gold particles were found to be 60–80 nm. We also evaluated the potential of biogenic gold nanoparticles to probe liver cancer cells by conjugating them with liver cancer cell surface-specific antibodies. The antibody-conjugated gold particles were found to bind specifically to the surface antigens of the cancer cells. Conclusion The antibody-conjugated gold particles synthesized in this study could successfully differentiate normal cell populations from cancerous cells. PMID:22072868

Manganese dioxide causes spurious gold values in flame atomic-absorption readings from HBr-Br2 digestions

USGS Publications Warehouse

Campbell, W.L.

1981-01-01

False readings, apparently caused by the presence of high concentrations of manganese dioxide, have been observed in our current flame atomic-absorption procedure for the determination of gold. After a hydrobromic acid (HBr)-bromine (Br2) leach, simply heating the sample to boiling to remove excess Br2 prior to extraction with methyl-isobutyl-ketone (MIBK) eliminates these false readings. ?? 1981.

Helium behavior in oxide dispersion strengthened (ODS) steel: Insights from ab initio modeling

NASA Astrophysics Data System (ADS)

Sun, Dan; Li, Ruihuan; Ding, Jianhua; Huang, Shaosong; Zhang, Pengbo; Lu, Zheng; Zhao, Jijun

2018-02-01

Using first-principles calculations, we systemically investigate the energetics and stability behavior of helium (He) atoms and small Hen (n = 2-4) clusters inside oxide dispersion strengthened (ODS) steel, as well as the incorporation of large amount of He atoms inside Y2O3 crystal. From the energetic point of view, He atom inside Y2O3 cluster is most stable, followed by the interstitial sites at the α-Fe/Y2O3 interface, and the tetrahedral interstitial sites inside α-Fe region. We further consider Hen (n = 2-4) clusters at the tetrahedral interstitial site surrounded by four Y atoms, which is the most stable site in the ODS steel model. The incorporation energies of all these Hen clusters are lower than that of single He atom in α-Fe, while the binding energy between two He atoms is relatively small. With insertion of 15 He atoms into 80-atom unit cell of Y2O3 crystal, the incorporation energy of He atoms is still lower than that of He4 cluster in α-Fe crystal. These theoretical results suggest that He atoms tend to aggregate inside Y2O3 clusters or at the α-Fe/Y2O3 interface, which is beneficial to prevent the He embrittlement in ODS steels.

Photoelectrochemical modulation of neuronal activity with free-standing coaxial silicon nanowires

NASA Astrophysics Data System (ADS)

Parameswaran, Ramya; Carvalho-de-Souza, João L.; Jiang, Yuanwen; Burke, Michael J.; Zimmerman, John F.; Koehler, Kelliann; Phillips, Andrew W.; Yi, Jaeseok; Adams, Erin J.; Bezanilla, Francisco; Tian, Bozhi

2018-02-01

Optical methods for modulating cellular behaviour are promising for both fundamental and clinical applications. However, most available methods are either mechanically invasive, require genetic manipulation of target cells or cannot provide subcellular specificity. Here, we address all these issues by showing optical neuromodulation with free-standing coaxial p-type/intrinsic/n-type silicon nanowires. We reveal the presence of atomic gold on the nanowire surfaces, likely due to gold diffusion during the material growth. To evaluate how surface gold impacts the photoelectrochemical properties of single nanowires, we used modified quartz pipettes from a patch clamp and recorded sustained cathodic photocurrents from single nanowires. We show that these currents can elicit action potentials in primary rat dorsal root ganglion neurons through a primarily atomic gold-enhanced photoelectrochemical process.

Atomic oxygen damage characterization by photothermal scanning

NASA Technical Reports Server (NTRS)

Williams, A. W.; Wood, N. J.; Zakaria, A. B.

1993-01-01

In this paper we use a photothermal imaging technique to characterize the damage caused to an imperfectly coated gold-coated Kapton sample exposed to successively increased fluences of atomic oxygen in a laboratory atomic source.

Novel Gold Intermetallics with Unique Properties and Bonding Patterns

NASA Astrophysics Data System (ADS)

Celania, Christopher Ranger

Gold has drawn the fascination of society through its brilliant color, malleability, and chemical resistance (hence its chemical nobility) since its discovery in ancient times. Today, this material is still highly coveted by consumers, but also for research within the scientific realm. The inclusion of gold in intermetallics often leads to notably unique structural and bonding features due to the pronounced relativistic effects on its 5d and 6s orbitals. Examples include quasicrystals and their approximants, unique gold clusters such as isolated Au7 clusters in A4Au7X2 (A = K, Rb, Cs; X = Ge, Sn), one dimensional columns such as Au zig-zag chains through Ca3Au3In, two dimensional slabs, such as in K2 Au3, as well as three dimensional gold networks as observed in the interconnected trigonal bipyramids in KAu5, hexagonal diamond-like frameworks of Au tetrahedra in Au-rich Sr-Au-Al systems; and combinations of tetrahedral and fourfold planar Au atoms in Rb3Au7. In recent years, compounds in the gold-rich region of the R-Au- M system (R = rare earth, M = groups 13-15) have come under increased study. Many compounds within this system produce varied electronic and magnetic properties such as Pauli paramagnetism, superconductivity, thermoelectricity, etc. The shielded 4f electrons of the added rare earth elements provide the unpaired spins that lead to the wealth of interesting magnetic properties in their compounds. Metals and metalloids from groups 13-15 may then be used as a bank of available options useful in tuning the valence electron count of the R-Au system toward the formation of stable compounds. Exploration of the Gd-Au-Sb system by utilizing common solid state synthesis techniques frequently used for the production of intermetallics (such as arc melting and high-temperature furnaces for self-flux reactions with low melting components) has yielded rich outcomes. These results include the discovery of a new R3Au9Pn series of compounds (R = Y, Gd-Ho; Pn = Sb, Bi), which undergo interesting metamagnetic transitions, varied coloring schemes for Sb substitutions in the known R14Au51 compound forming R 14(Au, M)51 (R = Y, La-Nd, Sm-Tb, Ho, Er, Yb, Lu; M = Al, Ga, Ge, In, Sn, Sb, Bi), and a complex tetragonal Gd-Au-Sb structure with significant Sb site mixing and positional disorder, as well as preliminary structure results of several other previously unreported compounds within the R-Au- M family.

The weak lensing analysis of the CFHTLS and NGVS RedGOLD galaxy clusters

NASA Astrophysics Data System (ADS)

Parroni, C.; Mei, S.; Erben, T.; Van Waerbeke, L.; Raichoor, A.; Ford, J.; Licitra, R.; Meneghetti, M.; Hildebrandt, H.; Miller, L.; Côté, P.; Covone, G.; Cuillandre, J.-C.; Duc, P.-A.; Ferrarese, L.; Gwyn, S. D. J.; Puzia, T. H.

2017-12-01

An accurate estimation of galaxy cluster masses is essential for their use in cosmological and astrophysical studies. We studied the accuracy of the optical richness obtained by our RedGOLD cluster detection algorithm tep{licitra2016a, licitra2016b} as a mass proxy, using weak lensing and X-ray mass measurements. We measured stacked weak lensing cluster masses for a sample of 1323 galaxy clusters in the Canada-France-Hawaii Telescope Legacy Survey W1 and the Next Generation Virgo Cluster Survey at 0.2

Change of Energy of the Cubic Subnanocluster of Iron Under Influence of Interstitial and Substitutional Atoms.

PubMed

Nedolya, Anatoliy V; Bondarenko, Natalya V

2016-12-01

Energy change of an iron face-centred cubic subnanocluster was evaluated using molecular mechanics method depending on the position of a carbon interstitial atom and substitutional atoms of nickel. Calculations of all possible positions of impurity atoms show that the energy change of the system are discrete and at certain positions of the atoms are close to continuous.In terms of energy, when all impurity atoms are on the same edge of an atomic cluster, their positions are more advantageous. The presence of nickel atoms on the edge of a cubic cluster resulted in decrease of potential barrier for a carbon atom and decrease in energy in the whole cluster. A similar drift of a carbon atom from central octahedral interstitial site to the surface in the direction <011> occurred under the influence of surface factors.Such configuration corresponds to decreasing symmetry and increasing the number of possible energy states of a subnanocluster, and it corresponds to the condition of spontaneous crystallization process in an isolated system.Taking into account accidental positions of the nickel atom in the iron cluster, such behaviour of the carbon atom can explain the mechanism of growth of a new phase and formation of new clusters in the presence of other kind of atoms because of surface influence.

Linker Dependent Bond Rupture Force Measurements in Single-Molecule Junctions

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

Frei M.; Hybertsen M.; Aradhya S.V.

We use a modified conducting atomic force microscope to simultaneously probe the conductance of a single-molecule junction and the force required to rupture the junction formed by alkanes terminated with four different chemical link groups which vary in binding strength and mechanism to the gold electrodes. Molecular junctions with amine, methylsulfide, and diphenylphosphine terminated molecules show clear conductance signatures and rupture at a force that is significantly smaller than the measured 1.4 nN force required to rupture the single-atomic gold contact. In contrast, measurements with a thiol terminated alkane which can bind covalently to the gold electrode show conductance andmore » force features unlike those of the other molecules studied. Specifically, the strong Au-S bond can cause structural rearrangements in the electrodes, which are accompanied by substantial conductance changes. Despite the strong Au-S bond and the evidence for disruption of the Au structure, the experiments show that on average these junctions also rupture at a smaller force than that measured for pristine single-atom gold contacts.« less

The study of structures and properties of PdnHm(n=1-10, m=1,2) clusters by density functional theory

NASA Astrophysics Data System (ADS)

Wen, Jun-Qing; Chen, Guo-Xiang; Zhang, Jian-Min; Wu, Hua

2018-04-01

The geometrical evolution, local relative stability, magnetism and charge transfer characteristics of PdnHm(n = 1-10, m = 1,2) have been systematically calculated by using density functional theory. The studied results show that the most stable geometries of PdnH and PdnH2 (n = 1-10) can be got by doping one or two H atoms on the sides of Pdn clusters except Pd6H and Pd6H2. It is found that doping one or two H atoms on Pdn clusters cannot change the basic framework of Pdn. The analysis of stability shows that Pd2H, Pd4H, Pd7H, Pd2H2, Pd4H2 and Pd7H2 clusters have higher local relative stability than neighboring clusters. The analysis of magnetic properties demonstrates that absorption of hydrogen atoms decreases the average atomic magnetic moments compared with pure Pdn clusters. More charges transfer from H atoms to Pd atoms for Pd6H and Pd6H2 clusters, demonstrating the adsorption of hydrogen atoms change from side adsorption to surface adsorption.

First principles calculation of current-induced forces in atomic gold contacts

NASA Astrophysics Data System (ADS)

Brandbyge, Mads; Stokbro, Kurt; Taylor, Jeremy; Mozos, Jose-Luis; Ordejon, Pablo

2002-03-01

We have recently developed an first principles method [1] for calculating the electronic structure, electronic transport, and forces acting on the atoms, for atomic scale systems connected to semi-infinite electrodes and with an applied voltage bias. Our method is based on the density functional theory (DFT) as implemented in the well tested SIESTA program [2]. We fully deal with the atomistic structure of the whole system, treating both the contact and the electrodes on the same footing. The effect of the finite bias (including selfconsistency and the solution of the electrostatic problem) is taken into account using nonequilibrium Green's functions. In this talk we show results for the forces acting on the contact atoms due to the nonequilibrium situation in the electronic subsystem, i.e. in the presence of an electronic current. We concentrate on one atom wide gold contacts/wires connected to bulk gold electrodes. References [1] Our implementation is called TranSIESTA and is described in M. Brandbyge, J. Taylor, K. Stokbro, J-L. Mozos, and P. Ordejon, cond-mat/0110650 [2] D. Sanchez-Portal, P. Ordejon, E. Artacho and J. Soler, Int. J. Quantum Chem. 65, 453 (1997).

Nanothermodynamics of iron clusters: Small clusters, icosahedral and fcc-cuboctahedral structures

NASA Astrophysics Data System (ADS)

Angelié, C.; Soudan, J.-M.

2017-05-01

The study of the thermodynamics and structures of iron clusters has been carried on, focusing on small clusters and initial icosahedral and fcc-cuboctahedral structures. Two combined tools are used. First, energy intervals are explored by the Monte Carlo algorithm, called σ-mapping, detailed in the work of Soudan et al. [J. Chem. Phys. 135, 144109 (2011), Paper I]. In its flat histogram version, it provides the classical density of states, gp(Ep), in terms of the potential energy of the system. Second, the iron system is described by a potential which is called "corrected EAM" (cEAM), explained in the work of Basire et al. [J. Chem. Phys. 141, 104304 (2014), Paper II]. Small clusters from 3 to 12 atoms in their ground state have been compared first with published Density Functional Theory (DFT) calculations, giving a complete agreement of geometries. The series of 13, 55, 147, and 309 atom icosahedrons is shown to be the most stable form for the cEAM potential. However, the 147 atom cluster has a special behaviour, since decreasing the energy from the liquid zone leads to the irreversible trapping of the cluster in a reproducible amorphous state, 7.38 eV higher in energy than the icosahedron. This behaviour is not observed at the higher size of 309 atoms. The heat capacity of the 55, 147, and 309 atom clusters revealed a pronounced peak in the solid zone, related to a solid-solid transition, prior to the melting peak. The corresponding series of 13, 55, and 147 atom cuboctahedrons has been compared, underscoring the unstability towards the icosahedral structure. This unstability occurs clearly in several steps for the 147 atom cluster, with a sudden transformation at a transition state. This illustrates the concerted icosahedron-cuboctahedron transformation of Buckminster Fuller-Mackay, which is calculated for the cEAM potential. Two other clusters of initial fcc structures with 24 and 38 atoms have been studied, as well as a 302 atom cluster. Each one relaxes towards a more stable structure without regularity. The 38 atom cluster exhibits a nearly glassy relaxation, through a cascade of six metastable states of long life. This behaviour, as that of the 147 atom cluster towards the amorphous state, shows that difficulties to reach ergodicity in the lower half of the solid zone are related to particular features of the potential energy landscape, and not necessarily to a too large size of the system. Comparisons of the cEAM iron system with published results about Lennard-Jones systems and DFT calculations are made. The results of the previous clusters have been combined with that of Paper II to plot the cohesive energy Ec and the melting temperature Tm in terms of the cluster atom number Nat. The Nat -1 /3 linear dependence of the melting temperature (Pawlow law) is observed again for Nat > 150. In contrast, for Nat < 150, the curve diverges strongly from the Pawlow law, giving it an overall V-shape, with a linear increase of Tm when Nat goes from 55 to 13 atoms. Surprisingly, the 38 atom cluster is anomalously below the overall curve.

Secondary ion mass spectra of gold super clusters up to 140000 Dalton

NASA Astrophysics Data System (ADS)

Feld, H.; Leute, A.; Rading, D.; Benninghoven, A.; Schmid, G.

1990-03-01

The bombardment of a two-shell gold complex (Au55(PPh3)12Cl6) with 10 keV Xe+-ions results in the formation of secondary ion masses up to 140000 u. These are by far the largest secondary ions observed under primary particle bombardment. The detection and identification of these ions with a Time-Of-Flight Secondary Ion Mass Spectrometer (TOF-SIMS) gives important information about the behavior of naked full-shell clusters. Au13 particles, generated from the Au55 cluster, serve as building blocks for a series of super-clusters up to (Au13)55. The results for keV-ion bombardment are compared to those for MeV-ion bombardment.

Atomic dynamics and the problem of the structural stability of free clusters of solidified inert gases

NASA Astrophysics Data System (ADS)

Verkhovtseva, É. T.; Gospodarev, I. A.; Grishaev, A. V.; Kovalenko, S. I.; Solnyshkin, D. D.; Syrkin, E. S.; Feodos'ev, S. B.

2003-05-01

The dependence of the rms amplitudes of atoms in free clusters of solidified inert gases on the cluster size is investigated theoretically and experimentally. Free clusters are produced by homogeneous nucleation in an adiabatically expanding supersonic stream. Electron diffraction is used to measure the rms amplitudes of the atoms; the Jacobi-matrix method is used for theoretical calculations. A series of distinguishing features of the atomic dynamics of microclusters was found. This was necessary to determine the character of the formation and the stability conditions of the crystal structure. It wass shown that for clusters consisting of less than N˜103 atoms, as the cluster size decreases, the rms amplitudes grow much more rapidly than expected from the increase in the specific contribution of the surface. It is also established that an fcc structure of a free cluster, as a rule, contains twinning defects (nuclei of an hcp phase). One reason for the appearance of such defects is the so-called vertex instability (anomalously large oscillation amplitudes) of the atoms in coordination spheres.

Interplay between Mechanics, Electronics, and Energetics in Atomic-Scale Junctions

NASA Astrophysics Data System (ADS)

Aradhya, Sriharsha V.

The physical properties of materials at the nanoscale are controlled to a large extent by their interfaces. While much knowledge has been acquired about the properties of material in the bulk, there are many new and interesting phenomena at the interfaces that remain to be better understood. This is especially true at the scale of their constituent building blocks - atoms and molecules. Studying materials at this intricate level is a necessity at this point in time because electronic devices are rapidly approaching the limits of what was once thought possible, both in terms of their miniaturization as well as our ability to design their behavior. In this thesis I present our explorations of the interplay between mechanical properties, electronic transport and binding energetics of single atomic contacts and single-molecule junctions. Experimentally, we use a customized conducting atomic force microscope (AFM) that simultaneously measures the current and force across atomic-scale junctions. We use this instrument to study single atomic contacts of gold and silver and single-molecule junctions formed in the gap between two gold metallic point contacts, with molecules with a variety of backbones and chemical linker groups. Combined with density functional theory based simulations and analytical modeling, these experiments provide insight into the correlations between mechanics and electronic structure at the atomic level. In carrying out these experimental studies, we repeatedly form and pull apart nanoscale junctions between a metallized AFM cantilever tip and a metal-coated substrate. The force and conductance of the contact are simultaneously measured as each junction evolves through a series of atomic-scale rearrangements and bond rupture events, frequently resulting in single atomic contacts before rupturing completely. The AFM is particularly optimized to achieve high force resolution with stiff probes that are necessary to create and measure forces across atomic-size junctions that are otherwise difficult to fabricate using conventional lithographic techniques. In addition to the instrumentation, we have developed new algorithmic routines to perform statistical analyses of force data, with varying degrees of reliance on the conductance signatures. The key results presented in this thesis include our measurements with gold metallic contacts, through which we are able to rigorously characterize the stiffness and maximum forces sustained by gold single atomic contacts and many different gold-molecule-gold single-molecule junctions. In our experiments with silver metallic contacts we use statistical correlations in conductance to distinguish between pristine and oxygen-contaminated silver single atomic contacts. This allows us to separately obtain mechanical information for each of these structural motifs. The independently measured force data also provides new insights about atomic-scale junctions that are not possible to obtain through conductance measurements alone. Using a systematically designed set of molecules, we are able to demonstrate that quantum interference is not quenched in single-molecule junctions even at room temperature and ambient conditions. We have also been successful in conducting one of the first quantitative measurements of van der Waals forces at the metal-molecule interface at the single-molecule level. Finally, towards the end of this thesis, we present a general analytical framework to quantitatively reconstruct the binding energy curves of atomic-scale junctions directly from experiments, thereby unifying all of our mechanical measurements. I conclude with a summary of the work presented in this thesis, and an outlook for potential future studies that could be guided by this work.

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

PubMed

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

2018-01-16

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

Fluorescence Imaging Assisted Photodynamic Therapy Using Photosensitizer-Linked Gold Quantum Clusters.

PubMed

Nair, Lakshmi V; Nazeer, Shaiju S; Jayasree, Ramapurath S; Ajayaghosh, Ayyappanpillai

2015-06-23

Fluorescence imaging assisted photodynamic therapy (PDT) is a viable two-in-one clinical tool for cancer treatment and follow-up. While the surface plasmon effect of gold nanorods and nanoparticles has been effective for cancer therapy, their emission properties when compared to gold nanoclusters are weak for fluorescence imaging guided PDT. In order to address the above issues, we have synthesized a near-infrared-emitting gold quantum cluster capped with lipoic acid (L-AuC with (Au)18(L)14) based nanoplatform with excellent tumor reduction property by incorporating a tumor-targeting agent (folic acid) and a photosensitizer (protoporphyrin IX), for selective PDT. The synthesized quantum cluster based photosensitizer PFL-AuC showed 80% triplet quantum yield when compared to that of the photosensitizer alone (63%). PFL-AuC having 60 μg (0.136 mM) of protoporphyrin IX was sufficient to kill 50% of the tumor cell population. Effective destruction of tumor cells was evident from the histopathology and fluorescence imaging, which confirm the in vivo PDT efficacy of PFL-AuC.

Effect of gold subsurface layer on the surface activity and segregation in Pt/Au/Pt3M (where M = 3d transition metals) alloy catalyst from first-principles.

PubMed

Kim, Chang-Eun; Lim, Dong-Hee; Jang, Jong Hyun; Kim, Hyoung Juhn; Yoon, Sung Pil; Han, Jonghee; Nam, Suk Woo; Hong, Seong-Ahn; Soon, Aloysius; Ham, Hyung Chul

2015-01-21

The effect of a subsurface hetero layer (thin gold) on the activity and stability of Pt skin surface in Pt3M system (M = 3d transition metals) is investigated using the spin-polarized density functional theory calculation. First, we find that the heterometallic interaction between the Pt skin surface and the gold subsurface in Pt/Au/Pt3M system can significantly modify the electronic structure of the Pt skin surface. In particular, the local density of states projected onto the d states of Pt skin surface near the Fermi level is drastically decreased compared to the Pt/Pt/Pt3M case, leading to the reduction of the oxygen binding strength of the Pt skin surface. This modification is related to the increase of surface charge polarization of outmost Pt skin atoms by the electron transfer from the gold subsurface atoms. Furthermore, a subsurface gold layer is found to cast the energetic barrier to the segregation loss of metal atoms from the bulk (inside) region, which can enhance the durability of Pt3M based catalytic system in oxygen reduction condition at fuel cell devices. This study highlights that a gold subsurface hetero layer can provide an additional mean to tune the surface activity toward oxygen species and in turn the oxygen reduction reaction, where the utilization of geometric strain already reaches its practical limit.

Many particle spectroscopy of atoms, molecules, clusters and surfaces: international conference MPS-2016

NASA Astrophysics Data System (ADS)

Grum-Grzhimailo, Alexei N.; Popov, Yuri V.; Gryzlova, Elena V.; Solov'yov, Andrey V.

2017-07-01

The conference on Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces (MPS-2016) brought together near to a hundred scientists in the field of electronic, photonic, atomic and molecular collisions, and spectroscopy from around the world. We deliver an Editorial of a topical issue presenting original research results from some of the participants on both experimental and theoretical studies involving many particle spectroscopy of atoms, molecules, clusters and surfaces. Contribution to the Topical Issue "Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces", edited by A.N. Grum-Grzhimailo, E.V. Gryzlova, Yu.V. Popov, and A.V. Solov'yov.

The nanocoherer: an electrically and mechanically resettable resistive switching device based on gold clusters assembled on paper

NASA Astrophysics Data System (ADS)

Minnai, Chloé; Mirigliano, Matteo; Brown, Simon A.; Milani, Paolo

2018-03-01

We report the realization of a resettable resistive switching device based on a nanostructured film fabricated by supersonic cluster beam deposition of gold clusters on plain paper substrates. Through the application of suitable voltage ramps, we obtain, in the same device, either a complex pattern of resistive switchings, or reproducible and stable switchings between low resistance and high resistance states, with an amplitude up to five orders of magnitude. Our device retains a state of internal resistance following the history of the applied voltage similar to that reported for memristors. The two different switching regimes in the same device are both stable, the transition between them is reversible, and it can be controlled by applying voltage ramps or by mechanical deformation of the substrate. The device behavior can be related to the formation, growth and breaking of junctions between the loosely aggregated gold clusters forming the nanostructured films. The fact that our cluster-assembled device is mechanically resettable suggests that it can be considered as the analog of the coherer: a switching device based on metallic powders used for the first radio communication system.

Observation of a barium xenon exciplex within a large argon cluster.

PubMed

Briant, M; Gaveau, M-A; Mestdagh, J-M

2010-07-21

Spectroscopic measurements provide fluorescence and excitation spectra of a single barium atom codeposited with xenon atoms on argon clusters of average size approximately 2000. The spectra are studied as a function of the number of xenon atoms per cluster. The excitation spectrum with approximately 10 xenon atoms per cluster is qualitatively similar to that observed when no xenon atom is present on the cluster. It consists of two bands located on each side of the 6s6p (1)P-6s(2) (1)S resonance line of the free barium. In contrast, the fluorescence spectrum differs qualitatively since a barium-xenon exciplex is observed, which has no counterpart in xenon free clusters. In particular an emission is observed, which is redshifted by 729 cm(-1) with respect to the Ba(6s6p (1)P-6s(2) (1)S) resonance line.

Cluster adsorption on amorphous and crystalline surfaces - A molecular dynamics study of model Pt on Cu and model Pd on Pt

NASA Technical Reports Server (NTRS)

Garofalini, S. H.; Halicioglu, T.; Pound, G. M.

1981-01-01

Molecular dynamics was used to study the structure, dispersion and short-time behavior of ten-atom clusters adsorbed onto amorphous and crystalline substrates, in which the cluster atoms differed from the substrate atoms. Two adatom-substrate model systems were chosen; one, in which the interaction energy between adatom pairs was greater than that between substrate pairs, and the other, in which the reverse was true. At relatively low temperature ranges, increased dispersion of cluster atoms occurred: (a) on the amorphous substrate as compared to the FCC(100) surface, (b) with increasing reduced temperature, and (c) with adatom-substrate interaction energy stronger than adatom-adatom interaction. Two-dimensional clusters (rafts) on the FCC(100) surface displayed migration of edge atoms only, indicating a mechanism for the cluster rotation and shape changes found in experimental studies.

Efficient and scalable ionization of neutral atoms by an orderly array of gold-doped silicon nanowires

NASA Astrophysics Data System (ADS)

Bucay, Igal; Helal, Ahmed; Dunsky, David; Leviyev, Alex; Mallavarapu, Akhila; Sreenivasan, S. V.; Raizen, Mark

2017-04-01

Ionization of atoms and molecules is an important process in many applications and processes such as mass spectrometry. Ionization is typically accomplished by electron bombardment, and while it is scalable to large volumes, is also very inefficient due to the small cross section of electron-atom collisions. Photoionization methods can be highly efficient, but are not scalable due to the small ionization volume. Electric field ionization is accomplished using ultra-sharp conducting tips biased to a few kilovolts, but suffers from a low ionization volume and tip fabrication limitations. We report on our progress towards an efficient, robust, and scalable method of atomic and molecular ionization using orderly arrays of sharp, gold-doped silicon nanowires. As demonstrated in earlier work, the presence of the gold greatly enhances the ionization probability, which was attributed to an increase in available acceptor surface states. We present here a novel process used to fabricate the nanowire array, results of simulations aimed at optimizing the configuration of the array, and our progress towards demonstrating efficient and scalable ionization.

Morphology manipulation of M13 bacteriophage template for nanostructure assembly

NASA Astrophysics Data System (ADS)

Ngo-Duc, Tam-Triet; Zaman, Mohammed S.; Moon, Chung-Hee; Haberer, Elaine D.

2014-08-01

A gold-binding M13 bacteriophage was used as a model system to explore templating of inorganic material on geometrically transformed viruses . Gold-binding filamentous phage were converted to spheroid form with a short chloroform treatment, and the resulting morphology was investigated with electron microscopy. Binding studies revealed that spheroid-shaped gold-binding phage preserved its affinity for gold. Spheroids adhered to a planar substrate assembled clusters or rings of gold nanoparticles. This gold-binding phage served as a demonstration of a highly shape-modifiable viral-template for inorganic materials.

Probing the Structural, Electronic, and Magnetic Properties of Ag n V (n = 1-12) Clusters.

