The Effect of Experimental Geometry and Initial Conditions on the Shape of Coherent Population Trapping Resonances on the Fine Structure Levels of Thallium Atoms

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

Karagodova, T.Ya.

2005-06-15

Specific features of the coherent population trapping effect are considered in the generalized {lambda} system whose lower levels are the magnetic sublevels of the fine structure levels of the thallium atom. Numerical experiments were performed aimed at examination of the coherent population trapping for the case of nontrivial, but feasible, initial populations of the upper metastable fine structure level. Such populations may be obtained, for example, due to the photodissociation of TlBr molecules. The possibility of reducing the number of resonances of the coherent population trapping in a multilevel system, which may be useful for high-resolution spectroscopy, is demonstrated. Itmore » is shown that the magnitude and shape of the resonances can be controlled by varying the orientation of the polarization vectors of the light field components with respect to each other and to a magnetic field. In addition, studying the shape of the coherent population trapping resonances for the atoms obtained by photodissociation of molecules may provide information about these molecules.« less

CS and IOS approximations for fine structure transitions in Na(/sup 2/P)--He(/sup 1/S) collisions

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

Fitz, D.E.; Kouri, D.J.

1980-11-15

The l-average CS and IOS approximations are extended to treat fine structure transitions in /sup 2/P atom--/sup 1/S atom scattering. Calculations of degeneracy averaged probabilities and differential cross sections for Na(/sup 2/P)+He(/sup 1/S) collisions in the CS and IOS methods agree well with the CC results. The present nonunitarized form of the CS approximation fails to properly predict all of the jm..-->..j'm' sections and in particular leads to a selection rule forbidding jm..-->..j--m transitions for j=half-odd integer values.

Identification of B-K near edge x-ray absorption fine structure peaks of boron nitride thin films prepared by sputtering deposition

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

Niibe, Masahito; Miyamoto, Kazuyoshi; Mitamura, Tohru

2010-09-15

Four {pi}{sup *} resonance peaks were observed in the B-K near edge x-ray absorption fine structure spectra of boron nitride thin films prepared by magnetron sputtering. In the past, these peaks have been explained as the K-absorption of boron atoms, which are present in environment containing nitrogen vacancies, the number of which is 1-3 corresponding to the three peaks at higher photon energy. However, the authors found that there was a strong correlation between the intensities of these three peaks and that of O-K absorption after wide range scanning and simultaneous measurement of nitrogen and oxygen K-absorptions of the BNmore » films. Therefore, the authors conclude that these three peaks at the higher energy side correspond to boron atoms bound to one-to-three oxygen atoms instead of three nitrogen atoms surrounding the boron atom in the h-BN structure. The result of the first-principles calculation with a simple cluster model supported the validity of this explanation.« less

Determination of the fine structure constant using helium fine structure.

PubMed

Smiciklas, Marc; Shiner, David

2010-09-17

We measure 31,908,131.25(30) kHz for the 2(3)}P J=0 to 2 fine structure interval in helium. The difference between this and theory to order mα7 (20 Hz numerical uncertainty) implies 0.22(30) kHz for uncalculated terms. The measurement is performed by using atomic beam and electro-optic laser techniques. Various checks include a 3He 2{3}S hyperfine measurement. We can obtain an independent value for the fine structure constant α with a 5 ppb experimental uncertainty. However, dominant mα8 terms (potentially 1.2 kHz) limit the overall uncertainty to a less competitive 20 ppb in α.

Neural network approach for characterizing structural transformations by X-ray absorption fine structure

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

Timoshenko, Janis; Frenkel, Anatoly I.; Cintins, Arturs

The knowledge of coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use artificial neural network approach to extract the information on the local structure and its in-situ changes directly from the X-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic andmore » austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from body-centered to face-centered cubic arrangement of iron atoms. Furthermore, this method is attractive for a broad range of materials and experimental conditions« less

Neural network approach for characterizing structural transformations by X-ray absorption fine structure

DOE PAGES

Timoshenko, Janis; Frenkel, Anatoly I.; Cintins, Arturs; ...

2018-05-25

The knowledge of coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use artificial neural network approach to extract the information on the local structure and its in-situ changes directly from the X-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic andmore » austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from body-centered to face-centered cubic arrangement of iron atoms. Furthermore, this method is attractive for a broad range of materials and experimental conditions« less

Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy

NASA Astrophysics Data System (ADS)

Timoshenko, Janis; Anspoks, Andris; Cintins, Arturs; Kuzmin, Alexei; Purans, Juris; Frenkel, Anatoly I.

2018-06-01

The knowledge of the coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use an artificial neural network approach to extract the information on the local structure and its in situ changes directly from the x-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic and austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from a body-centered to a face-centered cubic arrangement of iron atoms. This method is attractive for a broad range of materials and experimental conditions.

POLARIZED SCATTERING OF LIGHT FOR ARBITRARY MAGNETIC FIELDS WITH LEVEL-CROSSINGS FROM THE COMBINATION OF HYPERFINE AND FINE STRUCTURE SPLITTINGS

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

Sowmya, K.; Nagendra, K. N.; Sampoorna, M.

2015-12-01

Interference between magnetic substates of the hyperfine structure states belonging to different fine structure states of the same term influences the polarization for some of the diagnostically important lines of the Sun's spectrum, like the sodium and lithium doublets. The polarization signatures of this combined interference contain information on the properties of the solar magnetic fields. Motivated by this, in the present paper, we study the problem of polarized scattering on a two-term atom with hyperfine structure by accounting for the partial redistribution in the photon frequencies arising due to the Doppler motions of the atoms. We consider the scatteringmore » atoms to be under the influence of a magnetic field of arbitrary strength and develop a formalism based on the Kramers–Heisenberg approach to calculate the scattering cross section for this process. We explore the rich polarization effects that arise from various level-crossings in the Paschen–Back regime in a single scattering case using the lithium atomic system as a concrete example that is relevant to the Sun.« less

Additive Mixing and Conformal Coating of Noniridescent Structural Colors with Robust Mechanical Properties Fabricated by Atomization Deposition.

PubMed

Li, Qingsong; Zhang, Yafeng; Shi, Lei; Qiu, Huihui; Zhang, Suming; Qi, Ning; Hu, Jianchen; Yuan, Wei; Zhang, Xiaohua; Zhang, Ke-Qin

2018-04-24

Artificial structural colors based on short-range-ordered amorphous photonic structures (APSs) have attracted great scientific and industrial interest in recent years. However, the previously reported methods of self-assembling colloidal nanoparticles lack fine control of the APS coating and fixation on substrates and poorly realize three-dimensional (3D) conformal coatings for objects with irregular or highly curved surfaces. In this paper, atomization deposition of silica colloidal nanoparticles with poly(vinyl alcohol) as the additive is proposed to solve the above problems. By finely controlling the thicknesses of APS coatings, additive mixing of noniridescent structural colors is easily realized. Based on the intrinsic omnidirectional feature of atomization, a one-step 3D homogeneous conformal coating is also readily realized on various irregular or highly curved surfaces, including papers, resins, metal plates, ceramics, and flexible silk fabrics. The vivid coatings on silk fabrics by atomization deposition possess robust mechanical properties, which are confirmed by rubbing and laundering tests, showing great potential in developing an environmentally friendly coloring technique in the textile industry.

Tracing Magnetic Fields With The Polarization Of Submillimeter Lines

NASA Astrophysics Data System (ADS)

Zhang, Heshou; Yan, Huirong

2017-10-01

Magnetic fields play important roles in many astrophysical processes. However, there is no universal diagnostic for the magnetic fields in the interstellar medium (ISM) and each magnetic tracer has its limitation. Any new detection method is thus valuable. Theoretical studies have shown that submillimeter fine-structure lines are polarized due to atomic alignment by Ultraviolet (UV) photon-excitation, which opens up a new avenue to probe interstellar magnetic fields. The method is applicable to all radiative-excitation dominant region, e.g., H II Regions, PDRs. The polarization of the submillimeter fine-structure lines induced by atomic alignment could be substantial and the applicability of using the spectro-polarimetry of atomic lines to trace magnetic fields has been supported by synthetic observations of simulated ISM in our recent paper. Our results demonstrate that the polarization of submillimeter atomic lines is a powerful magnetic tracer and add great value to the observational studies of the submilimeter astronomy.

Atomic Fine-Structure Diagnostic and Cooling Transitions for Far Infrared and Submillimeter Observations

NASA Astrophysics Data System (ADS)

Balance, Connor

Some of the strongest emission lines observed from a variety of astronomical sources originate from transitions between fine-structure levels in the ground term of neutral atoms and lowly-charged ions. These fine-structure levels are populated due to collisions with -, H+, H, He, and/or H2 depending on the temperature and ionization fraction of e the environment. As fine-structure excitation measurements are rare, modeling applications depend on theoretically determined rate coefficients. However, for many ions electron collision studies have not been performed for a decade or more, while over that time period the theoretical/computational methodology has significantly advanced. For heavy-particle collisions, very few systems have been studied. As a result, most models rely on estimates or on low-quality collisional data for fine-structure excitation. To significantly advance the state of fine-structure data for astrophysical models, we propose a collaborative effort in electron collisions, heavy-particle collisions, and quantum chemistry. Using the R-matrix method, fine-structure excitation due to electron collisions will be investigated for C, O, Ne^+, Ne^2+, Ar^+, Ar^2+, Fe, Fe^+, and Fe^2+. Fine-structure excitation due to heavy-particle collisions will be studied with a fully quantum molecular-orbital approach using potential energy surfaces computed with a multireference configuration-interaction method. The systems to be studied include: C/H^+, C/H2, O/H^+, O/H2, Ne^+/H, Ne^+/H2, Ne^2+/H, Ne^2+/H2, Fe/H^+, Fe^+/H, and Fe^2+/H. 2D rigid-rotor surfaces will be constructed for H2 collisions, internuclear distance dependent spin-orbit coupling will be computed in some cases, and all rate coefficients will be obtained for the temperature range 10-2000 K. The availability the proposed fine-structure excitation data will lead to deeper examination and understanding of the properties of many astrophysical environments, including young stellar objects, protoplanetary disks, planetary nebulae, photodissociation regions, active galactic nuclei, and x-ray dominated regions, hence elevating the scientific return from current (SOFIA, Spitzer, Herschel, HST) and upcoming (JWST) NASA IR/Submm astrophysics missions, as well as from ground-based telescopes.

Effect of aluminum on the local structure of silicon in zeolites as studied by Si K edge X-ray absorption near-edge fine structure: spectra simulation with a non-muffin tin atomic background.

PubMed

Bugaev, Lusegen A; Bokhoven, Jeroen A van; Khrapko, Valerii V

2009-04-09

Experimental Si K edge X-ray absorption near-edge fine structure (XANES) of zeolite faujasite, mordenite, and beta are interpreted by means of the FEFF8 code, replacing the theoretical atomic background mu(0) by a background that was extracted from an experimental spectrum. To some extent, this diminished the effect of the inaccuracy introduced by the MT potential and accounted for the intrinsic loss of photoelectrons. The agreement of the theoretical and experimental spectra at energies above the white lines enabled us to identify structural distortion around silicon, which occurs with increasing aluminum content. The Si K edge XANES spectra are very sensitive to slight distortions in the silicon coordination. Placing an aluminum atom on a nearest neighboring T site causes a distortion in the silicon tetrahedron, shortening one of the silicon-oxygen bonds relative to the other three.

The use of C-near edge X-ray absorption fine structure spectroscopy for the elaboration of chemistry in lignocellulosics

Treesearch

Lucian A. Lucia; Hiroki Nanko; Alan W. Rudie; Doug G. Mancosky; Sue Wirick

2006-01-01

The research presented elucidates the oxidation chemistry occurring in hydrogen peroxide bleached kraft pulp fibers by employing carbon near edge x-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft x-ray technique that selectively interrogates atomic moieties using photoelectrons (Xrays) of variable energies. The X1A beam line at the National...

Local structure and polarization resistance of Ce doped SrMnO{sub 3} using extended x-ray fine structure analysis

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

Ryu, Jiseung; Lee, Heesoo, E-mail: heesoo@pusan.ac.kr

2014-09-15

Changes to the local structure of Sr and Mn atoms in Sr{sub 1−x}Ce{sub x}MnO{sub 3} (SCM) according to increasing Ce content and the effect of the structural change on the polarization resistance of SCM were investigated. The reduction of manganese was confirmed by the absorption edge shift of the Mn K-edge toward lower energies. The noise of oscillation in extended X-ray absorption fine structure k{sup 3}χ data at Mn K-edge reveals the distortion of the local structure of Mn atoms, and the peak that indicates the bonding length of Mn-O, Sr/Ce, and -Mn decreased with the addition of Ce contentmore » in Fourier transformations of the Mn K-edge. The distortion of the local structure at Mn atoms was affected by the reduced manganese ions having larger ionic radii than Mn{sup 4+}. Meanwhile, few distortions of local atomic structures of Sr atoms occurred, and the average nearest neighboring distances of Sr-O and Sr-Mn are ∼2.13 Å and ∼2.95 Å, respectively. The average bonding lengths of the Ce-O and Ce-Mn increased because the ionic radius of substituted Ce ion with 12 coordination number is smaller than that of Sr ion, which leads the reduction of Mn ions and the distortion of local structure at the substituted A-site. Therefore, we reasoned that the distortion of the local atomic structure at Mn atoms in MnO{sub 6} and Ce atoms in A-site is one of the causes for interrupting oxygen ion transfers as a geometric factor, which results in an increase in the polarization resistance of SCM within the Ce composition range from 10 mol. % to 30 mol. %.« less

Defect propagation in one-, two-, and three-dimensional compounds doped by magnetic atoms

DOE PAGES

Furrer, A.; Podlesnyak, A.; Krämer, K. W.; ...

2014-10-29

Inelastic neutron scattering experiments were performed to study manganese(II) dimer excitations in the diluted one-, two-, and three-dimensional compounds CsMn xMg 1-xBr 3, K 2Mn xZn 1-xF 4, and KMn xZn 1-xF 3 (x≤0.10), respectively. The transitions from the ground-state singlet to the excited triplet, split into a doublet and a singlet due to the single-ion anisotropy, exhibit remarkable fine structures. These unusual features are attributed to local structural inhomogeneities induced by the dopant Mn atoms which act like lattice defects. Statistical models support the theoretically predicted decay of atomic displacements according to 1/r 2, 1/r, and constant (for three-,more » two-, and one-dimensional compounds, respectively) where r denotes the distance of the displaced atoms from the defect. In conclusion, the observed fine structures allow a direct determination of the local exchange interactions J, and the local intradimer distances R can be derived through the linear law dJ/dR.« less

Validation and extraction of molecular-geometry information from small-molecule databases.

PubMed

Long, Fei; Nicholls, Robert A; Emsley, Paul; Graǽulis, Saulius; Merkys, Andrius; Vaitkus, Antanas; Murshudov, Garib N

2017-02-01

A freely available small-molecule structure database, the Crystallography Open Database (COD), is used for the extraction of molecular-geometry information on small-molecule compounds. The results are used for the generation of new ligand descriptions, which are subsequently used by macromolecular model-building and structure-refinement software. To increase the reliability of the derived data, and therefore the new ligand descriptions, the entries from this database were subjected to very strict validation. The selection criteria made sure that the crystal structures used to derive atom types, bond and angle classes are of sufficiently high quality. Any suspicious entries at a crystal or molecular level were removed from further consideration. The selection criteria included (i) the resolution of the data used for refinement (entries solved at 0.84 Å resolution or higher) and (ii) the structure-solution method (structures must be from a single-crystal experiment and all atoms of generated molecules must have full occupancies), as well as basic sanity checks such as (iii) consistency between the valences and the number of connections between atoms, (iv) acceptable bond-length deviations from the expected values and (v) detection of atomic collisions. The derived atom types and bond classes were then validated using high-order moment-based statistical techniques. The results of the statistical analyses were fed back to fine-tune the atom typing. The developed procedure was repeated four times, resulting in fine-grained atom typing, bond and angle classes. The procedure will be repeated in the future as and when new entries are deposited in the COD. The whole procedure can also be applied to any source of small-molecule structures, including the Cambridge Structural Database and the ZINC database.

Near-edge X-ray absorption spectra for metallic Cu and Mn

NASA Astrophysics Data System (ADS)

Greaves, G. N.; Durham, P. J.; Diakun, G.; Quinn, P.

1981-11-01

The measurement of X-ray absorption fine structure of metals- both in the extended region (EXAFS) as well as in the near edge region (XANES)-has been widely discussed (see refs 1-6 for Cu and refs 7-9 for Mn). The recent availability of intense X-ray fluxes from storage rings has usually been exploited for EXAFS leaving the XANES often with poorer resolution than earlier work performed on conventional sources (for example, compare the near edge structure for copper in ref. 1 with refs 3 or 6). In addition, whilst the theory and analysis of EXAFS is relatively well-established2,10, a theory for the strong scattering regime near to the absorption edge has only recently been developed11. We report here the first high resolution XANES spectra for Cu and Mn which were performed at the SRS storage ring at Daresbury. Although both metals have close-packed structures consisting of atoms of similar size their local atomic structure is different in detail. Significant differences are found in their respective XANES reflecting the senstivity of this region of the X-ray absorption fine structure to the local atomic structure. Spectra for the two metals have been analysed using the new multiple scattering formalism. This is a real space calculation and unlike a conventional band structure approach it does not require structural periodicity but works from the local arrangement of atoms.

Precise Measurements of the Masses of Cs, Rb and Na A New Route to the Fine Structure Constant

NASA Astrophysics Data System (ADS)

Rainville, Simon; Bradley, Michael P.; Porto, James V.; Thompson, James K.; Pritchard, David E.

2001-01-01

We report new values for the atomic masses of the alkali 133Cs, 87Rb, 85Rb, and 23Na with uncertainties ≤ 0.2 ppb. These results, obtained using Penning trap single ion mass spectrometry, are typically two orders of magnitude more accurate than previously measured values. Combined with values of h/m atom from atom interferometry measurements and accurate wavelength measurements for different atoms, these values will lead to new ppb-level determinations of the molar Planck constant N A h and the fine structure constant α. This route to α is based on simple physics. It can potentially achieve the several ppb level of accuracy needed to test the QED determination of α extracted from measurements of the electron g factor. We also demonstrate an electronic cooling technique that cools our detector and ion below the 4 K ambient temperature. This technique improves by about a factor of three our ability to measure the ion's axial motion.

Determination of the fine structure constant based on BLOCH oscillations of ultracold atoms in a vertical optical lattice.

PubMed

Cladé, Pierre; de Mirandes, Estefania; Cadoret, Malo; Guellati-Khélifa, Saïda; Schwob, Catherine; Nez, François; Julien, Lucile; Biraben, François

2006-01-27

We report an accurate measurement of the recoil velocity of 87Rb atoms based on Bloch oscillations in a vertical accelerated optical lattice. We transfer about 900 recoil momenta with an efficiency of 99.97% per recoil. A set of 72 measurements of the recoil velocity, each one with a relative uncertainty of about 33 ppb in 20 min integration time, leads to a determination of the fine structure constant with a statistical relative uncertainty of 4.4 ppb. The detailed analysis of the different systematic errors yields to a relative uncertainty of 6.7 ppb. The deduced value of alpha-1 is 137.035 998 78(91).

Combination of BLOCH oscillations with a Ramsey-Bordé interferometer: new determination of the fine structure constant.

PubMed

Cadoret, Malo; de Mirandes, Estefania; Cladé, Pierre; Guellati-Khélifa, Saïda; Schwob, Catherine; Nez, François; Julien, Lucile; Biraben, François

2008-12-05

We report a new experimental scheme which combines atom interferometry with Bloch oscillations to provide a new measurement of the ratio h/mRb. By using Bloch oscillations, we impart to the atoms up to 1600 recoil momenta and thus we improve the accuracy on the recoil velocity measurement. The deduced value of h/mRb leads to a new determination of the fine structure constant alpha(-1) =137.03599945 (62) with a relative uncertainty of 4.6 x 10(-9). The comparison of this result with the value deduced from the measurement of the electron anomaly provides the most stringent test of QED.

Spin-interaction effects for ultralong-range Rydberg molecules in a magnetic field

NASA Astrophysics Data System (ADS)

Hummel, Frederic; Fey, Christian; Schmelcher, Peter

2018-04-01

We investigate the fine and spin structure of ultralong-range Rydberg molecules exposed to a homogeneous magnetic field. Each molecule consists of a 87Rb Rydberg atom the outer electron of which interacts via spin-dependent s - and p -wave scattering with a polarizable 87Rb ground-state atom. Our model includes also the hyperfine structure of the ground-state atom as well as spin-orbit couplings of the Rydberg and ground-state atom. We focus on d -Rydberg states and principal quantum numbers n in the vicinity of 40. The electronic structure and vibrational states are determined in the framework of the Born-Oppenheimer approximation for varying field strengths ranging from a few up to hundred Gauss. The results show that the interplay between the scattering interactions and the spin couplings gives rise to a large variety of molecular states in different spin configurations as well as in different spatial arrangements that can be tuned by the magnetic field. This includes relatively regularly shaped energy surfaces in a regime where the Zeeman splitting is large compared to the scattering interaction but small compared to the Rydberg fine structure, as well as more complex structures for both weaker and stronger fields. We quantify the impact of spin couplings by comparing the extended theory to a spin-independent model.

Novel visualization studies of lignocellulosic oxidation chemistry by application of C-near edge X-ray absorption fine structure spectroscopy

Treesearch

Douglas G. Mancosky; Lucian A. Lucia; Hiroki Nanko; Sue Wirick; Alan W. Rudie; Robert Braun

2005-01-01

The research presented herein is the first attempt to probe the chemical nature of lignocellulosic samples by the application of carbon near edge X-ray absorption fine structure spectroscopy (C-NEXAFS). C-NEXAFS is a soft X-ray technique that principally provides selective interrogation of discrete atomic moieties using photoelectrons of variable energies. The X1A beam...

Sulfur K-edge extended X-ray absorption fine structure spectroscopy of homoleptic thiolato complexes with Zn(II) and Cd(II).

PubMed

Matsunaga, Yuki; Fujisawa, Kiyoshi; Ibi, Naoko; Fujita, Mitsuharu; Ohashi, Tetuya; Amir, Nagina; Miyashita, Yoshitaro; Aika, Ken-Ichi; Izumi, Yasuo; Okamoto, Ken-Ichi

2006-02-01

The sulfur K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy is applied to homoleptic thiolato complexes with Zn(II) and Cd(II), (Et(4)N)[Zn(SAd)(3)] (1), (Et(4)N)(2)[{Zn(ScHex)(2)}(2)(mu-ScHex)(2)] (2), (Et(4)N)(2)[{Cd(ScHex)(2)}(2)(mu-ScHex)(2)] (3), (Et(4)N)(2)[{Cd(ScHex)}(4)(mu-ScHex)(6)] (4), [Zn(mu-SAd)(2)](n) (5), and [Cd(mu-SAd)(2)](n) (6) (HSAd=1-adamantanethiol, HScHex=cyclohexanethiol). The EXAFS results are consistent with the X-ray crystal data of 1-4. The structures of 5 and 6, which have not been determined by X-ray crystallography, are proposed to be polynuclear structures on the basis of the sulfur K-edge EXAFS, far-IR spectra, and elemental analysis. Clear evidences of the S...S interactions (between bridging atoms or neighboring sulfur atoms) and the S...C(far) interactions (in which C(far) atom is next to carbon atom directly bonded to sulfur atom) were observed in the EXAFS data for all complexes and thus lead to the reliable determination of the structures of 5 and 6 in combination with conventional zinc K-edge EXAFS analysis for 5. This new methodology, sulfur K-edge EXAFS, could be applied for the structural determination of in vivo metalloproteins as well as inorganic compounds.

Reduced-temperature crystallization of thin amorphous Fe80B20 films studied via empirical modeling of extended x-ray absorption fine structure

NASA Astrophysics Data System (ADS)

Harris, V. G.; Oliver, S. A.; Ayers, J. D.; Das, B. N.; Koon, N. C.

1996-04-01

The evolution of the local atomic environment around Fe atoms in very thin (15 nm), amorphous, partially crystallized and fully crystallized films of Fe80B20 was studied using extended x-ray absorption fine structure (EXAFS) measurements. The relative atomic fraction of each crystalline phase present in the annealed samples was extracted from the Fe EXAFS data by a least-squares fitting procedure, using data collected from t-Fe3B, t-Fe2B, and α-Fe standards. The type and relative fraction of the crystallization products follows the trends previously measured in Fe80B20 melt-spun ribbons, except for the fact that crystallization temperatures are ≊200 K lower than those measured in bulk equivalents. This greatly reduced crystallization temperature may arise from the dominant role of surface nucleation sites in the crystallization of very thin amorphous films.

Hydrogen positions in single nanocrystals revealed by electron diffraction

NASA Astrophysics Data System (ADS)

Palatinus, L.; Brázda, P.; Boullay, P.; Perez, O.; Klementová, M.; Petit, S.; Eigner, V.; Zaarour, M.; Mintova, S.

2017-01-01

The localization of hydrogen atoms is an essential part of crystal structure analysis, but it is difficult because of their small scattering power. We report the direct localization of hydrogen atoms in nanocrystalline materials, achieved using the recently developed approach of dynamical refinement of precession electron diffraction tomography data. We used this method to locate hydrogen atoms in both an organic (paracetamol) and an inorganic (framework cobalt aluminophosphate) material. The results demonstrate that the technique can reliably reveal fine structural details, including the positions of hydrogen atoms in single crystals with micro- to nanosized dimensions.

Characterization of local atomic structure in Co/Zn based ZIFs by XAFS

NASA Astrophysics Data System (ADS)

Podkovyrina, Yulia; Butova, Vera; Bulanova, Elena; Budnyk, Andriy; Kremennaya, Maria; Soldatov, Alexander; Lamberti, Carlo

2018-03-01

The local atomic structure in bimetallic Co/Zn zeolitic imidazolate frameworks (ZIFs) was studied using X-ray Absorption Fine Structure (XAFS) spectroscopy and theoretical calculations. The experimental Co K-edge and Zn K-edge XANES (X-ray Absorption Near Edge Structure) spectra of Zn1-xCoxC8H10N4 samples (x = 0.05, 0.25, 0.75) synthesized by microwave synthesis were compared with the data for the ZIF-67 (x=1) and ZIF-8 (x=0). Theoretical XANES spectra for the bimetallic ZIFs were calculated. It was shown that in bimetallic ZIFs the Co and Zn atoms have the similar local environment.

Atomic quantum simulation of the lattice gauge-Higgs model: Higgs couplings and emergence of exact local gauge symmetry.

PubMed

Kasamatsu, Kenichi; Ichinose, Ikuo; Matsui, Tetsuo

2013-09-13

Recently, the possibility of quantum simulation of dynamical gauge fields was pointed out by using a system of cold atoms trapped on each link in an optical lattice. However, to implement exact local gauge invariance, fine-tuning the interaction parameters among atoms is necessary. In the present Letter, we study the effect of violation of the U(1) local gauge invariance by relaxing the fine-tuning of the parameters and showing that a wide variety of cold atoms is still a faithful quantum simulator for a U(1) gauge-Higgs model containing a Higgs field sitting on sites. The clarification of the dynamics of this gauge-Higgs model sheds some light upon various unsolved problems, including the inflation process of the early Universe. We study the phase structure of this model by Monte Carlo simulation and also discuss the atomic characteristics of the Higgs phase in each simulator.

Atoms and Molecules Interacting with Light

NASA Astrophysics Data System (ADS)

van der Straten, Peter; Metcalf, Harold

2016-02-01

Part I. Atom-Light Interaction: 1. The classical physics pathway; Appendix 1.A. Damping force on an accelerating charge; Appendix 1.B. Hanle effect; Appendix 1.C. Optical tweezers; 2. Interaction of two-level atoms and light; Appendix 2.A. Pauli matrices for motion of the bloch vector; Appendix 2.B. The Ramsey method; Appendix 2.C. Echoes and interferometry; Appendix 2.D. Adiabatic rapid passage; Appendix 2.E Superposition and entanglement; 3. The atom-light interaction; Appendix 3.A. Proof of the oscillator strength theorem; Appendix 3.B. Electromagnetic fields; Appendix 3.C. The dipole approximation; Appendix 3.D. Time resolved fluorescence from multi-level atoms; 4. 'Forbidden' transitions; Appendix 4.A. Higher order approximations; 5. Spontaneous emission; Appendix 5.A. The quantum mechanical harmonic oscillator; Appendix 5.B. Field quantization; Appendix 5.C. Alternative theories to QED; 6. The density matrix; Appendix 6.A. The Liouville-von Neumann equation; Part II. Internal Structure: 7. The hydrogen atom; Appendix 7.A. Center-of-mass motion; Appendix 7.B. Coordinate systems; Appendix 7.C. Commuting operators; Appendix 7.D. Matrix elements of the radial wavefunctions; 8. Fine structure; Appendix 8.A. The Sommerfeld fine-structure constant; Appendix 8.B. Measurements of the fine structure 9. Effects of the nucleus; Appendix 9.A. Interacting magnetic dipoles; Appendix 9.B. Hyperfine structure for two spin =2 particles; Appendix 9.C. The hydrogen maser; 10. The alkali-metal atoms; Appendix 10.A. Quantum defects for the alkalis; Appendix 10.B. Numerov method; 11. Atoms in magnetic fields; Appendix 11.A. The ground state of atomic hydrogen; Appendix 11.B. Positronium; Appendix 11.C. The non-crossing theorem; Appendix 11.D. Passage through an anticrossing: Landau-Zener transitions; 12. Atoms in electric fields; 13. Rydberg atoms; 14. The helium atom; Appendix 14.A. Variational calculations; Appendix 14.B. Detail on the variational calculations of the ground state; 15. The periodic system of the elements; Appendix 15. A paramagnetism; Appendix 15.B. The color of gold; 16. Molecules; Appendix 16.A. Morse potential; 17. Binding in the hydrogen molecule; Appendix 17.A. Confocal elliptical coordinates; Appendix 17.B. One-electron two-center integrals; Appendix 17.C. Electron-electron interaction in molecular hydrogen; 18. Ultra-cold chemistry; Part III. Applications: 19. Optical forces and laser cooling; 20. Confinement of neutral atoms; 21. Bose-Einstein condensation; Appendix 21.A. Distribution functions; Appendix 21.B. Density of states; 22. Cold molecules; 23. Three level systems; Appendix 23.A. General Case for _1 , _2; 24. Fundamental physics; Part IV. Appendices: Appendix A. Notation and definitions; Appendix B. Units and notation; Appendix C. Angular momentum in quantum mechanics; Appendix D. Transition strengths; References; Index.

Extended x-ray absorption fine structure study of phase transitions in the piezoelectric perovskite K0.5Na0.5NbO3

NASA Astrophysics Data System (ADS)

Kodre, A.; Tellier, J.; Arčon, I.; Malič, B.; Kosec, M.