PubMed

Xiong, Ran; Die, Dong; Xiao, Lu; Xu, Yong-Gen; Shen, Xu-Ying

2017-12-16

The structural, electronic, and magnetic properties of Ag n V (n = 1-12) clusters have been studied using density functional theory and CALYPSO structure searching method. Geometry optimizations manifest that a vanadium atom in low-energy Ag n V clusters favors the most highly coordinated location. The substitution of one V atom for an Ag atom in Ag n + 1 (n ≥ 5) cluster modifies the lowest energy structure of the host cluster. The infrared spectra, Raman spectra, and photoelectron spectra of Ag n V (n = 1-12) clusters are simulated and can be used to determine the most stable structure in the future. The relative stability, dissociation channel, and chemical activity of the ground states are analyzed through atomic averaged binding energy, dissociation energy, and energy gap. It is found that V atom can improve the stability of the host cluster, Ag 2 excepted. The most possible dissociation channels are Ag n V = Ag + Ag n - 1 V for n = 1 and 4-12 and Ag n V = Ag 2  + Ag n - 2 V for n = 2 and 3. The energy gap of Ag n V cluster with odd n is much smaller than that of Ag n + 1 cluster. Analyses of magnetic property indicate that the total magnetic moment of Ag n V cluster mostly comes from V atom and varies from 1 to 5 μ B . The charge transfer between V and Ag atoms should be responsible for the change of magnetic moment.

Aurophilicity in gold(I) catalysis: for better or worse?

PubMed

Weber, Dieter; Gagné, Michel R

2015-01-01

This book chapter discusses the effects of aurophilicity on gold catalysis. First, a brief historic account of aurophilicity in organogold chemistry is given, focusing on the pioneering results which set the stage for its association with catalytic intermediates (gold vinyl and gold aryl complexes); this is followed by an introduction to cationic gold(I) as an electrophilic catalyst, and the first isolation of organogold intermediates from catalysis. In the main section, the growing number of reports observing aurophilic interactions in catalysis or illustrative model systems is reviewed in a non-comprehensive tutorial way. The effects of aurophilicity are discussed in the following structures: (1) the geminal diauration of C(sp²)-atoms; (2) geminal diauration of other atoms; (3) σ-π-diauration of terminal alkynes. It is apparent that in most cases efficient catalysis is hindered by aurophilic effects as less active aggregates tend to be formed from more active species [LAu]⁺, but there are a growing number of reports using aurophilicity as a driving force to access new reactivity and selectivity.

Site-specific polarizabilities as descriptors of metallic behavior in atomic clusters

NASA Astrophysics Data System (ADS)

Jackson, Koblar; Jellinek, Julius

The electric dipole polarizability of a cluster is a measure of its response to an applied electric field. The site specific polarizability method decomposes the total cluster polarizability into contributions from individual atoms and also allows it to be partitioned into charge transfer and electric dipole contributions. By systematically examining the trends in these quantities for several types of metal atom clusters over a wide range of cluster sizes, we find common characteristics that uniquely link the behavior of the clusters to that of the corresponding bulk metals for clusters as small as 10 atoms. We discuss these trends and compare and contrast them with results for non-metal clusters. This work was supported by the Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences, U.S. Department of Energy under Grant SC0001330 (KAJ) and Contract No. DE-AC02-06CH11357 (JJ).

Quasi-planar elemental clusters in pair interactions approximation

NASA Astrophysics Data System (ADS)

Chkhartishvili, Levan

2016-01-01

The pair-interactions approximation, when applied to describe elemental clusters, only takes into account bonding between neighboring atoms. According to this approach, isomers of wrapped forms of 2D clusters - nanotubular and fullerene-like structures - and truly 3D clusters, are generally expected to be more stable than their quasi-planar counterparts. This is because quasi-planar clusters contain more peripheral atoms with dangling bonds and, correspondingly, fewer atoms with saturated bonds. However, the differences in coordination numbers between central and peripheral atoms lead to the polarization of bonds. The related corrections to the molar binding energy can make small, quasi-planar clusters more stable than their 2D wrapped allotropes and 3D isomers. The present work provides a general theoretical frame for studying the relative stability of small elemental clusters within the pair interactions approximation.

Modeling inelastic phonon scattering in atomic- and molecular-wire junctions

NASA Astrophysics Data System (ADS)

Paulsson, Magnus; Frederiksen, Thomas; Brandbyge, Mads

2005-11-01

Computationally inexpensive approximations describing electron-phonon scattering in molecular-scale conductors are derived from the nonequilibrium Green’s function method. The accuracy is demonstrated with a first-principles calculation on an atomic gold wire. Quantitative agreement between the full nonequilibrium Green’s function calculation and the newly derived expressions is obtained while simplifying the computational burden by several orders of magnitude. In addition, analytical models provide intuitive understanding of the conductance including nonequilibrium heating and provide a convenient way of parameterizing the physics. This is exemplified by fitting the expressions to the experimentally observed conductances through both an atomic gold wire and a hydrogen molecule.

Photothermolysis by laser-induced microbubbles generated around gold nanorod clusters selectively formed in leukemia cells

NASA Astrophysics Data System (ADS)

Lapotko, Dmitri; Lukianova-Hleb, Ekaterina; Zhdanok, Sergei; Rostro, Betty; Simonette, Rebecca; Hafner, Jason; Konopleva, Marina; Andreeff, Michael; Conjusteau, Andre; Oraevsky, Alexander

2008-02-01

In an effort of developing clinical LANTCET (laser-activated nano-thermolysis as cell elimination technology) we achieved selective destruction of individual tumor cells through laser generation of vapor microbubbles around clusters of light absorbing gold nanorods (GNR) selectively formed in target tumor cells. Among all gold nanoparticles, nanorods offer the highest optical absorption in the near-infrared. We applied covalent conjugates of gold nanorods with targeting vectors such as monoclonal antibodies CD33 (specific for Acute Myeloid Leukemia), while GNR conjugates with polyethylene-glycol (PEG) were used as nonspecific targeting control. GNR clusters were formed inside the tumor cells at 37 °C due to endocytosis of large concentration of nanorods accumulated on the surface of tumor cells targeted at 4 °C. Formation of GNR clusters significantly reduces the threshold of tumor cell damage making LANTCET safe for normal cells. Appearance of GNR clusters was verified directly with optical resonance scattering microscopy. LANTCET was performed in vitro with living cells of (1) model myeloid K562 cells (CD33 positive), (2) primary human bone marrow CD33-positive blast cells from patients diagnosed with acute myeloid leukemia. Laser-induced microbubbles were generated and detected with a photothermal microscope equipped with a tunable Ti-Sa pulsed laser. GNT cluster formation caused a 100-fold decrease in the threshold optical fluence for laser microbubble generation in tumor cells compared with that in normal cells under the same targeting and irradiation conditions. Combining imaging based on resonance optical scattering with photothermal imaging of microbubbles, we developed a method for detection, image-guided treatment and monitoring of LANTCET. Pilot experiments were performed in flow mode bringing LANTCET closer to reality of clinical procedure of purging tumor cells from bone marrow grafts.

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

Kira, M., E-mail: mackillo.kira@physik.uni-marburg.de

Atomic Bose–Einstein condensates (BECs) can be viewed as macroscopic objects where atoms form correlated atom clusters to all orders. Therefore, the presence of a BEC makes the direct use of the cluster-expansion approach–lucrative e.g. in semiconductor quantum optics–inefficient when solving the many-body kinetics of a strongly interacting Bose. An excitation picture is introduced with a nonunitary transformation that describes the system in terms of atom clusters within the normal component alone. The nontrivial properties of this transformation are systematically studied, which yields a cluster-expansion friendly formalism for a strongly interacting Bose gas. Its connections and corrections to the standard Hartree–Fock–Bogoliubov approachmore » are discussed and the role of the order parameter and the Bogoliubov excitations are identified. The resulting interaction effects are shown to visibly modify number fluctuations of the BEC. Even when the BEC has a nearly perfect second-order coherence, the BEC number fluctuations can still resolve interaction-generated non-Poissonian fluctuations. - Highlights: • Excitation picture expresses interacting Bose gas with few atom clusters. • Semiconductor and BEC many-body investigations are connected with cluster expansion. • Quantum statistics of BEC is identified in terms of atom clusters. • BEC number fluctuations show extreme sensitivity to many-body correlations. • Cluster-expansion friendly framework is established for an interacting Bose gas.« less

Structural evolutions and hereditary characteristics of icosahedral nano-clusters formed in Mg70Zn30 alloys during rapid solidification processes

NASA Astrophysics Data System (ADS)

Liang, Yong-Chao; Liu, Rang-Su; Xie, Quan; Tian, Ze-An; Mo, Yun-Fei; Zhang, Hai-Tao; Liu, Hai-Rong; Hou, Zhao-Yang; Zhou, Li-Li; Peng, Ping

2017-02-01

To investigate the structural evolution and hereditary mechanism of icosahedral nano-clusters formed during rapid solidification, a molecular dynamics (MD) simulation study has been performed for a system consisting of 107 atoms of liquid Mg70Zn30 alloy. Adopting Honeycutt-Anderson (HA) bond-type index method and cluster type index method (CTIM-3) to analyse the microstructures in the system it is found that for all the nano-clusters including 2~8 icosahedral clusters in the system, there are 62 kinds of geometrical structures, and those can be classified, by the configurations of the central atoms of basic clusters they contained, into four types: chain-like, triangle-tailed, quadrilateral-tailed and pyramidal-tailed. The evolution of icosahedral nano-clusters can be conducted by perfect heredity and replacement heredity, and the perfect heredity emerges when temperature is slightly less than Tm then increase rapidly and far exceeds the replacement heredity at Tg; while for the replacement heredity, there are three major modes: replaced by triangle (3-atoms), quadrangle (4-atoms) and pentagonal pyramid (6-atoms), rather than by single atom step by step during rapid solidification processes.

Hydroxyalkyl phosphine gold complexes for use as diagnostic and therapeutic pharmaceuticals and method of making same

DOEpatents

Katti, Kattesh V.; Berning, Douglas E.; Volkert, Wynn A.; Ketring, Alan R.

1998-01-01

A complex and method for making same for use as a diagnostic or therapeutic pharmaceutical includes a ligand comprising at least one hydroxyalkyl phosphine donor group bound to a gold atom to form a gold-ligand complex that is stable in aqueous solutions containing oxygen, serum and other body fluids.

Hydroxyalkyl phosphine gold complexes for use as diagnostic and therapeutic pharmaceuticals and method of making same

DOEpatents

Katti, K.V.; Berning, D.E.; Volkert, W.A.; Ketring, A.R.

1998-12-01

A complex and method for making a diagnostic or therapeutic pharmaceutical includes a ligand comprising at least one hydroxyalkyl phosphine donor group bound to a gold atom to form a gold-ligand complex that is stable in aqueous solutions containing oxygen, serum and other body fluids. 20 figs.

Spherical harmonics based descriptor for neural network potentials: Structure and dynamics of Au147 nanocluster.

PubMed

Jindal, Shweta; Chiriki, Siva; Bulusu, Satya S

2017-05-28

We propose a highly efficient method for fitting the potential energy surface of a nanocluster using a spherical harmonics based descriptor integrated with an artificial neural network. Our method achieves the accuracy of quantum mechanics and speed of empirical potentials. For large sized gold clusters (Au 147 ), the computational time for accurate calculation of energy and forces is about 1.7 s, which is faster by several orders of magnitude compared to density functional theory (DFT). This method is used to perform the global minimum optimizations and molecular dynamics simulations for Au 147 , and it is found that its global minimum is not an icosahedron. The isomer that can be regarded as the global minimum is found to be 4 eV lower in energy than the icosahedron and is confirmed from DFT. The geometry of the obtained global minimum contains 105 atoms on the surface and 42 atoms in the core. A brief study on the fluxionality in Au 147 is performed, and it is concluded that Au 147 has a dynamic surface, thus opening a new window for studying its reaction dynamics.

Spherical harmonics based descriptor for neural network potentials: Structure and dynamics of Au147 nanocluster

NASA Astrophysics Data System (ADS)

Jindal, Shweta; Chiriki, Siva; Bulusu, Satya S.

2017-05-01

We propose a highly efficient method for fitting the potential energy surface of a nanocluster using a spherical harmonics based descriptor integrated with an artificial neural network. Our method achieves the accuracy of quantum mechanics and speed of empirical potentials. For large sized gold clusters (Au147), the computational time for accurate calculation of energy and forces is about 1.7 s, which is faster by several orders of magnitude compared to density functional theory (DFT). This method is used to perform the global minimum optimizations and molecular dynamics simulations for Au147, and it is found that its global minimum is not an icosahedron. The isomer that can be regarded as the global minimum is found to be 4 eV lower in energy than the icosahedron and is confirmed from DFT. The geometry of the obtained global minimum contains 105 atoms on the surface and 42 atoms in the core. A brief study on the fluxionality in Au147 is performed, and it is concluded that Au147 has a dynamic surface, thus opening a new window for studying its reaction dynamics.

Does Each Atom Count in the Reactivity of Vanadia Nanoclusters?

PubMed

Zhang, Mei-Qi; Zhao, Yan-Xia; Liu, Qing-Yu; Li, Xiao-Na; He, Sheng-Gui

2017-01-11

Vanadium oxide cluster anions (V 2 O 5 ) n V x O y - (n = 1-31; x = 0, 1; and x + y ≤ 5) with different oxygen deficiencies (Δ = 2y-1-5x = 0, ± 1, and ±2) have been prepared by laser ablation and reacted to abstract hydrogen atoms from alkane molecules (n-butane) in a fast flow reactor. When the cluster size n is less than 25, the Δ = 1 series [(V 2 O 5 ) n O - clusters] that can contain atomic oxygen radical anions (O •- ) generally have much higher reactivity than the other four cluster series (Δ = -2, -1, 0, and 2), indicating that each atom counts in the hydrogen-atom abstraction (HAA) reactivity. Unexpectedly, all of the five cluster series have similar HAA reactivity when the cluster size is greater than 25. The critical dimension of vanadia particles separating the cluster behavior (each atom counts) from the bulk behavior (each atom contributes a little part) is thus about 1.6 nm (∼V 50 O 125 ). The strong electron-phonon coupling of the vanadia particles has been proposed to create the O •- radicals (V 5+ = O 2- + heat → V 4+ -O •- ) for the n > 25 clusters with Δ = -2, -1, 0, and 2. Such a mechanism is supported by a comparative study with the scandium system [(Sc 2 O 3 ) n Sc x O y - (n = 1-29; x = 0, 1; and x + y ≤ 4)] for which the Δ = 1 series [(Sc 2 O 3 ) n O - clusters] always have much higher HAA reactivity than the other cluster series.

Direct visualization of quasi-ordered oxygen chain structures on Au(110)-(1 × 2)

NASA Astrophysics Data System (ADS)

Hiebel, F.; Montemore, M. M.; Kaxiras, E.; Friend, C. M.

2016-08-01

The Au(110) surface offers unique advantages for atomically-resolved model studies of catalytic oxidation processes on gold. We investigate the adsorption of oxygen on Au(110) using a combination of scanning tunneling microscopy (STM) and density functional theory (DFT) methods. We identify the typical (empty-states) STM contrast resulting from adsorbed oxygen as atomic-sized dark features of electronic origin. DFT-based image simulations confirm that chemisorbed oxygen is generally detected indirectly, from the binding-induced electronic structure modification of gold. STM images show that adsorption occurs without affecting the general structure of the pristine Au(110) missing-row reconstruction. The tendency to form one-dimensional structures is observed already at low coverage (< 0.05 ML), with oxygen adsorbing on alternate sides of the reconstruction ridges. Consistently, calculations yield preferred adsorption on the (111) facets of the reconstruction, on a 3-fold coordination site, with increased stability when adsorbed in chains. Gold atoms with two oxygen neighbors exhibit enhanced electronic hybridization with the O states. Finally, the species observed are reactive to CO oxidation at 200 K and desorption of CO2 leaves a clean and ordered gold surface.

Study of Nanoscale Friction Behaviors of Graphene on Gold Substrates Using Molecular Dynamics

NASA Astrophysics Data System (ADS)

Zhu, Pengzhe; Li, Rui

2018-02-01

In this paper, we investigate the friction behaviors of graphene flakes sliding on a gold substrate using molecular dynamics simulations. The effects of flake size, flake shape, relative rotation angle between flake and substrate, and crystal orientation of substrate on the friction process are thoroughly studied. It is found that under the same load, the average friction forces per atom are smaller for a bigger graphene flake, which exhibits an obvious size effect. It is also shown that flake shape is critical in determining the friction in the sliding process. The average friction forces per atom for the square flake are much bigger than those for the triangular and round flakes. Moreover, the average friction forces per atom for the triangular flake are the smallest. We also find that the orientation of graphene flake relative to gold substrate plays a vital role in the friction process. The friction forces for the graphene flake sliding along the armchair direction are much bigger than those for the flakes with rotation. In addition, it is also found that single crystalline gold substrate exhibits a significant anisotropic effect of friction, which is attributed to the anisotropic effect of potential energy corrugation. These understandings not only shed light on the underlying mechanisms of graphene flake sliding on the gold substrates but also may guide the design and fabrication of nanoscale graphene-based devices.

Low gravity containerless processing of immiscible gold rhodium alloys

NASA Technical Reports Server (NTRS)

Andrews, J. Barry

1986-01-01

Under normal one-g conditions immiscible alloys segregate extensively during solidification due to sedementation of the more dense of the immiscible liquid phases. However, under low-g conditions it should be possible to form a dispersion of the two immiscible liquids and maintain this dispersed structure during solidification. Immiscible (hypermonotectic) gold-rhodium alloys were processed in the Marshall Space Flight Center 105 meter drop tube in order to investigate the influence of low gravity, containerless solidification on their microstructure. Hypermonotectic alloys composed of 65 atomic % rhodium exhibited a tendency for the gold rich liquid to wet the outer surface of the containerless processed samples. This tendency led to extensive segregation in several cases. However, well dispersed microstructures consisting of 2 to 3 micron diameter rhodium-rich spheres in a gold-rich matrix were produced in 23.4 atomic % rhodium alloys. This is one of the best dispersions obtained in research on immiscible alloy-systems to data.

AuNx stabilization with interstitial nitrogen atoms: A Density Functional Theory Study

NASA Astrophysics Data System (ADS)

Quintero, J. H.; Gonzalez-Hernandez, R.; Ospina, R.; Mariño, A.

2017-06-01

Researchers have been studying 4d and 5d Series Transition Metal Nitrides lately as a result of the experimental production of AuN, PtN, CuN. In this paper, we used the Density Functional Theory (DFT) implementing a pseudopotential plane-wave method to study the incorporation of nitrogen atoms in the face-centered cube (fcc) lattice of gold (Au). First, we took the fcc structure of gold, and gradually located the nitrogen atoms in tetrahedral (TH) and octahedral (OH) interstitial sites. AuN stabilized in: 2OH (30%), 4OH and 4TH (50%), 4OH - 2TH (close to the wurtzite structure) and 6TH (60%). This leads us to think that AuN behaves like a Transition Metal Nitride since the nitrogen atoms look for tetrahedral sites.

Enhanced Emission from Single Isolated Gold Quantum Dots Investigated Using Two-Photon-Excited Fluorescence Near-Field Scanning Optical Microscopy.

PubMed

Abeyasinghe, Neranga; Kumar, Santosh; Sun, Kai; Mansfield, John F; Jin, Rongchao; Goodson, Theodore

2016-12-21

New approaches in molecular nanoscopy are greatly desired for interrogation of biological, organic, and inorganic objects with sizes below the diffraction limit. Our current work investigates emergent monolayer-protected gold quantum dots (nanoclusters, NCs) composed of 25 Au atoms by utilizing two-photon-excited fluorescence (TPEF) near-field scanning optical microscopy (NSOM) at single NC concentrations. Here, we demonstrate an approach to synthesize and isolate single NCs on solid glass substrates. Subsequent investigation of the NCs using TPEF NSOM reveals that, even when they are separated by distances of several tens of nanometers, we can excite and interrogate single NCs individually. Interestingly, we observe an enhanced two-photon absorption (TPA) cross section for single Au 25 NCs that can be attributed to few-atom local field effects and to local field-induced microscopic cascading, indicating their potential for use in ultrasensitive sensing, disease diagnostics, cancer cell therapy, and molecular computers. Finally, we report room-temperature aperture-based TPEF NSOM imaging of these NCs for the first time at 30 nm point resolution, which is a ∼5-fold improvement compared to the previous best result for the same technique. This report unveils the unique combination of an unusually large TPA cross section and the high photostability of Au NCs to (non-destructively) investigate stable isolated single NCs using TPEF NSOM. This is the first reported optical study of monolayer-protected single quantum clusters, opening some very promising opportunities in spectroscopy of nanosized objects, bioimaging, ultrasensitive sensing, molecular computers, and high-density data storage.

Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

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

Zhou, Meng; Zeng, Chenjie; Sfeir, Matthew Y.

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacksmore » ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.« less

Evolution of Excited-State Dynamics in Periodic Au 28, Au 36, Au 44, and Au 52 Nanoclusters

DOE PAGES

Zhou, Meng; Zeng, Chenjie; Sfeir, Matthew Y.; ...

2017-08-10

An understanding of the correlation between the atomic structure and optical properties of gold nanoclusters is essential for exploration of their functionalities and applications involving light harvesting and electron transfer. We report the femto-nanosecond excited state dynamics of a periodic series of face-centered cubic (FCC) gold nanoclusters (including Au 28, Au 36, Au 44, and Au 52), which exhibit a set of unique features compared with other similar sized clusters. Molecular-like ultrafast S n → S 1 internal conversions (i.e., radiationless electronic transitions) are observed in the relaxation dynamics of FCC periodic series. Excited-state dynamics with near-HOMO–LUMO gap excitation lacksmore » ultrafast decay component, and only the structural relaxation dominates in the dynamical process, which proves the absence of core–shell relaxation. Interestingly, both the relaxation of the hot carriers and the band-edge carrier recombination become slower as the size increases. The evolution in excited-state properties of this FCC series offers new insight into the structure-dependent properties of metal nanoclusters, which will benefit their optical energy harvesting and photocatalytic applications.« less

Composition formulas of binary eutectics

PubMed Central

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

2015-01-01

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

Structural and electronic properties of Aun-xPtx (n = 2-14; x ⩽ n) clusters: The density functional theory investigation

NASA Astrophysics Data System (ADS)

Yuan, H. K.; Kuang, A. L.; Tian, C. L.; Chen, H.

2014-03-01

The structural evolutions and electronic properties of bimetallic Aun-xPtx (n = 2-14; x ⩽ n) clusters are investigated by using the density functional theory (DFT) with the generalized gradient approximation (GGA). The monatomic doping Aun-1Pt clusters are emphasized and compared with the corresponding pristine Aun clusters. The results reveal that the planar configurations are favored for both Aun-1Pt and Aun clusters with size up to n = 13, and the former often employ the substitution patterns based on the structures of the latter. The most stable clusters are Au6 and Au6Pt, which adopt regular planar triangle (D3h) and hexagon-ring (D6h) structures and can be regarded as the preferential building units in designing large clusters. For Pt-rich bimetallic clusters, their structures can be obtained from the substitution of Pt atoms by Au atoms from the Ptn structures, where Pt atoms assemble together and occupy the center yet Au atoms prefer the apex positions showing a segregation effect. With respect to pristine Au clusters, AunPt clusters exhibit somewhat weaker and less pronounced odd-even oscillations in the highest occupied and lowest unoccupied molecular-orbital gaps (HOMO-LUMO gap), electron affinity (EA), and ionization potential (IP) due to the partially released electron pairing effect. The analyses of electronic structure indicate that Pt atoms in AuPt clusters would delocalize their one 6s and one 5d electrons to contribute the electronic shell closure. The sp-d hybridizations as well as the d-d interactions between the host Au and dopant Pt atoms result in the enhanced stabilities of AuPt clusters.

Effect of gold nanoparticle on stability of the DNA molecule: A study of molecular dynamics simulation.

PubMed

Izanloo, Cobra

2017-09-02

An understanding of the mechanism of DNA interactions with gold nanoparticles is useful in today medicine applications. We have performed a molecular dynamics simulation on a B-DNA duplex (CCTCAGGCCTCC) in the vicinity of a gold nanoparticle with a truncated octahedron structure composed of 201 gold atoms (diameter ∼1.8 nm) to investigate gold nanoparticle (GNP) effects on the stability of DNA. During simulation, the nanoparticle is closed to DNA and phosphate groups direct the particles into the major grooves of the DNA molecule. Because of peeling and untwisting states that are occur at end of DNA, the nucleotide base lies flat on the surface of GNP. The configuration entropy is estimated using the covariance matrix of atom-positional fluctuations for different bases. The results show that when a gold nanoparticle has interaction with DNA, entropy increases. The results of conformational energy and the hydrogen bond numbers for DNA indicated that DNA becomes unstable in the vicinity of a gold nanoparticle. The radial distribution function was calculated for water hydrogen-phosphate oxygen pairs. Almost for all nucleotide, the presence of a nanoparticle around DNA caused water molecules to be released from the DNA duplex and cations were close to the DNA.

Gold nanoprobes for theranostics

PubMed Central

Panchapakesan, Balaji; Book-Newell, Brittany; Sethu, Palaniappan; Rao, Madhusudhana; Irudayaraj, Joseph

2011-01-01

Gold nanoprobes have become attractive diagnostic and therapeutic agents in medicine and life sciences research owing to their reproducible synthesis with atomic level precision, unique physical and chemical properties, versatility of their morphologies, flexibility in functionalization, ease of targeting, efficiency in drug delivery and opportunities for multimodal therapy. This review highlights some of the recent advances and the potential for gold nanoprobes in theranostics. PMID:22122586

Thermal Vapor Deposition and Characterization of Polymer-Ceramic Nanoparticle Thin Films and Capacitors

NASA Astrophysics Data System (ADS)

Iwagoshi, Joel A.

Research on alternative energies has become an area of increased interest due to economic and environmental concerns. Green energy sources, such as ocean, wind, and solar power, are subject to predictable and unpredictable generation intermittencies which cause instability in the electrical grid. This problem could be solved through the use of short term energy storage devices. Capacitors made from composite polymer:nanoparticle thin films have been shown to be an economically viable option. Through thermal vapor deposition, we fabricated dielectric thin films composed of the polymer polyvinylidine fluoride (PVDF) and the ceramic nanoparticle titanium dioxide (TiO2). Fully understanding the deposition process required an investigation of electrode and dielectric film deposition. Film composition can be controlled by the mass ratio of PVDF:TiO2 prior to deposition. An analysis of the relationship between the ratio of PVDF:TiO2 before and after deposition will improve our understanding of this novel deposition method. X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy were used to analyze film atomic concentrations. The results indicate a broad distribution of deposited TiO2 concentrations with the highest deposited amount at an initial mass concentration of 17% TiO2. The nanoparticle dispersion throughout the film is analyzed through atomic force microscopy and energy dispersive x-ray spectroscopy. Images from these two techniques confirm uniform TiO2 dispersion with cluster size less than 300 nm. These results, combined with spectroscopic analysis, verify control over the deposition process. Capacitors were fabricated using gold parallel plates with PVDF:TiO 2 dielectrics. These capacitors were analyzed using the atomic force microscope and a capacohmeter. Atomic force microscope images confirm that our gold films are acceptably smooth. Preliminary capacohmeter measurements indicate capacitance values of 6 nF and break down voltages of 2.4 V. Our research on the deposition process will contribute to the understanding of PVDF/TiO2 composite thin films. These results will lead to further investigation of PVDF/TiO2 high density energy storage capacitors. These capacitors can potentially increase the efficiency of alternative energy sources already in use.

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

Sun, Yudie; Institute of Intelligent Machines, Chinese Academy of Sciences, Hefei 230031; Liu, Honglin, E-mail: hlliu@iim.ac.cn

Graphical abstract: - Highlights: • Mercapto groups were grafted to chitosan molecule by a reactive amine reduction. • Functional polymer with well-defined monomer units controls AuNPs assembly. • Assembled morphologies depend on the ratio of AuNPs to thiolate groups. • Microcubes with side length of ∼20 μm was synthesized through a dialysis step. • A edge-to-middle growth mechanism of gold microcubes was observed. - Abstract: The L-cysteine molecules were successfully grafted to the 2-amino group of chitosan by a reactive amine reduction, and the as-synthesized thiolated chitosan (TC) molecules were used as the templates to direct the self-assembly of goldmore » nanoparticles and induce the transformation of these assemblies to gold microcubes through a deep-going dialysis. We found that the ratio of gold nanoparticles to TC molecules could greatly affect the shape of the assembled clusters. Different stages of these clusters and microstructures during the dialysis process were characterized by scanning electron microscope (SEM), and the microcubes with average side length of about 20 μm were successfully synthesized. According to the morphology evolution of the assembly, it could be concluded that the microcubes were formed from external to internal. The SERS area mapping images of microcubes and some clusters were also collected to study the formation mechanism of gold microcubes. Our work demonstrates a simple and highly effective way to assemble gold nanoparticles into microcubes with unique properties.« less

Relaxation channels of multi-photon excited xenon clusters

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

Serdobintsev, P. Yu.; Melnikov, A. S.; Department of Physics, St. Petersburg State University, Saint Petersburg 198904

2015-09-21

The relaxation processes of the xenon clusters subjected to multi-photon excitation by laser radiation with quantum energies significantly lower than the thresholds of excitation of atoms and ionization of clusters were studied. Results obtained by means of the photoelectron spectroscopy method showed that desorption processes of excited atoms play a significant role in the decay of two-photon excited xenon clusters. A number of excited states of xenon atoms formed during this process were discovered and identified.

Large scale structural optimization of trimetallic Cu-Au-Pt clusters up to 147 atoms

NASA Astrophysics Data System (ADS)

Wu, Genhua; Sun, Yan; Wu, Xia; Chen, Run; Wang, Yan

2017-10-01

The stable structures of Cu-Au-Pt clusters up to 147 atoms are optimized by using an improved adaptive immune optimization algorithm (AIOA-IC method), in which several motifs, such as decahedron, icosahedron, face centered cubic, sixfold pancake, and Leary tetrahedron, are randomly selected as the inner cores of the starting structures. The structures of Cu8AunPt30-n (n = 1-29), Cu8AunPt47-n (n = 1-46), and partial 75-, 79-, 100-, and 147-atom clusters are analyzed. Cu12Au93Pt42 cluster has onion-like Mackay icosahedral motif. The segregation phenomena of Cu, Au and Pt in clusters are explained by the atomic radius, surface energy, and cohesive energy.

Monoatomic and cluster beam effect on ToF-SIMS spectra of self-assembled monolayers on gold

NASA Astrophysics Data System (ADS)

Tuccitto, N.; Torrisi, V.; Delfanti, I.; Licciardello, A.

2008-12-01

Self-assembled monolayers represent well-defined systems that is a good model surface to study the effect of primary ion beams used in secondary ion mass spectrometry. The effect of polyatomic primary beams on both aliphatic and aromatic self-assembled monolayers has been studied. In particular, we analysed the variation of the relative secondary ion yield of both substrate metal-cluster (Au n-) in comparison with the molecular ions (M -) and clusters (M xAu y-) by using Bi +, Bi 3+, Bi 5+ beams. Moreover, the differences in the secondary ion generation efficiency are discussed. The main effect of the cluster beams is related to an increased formation of low-mass fragments and to the enhancement of the substrate related gold-clusters. The results show that, at variance of many other cases, the static SIMS of self-assembled monolayers does not benefit of the use of polyatomic primary ions.

Thermal stability of supported gold nanoparticles

NASA Astrophysics Data System (ADS)

Turba, Timothy Fredrick

Nanoparticle gold is of interest for a wide array of applications including catalysis, gas sensing, and light absorption for color filters and optical switches. Many of these applications are dependent upon the particles having sizes <5nm. In this paper, the thermal stability of nanoparticle gold is evaluated. Unsupported gold nanoparticles can grow (and in some cases double their size) even at room temperature. An important approach to stabilizing gold nanoparticles is through an interaction with a suitable substrate support material. Semiconductor substrates such as GaN are important supports for gold nanoparticles for applications such as sensors, but GaN does not provide a significant stabilizing effect at high temperatures. This paper covers a number of different substrate materials and in particular shows that for some substrates, such as SiO2, gold nanoparticles can be stable at temperatures up to 500°C, which is significantly above the Tammann temperature for bulk gold (395°C). In this dissertation, gold nanoparticles are shown to have complete stability on aluminum-supported silica nanosprings at 550°C in air. This stability window is one of the highest reported for nanoparticle gold and potentially enables a number of applications for this highly active catalyst. X-ray photoelectron spectroscopy measurements were performed before and after heating to 550°C to determine the nature of the interaction between gold and SiO2. A 1.2 eV drop in gold 4f binding energy after heating signified a shift to anionic gold particles (i.e., Au delta-) indicative of strong bonds to oxygen vacancies with neighboring Sidelta+ atoms. Heating in hydrogen at 550°C resulted in a binding energy decrease of 0.4 eV due to an increased fraction of particles with decreased coordination numbers (i.e., more atoms at edges and corners). Lastly, heating gold nanoparticles in an atmosphere of 10% relative humidity at 550°C resulted in apparent encapsulation of the gold.

Effect of surface roughness on substrate-tuned gold nanoparticle gap plasmon resonances.

PubMed

Lumdee, Chatdanai; Yun, Binfeng; Kik, Pieter G

2015-03-07

The effect of nanoscale surface roughness on the gap plasmon resonance of gold nanoparticles on thermally evaporated gold films is investigated experimentally and numerically. Single-particle scattering spectra obtained from 80 nm diameter gold particles on a gold film show significant particle-to-particle variation of the peak scattering wavelength of ±28 nm. The experimental results are compared with numerical simulations of gold nanoparticles positioned on representative rough gold surfaces, modeled based on atomic force microscopy measurements. The predicted spectral variation and average resonance wavelength show good agreement with the measured data. The study shows that nanometer scale surface roughness can significantly affect the performance of gap plasmon-based devices.

Transport in ultrathin gold films decorated with magnetic Gd atoms

NASA Astrophysics Data System (ADS)

Alemani, Micol; Helgren, Erik; Hugel, Addison; Hellman, Frances

2008-03-01

We have performed four-probe transport measurements of ultrathin Au films decorated with Gd ad-atoms. The samples were prepared by quench condensation, i.e., sequential evaporation on a cryogenically cooled substrate under UHV conditions while monitoring the film thickness and resistance. Electrically continuous Au films at thickness of about 2 mono-layers of material are grown on an amorphous Ge wetting layer. The quench condensation method provides a sensitive control on the sample growth process, allowing us to tune the morphological and electrical configuration of the system. The ultrathin gold films develop from an insulating to a metallic state as a function of film thickness. The temperature dependence of the Au conductivity for different thickness is studied. It evolves from hopping transport for the insulating films, to a ln T dependence for thicker films. For gold films in the insulating regime we found a decreasing resistance by adding Gd. This is in agreement with a decreasing tunneling barrier height between metallic atoms. The Gd magnetic moments are randomly oriented for isolated atoms. This magnetic disorder leads to scattering of the charge carriers and a reduced conductivity compared to nonmagnetic materials.

The structure and binding mode of citrate in the stabilization of gold nanoparticles

NASA Astrophysics Data System (ADS)

Al-Johani, Hind; Abou-Hamad, Edy; Jedidi, Abdesslem; Widdifield, Cory M.; Viger-Gravel, Jasmine; Sangaru, Shiv Shankar; Gajan, David; Anjum, Dalaver H.; Ould-Chikh, Samy; Hedhili, Mohamed Nejib; Gurinov, Andrei; Kelly, Michael J.; El Eter, Mohamad; Cavallo, Luigi; Emsley, Lyndon; Basset, Jean-Marie

2017-09-01

Elucidating the binding mode of carboxylate-containing ligands to gold nanoparticles (AuNPs) is crucial to understand their stabilizing role. A detailed picture of the three-dimensional structure and coordination modes of citrate, acetate, succinate and glutarate to AuNPs is obtained by 13C and 23Na solid-state NMR in combination with computational modelling and electron microscopy. The binding between the carboxylates and the AuNP surface is found to occur in three different modes. These three modes are simultaneously present at low citrate to gold ratios, while a monocarboxylate monodentate (1κO1) mode is favoured at high citrate:gold ratios. The surface AuNP atoms are found to be predominantly in the zero oxidation state after citrate coordination, although trace amounts of Auδ+ are observed. 23Na NMR experiments show that Na+ ions are present near the gold surface, indicating that carboxylate binding occurs as a 2e- L-type interaction for each oxygen atom involved. This approach has broad potential to probe the binding of a variety of ligands to metal nanoparticles.

Atomic cluster collisions

NASA Astrophysics Data System (ADS)

Korol, Andrey V.; Solov'yov, Andrey

2013-01-01

Atomic cluster collisions are a field of rapidly emerging research interest by both experimentalists and theorists. The international symposium on atomic cluster collisions (ISSAC) is the premier forum to present cutting-edge research in this field. It was established in 2003 and the most recent conference was held in Berlin, Germany in July of 2011. This Topical Issue presents original research results from some of the participants, who attended this conference. This issues specifically focuses on two research areas, namely Clusters and Fullerenes in External Fields and Nanoscale Insights in Radiation Biodamage.

The Impact of the Polymer Chain Length on the Catalytic Activity of Poly(N-vinyl-2-pyrrolidone)-supported Gold Nanoclusters.

PubMed

Haesuwannakij, Setsiri; Kimura, Tetsunari; Furutani, Yuji; Okumura, Kazu; Kokubo, Ken; Sakata, Takao; Yasuda, Hidehiro; Yakiyama, Yumi; Sakurai, Hidehiro

2017-08-29

Poly(N-vinyl-2-pyrrolidone) (PVP) of varying molecular weight (M w  = 40-360 kDa) were employed to stabilize gold nanoclusters of varying size. The resulting Au:PVP clusters were subsequently used as catalysts for a kinetic study on the sized-dependent aerobic oxidation of 1-indanol, which was monitored by time-resolved in situ infrared spectroscopy. The obtained results suggest that the catalytic behaviour is intimately correlated to the size of the clusters, which in turn depends on the molecular weight of the PVPs. The highest catalytic activity was observed for clusters with a core size of ~7 nm, and the size of the cluster should increase with the molecular weight of the polymer in order to maintain optimal catalytic activity. Studies on the electronic and colloid structure of these clusters revealed that the negative charge density on the cluster surface also strongly depends on the molecular weight of the stabilizing polymers.

Formation of neutral and charged gold carbonyls on highly facetted gold nanostructures

NASA Astrophysics Data System (ADS)

Chau, Thoi-Dai; Visart de Bocarmé, Thierry; Kruse, Norbert; Wang, Richard L. C.; Kreuzer, Hans Jürgen

2003-12-01

We show that gold mono- and di-carbonyls are formed on gold field emitter tips during interaction with carbon monoxide gas at room temperature and in the presence of high electrostatic fields. The experiments are done in a time-of-flight atom probe to obtain mass spectra. The yield of monocarbonyl cations is about twice that of di-carbonyl ions. Density functional theory calculations are reported that explain the field stabilization of adsorbed carbonyls and the desorption yield of their cations.

10 CFR 1002.11 - Description of official seal.

Code of Federal Regulations, 2013 CFR

2013-01-01

... is emblazoned a gold-colored symbolic sun, atom, oil derrick, windmill, and dynamo. It is crested by... increasing demands for energy. The sun, atom, oil derrick, windmill, and dynamo serve as representative...

10 CFR 1002.11 - Description of official seal.

Code of Federal Regulations, 2010 CFR

2010-01-01

... is emblazoned a gold-colored symbolic sun, atom, oil derrick, windmill, and dynamo. It is crested by... increasing demands for energy. The sun, atom, oil derrick, windmill, and dynamo serve as representative...

10 CFR 1002.11 - Description of official seal.

Code of Federal Regulations, 2011 CFR

2011-01-01

... is emblazoned a gold-colored symbolic sun, atom, oil derrick, windmill, and dynamo. It is crested by... increasing demands for energy. The sun, atom, oil derrick, windmill, and dynamo serve as representative...

10 CFR 1002.11 - Description of official seal.

Code of Federal Regulations, 2014 CFR

2014-01-01

... is emblazoned a gold-colored symbolic sun, atom, oil derrick, windmill, and dynamo. It is crested by... increasing demands for energy. The sun, atom, oil derrick, windmill, and dynamo serve as representative...

10 CFR 1002.11 - Description of official seal.

Code of Federal Regulations, 2012 CFR

2012-01-01

... is emblazoned a gold-colored symbolic sun, atom, oil derrick, windmill, and dynamo. It is crested by... increasing demands for energy. The sun, atom, oil derrick, windmill, and dynamo serve as representative...

Atom chips in the real world: the effects of wire corrugation

NASA Astrophysics Data System (ADS)

Schumm, T.; Estève, J.; Figl, C.; Trebbia, J.-B.; Aussibal, C.; Nguyen, H.; Mailly, D.; Bouchoule, I.; Westbrook, C. I.; Aspect, A.

2005-02-01

We present a detailed model describing the effects of wire corrugation on the trapping potential experienced by a cloud of atoms above a current carrying micro wire. We calculate the distortion of the current distribution due to corrugation and then derive the corresponding roughness in the magnetic field above the wire. Scaling laws are derived for the roughness as a function of height above a ribbon shaped wire. We also present experimental data on micro wire traps using cold atoms which complement some previously published measurements [CITE] and which demonstrate that wire corrugation can satisfactorily explain our observations of atom cloud fragmentation above electroplated gold wires. Finally, we present measurements of the corrugation of new wires fabricated by electron beam lithography and evaporation of gold. These wires appear to be substantially smoother than electroplated wires.

Interaction of intense laser pulses with hydrogen atomic clusters

NASA Astrophysics Data System (ADS)

Du, Hong-Chuan; Wang, Hui-Qiao; Liu, Zuo-Ye; Sun, Shao-Hua; Li, Lu; Ma, Ling-Ling; Hu, Bi-Tao

2010-03-01

The interaction between intense femtosecond laser pulses and hydrogen atomic clusters is studied by a simplified Coulomb explosion model. The dependences of average proton kinetic energy on cluster size, pulse duration, laser intensity and wavelength are studied respectively. The calculated results indicate that the irradiation of a femtosecond laser of longer wavelength on hydrogen atomic clusters may be a simple, economical way to produce highly kinetic hydrogen ions. The phenomenon suggests that the irradiation of femtosecond laser of longer wavelength on deuterium atomic clusters may be easier than that of shorter wavelength to drive nuclear fusion reactions. The product of the laser intensity and the squared laser wavelength needed to make proton energy saturated as a function of the squared cluster radius is also investigated. The proton energy distribution calculated is also shown and compared with the experimental data. Our results are in agreement with the experimental results fairly well.

The stability of vacancy clusters and their effect on helium behaviors in 3C-SiC

NASA Astrophysics Data System (ADS)

Sun, Jingjing; Li, B. S.; You, Yu-Wei; Hou, Jie; Xu, Yichun; Liu, C. S.; Fang, Q. F.; Wang, Z. G.

2018-05-01

We have carried out systematical ab initio calculations to study the stability of vacancy clusters and their effect on helium behaviors in 3C-SiC. It is found that the formation energies of vacancy clusters containing only carbon vacancies are the lowest although the vacancies are not closest to each other, while the binding energies of vacancy clusters composed of both silicon and carbon vacancies in the closest neighbors to each other are the highest. Vacancy clusters can provide with free space for helium atoms to aggregate, while interstitial sites are not favorable for helium atoms to accumulate. The binding energies of vacancy clusters with helium atoms increase almost linearly with the ratio of helium to vacancy, n/m. The binding strength of vacancy cluster having the participation of the silicon vacancy with helium is relatively stronger than that without silicon vacancy. The vacancy clusters with more vacancies can trap helium atoms more tightly. With the presence of vacancy clusters in the material, the diffusivity of helium will be significantly reduced. Moreover, the three-dimension electron density is calculated to analyze the interplay of vacancy clusters with helium.

Preparation and high-resolution microscopy of gold cluster labeled nucleic acid conjugates and nanodevices

PubMed Central

Powell, Richard D.; Hainfeld, James F.

2013-01-01

Nanogold and undecagold are covalently linked gold cluster labels which enable the identification and localization of biological components with molecular precision and resolution. They can be prepared with different reactivities, which means they can be conjugated to a wide variety of molecules, including nucleic acids, at specific, unique sites. The location of these sites can be synthetically programmed in order to preserve the binding affinity of the conjugate and impart novel characteristics and useful functionality. Methods for the conjugation of undecagold and Nanogold to DNA and RNA are discussed, and applications of labeled conjugates to the high-resolution microscopic identification of binding sites and characterization of biological macromolecular assemblies are described. In addition to providing insights into their molecular structure and function, high-resolution microscopic methods also show how Nanogold and undecagold conjugates can be synthetically assembled, or self-assemble, into supramolecular materials to which the gold cluster labels impart useful functionality. PMID:20869258

Electronic levels and charge distribution near the interface of nickel

NASA Technical Reports Server (NTRS)

Waber, J. T.

1982-01-01

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

Influence of gold additives on the stability and phase transformation of titanate nanostructures.

PubMed

Pusztai, P; Puskás, R; Varga, E; Erdőhelyi, A; Kukovecz, Á; Kónya, Z; Kiss, J

2014-12-28

Gold nanoparticles were prepared and characterized on protonated (H-form) titanate nanotubes (TiONTs) and nanowires (TiONWs). The chemical nature and morphology of gold particles were monitored by X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, X-ray diffraction (XRD) and high resolution electron microscopy (HRTEM). The optical properties of Au-containing titanate nanowires were explored by means of ultraviolet-visible diffuse reflectance spectroscopy. The size distribution and homogeneity of gold particles depend on the reduction mode from the corresponding gold salt to metal particles. Smaller clusters (3-8 nm) were obtained with the NaBH4 reactant at 293 K than with molecular hydrogen reduction. An unexpectedly high binding energy gold state was found by XPS in gold-loaded titanate nanostructures. This state was absent from the spectra of gold-loaded TiO2(110). A likely explanation for this phenomenon, supported also by the characteristic decrease of band gap energy from 3.10 eV to 2.74 eV with increasing Au content, is that depending on the metal loading and titanate structure, Au is stabilized on titanate nanowires partially in positively charged gold form by ion exchange and also as Au clusters. Our important new finding is that the thermal annealing behavior of Au-loaded titanate nanotubes and nanowires is different. The former lose their tubular morphology and are readily transformed into anatase even at a very low temperature of 473 K. On the other hand, gold stabilizes the layered structure of titanate nanowires up to 873 K.

Point defect induced segregation of alloying solutes in α-Fe

NASA Astrophysics Data System (ADS)

You, Yu-Wei; Zhang, Yange; Li, Xiangyan; Xu, Yichun; Liu, C. S.; Chen, J. L.; Luo, G.-N.

2016-10-01

Segregation of alloying solute toward clusters and precipitates can result in hardening and embrittlement of ferritic and ferritic/martensitic steels in aging nuclear power plants. Thus, it is essential to study the segregation of solute in α-Fe. In this study, the segregation of eight kinds of alloying solutes (Al, Si, P, S, Ga, Ge, As, Se) in defect-free system and at vacancy, divacancy, and self-interstitial atom in α-Fe has been systematically studied by first-principles calculations. We find that it is energetically favorable for multiple solute S or Se atoms to segregate in defect-free system to form solute clusters, whereas it is very difficult for the other solute atoms to form the similar clusters. With the presence of vacancy and divacancy, the segregation of all the solutes are significantly promoted to form vacancy-solute and divacancy-solute clusters. The divacancy-solute cluster is more stable than the vacancy-solute cluster. The most-stable self-interstitial atom 〈110〉 dumbbell is also found to tightly bind with multiple solute atoms. The 〈110〉-S is even more stable than divacancy-S cluster. Meanwhile, the law of mass action is employed to predict the concentration evolution of vacancy-Si, vacancy-P, and vacancy-S clusters versus temperature and vacancy concentration.

A Relativity Enhanced, Medium-Strong Au(I)···H-N Hydrogen Bond in a Protonated Phenylpyridine-Gold(I) Thiolate.

PubMed

Berger, Raphael J F; Schoiber, Jürgen; Monkowius, Uwe

2017-01-17

Gold is an electron-rich metal with a high electronegativity comparable to that of sulfur. Hence, hydrogen bonds of the Au(I)···H-E (E = electronegative element) type should be possible, but their existence is still under debate. Experimental results are scarce and often contradictory. As guidance for possible preparative work, we have theoretically investigated (ppyH)Au(SPh) (ppy = 2-phenylpyridine) bearing two monoanionic ligands which are not strongly electronegative at the same time to further increase the charge density on the gold(I) atom. The protonated pyridine nitrogen atom in ppy is geometrically ideally suited to place a proton in close proximity to the gold atom in a favorable geometry for a classical hydrogen bond arrangement. Indeed, the results of the calculations indicate that the hydrogen bonded conformation of (ppyH)Au(SPh) represents a minimum geometry with bond metrics in the expected range for medium-strong hydrogen bonds [r(N-H) = 1.043 Å, r(H···Au) = 2.060 Å, a(N-H···Au) = 141.4°]. The energy difference between the conformer containing the H···Au bond and another conformer without a hydrogen bond amounts to 7.8 kcal mol -1 , which might serve as an estimate of the hydrogen bond strength. Spectroscopic properties were calculated, yielding further characteristics of such hydrogen bonded gold species.

About the atomic structures of icosahedral quasicrystals

NASA Astrophysics Data System (ADS)

Quiquandon, Marianne; Gratias, Denis

2014-01-01

This paper is a survey of the crystallographic methods that have been developed these last twenty five years to decipher the atomic structures of the icosahedral stable quasicrystals since their discovery in 1982 by D. Shechtman. After a brief recall of the notion of quasiperiodicity and the natural description of Z-modules in 3-dim as projection of regular lattices in N>3-dim spaces, we give the basic geometrical ingredients useful to describe icosahedral quasicrystals as irrational 3-dim cuts of ordinary crystals in 6-dim space. Atoms are described by atomic surfaces (ASs) that are bounded volumes in the internal (or perpendicular) 3-dim space and the intersections of which with the physical space are the actual atomic positions. The main part of the paper is devoted to finding the major properties of quasicrystalline icosahedral structures. As experimentally demonstrated, they can be described with a surprisingly few high symmetry ASs located at high symmetry special points in 6-dim space. The atomic structures are best described by aggregations and intersections of high symmetry compact interpenetrating atomic clusters. We show here that the experimentally relevant clusters are derived from one generic cluster made of two concentric triacontahedra scaled by τ and an external icosidodecahedron. Depending on which ones of the orbits of this cluster are eventually occupied by atoms, the actual atomic clusters are of type Bergman, Mackay, Tsai and others….

Self-organized formation of quantum dots of a material on a substrate

DOEpatents

Zhang, Zhenyu; Wendelken, John F.; Chang, Ming-Che; Pai, Woei Wu

2001-01-01

Systems and methods are described for fabricating arrays of quantum dots. A method for making a quantum dot device, includes: forming clusters of atoms on a substrate; and charging the clusters of atoms such that the clusters of atoms repel one another. The systems and methods provide advantages because the quantum dots can be ordered with regard to spacing and/or size.

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

NASA Astrophysics Data System (ADS)

Majumder, Chiranjib; Kulshreshtha, S. K.

2004-12-01

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

Use of near-infrared luminescent gold nanoclusters for detection of macrophages

PubMed Central

Sapozhnikova, Veronika; Willsey, Brian; Asmis, Reto; Wang, Tianyi; Jenkins, James Travis; Mancuso, Jacob; Ma, Li Leo; Kuranov, Roman; Milner, Thomas E.; Johnston, Keith

2012-01-01

Abstract. We determined the effect of aggregation and coating thickness of gold on the luminescence of nanoparticles engulfed by macrophages and in gelatin phantoms. Thin gold-coated iron oxide nanoclusters (nanoroses) have been developed to target macrophages to provide contrast enhancement for near-infrared optical imaging applications. We compare the brightness of nanoroses luminescent emissions in response to 635 nm laser excitation to other nanoparticles including nanoshells, nanorods, and Cy5 conjugated iron oxide nanoparticles. Luminescent properties of all these nanoparticles were investigated in monomeric and aggregated form in gelatin phantoms and primary macrophage cell cultures using confocal microscopy. Aggregation of the gold nanoparticles increased luminescence emission and correlated with increased surface mass of gold per nanoparticle (nanoshells 37±14.30×10−3 brightness with 1.23×10−4 wt of gold (g)/nanoparticle versus original nanorose 1.45±0.37×10−3 with 2.10×10−16 wt of gold/nanoparticle, p<0.05). Nanoshells showed greater luminescent intensity than original nanoroses or Cy5 conjugated iron oxide nanoparticles when compared as nanoparticles per macrophage (38±10 versus 11±2.8 versus 17±6.5, p<0.05, respectively, ANOVA), but showed relatively poor macrophage uptake (1025±128 versus 7549±236 versus 96,000  nanoparticles/cell, p<0.05, student t-test nanoshells versus nanoroses). Enhancement of gold fluorescent emissions by nanoparticles can be achieved by reducing the thickness of the gold coating, by clustering the gold on the surface of the nanoparticles (nanoshells), and by clustering the gold nanoparticles themselves. PMID:22463038

Effect of collector molecular structure on the wettability of gold for froth flotation

NASA Astrophysics Data System (ADS)

Moncayo-Riascos, Ivan; Hoyos, Bibian A.

2017-10-01

Molecular dynamics simulations were conducted to evaluate the alteration of the hydrophilic state of gold surfaces caused by the adsorption of collectors with different molecular structures, using the contact angle of water droplets as an evaluation parameter. Four collectors were evaluated: SDS (with twelve hydrogenated carbon atoms), PAX (with five hydrogenated carbon atoms), DTP (with two branched aliphatic chains) and MBT (with an aromatic ring). The contact angle was evaluated for coatings of a monolayer (ML) and for surface densities of 2.89 μmol/m2 for each collector. For a ML, the hydrophobic effect generated by the aromatic ring of the MBT collector is comparable with the effect of the non-polar short chain of the PAX collector. The increase in hydrophobicity for the gold surfaces achieved by collectors with aliphatic chains is because the water-collector interaction energy is significantly higher (repulsive) than the water-gold interactions (attractive). The lowest increase in hydrophobicity was achieved with the MBT collector, since the carbon-water interaction energy of the aromatic ring is stronger than the interaction with the carbon atoms in the aliphatic chains. The calculated contact angles of the water droplets deviated less than 4% with respect to the experimental values.

Spectrally resolved opacities and Rosseland and Planck mean opacities of lowly ionized gold plasmas: a detailed level-accounting investigation.

PubMed

Zeng, Jiaolong; Yuan, Jianmin

2007-08-01

Calculation details of radiative opacity for lowly ionized gold plasmas by using our developed fully relativistic detailed level-accounting approach are presented to show the importance of accurate atomic data for a quantitative reproduction of the experimental observations. Even though a huge number of transition lines are involved in the radiative absorption of high- Z plasmas so that one believes that statistical models can often give a reasonable description of their opacities, we first show in detail that an adequate treatment of physical effects, in particular the configuration interaction (including the core-valence electron correlation), is essential to produce atomic data of bound-bound and bound-free processes for gold plasmas, which are accurate enough to correctly explain the relative intensity of two strong absorption peaks experimentally observed located near photon energy of 70 and 80 eV. A detailed study is also carried out for gold plasmas of an average ionization degree sequence of 10, for both spectrally resolved opacities and Rosseland and Planck means. For comparison, results obtained by using an average atom model are also given to show that even for a relatively higher density of matter, correlation effects are also important to predict the correct positions of absorption peaks of transition arrays.

Spectroscopic Non-LTE Modeling of Highly Charged Gold Plasma

NASA Astrophysics Data System (ADS)

Dasgupta, A.; Ouart, N. D.; Giuliani, J. L.; Obenschain, S. P.; Clark, R. W.; Aglitskiy, Y.

2013-10-01

An X-ray spectrometer is under development at the Naval Research Laboratory (NRL) to investigate emissions from gold targets irradiated by the NIKE KrF facility. This effort is in support of the indirect drive campaign on the National Ignition Facility (NIF). To analyze and interpret the NIKE experimental spectra, we are theoretically exploring line emissions from a gold plasma in the M-band, i.e., 1.5 to 3.5 keV. We employ a detailed Non-LTE atomic model for ions near Ni-like gold by including an adequate number of configurations to obtain spectroscopic details in this range. The atomic states are coupled both collisionally and radiatively, including all dominant atomic processes that have significant contributions to the ionization and emitted synthetic spectra. In particular, we will investigate the effect of dielectronic recombination, which can have a dominant effect on level populations for highly ionized high Z plasmas. Since the radiation field can affect level populations through photoionization and photoexcitation, our collisional-radiative model will include non-local radiation transport. The line shapes of the strong overlapping lines will be resolved by a multifrequency radiation transport method. Synthetic spectra with radiation transport, including resonant photo-pumping, will be generated for realistic densities and temperatures to compare with the NIKE data. Work supported by DOE/NNSA.

Electrodeposition of Isolated Platinum Atoms and Clusters on Bismuth-Characterization and Electrocatalysis.