2009-06-01

Following an x-ray diffraction study of phase transitions of the piezoelectric perovskite K0.5Na0.5NbO3 the structural changes of the material are studied using extended x-ray absorption fine structure analysis, whereby the neighborhood of Nb atom is determined in the temperature range of monoclinic, tetragonal, and cubic phases. Within the entire range Nb atom is displaced from the center of the octahedron of its immediate oxygen neighbors, as witnessed by the splitting of Nb-O distance. The model shows high prevalence of the displacement in the (111) crystallographic direction of the simple perovskite cell. The corresponding splitting of the Nb-Nb distance is negligible. There is no observable disalignment of the linear Nb-O-Nb bonds from the ideal cubic arrangement, judging from the intensity of the focusing of the photoelectron wave on the Nb-Nb scattering path by the interposed oxygen atom. As a general result, the phase transitions are found as an effect of the long-range order, while the placement of the atoms in the immediate vicinity remains largely unaffected.

The direct measurement of the 3 3P0-3 3P1 fine-structure interval and the gJ-factor of atomic silicon by laser magnetic resonance

NASA Technical Reports Server (NTRS)

Evenson, K. M.; Beltran-Lopez, V.; Ley-Koo, E.; Inguscio, M.

1984-01-01

The J - 1 fine structure interval and the g-factor of the 3P1 state have been determined with high precision in the present laser magnetic resonance measurements of the ground 3p2 3P multiplet of atomic Si. Delta-E(3P1-3P0) = 2,311,755.6(7) MHz, and gJ(3P1) = 1.500830(70). Single-configuration calculations of gJ for 3P1 and 3P2 yield a value for the latter which, at 1.501095, is noted to differ by an unexpectedly large margin from the experimental value.

Fine structure of the K X-ray absorption spectra of titanium in some hydrides, borides, and silicides (in Russian)

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

Vainshtein, �. E.; Zhurakovskii, E. A.

1959-08-01

X-ray spectral analyses confirmed the hypothesis on the metal-like state of hydrogen in tithnium hydrides. Experiments with titunium borides and silicides indicate the special character and degree of the 3d--level participation in the metallic'' bond between the atoms of various complexes. The structure of metalloid elements becomes more complicated with an increase in the specific number of boron and silicon atoms and the bond between the atoms tends to become covalent. (R.V.J.)

New determination of the fine structure constant from the electron value and QED.

PubMed

Gabrielse, G; Hanneke, D; Kinoshita, T; Nio, M; Odom, B

2006-07-21

Quantum electrodynamics (QED) predicts a relationship between the dimensionless magnetic moment of the electron (g) and the fine structure constant (alpha). A new measurement of g using a one-electron quantum cyclotron, together with a QED calculation involving 891 eighth-order Feynman diagrams, determine alpha(-1)=137.035 999 710 (96) [0.70 ppb]. The uncertainties are 10 times smaller than those of nearest rival methods that include atom-recoil measurements. Comparisons of measured and calculated g test QED most stringently, and set a limit on internal electron structure.

Structural investigations in helium charged titanium films using grazing incidence XRD and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Wan, Chubin; Zhou, Xiaosong; Wang, Yuting; Li, Shina; Ju, Xin; Peng, Shuming

2014-01-01

The crystal structure and local atomic arrangements surrounding Ti atoms were determined for He-charged hexagonal close-packed (hcp) Ti films and measured at glancing angles by synchrotron radiation X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, respectively. The charged specimens were prepared by direct current magnetron sputtering with a He/Ar mixture. He atoms with a relatively medium concentration (He/Ti atomic ratio as high as 17 at.%) were incorporated evenly in the deposited films. XRD results showed the changes in the peak intensities in Ti films with different He contents. EXAFS Fourier Transform analysis indicated that the average Ti-Ti distance decreased significantly, and proved the existence of phase transition.

Fine- and hyperfine structure investigations of even configuration system of atomic terbium

NASA Astrophysics Data System (ADS)

Stefanska, D.; Elantkowska, M.; Ruczkowski, J.; Furmann, B.

2017-03-01

In this work a parametric study of the fine structure (fs) and the hyperfine structure (hfs) for the even-parity configurations of atomic terbium (Tb I) is presented, based in considerable part on the new experimental results. Measurements on 134 spectral lines were performed by laser induced fluorescence (LIF) in a hollow cathode discharge lamp; on this basis, the hyperfine structure constants A and B were determined for 52 even-parity levels belonging to the configurations 4f85d6s2, 4f85d26s or 4f96s6p; in all the cases those levels were involved in the transitions investigated as the lower levels. For 40 levels the hfs was examined for the first time, and for the remaining 12 levels the new measurements supplement our earlier results. As a by-product, also preliminary values of the hfs constants for 84 odd-parity levels were determined (the investigations of the odd-parity levels system in the terbium atom are still in progress). This huge amount of new experimental data, supplemented by our earlier published results, were considered for the fine and hyperfine structure analysis. A multi-configuration fit of 7 configurations was performed, taking into account second-order of perturbation theory, including the effects of closed shell-open shell excitations. Predicted values of the level energies, as well as of magnetic dipole and electric quadrupole hyperfine structure constants A and B, are quoted in cases when no experimental values are available. By combining our experimental data with our own semi-empirical procedure it was possible to identify correctly the lower and upper level of the line 544.1440 nm measured by Childs with the use of the atomic-beam laser-rf double-resonance technique (Childs, J Opt Soc Am B 9;1992:191-6).

Fine-structure-resolution for Rovibrational Excitation of CN Due to H2

NASA Astrophysics Data System (ADS)

Byrd, Nat; Yang, Benhui H.; Stancil, Phillip C.

2018-06-01

Diatomic molecules can be readily excited in interstellar environments exposed to intense UV radiation, such as the inner rim of a protoplanetary disk. Non-thermal populations of excited rovibrational levels can result, for example, following decay from electronically excited states to the electronic ground state. Competition between radiative decay and collisional processes, mostly due to H2, determine the resulting rovibrational emission spectrum. For CN, and other open-shell molecules, the resulting spectrum will be complicated due to fine-structure splitting of the rotational levels. In some cases, fine-structure resolution has been previously computed for rotational transitions in atom- or diatom-diatom collisional processes. Here we present the first fine-structure resolution for vibrational deexcitation for CN colliding with H2. The collisional cross sections were computed using a 6D potential energy surface with a full close-coupling approach. Fine-structure resolution is obtained by adopting an angular momentum recoupling scheme to transform the scattering matrices to a recoupled basis. Here we present low-energy calculations for the v=1 to 0 transition.This work was supported by NASA Grant NNX16AF09G.

Dopant activation mechanism of Bi wire-δ-doping into Si crystal, investigated with wavelength dispersive fluorescence x-ray absorption fine structure and density functional theory.

PubMed

Murata, Koichi; Kirkham, Christopher; Shimomura, Masaru; Nitta, Kiyofumi; Uruga, Tomoya; Terada, Yasuko; Nittoh, Koh-Ichi; Bowler, David R; Miki, Kazushi

2017-04-20

We successfully characterized the local structures of Bi atoms in a wire-δ-doped layer (1/8 ML) in a Si crystal, using wavelength dispersive fluorescence x-ray absorption fine structure at the beamline BL37XU, in SPring-8, with the help of density functional theory calculations. It was found that the burial of Bi nanolines on the Si(0 0 1) surface, via growth of Si capping layer at 400 °C by molecular beam epitaxy, reduced the Bi-Si bond length from [Formula: see text] to [Formula: see text] Å. We infer that following epitaxial growth the Bi-Bi dimers of the nanoline are broken, and the Bi atoms are located at substitutional sites within the Si crystal, leading to the shorter Bi-Si bond lengths.

Shifts due to quantum-mechanical interference from distant neighboring resonances for saturated fluorescence spectroscopy of the 23S to 23P intervals of helium

NASA Astrophysics Data System (ADS)

Marsman, A.; Hessels, E. A.; Horbatsch, M.

2014-04-01

Quantum-mechanical interference with distant neighboring resonances is found to cause shifts for precision saturated fluorescence spectroscopy of the atomic helium 23S-to-23P transitions. The shifts are significant (larger than the experimental uncertainties for measurements of the intervals) despite the fact that the neighboring resonances are separated from the measured resonances by 1400 and 20000 natural widths. The shifts depend strongly on experimental parameters such as the angular position of the fluorescence detector, the intensity and size of laser beams, and the properties of the atomic beam. These shifts must be considered for the ongoing program of determining the fine-structure constant from the helium 23P fine structure.

Counting individual sulfur atoms in a protein by ultrahighresolution Fourier transform ion cyclotron resonance mass spectrometry: Experimental resolution of isotopic fine structure in proteins

PubMed Central

Shi, Stone D.-H.; Hendrickson, Christopher L.; Marshall, Alan G.

1998-01-01

A typical molecular ion mass spectrum consists of a sum of signals from species of various possible isotopic compositions. Only the monoisotopic peak (e.g., all carbons are 12C; all nitrogens are 14N, etc.) has a unique elemental composition. Every other isotope peak at approximately integer multiples of ∼1 Da higher in nominal mass represents a sum of contributions from isotope combinations differing by a few mDa (e.g., two 13C vs. two 15N vs. one 13C and one 15N vs. 34S, vs. 18O, etc., at ∼2 Da higher in mass than the monoisotopic mass). At sufficiently high mass resolving power, each of these nominal-mass peaks resolves into its isotopic fine structure. Here, we report resolution of the isotopic fine structure of proteins up to 15.8 kDa (isotopic 13C,15N doubly depleted tumor suppressor protein, p16), made possible by electrospray ionization followed by ultrahigh-resolution Fourier transform ion cyclotron resonance mass analysis at 9.4 tesla. Further, a resolving power of m/Δm50% ≈8,000,000 has been achieved on bovine ubiquitin (8.6 kDa). These results represent a 10-fold increase in the highest mass at which isotopic fine structure previously had been observed. Finally, because isotopic fine structure reveals elemental composition directly, it can be used to confirm or determine molecular formula. For p16, for example, we were able to determine (5.1 ± 0.3) the correct number (five) of sulfur atoms solely from the abundance ratio of the resolved 34S peak to the monoisotopic peak. PMID:9751700

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

NASA Astrophysics Data System (ADS)

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

2011-10-01

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

Light element opacities of astrophysical interest from ATOMIC

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

Colgan, J.; Kilcrease, D. P.; Magee, N. H. Jr.

We present new calculations of local-thermodynamic-equilibrium (LTE) light element opacities from the Los Alamos ATOMIC code for systems of astrophysical interest. ATOMIC is a multi-purpose code that can generate LTE or non-LTE quantities of interest at various levels of approximation. Our calculations, which include fine-structure detail, represent a systematic improvement over previous Los Alamos opacity calculations using the LEDCOP legacy code. The ATOMIC code uses ab-initio atomic structure data computed from the CATS code, which is based on Cowan's atomic structure codes, and photoionization cross section data computed from the Los Alamos ionization code GIPPER. ATOMIC also incorporates a newmore » equation-of-state (EOS) model based on the chemical picture. ATOMIC incorporates some physics packages from LEDCOP and also includes additional physical processes, such as improved free-free cross sections and additional scattering mechanisms. Our new calculations are made for elements of astrophysical interest and for a wide range of temperatures and densities.« less

Limit on the temporal variation of the fine-structure constant using atomic dysprosium.

PubMed

Cingöz, A; Lapierre, A; Nguyen, A-T; Leefer, N; Budker, D; Lamoreaux, S K; Torgerson, J R

2007-01-26

Over 8 months, we monitored transition frequencies between nearly degenerate, opposite-parity levels in two isotopes of atomic dysprosium (Dy). These frequencies are sensitive to variation of the fine-structure constant (alpha) due to relativistic corrections of opposite sign for the opposite-parity levels. In this unique system, in contrast to atomic-clock comparisons, the difference of the electronic energies of the opposite-parity levels can be monitored directly utilizing a rf electric-dipole transition between them. Our measurements show that the frequency variation of the 3.1-MHz transition in (163)Dy and the 235-MHz transition in (162)Dy are 9.0+/-6.7 Hz/yr and -0.6+/-6.5 Hz/yr, respectively. These results provide a rate of fractional variation of alpha of (-2.7+/-2.6) x 10(-15) yr(-1) (1 sigma) without assumptions on constancy of other fundamental constants, indicating absence of significant variation at the present level of sensitivity.

Subpicosecond X rotations of atomic clock states

NASA Astrophysics Data System (ADS)

Song, Yunheung; Lee, Han-gyeol; Kim, Hyosub; Jo, Hanlae; Ahn, Jaewook

2018-05-01

We demonstrate subpicosecond-timescale population transfer between the pair of hyperfine ground states of atomic rubidium using a single laser-pulse. Our scheme utilizes the geometric and dynamic phases induced during Rabi oscillation through the fine-structure excited state to construct an X rotation gate for the hyperfine-state qubit system. The experiment performed with a femtosecond laser and cold rubidium atoms, in a magnetooptical trap, shows over 98% maximal population transfer between the clock states.

Application of x-ray absorption fine structure (XAFS) to local-order analysis in Fe-Cr maghemite-like materials

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

Montero-Cabrera, M. E., E-mail: elena.montero@cimav.edu.mx; Fuentes-Cobas, L. E.; Macías-Ríos, E.

2015-07-23

The maghemite-like oxide system γ-Fe{sub 2-x}Cr{sub x}O{sub 3} (x=0.75, 1 and 1.25) was studied by X-ray absorption fine structure (XAFS) and by synchrotron radiation X-ray diffraction (XRD). Measurements were performed at the Stanford Synchrotron Radiation Lightsource at room temperature, at beamlines 2-1, 2-3 and 4-3. High-resolution XRD patterns were processed by means of the Rietveld method. In cases of atoms being neighbors in the Periodic Table, the order/disorder degree of the considered solutions is indiscernible by “normal” (absence of “anomalous scattering”) diffraction experiments. Thus, maghemite-like materials were investigated by XAFS in both Fe and Cr K-edges to clarify, via short-rangemore » structure characterization, the local ordering of the investigated system. Athena and Artemis graphic user interfaces for IFEFFIT and FEFF8.4 codes were employed for XAFS spectra interpretation. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure (XANES) transitions were performed. By analysis of the Cr K-edge XANES, it has been confirmed that Cr is located in an octahedral environment. Fitting of the extended X-ray absorption fine structure (EXAFS) spectra was performed under the consideration that the central atom of Fe is allowed to occupy octa- and tetrahedral positions, while Cr occupies only octahedral ones. Coordination number of neighboring atoms, interatomic distances and their quadratic deviation average were determined for x=1, by fitting simultaneously the EXAFS spectra of both Fe and Cr K-edges. The results of fitting the experimental spectra with theoretical standards showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO{sub 3})« less

Lamb shift and fine structure at n =2 in a hydrogenlike muonic atom with the nuclear spin I =0

NASA Astrophysics Data System (ADS)

Korzinin, Evgeny Yu.; Shelyuto, Valery A.; Ivanov, Vladimir G.; Karshenboim, Savely G.

2018-01-01

The paper is devoted to the Lamb shift and fine structure in a hydrogenlike muonic atom with a spinless nucleus up to the order α5m with all the recoil corrections included. Enhanced contributions of a higher order are also considered. We present the results on the pure QED contribution and on the finite-nuclear-size contribution, proportional to RN2, with the higher-order corrections included. We also consider the consistency of the pure QED theory and the evaluation of the nuclear-structure effects. Most of the QED theory is the same as the theory for the case of the nuclear spin 1/2. Additional nuclear-spin-dependent terms are considered in detail. The issue of the difference for the theories with a spinor nucleus and a scalar one is discussed for the recoil contributions in the order (Zα ) 4m ,α (Zα ) 4m , and (Zα ) 5m . The numerical results are presented for the muonic atoms with two lightest scalar nuclei, helium-4 and beryllium-10. We compare the theory of those muonic atoms with theory for the muonic hydrogen. Some higher-order finite-nuclear-size corrections for the Lamb shift in muonic hydrogen are revisited.

Local atomic and electronic structures of epitaxial strained LaCoO3 thin films

NASA Astrophysics Data System (ADS)

Sterbinsky, G. E.; Ryan, P. J.; Kim, J.-W.; Karapetrova, E.; Ma, J. X.; Shi, J.; Woicik, J. C.

2012-01-01

We have examined the atomic and electronic structures of perovskite lanthanum cobaltite (LaCoO3) thin films using Co K-edge x-ray absorption fine structure (XAFS) spectroscopy. Extended XAFS (EXAFS) demonstrates that a large difference between in-plane and out-of-plane Co-O bond lengths results from tetragonal distortion in highly strained films. The structural distortions are strongly coupled to the hybridization between atomic orbitals of the Co and O atoms, as shown by x-ray absorption near edge spectroscopy (XANES). Our results indicate that increased hybridization is not the cause of ferromagnetism in strained LaCoO3 films. Instead, we suggest that the strain-induced distortions of the oxygen octahedra increase the population of eg electrons and concurrently depopulate t2g electrons beyond a stabilization threshold for ferromagnetic order.

Modelling the atomic structure of Al92U8 metallic glass.

PubMed

Michalik, S; Bednarcik, J; Jóvári, P; Honkimäki, V; Webb, A; Franz, H; Fazakas, E; Varga, L K

2010-10-13

The local atomic structure of the glassy Al(92)U(8) alloy was modelled by the reverse Monte Carlo (RMC) method, fitting x-ray diffraction (XRD) and extended x-ray absorption fine structure (EXAFS) signals. The final structural model was analysed by means of partial pair correlation functions, coordination number distributions and Voronoi tessellation. In our study we found that the most probable atomic separations between Al-Al and U-Al pairs in the glassy Al(92)U(8) alloy are 2.7 Å and 3.1 Å with coordination numbers 11.7 and 17.1, respectively. The Voronoi analysis did not support evidence of the existence of well-defined building blocks directly embedded in the amorphous matrix. The dense-random-packing model seems to be adequate for describing the connection between solvent and solute atoms.

Extended X-ray absorption fine structure investigation of Sn local environment in strained and relaxed epitaxial Ge{sub 1−x}Sn{sub x} films

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

Gencarelli, F., E-mail: federica.gencarelli@imec.be; Heyns, M.; Department of Metallurgy and Materials Engineering, KU Leuven, Kasteelpark Arenberg 44, B-3001 Leuven

2015-03-07

We present an extended X-ray absorption fine structure investigation of the local environment of Sn atoms in strained and relaxed Ge{sub 1−x}Sn{sub x} layers with different compositions. We show that the preferred configuration for the incorporation of Sn atoms in these Ge{sub 1−x}Sn{sub x} layers is that of a α-Sn defect, with each Sn atom covalently bonded to four Ge atoms in a classic tetrahedral configuration. Sn interstitials, Sn-split vacancy complexes, or Sn dimers, if present at all, are not expected to involve more than 2.5% of the total Sn atoms. This finding, along with a relative increase of Snmore » atoms in the second atomic shell around a central Sn atom in Ge{sub 1−x}Sn{sub x} layers with increasing Sn concentrations, suggests that the investigated materials are homogeneous random substitutional alloys. Within the accuracy of the measurements, the degree of strain relaxation of the Ge{sub 1−x}Sn{sub x} layers does not have a significant impact on the local atomic surrounding of the Sn atoms. Finally, the calculated topological rigidity parameter a** = 0.69 ± 0.29 indicates that the strain due to alloying in Ge{sub 1−x}Sn{sub x} is accommodated via bond stretching and bond bending, with a slight predominance of the latter, in agreement with ab initio calculations reported in literature.« less

Atomic data and line intensities for the S V ion

NASA Astrophysics Data System (ADS)

Iorga, C.; Stancalie, V.

2017-05-01

The energy levels, oscillator strengths, spontaneous radiative decay rates, lifetimes and electron impact collision strengths have been obtained for the [ Ne ] 3s nl, [ Ne ] 3p nl, [ Ne ] 3d nl configurations belonging to S V ion, with n ≤ 7 and l ≤ 4, resulting in 567 fine-structure levels. The calculations have been performed within the fully relativistic Flexible Atomic Code (FAC, Gu, 2008) framework and the distorted wave approximation. To attain the desired accuracy for the levels energy, the valence-valence and valence-core correlations have been taken care of by including 96 configuration state functions (CSFs) in the model, reaching a total of 3147 fine-structure levels. Two separate calculations have been performed with the local central potential computed for two different average configurations. A third calculation is also performed without the addition of the core-excited states in the atomic model for completeness. The effects of slightly different mean configurations and valence-core correlations on the energy levels and decay rates are investigated. The collision data have been computed employing the relativistic distorted-wave method along with the atomic model containing the 96 CSFs and corresponding to the ground state mean configuration. The collision strengths corresponding to excitation from the first four fine-structure levels are given for five energy values of the scattered electron 2.65, 6.18, 11.02, 17.36, 25.43 Rydberg, plus an additional variable small energy value near the threshold. A collisional-radiative model has been employed to solve the rate equations for the populations of the 567 fine-structure levels, for a temperature of LogTE(K) = 5.2 corresponding to the maximum abundance of S V, and at densities 106-1016cm-3, assuming a Maxwellian electron energy distribution function and black body radiation of temperature 6000 K and dilution factor 0.35 for the photon distribution function. The main processes responsible for the level population variations are the electron-impact collisional excitation and the radiative decay along with their inverse processes. As a result, the level populations along with the spectral high-line intensity ratios are provided.

Order within disorder: The atomic structure of ion-beam sputtered amorphous tantala (a-Ta₂O₅)

DOE PAGES

Bassiri, Riccardo; Liou, Franklin; Abernathy, Matthew R.; ...

2015-03-01

Amorphous tantala (a-Ta₂O₅) is a technologically important material often used in high-performance coatings. Understanding this material at the atomic level provides a way to further improve performance. This work details extended X-ray absorption fine structure measurements of a-Ta₂O₅ coatings, where high-quality experimental data and theoretical fits have allowed a detailed interpretation of the nearest-neighbor distributions. It was found that the tantalum atom is surrounded by four shells of atoms in sequence; oxygen, tantalum, oxygen, and tantalum. A discussion is also included on how these models can be interpreted within the context of published crystalline Ta₂O₅ and other a-T₂O₅ studies.

Extended x-ray absorption fine structure spectroscopy and x-ray absorption near edge spectroscopy study of aliovalent doped ceria to correlate local structural changes with oxygen vacancies clustering

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

Shirbhate, S. C.; Acharya, S. A., E-mail: saha275@yahoo.com; Yadav, A. K.

2016-04-04

This study provides atomic scale insight to understand the role of aliovalent dopants on oxygen vacancies clustering and dissociation mechanism in ceria system in order to enhance the performance of oxy-ion conductor. Dopants induced microscale changes in ceria are probed by extended X-ray absorption fine structure spectroscopy, X-ray absorption near edge spectra, and Raman spectroscopy. The results are explored to establish a correlation between atomic level structural changes (coordination number, interatomic spacing) → formation of dimer and trimer type cation-oxygen vacancies defect complex (intrinsic and extrinsic) → dissociation of oxygen vacancies from defect cluster → ionic conductivity temperature. It ismore » a strategic approach to understand key physics of ionic conductivity mechanism in order to reduce operating temperature of electrolytes for intermediate temperature (300–450 °C) electrochemical devices for the first time.« less

Atomic scale structure and chemistry of interfaces by Z-contrast imaging and electron energy loss spectroscopy in the stem

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

McGibbon, M.M.; Browning, N.D.; Chisholm, M.F.

The macroscopic properties of many materials are controlled by the structure and chemistry at grain boundaries. A basic understanding of the structure-property relationship requires a technique which probes both composition and chemical bonding on an atomic scale. High-resolution Z-contrast imaging in the scanning transmission electron microscope (STEM) forms an incoherent image in which changes in atomic structure and composition across an interface can be interpreted directly without the need for preconceived atomic structure models. Since the Z-contrast image is formed by electrons scattered through high angles, parallel detection electron energy loss spectroscopy (PEELS) can be used simultaneously to provide complementarymore » chemical information on an atomic scale. The fine structure in the PEEL spectra can be used to investigate the local electronic structure and the nature of the bonding across the interface. In this paper we use the complimentary techniques of high resolution Z-contrast imaging and PEELS to investigate the atomic structure and chemistry of a 25{degree} symmetric tilt boundary in a bicrystal of the electroceramic SrTiO{sub 3}.« less

Atom Interferometry: A Matter Wave Clock and a Measurement of α

NASA Astrophysics Data System (ADS)

Estey, Brian; Lan, Shau-Yu; Kuan, Pei-Chen; Hohensee, Michael; Haslinger, Philipp; Kehayias, Pauli; English, Damon; Müller, Holger

2012-06-01

Developments in large-momentum transfer beamsplitters (eg. Bragg diffraction) and conjugate Ramsey-Bord'e interferometers have enabled atom interferometers with unparalleled size and sensitivity. The atomic wave packet separation is large enough that the Coriolis force due to the earth's rotation reduces interferometer contrast. We compensate for this effect using a tip-tilt mirror, improving our contrast by up to a factor of 3.5, allowing pulse separations of up to 250 ms with 10k beamsplitters. This interferometer can be used to make a precise measurement of the recoil frequency (h/m) and thus the fine structure constant. The interferometer also gives us indirect access to the Compton frequency (νC≡mc^2/h) oscillations of the matter wave, since h/m is simply c^2/νC. Using an optical frequency comb we reference the interferometer's laser frequency to a multiple of a cesium atom's recoil frequency. This self-referenced interferometer thus locks a local oscillator to a specified fraction of the cesium Compton frequency, with a fractional stability of 2 pbb over several hours. This has potential application in redefining the kilogram in terms of the second. We also present a preliminary measurement of the fine structure constant.

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

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

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

21-cm radiation: a new probe of variation in the fine-structure constant.

PubMed

Khatri, Rishi; Wandelt, Benjamin D

2007-03-16

We investigate the effect of variation in the value of the fine-structure constant (alpha) at high redshifts (recombination > z > 30) on the absorption of the cosmic microwave background (CMB) at 21 cm hyperfine transition of the neutral atomic hydrogen. We find that the 21 cm signal is very sensitive to the variations in alpha and it is so far the only probe of the fine-structure constant in this redshift range. A change in the value of alpha by 1% changes the mean brightness temperature decrement of the CMB due to 21 cm absorption by >5% over the redshift range z < 50. There is an effect of similar magnitude on the amplitude of the fluctuations in the brightness temperature. The redshift of maximum absorption also changes by approximately 5%.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond

NASA Astrophysics Data System (ADS)

Olivier, E. J.; Neethling, J. H.; Kroon, R. E.; Naidoo, S. R.; Allen, C. S.; Sawada, H.; van Aken, P. A.; Kirkland, A. I.

2018-03-01

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Imaging the atomic structure and local chemistry of platelets in natural type Ia diamond.

PubMed

Olivier, E J; Neethling, J H; Kroon, R E; Naidoo, S R; Allen, C S; Sawada, H; van Aken, P A; Kirkland, A I

2018-03-01

In the past decades, many efforts have been devoted to characterizing {001} platelet defects in type Ia diamond. It is known that N is concentrated at the defect core. However, an accurate description of the atomic structure of the defect and the role that N plays in it is still unknown. Here, by using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy we have determined the atomic arrangement within platelet defects in a natural type Ia diamond and matched it to a prevalent theoretical model. The platelet has an anisotropic atomic structure with a zigzag ordering of defect pairs along the defect line. The electron energy-loss near-edge fine structure of both carbon K- and nitrogen K-edges obtained from the platelet core is consistent with a trigonal bonding arrangement at interstitial sites. The experimental observations support an interstitial aggregate mode of formation for platelet defects in natural diamond.

Structural and electrical properties of In-implanted Ge

DOE PAGES

Feng, R.; Kremer, F.; Sprouster, D. J.; ...

2015-10-22

Here, we report on the effects of dopant concentration on the structural and electrical properties of In-implanted Ge. For In concentrations of ≤ 0.2 at. %, extended x-ray absorption fine structure and x-ray absorption near-edge structure measurements demonstrate that all In atoms occupy a substitutional lattice site while metallic In precipitates are apparent in transmission electron micrographs for In concentrations ≥0.6 at. %. Evidence of the formation of In-vacancy complexes deduced from extended x-ray absorption fine structure measurements is complimented by density functional theory simulations. Hall effect measurements of the conductivity, carrier density, and carrier mobility are then correlated withmore » the substitutional In fraction.« less

New Tests for Variations of the Fine Structure Constant

NASA Technical Reports Server (NTRS)

Prestage, John D.

1995-01-01

We describe a new test for possible variations of the fine structure constant, by comparisons of rates between clocks based on hyperfine transitions in alkali atomos with different atomic number Z. H- maser, Cs and Hg+ clocks have a different dependence on ia relativistic contributions of order (Z. Recent H-maser vs Hg+ clock comparison data improves laboratory limits on a time variation by 100-fold to giveFuture laser cooled clocks (Be+, Rb, Cs, Hg+, etc.), when compared, will yield the most senstive of all tests for.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

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

Zhang, Fuxiang; Tong, Yang; Jin, Ke

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Chemical complexity induced local structural distortion in NiCoFeMnCr high-entropy alloy

DOE PAGES

Zhang, Fuxiang; Tong, Yang; Jin, Ke; ...

2018-06-16

In order to study chemical complexity-induced lattice distortion in high-entropy alloys, the static Debye–Waller (D-W) factor of NiCoFeMnCr solid solution alloy is measured with low temperature neutron diffraction, ambient X-ray diffraction, and total scattering methods. Here, the static atomic displacement parameter of the multi-element component alloy at 0 K is 0.035–0.041 Å, which is obvious larger than that of element Ni (~0 Å). The atomic pair distance between individual atoms in the alloy investigated with extended X-ray absorption fine structure (EXAFS) measurements indicates that Mn has a slightly larger bond distance (~0.4%) with neighbor atoms than that of others.

Possibilities of Using Combined Optical and AFM Investigations of Albumin

NASA Astrophysics Data System (ADS)

Buzoverya, M. E.; Shishpor, I. V.; Shcherbak, Yu. P.

2018-02-01

The results of a complex study of 10% aqueous solution of human serum albumin using methods of optical and atomic force microscopy have been presented. The fine structure of main structures of albumin facies (vitreous matrix and concretions) has been revealed and some observed structural effects have been interpreted from the viewpoint of polymer materials science.

Electronic structure study of Ce1-xAxO2 (A = Zr & Hf) nanoparticles: NEXAFS and EXAFS investigations.