PubMed

Zhou, Min; Dick, Jeffrey E; Bard, Allen J

2017-12-06

We describe a method for the electrodeposition of an isolated single Pt atom or small cluster, up to 9 atoms, on a bismuth ultramicroelectrode (UME). This deposition was immediately followed by electrochemical characterization via the hydrogen evolution reaction (HER) that occurs readily on the electrodeposited Pt but not on Bi. The observed voltammetric current plateau, even for a single atom, which behaves as an electrode, allows the estimation of deposit size. Pt was plated from solutions of femtomolar PtCl 6 2- , which allowed precise control of the arrival of ions and thus the plating rate on the Bi UME, to one ion every few seconds. This allowed the atom-by-atom fabrication of isolated platinum deposits, ranging from single atoms to 9-atom clusters. The limiting currents in voltammetry gave the size and number of atoms of the clusters. Given the stochasticity of the plating process, we show that the number of atoms plated over a given time (10 and 20 s) follows a Poisson distribution. Taking the potential at a certain current density as a measure of the relative rate of the HER, we found that the potential shifted positively as the size increased, with single atoms showing the largest overpotentials compared to bulk Pt.

Charge-Induced (1 x 3) Reconstruction of Au(110): Mechanistic Insights from Potentiodynamic Scanning Tunneling Microscopy in Alkali Iodide Electrolytes

DTIC Science & Technology

1994-02-01

In potassium iodide electrolyte, the usual "three-missing-row" (1 x 3) structure is seen to be generated by single gold atomic-row segments shifting...observed, involving the intermediate local formation of "one-missing-row" (I x 3) domains by removal of one-third of the top layer gold rows onto nearby...structure is achieved by aggregation of the displaced monoatomic row segments. The mechanistic value of following atomic-level reconstruction processes by

First-principles Theory of Inelastic Transport and Local Heating in Atomic Gold Wires

NASA Astrophysics Data System (ADS)

Frederiksen, Thomas; Paulsson, Magnus; Brandbyge, Mads; Jauho, Antti-Pekka

2007-04-01

We present theoretical calculations of the inelastic transport properties in atomic gold wires. Our method is based on a combination of density functional theory and non-equilibrium Green's functions. The vibrational spectra for extensive series of wire geometries have been calculated using SIESTA, and the corresponding effects in the conductance are analyzed. In particular, we focus on the heating of the active vibrational modes. By a detailed comparison with experiments we are able to estimate an order of magnitude for the external damping of the active vibrations.

A Rutherford Scattering Simulation with Microcomputer Graphics.

ERIC Educational Resources Information Center

Calle, Carlos I.; Wright, Lavonia F.

1989-01-01

Lists a program for a simulation of Rutherford's gold foil experiment in BASIC for both Apple II and IBM compatible computers. Compares Rutherford's model of the atom with Thompson's plum pudding model of the atom. (MVL)

Atomically precise metal nanoclusters: stable sizes and optical properties

NASA Astrophysics Data System (ADS)

Jin, Rongchao

2015-01-01

Controlling nanoparticles with atomic precision has long been a major dream of nanochemists. Breakthroughs have been made in the case of gold nanoparticles, at least for nanoparticles smaller than ~3 nm in diameter. Such ultrasmall gold nanoparticles indeed exhibit fundamentally different properties from those of the plasmonic counterparts owing to the quantum size effects as well as the extremely high surface-to-volume ratio. These unique nanoparticles are often called nanoclusters to distinguish them from conventional plasmonic nanoparticles. Intense work carried out in the last few years has generated a library of stable sizes (or stable stoichiometries) of atomically precise gold nanoclusters, which are opening up new exciting opportunities for both fundamental research and technological applications. In this review, we have summarized the recent progress in the research of thiolate (SR)-protected gold nanoclusters with a focus on the reported stable sizes and their optical absorption spectra. The crystallization of nanoclusters still remains challenging; nevertheless, a few more structures have been achieved since the earlier successes in Au102(SR)44, Au25(SR)18 and Au38(SR)24 nanoclusters, and the newly reported structures include Au20(SR)16, Au24(SR)20, Au28(SR)20, Au30S(SR)18, and Au36(SR)24. Phosphine-protected gold and thiolate-protected silver nanoclusters are also briefly discussed in this review. The reported gold nanocluster sizes serve as the basis for investigating their size dependent properties as well as the development of applications in catalysis, sensing, biological labelling, optics, etc. Future efforts will continue to address what stable sizes are existent, and more importantly, what factors determine their stability. Structural determination and theoretical simulations will help to gain deep insight into the structure-property relationships.

Preparation and characterization of carbon-supported sub-monolayer palladium decorated gold nanoparticles for the electro-oxidation of ethanol in alkaline media

NASA Astrophysics Data System (ADS)

Zhu, L. D.; Zhao, T. S.; Xu, J. B.; Liang, Z. X.

Carbon-supported gold nanoparticles (Au/C) are successfully decorated with mono- or sub-monolayer palladium atoms with different Pd/Au atomic ratios by a chemically epitaxial seeded growth method. TEM, UV-vis spectrometry and XRD techniques are used to characterize the particle size, dispersion, palladium coverage on gold seeds and crystal structures of the prepared catalysts. Cyclic voltammetric tests show that the Pd-decorated Au/C (denoted by Pd@Au/C) have higher specific activities than that of Pd/C for the oxidation of ethanol in alkaline media. This suggests that the Pd utilization is improved with such a surface-alloyed nanostructure. In addition, stable chronoamperometric responses are achieved with the so-prepared electrocatalysts during ethanol oxidation.

Interaction of scandium and titanium atoms with a carbon surface containing five- and seven-membered rings

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

Krasnov, P. O., E-mail: kpo1980@gmail.com; Eliseeva, N. S.; Kuzubov, A. A., E-mail: alex_xx@rambler.ru

2012-01-15

The use of carbon nanotubes coated by atoms of transition metals to store molecular hydrogen is associated with the problem of the aggregation of these atoms, which leads to the formation of metal clusters. The quantum-chemical simulation of cluster models of the carbon surface of a graphene type with scandium and titanium atoms has been performed. It has been shown that the presence of five- and seven-membered rings, in addition to six-membered rings, in these structures makes it possible to strongly suppress the processes of the migration of metal atoms over the surface, preventing their clustering.

Synthesis of borophenes: Anisotropic, two-dimensional boron polymorphs

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

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

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

Sinter-Resistant Platinum Catalyst Supported by Metal-Organic Framework.

PubMed

Kim, In Soo; Li, Zhanyong; Zheng, Jian; Platero-Prats, Ana E; Mavrandonakis, Andreas; Pellizzeri, Steven; Ferrandon, Magali; Vjunov, Aleksei; Gallington, Leighanne C; Webber, Thomas E; Vermeulen, Nicolaas A; Penn, R Lee; Getman, Rachel B; Cramer, Christopher J; Chapman, Karena W; Camaioni, Donald M; Fulton, John L; Lercher, Johannes A; Farha, Omar K; Hupp, Joseph T; Martinson, Alex B F

2018-01-22

Single atoms and few-atom clusters of platinum are uniformly installed on the zirconia nodes of a metal-organic framework (MOF) NU-1000 via targeted vapor-phase synthesis. The catalytic Pt clusters, site-isolated by organic linkers, are shown to exhibit high catalytic activity for ethylene hydrogenation while exhibiting resistance to sintering up to 200 °C. In situ IR spectroscopy reveals the presence of both single atoms and few-atom clusters that depend upon synthesis conditions. Operando X-ray absorption spectroscopy and X-ray pair distribution analyses reveal unique changes in chemical bonding environment and cluster size stability while on stream. Density functional theory calculations elucidate a favorable reaction pathway for ethylene hydrogenation with the novel catalyst. These results provide evidence that atomic layer deposition (ALD) in MOFs is a versatile approach to the rational synthesis of size-selected clusters, including noble metals, on a high surface area support. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Wang, Lin -Lin; Johnson, Duane D.; Tringides, Michael C.

Density functional theory is used to study structural energetics of Pb vacancy cluster formation on C 60/Pb/Si(111) to explain the unusually fast and error-free transformations between the “Devil's Staircase” (DS) phases on the Pb/Si(111) wetting layer at low temperature (~110K). The formation energies of vacancy clusters are calculated in C 60/Pb/Si(111) as Pb atoms are progressively ejected from the initial dense Pb wetting layer. Vacancy clusters larger than five Pb atoms are found to be stable with seven being the most stable, while vacancy clusters smaller than five are highly unstable, which agrees well with the observed ejection rate ofmore » ~5 Pb atoms per C 60. Furthermore, the high energy cost (~0.8 eV) for the small vacancy clusters to form indicates convincingly that the unusually fast transformation observed experimentally between the DS phases, upon C 60 adsorption at low temperature, cannot be the result of single-atom random walk diffusion but of correlated multi-atom processes.« less

Adsorption of Pyridine at the Au(100)-Solution Interface.

DTIC Science & Technology

1987-09-25

quatiatively characterize the energetics of pyridine adsorption onto a gold ( 100) single crystal electrode surface. Over the potential region investigated...0.8 to +0.6 A., three orientationis of the pyridine molecules on the gold surface have been observed. The pyridine orientation Is strongly 1nflue ied by...the electrode potential. At a positively charged surface, the pyridine assumes a verticle orientation with .fie nitrogen atom facing the gold surface

Nano-scaling law: geometric foundation of thiolated gold nanomolecules.

PubMed

Dass, Amala

2012-04-07

Thiolated gold nanomolecules show a power correlation between the number of gold atoms and the thiolate ligands with a 2/3 scaling similar to Platonic and Archimedean solids. Nanomolecule stability is influenced by a universal geometric factor that is foundational to its stability through the Euclidean surface rule, in addition to the electronic shell closing factor and staple motif requirements. This journal is © The Royal Society of Chemistry 2012

Catalysis applications of size-selected cluster deposition

DOE PAGES

Vajda, Stefan; White, Michael G.

2015-10-23

In this Perspective, we review recent studies of size-selected cluster deposition for catalysis applications performed at the U.S. DOE National Laboratories, with emphasis on work at Argonne National Laboratory (ANL) and Brookhaven National Laboratory (BNL). The focus is on the preparation of model supported catalysts in which the number of atoms in the deposited clusters is precisely controlled using a combination of gas-phase cluster ion sources, mass spectrometry, and soft-landing techniques. This approach is particularly effective for investigations of small nanoclusters, 0.5-2 nm (<200 atoms), where the rapid evolution of the atomic and electronic structure makes it essential to havemore » precise control over cluster size. Cluster deposition allows for independent control of cluster size, coverage, and stoichiometry (e.g., the metal-to-oxygen ratio in an oxide cluster) and can be used to deposit on any substrate without constraints of nucleation and growth. Examples are presented for metal, metal oxide, and metal sulfide cluster deposition on a variety of supports (metals, oxides, carbon/diamond) where the reactivity, cluster-support electronic interactions, and cluster stability and morphology are investigated. Both UHV and in situ/operando studies are presented that also make use of surface-sensitive X-ray characterization tools from synchrotron radiation facilities. Novel applications of cluster deposition to electrochemistry and batteries are also presented. This review also highlights the application of modern ab initio electronic structure calculations (density functional theory), which can essentially model the exact experimental system used in the laboratory (i.e., cluster and support) to provide insight on atomic and electronic structure, reaction energetics, and mechanisms. As amply demonstrated in this review, the powerful combination of atomically precise cluster deposition and theory is able to address fundamental aspects of size-effects, cluster-support interactions, and reaction mechanisms of cluster materials that are central to how catalysts function. Lastly, the insight gained from such studies can be used to further the development of novel nanostructured catalysts with high activity and selectivity.« less

Myochrysine Solution Structure and Reactivity

PubMed Central

Jones, William B.; Zhao, Zheng; Dorsey, John G.; Tepperman, Katherine

1994-01-01

We have determined the framework structure of Myochrysine (disodium gold(I)thiomalate) in the solid state and extremely concentrated aqueous solution, previously. It consists of an open chain polymer with linear gold coordination to two thiolates from the thiomalic acid moieties which bridge between pairs of gold atoms providing an Au-S-Au angle of 95°. The question remained: was this structure relevant to the dilute solutions of drugs administered and the still lower concentrations of gold found in the bodies of patients (typically 1 ppm Au in blood and urine or 5 μM in Au). We have provided an answer to that question using extended X-ray absorption spectroscopy (EXAFS) and capillary zone electrophoresis (CZE). EXAFS studies confirm that the polymeric structure with two sulfur atoms per gold atom persists from molar concentrations down to millimolar concentrations. CZE is able to separate and detect Myochrysine at millimolar levels. More importantly, at micromolar levels Myochrysine solutions exhibit identical CZE behavior to that measured at millimolar levels. Thus, aqueous solutions of the drug remain oligomeric at concentrations commensurate with those found in patient blood and urine. The reactivity of Myochrysine with cyanide, a species especially prevalent in smoking patients, was explored using CZE. Cyanide freely replaces thiomalic acid to form [Au(CN)2]- and thiomalic acid via a mixed ligand intermediate. The overall apparent equilibrium constant (Kapp) for the reaction is 6×10-4M-1. Further reaction of [Au(CN)2]- with a large excess of L, where L is cysteine, N-acetylcysteine, or glutathione, shows that these amino acids readily replace cyanide to form [AuL2]-. These species are thus potential metabolites and could possibly be active forms of gold in vivo. That all of these species are readily separated and quantified using CZE demonstrates that capillary electrophoresis is an accessible and powerful tool to add to those used for the study of gold-based antiarthritis drugs. PMID:18476256

Using size-selected gold clusters on graphene oxide films to aid cryo-transmission electron tomography alignment

PubMed Central

Arkill, Kenton P.; Mantell, Judith M.; Plant, Simon R.; Verkade, Paul; Palmer, Richard E.

2015-01-01

A three-dimensional reconstruction of a nano-scale aqueous object can be achieved by taking a series of transmission electron micrographs tilted at different angles in vitreous ice: cryo-Transmission Electron Tomography. Presented here is a novel method of fine alignment for the tilt series. Size-selected gold clusters of ~2.7 nm (Au561 ± 14), ~3.2 nm (Au923 ± 22), and ~4.3 nm (Au2057 ± 45) in diameter were deposited onto separate graphene oxide films overlaying holes on amorphous carbon grids. After plunge freezing and subsequent transfer to cryo-Transmission Electron Tomography, the resulting tomograms have excellent (de-)focus and alignment properties during automatic acquisition. Fine alignment is accurate when the evenly distributed 3.2 nm gold particles are used as fiducial markers, demonstrated with a reconstruction of a tobacco mosaic virus. Using a graphene oxide film means the fiducial markers are not interfering with the ice bound sample and that automated collection is consistent. The use of pre-deposited size-selected clusters means there is no aggregation and a user defined concentration. The size-selected clusters are mono-dispersed and can be produced in a wide size range including 2–5 nm in diameter. The use of size-selected clusters on a graphene oxide films represents a significant technical advance for 3D cryo-electron microscopy. PMID:25783049

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

PubMed

Uţă, M M; King, R B

2012-05-31

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

High Intensity Femtosecond XUV Pulse Interactions with Atomic Clusters: Final Report

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

Ditmire, Todd

We propose to expand our recent studies on the interactions of intense extreme ultraviolet (XUV) femtosecond pulses with atomic and molecular clusters. The work described follows directly from work performed under BES support for the past grant period. During this period we upgraded the THOR laser at UT Austin by replacing the regenerative amplifier with optical parametric amplification (OPA) using BBO crystals. This increased the contrast of the laser, the total laser energy to ~1.2 J , and decreased the pulse width to below 30 fs. We built a new all reflective XUV harmonic beam line into expanded lab space. This enabled an increase influence by a factor ofmore » 25 and an increase in the intensity by a factor of 50. The goal of the program proposed in this renewal is to extend this class of experiments to available higher XUV intensity and a greater range of wavelengths. In particular we plan to perform experiments to confirm our hypothesis about the origin of the high charge states in these exploding clusters, an effect which we ascribe to plasma continuum lowering (ionization potential depression) in a cluster nano-­plasma. To do this we will perform experiments in which XUV pulses of carefully chosen wavelength irradiate clusters composed of only low-Z atoms and clusters with a mixture of this low-­Z atom with higher Z atoms. The latter clusters will exhibit higher electron densities and will serve to lower the ionization potential further than in the clusters composed only of low Z atoms. This should have a significant effect on the charge states produced in the exploding cluster. We will also explore the transition of explosions in these XUV irradiated clusters from hydrodynamic expansion to Coulomb explosion. The work proposed here will explore clusters of a wider range of constituents, including clusters from solids. Experiments on clusters from solids will be enabled by development we performed during the past grant period in which we constructed and tested a cluster generator based on the Laser Ablation of Microparticles (LAM) method.« less

Addition of a thallium vertex to empty and centered nine-atom deltahedral zintl ions of germanium and tin.

PubMed

Rios, Daniel; Gillett-Kunnath, Miriam M; Taylor, Jacob D; Oliver, Allen G; Sevov, Slavi C

2011-03-21

Nickel atoms were inserted into nine-atom deltahedral Zintl ions of E(9)(4-) (E = Ge, Sn) via reactions with Ni(cod)(2) (cod = cyclooctadiene), and [Ni@Sn(9)](3-) was structurally characterized. Both the empty and the Ni-centered clusters react with TlCp (Cp = cyclopentadienyl anion) and add a thallium vertex to form the deltahedral ten-atom closo-species [E(9)Tl](3-) and [Ni@E(9)Tl](3-), respectively. The structures of [Ge(9)Tl](3-) and [Ni@Sn(9)Tl](3-) showed that, as expected, the geometry of the ten-atom clusters is that of a bicapped square antiprism where the Tl-atom occupies one of the two capping vertices. This illustrates that centering a nine-atom cluster with a nickel atom does not change its reactivity toward TlCp. All compounds were characterized by electrospray mass spectrometry.

Polymer supported gold nanoparticles: Synthesis and characterization of functionalized polystyrene-supported gold nanoparticles and their application in catalytic oxidation of alcohols in water

NASA Astrophysics Data System (ADS)

Kaboudin, Babak; Khanmohammadi, Hamid; Kazemi, Foad

2017-12-01

Sulfonated polystyrene microsphere were functionalized using ethylene diamine to introduce amine groups to the polymer chains. The amine functionalized polymers were used as a support for gold nanoparticles. A thorough structural characterization has been carried out by means of transmission electron microscopy (TEM), scanning electron microscopy (SEM) images, EDS, CHN and atomic absorption spectroscopy. The polymer supported gold nanoparticles was found to be an efficient catalyst for the oxidation of alcohols in water.

Influence of α-amylase template concentration on systematic entrapment of highly stable and monodispersed colloidal gold nanoparticles

NASA Astrophysics Data System (ADS)

Ananth, A. Nitthin; Ananth, A. Nimrodh; Jose, Sujin P.; Umapathy, S.; Mathavan, T.

2016-01-01

Nano gold / α-amylase colloidal dispersions of profound stability were made using simple procedure with a conventional reducing agent. The surface plasmon resonance of the gold nanocrystals was used to quantify the extent of the dispersion stability and functionalization. It is found that the reduced gold nanoparticles were trapped into the protein network without denaturation the structure of α-amylase protein. This kind of entrapment of particles into the protein network prevents clustering of individual gold nanoparticles (6.42 nm ± 0.92 nm) by acting as a natural spacer. Systematic entrapment was facilitated by the affinity of gold to the sulfur moieties (Au-S) in the protein structure.

First-principles melting of gallium clusters down to nine atoms: structural and electronic contributions to melting.

PubMed

Steenbergen, Krista G; Gaston, Nicola

2013-10-07

First-principles Born-Oppenheimer molecular dynamics simulations of small gallium clusters, including parallel tempering, probe the distinction between cluster and molecule in the size range of 7-12 atoms. In contrast to the larger sizes, dynamic measures of structural change at finite temperature demonstrate that Ga7 and Ga8 do not melt, suggesting a size limit to melting in gallium exists at 9 atoms. Analysis of electronic structure further supports this size limit, additionally demonstrating that a covalent nature cannot be identified for clusters larger than the gallium dimer. Ga9, Ga10 and Ga11 melt at greater-than-bulk temperatures, with no evident covalent character. As Ga12 represents the first small gallium cluster to melt at a lower-than-bulk temperature, we examine the structural properties of each cluster at finite temperature in order to probe both the origins of greater-than-bulk melting, as well as the significant differences in melting temperatures induced by a single atom addition. Size-sensitive melting temperatures can be explained by both energetic and entropic differences between the solid and liquid phases for each cluster. We show that the lower-than-bulk melting temperature of the 12-atom cluster can be attributed to persistent pair bonding, reminiscent of the pairing observed in α-gallium. This result supports the attribution of greater-than-bulk melting in gallium clusters to the anomalously low melting temperature of the bulk, due to its dimeric structure.

Sizing protein-templated gold nanoclusters by time resolved fluorescence anisotropy decay measurements

NASA Astrophysics Data System (ADS)

Soleilhac, Antonin; Bertorelle, Franck; Antoine, Rodolphe

2018-03-01

Protein-templated gold nanoclusters (AuNCs) are very attractive due to their unique fluorescence properties. A major problem however may arise due to protein structure changes upon the nucleation of an AuNC within the protein for any future use as in vivo probes, for instance. In this work, we propose a simple and reliable fluorescence based technique measuring the hydrodynamic size of protein-templated gold nanoclusters. This technique uses the relation between the time resolved fluorescence anisotropy decay and the hydrodynamic volume, through the rotational correlation time. We determine the molecular size of protein-directed AuNCs, with protein templates of increasing sizes, e.g. insulin, lysozyme, and bovine serum albumin (BSA). The comparison of sizes obtained by other techniques (e.g. dynamic light scattering and small-angle X-ray scattering) between bare and gold clusters containing proteins allows us to address the volume changes induced either by conformational changes (for BSA) or the formation of protein dimers (for insulin and lysozyme) during cluster formation and incorporation.

Accelerating atomic structure search with cluster regularization

NASA Astrophysics Data System (ADS)

Sørensen, K. H.; Jørgensen, M. S.; Bruix, A.; Hammer, B.

2018-06-01

We present a method for accelerating the global structure optimization of atomic compounds. The method is demonstrated to speed up the finding of the anatase TiO2(001)-(1 × 4) surface reconstruction within a density functional tight-binding theory framework using an evolutionary algorithm. As a key element of the method, we use unsupervised machine learning techniques to categorize atoms present in a diverse set of partially disordered surface structures into clusters of atoms having similar local atomic environments. Analysis of more than 1000 different structures shows that the total energy of the structures correlates with the summed distances of the atomic environments to their respective cluster centers in feature space, where the sum runs over all atoms in each structure. Our method is formulated as a gradient based minimization of this summed cluster distance for a given structure and alternates with a standard gradient based energy minimization. While the latter minimization ensures local relaxation within a given energy basin, the former enables escapes from meta-stable basins and hence increases the overall performance of the global optimization.

The MUC1 Ectodomain: A Novel and Efficient Target for Gold Nanoparticle Clustering and Vapor Nanobubble Generation

PubMed Central

Danysh, Brian P.; Constantinou, Pamela E.; Lukianova-Hleb, Ekaterina Y.; Lapotko, Dmitri O.; Carson, Daniel D.

2012-01-01

MUC1 is a large, heavily glycosylated transmembrane glycoprotein that is proposed to create a protective microenvironment in many adenocarcinomas. Here we compare MUC1 and the well studied cell surface receptor target, EGFR, as gold nanoparticle (AuNP) targets and their subsequent vapor nanobubble generation efficacy in the human epithelial cell line, HES. Although EGFR and MUC1 were both highly expressed in these cells, TEM and confocal images revealed MUC1 as a superior target for nanoparticle intracellular accumulation and clustering. The MUC1-targeted AuNP intracellular clusters also generated significantly larger vapor nanobubbles. Our results demonstrate the promising opportunities MUC1 offers to improve the efficacy of targeted nanoparticle based approaches. PMID:22916077

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

PubMed

Cheng, Daojian; Wang, Wenchuan; Huang, Shiping

2008-05-14

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

Chemisorbed monolayers of corannulene penta-thioethers on gold.

PubMed

Angelova, Polina; Solel, Ephrath; Parvari, Galit; Turchanin, Andrey; Botoshansky, Mark; Gölzhäuser, Armin; Keinan, Ehud

2013-02-19

Penta(tert-butylthio)corannulene and penta(4-dimethylaminophenylthio)corannulene form highly stable monolayers on gold surfaces, as indicated by X-ray photoelectron spectroscopy (XPS). Formation of these homogeneous monolayers involves multivalent coordination of the five sulfur atoms to gold with the peripheral alkyl or aryl substituents pointing away from the surface. No dissociation of C-S bonds upon binding could be observed at room temperature. Yet, the XPS experiments reveal strong chemical bonding between the thioether groups and gold. Temperature-dependent XPS study shows that the thermal stability of the monolayers is higher than the typical stability of self-assembled monolayers (SAMs) of thiolates on gold.

Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds.

PubMed

Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

2015-04-22

Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

Two-dimensional gold nanostructures with high activity for selective oxidation of carbon-hydrogen bonds

NASA Astrophysics Data System (ADS)

Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

2015-04-01

Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold-gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon-hydrogen bonds with molecular oxygen.

Generalized Breit-Wigner treatment of molecular transport: Charging effects in a single decanedithiol molecule

NASA Astrophysics Data System (ADS)

Cabrera-Tinoco, Hugo Andres; Moreira, Augusto C. L.; de Melo, Celso P.

2018-05-01

We examine the relative contribution of ballistic and elastic cotunneling mechanisms to the charge transport through a single decanedithiol molecule linked to two terminal clusters of gold atoms. For this, we first introduced a conceptual model that permits a generalization of the Breit-Wigner scattering formalism where the cation, anion, and neutral forms of the molecule can participate with different probabilities of the charge transfer process, but in a simultaneous manner. We used a density functional theory treatment and considered the fixed geometry of each charge state to calculate the corresponding eigenvalues and eigenvectors of the extended system for different values of the external electric field. We have found that for the ballistic transport the HOMO and LUMO of the neutral species play a key role, while the charged states give a negligible contribution. On the other hand, an elastic cotunneling charge transfer can occur whenever a molecular orbital (MO) of the cation or anion species, even if localized in just one side of the molecule-gold clusters complex, has energy close to that of a delocalized MO of the neutral species. Under these conditions, a conduction channel is formed throughout the entire system, in a process that is controlled by the degree of resonance between the MOs involved. Our results indicate that while different charge transfer mechanisms contribute to the overall charge transport, quantum effects such as avoided-crossing situations between relevant frontier MOs can be of special importance. In these specific situations, the interchange of spatial localization of two MOs involved in the crossing can open a new channel of charge transfer that otherwise would not be available.

Correlation between the resistivity and the atomic clusters in liquid Cu-Sn alloys

NASA Astrophysics Data System (ADS)

Jia, Peng; Zhang, Jinyang; Hu, Xun; Li, Cancan; Zhao, Degang; Teng, XinYing; Yang, Cheng

2018-05-01

The liquid structure of CuxSn100-x (x = 0, 10, 20, 33, 40, 50, 60, 75, 80 and 100) alloys with atom percentage were investigated with resistivity and viscosity methods. It can be found from the resistivity data that the liquid Cu75Sn25 and Cu80Sn20 alloys had a negative temperature coefficient of resistivity (TCR), and liquid Cu75Sn25 alloy had a minimum value of -9.24 μΩ cm K-1. While the rest of liquid Cu-Sn alloys had a positive TCR. The results indicated that the Cu75Sn25 atomic clusters existed in Cu-Sn alloys. In addition, the method of calculating the percentage of Cu75Sn25 atomic clusters was established on the basis of resistivity theory and the law of conservation of mass. The Cu75Sn25 alloy had a maximum volume of the atomic clusters and a highest activation energy. The results further proved the existence of Cu75Sn25 atomic clusters. Furthermore, the correlation between the liquid structure and the resistivity was established. These results provide a useful reference for the investigation of liquid structure via the sensitive physical properties to the liquid structure.

Impact-parameter dependence of the energy loss of fast molecular clusters in hydrogen

NASA Astrophysics Data System (ADS)

Fadanelli, R. C.; Grande, P. L.; Schiwietz, G.

2008-03-01

The electronic energy loss of molecular clusters as a function of impact parameter is far less understood than atomic energy losses. For instance, there are no analytical expressions for the energy loss as a function of impact parameter for cluster ions. In this work, we describe two procedures to evaluate the combined energy loss of molecules: Ab initio calculations within the semiclassical approximation and the coupled-channels method using atomic orbitals; and simplified models for the electronic cluster energy loss as a function of the impact parameter, namely the molecular perturbative convolution approximation (MPCA, an extension of the corresponding atomic model PCA) and the molecular unitary convolution approximation (MUCA, a molecular extension of the previous unitary convolution approximation UCA). In this work, an improved ansatz for MPCA is proposed, extending its validity for very compact clusters. For the simplified models, the physical inputs are the oscillators strengths of the target atoms and the target-electron density. The results from these models applied to an atomic hydrogen target yield remarkable agreement with their corresponding ab initio counterparts for different angles between cluster axis and velocity direction at specific energies of 150 and 300 keV/u.