PubMed

Sharma, Aditya; Varshney, Mayora; Shin, Hyun-Joon; Park, Yong Jun; Kim, Min-Gyu; Ha, Tae-Kyun; Chae, Keun Hwa; Gautam, Sanjeev

2014-10-07

Single phase nanoparticles (NPs) of CeO2, Ce0.5Zr0.5O2, Ce0.5Hf0.5O2 and Ce0.5Hf0.25Zr0.25O2 were successfully synthesized by co-precipitation method at constant pH and temperature. The X-ray diffraction results revealed that the additive atoms did not segregate to form secondary phases but led to grain size variation in the NPs. The 10 Dq values in the near edge X-ray absorption fine structure (NEXAFS) spectra at the O K-edge did not vary in the same way as the average grain size was changed for the doped CeO2 NPs. The deconvolution of Ce M5-edge and detailed analysis of O K pre-edge peak have shown the higher Ce(+3)/(Ce(+3) + Ce(+4)) ratio in the Zr- and Hf-doped samples. The local atomic structure around the Ce, Zr and Hf atoms was investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy at Ce K-edge, Zr K-edge and Hf L3-edge, respectively, and the EXAFS data were fitted with the theoretical calculations. The 4f occupancy, Ce(+3)/(Ce(+3) + Ce(+4)) ratio of Ce ions, coordination number of Ce and Ce-Ce/Ce-O bond distances were sensitive to the additive atoms but not explicitly changed according to the grain size variation in the NPs.

Key experimental information on intermediate-range atomic structures in amorphous Ge2Sb2Te5 phase change material

NASA Astrophysics Data System (ADS)

Hosokawa, Shinya; Pilgrim, Wolf-Christian; Höhle, Astrid; Szubrin, Daniel; Boudet, Nathalie; Bérar, Jean-François; Maruyama, Kenji

2012-04-01

Laser-induced crystalline-amorphous phase change of Ge-Sb-Te alloys is the key mechanism enabling the fast and stable writing/erasing processes in rewritable optical storage devices, such as digital versatile disk (DVD) or blu-ray disk. Although the structural information in the amorphous phase is essential for clarifying this fast process, as well as long lasting stabilities of both the phases, experimental works were mostly limited to the short-range order by x ray absorption fine structure. Here we show both the short and intermediate-range atomic structures of amorphous DVD material, Ge2Sb2Te5 (GST), investigated by a combination of anomalous x ray scattering and reverse Monte Carlo modeling. From the obtained atomic configurations of amorphous GST, we have found that the Sb atoms and half of the Ge atoms play roles in the fast phase change process of order-disorder transition, while the remaining Ge atoms act for the proper activation energy of barriers between the amorphous and crystalline phases.

Two Clock Transitions in Neutral Yb for the Highest Sensitivity to Variations of the Fine-Structure Constant.

PubMed

Safronova, Marianna S; Porsev, Sergey G; Sanner, Christian; Ye, Jun

2018-04-27

We propose a new frequency standard based on a 4f^{14}6s6p ^{3}P_{0}-4f^{13}6s^{2}5d (J=2) transition in neutral Yb. This transition has a potential for high stability and accuracy and the advantage of the highest sensitivity among atomic clocks to variation of the fine-structure constant α. We find its dimensionless α-variation enhancement factor to be K=-15, in comparison to the most sensitive current clock (Yb^{+}  E3, K=-6), and it is 18 times larger than in any neutral-atomic clocks (Hg, K=0.8). Combined with the unprecedented stability of an optical lattice clock for neutral atoms, this high sensitivity opens new perspectives for searches for ultralight dark matter and for tests of theories beyond the standard model of elementary particles. Moreover, together with the well-established ^{1}S_{0}-^{3}P_{0} transition, one will have two clock transitions operating in neutral Yb, whose interleaved interrogations may further reduce systematic uncertainties of such clock-comparison experiments.

Two Clock Transitions in Neutral Yb for the Highest Sensitivity to Variations of the Fine-Structure Constant

NASA Astrophysics Data System (ADS)

Safronova, Marianna S.; Porsev, Sergey G.; Sanner, Christian; Ye, Jun

2018-04-01

We propose a new frequency standard based on a 4 f146 s 6 p P0 3 -4 f136 s25 d (J =2 ) transition in neutral Yb. This transition has a potential for high stability and accuracy and the advantage of the highest sensitivity among atomic clocks to variation of the fine-structure constant α . We find its dimensionless α -variation enhancement factor to be K =-15 , in comparison to the most sensitive current clock (Yb+ E 3 , K =-6 ), and it is 18 times larger than in any neutral-atomic clocks (Hg, K =0.8 ). Combined with the unprecedented stability of an optical lattice clock for neutral atoms, this high sensitivity opens new perspectives for searches for ultralight dark matter and for tests of theories beyond the standard model of elementary particles. Moreover, together with the well-established 1S0-3P0 transition, one will have two clock transitions operating in neutral Yb, whose interleaved interrogations may further reduce systematic uncertainties of such clock-comparison experiments.

Thermally activated decomposition of (Ga,Mn)As thin layer at medium temperature post growth annealing

NASA Astrophysics Data System (ADS)

Melikhov, Y.; Konstantynov, P.; Domagala, J.; Sadowski, J.; Chernyshova, M.; Wojciechowski, T.; Syryanyy, Y.; Demchenko, I. N.

2016-05-01

The redistribution of Mn atoms in Ga1-xMnxAs layer during medium-temperature annealing, 250-450 oC, by Mn K-edge X-ray absorption fine structure (XAFS) recorded at ALBA facility, was studied. For this purpose Ga1-xMnxAs thin layer with x=0.01 was grown on AlAs buffer layer deposited on GaAs(100) substrate by molecular beam epitaxy (MBE) followed by annealing. The examined layer was detached from the substrate using a “lift-off” procedure in order to eliminate elastic scattering in XAFS spectra. Fourier transform analysis of experimentally obtained EXAFS spectra allowed to propose a model which describes a redistribution/diffusion of Mn atoms in the host matrix. Theoretical XANES spectra, simulated using multiple scattering formalism (FEFF code) with the support of density functional theory (WIEN2k code), qualitatively describe the features observed in the experimental fine structure.

Limit on the present temporal variation of the fine structure constant.

PubMed

Peik, E; Lipphardt, B; Schnatz, H; Schneider, T; Tamm, Chr; Karshenboim, S G

2004-10-22

The comparison of different atomic transition frequencies over time can be used to determine the present value of the temporal derivative of the fine structure constant alpha in a model-independent way without assumptions on constancy or variability of other parameters, allowing tests of the consequences of unification theories. We have measured an optical transition frequency at 688 THz in 171Yb+ with a cesium atomic clock at 2 times separated by 2.8 yr and find a value for the fractional variation of the frequency ratio f(Yb)/f(Cs) of (-1.2+/-4.4)x10(-15) yr(-1), consistent with zero. Combined with recently published values for the constancy of other transition frequencies this measurement sets an upper limit on the present variability of alpha at the level of 2.0x10(-15) yr(-1) (1sigma), corresponding so far to the most stringent limit from laboratory experiments.

Local Structure and Short-Range Order in a NiCoCr Solid Solution Alloy

DOE PAGES

Zhang, F. X.; Zhao, Shijun; Jin, Ke; ...

2017-05-19

Multi-element solid solution alloys are intrinsically disordered on the atomic scale, and many of their advanced properties originate from the unique local structural characteristics. We measured the local structure of a NiCoCr solid solution alloy with X-ray/neutron total scattering and extended X-ray absorption fine structure (EXAFS) techniques. The atomic pair distribution function analysis (PDF) did not exhibit distinct structural distortion. But, EXAFS analysis suggested that the Cr atoms are favorably bonded with Ni and Co in the solid solution alloys. This short-range order (SRO) plays a role in the distinct low values of electrical and thermal conductivities in Ni-based solidmore » solution alloys when Cr is incorporated. Both the long-range and local structures of the NiCoCr alloy upon Ni ion irradiation were studied and an irradiation-induced enhancement of SRO was found.« less

Refined tip preparation by electrochemical etching and ultrahigh vacuum treatment to obtain atomically sharp tips for scanning tunneling microscope and atomic force microscope.

PubMed

Hagedorn, Till; El Ouali, Mehdi; Paul, William; Oliver, David; Miyahara, Yoichi; Grütter, Peter

2011-11-01

A modification of the common electrochemical etching setup is presented. The described method reproducibly yields sharp tungsten tips for usage in the scanning tunneling microscope and tuning fork atomic force microscope. In situ treatment under ultrahigh vacuum (p ≤10(-10) mbar) conditions for cleaning and fine sharpening with minimal blunting is described. The structure of the microscopic apex of these tips is atomically resolved with field ion microscopy and cross checked with field emission. © 2011 American Institute of Physics

Non-patchy strategy for inter-atomic distances from Extended X-ray Absorption Fine Structure

PubMed Central

Xu, Gu; Li, Guifang; LI, Xianya; Liang, Yi; Feng, Zhechuan

2017-01-01

Extended X-ray Absorption Fine Structure (EXAFS) has been one of the few structural probes available for crystalline, non-crystalline and even highly disordered specimens. However, the data analysis involves a patchy and tinkering process, including back-and-forth fitting and filtering, leading to ambiguous answers sometimes. Here we try to resolve this long standing problem, to extract the inter-atomic distances from the experimental data by a single step minimization, in order to replace the tedious and tinkering process. The new strategy is built firmly by the mathematical logic, and made straightforward and undeniable. The finding demonstrates that it is possible to break off from the traditional patchy model fitting, and to remove the logical confusion of a priori prediction of the structure to be matched with experimental data, making it a much more powerful technique than the existing methods. The new method is expected to benefit EXAFS users covering all disciplines. Also, it is anticipated that the current work to be the motivation and inspiration to the further efforts. PMID:28181529

Fine-structure excitation of Fe II and Fe III due to collisions with electrons

NASA Astrophysics Data System (ADS)

Wan, Yier; Qi, Yueying; Favreau, Connor; Loch, Stuart; Stancil, P.; Ballance, Connor; McLaughlin, Brendan

2018-06-01

Atomic data of iron peak elements are of great importance in astronomical observations. Among all the ionization stages of iron, Fe II and Fe III are of particular importance because of the high cosmic abundance, relatively low ionization potential and complex open d-shell atomic structure. Fe II and Fe III emission are observed from nearly all classes of astronomical objects over a wide spectral range from the infrared to the ultraviolet. To meaningfully interpret these spectra, astronomers have to employ highly complex modeling codes with reliable collision data to simulate the astrophysical observations. The major aim of this work is to provide reliable atomic data for diagnostics. We present new collision strengths and effective collisions for electron impact excitation of Fe II and Fe III for the forbidden transitions among the fine-structure levels of the ground terms. A very fine energy mesh is used for the collision strengths and the effective collision strengths are calculated over a wide range of electron temperatures of astrophysical importance (10-2000 K). The configuration interaction state wave functions are generated with a scaled Thomas-Fermi-Dirac-Amaldi (TFDA) potential, while the R-matrix plus intermediate coupling frame transformation (ICFT), Breit-Pauli R-matrix and Dirac R-matrix packages are used to obtain collision strengths. Influences of the different methods and configuration expansions on the collisional data are discussed. Comparison is made with earlier theoretical work and differences are found to occur at the low temperatures considered here.This work was funded by NASA grant NNX15AE47G.

Structure and conformational dynamics of scaffolded DNA origami nanoparticles

DTIC Science & Technology

2017-05-08

all-atom molecular dynamics and coarse-grained finite element modeling to DX-based nanoparticles to elucidate their fine-scale and global conforma... finite element (FE) modeling approach CanDo is also routinely used to predict the 3D equilibrium conformation of programmed DNA assemblies based on a...model with both experimental cryo-electron microscopy (cryo-EM) data and all-atom modeling. MATERIALS AND METHODS Lattice-free finite element model

Atomic scale structure and chemistry of interfaces by Z-contrast imaging and electron energy loss spectroscopy in the STEM

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

McGibbon, M.M.; Browning, N.D.; Chisholm, M.F.

The macroscopic properties of many materials are controlled by the structure and chemistry at the grain boundaries. A basic understanding of the structure-property relationship requires a technique which probes both composition and chemical bonding on an atomic scale. The high-resolution Z-contrast imaging technique in the scanning transmission electron microscope (STEM) forms an incoherent image in which changes in atomic structure and composition can be interpreted intuitively. This direct image allows the electron probe to be positioned over individual atomic columns for parallel detection electron energy loss spectroscopy (PEELS) at a spatial resolution approaching 0.22nm. The bonding information which can bemore » obtained from the fine structure within the PEELS edges can then be used in conjunction with the Z-contrast images to determine the structure at the grain boundary. In this paper we present 3 examples of correlations between the structural, chemical and electronic properties at materials interfaces in metal-semiconductor systems, superconducting and ferroelectric materials.« less

Laser Spectroscopy of the Fine-Structure Splitting in the 2^{3}P_{J} Levels of ^{4}He.

PubMed

Zheng, X; Sun, Y R; Chen, J-J; Jiang, W; Pachucki, K; Hu, S-M

2017-02-10

The fine-structure splitting in the 2^{3}P_{J} (J=0, 1, 2) levels of ^{4}He is of great interest for tests of quantum electrodynamics and for the determination of the fine-structure constant α. The 2^{3}P_{0}-2^{3}P_{2} and 2^{3}P_{1}-2^{3}P_{2} intervals are measured by laser spectroscopy of the ^{3}P_{J}-2^{3}S_{1} transitions at 1083 nm in an atomic beam, and are determined to be 31 908 130.98±0.13  kHz and 2 291 177.56±0.19  kHz, respectively. Compared with calculations, which include terms up to α^{5}Ry, the deviation for the α-sensitive interval 2^{3}P_{0}-2^{3}P_{2} is only 0.22 kHz. It opens the window for further improvement of theoretical predictions and an independent determination of the fine-structure constant α with a precision of 2×10^{-9}.

Extended electron energy loss fine structure simulation of the local boron environment in sodium aluminoborosilicate glasses containing gadolinium

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

Qian, Morris; Li, Hong; Li, Liyu

Gadolinium can be dissolved in sodium-alumino-borosilicate glasses up to 47 wt% in a baseline borosilicate glass (mol%) 20 B2O3, 5 Al2O3, 60 SiO2,and 20 Na2O. Understanding of Gd dissolution in borosilicate melts is important in glass formulation optimization. Electron energy loss fine structure (ELFS) spectroscopy is chosen, which provides well resolved local atomic structure information for both amorphous and crystalline materials with high sensitivity to low Z elements such as Al, B, Na, O, and Si where the x-ray absorption fine structure (XAFS) technique faces experimental difficulty. In this study, we report our results of boron K-edge ELFS study. Twomore » borosilicate glass samples with 30 and 47 mass% Gd2O3, B20Gd30 and B20Gd47were chosen for B K-edge ELFS study. EEL spectra were acquired on a Philips 430 TEM equipped with Gatan PEELS system 666 and EL/P 2.1 software with Custom function AcqLong. The ELFS data analysis was performed using UWELFS, UWXAFS and FEFF software. From our Gd solubility study, the local structure of Gd in the borate environment possibly resembles double chain structure found in crystalline Gd(BO2)3 as proposed by Chakraborty et al. The B/Gd ratio's in both glasses are smaller then 3, which means the excess Gd atoms in the Si-sites would be 17 and 60 mol% of the total Gd atoms, respectively according to the model, yet the local environment of borate sites saturated with Gd should be remained. To verity above hypothesis, the double chain structure model was applied to fit boron K-edge. The model was shown to well fit experimental boron K-edge EELS spectra for both glasses with some degree of distance distortion which is understandable in amorphous structure. Therefore, it is very likely that Gd stabilized in borate sites has a local structure resembling the double chain Gd(BO2)3 structure as proposed by our solubility study and literature.« less

High temperature extended x-ray absorption fine structure study of multiferroic BiFeO3

NASA Astrophysics Data System (ADS)

Raghavendra Reddy, V.; Meneghini, Carlo; Kothari, Deepti; Gupta, Ajay; Aquilanti, Giuliana

2012-08-01

Local atomic structure modifications around Fe atoms in polycrystalline multiferroic BiFeO3 are studied by Fe K edge x-ray absorption spectroscopy as a function of temperature across the Néel temperature (TN = 643 K) in order to reveal local structure modifications related to the magnetic transition. This work demonstrates that on crossing TN the local structure around Fe shows peculiar changes: the Fe-O bond lengths get shorter, the ligand symmetry increases and the Fe-O bond length disorder (σ2) deviates from Debye behaviour. These results suggest that the structural transition at the ferroelectric Curie temperature (TC = 1103 K) is anticipated by early local rearrangement of the structure starting already at TN.

Capturing local structure modulations of photoexcited BiVO4 by ultrafast transient XAFS.

PubMed

Uemura, Yohei; Kido, Daiki; Koide, Akihiro; Wakisaka, Yuki; Niwa, Yasuhiro; Nozawa, Shunsuke; Ichiyanagi, Kohei; Fukaya, Ryo; Adachi, Shin-Ichi; Katayama, Tetsuo; Togashi, Tadashi; Owada, Shigeki; Yabashi, Makina; Hatada, Keisuke; Iwase, Akihide; Kudo, Akihiko; Takakusagi, Satoru; Yokoyama, Toshihiko; Asakura, Kiyotaka

2017-06-29

Ultrafast excitation of photocatalytically active BiVO 4 was characterized by femto- and picosecond transient X-ray absorption fine structure spectroscopy. An initial photoexcited state (≪500 fs) changed to a metastable state accompanied by a structural change with a time constant of ∼14 ps. The structural change might stabilize holes on oxygen atoms since the interaction between Bi and O increases.

Hyperfine structure parametrisation in Maple

NASA Astrophysics Data System (ADS)

Gaigalas, G.; Scharf, O.; Fritzsche, S.

2006-02-01

In hyperfine structure examinations, routine high resolution spectroscopy methods have to be combined with exact fine structure calculations. The so-called magnetic A and electric B factor of the fine structure levels allow to check for a correct fine structure analysis, to find errors in the level designation, to find new levels and to probe the electron wavefunctions and its mixing coefficients. This is done by parametrisation of these factors into different contributions of the subshell electrons, which are split further into their radial and spin-angular part. Due to the routine with which hyperfine structure measurements are done, a tool for keeping the necessary information together, performing checks online with the experiment and deriving standard quantities is of great help. MAPLE [Maple is a registered trademark of Waterloo Maple Inc.] is a highly-developed symbolic programming language, often referred to as the pocket calculator of the future. Packages for theoretical atomic calculation exist ( RACAH and JUCYS) and the language meets all the requirements to keep and present information accessible for the user in a fast and practical way. We slightly extended the RACAH package [S. Fritzsche, Comput. Phys. Comm. 103 (1997) 51] and set up an environment for experimental hyperfine structure calculations, the HFS package. Supplying the fine structure and nuclear data, one is in the position to obtain information about the hyperfine spectrum, the different contributions to the splitting and to perform a least square fit of the radial parameters based on the semiempirical method. Experimentalist as well as theoretical physicist can do a complete hyperfine structure analysis using MAPLE. Program summaryTitle of program: H FS Catalogue number: ADXD Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADXD Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland Licensing provisions: none Computers for which the program is designed: All computers with a license of the computer algebra package MAPLE Installations: University of Kassel (Germany) Operating systems under which the program has been tested: Linux 9.0 Program language used:MAPLE, Release 7, 8 and 9 Memory required to execute with typical data: 5 MB No. of lines in distributed program, including test data, etc.: 34 300 No. of bytes in distributed program, including test data, etc.: 954 196 Distribution format: tar.gz Nature of the physical problem: Atomic state functions of an many configuration many electron atom with several open shells are defined by a number of quantum numbers, by their coupling and selection rules such as the Pauli exclusion principal or parity conservation. The matrix elements of any one-particle operator acting on these wavefunctions can be analytically integrated up to the radial part [G. Gaigalas, O. Scharf, S. Fritzsche, Central European J. Phys. 2 (2004) 720]. The decoupling of the interacting electrons is general, the obtained submatrix element holds all the peculiarities of the operator in question. These so-called submatrix elements are the key to do hyperfine structure calculations. The interaction between the electrons and the atomic nucleus leads to an additional splitting of the fine structure lines, the hyperfine structure. The leading components are the magnetic dipole interaction defining the so-called A factor and the electric quadrupole interaction, defining the so-called B factor. They express the energetic splitting of the spectral lines. Moreover, they are obtained directly by experiments and can be calculated theoretically in an ab initio approach. A semiempirical approach allows the fitting of the radial parts of the wavefunction to the experimentally obtained A and B factors. Method of solution: Extending the existing csf_LS() and asf_LS() to several open shells and implementing a data structure level_LS() for the fine structure level, the atomic environment is defined in MAPLE. It is used in a general approach to decouple the interacting shells for any one-particle operator. Further submatrix elements for the magnetic dipole and electric quadrupole interaction are implemented, allowing to calculate the A and B factors up to the radial part. Several procedures for standard quantities of the hyperfine structure are defined, too. The calculations are accelerated by using a hyper-geometric approach for three, six and nine symbols. Restrictions onto the complexity of the problem: Only atomic state functions in nonrelativistic LS-coupling with states having l⩽3 are supported. Typical running time: The program replies promptly on most requests. The least square fit depends heavily on the number of levels and can take a few minutes.

Improving precipitation hardening behavior of Mg−Zn based alloys with Ce−Ca microalloying additions

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

Langelier, B., E-mail: langelb@mcmaster.ca

2016-10-15

The precipitation hardening behavior of newly developed Mg−Zn−Ca−Ce alloys, with modified texture and improved ductility, is studied to delineate the microstructural characteristics that lead to effective hardening upon ageing treatments. Advanced electron microscopy and atom probe techniques are used to analyze the structural characteristics in relevance to the hardening potential. It has been found that the formation of a new basal precipitate phase, which evolves from a single atomic layer GP zone, and is finely distributed in both under-aged and peak-aged microstructures, has a significant impact in the improvement of the hardening response compared with the base Mg−Zn alloys. Itmore » has also been found that the β′{sub 1} rod precipitates, commonly formed during ageing treatments of Mg−Zn alloys, have their size and distribution significantly refined in the Ca−Ce containing alloys. The role of alloy chemistry in the formation of the fine basal plate GP zones and the refinement in β′{sub 1} precipitation and their relationships to the hardening behavior are discussed. It is proposed that Ca microalloying governs the formation of the GP zones and the enhancement of hardening, particularly in the under-aged conditions, but that this is aided by a beneficial effect from Ce. - Highlights: • Ce−Ca microalloying additions improve hardening in Mg−Zn, over Ce or Ca alone. • Improved hardening is due to refined β′{sub 1} rods, and fine basal plate precipitates. • Atom probe tomography identifies Ca in both β′{sub 1} and the fine basal plates. • The fine basal plates originate as ordered monolayer GP zones with 1:1 Zn:Ca (at.%). • With ageing GP zones become more Zn-rich and transform to the fine basal plates.« less

Dynamic Jahn-Teller effect: Calculation of fine structure spectrum, isotope shift and Zeeman behavior at deep center Ni2+ in CdS

NASA Astrophysics Data System (ADS)

Schoepp, Juergen

The internal transition of the deep center Ni2+ in II to IV semiconductor cadmium sulfide is examined with reference to crystal field theory. An algorithm was developed for calculation, in a basis fitted to trigonal symmetry, of fine structure operator matrix which is made of the sum of operators from spin trajectory coupling, trigonal field and electron phonon coupling. The dependence of energy level on the mass was calculated in order to examine the isotropy effect at Ni2+ transition. The mass dependence of phonon energy was estimated in an atomic cluster by using a valence force model from Keating for elastic energy. The Zeeman behavior of Ni2+ transition was examined for magnetic fields; the Zeeman operator was added to the fine structure operator and the resulting matrix was diagonalized. It is noticed that calculations are quantitatively and qualitatively in agreement with experiments.

X-ray absorption spectroscopy study on SiC-side interface structure of SiO2–SiC formed by thermal oxidation in dry oxygen

NASA Astrophysics Data System (ADS)

Isomura, Noritake; Kosaka, Satoru; Kataoka, Keita; Watanabe, Yukihiko; Kimoto, Yasuji

2018-06-01

Extended X-ray absorption fine structure (EXAFS) spectroscopy is demonstrated to measure the fine atomic structure of SiO2–SiC interfaces. The SiC-side of the interface can be measured by fabricating thin SiO2 films and using SiC-selective EXAFS measurements. Fourier transforms of the oscillations of the EXAFS spectra correspond to radial-structure functions and reveal a new peak of the first nearest neighbor of Si for m-face SiC, which does not appear in measurements of the Si-face. This finding suggests that the m-face interface could include a structure with shorter Si–C distances. Numerical calculations provide additional support for this finding.

The structure and properties of a nickel-base superalloy produced by osprey atomization-deposition

NASA Astrophysics Data System (ADS)

Bricknell, Rodger H.

1986-04-01

The production of a nickel-base superalloy, René* 80, by the Osprey atomization-deposition process has been investigated. Dense (>99 pct) material with a fine-grained equiaxed microstructure was deposited using either argon or nitrogen as the atomizing gas. Defects present in the material included a chill region at the collector plate interface, entrapped recirculated particles, porosity, and ceramic particles from the melting and dispensing system. In contrast to other rapid solidification techniques, low oxygen pick-ups are noted in the current technique. Tensile strengths above those displayed by castings are found in both nitrogen and argon atomized material, and in both the as-deposited and heat treated conditions. In addition, no profound mid-temperature ductility loss is displayed by this low oxygen material, in contrast to results on other rapidly solidified material with high oxygen contents. These results are explained in terms of oxygen embrittlement. In view of the excellent properties measured, the attractive economics of the process, and the fact that fine control of the gas/metal flow ratio is shown to be unnecessary, it is concluded that atomization-deposition presents an attractive potential production route for advanced alloys.

New limits on variation of the fine-structure constant using atomic dysprosium.

PubMed

Leefer, N; Weber, C T M; Cingöz, A; Torgerson, J R; Budker, D

2013-08-09

We report on the spectroscopy of radio-frequency transitions between nearly degenerate, opposite-parity excited states in atomic dysprosium (Dy). Theoretical calculations predict that these states are very sensitive to variation of the fine-structure constant α owing to large relativistic corrections of opposite sign for the opposite-parity levels. The near degeneracy reduces the relative precision necessary to place constraints on variation of α, competitive with results obtained from the best atomic clocks in the world. Additionally, the existence of several abundant isotopes of Dy allows isotopic comparisons that suppress common-mode systematic errors. The frequencies of the 754-MHz transition in 164Dy and 235-MHz transition in 162Dy are measured over the span of two years. The linear variation of α is α·/α=(-5.8±6.9([1σ]))×10(-17)  yr(-1), consistent with zero. The same data are used to constrain the dimensionless parameter kα characterizing a possible coupling of α to a changing gravitational potential. We find that kα=(-5.5±5.2([1σ]))×10(-7), essentially consistent with zero and the best constraint to date.

Laser Induced Optical Pumping Measurements of Cross Sections for Fine and Hyperfine Structure Transitions in Sodium Induced by Collisions with Helium Argon Atoms

NASA Technical Reports Server (NTRS)

Dobson, Chris C.; Sung, C. C.

1998-01-01

Optical pumping of the ground states of sodium can radically alter the shape of the laser induced fluorescence excitation spectrum, complicating measurements of temperature, pressure, etc., which are based on these spectra. Modeling of the fluorescence using rate equations for the eight hyperfine states of the sodium D manifolds can be used to quantify the contribution to the ground state pumping of transitions among the hyperfine excited states induced by collisions with buffer gas atoms. This model is used here to determine, from the shape of experimental spectra, cross sections for (Delta)F transitions of the P(sub 3/2) state induced by collisions with helium and argon atoms, for a range of values assumed for the P(sub 1/2), (Delta)F cross sections. The hyperfine cross sections measured using this method, which is thought to be novel, are compared with cross sections for transitions involving polarized magnetic substates, m(sub F), measured previously using polarization sensitive absorption. Also, fine structure transition ((Delta)J) cross sections were measured in the pumped vapor, giving agreement with previous measurements made in the absence of pumping.

Laser-Induced Optical Pumping Measurements of Cross Section for Fine- and Hyperfine-Structure Transitions in Sodium Induced by Collisions with Helium and Argon Atoms

NASA Technical Reports Server (NTRS)

Dobson, Chris C.; Sung, C. C.

1999-01-01

Optical pumping of the ground states of sodium can radically alter the shape of the laser-induced fluorescence excitation spectrum, complicating measurements of temperature, pressure, etc., which are based on these spectra. Modeling of the fluorescence using rate equations for the eight hyperfine states of the sodium D manifolds can be used to quantify the contribution to the ground state pumping of transitions among the hyperfine excited states induced by collisions with buffer gas atoms. This model is used here to determine, from the shape of experimental spectra, cross sections lor DELTA.F transitions of the P(sub 3/2) state induced by collisions with helium and argon atoms, for a range of values assumed for the P(sub 1/2), DELTA.F cross sections. The hyperfine cross sections measured using this method, which to our knowledge is novel, are compared with cross sections for transitions involving polarized magnetic substates m(sub F) measured previously using polarization sensitive absorption. Also, fine-structure transition cross sections were measured in the pumped vapor, giving agreement with previous measurements made in the absence of pumping.

Vanadium fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser–solid experiments

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

Palmeri, P., E-mail: patrick.palmeri@umons.ac.be; Quinet, P., E-mail: pascal.quinet@umons.ac.be; IPNAS, Université de Liège, B-4000 Liège

2015-09-15

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser–solid experiments through the K-shell emission cross section. In addition, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al. (2012)), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the vanadium isonuclear ions have been calculated. In this study, the K-shell EII cross sections connecting the ground and the metastable levels of the parent vanadium ions to the daughter ions K-vacancy levels considered in Palmerimore » et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 20 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic behavior of the modified relativistic binary encounter Bethe model (MRBEB) of Guerra et al. (2012) with the density-effect correction proposed by Davies et al. (2013)« less

Atomic Decay Data for Modeling K Lines of Iron Peak and Light Odd-Z Elements*

NASA Technical Reports Server (NTRS)

Palmeri, P.; Quinet, P.; Mendoza, C.; Bautista, M. A.; Garcia, J.; Witthoeft, M. C.; Kallman, T. R.

2012-01-01

Complete data sets of level energies, transition wavelengths, A-values, radiative and Auger widths and fluorescence yields for K-vacancy levels of the F, Na, P, Cl, K, Sc, Ti, V, Cr, Mn, Co, Cu and Zn isonuclear sequences have been computed by a Hartree-Fock method that includes relativistic corrections as implemented in Cowan's atomic structure computer suite. The atomic parameters for more than 3 million fine-structure K lines have been determined. Ions with electron number N greater than 9 are treated for the first time, and detailed comparisons with available measurements and theoretical data for ions with N less than or equal to 9 are carried out in order to estimate reliable accuracy ratings.

Experimental artefacts occurring during atom probe tomography analysis of oxide nanoparticles in metallic matrix: Quantification and correction

NASA Astrophysics Data System (ADS)

Hatzoglou, C.; Radiguet, B.; Pareige, P.

2017-08-01

Oxide Dispersion Strengthened (ODS) steels are promising candidates for future nuclear reactors, partly due to the fine dispersion of the nanoparticles they contain. Until now, there was no consensus as to the nature of the nanoparticles because their analysis pushed the techniques to their limits and in consequence, introduced some artefacts. In this study, the artefacts that occur during atom probe tomography analysis are quantified. The artefacts quantification reveals that the particles morphology, chemical composition and atomic density are biased. A model is suggested to correct these artefacts in order to obtain a fine and accurate characterization of the nanoparticles. This model is based on volume fraction calculation and an analytical expression of the atomic density. Then, the studied ODS steel reveals nanoparticles, pure in Y, Ti and O, with a core/shell structure. The shell is rich in Cr. The Cr content of the shell is dependent on that of the matrix by a factor of 1.5. This study also shows that 15% of the atoms that were initially in the particles are not detected during the analysis. This only affects O atoms. The particle stoichiometry evolves from YTiO2 for the smallest observed (<2 nm) to Y2TiO5 for the biggest (>8 nm).

General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

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

Fei, Huilong; Dong, Juncai; Feng, Yexin

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical predictionmore » of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.« less

General synthesis and definitive structural identification of MN 4C 4 single-atom catalysts with tunable electrocatalytic activities

DOE PAGES

Fei, Huilong; Dong, Juncai; Feng, Yexin; ...

2018-01-08

Single-atom catalysts (SACs) have recently attracted broad research interest as they combine the merits of both homogeneous and heterogeneous catalysts. Rational design and synthesis of SACs are of immense significance but have so far been plagued by the lack of a definitive correlation between structure and catalytic properties. Here, we report a general approach to a series of monodispersed atomic transition metals (for example, Fe, Co, Ni) embedded in nitrogen-doped graphene with a common MNsub>4C 4 moiety, identified by systematic X-ray absorption fine structure analyses and direct transmission electron microscopy imaging. The unambiguous structure determination allows density functional theoretical predictionmore » of MNsub>4C 4 moieties as efficient oxygen evolution catalysts with activities following the trend Ni > Co > Fe, which is confirmed by electrochemical measurements. Determination of atomistic structure and its correlation with catalytic properties represents a critical step towards the rational design and synthesis of precious or nonprecious SACs with exceptional atom utilization efficiency and catalytic activities.« less

Current and future constraints on extended Bekenstein-type models for a varying fine-structure constant

NASA Astrophysics Data System (ADS)

Alves, C. S.; Leite, A. C. O.; Martins, C. J. A. P.; Silva, T. A.; Berge, S. A.; Silva, B. S. A.

2018-01-01

There is a growing interest in astrophysical tests of the stability of dimensionless fundamental couplings, such as the fine-structure constant α , as an optimal probe of new physics. The imminent arrival of the ESPRESSO spectrograph will soon enable significant gains in the precision and accuracy of these tests and widen the range of theoretical models that can be tightly constrained. Here we illustrate this by studying proposed extensions of the Bekenstein-type models for the evolution of α that allow different couplings of the scalar field to both dark matter and dark energy. We use a combination of current astrophysical and local laboratory data (from tests with atomic clocks) to show that these couplings are constrained to parts per million level, with the constraints being dominated by the atomic clocks. We also quantify the expected improvements from ESPRESSO and other future spectrographs, and briefly discuss possible observational strategies, showing that these facilities can improve current constraints by more than an order of magnitude.

Lamb Shift of n = 1 and n = 2 States of Hydrogen-like Atoms, 1 ≤ Z ≤ 110

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

Yerokhin, V. A.; Shabaev, V. M.

2015-09-15

Theoretical energy levels of the n = 1 and n = 2 states of hydrogen-like atoms with the nuclear charge numbers 1 ≤ Z ≤ 110 are tabulated. The tabulation is based on ab initio quantum electrodynamics calculations performed to all orders in the nuclear binding strength parameter Zα, where α is the fine structure constant. Theoretical errors due to various effects are critically examined and estimated.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

NASA Astrophysics Data System (ADS)

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-05-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Single-atom Catalysis Using Pt/Graphene Achieved through Atomic Layer Deposition

PubMed Central

Sun, Shuhui; Zhang, Gaixia; Gauquelin, Nicolas; Chen, Ning; Zhou, Jigang; Yang, Songlan; Chen, Weifeng; Meng, Xiangbo; Geng, Dongsheng; Banis, Mohammad N.; Li, Ruying; Ye, Siyu; Knights, Shanna; Botton, Gianluigi A.; Sham, Tsun-Kong; Sun, Xueliang

2013-01-01

Platinum-nanoparticle-based catalysts are widely used in many important chemical processes and automobile industries. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their use efficiency, however, very challenging. Here we report a practical synthesis for isolated single Pt atoms anchored to graphene nanosheet using the atomic layer deposition (ALD) technique. ALD offers the capability of precise control of catalyst size span from single atom, subnanometer cluster to nanoparticle. The single-atom catalysts exhibit significantly improved catalytic activity (up to 10 times) over that of the state-of-the-art commercial Pt/C catalyst. X-ray absorption fine structure (XAFS) analyses reveal that the low-coordination and partially unoccupied densities of states of 5d orbital of Pt atoms are responsible for the excellent performance. This work is anticipated to form the basis for the exploration of a next generation of highly efficient single-atom catalysts for various applications.

Evidence for a novel chemisorption bond: Formate (HCO/sub 2/) on Cu(100)

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

Stoehr, J.; Outka, D.A.; Madix, R.J.

1985-03-25

Surface extended-x-ray-absorption fine-structure measurements reveal that formate (HCO/sub 2/) groups on Cu(100) chemisorb via the two oxygen atoms in adjacent fourfold hollow sites with an average O-Cu nearest-neighbor bond length of 2.38 +- 0.03 A. This distance is sig- nificantly (approx.0.4 A) longer than typical O-Cu bonds in bulk compounds and all known surface complexes. The unusually large O-Cu distance is attributed to a steric effect involving the C atom in HCO/sub 2/ and the nearest-neighbor Cu surface atoms.

Accurate determination of the fine-structure intervals in the 3P ground states of C-13 and C-12 by far-infrared laser magnetic resonance

NASA Technical Reports Server (NTRS)

Cooksy, A. L.; Saykally, R. J.; Brown, J. M.; Evenson, K. M.

1986-01-01

Accurate values are presented for the fine-structure intervals in the 3P ground state of neutral atomic C-12 and C-13 as obtained from laser magnetic resonance spectroscopy. The rigorous analysis of C-13 hyperfine structure, the measurement of resonant fields for C-12 transitions at several additional far-infrared laser frequencies, and the increased precision of the C-12 measurements, permit significant improvement in the evaluation of these energies relative to earlier work. These results will expedite the direct and precise measurement of these transitions in interstellar sources and should assist in the determination of the interstellar C-12/C-13 abundance ratio.

Size-dependent characteristics of ultra-fine oxygen-enriched nanoparticles in austenitic steels

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

Miao, Yinbin; Mo, Kun; Zhou, Zhangjian

2016-11-01

Here, a coordinated investigation of the elemental composition and morphology of ultra-fine-scale nanoparticles as a function of size within a variety of austenitic oxide dispersion-strengthened (ODS) steels is reported. Atom probe tomography was utilized to evaluate the elemental composition of these nanoparticles. Meanwhile, the crystal structures and orientation relationships were determined by high resolution transmission electron microscopy. The nanoparticles with sufficient size (>4 nm) to maintain a Y2Ti2-xO7-2x stoichiometry were found to have a pyrochlore structure, whereas smaller YxTiyOz nanoparticles lacked a well-defined structure. The size-dependent characteristics of the nanoparticles in austenitic ODS steels differ from those in ferritic/martensitic ODSmore » steels.« less

Electronic and atomic structures of Ti{sub 1-x}Al{sub x}N thin films related to their damage behavior

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

Tuilier, M.-H.; Pac, M.-J.; Girleanu, M.

2008-04-15

Ti and Al K-edge x-ray absorption spectroscopy is used to investigate the electronic structure of Ti{sub 1-x}Al{sub x}N thin films deposited by reactive magnetron sputtering. The experimental near edge spectra of TiN and AlN are interpreted in the light of unoccupied density of state band structure calculations. The comparison of the structural parameters derived from x-ray absorption fine structure and x-ray diffraction reveals segregation between Al-rich and Ti-rich domains within the Ti{sub 1-x}Al{sub x}N films. Whereas x-ray diffraction probes only the crystallized domains, the structural information derived from extended x-ray absorption fine structure analysis turns on both crystalline and grainmore » boundaries. The results are discussed by considering the damage behavior of the films depending on the composition.« less

Separated oscillatory field microwave measurement of the n=2 3P1 to n=2 3P2 fine-structure interval of helium

NASA Astrophysics Data System (ADS)

Borbely, Joseph S.

2009-11-01

The fine-structure constant is a fundamental constant of nature that represents the strength of the coupling interaction between charged particles. Comparison of high-precision theory and high-precision experiment of the n=2 3PJ fine-structure intervals of helium will allow for a determination of the fine-structure constant. The 23P1(mJ=0)-to-23P 2(mJ=0) magnetic-dipole transition in helium is measured to be 2 291 177.53(35) kHz using Ramsey separated oscillatory fields. A thermal beam of 23S1 metastable helium atoms is produced in a DC discharge source and enters a chamber where a vertical DC magnetic field lifts the degeneracy of the mJ states. Initially, the 2 3S1(mJ=-1, 0, 1) states are equally populated. A linearly polarized 1083-nm diode laser drives the 23S 1(mJ=0) atoms up to the 23P0(m J=0) state, emptying the 23S1(mJ=0) state. A 15-ns laser pulse drives the 23S1(m J=+1)-to-23P1(mJ=0) transitions and this laser pulse is followed by two microwave pulses that drive the 2.29-GHz 23P1(mJ=0)-to-23P 2(mJ=0) transition. The atoms which undergo this microwave transition can spontaneously decay to the previously-emptied 23S 1(mJ=0) state. The 23P1(m J=0) state is forbidden to decay to the 23S1(m J=0) state since the transition has a zero electric-dipole matrix element. Therefore, any re-population of the 23S1(m J=0) state is a direct indication that the 2.29-GHz microwave transition has been driven. A linearly polarized 1083-nm diode laser detects the 2 3S1(mJ=0) atoms by exciting them up to the 2 3P0(mJ=0) state and the radiation from the resulting spontaneous decay is observed by focusing it onto a liquid-nitrogen-cooled InGaAs photodiode. The two microwave pulses are alternatively in phase or 180°out of phase and the difference of these signals versus microwave frequency leads to a Ramsey separated oscillatory field interference pattern.

Nonrelativistic quantum theory of the contact inelastic scattering of an x-ray photon by an atom

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

Hopersky, Alexey N.; Nadolinsky, Alexey M.

The nonrelativistic analytical structure of the doubly differential cross section of the contact inelastic scattering of an x-ray photon by a free atom is determined by means of the irreducible tensor operator theory outside the frame of the impulse approximation. For the neon atom in the vicinity of the 1s shell ionization threshold our theory predicts the existence of the distinct fine structure of the cross section caused by transitions of the atomic core electrons into the excited discrete spectrum states. The results of our calculations with inclusion of the effects of radial relaxation, inelastic scattering through the intermediate states,more » and elastic Rayleigh scattering, are predictions, while at the 22 keV incident photons they compare well with the synchrotron experiment by Jung et al. [Phys. Rev. Lett. 81, 1596 (1998)].« less

Cold Rydberg molecules

NASA Astrophysics Data System (ADS)

Raithel, Georg

2017-04-01

Cold atomic systems have opened new frontiers in atomic and molecular physics, including several types of Rydberg molecules. Three types will be reviewed. Long-range Rydberg-ground molecules, first predicted in and observed in, are formed via low-energy electron scattering of the Rydberg electron from a ground-state atom within the Rydberg atom's volume. The binding mostly arises from S- and P-wave triplet scattering. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering, the fine structure coupling of the Rydberg atom and the hyperfine structure coupling of the 5S1/2 atom (in rubidium). The hyperfine structure gives rise to mixed singlet-triplet potentials for both low-L and high-L Rydberg molecules. A classification into Hund's cases will be discussed. The talk further includes results on adiabatic potentials and adiabatic states of Rydberg-Rydberg molecules in Rb and Cs. These molecules, which have even larger bonding length than Rydberg-ground molecules, are formed via electrostatic multipole interactions. The leading interaction of neutral Rydberg-Rydberg molecules is dipole-dipole, while for ionic Rydberg molecules it is dipole-monopole. Higher-order terms are discussed. FUNDING: NSF (PHY-1506093), NNSF of China (61475123).

Homogeneity of Pb(Zr ,Ti)O3 thin films by chemical solution deposition: Extended x-ray absorption fine structure spectroscopy study of zirconium local environment

NASA Astrophysics Data System (ADS)

Malic, Barbara; Arcon, Iztok; Kodre, Alojz; Kosec, Marija

2006-09-01

Sols for Pb(Zr0.53Ti0.47)O3 (PZT) thin films were prepared by 2-methoxyethanol route from lead acetate, titanium n-propoxide, and zirconium n-propoxide, the latter either unmodified or modified with acetylacetone or acetic acid in a 2/1 molar ratio and deposited on sapphire (0001). By Zr K-edge extended x-ray absorption fine structure (EXAFS) spectroscopy, the structural changes in the Zr local environment, induced by the addition of the two modifiers, were followed from the synthesis of the PZT sol to the transition to the amorphous film. In the unmodified PZT sol segregation of Zr species occurs from the original dimers present in the Zr propoxide solution in 2-methoxyethanol. The immediate neighborhood of Zr atoms changes markedly at the transition from the sol to the amorphous film: the local structure around Zr atoms is similar to the one found in tetragonal zirconia particles. The modification of Zr propoxide with acetylacetone in 2-methoxyethanol results in Zr monomers. In PZT sol, clustering of Zr species is observed continuing into the amorphous film. By modification with acetic acid the original dimeric structure of the Zr precursor is retained in the PZT sol and further in the amorphous film. Selective modification of Zr propoxide with acetic acid therefore results in a more homogeneous distribution of Zr atoms in the PZT sol and amorphous film than in both as-received and acetylacetone-modified Zr propoxide.

Local atomic and electronic structures in ferromagnetic topological insulator Cr-doped (BixSb1-x) 2Te3 studied by XAFS and ab initio calculations

NASA Astrophysics Data System (ADS)

Liu, Zhen; Wei, Xinyuan; Wang, Jiajia; Pan, Hong; Ji, Fuhao; Ye, Mao; Yang, Zhongqin; Qiao, Shan

2015-09-01

The local atomic and electronic structures around the dopants in Cr-doped (BixSb1 -x )2Te3 are studied by x-ray absorption fine structure (XAFS) measurements and first-principles calculations. Both Cr and Bi are confirmed substituting Sb sites (CrSb and BiSb). The six nearest Te atoms around Cr move towards Cr and shorten the Cr-Te bond lengths to 2.76 Å and 2.77 Å for x =0.1 and x =0.2 , respectively. Importantly, we reveal the hybridization between the Sb/Te p states and Cr d states by the presence of a pre-edge peak at Cr K -absorption edge, which is also supported by our ab initio calculations. These findings provide important clues to understand the mechanism of ferromagnetic order in this system with quantum anomalous Hall effect.

The atomic scale structure of CXV carbon: wide-angle x-ray scattering and modeling studies.

PubMed

Hawelek, L; Brodka, A; Dore, J C; Honkimaki, V; Burian, A

2013-11-13

The disordered structure of commercially available CXV activated carbon produced from finely powdered wood-based carbon has been studied using the wide-angle x-ray scattering technique, molecular dynamics and density functional theory simulations. The x-ray scattering data has been converted to the real space representation in the form of the pair correlation function via the Fourier transform. Geometry optimizations using classical molecular dynamics based on the reactive empirical bond order potential and density functional theory at the B3LYP/6-31g* level have been performed to generate nanoscale models of CXV carbon consistent with the experimental data. The final model of the structure comprises four chain-like and buckled graphitic layers containing a small percentage of four-fold coordinated atoms (sp(3) defects) in each layer. The presence of non-hexagonal rings in the atomic arrangement has been also considered.

Interatomic scattering in energy dependent photoelectron spectra of Ar clusters

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

Patanen, M.; Benkoula, S.; Nicolas, C.

2015-09-28

Soft X-ray photoelectron spectra of Ar 2p levels of atomic argon and argon clusters are recorded over an extended range of photon energies. The Ar 2p intensity ratios between atomic argon and clusters’ surface and bulk components reveal oscillations similar to photoelectron extended X-ray absorption fine structure signal (PEXAFS). We demonstrate here that this technique allows us to analyze separately the PEXAFS signals from surface and bulk sites of free-standing, neutral clusters, revealing a bond contraction at the surface.

Near-neighbor mixing and bond dilation in mechanically alloyed Cu-Fe

NASA Astrophysics Data System (ADS)

Harris, V. G.; Kemner, K. M.; Das, B. N.; Koon, N. C.; Ehrlich, A. E.; Kirkland, J. P.; Woicik, J. C.; Crespo, P.; Hernando, A.; Garcia Escorial, A.

1996-09-01

Extended x-ray-absorption fine-structure (EXAFS) measurements were used to obtain element-specific, structural, and chemical information of the local environments around Cu and Fe atoms in high-energy ball-milled CuxFe1-x samples (x=0.50 and 0.70). Analysis of the EXAFS data shows both Fe and Cu atoms reside in face-centered-cubic sites where the first coordination sphere consists of a mixture of Fe and Cu atoms in a ratio which reflects the as-prepared stoichiometry. The measured bond distances indicate a dilation in the bonds between unlike neighbors which accounts for the lattice expansion measured by x-ray diffraction. These results indicate that metastable alloys having a positive heat of mixing can be prepared via the high-energy ball-milling process.

Investigating the Defect Structures in Transparent Conducting Oxides Using X-ray and Neutron Scattering Techniques

PubMed Central

González, Gabriela B.

2012-01-01

Transparent conducting oxide (TCO) materials are implemented into a wide variety of commercial devices because they possess a unique combination of high optical transparency and high electrical conductivity. Created during the processing of the TCOs, defects within the atomic-scale structure are responsible for their desirable optical and electrical properties. Therefore, studying the defect structure is essential to a better understanding of the behavior of transparent conductors. X-ray and neutron scattering techniques are powerful tools to investigate the atomic lattice structural defects in these materials. This review paper presents some of the current developments in the study of structural defects in n-type TCOs using x-ray diffraction (XRD), neutron diffraction, extended x-ray absorption fine structure (EXAFS), pair distribution functions (PDFs), and x-ray fluorescence (XRF). PMID:28817010

Metal powder production by gas atomization

NASA Technical Reports Server (NTRS)

Ting, E. Y.; Grant, N. J.

1986-01-01

The confined liquid, gas-atomization process was investigated. Results from a two-dimensional water model showed the importance of atomization pressure, as well as delivery tube and atomizer design. The atomization process at the tip of the delivery tube was photographed. Results from the atomization of a modified 7075 aluminum alloy yielded up to 60 wt pct. powders that were finer than 45 microns in diameter. Two different atomizer designs were evaluated. The amount of fine powders produced was correlated to a calculated gas-power term. An optimal gas-power value existed for maximized fine powder production. Atomization at gas-power greater than or less than this optimal value produced coarser powders.

Copper fine-structure K-shell electron impact ionization cross sections for fast-electron diagnostic in laser-solid experiments

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

Palmeri, P., E-mail: patrick.palmeri@umons.ac.be; Quinet, P., E-mail: pascal.quinet@umons.ac.be; IPNAS, Université de Liège, B-4000 Liège

2015-03-15

The K-shell electron impact ionization (EII) cross section, along with the K-shell fluorescence yield, is one of the key atomic parameters for fast-electron diagnostic in laser-solid experiments through the K-shell emission cross section. In addition, copper is a material that has been often used in those experiments because it has a maximum total K-shell emission yield. Furthermore, in a campaign dedicated to the modeling of the K lines of astrophysical interest (Palmeri et al., 2012), the K-shell fluorescence yields for the K-vacancy fine-structure atomic levels of all the copper isonuclear ions have been calculated. In this study, the K-shell EII crossmore » sections connecting the ground and the metastable levels of the parent copper ions to the daughter ions K-vacancy levels considered in Palmeri et al. (2012) have been determined. The relativistic distorted-wave (DW) approximation implemented in the FAC atomic code has been used for the incident electron kinetic energies up to 10 times the K-shell threshold energies. Moreover, the resulting DW cross sections have been extrapolated at higher energies using the asymptotic form proposed by Davies et al. (2013)« less

Theoretical Study of Energy Levels and Transition Probabilities of Boron Atom

NASA Astrophysics Data System (ADS)

Tian Yi, Zhang; Neng Wu, Zheng

2009-08-01

Full Text PDF Though the electrons configuration for boron atom is simple and boron atom has long been of interest for many researchers, the theoretical studies for properties of BI are not systematic, there are only few results reported on energy levels of high excited states of boron, and transition measurements are generally restricted to transitions involving ground states and low excited states without considering fine structure effects, provided only multiplet results, values for transitions between high excited states are seldom performed. In this article, by using the scheme of the weakest bound electron potential model theory calculations for energy levels of five series are performed and with the same method we give the transition probabilities between excited states with considering fine structure effects. The comprehensive set of calculations attempted in this paper could be of some value to workers in the field because of the lack of published calculations for the BI systems. The perturbations coming from foreign perturbers are taken into account in studying the energy levels. Good agreement between our results and the accepted values taken from NIST has been obtained. We also reported some values of energy levels and transition probabilities not existing on the NIST data bases.

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

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

Song, Zhen; Kenney, Janice P.L.; Fein, Jeremy B.

2015-02-09

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has beenmore » observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.« less

An X-ray Absorption Fine Structure study of Au adsorbed onto the non-metabolizing cells of two soil bacterial species

NASA Astrophysics Data System (ADS)

Song, Zhen; Kenney, Janice P. L.; Fein, Jeremy B.; Bunker, Bruce A.

2012-06-01

Gram-positive and Gram-negative bacterial cells can remove Au from Au(III)-chloride solutions, and the extent of removal is strongly pH dependent. In order to determine the removal mechanisms, X-ray Absorption Fine Structure (XAFS) spectroscopy experiments were conducted on non-metabolizing biomass of Bacillus subtilis and Pseudomonas putida with fixed Au(III) concentrations over a range of bacterial concentrations and pH values. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) data on both bacterial species indicate that more than 90% of the Au atoms on the bacterial cell walls were reduced to Au(I). In contrast to what has been observed for Au(III) interaction with metabolizing bacterial cells, no Au(0) or Au-Au nearest neighbors were observed in our experimental systems. All of the removed Au was present as adsorbed bacterial surface complexes. For both species, the XAFS data suggest that although Au-chloride-hydroxide aqueous complexes dominate the speciation of Au in solution, Au on the bacterial cell wall is characterized predominantly by binding of Au atoms to sulfhydryl functional groups and amine and/or carboxyl functional groups, and the relative importance of the sulfhydryl groups increases with increasing pH and with decreasing Au loading. The XAFS data for both microorganism species suggest that adsorption is the first step in the formation of Au nanoparticles by bacteria, and the results enhance our ability to account for the behavior of Au in bacteria-bearing geologic systems.

Measurement of local structural configurations associated with reversible photostructural changes in arsenic trisulfide films

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

Yang, C.Y.; Paesler, M.A.; Sayers, D.E.

1987-12-15

Extended x-ray-absorption fine-structure measurements have been made on three reversible and reproducible cycles of thermally annealed and light-soaked amorphous As/sub 2/S/sub 3/ films. Associated with the light-soaked material are (1) a very small increase in the population of wrong bonds in the first shell, (2) an enlarged As: S: As bond angle with an expansion of As: As distance in the second shell, (3) a larger spread in the distribution of As: S: As bond angles, and (4) an absence of any change in the third As: S shell. From these data, we present the first quantitative correlation between observedmore » local atomic structural changes and measured macroscopic properties that are associated with photodarkening. Our data demonstrate that the photoinduced structural changes mainly involve bonding alterations at S atoms as well as a change in the dihedral angle relationship between adjacent AsS/sub 3/ pyramids joined at S atoms.« less

The performance of fine-grained and coarse-grained elastic network models and its dependence on various factors.

PubMed

Na, Hyuntae; Song, Guang

2015-07-01

In a recent work we developed a method for deriving accurate simplified models that capture the essentials of conventional all-atom NMA and identified two best simplified models: ssNMA and eANM, both of which have a significantly higher correlation with NMA in mean square fluctuation calculations than existing elastic network models such as ANM and ANMr2, a variant of ANM that uses the inverse of the squared separation distances as spring constants. Here, we examine closely how the performance of these elastic network models depends on various factors, namely, the presence of hydrogen atoms in the model, the quality of input structures, and the effect of crystal packing. The study reveals the strengths and limitations of these models. Our results indicate that ssNMA and eANM are the best fine-grained elastic network models but their performance is sensitive to the quality of input structures. When the quality of input structures is poor, ANMr2 is a good alternative for computing mean-square fluctuations while ANM model is a good alternative for obtaining normal modes. © 2015 Wiley Periodicals, Inc.

Insight into the biological effects of acupuncture points by X-ray absorption fine structure.

PubMed

Liu, Chenglin; Liu, Qinghua; Zhang, Dongming; Liu, Wei; Yan, Xiaohui; Zhang, Xinyi; Oyanagi, Hiroyuki; Pan, Zhiyun; Hu, Fengchun; Wei, Shiqiang

2018-06-02

Exploration of the biological effects of transition metal ions in acupuncture points is essential to clarify the functional mechanism of acupuncture treatment. Here we show that in the SP6 acupuncture point (Sanyinjiao) the Fe ions are in a high-spin state of approximately t 2g 4.5 e g 1.5 in an Fe-N(O) octahedral crystal field. The Fe K-edge synchrotron radiation X-ray absorption fine structure results reveal that the Fe-N and Fe-O bond lengths in the SP6 acupuncture point are 2.05 and 2.13 Å, respectively, and are 0.05-0.10 Å longer than those in the surrounding tissue. The distorted atomic structure reduces the octahedral symmetry and weakens the crystal field around the Fe ions by approximately 0.3 eV, leading to the high-spin configuration of the Fe ions, which is favorable for strengthening the magnetotransport and oxygen transportation properties in the acupuncture point by the enhanced spin coherence. This finding might provide some insight into the microscopic effect of the atomic and electronic interactions of transition metal ions in the acupuncture point. Graphical Abstract ᅟ.

Production of a Powder Metallurgical Hot Work Tool Steel with Harmonic Structure by Mechanical Milling and Spark Plasma Sintering

NASA Astrophysics Data System (ADS)

Deirmina, Faraz; Pellizzari, Massimo; Federici, Matteo

2017-04-01

Commercial AISI-H13 gas atomized powders (AT) were mechanically milled (MM) to refine both the particle size and the microstructure. Different volume fractions of coarser grained (CG) AT powders were mixed with the ultra-fine grained (UFG) MM and consolidated by spark plasma sintering to obtain bulks showing a harmonic structure ( i.e. a 3D interconnected network of UFG areas surrounding the CG atomized particles). The low sintering temperature, 1373.15 K (1100 °C) and the short sintering time (30 minutes) made it possible to obtain near full density samples while preserving the refined microstructure induced by MM. A combination of high hardness and significantly improved fracture toughness is achieved by the samples containing 50 to 80 vol pct MM, essentially showing harmonic structure. The design allows to easily achieve specific application oriented properties by varying the MM volume fraction in the initial mixture. Hardness is governed by the fine-grained MM matrix and improved toughening is due to (1) deviatory effect of AT particles and (2) energy dissipation as a result of the decohesion in MM regions or AT and MM interface.

Atomic and electronic structure of Mo6S9-xIx nanowires

NASA Astrophysics Data System (ADS)

Meden, A.; Kodre, A.; Padeznik Gomilsek, J.; Arcon, I.; Vilfan, I.; Vrbanic, D.; Mrzel, A.; Mihailovic, D.

2005-09-01

Moybdenum-based subnanometre diameter nanowires are easy to synthesize and disperse, and they exhibit a variety of functional properties in which they are superior to other one-dimensional materials. However, further progress in the understanding of physical properties and the development of new and specific applications have so far been impeded by the fact that their structure was not accurately known. Here we report on a combination of systematic x-ray diffraction and extended x-ray absorption fine structure experiments, and first-principles theoretical structure calculations, which are used to determine the atomic skeletal structure of individual Mo6S9-xIx (MoSIx) nanowires, their packing arrangement within bundles and their electronic band structure. From this work we conclude that the variations in functional properties appear to arise from different stoichiometry, not skeletal structure. A supplementary data file is available from http://stacks.iop.org/0957-4484/16/1578

Local Structure and Anisotropy in the Amorphous Precursor= to Ba-Hexaferrite Thin Films

NASA Astrophysics Data System (ADS)

Snyder, J. E.; Harris, V. G.; Koon, N. C.; Sui, X.; Kryder, M. H.

1996-03-01

Ba-hexaferrite thin-films for recording media applications are commonly fabricated by a two-step process: sputter-deposition of an amorphous precursor, followed by annealing to crystallize the BaFe_12O_19 phase. The magnetic anisotropy of the crystalline films can be either in-plane or perpendicular, depending on the sputtering process used in the first step. However, conventional characterization techniques (x-ray diffraction and TEM) have been unable to observe any structure in the amorphous precursor films. In this study, such films are investigated by PD-EXAFS (polarization-dependent extended x-ray absorption fine structure). An anisotropic local ordered structure is observed around both Fe and Ba atoms in the "amorphous" films. This anisotropic local structure appears to determine the orientation of the fast-growing basal plane directions during crystallization, and thus the directions of the c-axes and the magnetic anisotropy. Results suggest that the structure of the amorphous films consists of networks made up of units of Fe atoms surrounded by their O nearest neighbors, that are connected together. Ba atoms appear to fit into in-between spaces as network-modifiers.

Controlling octahedral rotations in a perovskite via strain doping

DOE PAGES

Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; ...

2016-05-24

The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film canmore » be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO 3 films coherently grown on SrTiO 3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.« less

Quantitative Phase Analysis of Plasma-Treated High-Silica Materials

NASA Astrophysics Data System (ADS)

Kosmachev, P. V.; Abzaev, Yu. A.; Vlasov, V. A.

2018-06-01

The paper presents the X-ray diffraction (XRD) analysis of the crystal structure of SiO2 in two modifications, namely quartzite and quartz sand before and after plasma treatment. Plasma treatment enables the raw material to melt and evaporate after which the material quenches and condenses to form nanoparticles. The Rietveld refinement method is used to identify the lattice parameters of SiO2 phases. It is found that after plasma treatment SiO2 oxides are in the amorphous state, which are modeled within the microcanonical ensemble. Experiments show that amorphous phases are stable, and model X-ray reflection intensities approximate the experimental XRD patterns with fine precision. Within the modeling, full information is obtained for SiO2 crystalline and amorphous phases, which includes atom arrangement, structural parameters, atomic population of silicon and oxygen atoms in lattice sites.