Autoionization following nanoplasma formation in atomic and molecular clusters

NASA Astrophysics Data System (ADS)

Schütte, Bernd; Lahl, Jan; Oelze, Tim; Krikunova, Maria; Vrakking, Marc J. J.; Rouzée, Arnaud

2016-05-01

Nanoplasmas resulting from the ionization of nano-scale particles by intense laser pulses are typically described by quasiclassical models, where electron emission is understood to take place via thermal processes. Recently, we discovered that, following the interaction of intense near-infrared (NIR) laser pulses with molecular oxygen clusters, electron emission from nanoplasmas can also occur from atomic bound states via autoionization [Schütte et al., Phys. Rev. Lett. 114, 123002 (2015)]. Here we extend these studies and demonstrate that the formation and decay of doubly-excited atoms and ions is a very common phenomenon in nanoplasmas. We report on the observation of autoionization involving spin-orbit excited states in molecular oxygen and carbon dioxide clusters as well as in atomic krypton and xenon clusters ionized by intense NIR pulses, for which we find clear bound-state signatures in the electron kinetic energy spectra. By applying terahertz (THz) streaking, we show that the observed autoionization processes take place on a picosecond to nanosecond timescale after the interaction of the NIR laser pulse with the clusters. Contribution to the Topical Issue "Atomic Cluster Collisions (7th International Symposium)", edited by Gerardo Delgado Barrio, Andrey Solov'Yov, Pablo Villarreal, Rita Prosmiti.

Phase stability and electronic structure of UMo2Al20: A first-principles study

NASA Astrophysics Data System (ADS)

Liu, Peng-Chuang; Xian, Ya-Jiang; Wang, Xin; Zhang, Yu-Ting; Zhang, Peng-Cheng

2017-09-01

In this paper, the phase stability of UMo2Al20 was explored using cluster formula in combination with first-principles calculations. Cluster formula analysis uncovered that the compound was composed of two principal clusters, i.e. [Mo-Al12] and [U-Al16]. The electronic interactions between U, Mo and Al atoms in this compound were discussed using elastic property, Bader charges and energy-resolved local bonding analysis, as well as the electronic interactions between Mo and Al atoms in [Mo-Al12] cluster and between U and Al atoms in [U-Al16] cluster. It revealed that UMo2Al20 satisfied the mechanical stability criterion for cubic system, and exhibited near ionic bonding character with weak bonding directionality. The calculations within both standard DFT and HSE frameworks demonstrated that U and Al atoms acted as an electron donor while Mo atoms acted as electron acceptor. The intrinsic stability of UMo2Al20 mainly stemmed from the bonding states of Mo-Al bonds and Al-Al bonds in [Mo-Al12] cluster. These calculations provide a further insight on the CeCr2Al20-type ternary compounds.

In-situ suspended aggregate microextraction of gold nanoparticles from water samples and determination by electrothermal atomic absorption spectrometry.

PubMed

Choleva, Tatiana G; Kappi, Foteini A; Tsogas, George Z; Vlessidis, Athanasios G; Giokas, Dimosthenis L

2016-05-01

This work describes a new method for the extraction and determination of gold nanoparticles in environmental samples by means of in-situ suspended aggregate microextraction and electrothermal atomic absorption spectrometry. The method relies on the in-situ formation of a supramolecular aggregate phase through ion-association between a cationic surfactant and a benzene sulfonic acid derivative. Gold nanoparticles are physically entrapped into the aggregate phase which is separated from the bulk aqueous solution by vacuum filtration on the surface of a cellulose filter in the form of a thin film. The film is removed from the filter surface and is dissociated into an acidified methanolic solution which is used for analysis. Under the optimized experimental conditions, gold nanoparticles can be efficiently extracted from water samples with recovery rates between 81.0-93.3%, precision 5.4-12.0% and detection limits as low as 75femtomolL(-1) using only 20mL of sample volume. The satisfactory analytical features of the method along with the simplicity indicate the efficiency of this new approach to adequately collect and extract gold nanoparticle species from water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Direct writing of gold nanostructures with an electron beam: On the way to pure nanostructures by combining optimized deposition with oxygen-plasma treatment

PubMed Central

Belić, Domagoj; Shawrav, Mostafa M; Bertagnolli, Emmerich

2017-01-01

This work presents a highly effective approach for the chemical purification of directly written 2D and 3D gold nanostructures suitable for plasmonics, biomolecule immobilisation, and nanoelectronics. Gold nano- and microstructures can be fabricated by one-step direct-write lithography process using focused electron beam induced deposition (FEBID). Typically, as-deposited gold nanostructures suffer from a low Au content and unacceptably high carbon contamination. We show that the undesirable carbon contamination can be diminished using a two-step process – a combination of optimized deposition followed by appropriate postdeposition cleaning. Starting from the common metal-organic precursor Me2-Au-tfac, it is demonstrated that the Au content in pristine FEBID nanostructures can be increased from 30 atom % to as much as 72 atom %, depending on the sustained electron beam dose. As a second step, oxygen-plasma treatment is established to further enhance the Au content in the structures, while preserving their morphology to a high degree. This two-step process represents a simple, feasible and high-throughput method for direct writing of purer gold nanostructures that can enable their future use for demanding applications. PMID:29259868

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

PubMed

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

2015-12-18

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

Evaluation of Solute Clusters Associated with Bake-Hardening Response in Isothermal Aged Al-Mg-Si Alloys Using a Three-Dimensional Atom Probe

NASA Astrophysics Data System (ADS)

Aruga, Yasuhiro; Kozuka, Masaya; Takaki, Yasuo; Sato, Tatsuo

2014-12-01

Temporal changes in the number density, size distribution, and chemical composition of clusters formed during natural aging at room temperature and pre-aging at 363 K (90 °C) in an Al-0.62Mg-0.93Si (mass pct) alloy were evaluated using atom probe tomography. More than 10 million atoms were examined in the cluster analysis, in which about 1000 clusters were obtained for each material after various aging treatments. The statistically proven records show that both number density and the average radius of clusters in pre-aged materials are larger than in naturally aged materials. It was revealed that the fraction of clusters with a low Mg/Si ratio after natural aging for a short time is higher than with other aging treatments, regardless of cluster size. This indicates that Si-rich clusters form more easily after short-period natural aging, and that Mg atoms can diffuse into the clusters or possibly form another type of Mg-Si cluster after prolonged natural aging. The formation of large clusters with a uniform Mg/Si ratio is encouraged by pre-aging. It can be concluded that an increase of small clusters with various Mg/Si ratios does not promote the bake-hardening (BH) response, whereas large clusters with a uniform Mg/Si ratio play an important role in hardening during the BH treatment at 443 K (170 °C).

Growth of Ni nanoclusters on irradiated graphene: a molecular dynamics study.

PubMed

Valencia, F J; Hernandez-Vazquez, E E; Bringa, E M; Moran-Lopez, J L; Rogan, J; Gonzalez, R I; Munoz, F

2018-04-23

We studied the soft landing of Ni atoms on a previously damaged graphene sheet by means of molecular dynamics simulations. We found a monotonic decrease of the cluster frequency as a function of its size, but few big clusters comprise an appreciable fraction of the total number of Ni atoms. The aggregation of Ni atoms is also modeled by means of a simple phenomenological model. The results are in clear contrast with the case of hard or energetic landing of metal atoms, where there is a tendency to form mono-disperse metal clusters. This behavior is attributed to the high diffusion of unattached Ni atoms, together with vacancies acting as capture centers. The findings of this work show that a simple study of the energetics of the system is not enough in the soft landing regime, where it is unavoidable to also consider the growth process of metal clusters.

Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

NASA Technical Reports Server (NTRS)

Slaby, Scott M.; Ewing, David W.; Zehe, Michael J.

1997-01-01

The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

The interaction between atomic displacement cascades and tilt symmetrical grain boundaries in α-zirconium

NASA Astrophysics Data System (ADS)

Kapustin, P.; Svetukhin, V.; Tikhonchev, M.

2017-06-01

The atomic displacement cascade simulations near symmetric tilt grain boundaries (GBs) in hexagonal close packed-Zirconium were considered in this paper. Further defect structure analysis was conducted. Four symmetrical tilt GBs -∑14?, ∑14? with the axis of rotation [0 0 0 1] and ∑32?, ∑32? with the axis of rotation ? - were considered. The molecular dynamics method was used for atomic displacement cascades' simulation. A tendency of the point defects produced in the cascade to accumulate near the GB plane, which was an obstacle to the spread of the cascade, was discovered. The results of the point defects' clustering produced in the cascade were obtained. The clusters of both types were represented mainly by single point defects. At the same time, vacancies formed clusters of a large size (more than 20 vacancies per cluster), while self-interstitial atom clusters were small-sized.

Sequential desorption energy of hydrogen from nickel clusters

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

Deepika,; Kumar, Rakesh, E-mail: rakesh@iitrpr.ac.in; R, Kamal Raj.

2015-06-24

We report reversible Hydrogen adsorption on Nickel clusters, which act as a catalyst for solid state storage of Hydrogen on a substrate. First-principles technique is employed to investigate the maximum number of chemically adsorbed Hydrogen molecules on Nickel cluster. We observe a maximum of four Hydrogen molecules adsorbed per Nickel atom, but the average Hydrogen molecules adsorbed per Nickel atom decrease with cluster size. The dissociative chemisorption energy per Hydrogen molecule and sequential desorption energy per Hydrogen atom on Nickel cluster is found to decrease with number of adsorbed Hydrogen molecules, which on optimization may help in economical storage andmore » regeneration of Hydrogen as a clean energy carrier.« less

Nanoscale Structural Changes Upon Electrooxidation of Au(111) as Probed by Potentiodynamic Scanning Tunneling Microscopy

DTIC Science & Technology

1994-02-01

electrochemical formation and removal of oxide films is of broadbased practical as well as fundamental importance. Studies of noble metals, such as gold and...atomic level. At the current state of development of STM, monocrystalline gold electrodes provide efficacious choices of systems, partly in view of...several in-situ STM studies have focussed on the surface morphological changes attending oxidation and rereduction of single-crystal gold electrodes

Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate.

PubMed

Schauer, Andrew J; Kunasek, Shelley A; Sofen, Eric D; Erbland, Joseph; Savarino, Joel; Johnson, Ben W; Amos, Helen M; Shaheen, Robina; Abaunza, Mariana; Jackson, Terri L; Thiemens, Mark H; Alexander, Becky

2012-09-30

Triple oxygen isotopes of sulfate and nitrate are useful metrics for the chemistry of their formation. Existing measurement methods, however, do not account for oxygen atom exchange with quartz during the thermal decomposition of sulfate. We present evidence for oxygen atom exchange, a simple modification to prevent exchange, and a correction for previous measurements. Silver sulfates and silver nitrates with excess (17)O were thermally decomposed in quartz and gold (for sulfate) and quartz and silver (for nitrate) sample containers to O(2) and byproducts in a modified Temperature Conversion/Elemental Analyzer (TC/EA). Helium carries O(2) through purification for isotope-ratio analysis of the three isotopes of oxygen in a Finnigan MAT253 isotope ratio mass spectrometer. The Δ(17)O results show clear oxygen atom exchange from non-zero (17)O-excess reference materials to zero (17)O-excess quartz cup sample containers. Quartz sample containers lower the Δ(17)O values of designer sulfate reference materials and USGS35 nitrate by 15% relative to gold or silver sample containers for quantities of 2-10 µmol O(2). Previous Δ(17)O measurements of sulfate that rely on pyrolysis in a quartz cup have been affected by oxygen exchange. These previous results can be corrected using a simple linear equation (Δ(17)O(gold) = Δ(17)O(quartz) * 1.14 + 0.06). Future pyrolysis of silver sulfate should be conducted in gold capsules or corrected to data obtained from gold capsules to avoid obtaining oxygen isotope exchange-affected data. Copyright © 2012 John Wiley & Sons, Ltd.

Structure–activity relationships for biodistribution, pharmacokinetics, and excretion of atomically precise nanoclusters in a murine model†

PubMed Central

Wong, O. Andrea; Hansen, Ryan J.; Ni, Thomas W.; Heinecke, Christine L.; Compel, W. Scott; Gustafson, Daniel L.

2013-01-01

The absorption, distribution, metabolism and excretion (ADME) and pharmacokinetic (PK) properties of inorganic nanoparticles with hydrodynamic diameters between 2 and 20 nm are presently unpredictable. It is unclear whether unpredictable in vivo properties and effects arise from a subset of molecules in a nanomaterials preparation, or if the ADME/PK properties are ensemble properties of an entire preparation. Here we characterize the ADME/PK properties of atomically precise preparations of ligand protected gold nanoclusters in a murine model system. We constructed atomistic models and tested in vivo properties for five well defined compounds, based on crystallographically resolved Au25(SR)18 and Au102(SR)44 nanoclusters with different (SR) ligand shells. To rationalize unexpected distribution and excretion properties observed for several clusters in this study and others, we defined a set of atomistic structure–activity relationships (SAR) for nanoparticles, which includes previously investigated parameters such as particle hydrodynamic diameter and net charge, and new parameters such as hydrophobic surface area and surface charge density. Overall we find that small changes in particle formulation can provoke dramatic yet potentially predictable changes in ADME/PK. PMID:24057086

Structure and reactivity of a mononuclear gold(II) complex

NASA Astrophysics Data System (ADS)

Preiß, Sebastian; Förster, Christoph; Otto, Sven; Bauer, Matthias; Müller, Patrick; Hinderberger, Dariush; Hashemi Haeri, Haleh; Carella, Luca; Heinze, Katja

2017-12-01

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

RBS, TEM and SEM Characterization of Gold Nanoclusters in TiO2(110)

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

Shutthanandan, V; Zhang, Yanwen; Wang, Chong M.

2004-05-01

Nucleation of gold nanoclusters in TiO2(110) single crystal using ion implantation and subsequent annealing were studied by Rutherford backscattering spectrometry /channeling (RBS/C), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Approximately 1000 Au2+/nm2 was implanted at room temperature in TiO2(110) substrates. TEM and SEM measurements revel that rounded nanoclusters were formed during the implantation. In contrast subsequent annealing in air for 10 hours at 1275 K promoted the formation of faceted (rectangular shaped) Au nano structures in TiO2. RBS channeling measurements further reveled that Au atoms randomly occupied in the host TiO2 lattice during the implantation. However, some ofmore » the gold atoms were moved into the Ti lattice position after annealing.« less

Comparison of Adsorbed Mercury Screening Method With Cold-Vapor Atomic Absorption Spectrophotometry for Determination of Mercury in Soil

NASA Technical Reports Server (NTRS)

Easterling, Donald F.; Hovanitz, Edward S.; Street, Kenneth W.

2000-01-01

A field screening method for the determination of elemental mercury in environmental soil samples involves the thermal desorption of the mercury from the sample onto gold and then the thermal desorption from the gold to a gold-film mercury vapor analyzer. This field screening method contains a large number of conditions that could be optimized for the various types of soils encountered. In this study, the conditions were optimized for the determination of mercury in silty clay materials, and the results were comparable to the cold-vapor atomic absorption spectrophotometric method of determination. This paper discusses the benefits and disadvantages of employing the field screening method and provides the sequence of conditions that must be optimized to employ this method of determination on other soil types.

Molecular ion yield enhancement induced by gold deposition in static secondary ion mass spectrometry

NASA Astrophysics Data System (ADS)

Wehbe, Nimer; Delcorte, Arnaud; Heile, Andreas; Arlinghaus, Heinrich F.; Bertrand, Patrick

2008-12-01

Static ToF-SIMS was used to evaluate the effect of gold condensation as a sample treatment prior to analysis. The experiments were carried out with a model molecular layer (Triacontane M = 422.4 Da), upon atomic (In +) and polyatomic (Bi 3+) projectile bombardment. The results indicate that the effect of molecular ion yield improvement using gold metallization exists only under atomic projectile impact. While the quasi-molecular ion (M+Au) + signal can become two orders of magnitude larger than that of the deprotonated molecular ion from the pristine sample under In + bombardment, it barely reaches the initial intensity of (M-H) + when Bi 3+ projectiles are used. The differences observed for mono- and polyatomic primary ion bombardment might be explained by differences in near-surface energy deposition, which influences the sputtering and ionization processes.

Structural, electronic, and magnetic properties of Y(n)O (n=2-14) clusters: Density functional study.

PubMed

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.

Green synthesis of stabilized spherical shaped gold nanoparticles using novel aqueous Elaeis guineensis (oil palm) leaves extract

NASA Astrophysics Data System (ADS)

Ahmad, Tausif; Bustam, Mohamad Azmi; Irfan, Muhammad; Moniruzzaman, Muhammad; Anwaar Asghar, Hafiz Muhammad; Bhattacharjee, Sekhar

2018-05-01

In the last decade, development of bioinspired protocols to synthesize gold nanoparticles (AuNPs) using plants and their extracts have been dealt by researchers due to their low cost, renewability and non-toxic features. A simple, cheap and ecofriendly method is reported to synthesize stabilized AuNPs of size 35-75 nm at room temperature using aqueous Elaeis guineensis (oil palm) leaves extract without addition of any external agent. Oil palm leaves mediated AuNPs were characterized using FTIR, UV-vis spectrophotometer, EDAX, XPS, FESEM, TEM, DLS and TGA. FTIR spectra results revealed contribution of phenolic, carboxylic, amines and amides in reduction of trivalent gold ions and stabilization of formed gold atoms. Reaction solution color change and UV-vis spectra confirmed reduction of gold ions to generate gold atoms. Reaction mechanism explained the role of phenolic compounds in reduction reaction using FTIR and UV-vis spectra results. EDAX and XPS results further validated the formation of metallic gold particles through bioreduction of gold ions. Crystal structure of metallic gold particles was confirmed through XRD peaks indexing to (111), (200), (220) and (311) planes. TEM and FESEM particles size measurements exhibited the formation of nanostructured AuNPs. Synthesis of well scattered and spherical shaped AuNPs was revealed through FESEM and TEM images. The excellent stability of AuNPs was shown through high negative zeta potential value (-14.7 ± 4.68 mV) and uniform dispersion in aqueous media. Our results disclosed the excellent potential of Elaeis guineensis (oil palm) leaves as reducing and stabilizing agents in green synthesis of well scattered spherical shaped AuNPs, which can be employed as strong candidates in medical drug delivery and industrial applications.

Unraveling the Planar-Globular Transition in Gold Nanoclusters through Evolutionary Search

DOE PAGES

Kinaci, Alper; Narayanan, Badri; Sen, Fatih G.; ...

2016-11-28

Au nanoclusters are of technological relevance for catalysis, photonics, sensors, and of fundamental scientific interest owing to planar to globular structural transformation at an anomalously high number of atoms i.e. in the range 12-14. The nature and causes of this transition remain a mystery. In order to unravel this conundrum, high throughput density functional theory (DFT) calculations, coupled with a global structural optimization scheme based on a modified genetic algorithm (GA) are conducted. Furthermore, more than 20,000 Au 12, Au 13, and Au 14 nanoclusters are evaluated. With any DFT functional, globular and planar structures coexist across the size rangemore » of interest. Contrary to what was previously believed, the planar-globular transition is gradual at room temperature rather than a sharp transition. The effects of anionicity, s-d band hybridization and long range interactions on the dimensional transition are quantified by using the structures adjacent to minima. Anionicity marginally changes the relative stability of the clusters. The degree of s-d hybridization is varied via changing the Hubbard U value which corroborate that s-d hybridization alone does not stabilize planar structures. van der Waals interactions, on the other hand, stabilize globular structures. Our results elucidate the balance between the different reasons of the dimensional transition in gold nanoclusters.« less

Synthesis of camptothecin-loaded gold nanomaterials

NASA Astrophysics Data System (ADS)

Xing, Zhimin; Liu, Zhiguo; Zu, Yuangang; Fu, Yujie; Zhao, Chunjian; Zhao, Xiuhua; Meng, Ronghua; Tan, Shengnan

2010-04-01

Camptothecin-loaded gold nanomaterials have been synthesized by the sodium borohydride reduction method under a strong basic condition. The obtained gold nanomaterials have been characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM) and UV-vis absorption spectroscopy. The camptothecin-loaded gold colloidal solution was very stable and can be stored for more than two months at room temperature without obvious changes. The color of the colloidal solution can change from wine red to purple and blue during the acidifying process. It was revealed that the release of camptothecin and the aggregation of gold nanoparticles can be controlled by tuning the solution pH. The present study implied that the gold nanomaterials can be used as the potential carrier for CPT delivery.

C 60 -induced Devil's Staircase transformation on a Pb/Si(111) wetting layer

DOE PAGES

Wang, Lin -Lin; Johnson, Duane D.; Tringides, Michael C.

2015-12-03

Density functional theory is used to study structural energetics of Pb vacancy cluster formation on C 60/Pb/Si(111) to explain the unusually fast and error-free transformations between the “Devil's Staircase” (DS) phases on the Pb/Si(111) wetting layer at low temperature (~110K). The formation energies of vacancy clusters are calculated in C 60/Pb/Si(111) as Pb atoms are progressively ejected from the initial dense Pb wetting layer. Vacancy clusters larger than five Pb atoms are found to be stable with seven being the most stable, while vacancy clusters smaller than five are highly unstable, which agrees well with the observed ejection rate ofmore » ~5 Pb atoms per C 60. Furthermore, the high energy cost (~0.8 eV) for the small vacancy clusters to form indicates convincingly that the unusually fast transformation observed experimentally between the DS phases, upon C 60 adsorption at low temperature, cannot be the result of single-atom random walk diffusion but of correlated multi-atom processes.« less

Theoretical studies on structural, magnetic, and spintronic characteristics of sandwiched Eu(n)COT(n+1) (n = 1-4) clusters.

PubMed

Zhang, Xiuyun; Ng, Man-Fai; Wang, Yanbiao; Wang, Jinlan; Yang, Shuo-Wang

2009-09-22

Europium (Eu)-cyclootetatrene (COT = C(8)H(8)) multidecker clusters (Eu(n)COT(n+1), n = 1-4) are studied by relativistic density functional theory calculations. These clusters are found to be thermodynamically stable with freely rotatable COT rings, and their total magnetic moments (MMs) increase linearly along with the number of Eu atoms. Each Eu atom contributes about 7 mu(B) to the cluster. Meanwhile, the internal COT rings have little MM contribution while the external COT rings have about 1 mu(B) MM aligned in opposite direction to that of the Eu atoms. The total MM of the Eu(n)COT(n+1) clusters can thus be generalized as 7n - 2 mu(B) where n is the number of Eu atoms. Besides, the ground states of these clusters are ferromagnetic and energetically competitive with the antiferromagnetic states, meaning that their spin states are very unstable, especially for larger clusters. More importantly, we uncover an interesting bonding characteristic of these clusters in which the interior ionic structure is capped by two hybrid covalent-ionic terminals. We suggest that such a characteristic makes the Eu(n)COT(n+1) clusters extremely stable. Finally, we reveal that for the positively charged clusters, the hybrid covalent-ionic terminals will tip further toward the interior part of the clusters to form deeper covalent-ionic caps. In contrast, the negatively charged clusters turn to pure ionic structures.

Simulation and Implementation of a Morphology-Tuned Gold Nano-Islands Integrated Plasmonic Sensor

PubMed Central

Ozhikandathil, Jayan; Packirisamy, Muthukumaran

2014-01-01

This work presents simulation, analysis and implementation of morphology tuning of gold nano-island structures deposited by a novel convective assembly technique. The gold nano-islands were simulated using 3D Finite-Difference Time-Domain (FDTD) techniques to investigate the effect of morphological changes and adsorption of protein layers on the localized surface plasmon resonance (LSPR) properties. Gold nano-island structures were deposited on glass substrates by a novel and low-cost convective assembly process. The structure formed by an uncontrolled deposition method resulted in a nano-cluster morphology, which was annealed at various temperatures to tune the optical absorbance properties by transforming the nano-clusters to a nano-island morphology by modifying the structural shape and interparticle separation distances. The dependence of the size and the interparticle separation distance of the nano-islands on the LSPR properties were analyzed in the simulation. The effect of adsorption of protein layer on the nano-island structures was simulated and a relation between the thickness and the refractive index of the protein layer on the LSPR peak was presented. Further, the sensitivity of the gold nano-island integrated sensor against refractive index was computed and compared with the experimental results. PMID:24932868

Preparation of gold nanocluster bioconjugates for electron microscopy.

PubMed

Heinecke, Christine L; Ackerson, Christopher J

2013-01-01

In this chapter, we describe types of gold nanoparticle-biomolecule conjugates and their use in electron microscopy. Included are two detailed protocols for labeling an IgG antibody with gold monolayer protected clusters. The first approach is a direct bonding approach that utilizes the ligand place exchange reaction. The second approach describes NHS-EDC coupling of Au(144)(pMBA)(60) with IgG. Also included are various characterization techniques for determining labeling efficiency.

Helium cluster isolation spectroscopy

NASA Astrophysics Data System (ADS)

Higgins, John Paul

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

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

PubMed

Aguado, Andrés; López, José M

2010-09-07

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

Effect of charge and composition on the structural fluxionality and stability of nine atom tin-bismuth Zintl analogues.

PubMed

Gupta, Ujjwal; Reber, Arthur C; Clayborne, Penee A; Melko, Joshua J; Khanna, Shiv N; Castleman, A W

2008-12-01

Synergistic studies of bismuth doped tin clusters combining photoelectron spectra with first principles theoretical investigations establish that highly charged Zintl ions, observed in the condensed phase, can be stabilized as isolated gas phase clusters through atomic substitution that preserves the overall electron count but reduces the net charge and thereby avoids instability because of coulomb repulsion. Mass spectrometry studies reveal that Sn(8)Bi(-), Sn(7)Bi(2)(-), and Sn(6)Bi(3)(-) exhibit higher abundances than neighboring species, and photoelectron spectroscopy show that all of these heteroatomic gas phase Zintl analogues (GPZAs) have high adiabatic electron detachment energies. Sn(6)Bi(3)(-) is found to be a particularly stable cluster, having a large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap. Theoretical calculations demonstrate that the Sn(6)Bi(3)(-) cluster is isoelectronic with the well know Sn(9)(-4) Zintl ion; however, the fluxionality reported for Sn(9)(-4) is suppressed by substituting Sn atoms with Bi atoms. Thus, while the electronic stability of the clusters is dominated by electron count, the size and position of the atoms affects the dynamics of the cluster as well. Substitution with Bi enlarges the cage compared with Sn(9)(-4) making it favorable for endohedral doping, findings which suggest that these cages may find use for building blocks of cluster assembled materials.

Probing cluster surface morphology by cryo spectroscopy of N2 on cationic nickel clusters

NASA Astrophysics Data System (ADS)

Dillinger, Sebastian; Mohrbach, Jennifer; Niedner-Schatteburg, Gereon

2017-11-01

We present the cryogenic (26 K) IR spectra of selected [Nin(N2)m]+ (n = 5-20, m = 1 - mmax), which strongly reveal n- and m-dependent features in the N2 stretching region, in conjunction with density functional theory modeling of some of these findings. The observed spectral features allow us to refine the kinetic classification [cf. J. Mohrbach, S. Dillinger, and G. Niedner-Schatteburg, J. Chem. Phys. 147, 184304 (2017)] and to define four classes of structure related surface adsorption behavior: Class (1) of Ni6+, Ni13+, and Ni19+ are highly symmetrical clusters with all smooth surfaces of equally coordinated Ni atoms that entertain stepwise N2 adsorption up to stoichiometric N2:Nisurface saturation. Class (2) of Ni12+ and Ni18+ are highly symmetrical clusters minus one. Their relaxed smooth surfaces reorganize by enhanced N2 uptake toward some low coordinated Ni surface atoms with double N2 occupation. Class (3) of Ni5+ and Ni7+ through Ni11+ are small clusters of rough surfaces with low coordinated Ni surface atoms, and some reveal semi-internal Ni atoms of high next-neighbor coordination. Surface reorganization upon N2 uptake turns rough into rough surface by Ni atom migration and turns octahedral based structures into pentagonal bipyramidal structures. Class (4) of Ni14+ through Ni17+ and Ni20+ are large clusters with rough and smooth surface areas. They possess smooth icosahedral surfaces with some proximate capping atom(s) on one hemisphere of the icosahedron with the other one largely unaffected.