Structural Characterization of CO-Inhibited Mo-Nitrogenase by Combined Application of Nuclear Resonance Vibrational Spectroscopy, Extended X-ray Absorption Fine Structure, and Density Functional Theory: New Insights into the Effects of CO Binding and the Role of the Interstitial Atom

DOE PAGES

Scott, Aubrey D.; Pelmenschikov, Vladimir; Guo, Yisong; ...

2014-10-02

The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N 2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm –1 mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N 2ase variant. In the frequency region above 450 cm –1, additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by 13CO isotope shifts). The EXAFSmore » for wild-type N 2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal ₋CO and a partially reduced ₋CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational “shake” modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. We discuss implications for the CO and N 2 reactivity of N 2ase.« less

Structural characterization of CO-inhibited Mo-nitrogenase by combined application of nuclear resonance vibrational spectroscopy, extended X-ray absorption fine structure, and density functional theory: new insights into the effects of CO binding and the role of the interstitial atom.

PubMed

Scott, Aubrey D; Pelmenschikov, Vladimir; Guo, Yisong; Yan, Lifen; Wang, Hongxin; George, Simon J; Dapper, Christie H; Newton, William E; Yoda, Yoshitaka; Tanaka, Yoshihito; Cramer, Stephen P

2014-11-12

The properties of CO-inhibited Azotobacter vinelandii (Av) Mo-nitrogenase (N2ase) have been examined by the combined application of nuclear resonance vibrational spectroscopy (NRVS), extended X-ray absorption fine structure (EXAFS), and density functional theory (DFT). Dramatic changes in the NRVS are seen under high-CO conditions, especially in a 188 cm(-1) mode associated with symmetric breathing of the central cage of the FeMo-cofactor. Similar changes are reproduced with the α-H195Q N2ase variant. In the frequency region above 450 cm(-1), additional features are seen that are assigned to Fe-CO bending and stretching modes (confirmed by (13)CO isotope shifts). The EXAFS for wild-type N2ase shows evidence for a significant cluster distortion under high-CO conditions, most dramatically in the splitting of the interaction between Mo and the shell of Fe atoms originally at 5.08 Å in the resting enzyme. A DFT model with both a terminal -CO and a partially reduced -CHO ligand bound to adjacent Fe sites is consistent with both earlier FT-IR experiments, and the present EXAFS and NRVS observations for the wild-type enzyme. Another DFT model with two terminal CO ligands on the adjacent Fe atoms yields Fe-CO bands consistent with the α-H195Q variant NRVS. The calculations also shed light on the vibrational "shake" modes of the interstitial atom inside the central cage, and their interaction with the Fe-CO modes. Implications for the CO and N2 reactivity of N2ase are discussed.

Continuous Faraday measurement of spin precession without light shifts

NASA Astrophysics Data System (ADS)

Jasperse, M.; Kewming, M. Â. J.; Fischer, S. Â. N.; Pakkiam, P.; Anderson, R. Â. P.; Turner, L. Â. D.

2017-12-01

We describe a dispersive Faraday optical probe of atomic spin which performs a weak measurement of spin projection of a quantum gas continuously for more than one second. To date, focusing bright far-off-resonance probes onto quantum gases has proved invasive due to strong scalar and vector light shifts exerting dipole and Stern-Gerlach forces. We show that tuning the probe near the magic-zero wavelength at 790 nm between the fine-structure doublet of 87Rb cancels the scalar light shift, and careful control of polarization eliminates the vector light shift. Faraday rotations due to each fine-structure line reinforce at this wavelength, enhancing the signal-to-noise ratio for a fixed rate of probe-induced decoherence. Using this minimally invasive spin probe, we perform microscale atomic magnetometry at high temporal resolution. Spectrogram analysis of the Larmor precession signal of a single spinor Bose-Einstein condensate measures a time-varying magnetic field strength with 1 μ G accuracy every 5 ms; or, equivalently, makes more than 200 successive measurements each at 10 pT /√{Hz } sensitivity.

Marvels of enzyme catalysis at true atomic resolution: distortions, bond elongations, hidden flips, protonation states and atom identities.

PubMed

Neumann, Piotr; Tittmann, Kai

2014-12-01

Although general principles of enzyme catalysis are fairly well understood nowadays, many important details of how exactly the substrate is bound and processed in an enzyme remain often invisible and as such elusive. In fortunate cases, structural analysis of enzymes can be accomplished at true atomic resolution thus making possible to shed light on otherwise concealed fine-structural traits of bound substrates, intermediates, cofactors and protein groups. We highlight recent structural studies of enzymes using ultrahigh-resolution X-ray protein crystallography showcasing its enormous potential as a tool in the elucidation of enzymatic mechanisms and in unveiling fundamental principles of enzyme catalysis. We discuss the observation of seemingly hyper-reactive, physically distorted cofactors and intermediates with elongated scissile substrate bonds, the detection of 'hidden' conformational and chemical equilibria and the analysis of protonation states with surprising findings. In delicate cases, atomic resolution is required to unambiguously disclose the identity of atoms as demonstrated for the metal cluster in nitrogenase. In addition to the pivotal structural findings and the implications for our understanding of enzyme catalysis, we further provide a practical framework for resolution enhancement through optimized data acquisition and processing. Copyright © 2014 Elsevier Ltd. All rights reserved.

Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

PubMed

Chen, Wenxing; Pei, Jiajing; He, Chun-Ting; Wan, Jiawei; Ren, Hanlin; Zhu, Youqi; Wang, Yu; Dong, Juncai; Tian, Shubo; Cheong, Weng-Chon; Lu, Siqi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Zhuang, Zhongbin; Chen, Chen; Peng, Qing; Wang, Dingsheng; Li, Yadong

2017-12-11

The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo 1 N 1 C 2 ). Importantly, the Mo 1 N 1 C 2 catalyst displayed much more excellent activity compared with Mo 2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo 1 N 1 C 2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cold Rydberg molecules

NASA Astrophysics Data System (ADS)

Raithel, Georg; Zhao, Jianming

2017-04-01

Cold atomic systems have opened new frontiers at the interface of atomic and molecular physics. These include research on novel types of Rydberg molecules. Three types of molecules will be reviewed. Long-range, homonuclear Rydberg molecules, first predicted in [1] and observed in [2], are formed via low-energy electron scattering of the Rydberg electron from a ground-state atom within the Rydberg atom's volume. The binding mostly arises from S- and P-wave triplet scattering. We use a Fermi model that includes S-wave and P-wave singlet and triplet scattering, the fine structure coupling of the Rydberg atom and the hyperfine structure coupling of the 5S1/2 atom (in rubidium [3]). The hyperfine structure gives rise to mixed singlet-triplet potentials for both low-L and high-L Rydberg molecules [3]. A classification into Hund's cases [3, 4, 5] will be discussed. The talk further includes results on adiabatic potentials and adiabatic states of Rydberg-Rydberg molecules in Rb and Cs. These molecules, which have even larger bonding length than Rydberg-ground molecules, are formed via electrostatic multipole interactions. The leading interaction term of neutral Rydberg-Rydberg molecules is between two dipoles, while for ionic Rydberg molecules it is between a dipole and a monopole. NSF (PHY-1506093), NNSF of China (61475123).

Atomic-scale distortion of optically activated Sm dopants identified with site-selective X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Ishii, Masashi; Crowe, Iain F.; Halsall, Matthew P.; Hamilton, Bruce; Hu, Yongfeng; Sham, Tsun-Kong; Harako, Susumu; Zhao, Xin-Wei; Komuro, Shuji

2013-10-01

The local structure of luminescent Sm dopants was investigated using an X-ray absorption fine-structure technique with X-ray-excited optical luminescence. Because this technique evaluates X-ray absorption from luminescence, only optically active sites are analyzed. The Sm L3 near-edge spectrum contains split 5d states and a shake-up transition that are specific to luminescent Sm. Theoretical calculations using cluster models identified an atomic-scale distortion that can reproduce the split 5d states. The model with C4v local symmetry and compressive bond length of Sm-O of a six-fold oxygen (SmO6) cluster is most consistent with the experimental results.

Development of a force sensor using atom interferometry to constrain theories on dark matter and dark energy

NASA Astrophysics Data System (ADS)

Schlupf, Chandler; Niederriter, Robert; Bohr, Eliot; Khamis, Sami; Park, Youna; Szwed, Erik; Hamilton, Paul

2017-04-01

Atom interferometry has been used in many precision measurements such as Newton's gravitational constant, the fine structure constant, and tests of the equivalence principle. We will perform atom interferometry in an optical lattice to measure the force felt by an atom due to a test mass in search of new forces suggested by dark matter and dark energy theories. We will be developing a new apparatus using laser-cooled ytterbium to continuously measure this force by observing their Bloch oscillations. Interfering atoms in an optical lattice allows continuous measurements in a small volume over a long period of time, enabling our device to be sensitive to time-varying forces while minimizing vibrational noise. We present the details of this experiment and the progress on it thus far.

Dynamic polarizability of tungsten atoms reconstructed from fast electrical explosion of fine wires in vacuum

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

Sarkisov, G. S.; Rosenthal, S. E.; Struve, K. W.

For nanosecond electrical explosion of fine metal wires in vacuum generates calibrated, radially expanded gas cylinders of metal atoms are surrounded by low-density fast expanding plasma corona. Here, a novel integrated-phase technique, based on laser interferometry, provides the dynamic dipole polarizability of metal atoms. This data was previously unavailable for tungsten atoms. Furthermore, an extremely high melting temperature and significant pre-melt electronic emission make these measurements particularly complicated for this refractory metal.

Dynamic polarizability of tungsten atoms reconstructed from fast electrical explosion of fine wires in vacuum

DOE PAGES

Sarkisov, G. S.; Rosenthal, S. E.; Struve, K. W.

2016-10-12

For nanosecond electrical explosion of fine metal wires in vacuum generates calibrated, radially expanded gas cylinders of metal atoms are surrounded by low-density fast expanding plasma corona. Here, a novel integrated-phase technique, based on laser interferometry, provides the dynamic dipole polarizability of metal atoms. This data was previously unavailable for tungsten atoms. Furthermore, an extremely high melting temperature and significant pre-melt electronic emission make these measurements particularly complicated for this refractory metal.

Electron-beam induced amorphization of stishovite: Silicon-coordination change observed using Si K-edge extended electron energy-loss fine structure

NASA Astrophysics Data System (ADS)

van Aken, P. A.; Sharp, T. G.; Seifert, F.

The analysis of the extended energy-loss fine structure (EXELFS) of the Si K-edge for sixfold-coordinated Si in synthetic stishovite and fourfold-coordinated Si in natural α-quartz is reported by using electron energy-loss spectroscopy (EELS) in combination with transmission electron microscopy (TEM). The stishovite Si K-edge EXELFS spectra were measured as a time-dependent series to document irradiation-induced amorphization. The amorphization was also investigated through the change in Si K- and O K-edge energy-loss near edge structure (ELNES). For α-quartz, in contrast to stishovite, electron irradiation-induced vitrification, verified by selected area electron diffraction (SAED), produced no detectable changes of the EXELFS. The Si K-edge EXELFS were analysed with the classical extended X-ray absorption fine structure (EXAFS) treatment and compared to ab initio curve-waved multiple-scattering (MS) calculations of EXAFS spectra for stishovite and α-quartz. Highly accurate information on the local atomic environment of the silicon atoms during the irradiation-induced amorphization of stishovite is obtained from the EXELFS structure parameters (Si-O bond distances, coordination numbers and Debye-Waller factors). The mean Si-O bond distance R and mean Si coordination number N changes from R=0.1775 nm and N=6 for stishovite through a disordered intermediate state (R 0.172 nm and N 5) to R 0.167 nm and N 4.5 for a nearly amorphous state similar to α-quartz (R=0.1609 nm and N=4). During the amorphization process, the Debye-Waller factor (DWF) passes through a maximum value of as it changes from for sixfold to for fourfold coordination of Si. This increase in Debye-Waller factor indicates an increase in mean-square relative displacement (MSRD) between the central silicon atom and its oxygen neighbours that is consistent with the presence of an intermediate structural state with fivefold coordination of Si. The distribution of coordination states can be estimated by modelling the amorphization as a decay process. Using the EXELFS data for amorphization, a new method is developed to derive the relative amounts of Si coordinations in high-pressure minerals with mixed coordination. For the radiation-induced amorphization process of stishovite the formation of a transitory structure with Si largely in fivefold coordination is deduced.

New determination of the fine structure constant and test of the quantum electrodynamics.

PubMed

Bouchendira, Rym; Cladé, Pierre; Guellati-Khélifa, Saïda; Nez, François; Biraben, François

2011-02-25

We report a new measurement of the ratio h/m(Rb) between the Planck constant and the mass of (87)Rb atom. A new value of the fine structure constant is deduced, α(-1)=137.035999037(91) with a relative uncertainty of 6.6×10(-10). Using this determination, we obtain a theoretical value of the electron anomaly a(e)=0.00115965218113(84), which is in agreement with the experimental measurement of Gabrielse [a(e)=0.00115965218073(28)]. The comparison of these values provides the most stringent test of the QED. Moreover, the precision is large enough to verify for the first time the muonic and hadronic contributions to this anomaly. © 2011 American Physical Society

Optical transitions in highly charged californium ions with high sensitivity to variation of the fine-structure constant.

PubMed

Berengut, J C; Dzuba, V A; Flambaum, V V; Ong, A

2012-08-17

We study electronic transitions in highly charged Cf ions that are within the frequency range of optical lasers and have very high sensitivity to potential variations in the fine-structure constant, α. The transitions are in the optical range despite the large ionization energies because they lie on the level crossing of the 5f and 6p valence orbitals in the thallium isoelectronic sequence. Cf(16+) is a particularly rich ion, having several narrow lines with properties that minimize certain systematic effects. Cf(16+) has very large nuclear charge and large ionization energy, resulting in the largest α sensitivity seen in atomic systems. The lines include positive and negative shifters.

Development of ultrasonic atomizer and its application to S. I. engines

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

Namiyama, K.; Nakamura, H.; Kokubo, K.

1989-01-01

This paper describes a fuel atomizer developed for S.I. engines based on ultrasonic vibrations. As the spray is characterized by fine droplet size and low penetration, it facilitates fuel movement and the formation of a homogeneous mixture. The spray behavior of this atomizer is easily influenced by ambient air motion. Therefore, the spray is most effectively delivered to the cylinders by precise injection timing. The ultrasonic atomizer disperses a fine spray over a wide flow rate range. A single cylinder engine fitted with the atomizer showed advantages in combustion speed and transient response performance.

The interaction of excited atoms and few-cycle laser pulses

PubMed Central

Calvert, J. E.; Xu, Han; Palmer, A. J.; Glover, R. D.; Laban, D. E.; Tong, X. M.; Kheifets, A. S.; Bartschat, K.; Litvinyuk, I. V.; Kielpinski, D.; Sang, R. T.

2016-01-01

This work describes the first observations of the ionisation of neon in a metastable atomic state utilising a strong-field, few-cycle light pulse. We compare the observations to theoretical predictions based on the Ammosov-Delone-Krainov (ADK) theory and a solution to the time-dependent Schrödinger equation (TDSE). The TDSE provides better agreement with the experimental data than the ADK theory. We optically pump the target atomic species and measure the ionisation rate as the a function of different steady-state populations in the fine structure of the target state which shows significant ionisation rate dependence on populations of spin-polarised states. The physical mechanism for this effect is unknown. PMID:27666403

The interaction of excited atoms and few-cycle laser pulses.

PubMed

Calvert, J E; Xu, Han; Palmer, A J; Glover, R D; Laban, D E; Tong, X M; Kheifets, A S; Bartschat, K; Litvinyuk, I V; Kielpinski, D; Sang, R T

2016-09-26

This work describes the first observations of the ionisation of neon in a metastable atomic state utilising a strong-field, few-cycle light pulse. We compare the observations to theoretical predictions based on the Ammosov-Delone-Krainov (ADK) theory and a solution to the time-dependent Schrödinger equation (TDSE). The TDSE provides better agreement with the experimental data than the ADK theory. We optically pump the target atomic species and measure the ionisation rate as the a function of different steady-state populations in the fine structure of the target state which shows significant ionisation rate dependence on populations of spin-polarised states. The physical mechanism for this effect is unknown.

Raman spectroscopy as a tool to investigate the structure and electronic properties of carbon-atom wires

PubMed Central

Milani, Alberto; Tommasini, Matteo; Russo, Valeria; Li Bassi, Andrea; Lucotti, Andrea; Cataldo, Franco

2015-01-01

Summary Graphene, nanotubes and other carbon nanostructures have shown potential as candidates for advanced technological applications due to the different coordination of carbon atoms and to the possibility of π-conjugation. In this context, atomic-scale wires comprised of sp-hybridized carbon atoms represent ideal 1D systems to potentially downscale devices to the atomic level. Carbon-atom wires (CAWs) can be arranged in two possible structures: a sequence of double bonds (cumulenes), resulting in a 1D metal, or an alternating sequence of single–triple bonds (polyynes), expected to show semiconducting properties. The electronic and optical properties of CAWs can be finely tuned by controlling the wire length (i.e., the number of carbon atoms) and the type of termination (e.g., atom, molecular group or nanostructure). Although linear, sp-hybridized carbon systems are still considered elusive and unstable materials, a number of nanostructures consisting of sp-carbon wires have been produced and characterized to date. In this short review, we present the main CAW synthesis techniques and stabilization strategies and we discuss the current status of the understanding of their structural, electronic and vibrational properties with particular attention to how these properties are related to one another. We focus on the use of vibrational spectroscopy to provide information on the structural and electronic properties of the system (e.g., determination of wire length). Moreover, by employing Raman spectroscopy and surface enhanced Raman scattering in combination with the support of first principles calculations, we show that a detailed understanding of the charge transfer between CAWs and metal nanoparticles may open the possibility to tune the electronic structure from alternating to equalized bonds. PMID:25821689

Interfacial structure of two-dimensional epitaxial Er silicide on Si(111)

NASA Astrophysics Data System (ADS)

Tuilier, M. H.; Wetzel, P.; Pirri, C.; Bolmont, D.; Gewinner, G.

1994-07-01

Auger-electron diffraction (AED) and surface-extended x-ray-absorption fine structure (SEXAFS) have been used to obtain a complete description of the atomic structure of a two-dimensional epitaxial Er silicide layer on Si(111). AED reveals that a monolayer of Er is located underneath a buckled Si double layer. The relevant Er-Si interlayer spacings are determined by means of single scattering cluster simulations and a R-factor analysis to be 1.92+/-0.05 Å to the first and 2.70+/-0.05 Å to the second Si top layer. Er near-neighbor bond lengths and coordination numbers are obtained independently from polarization-dependent SEXAFS. The SEXAFS data, when combined with the Si top-layer geometry inferred from AED, permit the determination of the atomic positions at the silicide/Si(111) interface. The Er is found to reside in relaxed T4 sites of Si(111) with a single Er-Si distance of 3.09+/-0.04 Å to the first- and second-layer Si atoms of the substrate.

Thermally induced anchoring of fullerene in copolymers with Si-bridging atom: Spectroscopic evidences

NASA Astrophysics Data System (ADS)

Marchiori, Cleber F. N.; Garcia-Basabe, Yunier; de A. Ribeiro, Fabio; Koehler, Marlus; Roman, Lucimara S.; Rocco, Maria Luiza M.

2017-01-01

We use X-ray photoelectron spectroscopy (XPS), Near-edge X-ray absorption fine structure (NEXAFS), resonant Auger spectroscopy (RAS), Attenuation Total Reflection Infrared (ATR-IR) and Atomic Force Microscopy (AFM) to study the blend between the copolymer poly[2,7-(9,9-bis(2-ethylhexyl)-dibenzosilole)-alt-4,7-bis(thiophen-2-yl)benzo-2,1,3-thiadiazole] (PSiF-DBT) and the fullerene derivative PC71BM submitted to different annealing temperatures. Those measurements indicate that there is an incidental anchoring of a fullerene derivative to the Si-bridging atoms of a copolymer induced by thermal annealing of the film. Insights about the physical properties of one possible PSiF-DBT/PC71BM anchored structure are obtained using Density Functional Theory calculations. Since the performance of organic photovoltaic based on polymer-fullerene blends depends on the chemical structure of the blend components, the anchoring effect might affect the photovoltaic properties of those devices.

Structural investigations in helium implanted cubic zirconia using grazing incidence XRD and EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Kuri, G.; Degueldre, C.; Bertsch, J.; Döbeli, M.

2010-06-01

The crystal structure and local atom arrangements surrounding Zr atoms were determined for a helium implanted cubic stabilized zirconia (CSZ) using X-ray diffraction (XRD) and extended X-ray absorption fine structure (EXAFS) spectroscopy, respectively, measured at glancing angles. The implanted specimen was prepared at a helium fluence of 2 × 10 16 cm -2 using He + beams at two energies (2.54 and 2.74 MeV) passing through a 8.0 μm Al absorber foil. XRD results identified the formation of a new rhombohedral phase in the helium embedded layer, attributed to internal stress as a result of expansion of the CSZ-lattice. Zr K-edge EXAFS data suggested loss of crystallinity in the implanted lattice and disorder of the Zr atoms environment. EXAFS Fourier transforms analysis showed that the average first-shell radius of the Zr sbnd O pair in the implanted sample was slightly larger than that of the CSZ standard. Common general disorder features were explained by rhombohedral type short-range ordered clusters. The average structural parameters estimated from the EXAFS data of unimplanted and implanted CSZ are compared and discussed. Potential of EXAFS as a local probe of atomic-scale structural modifications induced by helium implantation in CSZ is demonstrated.

Measurement of the fine-structure constant as a test of the Standard Model

NASA Astrophysics Data System (ADS)

Parker, Richard H.; Yu, Chenghui; Zhong, Weicheng; Estey, Brian; Müller, Holger

2018-04-01

Measurements of the fine-structure constant α require methods from across subfields and are thus powerful tests of the consistency of theory and experiment in physics. Using the recoil frequency of cesium-133 atoms in a matter-wave interferometer, we recorded the most accurate measurement of the fine-structure constant to date: α = 1/137.035999046(27) at 2.0 × 10‑10 accuracy. Using multiphoton interactions (Bragg diffraction and Bloch oscillations), we demonstrate the largest phase (12 million radians) of any Ramsey-Bordé interferometer and control systematic effects at a level of 0.12 part per billion. Comparison with Penning trap measurements of the electron gyromagnetic anomaly ge ‑ 2 via the Standard Model of particle physics is now limited by the uncertainty in ge ‑ 2; a 2.5σ tension rejects dark photons as the reason for the unexplained part of the muon’s magnetic moment at a 99% confidence level. Implications for dark-sector candidates and electron substructure may be a sign of physics beyond the Standard Model that warrants further investigation.

A New Generation of Los Alamos Opacity Tables

DOE PAGES

Colgan, James Patrick; Kilcrease, David Parker; Magee, Jr., Norman H.; ...

2016-01-26

We present a new, publicly available, set of Los Alamos OPLIB opacity tables for the elements hydrogen through zinc. Our tables are computed using the Los Alamos ATOMIC opacity and plasma modeling code, and make use of atomic structure calculations that use fine-structure detail for all the elements considered. Our equation-of-state (EOS) model, known as ChemEOS, is based on the minimization of free energy in a chemical picture and appears to be a reasonable and robust approach to determining atomic state populations over a wide range of temperatures and densities. In this paper we discuss in detail the calculations thatmore » we have performed for the 30 elements considered, and present some comparisons of our monochromatic opacities with measurements and other opacity codes. We also use our new opacity tables in solar modeling calculations and compare and contrast such modeling with previous work.« less

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

NASA Astrophysics Data System (ADS)

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-11-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

PubMed Central

Cheng, Niancai; Stambula, Samantha; Wang, Da; Banis, Mohammad Norouzi; Liu, Jian; Riese, Adam; Xiao, Biwei; Li, Ruying; Sham, Tsun-Kong; Liu, Li-Min; Botton, Gianluigi A.; Sun, Xueliang

2016-01-01

Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5d orbitals on the nitrogen-doped graphene are responsible for the excellent performance. PMID:27901129

Determination of local order in the amorphous precursor to Ba-hexaferrite thin-film recording media

NASA Astrophysics Data System (ADS)

Snyder, J. E.; Harris, V. G.; Das, B. N.; Koon, N. C.; Sui, X.; Kryder, M. H.

1996-04-01

Ba-hexaferrite thin films for recording media applications are often fabricated by a two-step process: sputter deposition of an amorphous precursor, followed by annealing to crystallize the BaFe12O19 phase. The magnetic anisotropy of the crystalline films can be either in-plane or perpendicular, depending on the sputtering process used in the first step. However, conventional structural characterization techniques have not been able to distinguish between different as-sputtered films. Using polarization-dependent extended x-ray absorption fine structure (PD-EXAFS), we have observed anisotropic local structure around both Ba and Fe atoms in the amorphous precursor films. Comparison of the results suggests that the amorphous films consist of networks of Fe atoms surrounded by their O nearest neighbors, with Ba atoms fitting into in-between spaces as network modifiers (there might also be some minor Fe network modifying contribution). The local structural anisotropy of the amorphous films appears to determine the orientation of the fast-growing basal plane directions during annealing, and thus the directions of the c axes and the magnetic anisotropy.

Effect of oxygen impurities on properties of the ternary superconductor SnMo/sub 6/S/sub 8/: Extended x-ray-absorption fine-structure determination of bond distances and local-density cluster calculations

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

Guenzburger, D.; Ellis, D.E.; Montano, P.A.

1985-10-01

Electronic structure calculations were performed for clusters representing the Chevrel-phase SnMo/sub 6/S/sub 8/, with and without oxygen doping. In order to obtain the local structure around the Sn atom, extended x-ray-absorption fine-structure (EXAFS) measurements were made with synchro- tron radiation. The interatomic distances obtained experimentally were used in the calculations. The effect of oxygen doping on the Moessbauer isomer shift and quadrupole splitting values of /sup 119/Sn was investigated theoretically and compared with reported experimental values. The effect of oxygen substitution on the density of states at the Fermi energy of the (Mo/sub 6/S/sub 8/)/sup 2 -/ cluster was alsomore » studied. The results suggest that oxygen doping does not alter significantly the electronic structure of SnMo/sub 6/S/sub 8/.« less

Wet-chemical synthesis of nanoscale iron boride, XAFS analysis and crystallisation to α-FeB.

PubMed

Rades, Steffi; Kornowski, Andreas; Weller, Horst; Albert, Barbara

2011-06-20

The reaction of lithium tetrahydridoborate and iron bromide in high boiling ether as reaction medium produces an ultrafine, pyrophoric and magnetic precipitate. X-ray and electron diffraction proved the product to be amorphous. According to X-ray absorption fine structure spectroscopy (XAFS) the precipitate has FeB structure up to nearly two coordination spheres around an iron absorber atom. Transmission electron microscopy (TEM) confirms the ultrafine powder to be nanoscale. Subsequent annealing at 450 °C causes the atoms to arrange in a more distinct FeB structure, and further thermal treatment to 1050 °C extends the local structure to the α-modification of FeB. Between 1050 °C and 1500 °C α-FeB is transformed into β-FeB. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

X-ray absorption spectroscopic studies of the active sites of nickel- and copper-containing metalloproteins

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

Tan, Grace O.

1993-06-01

X-ray absorption spectroscopy (XAS) is a useful tool for obtaining structural and chemical information about the active sites of metalloproteins and metalloenzymes. Information may be obtained from both the edge region and the extended X-ray absorption fine structure (EXAFS) or post-edge region of the K-edge X-ray absorption spectrum of a metal center in a compound. The edge contains information about the valence electronic structure of the atom that absorbs the X-rays. It is possible in some systems to infer the redox state of the metal atom in question, as well as the geometry and nature of ligands connected to it,more » from the features in the edge in a straightforward manner. The EXAFS modulations, being produced by the backscattering of the ejected photoelectron from the atoms surrounding the metal atom, provide, when analyzed, information about the number and type of neighbouring atoms, and the distances at which they occur. In this thesis, analysis of both the edge and EXAFS regions has been used to gain information about the active sites of various metalloproteins. The metalloproteins studied were plastocyanin (Pc), laccase and nickel carbon monoxide dehydrogenase (Ni CODH). Studies of Cu(I)-imidazole compounds, related to the protein hemocyanin, are also reported here.« less

Single-Atom Catalysts of Precious Metals for Electrochemical Reactions.

PubMed

Kim, Jiwhan; Kim, Hee-Eun; Lee, Hyunjoo

2018-01-10

Single-atom catalysts (SACs), in which metal atoms are dispersed on the support without forming nanoparticles, have been used for various heterogeneous reactions and most recently for electrochemical reactions. In this Minireview, recent examples of single-atom electrocatalysts used for the oxygen reduction reaction (ORR), hydrogen oxidation reaction (HOR), hydrogen evolution reaction (HER), formic acid oxidation reaction (FAOR), and methanol oxidation reaction (MOR) are introduced. Many density functional theory (DFT) simulations have predicted that SACs may be effective for CO 2 reduction to methane or methanol production while suppressing H 2 evolution, and those cases are introduced here as well. Single atoms, mainly Pt single atoms, have been deposited on TiN or TiC nanoparticles, defective graphene nanosheets, N-doped covalent triazine frameworks, graphitic carbon nitride, S-doped zeolite-templated carbon, and Sb-doped SnO 2 surfaces. Scanning transmission electron microscopy, extended X-ray absorption fine structure measurement, and in situ infrared spectroscopy have been used to detect the single-atom structure and confirm the absence of nanoparticles. SACs have shown high mass activity, minimizing the use of precious metal, and unique selectivity distinct from nanoparticle catalysts owing to the absence of ensemble sites. Additional features that SACs should possess for effective electrochemical applications were also suggested. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Breakdown of ionic character of molecular alkali bromides in inner-valence photoionization

NASA Astrophysics Data System (ADS)

Karpenko, A.; Iablonskyi, D.; Urpelainen, S.; Kettunen, J. A.; Cao, W.; Huttula, M.; Aksela, H.

2014-05-01

The inner-valence region of alkali bromide XBr (X=Li, Na, K, Rb) vapours has been studied experimentally by means of synchrotron radiation excited photoelectron spectroscopy. Experimental spectra were analyzed by comparing them with available theoretical results and previous experiments. Ionic character of alkali bromides is seen to change in the inner-valence region with increasing atomic number of the alkali atom. A mechanism involving mixing between Br 4s and Rb 4p orbitals has been suggested to account for the fine structure observed in inner-valence ionization region of RbBr.