Rainbow Plasmonic Nanobubbles: Synergistic Activation of Gold Nanoparticle Clusters

PubMed Central

Lukianova-Hleb, Ekaterina Y; Oginsky, Alexander O; Shenefelt, Derek L; Drezek, Rebekah A; Hafner, Jason H; Farach-Carson, Mary C; Lapotko, Dmitri O

2011-01-01

The synergistic physical and biological effects of selective targeting and activation of plasmonic nanoparticles were studied for a transient vapor nanobubble mode. Simultaneous optical activation of two plasmon resonances in multi-nanoparticle clusters significantly improved the selectivity and efficacy of the nanobubble generation through and was termed “rainbow plasmonic nanobubbles.” The rainbow nanobubble mechanism has been studied in water and in living cells in vitro. This mechanism provided maximal selectivity of the nanobubble generation in both models and therefore, can the therapeutic selectivity and optical contrast of gold nanoparticles in a heterogeneous physiological microenvironment at cell level. PMID:21804947

Visualizing gold nanoparticle uptake in live cells with liquid scanning transmission electron microscopy.

PubMed

Peckys, Diana B; de Jonge, Niels

2011-04-13

The intracellular uptake of 30 nm diameter gold nanoparticles (Au-NPs) was studied at the nanoscale in pristine eukaryotic cells. Live COS-7 cells were maintained in a microfluidic chamber and imaged using scanning transmission electron microscopy. A quantitative image analysis showed that Au-NPs bound to the membranes of vesicles, possibly lysosomes, and occupied 67% of the available surface area. The vesicles accumulated to form a micrometer-sized cluster after 24 h of incubation. Two clusters were analyzed and found to consist of 117 ± 9 and 164 ± 4 NP-filled vesicles.

Cluster perturbation theory for calculation of electronic properties of ensembles of metal nanoclusters

NASA Astrophysics Data System (ADS)

Zhumagulov, Yaroslav V.; Krasavin, Andrey V.; Kashurnikov, Vladimir A.

2018-05-01

The method is developed for calculation of electronic properties of an ensemble of metal nanoclusters with the use of cluster perturbation theory. This method is applied to the system of gold nanoclusters. The Greens function of single nanocluster is obtained by ab initio calculations within the framework of the density functional theory, and then is used in Dyson equation to group nanoclusters together and to compute the Greens function as well as the electron density of states of the whole ensemble. The transition from insulator state of a single nanocluster to metallic state of bulk gold is observed.

Au102(p-MBA)44 nanocluster, a superatom suitable for bio-applications

NASA Astrophysics Data System (ADS)

Häkkinen, Hannu

2016-12-01

Inorganic nanoparticles, including metals, semiconductors and metal oxides, comprise a common set of structures exhibiting an inorganic core `passivated' by an organic shell. Ligated inorganic nanoparticles currently provoke widespread fundamental interest in their structural, optical and magnetic properties, which differ fundamentally from bulk counterparts. These nanomaterials are already finding applications in biology, medicine, solar energy, and display panels. 1-6 Conjugating inorganic nanoparticles with organic (biological) material for applications in nanobiology and nanomedicine creates significant challenges for controlling the effects on the environment, particularly regarding toxicity. Chemical reactions of almost identical substances can lead to drastically different outcomes in a biological environment. As a simplistic example one can consider the case of ethanol vs. methanol. Ethanol (CH3CH2OH) can be consumed by humans while even a small dose of methanol (CH3OH) can be fatal, yet the difference between the molecular formulas of these substances is just the smallest meaningful hydrocarbon unit CH2. This illuminates the fact that minute differences in the size and structure of molecular compounds can have drastically different end effects in a biological environment due to the way the compounds start to react with the environment. In recent years, gold nanoparticles covered by ligands that make them water-soluble have become a popular target for research in nanobiology and nanomedicine. 1,2 In most cases up to now, colloidal nanoparticles (5 nm and larger) have been used for sensing and photothermal applications. However, this class of gold-based nanomaterials still has large uncertainties regarding the atomic composition of the nanoparticle surface and particularly the metal-ligand interface. A simple example illuminates the facts. The density of atoms in the fcc lattice of macrosocopic gold metal is about 59 atoms/nm3. This means that a spherical colloidal gold nanoparticle with radius of 5 nm has about 3850 atoms. Even in a sample of extremely narrow range of diameters ranging from 5.25 nm to 4.75 nm (+/- 5% of the mean) the particles will have anywhere between 3300 and 4750 atoms, and their surface area can differ up to 20%. It is clear that such particles are not suitable for applications that would need molecularly precise size, structure and shape of the metal nanoparticle and precise knowledge of the composition of its organic surface. In 1994, Brust, Schiffrin and coworkers published a landmark synthesis recipe on how to prepare thiol(ate)-stabilized small gold nanoparticles of about 2 nm in size. 7 This paper started a completely new field which has now matured to studies of several "atom-precise" or "molecularly precise" gold-thiolate compounds for which molecular formulas Aux(SR)y can be written and the substances in most cases have a good ambient stability allowing for storage and later use.8 Atomic structures of the gold core and the thiolate layer have been resolved for many of these compounds, opening doors for detailed density functional theory (DFT) simulations of their properties. This Perspective discusses developments in understanding the structure and properties of one of such compounds, which can be used for site-specific (or "molecularly precise") targeting of capsid proteins on a viral surface.

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

NASA Astrophysics Data System (ADS)

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

2000-12-01

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

A porphyrin complex of Gold(I): (Phosphine)gold(I) azides as cation precursors

PubMed Central

Partyka, David V.; Robilotto, Thomas J.; Zeller, Matthias; Hunter, Allen D.; Gray, Thomas G.

2008-01-01

A silver- and Brönsted acid-free protocol for generating the (tricyclohexylphosphine)gold(I) cation from the corresponding azide complexes is disclosed. The gold(I) cations so liberated are trapped by complexation with octaethylporphyrin. The first structurally authenticated gold(I) porphyrin complex crystallizes with formula C72H112Au2F12N4P2Sb2, space group C2/c, a = 21.388 (4), b = 19.679 (4), c = 19.231 (3) Å; β = 111.030 (3)°. Solution spectroscopic studies indicate that the di-gold complex fragments on dissolution in organic solvents. Approximate density-functional theory calculations find an electrostatic origin for the binding of two gold(I) centers to the unprotonated nitrogen atoms, despite greater orbital density on the porphyrin meso carbons. PMID:18780788

Spectrometric characteristics and tumor-affinity of a novel photosensitizer: mono-l-aspartyl aurochlorin e6 (Au-NPe6).

PubMed

Ishizumi, Taichiro; Aizawa, Katsuo; Tsuchida, Takaaki; Okunaka, Tetsuya; Kato, Harubumi

2004-12-01

Photodiagnosis and photodynamic therapy with photosensitizers can be indicated only for tumors of the superficial type, because these approaches utilizing visible light are limited by said light penetrability. To overcome this disadvantage, we innovated a novel photosensitizer, mono-l-aspartyl aurochlorin e6 (Au-NPe6), by incorporating a gold atom in the center of tetrapyrrole ring of NPe6 with a coordination bond. The gold atom in Au-NPe6 plays a role as an X-ray interceptor to detect deeply sited tumors. In this study, the absorption spectrum of novel Au-NPe6 in the diagnosis of deeply sited tumors was investigated, and the results were compared with the parent photosensitizer NPe6. Furthermore, the tumor-affinity of Au-NPe6 was evaluated using atomic absorption spectrometry. Despite the fact that both photosensitizers display a difference in the absorption spectrum, waveform changes of either photosensitizer with human serum albumin established a saturation point at a molar ratio of 1:1. The results indicate that it is highly possible that Au-NPe6 bound with albumin at a molar ratio (1:1) similar to NPe6. The accumulation rate of gold in tumor tissues was always significantly (p<0.05) higher than that in normal muscle tissues during the observation terms. Moreover, absorption spectra of tumor-tissue homogenates obtained from tumor-bearing mice after Au-NPe6 administration revealed a common peak with a wavelength equivalent to that of albumin-bond Au-NPe. This result suggests that the gold atom and NPe6 probably remained bonded even when Au-NPe6 was incorporated in tumor tissues.

Melting behavior of nanometer sized gold isomers

NASA Astrophysics Data System (ADS)

Liu, H. B.; Ascencio, J. A.; Perez-Alvarez, M.; Yacaman, M. J.

2001-09-01

In the present work, the melting behavior of nanometer sized gold isomers was studied using a tight-binding potential with a second momentum approximation. The cases of cuboctahedra, icosahedra, Bagley decahedra, Marks decahedra and star-like decahedra were considered. We calculated the temperature dependence of the total energy and volume during melting and the melting point for different types and sizes of clusters. In addition, the structural evolutions of the nanosized clusters during the melting transition were monitored and revealed. It is found that the melting process has three characteristic time periods for the intermediate nanosized clusters. The whole process includes surface disordering and reordering, followed by surface melting and a final rapid overall melting. This is a new observation, which it is in contrast with previous reports where surface melting is the dominant step.

Metal-atom Interactions and Clustering in Organic Semiconductor Systems

NASA Astrophysics Data System (ADS)

Tomita, Yoko; Park, Tea-uk; Nakayama, Takashi

2017-07-01

The interatomic interactions and clustering of metal atoms have been studied by first-principles calculations in graphene, pentacene, and polyacetylene as representative organic systems. It is shown that long-range repulsive Coulomb interaction appears between metal atoms with small electronegativity such as Al due to their ionization on host organic molecules, inducing their scattered distribution in organic systems. On the other hand, metal atoms with large electronegativity such as Au are weakly bonded to organic molecules, easily diffuse in molecular solids, and prefer to combine with each other owing to their short-range strong metallic-bonding interaction, promoting metal cluster generation in organic systems.

Electric-field control of conductance in metal quantum point contacts by electric-double-layer gating

NASA Astrophysics Data System (ADS)

Shibata, K.; Yoshida, K.; Daiguji, K.; Sato, H.; , T., Ii; Hirakawa, K.

2017-10-01

An electric-field control of quantized conductance in metal (gold) quantum point contacts (QPCs) is demonstrated by adopting a liquid-gated electric-double-layer (EDL) transistor geometry. Atomic-scale gold QPCs were fabricated by applying the feedback-controlled electrical break junction method to the gold nanojunction. The electric conductance in gold QPCs shows quantized conductance plateaus and step-wise increase/decrease by the conductance quantum, G0 = 2e2/h, as EDL-gate voltage is swept, demonstrating a modulation of the conductance of gold QPCs by EDL gating. The electric-field control of conductance in metal QPCs may open a way for their application to local charge sensing at room temperature.

Comparative Study of the Binding of Concanavalin A to Self-Assembled Monolayers Containing a Thiolated α-Mannoside on Flat Gold and on Nanoporous Gold

PubMed Central

Pandey, Binod; Tan, Yih Horng; Fujikawa, Kohki; Demchenko, Alexei V.

2013-01-01

We have prepared SAMs containing 8-mercaptooctyl α-D-mannopyranoside, either as a single component or in mixed SAMs with n-octanethiol on flat gold surfaces and on nanoporous gold. Electrochemical impedance spectroscopy showed that the mixed SAMs on flat gold surfaces showed the highest Con A binding near 1:9 solution molar ratio of thiolatedα-mannoside to n-octanethiol whereas those on NPG showed the highest response at 1:19 solution molar ratio of thiolated α-mannoside to n-octanethiol. Atomic force microscopy was employed to image the monolayers, and also to image the bound Con A protein. PMID:23519474

Classification Order of Surface-Confined Intermixing at Epitaxial Interface

NASA Astrophysics Data System (ADS)

Michailov, M.

The self-organization phenomena at epitaxial interface hold special attention in contemporary material science. Being relevant to the fundamental physical problem of competing, long-range and short-range atomic interactions in systems with reduced dimensionality, these phenomena have found exacting academic interest. They are also of great technological importance for their ability to bring spontaneous formation of regular nanoscale surface patterns and superlattices with exotic properties. The basic phenomenon involved in this process is surface diffusion. That is the motivation behind the present study which deals with important details of diffusion scenarios that control the fine atomic structure of epitaxial interface. Consisting surface imperfections (terraces, steps, kinks, and vacancies), the interface offers variety of barriers for surface diffusion. Therefore, the adatoms and clusters need a certain critical energy to overcome the corresponding diffusion barriers. In the most general case the critical energies can be attained by variation of the system temperature. Hence, their values define temperature limits of system energy gaps associated with different diffusion scenarios. This systematization imply classification order of surface alloying: blocked, incomplete, and complete. On that background, two diffusion problems, related to the atomic-scale surface morphology, will be discussed. The first problem deals with diffusion of atomic clusters on atomically smooth interface. On flat domains, far from terraces and steps, we analyzed the impact of size, shape, and cluster/substrate lattice misfit on the diffusion behavior of atomic clusters (islands). We found that the lattice constant of small clusters depends on the number N of building atoms at 1 < N ≤ 10. In heteroepitaxy, this effect of variable lattice constant originates from the enhanced charge transfer and the strong influence of the surface potential on cluster atomic arrangement. At constant temperature, the variation of the lattice constant leads to variable misfit which affects the island migration. The cluster/substrate commensurability influences the oscillation behavior of the diffusion coefficient caused by variation in the cluster shape. We discuss the results in a physical model that implies cluster diffusion with size-dependent cluster/substrate misfit. The second problem is devoted to diffusion phenomena in the vicinity of atomic terraces on stepped or vicinal surfaces. Here, we develop a computational model that refines important details of diffusion behavior of adatoms accounting for the energy barriers at specific atomic sites (smooth domains, terraces, and steps) located on the crystal surface. The dynamic competition between energy gained by mixing and substrate strain energy results in diffusion scenario where adatoms form alloyed islands and alloyed stripes in the vicinity of terrace edges. Being in agreement with recent experimental findings, the observed effect of stripe and island alloy formation opens up a way regular surface patterns to be configured at different atomic levels on the crystal surface. The complete surface alloying of the entire interface layer is also briefly discussed with critical analysis and classification of experimental findings and simulation data.

Electronic and magnetic properties of small rhodium clusters

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

Soon, Yee Yeen; Yoon, Tiem Leong; Lim, Thong Leng

2015-04-24

We report a theoretical study of the electronic and magnetic properties of rhodium-atomic clusters. The lowest energy structures at the semi-empirical level of rhodium clusters are first obtained from a novel global-minimum search algorithm, known as PTMBHGA, where Gupta potential is used to describe the atomic interaction among the rhodium atoms. The structures are then re-optimized at the density functional theory (DFT) level with exchange-correlation energy approximated by Perdew-Burke-Ernzerhof generalized gradient approximation. For the purpose of calculating the magnetic moment of a given cluster, we calculate the optimized structure as a function of the spin multiplicity within the DFT framework.more » The resultant magnetic moments with the lowest energies so obtained allow us to work out the magnetic moment as a function of cluster size. Rhodium atomic clusters are found to display a unique variation in the magnetic moment as the cluster size varies. However, Rh{sub 4} and Rh{sub 6} are found to be nonmagnetic. Electronic structures of the magnetic ground-state structures are also investigated within the DFT framework. The results are compared against those based on different theoretical approaches available in the literature.« less

Structural and magnetic properties of FeGen-/0 (n = 3-12) clusters: Mass-selected anion photoelectron spectroscopy and density functional theory calculations

NASA Astrophysics Data System (ADS)

Deng, Xiao-Jiao; Kong, Xiang-Yu; Liang, Xiaoqing; Yang, Bin; Xu, Hong-Guang; Xu, Xi-Ling; Feng, Gang; Zheng, Wei-Jun

2017-12-01

The structural, electronic, and magnetic properties of FeGen-/0 (n = 3-12) clusters were investigated by using anion photoelectron spectroscopy in combination with density functional theory calculations. For both anionic and neutral FeGen (n = 3-12) clusters with n ≤ 7, the dominant structures are exohedral. The FeGe8-/0 clusters have half-encapsulated boat-shaped structures, and the opening of the boat-shaped structure is gradually covered by the additional Ge atoms to form Gen cage from n = 9 to 11. The structures of FeGe10-/0 can be viewed as two Ge atoms symmetrically capping the opening of the boat-shaped structure of FeGe8, and those of FeGe12-/0 are distorted hexagonal prisms with the Fe atom at the center. Natural population analysis shows that there is an electron transfer from the Ge atoms to the Fe atom at n = 8-12. The total magnetic moment of FeGen-/0 and local magnetic moment of the Fe atom have not been quenched.

Density functional theory study of small X-doped Mg(n) (X = Fe, Co, Ni, n = 1-9) bimetallic clusters: equilibrium structures, stabilities, electronic and magnetic properties.

PubMed

Kong, Fanjie; Hu, Yanfei

2014-03-01

The geometries, stabilities, and electronic and magnetic properties of Mg(n) X (X = Fe, Co, Ni, n = 1-9) clusters were investigated systematically within the framework of the gradient-corrected density functional theory. The results show that the Mg(n)Fe, Mg(n)Co, and Mg(n)Ni clusters have similar geometric structures and that the X atom in Mg(n)X clusters prefers to be endohedrally doped. The average atomic binding energies, fragmentation energies, second-order differences in energy, and HOMO-LUMO gaps show that Mg₄X (X = Fe, Co, Ni) clusters possess relatively high stability. Natural population analysis was performed and the results showed that the 3s and 4s electrons always transfer to the 3d and 4p orbitals in the bonding atoms, and that electrons also transfer from the Mg atoms to the doped atoms (Fe, Co, Ni). In addition, the spin magnetic moments were analyzed and compared. Several clusters, such as Mg₁,₂,₃,₄,₅,₆,₈,₉Fe, Mg₁,₂,₄,₅,₆,₈,₉Co, and Mg₁,₂,₅,₆,₇,₉Ni, present high magnetic moments (4 μ(B), 3 μ(B), and 2 μ(B), respectively).

Statistical analysis of atom probe data: detecting the early stages of solute clustering and/or co-segregation.

PubMed

Hyde, J M; Cerezo, A; Williams, T J

2009-04-01

Statistical analysis of atom probe data has improved dramatically in the last decade and it is now possible to determine the size, the number density and the composition of individual clusters or precipitates such as those formed in reactor pressure vessel (RPV) steels during irradiation. However, the characterisation of the onset of clustering or co-segregation is more difficult and has traditionally focused on the use of composition frequency distributions (for detecting clustering) and contingency tables (for detecting co-segregation). In this work, the authors investigate the possibility of directly examining the neighbourhood of each individual solute atom as a means of identifying the onset of solute clustering and/or co-segregation. The methodology involves comparing the mean observed composition around a particular type of solute with that expected from the overall composition of the material. The methodology has been applied to atom probe data obtained from several irradiated RPV steels. The results show that the new approach is more sensitive to fine scale clustering and co-segregation than that achievable using composition frequency distribution and contingency table analyses.

Origin of the selectivity in the gold-mediated oxidation of benzyl alcohol

NASA Astrophysics Data System (ADS)

Rodríguez-Reyes, Juan Carlos F.; Friend, Cynthia M.; Madix, Robert J.

2012-08-01

Benzyl alcohol has received substantial attention as a probe molecule to test the selectivity and efficiency of novel metallic gold catalysts. Herein, the mechanisms of benzyl alcohol oxidation on a gold surface covered with atomic oxygen are elucidated; the results show direct correspondence to the reaction on gold-based catalysts. The selective, partial oxidation of benzyl alcohol to benzaldehyde is achieved with low oxygen surface concentrations and takes place through dehydrogenation of the alcohol to form benzaldehyde via a benzyloxy (C6H5-CH2O) intermediate. While in this case atomic oxygen plays solely a dehydrogenating role, at higher concentrations it leads to the formation of intermediates from benzaldehyde, producing benzoic acid and CO2. Facile ester (benzyl benzoate) formation also occurs at low oxygen concentrations, which indicates that benzoic acid is not a precursor of further oxidation of the ester; instead, the ester is produced by the coupling of adsorbed benzyloxy and benzaldehyde. Key to the high selectivity seen at low oxygen concentrations is the fact that the production of the aldehyde (and esters) is kinetically favored over the production of benzoic acid.

Classical plasma dynamics of Mie-oscillations in atomic clusters

NASA Astrophysics Data System (ADS)

Kull, H.-J.; El-Khawaldeh, A.

2018-04-01

Mie plasmons are of basic importance for the absorption of laser light by atomic clusters. In this work we first review the classical Rayleigh-theory of a dielectric sphere in an external electric field and Thomson’s plum-pudding model applied to atomic clusters. Both approaches allow for elementary discussions of Mie oscillations, however, they also indicate deficiencies in describing the damping mechanisms by electrons crossing the cluster surface. Nonlinear oscillator models have been widely studied to gain an understanding of damping and absorption by outer ionization of the cluster. In the present work, we attempt to address the issue of plasmon relaxation in atomic clusters in more detail based on classical particle simulations. In particular, we wish to study the role of thermal motion on plasmon relaxation, thereby extending nonlinear models of collective single-electron motion. Our simulations are particularly adopted to the regime of classical kinetics in weakly coupled plasmas and to cluster sizes extending the Debye-screening length. It will be illustrated how surface scattering leads to the relaxation of Mie oscillations in the presence of thermal motion and of electron spill-out at the cluster surface. This work is intended to give, from a classical perspective, further insight into recent work on plasmon relaxation in quantum plasmas [1].

Molecular dynamics investigation of dynamical heterogeneity and local structure in the supercooled liquid and glass states of Al

NASA Astrophysics Data System (ADS)

Li, Maozhi; Wang, Cai-Zhuang; Mendelev, Mikhail I.; Ho, Kai-Ming

2008-05-01

Molecular dynamics simulations are performed to study the structure and dynamical heterogeneity in the liquid and glass states of Al using a frequently employed embedded atom potential. While the pair correlation function of the glass and liquid states displays only minor differences, the icosahedral short-range order (ISRO) and the dynamics of the two states are very different. The ISRO is much stronger in the glass than in the liquid. It is also found that both the most mobile and the most immobile atoms in the glass state tend to form clusters, and the clusters formed by the immobile atoms are more compact. In order to investigate the local environment of each atom in the liquid and glass states, a local density is defined to characterize the local atomic packing. There is a strong correlation between the local packing density and the mobility of the atoms. These results indicate that dynamical heterogeneity in glasses is directly correlated to the local structure. We also analyze the diffusion mechanisms of atoms in the liquid and glass states. It is found that for the mobile atoms in the glass state, initially they are confined in the cages formed by their nearest neighbors and vibrating. On the time scale of β relaxation, the mobile atoms try to break up the cage confinement and hop into new cages. In the supercooled liquid states, however, atoms continuously diffuse. Furthermore, it is found that on the time scale of β relaxation, some of the mobile atoms in the glass state cooperatively hop, which is facilitated by the stringlike cluster structures. On the longer time scale, it is found that a certain fraction of atoms can simultaneously hop, although they are not nearest neighbors. Further analysis shows that these hopping atoms form big and more compact clusters than the characterized most mobile atoms. The cooperative rearrangement of these big compact clusters might facilitate the simultaneous hopping of atoms in the glass states on the long time scale.

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode.

PubMed

Yang, Haifeng; Liu, Yanli; Liu, Zhimin; Yang, Yu; Jiang, Jianhui; Zhang, Zongrang; Shen, Guoli; Yu, Ruqin

2005-02-24

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.

Single-atom gold catalysis in the context of developments in parahydrogen-induced polarization.

PubMed

Corma, Avelino; Salnikov, Oleg G; Barskiy, Danila A; Kovtunov, Kirill V; Koptyug, Igor V

2015-05-04

A highly isolated monoatomic gold catalyst, with single gold atoms dispersed on multiwalled carbon nanotubes (MWCNTs), has been synthesized, characterized, and tested in heterogeneous hydrogenation of 1,3-butadiene and 1-butyne with parahydrogen to maximize the polarization level and the contribution of the pairwise hydrogen addition route. The Au/MWCNTs catalyst was found to be active and efficient in pairwise hydrogen addition and the estimated contributions from the pairwise hydrogen addition route are at least an order of magnitude higher than those for supported metal nanoparticle catalysts. Therefore, the use of the highly isolated monoatomic catalysts is very promising for production of hyperpolarized fluids that can be used for the significant enhancement of NMR signals. A mechanism of 1,3-butadiene hydrogenation with parahydrogen over the highly isolated monoatomic Au/MWCNTs catalyst is also proposed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen in Mono-Atomic Gold Wires

NASA Astrophysics Data System (ADS)

Barnett, Robert N.; Sherbakov, Andrew G.; Landman, Uzi; Hakkinen, Hannu

2004-03-01

Results of ab-initio scalar relativistic density functional calculations of the interaction between a mono-atomic gold wire (suspended between two gold tips) and a hydrogen molecule, at various stages of wire stretching, are presented. The hydrogen molecule does not bind to the wire until the wire is sufficiently stretched, i.e. starting to break, at which time the molecule inserts itself into the wire restoring a fraction of the conductance quantum g. With subsequent compression of the wire the axis of the molecule gradually tips away from the wire axis until it becomes "quasi-dissociated" with the H-H axis perpendicular to the wire. At this point the conductance almost vanishes, while for the bare wire the conductance at this tip-to-tip separation is close to 1g. These results, and the frequency of various vibrational modes of the hydrogen molecule, are compared with recent experimental and theoretical work involving platinum wires.

Nature of bonding and cooperativity in linear DMSO clusters: A DFT, AIM and NCI analysis.

PubMed

Venkataramanan, Natarajan Sathiyamoorthy; Suvitha, Ambigapathy

2018-05-01

This study aims to cast light on the nature of interactions and cooperativity that exists in linear dimethyl sulfoxide (DMSO) clusters using dispersion corrected density functional theory. In the linear DMSO, DMSO molecules in the middle of the clusters are bound strongly than at the terminal. The plot of the total binding energy of the clusters vs the cluster size and mean polarizabilities vs cluster size shows an excellent linearity demonstrating the presence of cooperativity effect. The computed incremental binding energy of the clusters remains nearly constant, implying that DMSO addition at the terminal site can happen to form an infinite chain. In the linear clusters, two σ-hole at the terminal DMSO molecules were found and the value on it was found to increase with the increase in cluster size. The quantum theory of atoms in molecules topography shows the existence of hydrogen and SO⋯S type in linear tetramer and larger clusters. In the dimer and trimer SO⋯OS type of interaction exists. In 2D non-covalent interactions plot, additional peaks in the regions which contribute to the stabilization of the clusters were observed and it splits in the trimer and intensifies in the larger clusters. In the trimer and larger clusters in addition to the blue patches due to hydrogen bonds, additional, light blue patches were seen between the hydrogen atom of the methyl groups and the sulphur atom of the nearby DMSO molecule. Thus, in addition to the strong H-bonds, strong electrostatic interactions between the sulphur atom and methyl hydrogens exists in the linear clusters. Copyright © 2018 Elsevier Inc. All rights reserved.

The adsorption of Run (n = 1-4) on γ-Al2O3 Surface: A DFT study

NASA Astrophysics Data System (ADS)

Liu, Zhe; Guo, Yafei; Chen, Yu; Shen, Rong

2018-05-01

The density functional theory (DFT) was adopted to study the adsorption and growth of Run (n = 1-4) clusters on γ-Al2O3 surface, which is of great significances for the design of many important catalysts, especially for carbon dioxide methanation. It is found that both the Rusbnd Ru bond length and adsorption energy Eads of Ru clusters with the surface increase with the Run clusters increasing. The growth ability of the supported Run cluster is weaker than the gas phase Run clusters through comparing their respective growth process, which ascribes to the stabilization of γ-Al2O3 support. An interesting discovery is that the basin structure was supposed to be the most favorable adsorption geometry for Run clusters. Additionally, the distances between Ru atoms in the adsorbed clusters are longer than that in their isolated counterparts. Bader charge analysis was conducted for the most stable configurations of Run (n = 1-4) clusters on γ-Al2O3 surface as well. And the results suggest that Run (n = 1-4) clusters serve as the electron donators. The result of projected density of states (PDOS) shows that strong adsorption of Ru atom on the γ-Al2O3 surface correlates with strong interaction between d orbital of Ru atom and p orbital of Al or O atom of the Al2O3 support.

Surface passivation for tight-binding calculations of covalent solids.