Quantum Yield Heterogeneity among Single Nonblinking Quantum Dots Revealed by Atomic Structure-Quantum Optics Correlation

DOE PAGES

Orfield, Noah J.; McBride, James R.; Wang, Feng; ...

2016-02-05

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

Atomically thick bismuth selenide freestanding single layers achieving enhanced thermoelectric energy harvesting.

PubMed

Sun, Yongfu; Cheng, Hao; Gao, Shan; Liu, Qinghua; Sun, Zhihu; Xiao, Chong; Wu, Changzheng; Wei, Shiqiang; Xie, Yi

2012-12-19

Thermoelectric materials can realize significant energy savings by generating electricity from untapped waste heat. However, the coupling of the thermoelectric parameters unfortunately limits their efficiency and practical applications. Here, a single-layer-based (SLB) composite fabricated from atomically thick single layers was proposed to optimize the thermoelectric parameters fully. Freestanding five-atom-thick Bi(2)Se(3) single layers were first synthesized via a scalable interaction/exfoliation strategy. As revealed by X-ray absorption fine structure spectroscopy and first-principles calculations, surface distortion gives them excellent structural stability and a much increased density of states, resulting in a 2-fold higher electrical conductivity relative to the bulk material. Also, the surface disorder and numerous interfaces in the Bi(2)Se(3) SLB composite allow for effective phonon scattering and decreased thermal conductivity, while the 2D electron gas and energy filtering effect increase the Seebeck coefficient, resulting in an 8-fold higher figure of merit (ZT) relative to the bulk material. This work develops a facile strategy for synthesizing atomically thick single layers and demonstrates their superior ability to optimize the thermoelectric energy harvesting.

Single-crystal growth, structure refinement and the properties of Bis(glycine) Strontium Chloride

NASA Astrophysics Data System (ADS)

Balaji, S. R.; Balu, T.; Rajasekaran, T. R.

2018-02-01

Single crystals of Bis (glycine) Strontium Chloride (BGSC) were grown by means of slow evaporation process by using analar grade Glycine and Strontium Chloride Hexahydrate as a parent compound from its aqueous solution at room temperature. The final chemical composition, [{{Sr}}{({{{C}}}2{{{H}}}5{{{NO}}}2)}2{{{Cl}}}2].{{{H}}}4{{{O}}}3+{{{H}}}8{{{O}}}3, formed were metallic light colorless block, about the size of 28 mm × 9 mm × 8 mm. A single-crystal x-ray diffraction study revealed an ordered superstructure with orthorhombic symmetry that could be assigned to the space group Pbcn. The structure in BGSC, revealed in the electron density distribution was analyzed by the direct methods (SHELXS-2014) and refined by least squares full matrix method (SHELXL-2014). The crystal structure, including anisotropic atomic displacement parameters for each atom and isotropic atomic displacement parameters for hydrogen atom, was refined to R1 = 0.0395, wR2 = 0.0776 using 1097 independent reflections. The FTIR spectrum of BGSC confirms the protonation of amino groups and the different molecular groups present in BGSC vibrate in different modes. Reverse Indentation Size Effect (RISE) was revealed in BGSC in the micro-hardness analysis using Vicker’s micro-hardness analysis. DTA and DSC results ruled out the possibility of structural change independent of mass change. The AFM studies shows fine nano size fiber like structure of the grown crystals.

Scrutinizing Al-like 10+51V, 11+53Cr, 12+55Mn, 13+57Fe, 14+59Co, 15+61Ni, and 16+63Cu 1ions for atomic clocks with uncertainties below the 10-19 level

NASA Astrophysics Data System (ADS)

Yu, Yan-mei; Sahoo, B. K.

2016-12-01

We investigate the transition between the fine structure levels of the ground state, 3 p 2P1 /2→3 p 2P3 /2 , of the highly charged Al-like 10+51V, 11+53Cr, 12+55Mn, 13+57Fe, 14+59Co, 15+61Ni, and 16+63Cu ions for frequency standards. To comprehend them as prospective atomic clocks, we determine their transition wavelengths, quality factors, and various plausible systematics during the measurements. Since most of these ions have nuclear spin I =3 /2 , uncertainties due to dominant quadrupole shifts can be evaded in the F =0 hyperfine level of the 3 p 2P3 /2 state. Other dominant systematics such as quadratic Stark and black-body radiation shifts have been evaluated precisely demonstrating the feasibility of achieving high accuracy, below 10-19 fractional uncertainty, atomic clocks using the above transitions. Moreover, relativistic sensitivity coefficients are determined to find out the aptness of these proposed clocks to investigate possible temporal variation of the fine structure constant. To carry out these analysis, a relativistic coupled-cluster method considering Dirac-Coulomb-Breit Hamiltonian along with lower-order quantum electrodynamics interactions is employed and many spectroscopic properties are evaluated. These properties are also of immense interest for astrophysical studies.

Substrate temperature effect on the structural anisotropy in amorphous Tb-Fe films

NASA Astrophysics Data System (ADS)

Harris, V. G.; Hellman, F.; Elam, W. T.; Koon, N. C.

1993-05-01

Using extended x-ray absorption fine structures (EXAFS) measurements we have investigated the atomic environment around the Fe atom in a series of amorphous Tb0.26Fe0.74 films having different magnetic anisotropy energies owing to different deposition temperatures. The polarization properties of synchrotron radiation allowed the separate study of structure parallel and perpendicular to the sample plane. An anisotropy between these two structures was observed. Modeling results indicate this anisotropy is due to anisotropic pair correlations where the Fe-Fe pairs are statistically preferred in-plane and the Fe-Tb pairs out-of-plane. The amplitude of this anisotropy scales with both the substrate temperature and the magnetic anisotropy energy. A ≊1% in-plane compression of the Fe-Fe distance was measured between the in-plane and out-of-plane structure of the sample grown at 77 K. This sample had no detectable local chemical anisotropy suggesting that intrinsic stress plays an important role in determining its magnetic anisotropy.

Atomic charges of sulfur in ionic liquids: experiments and calculations.

PubMed

Fogarty, Richard M; Rowe, Rebecca; Matthews, Richard P; Clough, Matthew T; Ashworth, Claire R; Brandt, Agnieszka; Corbett, Paul J; Palgrave, Robert G; Smith, Emily F; Bourne, Richard A; Chamberlain, Thomas W; Thompson, Paul B J; Hunt, Patricia A; Lovelock, Kevin R J

2017-12-14

Experimental near edge X-ray absorption fine structure (NEXAFS) spectra, X-ray photoelectron (XP) spectra and Auger electron spectra are reported for sulfur in ionic liquids (ILs) with a range of chemical structures. These values provide experimental measures of the atomic charge in each IL and enable the evaluation of the suitability of NEXAFS spectroscopy and XPS for probing the relative atomic charge of sulfur. In addition, we use Auger electron spectroscopy to show that when XPS binding energies differ by less than 0.5 eV, conclusions on atomic charge should be treated with caution. Our experimental data provides a benchmark for calculations of the atomic charge of sulfur obtained using different methods. Atomic charges were computed for lone ions and ion pairs, both in the gas phase (GP) and in a solvation model (SMD), with a wide range of ion pair conformers considered. Three methods were used to compute the atomic charges: charges from the electrostatic potential using a grid based method (ChelpG), natural bond orbital (NBO) population analysis and Bader's atoms in molecules (AIM) approach. By comparing the experimental and calculated measures of the atomic charge of sulfur, we provide an order for the sulfur atoms, ranging from the most negative to the most positive atomic charge. Furthermore, we show that both ChelpG and NBO are reasonable methods for calculating the atomic charge of sulfur in ILs, based on the agreement with both the XPS and NEXAFS spectroscopy results. However, the atomic charges of sulfur derived from ChelpG are found to display significant, non-physical conformational dependence. Only small differences in individual atomic charge of sulfur were observed between lone ion (GP) and ion pair IL(SMD) model systems, indicating that ion-ion interactions do not strongly influence individual atomic charges.

Sodium-induced ordering of the benzoate species on Si(100)-2×1: a combined HREELS, XPS and NEXAFS study

NASA Astrophysics Data System (ADS)

Bitzer, T.; Richardson, N. V.; Reiss, S.; Wühn, M.; Wöll, Ch.

2000-06-01

The structure of benzoate on Na/Si(100)-2×1 has been studied by high resolution electron energy loss spectroscopy, X-ray photoelectron spectroscopy and near edge X-ray adsorption fine structure spectroscopy. At room temperature, benzoic acid (C 6H 5COOH) chemisorbs on Na/Si(100)-2×1 through a cleavage of the OH bond in the carboxylic group. The benzoate molecules formed are bonded exclusively to the sodium atoms in a bidentate coordination, in which the oxygen atoms are equivalent. At room temperature, benzoate saturation on Na/Si(100)-2×1 is reached at a coverage of one benzoate species for each Na atom or silicon dimer. At this coverage, the molecules are tilted in polar direction by 62°±4° to the surface plane and azimuthally rotated by 41°±4° with respect to the [01 1] surface azimuth. We propose an adsorbate structure, in which the benzoate molecules are oriented parallel to each other in densely packed rows.

RENU 2 UV Measurements of Atomic Oxygen in the Cusp Region

NASA Astrophysics Data System (ADS)

Fritz, B.; Lessard, M.; Paxton, L. J.; Cook, T.; Lynch, K. A.; Clemmons, J. H.; Hecht, J. H.; Hysell, D. L.; Crowley, G.

2016-12-01

The RENU 2 NASA sounding rocket mission launched from the Andoya Space Center on 13 December, 2015 into the dayside cusp region. A UV Photometer (UV PMT) provided by the University of New Hampshire was oriented to look up along the local magnetic field line as the payload passed through a poleward moving auroral form (PMAF). The bandpass filter on the UV PMT isolated emissions of atomic oxygen at both 130.4 nm and 135.6 nm. The instrument measured a clear enhancement in the topside ionosphere as the payload descended through a region of soft electron precipitation. The RENU 2 UV PMT was flown uncalibrated but measured a clear signal with both a major overall structure as well as several smaller peaks of fine structure. An identical spare has been built and calibrated using a Paresce UV light source at UMass-Lowell to compare and correlate with the flight data. An approximation of the flight data luminosity from the spare instrument and other flight data from RENU 2 is used in a radiative transport model to infer structure of upwelling neutral atomic oxygen above the PMAF.

Fine structure of Fe-Co-Ga and Fe-Cr-Ga alloys with low Ga content

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

Kleinerman, Nadezhda M., E-mail: kleinerman@imp.uran.ru; Serikov, Vadim V., E-mail: kleinerman@imp.uran.ru; Vershinin, Aleksandr V., E-mail: kleinerman@imp.uran.ru

2014-10-27

Investigation of Ga influence on the structure of Fe-Cr and Fe-Co alloys was performed with the use of {sup 57}Fe Mössbauer spectroscopy and X-ray diffraction methods. In the alloys of the Fe-Cr system, doping with Ga handicaps the decomposition of solid solutions, observed in the binary alloys, and increases its stability. In the alloys with Co, Ga also favors the uniformity of solid solutions. The analysis of Mössbauer experiments gives some grounds to conclude that if, owing to liquation, clusterization, or initial stages of phase separation, there exist regions enriched in iron, some amount of Ga atoms prefer to entermore » the nearest surroundings of iron atoms, thus forming binary Fe-Ga regions (or phases)« less

Rate Constants for Fine-Structure Excitations in O - H Collisions with Error Bars Obtained by Machine Learning

NASA Astrophysics Data System (ADS)

Vieira, Daniel; Krems, Roman

2017-04-01

Fine-structure transitions in collisions of O(3Pj) with atomic hydrogen are an important cooling mechanism in the interstellar medium; knowledge of the rate coefficients for these transitions has a wide range of astrophysical applications. The accuracy of the theoretical calculation is limited by inaccuracy in the ab initio interaction potentials used in the coupled-channel quantum scattering calculations from which the rate coefficients can be obtained. In this work we use the latest ab initio results for the O(3Pj) + H interaction potentials to improve on previous calculations of the rate coefficients. We further present a machine-learning technique based on Gaussian Process regression to determine the sensitivity of the rate coefficients to variations of the underlying adiabatic interaction potentials. To account for the inaccuracy inherent in the ab initio calculations we compute error bars for the rate coefficients corresponding to 20% variation in each of the interaction potentials. We obtain these error bars by fitting a Gaussian Process model to a data set of potential curves and rate constants. We use the fitted model to do sensitivity analysis, determining the relative importance of individual adiabatic potential curves to a given fine-structure transition. NSERC.

Measurement of the fine-structure constant as a test of the Standard Model.

PubMed

Parker, Richard H; Yu, Chenghui; Zhong, Weicheng; Estey, Brian; Müller, Holger

2018-04-13

Measurements of the fine-structure constant α require methods from across subfields and are thus powerful tests of the consistency of theory and experiment in physics. Using the recoil frequency of cesium-133 atoms in a matter-wave interferometer, we recorded the most accurate measurement of the fine-structure constant to date: α = 1/137.035999046(27) at 2.0 × 10 -10 accuracy. Using multiphoton interactions (Bragg diffraction and Bloch oscillations), we demonstrate the largest phase (12 million radians) of any Ramsey-Bordé interferometer and control systematic effects at a level of 0.12 part per billion. Comparison with Penning trap measurements of the electron gyromagnetic anomaly g e - 2 via the Standard Model of particle physics is now limited by the uncertainty in g e - 2; a 2.5σ tension rejects dark photons as the reason for the unexplained part of the muon's magnetic moment at a 99% confidence level. Implications for dark-sector candidates and electron substructure may be a sign of physics beyond the Standard Model that warrants further investigation. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

Production of fine calcium powders by centrifugal atomization with rotating quench bath

DOE PAGES

Tian, Liang; Ames Lab. and Iowa State Univ., Ames, IA; Anderson, Iver; ...

2016-02-08

Recently, a novel Al/Ca composite was produced by severe plastic deformation of Al powders and Ca granules for possible use as a high-voltage power transmission conductor. Since the strength of such composites is inversely proportional to the Ca filament size, fine Ca powders (less than ~250 μm) are needed to achieve the desired high strength for the powder metallurgy production of an Al-matrix composite reinforced by nano-scale Ca filaments. However, fine Ca powders are not commercially available. Therefore, we have developed a method to produce fine Ca powders via centrifugal atomization to supply Ca powder for prototype development of Al/Camore » composite conductor. A secondary goal of the project was to demonstrate that Ca powder can be safely prepared, stored, and handled and could potentially be scaled for commercial production. Our results showed that centrifugal atomization can yield as much as 83 vol. % Ca powder particles smaller than 250 μm. The mean particle size sometimes matches, sometimes deviates substantially from the predictions of the Champagne & Anger equation likely due to unexpected secondary atomization. The particle size distribution is typical for a ligament-disintegration atomization mode. Scanning electron micrographs showed that the morphology of these Ca powders varied with powder size. Spark testing and auto-ignition tests indicated that the atomized powders were difficult to ignite, providing confidence that this material can be handled safely in air.« less

The fine art of integral membrane protein crystallisation.

PubMed

Birch, James; Axford, Danny; Foadi, James; Meyer, Arne; Eckhardt, Annette; Thielmann, Yvonne; Moraes, Isabel

2018-05-18

Integral membrane proteins are among the most fascinating and important biomolecules as they play a vital role in many biological functions. Knowledge of their atomic structures is fundamental to the understanding of their biochemical function and key in many drug discovery programs. However, over the years, structure determination of integral membrane proteins has proven to be far from trivial, hence they are underrepresented in the protein data bank. Low expression levels, insolubility and instability are just a few of the many hurdles one faces when studying these proteins. X-ray crystallography has been the most used method to determine atomic structures of membrane proteins. However, the production of high quality membrane protein crystals is always very challenging, often seen more as art than a rational experiment. Here we review valuable approaches, methods and techniques to successful membrane protein crystallisation. Copyright © 2018 Diamond Light Source LTD. Published by Elsevier Inc. All rights reserved.

Microstructural characterization of a Zr-Ti-Ni-Mn-V-Cr based AB 2-type battery alloy

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

Shi, Zhan

1999-01-01

Transmission Electron Microscopy (TEM), combined with X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) was employed to investigate a proprietary and multicomponent AB 2 type Nickel-Metal Hydride (Ni-MH) battery alloy. This material was prepared by High Pressure Gas Atomization (HPGA) and examined in both the as-atomized and heat treated condition. TEM examination showed a heavily faulted dendritic growth structure in as-atomized powder. Selected Area Diffraction (SAD) showed that this region consisted of both a cubic C15 structure with lattice constant a=7.03 and a hexagonal C14 structure with lattice parameter a=4.97 Å, c=8.11 Å. The Orientation Relationship (OR) between the C14 and C15 structures was determined to be (111)[1more » $$\\bar{1}$$0] C15//(0001)[11$$\\bar{2}$$0] C14. An interdendritic phase possessing the C14 structure was also seen. There was also a very fine grain region consisting of the C14 structure. Upon heat treatment, the faulted structure became more defined and appeared as intercalation layers within the grains. Spherical particles rich in Zr and Ni appeared scattered at the grain boundaries instead of the C14 interdendritic phase. The polycrystalline region also changed to a mixture of C14 and C15 structures. These results as well as phase stability of the C15 and C14 structures based on a consideration of atomic size factor and the average electron concentration are discussed.« less

Kicking atoms with finite duration pulses

NASA Astrophysics Data System (ADS)

Fekete, Julia; Chai, Shijie; Daszuta, Boris; Andersen, Mikkel F.

2016-05-01

The atom optics delta-kicked particle is a paradigmatic system for experimental studies of quantum chaos and classical-quantum correspondence. It consists of a cloud of laser cooled atoms exposed to a periodically pulsed standing wave of far off-resonant laser light. A purely quantum phenomena in such systems are quantum resonances which transfers the atoms into a coherent superposition of largely separated momentum states. Using such large momentum transfer ``beamsplitters'' in atom interferometers may have applications in high precision metrology. The growth in momentum separation cannot be maintained indefinitely due to finite laser power. The largest momentum transfer is achieved by violating the usual delta-kick assumption. Therefore we explore the behavior of the atom optics kicked particle with finite pulse duration. We have developed a semi-classical model which shows good agreement with the full quantum description as well as our experiments. Furthermore we have found a simple scaling law that helps to identify optimal parameters for an atom interferometer. We verify this by measurements of the ``Talbot time'' (a measurement of h/m) which together with other well-known constants constitute a measurement of the fine structure constant.

Ultrafast time scale X-rotation of cold atom storage qubit using Rubidium clock states

NASA Astrophysics Data System (ADS)

Song, Yunheung; Lee, Han-Gyeol; Kim, Hyosub; Jo, Hanlae; Ahn, Jaewook

2017-04-01

Ultrafast-time-scale optical interaction is a local operation on the electronic subspace of an atom, thus leaving its nuclear state intact. However, because atomic clock states are maximally entangled states of the electronic and nuclear degrees of freedom, their entire Hilbert space should be accessible only with local operations and classical communications (LOCC). Therefore, it may be possible to achieve hyperfine qubit gates only with electronic transitions. Here we show an experimental implementation of ultrafast X-rotation of atomic hyperfine qubits, in which an optical Rabi oscillation induces a geometric phase between the constituent fine-structure states, thus bringing about the X-rotation between the two ground hyperfine levels. In experiments, cold atoms in a magneto-optical trap were controlled with a femtosecond laser pulse from a Ti:sapphire laser amplifier. Absorption imaging of the as-controlled atoms initially in the ground hyperfine state manifested polarization dependence, strongly agreeing with the theory. The result indicates that single laser pulse implementations of THz clock speed qubit controls are feasible for atomic storage qubits. Samsung Science and Technology Foundation [SSTF-BA1301-12].

Fine structure transitions in Fe XIV

NASA Astrophysics Data System (ADS)

Nahar, Sultana N.

2013-07-01

Results are reported for Fe XIV energy levels and transitions obtained from the ab initio relativistic Breit-Pauli R-matrix (BPRM) method. BPRM method developed under the Iron Project is capable of calculating very large number of fine structure energy levels and corresponding transitions. However, unlike in the atomic structure calculations, where levels are identified spectroscopically based on the leading percentage contributions of configurations, BPRM is incapable of such identification of the levels and hence the transitions. The main reason for it is that the percentage contributions can not be determined exactly from the large number of channels in the R-matrix space. The present report describes an identification method that uses considerations of quantum defects of channels, contributions of channel from outer regions, Hund's rule, and angular momenta algebra for addition and completeness of fine structure components. The present calculations are carried out using a close coupling wave function expansion that included 26 core excitations from configurations 2s22p63s2, 2s22p63s3p,2s22p63p2,2s22p63s3d, and 2s22p63p3d. A total of 1002 fine structure levels with n ⩽ 10, l⩽9, and 0.5 ⩽J⩽ 9.5 with even and odd parities and the corresponding 130,520 electric dipole allowed (E1) fine structure transitions, a most complete set for astrophysical modelings of spectral analysis and opacities, is presented. Large number of new energy levels are found and identified. The energies agree very well, mostly in less than 1% with the highest being 1.9%, with the 68 observed fine structure levels. While the high lying levels may have some uncertainty, an overall accuracy of energy levels should be within 10%. BPRM transitions have been benchmarked with the existing most accurate calculated transition probabilities with very good agreement for most cases. Based on the accuracy of the method and comparisons, most of the transitions can be rated with A (⩽10%) to C (⩽30%).

One Electron Atom in Special Relativity with de Sitter Space-Time Symmetry

NASA Astrophysics Data System (ADS)

Yan, Mu-Lin

2012-06-01

The de Sitter invariant Special Relativity (dS-SR) is SR with constant curvature, and a natural extension of usual Einstein SR (E-SR). In this paper, we solve the dS-SR Dirac equation of Hydrogen by means of the adiabatic approach and the quasi-stationary perturbation calculations of QM. Hydrogen atom is located in the light cone of the Universe. FRW metric and ΛCDM cosmological model are used to discuss this issue. To the atom, effects of de Sitter space-time geometry described by Beltrami metric are taken into account. The dS-SR Dirac equation turns out to be a time dependent quantum Hamiltonian system. We reveal that: (i) The fundamental physics constants me, ℏ, e variate adiabatically along with cosmologic time in dS-SR QM framework. But the fine-structure constant α ≡ e2/(ℏc) keeps to be invariant; (ii) (2s1/2-2p1/2)-splitting due to dS-SR QM effects: By means of perturbation theory, that splitting ΔE(z) are calculated analytically, which belongs to Script O(1/R2)-physics of dS-SR QM. Numerically, we find that when |R| ≃ {103 Gly, 104 Gly, 105 Gly}, and z ≃ {1, or 2}, the ΔE(z) ≫ 1 (Lamb shift). This indicates that for these cases the hyperfine structure effects due to QED could be ignored, and the dS-SR fine structure effects are dominant. This effect could be used to determine the universal constant R in dS-SR, and be thought as a new physics beyond E-SR.

Identifying the Atomic-Level Effects of Metal Composition on the Structure and Catalytic Activity of Peptide-Templated Materials

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

Merrill, Nicholas A.; McKee, Erik M.; Merino, Kyle C.

2015-10-12

Bioinspired approaches for the formation of metallic nanomaterials have been extensively employed for a diverse range of applications including diagnostics and catalysis. These materials can often be used under sustainable conditions; however, it is challenging to control the material size, morphology, and composition simultaneously. Here we have employed the R5 peptide, which forms a 3D scaffold to direct the size and linear shape of bimetallic PdAu nanomaterials for catalysis. The materials were prepared at varying Pd:Au ratios to probe optimal compositions to achieve maximal catalytic efficiency. These materials were extensively characterized at the atomic level using transmission electron microscopy, extendedmore » X-ray absorption fine structure spectroscopy, and atomic pair distribution function analysis derived from high-energy X-ray diffraction patterns to provide highly resolved structural information. The results confirmed PdAu alloy formation, but also demonstrated that significant surface structural disorder was present. The catalytic activity of the materials was studied for olefin hydrogenation, which demonstrated enhanced reactivity from the bimetallic structures.These results present a pathway to the bioinspired production of multimetallic materials with enhanced properties, which can be assessed via a suite of characterization methods to fully ascertain structure/function relationships.« less

Semiclassical quantization of Bohr orbits in the helium atom

NASA Astrophysics Data System (ADS)

Belov, V. V.; Maksimov, V. A.

2007-05-01

We use the complex WKB-Maslov method to construct the semiclassical spectral series corresponding to the resonance Bohr orbits in the helium atom. The semiclassical energy levels represented as the Rydberg tetra series correspond to the doubly symmetrically excited states of helium-like atoms. This level series contains the Rydberg triple series reported by Richter and Wintgen in 1991, which corresponds to the Z2+e-e- configuration of electrons observed by Eichmann and his collaborators in experiments on the laser excitation of the barium atom in 1992. The lower-level extrapolation of the formula obtained for the semiclassical spectrum gives the value of the ground state energy, which differs by 6% from the experimental value obtained by Bergeson and his collaborators in 1998. We also calculate the fine structure of the semiclassical spectrum due to the spin-orbit and spin-spin interactions of electrons.

Experimental validation of calculated atomic charges in ionic liquids

NASA Astrophysics Data System (ADS)

Fogarty, Richard M.; Matthews, Richard P.; Ashworth, Claire R.; Brandt-Talbot, Agnieszka; Palgrave, Robert G.; Bourne, Richard A.; Vander Hoogerstraete, Tom; Hunt, Patricia A.; Lovelock, Kevin R. J.

2018-05-01

A combination of X-ray photoelectron spectroscopy and near edge X-ray absorption fine structure spectroscopy has been used to provide an experimental measure of nitrogen atomic charges in nine ionic liquids (ILs). These experimental results are used to validate charges calculated with three computational methods: charges from electrostatic potentials using a grid-based method (ChelpG), natural bond orbital population analysis, and the atoms in molecules approach. By combining these results with those from a previous study on sulfur, we find that ChelpG charges provide the best description of the charge distribution in ILs. However, we find that ChelpG charges can lead to significant conformational dependence and therefore advise that small differences in ChelpG charges (<0.3 e) should be interpreted with care. We use these validated charges to provide physical insight into nitrogen atomic charges for the ILs probed.

Preparation and evaluation of highly drug-loaded fine globular granules using a multi-functional rotor processor.

PubMed

Iwao, Yasunori; Kimura, Shin-Ichiro; Ishida, Masayuki; Mise, Ryohei; Yamada, Masaki; Namiki, Noriyuki; Noguchi, Shuji; Itai, Shigeru

2015-01-01

The manufacture of highly drug-loaded fine globular granules eventually applied for orally disintegrating tablets has been investigated using a unique multi-functional rotor processor with acetaminophen, which was used as a model drug substance. Experimental design and statistical analysis were used to evaluate potential relationships between three key operating parameters (i.e., the binder flow rate, atomization pressure and rotating speed) and a series of associated micromeritics (i.e., granule mean size, proportion of fine particles (106-212 µm), flowability, roundness and water content). The results of multiple linear regression analysis revealed several trends, including (1) the binder flow rate and atomization pressure had significant positive and negative effects on the granule mean size value, Carr's flowability index, granular roundness and water content, respectively; (2) the proportion of fine particles was positively affected by the product of interaction between the binder flow rate and atomization pressure; and (3) the granular roundness was negatively and positively affected by the product of interactions between the binder flow rate and the atomization pressure, and the binder flow rate and rotating speed, respectively. The results of this study led to the identification of optimal operating conditions for the preparation of granules, and could therefore be used to provide important information for the development of processes for the manufacture of highly drug-loaded fine globular granules.

Synthesis-atomic structure-properties relationships in metallic nanoparticles by total scattering experiments and 3D computer simulations: case of Pt-Ru nanoalloy catalysts

NASA Astrophysics Data System (ADS)

Prasai, Binay; Ren, Yang; Shan, Shiyao; Zhao, Yinguang; Cronk, Hannah; Luo, Jin; Zhong, Chuan-Jian; Petkov, Valeri

2015-04-01

An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the observed enhancement of the catalytic activity of PtxRu100-x alloy NPs at x ~ 50. Implications of so-established relationships between the atomic structure and catalytic activity of Pt-Ru alloy NPs on efforts aimed at improving further the latter by tuning-up the former are discussed and the usefulness of detailed NP structure studies to advancing science and technology of metallic NPs - exemplified.An approach to determining the 3D atomic structure of metallic nanoparticles (NPs) in fine detail and using the unique knowledge obtained for rationalizing their synthesis and properties targeted for optimization is described and exemplified on Pt-Ru alloy NPs of importance to the development of devices for clean energy conversion such as fuel cells. In particular, PtxRu100-x alloy NPs, where x = 31, 49 and 75, are synthesized by wet chemistry and activated catalytically by a post-synthesis treatment involving heating under controlled N2-H2 atmosphere. So-activated NPs are evaluated as catalysts for gas-phase CO oxidation and ethanol electro-oxidation reactions taking place in fuel cells. Both as-synthesized and activated NPs are characterized structurally by total scattering experiments involving high-energy synchrotron X-ray diffraction coupled to atomic pair distribution functions (PDFs) analysis. 3D structure models both for as-synthesized and activated NPs are built by molecular dynamics simulations based on the archetypal for current theoretical modelling Sutton-Chen method. Models are refined against the experimental PDF data by reverse Monte Carlo simulations and analysed in terms of prime structural characteristics such as metal-to-metal bond lengths, bond angles and first coordination numbers for Pt and Ru atoms. Analysis indicates that, though of a similar type, the atomic structure of as-synthesized and respective activated NPs differ in several details of importance to NP catalytic properties. Structural characteristics of activated NPs and data for their catalytic activity are compared side by side and strong evidence found that electronic effects, indicated by significant changes in Pt-Pt and Ru-Ru metal bond lengths at NP surface, and practically unrecognized so far atomic ensemble effects, indicated by distinct stacking of atomic layers near NP surface and prevalence of particular configurations of Pt and Ru atoms in these layers, contribute to the observed enhancement of the catalytic activity of PtxRu100-x alloy NPs at x ~ 50. Implications of so-established relationships between the atomic structure and catalytic activity of Pt-Ru alloy NPs on efforts aimed at improving further the latter by tuning-up the former are discussed and the usefulness of detailed NP structure studies to advancing science and technology of metallic NPs - exemplified. Electronic supplementary information (ESI) available: XRD patterns, TEM and 3D structure modelling methodology. See DOI: 10.1039/c5nr00800j

A coarse-grained model for DNA origami.

PubMed

Reshetnikov, Roman V; Stolyarova, Anastasia V; Zalevsky, Arthur O; Panteleev, Dmitry Y; Pavlova, Galina V; Klinov, Dmitry V; Golovin, Andrey V; Protopopova, Anna D

2018-02-16

Modeling tools provide a valuable support for DNA origami design. However, current solutions have limited application for conformational analysis of the designs. In this work we present a tool for a thorough study of DNA origami structure and dynamics. The tool is based on a novel coarse-grained model dedicated to geometry optimization and conformational analysis of DNA origami. We explored the ability of the model to predict dynamic behavior, global shapes, and fine details of two single-layer systems designed in hexagonal and square lattices using atomic force microscopy, Förster resonance energy transfer spectroscopy, and all-atom molecular dynamic simulations for validation of the results. We also examined the performance of the model for multilayer systems by simulation of DNA origami with published cryo-electron microscopy and atomic force microscopy structures. A good agreement between the simulated and experimental data makes the model suitable for conformational analysis of DNA origami objects. The tool is available at http://vsb.fbb.msu.ru/cosm as a web-service and as a standalone version.

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

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

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

Atomic-Level Structural Dynamics of Polyoxoniobates during DMMP Decomposition

DOE PAGES

Wang, Qi; Chapleski, Robert C.; Plonka, Anna M.; ...

2017-04-10

Ambient pressure in situ synchrotron-based spectroscopic techniques have been correlated to illuminate atomic-level details of bond breaking and formation during the hydrolysis of a chemical warfare nerve agent simulant over a polyoxometalate catalyst. Specifically, a Cs 8[Nb 6O 19] polyoxoniobate catalyst has been shown to react readily with dimethyl methylphosphonate (DMMP). The atomic-level transformations of all reactant moieties, the [Nb 6O 19] 8- polyanion, its Cs + counterions, and the DMMP substrate, were tracked under ambient conditions by a combination of X-ray absorption fine structure spectroscopy, Raman spectroscopy, and X-ray diffraction. Results reveal that the reaction mechanism follows general basemore » (in contrast to specific base) hydrolysis. Together with computational results, the work demonstrates that the ultimate fate of DMMP hydrolysis at the Cs 8[Nb 6O 19] catalyst is strong binding of the (methyl) methylphosphonic acid ((M)MPA) product to the polyanions, which ultimately inhibits catalytic turnover.« less

A coarse-grained model for DNA origami

PubMed Central

Stolyarova, Anastasia V; Zalevsky, Arthur O; Panteleev, Dmitry Y; Pavlova, Galina V; Klinov, Dmitry V; Golovin, Andrey V; Protopopova, Anna D

2018-01-01

Abstract Modeling tools provide a valuable support for DNA origami design. However, current solutions have limited application for conformational analysis of the designs. In this work we present a tool for a thorough study of DNA origami structure and dynamics. The tool is based on a novel coarse-grained model dedicated to geometry optimization and conformational analysis of DNA origami. We explored the ability of the model to predict dynamic behavior, global shapes, and fine details of two single-layer systems designed in hexagonal and square lattices using atomic force microscopy, Förster resonance energy transfer spectroscopy, and all-atom molecular dynamic simulations for validation of the results. We also examined the performance of the model for multilayer systems by simulation of DNA origami with published cryo-electron microscopy and atomic force microscopy structures. A good agreement between the simulated and experimental data makes the model suitable for conformational analysis of DNA origami objects. The tool is available at http://vsb.fbb.msu.ru/cosm as a web-service and as a standalone version. PMID:29267876

Unoccupied states in Cu and Zn octaethyl-porphyrin and phthalocyanine.

PubMed

Cook, Peter L; Yang, Wanli; Liu, Xiaosong; García-Lastra, Juan María; Rubio, Angel; Himpsel, F J

2011-05-28

Copper and zinc phthalocyanines and porphyrins are used in organic light emitting diodes and dye-sensitized solar cells. Using near edge x-ray absorption fine structure (NEXAFS) spectroscopy at the Cu 2p and Zn 2p edges, the unoccupied valence states at the Cu and Zn atoms are probed and decomposed into 3d and 4s contributions with the help of density functional calculations. A comparison with the N 1s edge provides the 2p states of the N atoms surrounding the metal, and a comparison with inverse photoemission provides a combined density of states. © 2011 American Institute of Physics

Relativistic corrections for screening effects on the energies of hydrogen-like atoms embedded in plasmas

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

Poszwa, A., E-mail: poszwa@matman.uwm.edu.p; Bahar, M. K., E-mail: mussiv58@gmail.com

2015-01-15

The influence of relativistic and plasma screening effects on energies of hydrogen-like atoms embedded in plasmas has been studied. The Dirac equation with a more general exponential cosine screened potential has been solved numerically and perturbatively, by employing the direct perturbation theory. Properties of spectra corresponding to bound states and to different sets of the potential parameters have been studied both in nonrelativistic and relativistic approximations. Binding energies, fine-structure splittings, and relativistic energy shifts have been determined as functions of parameters of the potential. The results have been compared with the ones known from the literature.

Far-infrared Spectroscopy of Interstellar Gas

NASA Technical Reports Server (NTRS)

Phillips, T. G.

1984-01-01

Research results of far-infrared spectroscopy with the Kuiper Airborne Observatory are discussed. Both high and intermediate resolution have been successfully employed in the detection of many new molecular and atomic lines including rotational transition of hydrides such as OH, H2O, NH3 and HCl; high J rotational transitions of CO; and the ground state fine structure transitions of atomic carbon, oxygen, singly ionized carbon and doubly ionized oxygen and nitrogen. These transitions have been used to study the physics and chemistry of clouds throughout the galaxy, in the galactic center region and in neighboring galaxies. This discussion is limited to spectroscopic studies of interstellar gas.

Copper-catalyzed aerobic oxidative coupling: From ketone and diamine to pyrazine

PubMed Central

Wu, Kun; Huang, Zhiliang; Qi, Xiaotian; Li, Yingzi; Zhang, Guanghui; Liu, Chao; Yi, Hong; Meng, Lingkui; Bunel, Emilio E.; Miller, Jeffrey T.; Pao, Chih-Wen; Lee, Jyh-Fu; Lan, Yu; Lei, Aiwen

2015-01-01

Copper-catalyzed aerobic oxidative C–H/N–H coupling between simple ketones and diamines was developed toward the synthesis of a variety of pyrazines. Various substituted ketones were compatible for this transformation. Preliminary mechanistic investigations indicated that radical species were involved. X-ray absorption fine structure experiments elucidated that the Cu(II) species 5 coordinated by two N atoms at a distance of 2.04 Å and two O atoms at a shorter distance of 1.98 Å was a reactive one for this aerobic oxidative coupling reaction. Density functional theory calculations suggested that the intramolecular coupling of cationic radicals was favorable in this transformation. PMID:26601302

Final Technical Report of Project DE-FG02-96ER14647

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

Lundeen, Stephen R.

This is the final technical report of work completed under DOE support over the period Sept. 1, 1996 until May 31, 2015. The title of the project was "Ion/Excited Atom Collision Studies with a Rydberg Target and a CO2 Laser" from 9/1/96 to 10/31/06, and "Properties of Actinide Ions from Measurements of Rydberg Ion Fine Structure" from 11/1/06 until 5/31/15. The primary technical results were a detailed experimental study of resonant charge transfer between Rydberg atoms and highly-charged ions, and unique measurements of many properties of multiply-charged Thorium ions.

Optically probing the fine structure of a single Mn atom in an InAs quantum dot.

PubMed

Kudelski, A; Lemaître, A; Miard, A; Voisin, P; Graham, T C M; Warburton, R J; Krebs, O

2007-12-14

We report on the optical spectroscopy of a single InAs/GaAs quantum dot doped with a single Mn atom in a longitudinal magnetic field of a few Tesla. Our findings show that the Mn impurity is a neutral acceptor state A0 whose effective spin J=1 is significantly perturbed by the quantum dot potential and its associated strain field. The spin interaction with photocarriers injected in the quantum dot is shown to be ferromagnetic for holes, with an effective coupling constant of a few hundreds of mueV, but vanishingly small for electrons.

Process for making ultra-fine ceramic particles

DOEpatents

Stangle, Gregory C.; Venkatachari, Koththavasal R.; Ostrander, Steven P.; Schulze, Walter A.

1995-01-01

A process for producing ultra-fine ceramic particles in which droplets are formed from a ceramic precursor mixture containing a metal cation, a nitrogen-containing fuel, a solvent, and an anion capable of participating in an anionic oxidation-reduction reaction with the nitrogen containing fuel. The nitrogen-containing fuel contains at least three nitrogen atoms, at least one oxygen atom, and at least one carbon atom. The ceramic precursor mixture is dried to remove at least 85 weight percent of the solvent, and the dried mixture is then ignited to form a combusted powder.

Anomalous Abundances in Gaseous Nebulae From Recombination and Collisional Lines: Improved Photoionization and Recombination Studies

NASA Astrophysics Data System (ADS)

Pradhan, Anil Kumar; Nahar, S. N.; Eissner, W. B.; Montenegro, M.

2011-01-01

A perplexing anomaly arises in the determination of abundances of common elements in gaseous nebulae, as derived from collisionally excited lines (CEL) as opposed to those from Recombination Lines (RCL). The "abundance discrepancy factors" can range from a factor of 2 to an order of magnitude or more. That has led to quite different interpretation of the physical structure and processes in gaseous nebulae, such as temperature fluctuations across the object, or metal-rich concentrations leading to a dual-abundnace scenario. We show that the problem may lie in inaccuracies in photoionization and recombination models neglecting low-energy resonance phenomena due to fine structure. Whereas the atomic physics of electron impact excitation of forbidden lines is well understood, and accurate collision strengths have long been available, that is not generally the case for electron-ion recombination cross sections. A major problem is the inclusion of relativisitic effects as it pertains to the existence of very low-energy fine structure resonances in photoionization cross sections. We carry out new relativistic calculations for photoionization and recombination cross sections using a recently extended version of the Breit-Pauli R-matrix codes, and the unified electron-ion recombination method that subsumes both the radiative and the dielectronic recombination (RR and DR) processes in an ab initio and self-consistent manner. We find that near-thresold resonances manifest themselves within fine structure levels of the ground state of ions, enhancing low-temperature recombination rate coefficients at 1000-10,000 K. The resulting enahncement in level-specific and total recombination rate coefficients should therefore lead to reduced abundances derived from RCL, and in accordance with those from CEL. We present results for photoionization of O II into, and recombination from, O III. Theoretical cross sections are benchmarked against high-resolution measurements from synchrotron based light sources. Work on other atomic species is in progress.

The role of yttrium and titanium during the development of ODS ferritic steels obtained through the STARS route: TEM and XAS study

NASA Astrophysics Data System (ADS)

Ordás, Nerea; Gil, Emma; Cintins, Arturs; de Castro, Vanessa; Leguey, Teresa; Iturriza, Iñigo; Purans, Juris; Anspoks, Andris; Kuzmin, Alexei; Kalinko, Alexandr

2018-06-01

Oxide Dispersion Strengthened Ferritic Steels (ODS FS) are candidate materials for structural components in future fusion reactors. Their high strength and creep resistance at elevated temperatures and their good resistance to neutron radiation damage is obtained through extremely fine microstructures containing a high density of nanometric precipitates, generally yttrium and titanium oxides. This work shows transmission electron microscopy (TEM) and extended X-ray absorption fine structure (EXAFS) characterization of Fe-14Cr-2W-0.3Ti-0.24Y ODS FS obtained by the STARS route (Surface Treatment of gas Atomized powder followed by Reactive Synthesis), an alternative method to obtain ODS alloys that avoids the mechanical alloying to introduce Y2O3 powder particles. In this route, FS powders already containing Ti and Y, precursors of the nanometric oxides, are obtained by gas atomization. Then, a metastable Cr- and Fe-rich oxide layer is formed on the surface of the powder particles. During consolidation by HIP at elevated temperatures, and post-HIP heat treatments above the HIP temperature, this oxide layer at Prior Particle Boundaries (PPBs) dissociates, the oxygen diffuses, and Y-Ti-O nano-oxides precipitate in the ferritic matrix. TEM characterization combined with XAFS and XANES analyses have proven to be suitable tools to follow the evolution of the nature of the different oxides present in the material during the whole processing route and select appropriate HIP and post-HIP parameters to promote profuse and fine Y-Ti-O nanometric precipitates.

An x-ray absorption spectroscopy study of Ni-Mn-Ga shape memory alloys.

PubMed

Sathe, V G; Dubey, Aditi; Banik, Soma; Barman, S R; Olivi, L

2013-01-30

The austenite to martensite phase transition in Ni-Mn-Ga ferromagnetic shape memory alloys was studied by extended x-ray absorption fine structure (EXAFS) and x-ray absorption near-edge structure (XANES) spectroscopy. The spectra at all the three elements', namely, Mn, Ga and Ni, K-edges in several Ni-Mn-Ga samples (with both Ni and Mn excess) were analyzed at room temperature and low temperatures. The EXAFS analysis suggested a displacement of Mn and Ga atoms in opposite direction with respect to the Ni atoms when the compound transforms from the austenite phase to the martensite phase. The first coordination distances around the Mn and Ga atoms remained undisturbed on transition, while the second and subsequent shells showed dramatic changes indicating the presence of a modulated structure. The Mn rich compounds showed the presence of antisite disorder of Mn and Ga. The XANES results showed remarkable changes in the unoccupied partial density of states corresponding to Mn and Ni, while the electronic structure of Ga remained unperturbed across the martensite transition. The post-edge features in the Mn K-edge XANES spectra changed from a double peak like structure to a flat peak like structure upon phase transition. The study establishes strong correlation between the crystal structure and the unoccupied electronic structure in these shape memory alloys.

Predicting RNA 3D structure using a coarse-grain helix-centered model

PubMed Central

Kerpedjiev, Peter; Höner zu Siederdissen, Christian; Hofacker, Ivo L.

2015-01-01

A 3D model of RNA structure can provide information about its function and regulation that is not possible with just the sequence or secondary structure. Current models suffer from low accuracy and long running times and either neglect or presume knowledge of the long-range interactions which stabilize the tertiary structure. Our coarse-grained, helix-based, tertiary structure model operates with only a few degrees of freedom compared with all-atom models while preserving the ability to sample tertiary structures given a secondary structure. It strikes a balance between the precision of an all-atom tertiary structure model and the simplicity and effectiveness of a secondary structure representation. It provides a simplified tool for exploring global arrangements of helices and loops within RNA structures. We provide an example of a novel energy function relying only on the positions of stems and loops. We show that coupling our model to this energy function produces predictions as good as or better than the current state of the art tools. We propose that given the wide range of conformational space that needs to be explored, a coarse-grain approach can explore more conformations in less iterations than an all-atom model coupled to a fine-grain energy function. Finally, we emphasize the overarching theme of providing an ensemble of predicted structures, something which our tool excels at, rather than providing a handful of the lowest energy structures. PMID:25904133

Ab initio electronic structure calculations for metallic intermediate band formation in photovoltaic materials

NASA Astrophysics Data System (ADS)

Wahnón, P.; Tablero, C.

2002-04-01

A metallic isolated band in the middle of the band gap of several III-V semiconductors has been predicted as photovoltaic materials with the possibility of providing substantially enhanced efficiencies. We have investigated the electronic band structures and lattice constants of GanAsmM and GanPmM with M=Sc, Ti, V, and Cr, to identify whether this isolated band is likely to exist by means of accurate calculations. For this task, we use the SIESTA program, an ab initio periodic density-functional method, fully self consistent in the local-density approximation. Norm-conserving, nonlocal pseudopotentials and confined linear combination of atomic orbitals have been used. We have carried out a case study of GanAsmTi and GanPmTi energy-band structure including analyses of the effect of the basis set, fine k-point mesh to ensure numerical convergence, structural parameters, and generalized gradient approximation for exchange and correlation corrections. We find the isolated intermediate band when one Ti atom replaces the position of one As (or P) atom in the crystal structure. For this kind of compound we show that the intermediate band relative position inside the band gap and width are sensitive to the dynamic relaxation of the crystal and the size of the basis set.

First principles simulation of amorphous InSb

NASA Astrophysics Data System (ADS)

Los, Jan H.; Kühne, Thomas D.; Gabardi, Silvia; Bernasconi, Marco

2013-05-01

Ab initio molecular dynamics simulations based on density functional theory have been performed to generate a model of amorphous InSb by quenching from the melt. The resulting network is mostly tetrahedral with a minor fraction (10%) of atoms in a fivefold coordination. The structural properties are in good agreement with available x-ray diffraction and extended x-ray-absorption fine structure data and confirm the proposed presence of a sizable fraction of homopolar In-In and Sb-Sb bonds whose concentration in our model amounts to about 20% of the total number of bonds.

Energy Levels and Oscillator Strengths for Ne-like Iron Ions

NASA Astrophysics Data System (ADS)

Zhong, J. Y.; Zhang, J.; Zhao, G.; Lu, X..

2004-02-01

Energy levels and oscillator strengths among the 27 fine-structure levels belonging to the (1s22s2)2p6, 2p53s, 2p53p and 2p53d configurations of neon-like iron ion have been calculated by using three atomic structure codes, RCN/RCG, AUTOSTRUCTURE (AS) and GRASP. The relativistic corrections of the wave functions are taken into account in RCN/RCG calculations. The results well agree with experimental and theoretical data wherever available. Finally the accuracy of three codes was analyzed.

Fine structure constant defines visual transparency of graphene.

PubMed

Nair, R R; Blake, P; Grigorenko, A N; Novoselov, K S; Booth, T J; Stauber, T; Peres, N M R; Geim, A K

2008-06-06

There are few phenomena in condensed matter physics that are defined only by the fundamental constants and do not depend on material parameters. Examples are the resistivity quantum, h/e2 (h is Planck's constant and e the electron charge), that appears in a variety of transport experiments and the magnetic flux quantum, h/e, playing an important role in the physics of superconductivity. By and large, sophisticated facilities and special measurement conditions are required to observe any of these phenomena. We show that the opacity of suspended graphene is defined solely by the fine structure constant, a = e2/hc feminine 1/137 (where c is the speed of light), the parameter that describes coupling between light and relativistic electrons and that is traditionally associated with quantum electrodynamics rather than materials science. Despite being only one atom thick, graphene is found to absorb a significant (pa = 2.3%) fraction of incident white light, a consequence of graphene's unique electronic structure.

Effect of local atomic and electronic structures on thermoelectric properties of chemically substituted CoSi

NASA Astrophysics Data System (ADS)

Hsu, C. C.; Pao, C. W.; Chen, J. L.; Chen, C. L.; Dong, C. L.; Liu, Y. S.; Lee, J. F.; Chan, T. S.; Chang, C. L.; Kuo, Y. K.; Lue, C. S.

2014-05-01

We report the effects of Ge partial substitution for Si on local atomic and electronic structures of thermoelectric materials in binary compound cobalt monosilicides (\\text{CoSi}_{1-x}\\text{Ge}_{x}\\text{:}\\ 0 \\le x \\le 0.15 ). Correlations between local atomic/electronic structure and thermoelectric properties are investigated by means of X-ray absorption spectroscopy. The spectroscopic results indicate that as Ge is partially substituted onto Si sites at x \\le 0.05 , Co in CoSi1-xGex gains a certain amount of charge in its 3d orbitals. Contrarily, upon further replacing Si with Ge at x \\ge 0.05 , the Co 3d orbitals start to lose some of their charge. Notably, thermopower is strongly correlated with charge redistribution in the Co 3d orbital, and the observed charge transfer between Ge and Co is responsible for the variation of Co 3d occupancy number. In addition to Seebeck coefficient, which can be modified by tailoring the Co 3d states, local lattice disorder may also be beneficial in enhancing the thermoelectric properties. Extended X-ray absorption fine structure spectrum results further demonstrate that the lattice phonons can be enhanced by Ge doping, which results in the formation of the disordered Co-Co pair. Improvements in the thermoelectric properties are interpreted based on the variation of local atomic and electronic structure induced by lattice distortion through chemical substitution.

The effect of local atomic structure on the optical properties of GeSi self-assembled islands buried in silicon matrix

NASA Astrophysics Data System (ADS)

Demchenko, I. N.; Lawniczak-Jablonska, K.; Kret, S.; Novikov, A. V.; Laval, J.-Y.; Zak, M.; Szczepanska, A.; Yablonskiy, A. N.; Krasilnik, Z. F.

2007-03-01

The local atomic structure of GeSi self-assembled islands buried in a silicon matrix strongly influences the optical properties of such systems. In the present paper this structure was determined by x-ray absorption fine-structure (XAFS) spectroscopy and high resolution transmission electron microscopy (HRTEM) and used to build a schematic description of the band structure model. Quantitative analysis of the extended XAFS (EXAFS) spectrum was performed for three coordination shells around the Ge absorbing atom with multiple scattering taken into account. It was proved that the coordination number of elements in an alloy resulting from EXAFS analysis for all three coordination spheres (i.e. 'mixing degree' parameters) cannot be taken as the concentration of alloy but can be used together with a proper model of the alloy unit cell to calculate a realistic concentration. The fraction of Ge calculated in this way is consistent with HRTEM results. The found model of the unit cell was used to generate a x-ray absorption near edge structure spectrum by ab initio calculations. This approach yielded a spectrum in good agreement with the experimental one. The information gained from XAFS and HRTEM was then used for calculation of the band structure diagram. Results of the calculation are discussed and compared with the experimental photoluminescence spectrum.

Atomic force microscopy based nanoassay: a new method to study α-Synuclein-dopamine bioaffinity interactions

NASA Astrophysics Data System (ADS)

Corvaglia, Stefania; Sanavio, Barbara; Sorce, Barbara; Bosco, Alessandro; Sabella, Stefania; Pompa, Pierpaolo; Scoles, Giacinto; Casalis, Loredana

2015-03-01

Intrinsically Disordered Proteins (IDPs) are characterized by the lack of well-defined 3-D structure and show high conformational plasticity. For this reason, they are a strong challenge for the traditional characterization of structure, supramolecular assembly and biorecognition phenomena. We show here how the fine tuning of protein orientation on a surface turns useful in the reliable testing of biorecognition interactions of IDPs, in particular α-Synuclein. We exploited atomic force microscopy (AFM) for the selective, nanoscale confinement of α-Synuclein on gold to study the early stages of α-Synuclein aggregation and the effect of small molecules, like dopamine, on the aggregation process. Capitalizing on the high sensitivity of AFM topographic height measurements we determined, for the first time in the literature, the dissociation constant of dopamine- α-Synuclein adducts.

Atomic force microscopy based nanoassay: a new method to study α-Synuclein-dopamine bioaffinity interactions

NASA Astrophysics Data System (ADS)

Corvaglia, Stefania; Sanavio, Barbara; Hong Enriquez, Rolando P.; Sorce, Barbara; Bosco, Alessandro; Scaini, Denis; Sabella, Stefania; Pompa, Pier Paolo; Scoles, Giacinto; Casalis, Loredana

2014-06-01

Intrinsically Disordered Proteins (IDPs) are characterized by the lack of well-defined 3-D structure and show high conformational plasticity. For this reason, they are a strong challenge for the traditional characterization of structure, supramolecular assembly and biorecognition phenomena. We show here how the fine tuning of protein orientation on a surface turns useful in the reliable testing of biorecognition interactions of IDPs, in particular α-Synuclein. We exploited atomic force microscopy (AFM) for the selective, nanoscale confinement of α-Synuclein on gold to study the early stages of α-Synuclein aggregation and the effect of small molecules, like dopamine, on the aggregation process. Capitalizing on the high sensitivity of AFM topographic height measurements we determined, for the first time in the literature, the dissociation constant of dopamine-α-Synuclein adducts.

Infrared-Bright Interacting Galaxies

NASA Astrophysics Data System (ADS)

Rojas Ruiz, Sofia; Murphy, Eric Joseph; Armus, Lee; Smith, John-David; Bradford, Charles Matt; Stierwalt, Sabrina

2018-01-01

We present the mid-infrared spectral mapping of eight LIRG-class interacting galaxies: NGC 6670, NGC 7592, IIZw 96, IIIZw 35, Arp 302, Arp 236, Arp 238, Arp 299. The properties of galaxy mergers, which are bright and can be studied at high resolutions at low-z, provide local analogs for sources that may be important contributors to the Far Infrared Background (FIRB.) In order to study star formation and the physical conditions in the gas and dust in our sample galaxies, we used the Spitzer InfraRed Spectrograph (IRS) to map the galaxies over the 5-35 μm window to trace the PAH, molecular hydrogen, and atomic fine structure line emission on scales of 1.4 – 5.3 kpc. Here we present the reduction for low and high-resolution data, and preliminary results in the analysis of fine structure line ratios and dust features in the two nuclei and interacting regions from one of our sample galaxies, NGC 6670.

Shifts due to quantum-mechanical interference from distant neighboring resonances for saturated fluorescence spectroscopy

NASA Astrophysics Data System (ADS)

Marsman, Alain; Horbatsch, Marko; Hessels, Eric A.

2014-05-01

Quantum-mechanical interference with distant neighboring resonances is found to cause shifts for precision saturated fluorescence spectroscopy of the atomic helium 23 S -to- 23 P transitions. The shifts are significant (larger than the experimental uncertainties for measurements of the intervals) despite the fact that the neighboring resonances are separated from the measured resonances by 1400 and 20 000 natural widths. The shifts depend strongly on experimental parameters such as the angular position of the fluorescence detector and the intensity and size of laser beams. These shifts must be considered for the ongoing program of determining the fine-structure constant from the helium 23 P fine structure. The work represents the first study of such interference shifts for saturated fluorescence spectroscopy and follows up on our previous study of similar shifts for laser spectroscopy. This work is supported by NSERC, CRC, ORF, CFI, NIST and SHARCNET.

Iowa Powder Atomization Technologies

ScienceCinema

Ricken, Joel and Heidloff, Andrew

2018-05-07

The same atomization effect seen in a fuel injector is being applied to titanium metal resulting in fine titanium powders that are less than half the width of a human hair. Titanium melts above 3,000°F and is highly corrosive therefore requiring specialized containers. The liquid titanium is poured through an Ames Laboratory - USDOE patented tube which is intended to increase the energy efficiency of the atomization process, which has the ability to dramatically decrease the cost of fine titanium powders. This novel process could open markets for green manufacturing of titanium components from jet engines to biomedical implants.

Local Chemical Ordering and Negative Thermal Expansion in PtNi Alloy Nanoparticles.

PubMed

Li, Qiang; Zhu, He; Zheng, Lirong; Fan, Longlong; Wang, Na; Rong, Yangchun; Ren, Yang; Chen, Jun; Deng, Jinxia; Xing, Xianran

2017-12-13

An atomic insight into the local chemical ordering and lattice strain is particular interesting to recent emerging bimetallic nanocatalysts such as PtNi alloys. Here, we reported the atomic distribution, chemical environment, and lattice thermal evolution in full-scale structural description of PtNi alloy nanoparticles (NPs). The different segregation of elements in the well-faceted PtNi nanoparticles is convinced by extended X-ray absorption fine structure (EXAFS). Atomic pair distribution function (PDF) study evidences the coexistence of the face-centered cubic and tetragonal ordering parts in the local environment of PtNi nanoparticles. Further reverse Monte Carlo (RMC) simulation with PDF data obviously exposed the segregation as Ni and Pt in the centers of {111} and {001} facets, respectively. Layer-by-layer statistical analysis up to 6 nm for the local atomic pairs revealed the distribution of local tetragonal ordering on the surface. This local coordination environment facilitates the distribution of heteroatomic Pt-Ni pairs, which plays an important role in the negative thermal expansion of Pt 41 Ni 59 NPs. The present study on PtNi alloy NPs from local short-range coordination to long-range average lattice provides a new perspective on tailoring physical properties in nanomaterials.

Atomic structure calculations and identification of EUV and SXR spectral lines in Sr XXX

NASA Astrophysics Data System (ADS)

Goyal, Arun; Khatri, Indu; Aggarwal, Sunny; Singh, A. K.; Mohan, Man

2015-08-01

We report an extensive theoretical study of atomic data for Sr XXX in a wide range with L-shell electron excitations to the M-shell. We have calculated energy levels, wave-function compositions and lifetimes for lowest 113 fine structure levels and wavelengths of an extreme Ultraviolet (EUV) and soft X-ray (SXR) transitions. We have employed multi-configuration Dirac Fock method (MCDF) approach within the framework of Dirac-Coulomb Hamiltonian including quantum electrodynamics (QED) and Breit corrections. We have also presented the radiative data for electric and magnetic dipole (E1, M1) and quadrupole (E2, M2) transitions from the ground state. We have made comparisons with available energy levels compiled by NIST and achieve good agreement. But due to inadequate data in the literature, analogous relativistic distorted wave calculations have also been performed using flexible atomic code (FAC) to assess the reliability and accuracy of our results. Additionally, we have provided new atomic data for Sr XXX which is not published elsewhere in the literature and we believe that our results may be beneficial in fusion plasma research and astrophysical investigations and applications.

Atomic resolution holography.

PubMed

Hayashi, Kouichi

2014-11-01

Atomic resolution holography, such as X-ray fluorescence holography (XFH)[1] and photoelectron holography (PH), has the attention of researcher as an informative local structure analysis, because it provides three dimensional atomic images around specific elements within a range of a few nanometers. It can determine atomic arrangements around a specific element without any prior knowledge of structures. It is considered that the atomic resolution holographic is a third method of structural analysis at the atomic level after X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). As known by many researchers, XRD and XAFS are established methods that are widespread use in various fields. XRD and XAFS provide information on long-range translational periodicities and very local environments, respectively, whereas the atomic resolution holography gives 3D information on the local order and can visualize surrounding atoms with a large range of coordination shells. We call this feature "3D medium-range local structure observation".In addition to this feature, the atomic resolution holography is very sensitive to the displacement of atoms from their ideal positions, and one can obtain quantitative information about local lattice distortions by analyzing reconstructed atomic images[2] When dopants with different atomic radii from the matrix elements are present, the lattices around the dopants are distorted. However, using the conventional methods of structural analysis, one cannot determine the extent to which the local lattice distortions are preserved from the dopants. XFH is a good tool for solving this problem.Figure 1 shows a recent achievement on a relaxor ferroelectric of Pb(Mg1/3Nb2/3)O3 (PMN) using XFH. The structural studies of relaxor ferroelectrics have been carried out by X-ray or neutron diffractions, which suggested rhombohedral distortions of their lattices. However, their true pictures have not been obtained, yet. The Nb Kα holograms showed four separate Pb images, as shown in Fig.1. Using these images, we could obtain acute and obtuse rhombohedral structures of the crystal unit cells. Moreover, the Pb-Pb correlated images reconstructed from Pb Lα holograms showed a local structure of body center-like 2a0 ×2a0 × 2a0 superlattice, proving a rigid 3D network structural model combining the two kinds of rhombohedrons. This superstructure are believed to play an important role in the relaxor behaviour of PMN at atomic level[3].jmicro;63/suppl_1/i13/DFU047F1F1DFU047F1Fig. 1.3D images of the nearest Pb and O atoms around Nb in Pb(Mg1/3Nb2/3)O3. The cube represents 1/8 of the unit cell. © The Author 2014. Published by Oxford University Press on behalf of The Japanese Society of Microscopy. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Polarization of submillimetre lines from interstellar medium

NASA Astrophysics Data System (ADS)

Zhang, Heshou; Yan, Huirong

2018-04-01

Magnetic fields play important roles in many astrophysical processes. However, there is no universal diagnostic for the magnetic fields in the interstellar medium (ISM) and each magnetic tracer has its limitation. Any new detection method is thus valuable. Theoretical studies have shown that submillimetre fine-structure lines are polarized due to atomic alignment by ultraviolet photon-excitation, which opens up a new avenue to probe interstellar magnetic fields. We will, for the first time, perform synthetic observations on the simulated three-dimensional ISM to demonstrate the measurability of the polarization of submillimetre atomic lines. The maximum polarization for different absorption and emission lines expected from various sources, including star-forming regions are provided. Our results demonstrate that the polarization of submillimetre atomic lines is a powerful magnetic tracer and add great value to the observational studies of the submilimetre astronomy.