PubMed

Bernstein, N

2007-07-04

Simulation of a cluster representing a finite portion of a larger covalently bonded system requires the passivation of the cluster surface. We compute the effects of an explicit hybrid orbital passivation (EHOP) on the atomic structure in a model bulk, three-dimensional, narrow gap semiconductor, which is very different from the wide gap, quasi-one-dimensional organic molecules where most passivation schemes have been studied in detail. The EHOP approach is directly applicable to minimal atomic orbital basis methods such as tight-binding. Each broken bond is passivated by a hybrid created from an explicitly expressed linear combination of basis orbitals, chosen to represent the contribution of the missing neighbour, e.g. a sp(3) hybrid for a single bond. The method is tested by computing the forces on atoms near a point defect as a function of cluster geometry. We show that, compared to alternatives such as pseudo-hydrogen passivation, the force on an atom converges to the correct bulk limit more quickly as a function of cluster radius, and that the force is more stable with respect to perturbations in the position of the cluster centre. The EHOP method also obviates the need for parameterizing the interactions between the system atoms and the passivating atoms. The method is useful for cluster calculations of non-periodic defects in large systems and for hybrid schemes that simulate large systems by treating finite regions with a quantum-mechanical model, coupled to an interatomic potential description of the rest of the system.

Surface passivation for tight-binding calculations of covalent solids

NASA Astrophysics Data System (ADS)

Bernstein, N.

2007-07-01

Simulation of a cluster representing a finite portion of a larger covalently bonded system requires the passivation of the cluster surface. We compute the effects of an explicit hybrid orbital passivation (EHOP) on the atomic structure in a model bulk, three-dimensional, narrow gap semiconductor, which is very different from the wide gap, quasi-one-dimensional organic molecules where most passivation schemes have been studied in detail. The EHOP approach is directly applicable to minimal atomic orbital basis methods such as tight-binding. Each broken bond is passivated by a hybrid created from an explicitly expressed linear combination of basis orbitals, chosen to represent the contribution of the missing neighbour, e.g. a sp3 hybrid for a single bond. The method is tested by computing the forces on atoms near a point defect as a function of cluster geometry. We show that, compared to alternatives such as pseudo-hydrogen passivation, the force on an atom converges to the correct bulk limit more quickly as a function of cluster radius, and that the force is more stable with respect to perturbations in the position of the cluster centre. The EHOP method also obviates the need for parameterizing the interactions between the system atoms and the passivating atoms. The method is useful for cluster calculations of non-periodic defects in large systems and for hybrid schemes that simulate large systems by treating finite regions with a quantum-mechanical model, coupled to an interatomic potential description of the rest of the system.

MRI-alone radiation therapy planning for prostate cancer: Automatic fiducial marker detection

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

Ghose, Soumya, E-mail: soumya.ghose@case.edu; Mitra, Jhimli; Rivest-Hénault, David

Purpose: The feasibility of radiation therapy treatment planning using substitute computed tomography (sCT) generated from magnetic resonance images (MRIs) has been demonstrated by a number of research groups. One challenge with an MRI-alone workflow is the accurate identification of intraprostatic gold fiducial markers, which are frequently used for prostate localization prior to each dose delivery fraction. This paper investigates a template-matching approach for the detection of these seeds in MRI. Methods: Two different gradient echo T1 and T2* weighted MRI sequences were acquired from fifteen prostate cancer patients and evaluated for seed detection. For training, seed templates from manual contoursmore » were selected in a spectral clustering manifold learning framework. This aids in clustering “similar” gold fiducial markers together. The marker with the minimum distance to a cluster centroid was selected as the representative template of that cluster during training. During testing, Gaussian mixture modeling followed by a Markovian model was used in automatic detection of the probable candidates. The probable candidates were rigidly registered to the templates identified from spectral clustering, and a similarity metric is computed for ranking and detection. Results: A fiducial detection accuracy of 95% was obtained compared to manual observations. Expert radiation therapist observers were able to correctly identify all three implanted seeds on 11 of the 15 scans (the proposed method correctly identified all seeds on 10 of the 15). Conclusions: An novel automatic framework for gold fiducial marker detection in MRI is proposed and evaluated with detection accuracies comparable to manual detection. When radiation therapists are unable to determine the seed location in MRI, they refer back to the planning CT (only available in the existing clinical framework); similarly, an automatic quality control is built into the automatic software to ensure that all gold seeds are either correctly detected or a warning is raised for further manual intervention.« less

MRI-alone radiation therapy planning for prostate cancer: Automatic fiducial marker detection.

PubMed

Ghose, Soumya; Mitra, Jhimli; Rivest-Hénault, David; Fazlollahi, Amir; Stanwell, Peter; Pichler, Peter; Sun, Jidi; Fripp, Jurgen; Greer, Peter B; Dowling, Jason A

2016-05-01

The feasibility of radiation therapy treatment planning using substitute computed tomography (sCT) generated from magnetic resonance images (MRIs) has been demonstrated by a number of research groups. One challenge with an MRI-alone workflow is the accurate identification of intraprostatic gold fiducial markers, which are frequently used for prostate localization prior to each dose delivery fraction. This paper investigates a template-matching approach for the detection of these seeds in MRI. Two different gradient echo T1 and T2* weighted MRI sequences were acquired from fifteen prostate cancer patients and evaluated for seed detection. For training, seed templates from manual contours were selected in a spectral clustering manifold learning framework. This aids in clustering "similar" gold fiducial markers together. The marker with the minimum distance to a cluster centroid was selected as the representative template of that cluster during training. During testing, Gaussian mixture modeling followed by a Markovian model was used in automatic detection of the probable candidates. The probable candidates were rigidly registered to the templates identified from spectral clustering, and a similarity metric is computed for ranking and detection. A fiducial detection accuracy of 95% was obtained compared to manual observations. Expert radiation therapist observers were able to correctly identify all three implanted seeds on 11 of the 15 scans (the proposed method correctly identified all seeds on 10 of the 15). An novel automatic framework for gold fiducial marker detection in MRI is proposed and evaluated with detection accuracies comparable to manual detection. When radiation therapists are unable to determine the seed location in MRI, they refer back to the planning CT (only available in the existing clinical framework); similarly, an automatic quality control is built into the automatic software to ensure that all gold seeds are either correctly detected or a warning is raised for further manual intervention.

The interaction of a gold atom with carbon nanohorn and carbon nanotube tips and their complexes with a CO molecule: A first principle calculation

NASA Astrophysics Data System (ADS)

Khongpracha, P.; Probst, M.; Limtrakul, J.

2008-07-01

The interactions of a gold atom with: (a) a single-wall carbon nanohorn (SWNH) conic tip; (b) with a single-wall carbon nanotube (SWNT) tip; and (c) their complexes with a CO molecule were studied using first-principle calculations based on density functional theory. The analysis of the pyramidalization angle (θp) as well as the π-orbital misalignment angles indicate that there should be many reactive carbon sites on the tips of SWNH and SWNT. It was found that SWNH provides reactive sites that can more selectively interact with the target atom. We identified five sites on both the SWNT tip and the nanohorn where attachment of a gold atom leads to a stable complex. This metal is found to be bi-coordinated with the tip of SWNH, while it is mono-coordinated with the SWNT tip. The largest interaction energies are -10.75 kcal/mol and -16.17 kcal/mol, respectively. The CO probe molecule binds to Au on the Au/SWNH or Au/SWNT tips with interaction energies of -22.34 and -18.29 kcal/mol, respectively. The main contributions of the interaction with both carbon nanostructures stems from σ-donation and π-backbonding. The results suggest that SWNHs could be one of the promising candidates for the development of high-specifity nanosensors.

Clustering on Magnesium Surfaces - Formation and Diffusion Energies.

PubMed

Chu, Haijian; Huang, Hanchen; Wang, Jian

2017-07-12

The formation and diffusion energies of atomic clusters on Mg surfaces determine the surface roughness and formation of faulted structure, which in turn affect the mechanical deformation of Mg. This paper reports first principles density function theory (DFT) based quantum mechanics calculation results of atomic clustering on the low energy surfaces {0001} and [Formula: see text]. In parallel, molecular statics calculations serve to test the validity of two interatomic potentials and to extend the scope of the DFT studies. On a {0001} surface, a compact cluster consisting of few than three atoms energetically prefers a face-centered-cubic stacking, to serve as a nucleus of stacking fault. On a [Formula: see text], clusters of any size always prefer hexagonal-close-packed stacking. Adatom diffusion on surface [Formula: see text] is high anisotropic while isotropic on surface (0001). Three-dimensional Ehrlich-Schwoebel barriers converge as the step height is three atomic layers or thicker. Adatom diffusion along steps is via hopping mechanism, and that down steps is via exchange mechanism.

Structure assignment, electronic properties, and magnetism quenching of endohedrally doped neutral silicon clusters, Si(n)Co (n = 10-12).

PubMed

Li, Yejun; Tam, Nguyen Minh; Claes, Pieterjan; Woodham, Alex P; Lyon, Jonathan T; Ngan, Vu Thi; Nguyen, Minh Tho; Lievens, Peter; Fielicke, André; Janssens, Ewald

2014-09-18

The structures of neutral cobalt-doped silicon clusters have been assigned by a combined experimental and theoretical study. Size-selective infrared spectra of neutral Si(n)Co (n = 10-12) clusters are measured using a tunable IR-UV two-color ionization scheme. The experimental infrared spectra are compared with calculated spectra of low-energy structures predicted at the B3P86 level of theory. It is shown that the Si(n)Co (n = 10-12) clusters have endohedral caged structures, where the silicon frameworks prefer double-layered structures encapsulating the Co atom. Electronic structure analysis indicates that the clusters are stabilized by an ionic interaction between the Co dopant atom and the silicon cage due to the charge transfer from the silicon valence sp orbitals to the cobalt 3d orbitals. Strong hybridization between the Co dopant atom and the silicon host quenches the local magnetic moment on the encapsulated Co atom.

Reversible Self-Assembly of Glutathione-Coated Gold Nanoparticle Clusters via pH-Tunable Interactions

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

Moaseri, Ehsan; Bollinger, Jonathan A.; Changalvaie, Behzad

In this study, nanoparticle (NP) clusters with diameters ranging from 20 to 100 nm are reversibly assembled from 5 nm gold (Au) primary particles coated with glutathione (GSH) in aqueous solution as a function of pH in the range of 5.4 to 3.8. As the pH is lowered, the GSH surface ligands become partially zwitterionic and form interparticle hydrogen bonds that drive the self-limited assembly of metastable clusters in <1 min. Whereas clusters up to 20 nm in size are stable against cluster–cluster aggregation for up to 1 day, clusters up to 80 nm in size can be stabilized overmore » this period via the addition of citrate to the solution in equal molarity with GSH molecules. The cluster diameter may be cycled reversibly by tuning pH to manipulate the colloidal interactions; however, modest background cluster–cluster aggregation occurs during cycling. Cluster sizes can be stabilized for at least 1 month via the addition of PEG-thiol as a grafted steric stabilizer, where PEG-grafted clusters dissociate back to starting primary NPs at pH 7 in fewer than 3 days. Whereas the presence of excess citrate has little effect on the initial size of the metastable clusters, it is necessary for both the cycling and dissociation to mediate the GSH–GSH hydrogen bonds. In conclusion, these metastable clusters exhibit significant characteristics of equilibrium self-limited assembly between primary particles and clusters on time scales where cluster–cluster aggregation is not present.« less

Reversible Self-Assembly of Glutathione-Coated Gold Nanoparticle Clusters via pH-Tunable Interactions

DOE PAGES

Moaseri, Ehsan; Bollinger, Jonathan A.; Changalvaie, Behzad; ...

2017-10-06

In this study, nanoparticle (NP) clusters with diameters ranging from 20 to 100 nm are reversibly assembled from 5 nm gold (Au) primary particles coated with glutathione (GSH) in aqueous solution as a function of pH in the range of 5.4 to 3.8. As the pH is lowered, the GSH surface ligands become partially zwitterionic and form interparticle hydrogen bonds that drive the self-limited assembly of metastable clusters in <1 min. Whereas clusters up to 20 nm in size are stable against cluster–cluster aggregation for up to 1 day, clusters up to 80 nm in size can be stabilized overmore » this period via the addition of citrate to the solution in equal molarity with GSH molecules. The cluster diameter may be cycled reversibly by tuning pH to manipulate the colloidal interactions; however, modest background cluster–cluster aggregation occurs during cycling. Cluster sizes can be stabilized for at least 1 month via the addition of PEG-thiol as a grafted steric stabilizer, where PEG-grafted clusters dissociate back to starting primary NPs at pH 7 in fewer than 3 days. Whereas the presence of excess citrate has little effect on the initial size of the metastable clusters, it is necessary for both the cycling and dissociation to mediate the GSH–GSH hydrogen bonds. In conclusion, these metastable clusters exhibit significant characteristics of equilibrium self-limited assembly between primary particles and clusters on time scales where cluster–cluster aggregation is not present.« less

Imaging and manipulation of adatoms on an alumina surface by noncontact atomic force microscopy

NASA Astrophysics Data System (ADS)

Simon, G. H.; Heyde, M.; Freund, H.-J.

2012-02-01

Noncontact atomic force microscopy (NC-AFM) has been performed on an aluminum oxide film grown on NiAl(110) in ultrahigh vacuum (UHV) at low temperature (5 K). Results reproduce the topography of the structural model, unlike scanning tunnelling microscopy (STM) images. Equipped with this extraordinary contrast the network of extended defects, which stems from domain boundaries intersecting the film surface, can be analysed in atomic detail. The knowledge of occurring surface structures opens up the opportunity to determine adsorption sites of individual adsorbates on the alumina film. The level of difficulty for such imaging depends on the imaging characteristics of the substrate and the interaction which can be maintained above the adsorbate. Positions of single adsorbed gold atoms within the unit cell have been determined despite their easy removal at slightly higher interaction strength. Preliminary manipulation experiments indicate a pick-up process for the vanishing of the gold adatoms from the film surface.

Mono-Mercury Doping of Au25 and the HOMO/LUMO Energies Evaluation Employing Differential Pulse Voltammetry.

PubMed

Liao, Lingwen; Zhou, Shiming; Dai, Yafei; Liu, Liren; Yao, Chuanhao; Fu, Cenfeng; Yang, Jinlong; Wu, Zhikun

2015-08-05

Controlling the bimetal nanoparticle with atomic monodispersity is still challenging. Herein, a monodisperse bimetal nanoparticle is synthesized in 25% yield (on gold atom basis) by an unusual replacement method. The formula of the nanoparticle is determined to be Au24Hg1(PET)18 (PET: phenylethanethiolate) by high-resolution ESI-MS spectrometry in conjunction with multiple analyses including X-ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). X-ray single-crystal diffraction reveals that the structure of Au24Hg1(PET)18 remains the structural framework of Au25(PET)18 with one of the outer-shell gold atoms replaced by one Hg atom, which is further supported by theoretical calculations and experimental results as well. Importantly, differential pulse voltammetry (DPV) is first employed to estimate the highest occupied molecular orbit (HOMO) and the lowest unoccupied molecular orbit (LUMO) energies of Au24Hg1(PET)18 based on previous calculations.

Tunable synthesis and acetylation of dendrimer-entrapped or dendrimer-stabilized gold-silver alloy nanoparticles.

PubMed

Liu, Hui; Shen, Mingwu; Zhao, Jinglong; Guo, Rui; Cao, Xueyan; Zhang, Guixiang; Shi, Xiangyang

2012-06-01

In this study, amine-terminated generation 5 poly(amidoamine) dendrimers were used as templates or stabilizers to synthesize dendrimer-entrapped or dendrimer-stabilized Au-Ag alloy nanoparticles (NPs) with different gold atom/silver atom/dendrimer molar ratios with the assistance of sodium borohydride reduction chemistry. Following a one-step acetylation reaction to transform the dendrimer terminal amines to acetyl groups, a series of dendrimer-entrapped or dendrimer-stabilized Au-Ag alloy NPs with terminal acetyl groups were formed. The formed Au-Ag alloy NPs before and after acetylation reaction were characterized using different techniques. We showed that the optical property and the size of the bimetallic NPs were greatly affected by the metal composition. At the constant total metal atom/dendrimer molar ratio, the size of the alloy NPs decreased with the gold content. The formed Au-Ag alloy NPs were stable at different pH (pH 5-8) and temperature (4-50°C) conditions. X-ray absorption coefficient measurements showed that the attenuation of the binary NPs was dependent on both the gold content and the surface modification. With the increase of gold content in the binary NPs, their X-ray attenuation intensity was significantly enhanced. At a given metal composition, the X-ray attenuation intensity of the binary NPs was enhanced after acetylation. Cytotoxicity assays showed that after acetylation, the cytocompatibility of Au-Ag alloy NPs was significantly improved. With the controllable particle size and optical property, metal composition-dependent X-ray attenuation characteristics, and improved cytocompatibility after acetylation, these dendrimer-entrapped or dendrimer-stabilized Au-Ag alloy NPs should have a promising potential for CT imaging and other biomedical applications. Copyright © 2012 Elsevier B.V. All rights reserved.

Atomically precise arrays of fluorescent silver clusters: a modular approach for metal cluster photonics on DNA nanostructures.

PubMed

Copp, Stacy M; Schultz, Danielle E; Swasey, Steven; Gwinn, Elisabeth G

2015-03-24

The remarkable precision that DNA scaffolds provide for arraying nanoscale optical elements enables optical phenomena that arise from interactions of metal nanoparticles, dye molecules, and quantum dots placed at nanoscale separations. However, control of ensemble optical properties has been limited by the difficulty of achieving uniform particle sizes and shapes. Ligand-stabilized metal clusters offer a route to atomically precise arrays that combine desirable attributes of both metals and molecules. Exploiting the unique advantages of the cluster regime requires techniques to realize controlled nanoscale placement of select cluster structures. Here we show that atomically monodisperse arrays of fluorescent, DNA-stabilized silver clusters can be realized on a prototypical scaffold, a DNA nanotube, with attachment sites separated by <10 nm. Cluster attachment is mediated by designed DNA linkers that enable isolation of specific clusters prior to assembly on nanotubes and preserve cluster structure and spectral purity after assembly. The modularity of this approach generalizes to silver clusters of diverse sizes and DNA scaffolds of many types. Thus, these silver cluster nano-optical elements, which themselves have colors selected by their particular DNA templating oligomer, bring unique dimensions of control and flexibility to the rapidly expanding field of nano-optics.

The application of aberration-corrected electron microscopy to the characterization of gold-based catalysts

NASA Astrophysics Data System (ADS)

Herzing, Andrew A.

Electron microscopy has long been used to study the morphology of heterogeneous catalysts. Recent advances in electron optics now allow for the correction of the inherent spherical aberration (Cs) produced by the objective lens in the scanning transmission electron microscope (STEM, resulting in a significantly improved spatial resolution as well as the ability to use a much larger probe-current than was previously possible. In this thesis, the combination of high-angle annular dark-field (HAADF) imaging and microanalysis by x-ray energy dispersive spectroscopy (XEDS) in an aberration-corrected STEM has been applied for the first time to the characterization of gold-based heterogeneous catalysts. Multi-variate statistical analysis (MSA) has been employed in order to further improve the STEM-XEDS spectrum image data acquired with this technique. In addition, supplemental analysis using electron-energy loss spectroscopy (EELS) and energy-filtered transmission electron microscopy (EFTEM) in an aberration-corrected instrument has also been attempted. These techniques have proven extremely valuable in providing complimentary information to more traditional catalyst characterization techniques such as x-ray photoelectron spectroscopy and x-ray diffraction in four specific problems relating to catalysis. Firstly, the atomic-scale resolution of Cs-corrected HAADF imaging has been utilized to study Au/FeOx catalysts in order to determine the size and structure of the Au clusters present on the support surface. It was discovered that, while both inactive and active catalysts for low-temperature CO oxidation contained large Au particles (> 5 nm) and individual Au atoms, the active catalyst also contained sub-nm clusters comprised of only a few Au atoms. Secondly, novel CeO2 support materials for Au and Au-Pd catalysts were synthesized by precipitation with supercritical CO2. These supports were found to produce significantly more active catalysts than those based on CeO2 prepared using more traditional methods. The combination of STEM-HAADF imaging and XEDS mapping has been used to characterize these catalysts and a strong correlation between the catalytic activity and the enhanced degree of metal dispersion over the support is demonstrated. Thirdly, a systematic series of Au-Pd/Al2O3 catalysts has been studied in order to characterize the effects of various heat treatments on the development of core-shell morphologies within the bi-metallic particles and its subsequent effect on their catalytic performance for H2O 2 synthesis. STEM-XEDS spectrum imaging was employed in order to determine the degree of alloying and segregation behavior within the individual Au-Pd particles as a function of calcination/reduction temperature. It was found that the as prepared catalyst contained homogeneous Au-Pd alloy particles and that a Pd-rich shell/Au-rich core morphology gradually developed upon calcination. Subsequent reduction of the catalyst caused a large fraction of the particles to invert and form Pd-rich core/Au-rich shell structures. These changes are related to both the activity and stability of the catalyst. Finally, the washing of activated carbon support materials in acid was found to be extremely beneficial for producing Au-Pd catalysts for the direct synthesis of H2O2. STEM-HAADF imaging revealed that the acid-washing treatment increased the dispersion of the metal on the carbon supports. Aberration-corrected STEM-XEDS spectrum imaging demonstrated a strong size dependence of the Au-Pd particle composition. Crucially, the acid-washing pre-treatment enhanced the alloying of Au and Pd by suppressing the formation of large (> 25 nm) Au-rich particles. In summary, the application of aberration-corrected HAADF imaging and STEM-XEDS spectrum imaging to the characterization of Au-based catalysts has enhanced the understanding of the structural and chemical features that determine their catalytic behavior. Specifically, they have allowed us to achieve the following: (a) image individual metal atoms and clusters of just a few atoms dispersed in a real, high surface area catalyst, (b) detect and follow the development of core-shell structures in Au-Pd bi-metallic catalysts, (c) determine composition/size correlations in Au-Pd catalysts, (d) detect minor alloying elements in bi-metallic catalysts, (e) and chemically map atomic or near atomic dispersions of metals on oxide supports.

Influence of the pH value of a colloidal gold solution on the absorption spectra of an LSPR-assisted sensor

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

Zhu, Jin; Li, Wenbin; Zhu, Mao

2014-03-15

The localized surface plasmon resonances (LSPRs) of gold particles assembled on a crystal plate are a powerful tool for biological sensors. Here, we prepare gold colloids in different pH solutions. We monitor the effects of the particle radius and particle coverage on the absorption spectra of AT-cut (r-face dihedral angle of about 3°) crystal plates supporting gold nanoparticles. The surface morphologies were monitored on silicon dioxide substrates using ultraviolet and visible (UV-vis) spectroscopy, and atomic force microscopy (AFM). The results showed that the gold particle coverage decreases with increasing pH value of the gold colloid solution. This phenomenon demonstrates thatmore » self-assembled gold surfaces were formed via the electrostatic adsorption of gold particles on the positively charged, ionized amino groups on the crystal plates in the acidic solution. The spectrum of gold nanoparticles with different coverage degree on the crystal plates showed that the LSPR properties are highly dependent on pH.« less

In Situ Gold Nanoparticle Gradient Formation in a 3D Meso- and Macroporous Polymer Matrix.

PubMed

Penders, Jelle; Rajasekharan, Anand K; Hulander, Mats; Andersson, Martin

2017-08-01

Herein, the development and characterization of a 3D gradient structure of gold nanoparticles is described. The gradient of gold nanoparticles is made in situ in a macroporous nonionic block copolymer hydrogel matrix, through gold ion diffusion control. The polymer provides a matrix for diffusion of gold ions, acts as a template for controlling nanoparticle growth, and facilitates the in situ reduction of gold ions to gold nanoparticles. A clear gradient in gold nanoparticles is observed across the 3D space of the polymer matrix using scanning electron microscopy, fluorescence microscopy, atomic force microscopy, and thermogravimetric analysis. The particle gradient is further functionalized with both hydrophobic and hydrophilic groups via thiol-gold linkage to demonstrate the ability to form gradients with different chemical functionalities. Using additive manufacturing, the polymer can also be printed as a porous network with possible applications for 3D cell culturing in, e.g., biomaterials research. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimal energy for cell radiosensitivity enhancement by gold nanoparticles using synchrotron-based monoenergetic photon beams

PubMed Central

Rahman, Wan Nordiana; Corde, Stéphanie; Yagi, Naoto; Abdul Aziz, Siti Aishah; Annabell, Nathan; Geso, Moshi

2014-01-01

Gold nanoparticles have been shown to enhance radiation doses delivered to biological targets due to the high absorption coefficient of gold atoms, stemming from their high atomic number (Z) and physical density. These properties significantly increase the likelihood of photoelectric effects and Compton scattering interactions. Gold nanoparticles are a novel radiosensitizing agent that can potentially be used to increase the effectiveness of current radiation therapy techniques and improve the diagnosis and treatment of cancer. However, the optimum radiosensitization effect of gold nanoparticles is strongly dependent on photon energy, which theoretically is predicted to occur in the kilovoltage range of energy. In this research, synchrotron-generated monoenergetic X-rays in the 30–100 keV range were used to investigate the energy dependence of radiosensitization by gold nanoparticles and also to determine the photon energy that produces optimum effects. This investigation was conducted using cells in culture to measure dose enhancement. Bovine aortic endothelial cells with and without gold nanoparticles were irradiated with X-rays at energies of 30, 40, 50, 60, 70, 81, and 100 keV. Trypan blue exclusion assays were performed after irradiation to determine cell viability. Cell radiosensitivity enhancement was indicated by the dose enhancement factor which was found to be maximum at 40 keV with a value of 3.47. The dose enhancement factor obtained at other energy levels followed the same direction as the theoretical calculations based on the ratio of the mass energy absorption coefficients of gold and water. This experimental evidence shows that the radiosensitization effect of gold nanoparticles varies with photon energy as predicted from theoretical calculations. However, prediction based on theoretical assumptions is sometimes difficult due to the complexity of biological systems, so further study at the cellular level is required to fully characterize the effects of gold nanoparticles with ionizing radiation. PMID:24899803

Optimal energy for cell radiosensitivity enhancement by gold nanoparticles using synchrotron-based monoenergetic photon beams.

PubMed

Rahman, Wan Nordiana; Corde, Stéphanie; Yagi, Naoto; Abdul Aziz, Siti Aishah; Annabell, Nathan; Geso, Moshi

2014-01-01

Gold nanoparticles have been shown to enhance radiation doses delivered to biological targets due to the high absorption coefficient of gold atoms, stemming from their high atomic number (Z) and physical density. These properties significantly increase the likelihood of photoelectric effects and Compton scattering interactions. Gold nanoparticles are a novel radiosensitizing agent that can potentially be used to increase the effectiveness of current radiation therapy techniques and improve the diagnosis and treatment of cancer. However, the optimum radiosensitization effect of gold nanoparticles is strongly dependent on photon energy, which theoretically is predicted to occur in the kilovoltage range of energy. In this research, synchrotron-generated monoenergetic X-rays in the 30-100 keV range were used to investigate the energy dependence of radiosensitization by gold nanoparticles and also to determine the photon energy that produces optimum effects. This investigation was conducted using cells in culture to measure dose enhancement. Bovine aortic endothelial cells with and without gold nanoparticles were irradiated with X-rays at energies of 30, 40, 50, 60, 70, 81, and 100 keV. Trypan blue exclusion assays were performed after irradiation to determine cell viability. Cell radiosensitivity enhancement was indicated by the dose enhancement factor which was found to be maximum at 40 keV with a value of 3.47. The dose enhancement factor obtained at other energy levels followed the same direction as the theoretical calculations based on the ratio of the mass energy absorption coefficients of gold and water. This experimental evidence shows that the radiosensitization effect of gold nanoparticles varies with photon energy as predicted from theoretical calculations. However, prediction based on theoretical assumptions is sometimes difficult due to the complexity of biological systems, so further study at the cellular level is required to fully characterize the effects of gold nanoparticles with ionizing radiation.

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

PubMed

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

2015-05-28

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

Elucidating Complex Surface Reconstructions with Atomic-Resolution Scanning Tunneling Microscopy: Au(100)-Aqueous Electrochemical Interface

DTIC Science & Technology

1992-05-01

that unusually high-quality STM data of this type 5-7can be obtained at ordered gold -aqueous interfaces. Reconstruction is seen 2 to be triggered on...all three low-index gold surfaces by altering the potential to values corresponding to small (10-15 pC cm-2 ) negative surface electronic 5-7 charges...connections. The former was platinum and the latter was a freshly electrooxidized gold wire. All electrode potentials quoted here, however, are

Functionalization of surfactant wrapped graphenenanosheets with alkylazides for enhanced dispersibility

NASA Astrophysics Data System (ADS)

Vadukumpully, Sajini; Gupta, Jhinuk; Zhang, Yongping; Xu, Guo Qin; Valiyaveettil, Suresh

2011-01-01

A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acidgroups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials.A facile and simple approach for the covalent functionalization of surfactant wrapped graphene sheets is described. The approach involves functionalization of dispersible graphene sheets with various alkylazides and 11-azidoundecanoic acid proved the best azide for enhanced dispersibility. The functionalization was confirmed by infrared spectroscopy and scanning tunneling microscopy. The free carboxylic acidgroups can bind to gold nanoparticles, which were introduced as markers for the reactive sites. The interaction between gold nanoparticles and the graphene sheets was followed by UV-vis spectroscopy. The gold nanoparticle-graphene composite was characterized by transmission electron microscopy and atomic force microscopy, demonstrating the uniform distribution of gold nanoparticles all over the surface. Our results open the possibility to control the functionalization on graphene in the construction of composite nanomaterials. Electronic Supplementary Information (ESI) available: Synthesis and characterization details of dodecylazide, hexylazide, 11-azidoundecanol (AUO), micrographs (SEM and TEM images) of the various azide functionalized samples and the statistical analysis of the graphene thickness. See 10.1039/c0nr00547a.

Separation and Enrichment of Gold in Water, Geological and Environmental Samples by Solid Phase Extraction on Multiwalled Carbon Nanotubes Prior to its Determination by Flame Atomic Absorption Spectrometry.

PubMed

Duran, Ali; Tuzen, Mustafa; Soylak, Mustafa

2015-01-01

This study proposes the application of multi-walled carbon nanotubes as a solid sorbent for the preconcentration of gold prior to its flame atomic absorption spectrometry determination. Extraction was achieved by using a glass column (15.0 cm in length and 1.0 cm in diameter). Quantitative recoveries were obtained in the pH range of 2.5-4.0; the elution step was carried out with 5.0 ml of 1.0 mol/L HNO3 in acetone. In the ligand-free study, variables such as pH, eluent type, sample volume, flow rates, and matrix effect were examined for the optimum recovery of gold ions. The gold ions were able to be pre-concentrated by a factor of 150 and their LOD was determined to be 1.71 μg/L. In order to evaluate the accuracy of the developed method, addition-recovery tests were applied for the tap water, mineral water, and sea water samples. Gold recovery studies were implemented using a wet digestion technique for mine and soil samples taken from various media, and this method was also applied for anodic slime samples taken from the factories located in the Kayseri Industrial Zone of Turkey.

Coprecipitation of gold(III) complex ions with manganese(II) hydroxide and their stoichiometric reduction to atomic gold (Au(0)): analysis by Mössbauer spectroscopy and XPS.

PubMed

Yamashita, Mamiko; Ohashi, Hironori; Kobayashi, Yasuhiro; Okaue, Yoshihiro; Kurisaki, Tsutomu; Wakita, Hisanobu; Yokoyama, Takushi

2008-03-01

To elucidate the formation process of precursor of gold-supported manganese dioxide (MnO2), the coprecipitation behavior of [AuCl4-n(OH)n](-) (n=0-4) (Au(III)) complex ions with manganese(II) hydroxide (Mn(OH)2 and the change in their chemical state were examined. The Au(III) complex ions were rapidly and effectively coprecipitated with Mn(OH)(2) at pH 9. According to the Mössbauer spectra for gold (Au) coprecipitated with Mn(OH)2, below an Au content of 60 wt% in the coprecipitates, all of the coprecipitated Au existed in the atomic state (Au(0)), while, above an Au content of 65 wt%, part of the gold existed in the Au(III) state, and the proportion increased with increasing coprecipitated Au content. Based on the results of X-ray photoelectron spectroscopy, Mn(II) in Mn(OH)2 converted to Mn(IV) in conjunction with coprecipitation of Au(III) complex ions. These results indicate that the rapid stoichiometric reduction of Au(III) to Au(0) is caused by electron transfer from Mn(II) in Mn(OH)2 to the Au(III) complex ion through an Mn-O-Au bond.

Solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry for gold determination in geological samples after preconcentration onto carbon nanotubes

NASA Astrophysics Data System (ADS)

Dobrowolski, Ryszard; Mróz, Agnieszka; Dąbrowska, Marzena; Olszański, Piotr

2017-06-01

A novelty method for the determination of gold in geological samples by solid sampling high-resolution continuum source graphite furnace atomic absorption spectrometry (SS HR CS GF AAS) after solid-phase extraction onto modified carbon nanotubes (CNT) was described. The methodology developed is based on solid phase extraction of Au(III) ions from digested samples to eliminate strong interference caused by iron compounds and problems related to inhomogeneities of the samples. The use of aqueous or solid standard for calibration was studied and the slope of calibration curve was the same for both of these modes. This statement indicates the possibility to perform the calibration of the method using aqueous standard solutions. Under optimum conditions the absolute detection limit for gold was equal to 2.24 · 10- 6 μg g- 1 while the adsorption capacity of modified carbon nanotubes was 264 mg g- 1. The proposed procedure was validated by the application of certified reference materials (CRMs) with different content of gold and different matrix, the results were in good agreement with certified values. The method was successfully applied for separation and determination of gold ions in complex geological samples, with precision generally better than 8%.

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

PubMed

Pauling, L

1988-06-01

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

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

PubMed Central

Pauling, Linus

1988-01-01

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

Tailoring Ion Charge State Distribution in Tetramethyltin Clusters under Influence of Moderate Intensity Picosecond Laser Pulse: Role of Laser Wavelength and Rate of Energy Deposition

NASA Astrophysics Data System (ADS)

Sharma, Pramod; Das, Soumitra; Vatsa, Rajesh K.

2017-07-01

Systematic manipulation of ionic-outcome in laser-cluster interaction process has been realized for studies carried out on tetramethyltin (TMT) clusters under picosecond laser conditions, determined by choice of laser wavelength and intensity. As a function of laser intensity, TMT clusters exhibit gradual enhancement in overall ionization of its cluster constituents, up to a saturation level of ionization, which was distinct for different wavelengths (266, 355, and 532 nm). Simultaneously, systematic appearance of higher multiply charged atomic ions and shift in relative abundance of multiply charged atomic ions towards higher charge state was observed, using time-of-flight mass spectrometer. At saturation level, multiply charged atomic ions up to (C2+, Sn2+) at 266 nm, (C4+, Sn4+) at 355 nm, and (C4+, Sn6+) at 532 nm were detected. In addition, at 355 nm intra-cluster ion chemistry within the ionized cluster leads to generation of molecular hydrogen ion (H2 +) and triatomic molecular hydrogen ion (H3 +). Generation of multiply charged atomic ions is ascribed to efficient coupling of laser pulse with the cluster media, facilitated by inner-ionized electrons produced within the cluster, at the leading edge of laser pulse. Role of inner-ionized electrons is authenticated by measuring kinetic energy distribution of electrons liberated upon disintegration of excessively ionized cluster, under the influence of picosecond laser pulse.

Isolated single-molecule magnets on native gold.

PubMed

Zobbi, Laura; Mannini, Matteo; Pacchioni, Mirko; Chastanet, Guillaume; Bonacchi, Daniele; Zanardi, Chiara; Biagi, Roberto; Del Pennino, Umberto; Gatteschi, Dante; Cornia, Andrea; Sessoli, Roberta

2005-03-28

The incorporation of thioether groups in the structure of a Mn12 single-molecule magnet, [Mn12(O12)(L)16(H2O)4] with L = 4-(methylthio)benzoate, is a successful route to the deposition of well-separated clusters on native gold surfaces and to the addressing of individual molecules by scanning tunnelling microscopy.

Sizing protein-templated gold nanoclusters by time resolved fluorescence anisotropy decay measurements.

PubMed

Soleilhac, Antonin; Bertorelle, Franck; Antoine, Rodolphe

2018-03-15

Protein-templated gold nanoclusters (AuNCs) are very attractive due to their unique fluorescence properties. A major problem however may arise due to protein structure changes upon the nucleation of an AuNC within the protein for any future use as in vivo probes, for instance. In this work, we propose a simple and reliable fluorescence based technique measuring the hydrodynamic size of protein-templated gold nanoclusters. This technique uses the relation between the time resolved fluorescence anisotropy decay and the hydrodynamic volume, through the rotational correlation time. We determine the molecular size of protein-directed AuNCs, with protein templates of increasing sizes, e.g. insulin, lysozyme, and bovine serum albumin (BSA). The comparison of sizes obtained by other techniques (e.g. dynamic light scattering and small-angle X-ray scattering) between bare and gold clusters containing proteins allows us to address the volume changes induced either by conformational changes (for BSA) or the formation of protein dimers (for insulin and lysozyme) during cluster formation and incorporation. Copyright © 2017 Elsevier B.V. All rights reserved.

Structures of ˜100 nm Size Produced by Atom Lithography with Metastable He

NASA Astrophysics Data System (ADS)

Reeves, Jason; Corder, Christopher; Lu, Xiaoxu; Allred, Claire; Metcalf, Harold

2010-03-01

We have used neutral atom lithography with metastable 2^3S He (He*) to produce structures of size ˜100 nm. A beam of He* from our source is collimated by the bichromatic forceootnotetextM. Partlow et al., Phys. Rev. Lett. 93, 213004 (2004) and then by optical molasses. Atoms cross a standing wave of λ= 389 nm light tuned ˜80 MHz below the 2^3S1->3^3P2 transition and are focussed into lines striking a self assembled monolayer (SAM) of nonanethiol coated over a gold film on a single crystal Si wafer. The 20 eV internal energy of He* destroys the SAM molecules ultimately leaving a pattern of SAM on the gold. Subsequent etching of the unprotected region of the gold results in these featuresootnotetextC. Allred et al., submitted to J. Appl. Phys.^,ootnotetextC. Allred, Ph.D. Thesis, Stony Brook, NY (2009) - unpublished.. The lines are separated by 194.5 nm and they occupy about 60% of their spacing. AFM measurements of our first samples show their width to be ˜120 nm and their depth to be ˜10 nm.

Structures of ˜100 nm Size Produced by Atom Lithography with Metastable He

NASA Astrophysics Data System (ADS)

Reeves, Jason; Corder, Christopher; Lu, Xiaoxu; Allred, Claire; Metcalf, Harold

2010-03-01

We have used neutral atom lithography with metastable 2^3S He (He*) to produce structures of size ˜100 nm. A beam of He* from our source is collimated by the bichromatic forcefootnotetextM. Partlow et al., Phys. Rev. Lett. 93, 213004 (2004) and then by optical molasses. Atoms cross a standing wave of λ= 389 nm light tuned ˜80 MHz below the 2^3S1->3^3P2 transition and are focussed into lines striking a self assembled monolayer (SAM) of nonanethiol coated over a gold film on a single crystal Si wafer. The 20 eV internal energy of He* destroys the SAM molecules ultimately leaving a pattern of SAM on the gold. Subsequent etching of the unprotected region of the gold results in these featuresfootnotetextC. Allred et al., submitted to J. Appl. Phys.^,footnotetextC. Allred, Ph.D. Thesis, Stony Brook, NY (2009) - unpublished.. The lines are separated by 194.5 nm and they occupy about 60% of their spacing. AFM measurements of our first samples show their width to be ˜120 nm and their depth to be ˜10 nm.

Kramers degeneracy and relaxation in vanadium, niobium and tantalum clusters

NASA Astrophysics Data System (ADS)

Diaz-Bachs, A.; Katsnelson, M. I.; Kirilyuk, A.

2018-04-01

In this work we use magnetic deflection of V, Nb, and Ta atomic clusters to measure their magnetic moments. While only a few of the clusters show weak magnetism, all odd-numbered clusters deflect due to the presence of a single unpaired electron. Surprisingly, for the majority of V and Nb clusters an atomic-like behavior is found, which is a direct indication of the absence of spin–lattice interaction. This is in agreement with Kramers degeneracy theorem for systems with a half-integer spin. This purely quantum phenomenon is surprisingly observed for large systems of more than 20 atoms, and also indicates various quantum relaxation processes, via Raman two-phonon and Orbach high-spin mechanisms. In heavier, Ta clusters, the relaxation is always present, probably due to larger masses and thus lower phonon energies, as well as increased spin–orbit coupling.

Formation of fivefold axes in the FCC-metal nanoclusters

NASA Astrophysics Data System (ADS)

Myasnichenko, Vladimir S.; Starostenkov, Mikhail D.

2012-11-01

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

Catalysis by clusters with precise numbers of atoms

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

Tyo, Eric C.; Vajda, Stefan

2015-07-03

Clusters that contain only a small number of atoms can exhibit unique and often unexpected properties. The clusters are of particular interest in catalysis because they can act as individual active sites, and minor changes in size and composition – such as the addition or removal of a single atom – can have a substantial influence on the activity and selectivity of a reaction. Here we review recent progress in the synthesis, characterization and catalysis of well-defined sub-nanometre clusters. We examine work on size-selected supported clusters in ultra-high vacuum environments and under realistic reaction conditions, and explore the use ofmore » computational methods to provide a mechanistic understanding of their catalytic properties. We also highlight the potential of size-selected clusters to provide insights into important catalytic processes and their use in the development of novel catalytic systems.« less

Thermodynamic properties of small aggregates of rare-gas atoms

NASA Technical Reports Server (NTRS)

Etters, R. D.; Kaelberer, J.

1975-01-01

The present work reports on the equilibrium thermodynamic properties of small clusters of xenon, krypton, and argon atoms, determined from a biased random-walk Monte Carlo procedure. Cluster sizes ranged from 3 to 13 atoms. Each cluster was found to have an abrupt liquid-gas phase transition at a temperature much less than for the bulk material. An abrupt solid-liquid transition is observed for thirteen- and eleven-particle clusters. For cluster sizes smaller than 11, a gradual transition from solid to liquid occurred over a fairly broad range of temperatures. Distribution of number of bond lengths as a function of bond length was calculated for several systems at various temperatures. The effects of box boundary conditions are discussed. Results show the importance of a correct description of boundary conditions. A surprising result is the slow rate at which system properties approach bulk behavior as cluster size is increased.

Photodissociation and caging of HBr and HI molecules on the surface of large rare gas clusters.

PubMed

Baumfalk, R; Nahler, N H; Buck, U

2001-01-01

Photodissociation experiments were carried out at a wavelength of 243 nm for single HBr and HI molecules adsorbed on the surface of large Nen, Arn, Krn and Xen clusters. The average size is about = 130; the size ranges = 62-139 for the system HBr-Arn and = 110-830 for HI-Xen were covered. In this way the dependence of the photodissociation dynamics on both the size and the rare gas host cluster was investigated. The main observable is the kinetic energy distribution of the outgoing H atoms. The key results are that we do not find any size dependence for either system but that we observe a strong dependence on the rare gas clusters. All systems exhibit H atoms with no energy loss that indicate direct cage exit and those with nearly zero energy that are an indication of complete caging. The intensity ratio of caged to uncaged H atoms is largest for Nen, decreases with increasing mass of the cage atoms, and is weakest for Xen. On the basis of accompanying calculations this behaviour is attributed to the large amplitude motion of the light H atom. This leads to direct cage exit and penetration of the atom through the cluster with different energy transfer per collision depending on the rare gas atoms. The differences between HBr and HI molecules are attributed to different surface states, a flat and an encapsulated site.

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

Numakura, H.

The structure and the formation mechanism of oxides during internal oxidation have attracted much attention, and extensive studies have been carried out on this subject. Recently, Jang et al. reported the results of atom-probe microanalysis of oxide particles, or solute-oxygen clusters, in an internally oxidized Cu-0.16 at.% Mg alloy. They found that the composition varies from particle to particle even in the same specimen, and reported that some clusters consist only of magnesium atoms. On the basis of the results, they suggested that the oxidation proceeds in this alloy as follows: (1) the solute atoms form clusters, (2) the clustersmore » absorb oxygen atoms to form both hypo- and hyperstoichiometric oxide particles, (3) the particles grow to form the stoichiometric oxide, MgO. They show the presence of Mg atom clusters with no oxygen association. By assuming that the analyzed area is in the unoxidized region, i.e., ahead of the oxidation front, they interpret this observation as evidence for clustering of the solute atoms prior to oxide formation. However, according to the phase diagram, such clustering is not expected in the absence of oxygen, since the solute concentration, 0.16 at.%, is far below the solubility limit at the oxidation temperature of 900[degree]C, about 3.5 at.%. In atom probe experiments, it sometimes happens that detection efficiencies for different ion species are considerably different because some experimental parameters are not chosen properly. It seems possible that the data resulted from an unusually low detection efficiency for O ions. Since their conclusion raises an important issue on the mechanism of internal oxidation, it is desirable to examine experimental conditions carefully, and to check the reproducibility of data.« less

Structures and stability of metal-doped Ge nM (n = 9, 10) clusters

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

Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua

The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge 9 and Ge 10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge n clusters. However, the neutral and cationic FeGe 9,10,MnGe 9,10 and Ge 10Al are cage-like withmore » the metal atom encapsulated inside. Such cage-like transition metal doped Ge n clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge 9,10Fe and Ge 9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

Structures and stability of metal-doped Ge nM (n = 9, 10) clusters

DOE PAGES

Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; ...

2015-06-26

The lowest-energy structures of neutral and cationic Ge nM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge 9 and Ge 10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Ge n clusters. However, the neutral and cationic FeGe 9,10,MnGe 9,10 and Ge 10Al are cage-like withmore » the metal atom encapsulated inside. Such cage-like transition metal doped Ge n clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge 9,10Fe and Ge 9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.« less

Structures and stability of metal-doped GenM (n = 9, 10) clusters

NASA Astrophysics Data System (ADS)

Qin, Wei; Lu, Wen-Cai; Xia, Lin-Hua; Zhao, Li-Zhen; Zang, Qing-Jun; Wang, C. Z.; Ho, K. M.

2015-06-01

The lowest-energy structures of neutral and cationic GenM (n = 9, 10; M = Si, Li, Mg, Al, Fe, Mn, Pb, Au, Ag, Yb, Pm and Dy) clusters were studied by genetic algorithm (GA) and first-principles calculations. The calculation results show that doping of the metal atoms and Si into Ge9 and Ge10 clusters is energetically favorable. Most of the metal-doped Ge cluster structures can be viewed as adding or substituting metal atom on the surface of the corresponding ground-state Gen clusters. However, the neutral and cationic FeGe9,10,MnGe9,10 and Ge10Al are cage-like with the metal atom encapsulated inside. Such cage-like transition metal doped Gen clusters are shown to have higher adsorption energy and thermal stability. Our calculation results suggest that Ge9,10Fe and Ge9Si would be used as building blocks in cluster-assembled nanomaterials because of their high stabilities.

Faraday rotation enhancement of gold coated Fe2O3 nanoparticles: comparison of experiment and theory.

PubMed

Dani, Raj Kumar; Wang, Hongwang; Bossmann, Stefan H; Wysin, Gary; Chikan, Viktor

2011-12-14

Understanding plasmonic enhancement of nanoscale magnetic materials is important to evaluate their potential for application. In this study, the Faraday rotation (FR) enhancement of gold coated Fe(2)O(3) nanoparticles (NP) is investigated experimentally and theoretically. The experiment shows that the Faraday rotation of a Fe(2)O(3) NP solution changes from approximately 3 rad/Tm to 10 rad/Tm as 5 nm gold shell is coated on a 9.7 nm Fe(2)O(3) core at 632 nm. The results also show how the volume fraction normalized Faraday rotation varies with the gold shell thickness. From the comparison of experiment and calculated Faraday rotation based on the Maxwell-Garnett theory, it is concluded that the enhancement and shell dependence of Faraday rotation of Fe(2)O(3) NPs is a result of the shifting plasmon resonance of the composite NP. In addition, the clustering of the NPs induces a different phase lag on the Faraday signal, which suggests that the collective response of the magnetic NP aggregates needs to be considered even in solution. From the Faraday phase lag, the estimated time of the full alignment of the magnetic spins of bare (cluster size 160 nm) and gold coated NPs (cluster size 90 nm) are found to be 0.65 and 0.17 μs. The calculation includes a simple theoretical approach based on the Bruggeman theory to account for the aggregation and its effect on the Faraday rotation. The Bruggeman model provides a qualitatively better agreement with the experimentally observed Faraday rotation and points out the importance of making a connection between component properties and the average "effective" optical behavior of the Faraday medium containing magnetic nanoparticles. © 2011 American Institute of Physics

Structural, electronic and vibrational properties of small GaxNy (x+y = 2 5) nanoclusters: a B3LYP-DFT study

NASA Astrophysics Data System (ADS)

Yadav, P. S.; Yadav, R. K.; Agrawal, B. K.

2007-02-01

An ab initio study of the stability, structural and electronic properties has been made for 49 gallium nitride nanoclusters, GaxNy (x+y = 2-5). Among the various configurations corresponding to a fixed x+y = n value, the configuration possessing the maximum value of binding energy (BE) is named as the most stable structure. The vibrational and optical properties have been investigated only for the most stable structures. A B3LYP-DFT/6-311G(3df) method has been employed to optimize the geometries of the nanoclusters fully. The binding energies (BEs), highest-occupied and lowest-unoccupied molecular orbital (HOMO-LUMO) gaps and the bond lengths have been obtained for all the clusters. We have considered the zero-point energy (ZPE) corrections ignored by the earlier workers. The adiabatic and vertical ionization potentials (IPs) and electron affinities (EAs), charge on atoms, dipole moments, vibrational frequencies, infrared intensities (IR Int.), relative infrared intensities (Rel. IR Int.) and Raman scattering activities have been investigated for the most stable structures. The configurations containing the N atoms in majority are seen to be the most stable structures. The strong N-N bond has an important role in stabilizing the clusters. For clusters containing one Ga atom and all the others as N atoms, the BE increases monotonically with the number of the N atoms. The HOMO-LUMO gap and IP fluctuate with the cluster size n, having larger values for the clusters containing odd number of N atoms. On the other hand, the EA decreases with the cluster size up to n = 3, and shows slow fluctuations thereafter for the larger clusters. In general, the adiabatic IP (EA) is smaller (greater) than the vertical IP (EA) because of the lower energies of the most stable ground state of the cationic (anionic) clusters. The optical absorption spectrum or electron energy loss spectrum (EELS) is unique for every cluster, and may be used to characterize a specific cluster. All the predicted physical quantities are in good agreement with the experimental data wherever available. The growth of these most stable structures should be possible in experiments.

Towards of Vanadium Pentoxide Nanotubes and Thiols using Gold Nanoparticles

NASA Astrophysics Data System (ADS)

Lavayen, V.; Gonzalez, G.; Cardenas, G.; Sotomayor Torres, C. M.

2005-09-01

The template-directed synthesis is a promising route to realise 1-D nanostructures, an example of which is the formation of vanadium pentoxide nanotubes. In this work we report the interchange of long alkyl amines with alkyl thiols, this reaction was followed using gold nanoparticles prepared by the Chemical Liquid Deposition (CLD) method. The diameter of the gold clusters was 9 Å with a stability of about 85 days. SEM, TEM, EDAX and electron diffraction was the techniques used for the characterization of the reactions.

Secret in the Margins: Rutherford's Gold Foil Experiment

ERIC Educational Resources Information Center

Aydin, Sevgi; Hanuscin, Deborah L.

2011-01-01

In this article, the authors describe a lesson that uses the 5E Learning Cycle to help students not only understand the atomic model but also how Ernest Rutherford helped develop it. The lesson uses Rutherford's gold foil experiment to focus on three aspects of the nature of science: the empirical nature of science, the tentativeness of scientific…

Recovery of gold from electronic waste using chemical assisted microbial biosorption (hybrid) technique.

PubMed

Sheel, Anvita; Pant, Deepak

2018-01-01

The aim of present study was to develop a modified method of gold recovery from e-waste. Selective biosorption of gold from contact point of printed circuit board was achieved by using the combination of ammonium thiosulfate (AT) and Lactobacillus acidophilus (LA).Improvement in biosorption was due to the π-π interaction and resultant change in amide absorption bond between AT and LA, as evidenced by infrared spectroscopy. Selection was justified by some basic postulates of ionic radii and confirmed by inductively coupled plasma atomic emission spectroscopy. This methodology provides a unique leaching-sorption method for gold recovery and 85% of gold was recovered (from AT leachant) by the proposed combination. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2018-06-25

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

New Scenario of Dynamical Heterogeneity in Supercooled Liquid and Glassy States of 2D Monatomic System.

PubMed

Van Hoang, Vo; Teboul, Victor; Odagaki, Takashi

2015-12-24

Via analysis of spatiotemporal arrangements of atoms based on their dynamics in supercooled liquid and glassy states of a 2D monatomic system with a double-well Lennard-Jones-Gauss (LJG) interaction potential, we find a new scenario of dynamical heterogeneity. Atoms with the same or very close mobility have a tendency to aggregate into clusters. The number of atoms with high mobility (and size of their clusters) increases with decreasing temperature passing over a maximum before decreasing down to zero. Position of the peak moves toward a lower temperature if mobility of atoms in clusters is lower together with an enhancement of height of the peak. In contrast, the number of atoms with very low mobility or solidlike atoms (and size of their clusters) has a tendency to increase with decreasing temperature and then it suddenly increases in the vicinity of the glass transition temperature leading to the formation of a glassy state. A sudden increase in the number of strongly correlated solidlike atoms in the vicinity of a glass transition temperature (Tg) may be an origin of a drastical increase in viscosity of the glass-forming systems approaching the glass transition. In fact, we find that the diffusion coefficient decays exponentially with a fraction of solidlike atoms exhibiting a sudden decrease in the vicinity of the glass transition region.

Synthesis of gold nanoparticles with graphene oxide.

PubMed

Wang, Wenshuo; He, Dawei; Zhang, Xiqing; Duan, Jiahua; Wu, Hongpeng; Xu, Haiteng; Wang, Yongsheng

2014-05-01

Single sheets of functionalized graphene oxide are derived through chemical exfoliation of natural flake graphite. We present an effective synthetic method of graphene-gold nanoparticles hybrid nanocomposites. AFM (Atomic Force Microscope) was used to measure the thickness of the individual GO nanosheet. FTIR (Fourier transform infrared) spectroscopy was used to verify the attachment of oxygen functionalities on the surface of graphene oxide. TEM (Transmission Electron Microscope) data revealed the average diameters of the gold colloids and characterized the composite particles situation. Absorption spectroscopy showed that before and after synthesis the gold particle size did not change. Our studies indicate that the hybrid is potential substrates for catalysts and biosensors.

Two-dimensional gold nanostructures with high activity for selective oxidation of carbon–hydrogen bonds

PubMed Central

Wang, Liang; Zhu, Yihan; Wang, Jian-Qiang; Liu, Fudong; Huang, Jianfeng; Meng, Xiangju; Basset, Jean-Marie; Han, Yu; Xiao, Feng-Shou

2015-01-01

Efficient synthesis of stable two-dimensional (2D) noble metal catalysts is a challenging topic. Here we report the facile synthesis of 2D gold nanosheets via a wet chemistry method, by using layered double hydroxide as the template. Detailed characterization with electron microscopy and X-ray photoelectron spectroscopy demonstrates that the nanosheets are negatively charged and [001] oriented with thicknesses varying from single to a few atomic layers. X-ray absorption spectroscopy reveals unusually low gold–gold coordination numbers. These gold nanosheets exhibit high catalytic activity and stability in the solvent-free selective oxidation of carbon–hydrogen bonds with molecular oxygen. PMID:25902034

Comparison of amino acids interaction with gold nanoparticle.

PubMed

Ramezani, Fatemeh; Amanlou, Massoud; Rafii-Tabar, Hashem

2014-04-01

The study of nanomaterial/biomolecule interface is an important emerging field in bionanoscience, and additionally in many biological processes such as hard-tissue growth and cell-surface adhesion. To have a deeper understanding of the amino acids/gold nanoparticle assemblies, the adsorption of these amino acids on the gold nanoparticles (GNPs) has been investigated via molecular dynamics simulation. In these simulations, all the constituent atoms of the nanoparticles were considered to be dynamic. The geometries of amino acids, when adsorbed on the nanoparticle, were studied and their flexibilities were compared with one another. The interaction of each of 20 amino acids was considered with 3 and 8 nm gold GNPs.

Environmental impact of the gold mining industry in Ghana.

PubMed

Bamford, S A; Osae, E; Aboh, I; Biney, C A; Antwi, L A

1990-01-01

X-ray Fluorescence (XRF) Analysis and Atomic Absorption Spectrophotometry (AAS) have been used in assessing heavy metal pollution from some gold mines in Ghana. The presence and levels of heavy metals in gold ore, gold tailings, inland waters, and river sediments have been determined. Using these techniques, the heavy metals: Cr, Mn, Fe, Cu, Zn, As, Pb, Rb, Sr, Y, Zr, and Nb were identified in some of the solid samples within a concentration range of 0.08 ppm--4.9%. However, the inland waters showed the presence of only Fe and Zn at levels of 0.08-2.4 micrograms/mL.