10 CFR 810.15 - Violations.

Code of Federal Regulations, 2012 CFR

2012-01-01

... ENERGY ASSISTANCE TO FOREIGN ATOMIC ENERGY ACTIVITIES § 810.15 Violations. (a) The Atomic Energy Act... person from violating any provision of the Atomic Energy Act or its implementing regulations. (2) Any... Atomic Energy Act may be fined up to $10,000 or imprisoned up to 10 years, or both. If the offense is...

10 CFR 810.15 - Violations.

Code of Federal Regulations, 2014 CFR

2014-01-01

... ENERGY ASSISTANCE TO FOREIGN ATOMIC ENERGY ACTIVITIES § 810.15 Violations. (a) The Atomic Energy Act... person from violating any provision of the Atomic Energy Act or its implementing regulations. (2) Any... Atomic Energy Act may be fined up to $10,000 or imprisoned up to 10 years, or both. If the offense is...

10 CFR 810.15 - Violations.

Code of Federal Regulations, 2013 CFR

2013-01-01

... ENERGY ASSISTANCE TO FOREIGN ATOMIC ENERGY ACTIVITIES § 810.15 Violations. (a) The Atomic Energy Act... person from violating any provision of the Atomic Energy Act or its implementing regulations. (2) Any... Atomic Energy Act may be fined up to $10,000 or imprisoned up to 10 years, or both. If the offense is...

10 CFR 810.15 - Violations.

Code of Federal Regulations, 2011 CFR

2011-01-01

... ENERGY ASSISTANCE TO FOREIGN ATOMIC ENERGY ACTIVITIES § 810.15 Violations. (a) The Atomic Energy Act... person from violating any provision of the Atomic Energy Act or its implementing regulations. (2) Any... Atomic Energy Act may be fined up to $10,000 or imprisoned up to 10 years, or both. If the offense is...

10 CFR 810.15 - Violations.

Code of Federal Regulations, 2010 CFR

2010-01-01

... ENERGY ASSISTANCE TO FOREIGN ATOMIC ENERGY ACTIVITIES § 810.15 Violations. (a) The Atomic Energy Act... person from violating any provision of the Atomic Energy Act or its implementing regulations. (2) Any... Atomic Energy Act may be fined up to $10,000 or imprisoned up to 10 years, or both. If the offense is...

Master equation theory applied to the redistribution of polarized radiation in the weak radiation field limit. V. The two-term atom

NASA Astrophysics Data System (ADS)

Bommier, Véronique

2017-11-01

Context. In previous papers of this series, we presented a formalism able to account for both statistical equilibrium of a multilevel atom and coherent and incoherent scatterings (partial redistribution). Aims: This paper provides theoretical expressions of the redistribution function for the two-term atom. This redistribution function includes both coherent (RII) and incoherent (RIII) scattering contributions with their branching ratios. Methods: The expressions were derived by applying the formalism outlined above. The statistical equilibrium equation for the atomic density matrix is first formally solved in the case of the two-term atom with unpolarized and infinitely sharp lower levels. Then the redistribution function is derived by substituting this solution for the expression of the emissivity. Results: Expressions are provided for both magnetic and non-magnetic cases. Atomic fine structure is taken into account. Expressions are also separately provided under zero and non-zero hyperfine structure. Conclusions: Redistribution functions are widely used in radiative transfer codes. In our formulation, collisional transitions between Zeeman sublevels within an atomic level (depolarizing collisions effect) are taken into account when possible (I.e., in the non-magnetic case). However, the need for a formal solution of the statistical equilibrium as a preliminary step prevents us from taking into account collisional transfers between the levels of the upper term. Accounting for these collisional transfers could be done via a numerical solution of the statistical equilibrium equation system.

Precision Laser Spectroscopic Measurement of Helium -4(1S2S S(3) to 1S2P P(3)) Lamb Shift and Fine Structure

NASA Astrophysics Data System (ADS)

Dixson, Ronald Gene

This thesis is a presentation of the results of a precise measurement of the absolute wavelength and fine structure splitting of the 1s2s ^3S to 1s2p ^3P transition of the ^4He atom. The experiment described in this thesis is the first one in which laser spectroscopy has been done on the 2 ^3S to 2^3 P transition in a metastable atomic beam. The energy interval between the 2^3S and the 2^3P state is precisely determined by comparison of the absolute wavelength of the transition with our standard laser (an iodine stabilized He-Ne laser with an accuracy of 1.6 parts in 10^{10 }) in a Fabry-Perot interferometer. The experimental Lamb shift of the transition is determined by subtracting from the measured frequency the precisely known non-quantum electrodynamic contributions to the theoretical value of the interval. From our measurements of the absolute wavelength, the following weighted (2J + 1) average for the 2^3S to 2^3P transition frequency and experimental Lamb Shift are obtained:eqalign{& rm f_{2S{-}2P} = 276 736 495.59 (5) rm MHz.cr& {bf L}[ 2^3Sto2 ^3P] = 5311.26 (5) rm MHz.cr} Our value for the Lamb Shift is in agreement with the best previous measurement but a factor of 60 more precise. It is also two orders of magnitude more precise than the present theoretical calculation, presenting quite a challenge to theorists. Nevertheless, this work is very timely since it is anticipated (DRA94) (MOR94) that the theory will reach this level in the near future. The measured fine structure splittings of the 2^3P level are: eqalign{rm 2^3P_0to rm2^3P_2 &: 31908.135 (3) rm MHzcrrm 2^3P_1to rm2^3P_2 &: sk{5}2291.173 (3) rm MHz}These results are more precise than previous microwave measurements and in significant disagreement with them, a situation which is especially timely and interesting since new theoretical calculations of these fine structure intervals (DRA94) at this level of precision are nearing completion.

Reaction dynamics of H + O2 at 1.6 eV collision energy

NASA Technical Reports Server (NTRS)

Bronikowski, Michael J.; Zhang, Rong; Rakestraw, David J.; Zare, Richard N.

1989-01-01

The hot hydrogen atom reaction, H + O2 yields OH + O, has been studied at a center of mass collision energy of 1.6 eV. H atoms were generated by 266 nm photolysis of HI in a mixture of HI and O2 at 293 K. The OH product was probed by laser induced fluorescence and the nascent OH vibrational, rotational, and fine structure distributions were determined. The OH(v=0)/OH(v=1) vibrational branching ratio was measured to be 1.72 + or - 0.09. The data suggest that the H + O2 reaction at this collision energy proceeds via two competing mechanisms: reaction involving a long-lived complex and direct reaction.

Reaction dynamics of H + O2 at 1.6 eV collision energy

NASA Technical Reports Server (NTRS)

Bronikowski, Michael J.; Rong, Zhang; Rakestraw, David J.; Zare, Richard N.

1989-01-01

The hot hydrogen atom reaction, H + O2 yields OH + O, has been studied at a center of mass collision energy of 1.6 eV. H atoms were generated by 266 nm photolysis of HI in a mixture of HI and O2 at 293 K. The OH product was probed by laser induced fluorescence and the nascent OH vibrational, rotational, and fine structure distributions were determined. The OH(v=0/OH(v=1) vibrational branching ratio was measured to be 1.72 + or - 0.09. The data suggest that the H + O2 reaction at this collision energy proceeds via two competing mechanisms: reaction involving a long-lived complex and direct reaction.

Nonlinear resonance scattering of femtosecond X-ray pulses on atoms in plasmas

NASA Astrophysics Data System (ADS)

Rosmej, F. B.; Astapenko, V. A.; Lisitsa, V. S.; Moroz, N. N.

2017-11-01

It is shown that for sufficiently short pulses the resonance scattering probability becomes a nonlinear function of the pulse duration. For fs X-ray pulses scattered on atoms in plasmas maxima and minima develop in the nonlinear regime whereas in the limit of long pulses the probability becomes linear and turns over into the standard description of the electromagnetic pulse scattering. Numerical calculations are carried out in terms of a generalized scattering probability for the total time of pulse duration including fine structure splitting and ion Doppler broadening in hot plasmas. For projected X-ray monocycles, the generalized nonlinear approach differs by 1-2 orders of magnitude from the standard theory.

Frequency Combs in the XUV by Intra-Laser High Harmonic Generation for Ultra-Precise Measurements of the Fine Structure Constant

DTIC Science & Technology

2015-06-03

example, all atomic clocks for the European satellite -based global positioning system GALLILEO were manufactured in Neuchatel. With the integration...realization of numerous other exciting devices in various areas like advancement of sensors and nano- technological devices. Summary of Project...losses of the resonator . Achieving passive femtosecond pulse formation at these record-high power levels will require eliminating any destabilizing

Local structure in LaMnO3 and CaMnO3 perovskites: A quantitative structural refinement of Mn K -edge XANES data

NASA Astrophysics Data System (ADS)

Monesi, C.; Meneghini, C.; Bardelli, F.; Benfatto, M.; Mobilio, S.; Manju, U.; Sarma, D. D.

2005-11-01

Hole-doped perovskites such as La1-xCaxMnO3 present special magnetic and magnetotransport properties, and it is commonly accepted that the local atomic structure around Mn ions plays a crucial role in determining these peculiar features. Therefore experimental techniques directly probing the local atomic structure, like x-ray absorption spectroscopy (XAS), have been widely exploited to deeply understand the physics of these compounds. Quantitative XAS analysis usually concerns the extended region [extended x-ray absorption fine structure (EXAFS)] of the absorption spectra. The near-edge region [x-ray absorption near-edge spectroscopy (XANES)] of XAS spectra can provide detailed complementary information on the electronic structure and local atomic topology around the absorber. However, the complexity of the XANES analysis usually prevents a quantitative understanding of the data. This work exploits the recently developed MXAN code to achieve a quantitative structural refinement of the Mn K -edge XANES of LaMnO3 and CaMnO3 compounds; they are the end compounds of the doped manganite series LaxCa1-xMnO3 . The results derived from the EXAFS and XANES analyses are in good agreement, demonstrating that a quantitative picture of the local structure can be obtained from XANES in these crystalline compounds. Moreover, the quantitative XANES analysis provides topological information not directly achievable from EXAFS data analysis. This work demonstrates that combining the analysis of extended and near-edge regions of Mn K -edge XAS spectra could provide a complete and accurate description of Mn local atomic environment in these compounds.

To acquire more detailed radiation drive by use of ``quasi-steady'' approximation in atomic kinetics

NASA Astrophysics Data System (ADS)

Ren, Guoli; Pei, Wenbing; Lan, Ke; Gu, Peijun; Li, Xin

2012-10-01

In current routine 2D simulation of hohlraum physics, we adopt the principal-quantum- number(n-level) average atom model(AAM) in NLTE plasma description. However, the detailed experimental frequency-dependant radiative drive differs from our n-level simulated drive, which reminds us the need of a more detailed atomic kinetics description. The orbital-quantum- number(nl-level) average atom model is a natural consideration, however the nl-level in-line calculation needs much more computational resource. By distinguishing the rapid bound-bound atomic processes from the relative slow bound-free atomic processes, we found a method to build up a more detailed bound electron distribution(nl-level even nlm-level) using in-line n-level calculated plasma conditions(temperature, density, and average ionization degree). We name this method ``quasi-steady approximation'' in atomic kinetics. Using this method, we re-build the nl-level bound electron distribution (Pnl), and acquire a new hohlraum radiative drive by post-processing. Comparison with the n-level post-processed hohlraum drive shows that we get an almost identical radiation flux but with more fine frequency-denpending spectrum structure which appears only in nl-level transition with same n number(n=0) .

Complexation- and ligand-induced metal release from 316L particles: importance of particle size and crystallographic structure.

PubMed

Hedberg, Yolanda; Hedberg, Jonas; Liu, Yi; Wallinder, Inger Odnevall

2011-12-01

Iron, chromium, nickel, and manganese released from gas-atomized AISI 316L stainless steel powders (sized <45 and <4 μm) were investigated in artificial lysosomal fluid (ALF, pH 4.5) and in solutions of its individual inorganic and organic components to determine its most aggressive component, elucidate synergistic effects, and assess release mechanisms, in dependence of surface changes using atomic absorption spectroscopy, Raman, XPS, and voltammetry. Complexation is the main reason for metal release from 316L particles immersed in ALF. Iron was mainly released, while manganese was preferentially released as a consequence of the reduction of manganese oxide on the surface. These processes resulted in highly complexing media in a partial oxidation of trivalent chromium to hexavalent chromium on the surface. The extent of metal release was partially controlled by surface properties (e.g., availability of elements on the surface and structure of the outermost surface) and partially by the complexation capacity of the different metals with the complexing agents of the different media. In general, compared to the coarse powder (<45 μm), the fine (<4 μm) powder displayed significantly higher released amounts of metals per surface area, increased with increased solution complexation capacity, while less amounts of metals were released into non-complexing solutions. Due to the ferritic structure of lower solubility for nickel of the fine powder, more nickel was released into all solutions compared with the coarser powder.

The gating cycle of a K+ channel at atomic resolution

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

Cuello, Luis G.; Cortes, D. Marien; Perozo, Eduardo

C-type inactivation in potassium channels helps fine-tune long-term channel activity through conformational changes at the selectivity filter. Here, through the use of cross-linked constitutively open constructs, we determined the structures of KcsA’s mutants that stabilize the selectivity filter in its conductive (E71A, at 2.25 Å) and deep C-type inactivated (Y82A at 2.4 Å) conformations. These structural snapshots represent KcsA’s transient open-conductive (O/O) and the stable open deep C-type inactivated states (O/I), respectively. The present structures provide an unprecedented view of the selectivity filter backbone in its collapsed deep C-type inactivated conformation, highlighting the close interactions with structural waters and themore » local allosteric interactions that couple activation and inactivation gating. Together with the structures associated with the closed-inactivated state (C/I) and in the well-known closed conductive state (C/O), this work recapitulates, at atomic resolution, the key conformational changes of a potassium channel pore domain as it progresses along its gating cycle.« less

Deposition-temperature dependence of structural anisotropy in amorphous Tb-Fe films

NASA Astrophysics Data System (ADS)

Harris, V. G.; Elam, W. T.; Koon, N. C.; Hellman, F.

1994-02-01

The anisotropic local structure in a series of amorphous Tb26Fe74 films deposited at different deposition temperatures and having different magnetic anisotropy energies have been investigated using polarization-dependent extended x-ray-absorption fine-structure measurements. Samples deposited at temperatures >=300 K exhibit anisotropic pair correlations where like atomic pairs are favored in plane and unlike pairs are favored out of plane. Both the anisotropic pair correlations and the perpendicular magnetic anisotropy increase with increasing deposition temperature. In contrast, a sample deposited at 77 K was found to have isotropic pair correlations, low perpendicular magnetic anisotropy, and a large (~=1%) in-plane compression.

Relating structure with morphology: A comparative study of perfect Langmuir Blodgett multilayers

NASA Astrophysics Data System (ADS)

Mukherjee, Smita; Datta, Alokmay; Giglia, Angelo; Mahne, Nichole; Nannarone, Stefano

2008-01-01

Atomic force microscopy and X-ray reflectivity of metal-stearate (MSt) Langmuir-Blodgett films on hydrophilic Silicon (1 0 0), show dramatic reduction in 'pinhole' defects when metal M is changed from Cd to Co, along with excellent periodicity in multilayer, with hydrocarbon tails tilted 9.6° from vertical for CoSt (untilted for CdSt). Near edge X-ray absorption fine structure (NEXAFS) and Fourier transform infra-red (FTIR) spectroscopies indicate bidentate bridging metal-carboxylate coordination in CoSt (unidentate in CdSt), underscoring role of headgroup structure in determining morphology. FTIR studies also show increased packing density in CoSt, consistent with increased coverage.

Local and electronic structure around manganese in Cd0.98Mn0.02Te0.97Se0.03 studied by XAFS

NASA Astrophysics Data System (ADS)

Radisavljević, I.; Novaković, N.; Romčević, N.; Ivanović, N.

2013-04-01

X-ray Absorption Fine Structure (XAFS) technique was employed to study local electronic and structural features of Mn ions incorporated in Cd0.98Mn0.02Te0.97Se0.03. XAFS measurements performed at Mn K edge revealed that manganese Mn(II) ions are well incorporated into the host CdTe lattice (cubic zinc-blende structure type) and their immediate surrounding is found to be composed exclusively of Te atoms. The observed preference of Mn ions distribution around Te opposes earlier observations on the similar systems, where preferential Mn-Se over Mn-Te paring was found.

Fine tuning the ionic liquid-vacuum outer atomic surface using ion mixtures.

PubMed

Villar-Garcia, Ignacio J; Fearn, Sarah; Ismail, Nur L; McIntosh, Alastair J S; Lovelock, Kevin R J

2015-03-28

Ionic liquid-vacuum outer atomic surfaces can be created that are remarkably different from the bulk composition. In this communication we demonstrate, using low-energy ion scattering (LEIS), that for ionic liquid mixtures the outer atomic surface shows significantly more atoms from anions with weaker cation-anion interactions (and vice versa).

Ab initio studies of isolated boron substitutional defects in graphane

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Chetty, N.

2017-10-01

We have systematically studied energetics, structural and electronic properties of different configurations of the B atoms substituting C-H pairs located on a single hexagonal ring in a graphane system using the first-principles density functional theory (DFT). A total number of 12 distinct B dopants configurations were identified and characterized. Based on the formation energy analysis, we found that relative stability of B dopants depends greatly on the defect configurations. Our results suggest that the B substitutions prefer to be distributed randomly but avoiding the formation of homo-elemental B-B bonds in a graphane system, at any concentration. Generally, the values of band gap decrease as the number of B dopants increases, but the low energy configurations have large band gaps compared to those that have homo-elemental bonds. As a result, the band gap of graphane can be fine tuned through the change in the structural arrangement of B atoms. The adequate control of the electronic structure of graphane through doping should be essential for technological device applications.

Study of zinc-induced changes in lymphocyte membranes using atomic force microscopy, luminescence, and light scattering methods

NASA Astrophysics Data System (ADS)

Filimonenko, D. S.; Khairullina, A. Ya.; Yasinskii, V. M.; Kozlova, N. M.; Zubritskaja, G. P.; Slobozhanina, E. I.

2011-07-01

Changes in the surface structure of lymphocyte membranes exposed to various concentrations of zinc ions are studied. It is found by atomic force microscopy that increasing the concentration of zinc ions leads to a reduction in the correlation length of the autocorrelation function of the roughness profile of a lymphocyte compared to control samples; this may indicate the existence of fine structure in the membrane surface. Fluorescence markers are used to observe a reduction in the microviscosity of the lipids in the outer monolayer of the lipid bilayer after lymphocytes are exposed to Zn ions, as well as the exposure of phosphatidylserine on the surface membrane, and the oxidation of HS-groups of membrane proteins. Calculations of the absorption coefficients of lymphocytes modified with zinc reveal the existence of absorption bands owing to the formation of metal-protein complexes and zinc oxide nanoparticles. These results indicate significant changes in the structural and functional state of lymphocyte membranes exposed to zinc ions.

Microstructural investigation of Sr-modified Al-15 wt%Si alloys in the range from micrometer to atomic scale.

PubMed

Timpel, M; Wanderka, N; Vinod Kumar, G S; Banhart, J

2011-05-01

Strontium-modified Al-15 wt%Si casting alloys were investigated after 5 and 60 min of melt holding. The eutectic microstructures were studied using complementary methods at different length scales: focused ion beam-energy selective backscattered tomography, transmission electron microscopy and 3D atom probe. Whereas the samples after 5 min of melt holding show that the structure of eutectic Si changes into a fine fibrous morphology, the increase of prolonged melt holding (60 min) leads to the loss of Sr within the alloy with an evolution of an unmodified eutectic microstructure displaying coarse interconnected Si plates. Strontium was found at the Al/Si eutectic interfaces on the side of the eutectic Al region, measured by 3D atom probe. The new results obtained using 3D atom probe shed light on the location of Sr within the Al-Si eutectic microstructure. Copyright © 2010 Elsevier B.V. All rights reserved.

Scanning tunneling microscopy of atomically precise graphene nanoribbons exfoliated onto H:Si(100)

NASA Astrophysics Data System (ADS)

Radocea, Adrian; Mehdi Pour, Mohammad; Vo, Timothy; Shekhirev, Mikhail; Sinitskii, Alexander; Lyding, Joseph

Atomically precise graphene nanoribbons (GNRs) are promising materials for next generation transistors due to their well-controlled bandgaps and the high thermal conductivity of graphene. The solution synthesis of graphene nanoribbons offers a pathway towards scalable manufacturing. While scanning tunneling microscopy (STM) can access size scales required for characterization, solvent residue increases experimental difficulty and precludes band-gap determination via scanning tunneling spectroscopy (STS). Our work addresses this challenge through a dry contact transfer method that cleanly transfers solution-synthesized GNRs onto H:Si(100) under UHV using a fiberglass applicator. The semiconducting silicon surface avoids problems with image charge screening enabling intrinsic bandgap measurements. We characterize the nanoribbons using STM and STS. For chevron GNRs, we find a 1.6 eV bandgap, in agreement with computational modeling, and map the electronic structure spatially with detailed spectra lines and current imaging tunneling spectroscopy. Mapping the electronic structure of graphene nanoribbons is an important step towards taking advantage of the ability to form atomically precise nanoribbons and finely tune their properties.

Experimental and theoretical investigation of the temperature dependent electronic quenching of O(1D) atoms in collisions with Kr

NASA Astrophysics Data System (ADS)

Nuñez-Reyes, Dianailys; Kłos, Jacek; Alexander, Millard H.; Dagdigian, Paul J.; Hickson, Kevin M.

2018-03-01

The kinetics and dynamics of the collisional electronic quenching of O(1D) atoms by Kr have been investigated in a joint experimental and theoretical study. The kinetics of quenching were measured over the temperature range 50-296 K using the Laval nozzle method. O(1D) atoms were prepared by 266 nm photolysis of ozone, and the decay of the O(1D) concentration was monitored through vacuum ultraviolet fluorescence at 115.215 nm, from which the rate constant was determined. To interpret the experiments, a quantum close-coupling treatment of the quenching transition from the 1D state to the 3Pj fine-structure levels in collisions with Kr, and also Ar and Xe, was carried out. The relevant potential energy curves and spin-orbit coupling matrix elements were obtained in electronic structure calculations. We find reasonable agreement between computed temperature-dependent O(1D)-Rg (Rg = Ar, Kr, Xe) quenching rate constants and the present measurements for Kr and earlier measurements. In particular, the temperature dependence is well described.

Local structural and chemical ordering of nanosized Pt3±δCo probed by multiple-scattering x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Greco, Giorgia; Witkowska, Agnieszka; Principi, Emiliano; Minicucci, Marco; di Cicco, Andrea

2011-04-01

This work reports a detailed investigation of the local structure and chemical disorder of a Pt3±δCo thin film and Pt3±δCo nanoparticles. We have used a combination of techniques including x-ray absorption spectroscopy (XAS), x-ray diffraction (XRD), and high-resolution transmission electron microscopy (TEM). High-quality XAS spectra at the Co K edge and Pt L3 edge have been analyzed using double-edge multiple-scattering data analysis. Structural extended x-ray absorption fine structure (EXAFS) refinements have been performed accounting for the reduction of the coordination numbers and degeneracy of three-atom configurations, resulting from the measured size distribution and stoichiometry. The important effect of chemical ordering on pair and three-atom configurations has been studied using computer simulations based on a simple model accounting for substitutional disorder, defined by an order parameter s. It has been found that individual EXAFS signals related to the minority species (Co) are extremely sensitive to substitutional disorder so their intensities, especially those of the collinear three-atom configurations, can be used as a measure of the ordering level. The thin film has been found to be chemically disordered (s⩽0.4), in agreement with previous estimates. The Pt3±δCo nanoalloy has been found to be partially ordered (s=0.6±0.1) while the local structure around Co atoms is characterized by a higher level of structural disorder as compared to the bulk-like thin film. The robust approach for nanomaterial characterization used in this work combining different techniques can, in principle, be applied for structural refinements of any binary nanocrystalline functional system.

Two-photon Direct Frequency Comb Spectroscopy of Alkali Atoms

NASA Astrophysics Data System (ADS)

Nguyen, Khoa; Pradhananga, Trinity; Palm, Christopher; Stalnaker, Jason; Kimball, Derek Jackson

2012-06-01

We are using direct frequency comb spectroscopy to study transition frequencies and excited state hyperfine structure in potassium and rubidium using 2-photon transitions excited directly with the frequency-doubled output of a erbium fiber optical frequency comb. The frequency comb output is directed in two counterpropagating directions through a vapor cell containing the atomic vapor of interest. A pair of optical filters is used to select teeth of the comb in order to identify the transition wavelengths. A photomultiplier tube (PMT) measures fluorescence from a decay channel wavelength selected with another optical filter. Using different combinations of filters enables a wide range of transitions to be investigated. By scanning the repetition rate, a Doppler-free spectrum can be obtained enabling kHz-resolution spectral measurements. The thermal motion of the atoms in the vapor cell actually eliminates the need to fine-tune the offset frequency and repetition rate, alleviating a somewhat challenging requirement for spectroscopy of cold atoms. Our investigations are laying the groundwork for a long-term research program to use direct frequency comb spectroscopy to understand the complex spectra of rare-earth atoms.

Direct Frequency Comb Spectroscopy of Alkali Atoms

NASA Astrophysics Data System (ADS)

Pradhananga, Trinity; Palm, Christopher; Nguyen, Khoa; Guttikonda, Srikanth; Kimball, Derek Jackson

2011-11-01

We are using direct frequency comb spectroscopy to study transition frequencies and excited state hyperfine structure in potassium and rubidium using 2-photon transitions excited directly with the frequency-doubled output of a erbium fiber optical frequency comb. The frequency comb output is directed in two counterpropagating directions through a vapor cell containing the atomic vapor of interest. A pair of optical filters is used to select teeth of the comb in order to identify the transition wavelengths. A photomultiplier tube (PMT) measures fluorescence from a decay channel wavelength selected with another optical filter. Using different combinations of filters enables a wide range of transitions to be investigated. By scanning the repetition rate, a Doppler-free spectrum can be obtained enabling kHz-resolution spectral measurements. The thermal motion of the atoms in the vapor cell actually eliminates the need to fine-tune the offset frequency and repetition rate, alleviating a somewhat challenging requirement for spectroscopy of cold atoms. Our investigations are laying the groundwork for a long-term research program to use direct frequency comb spectroscopy to understand the complex spectra of rare-earth atoms.

C and RB Fountains:. Recent Results

NASA Astrophysics Data System (ADS)

Bize, S.; Sortais, Y.; Abgrall, M.; Zhang, S.; Calonico, D.; Mandache, C.; Lemonde, P.; Laurent, P.; Santarelli, G.; Salomon, C.; Clairon, A.; Luiten, A.; Tobar, M.

2002-04-01

We discuss the present performance and limits of our Cs and Rb fountains. The BNM/LPTF operates three cold atom clocks: two Cs fountains and a dual Cs-Rb fountain. By using an ultra-stable cryogenic sapphire oscillator to interrogate the atoms the frequency stability reaches 3.6 × 10-14τ-1/2. The accuracy of our fountains is now near 10-15. We discuss here the problems to be solved to reach a 10-16 accuracy. For instance this implies a continuous monitoring of the collisional frequency shift at the percent level in Cs. In contrast, 87Rb cold atom clocks exhibit a collisional shift ~ 100 times smaller than Cs which should lead to a better ultimate accuracy. Comparing the hyperfine energies of atoms with different atomic numbers Z, one can search for a possible violation of the Einstein Equivalence Principle. When interpreted as a test of the stability of the fine structure constant (α = e2/4πγ0ħc), measurements of the ratio νRb/νCs spread over a two year interval show no change of α at the 7 × 10-15/year level.

Calculations of the energy levels and oscillator strengths of the Ne-like Fe Ion (Fe XVII)

NASA Astrophysics Data System (ADS)

Zhong, Jia-yong; Zhang, Jie; Zhao, Gang; Lu, Xin

Energy levels and oscillator strengths among the 27 fine-structure levels belonging to the (ls 22s 2)2p 6, 2p 53s, 2p 53p and 2p 53d configurations of the neon-like iron ion have been calculated using three atomic structure codes RCN/RCG, AUTOSTRUCTURE (AS) and GRASP. Relativistic corrections of the wave functions are taken into account in the RCN/RCG calculation. The results agree well with the available experimental and theoretical data. The accuracy of the three codes is analysed.

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

Jung, Min-Cherl; Zhang, Dongrong; Nikiforov, Gueorgui O.

Ultrathin (<6 nm) polycrystalline films of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS-P) are deposited with a two-step spin-coating process. The influence of spin-coating conditions on morphology of the resulting film was examined by atomic force microscopy. Film thickness and RMS surface roughness were in the range of 4.0–6.1 and 0.6–1.1 nm, respectively, except for small holes. Polycrystalline structure was confirmed by grazing incidence x-ray diffraction measurements. Near-edge x-ray absorption fine structure measurements suggested that the plane through aromatic rings of TIPS-P molecules was perpendicular to the substrate surface.

Probing Sub-atomistic Free-Volume Imperfections in Dry-Milled Nanoarsenicals with PAL Spectroscopy.

PubMed

Shpotyuk, Oleh; Ingram, Adam; Bujňáková, Zdenka; Baláž, Peter; Shpotyuk, Yaroslav

2016-12-01

Structural transformations caused by coarse-grained powdering and fine-grained mechanochemical milling in a dry mode were probed in high-temperature modification of tetra-arsenic tetra-sulfide known as β-As4S4. In respect to X-ray diffraction analysis, the characteristic sizes of β-As4S4 crystallites in these coarse- and fine-grained powdered pellets were 90 and 40 nm, respectively. Positron annihilation lifetime spectroscopy was employed to characterize transformations occurred in free-volume structure of these nanoarsenicals. Experimentally measured positron lifetime spectra were parameterized in respect to three- or two-term fitting procedures and respectively compared with those accumulated for single crystalline realgar α-As4S4 polymorph. The effect of coarse-grained powdering was found to result in generation of large amount of positron and positronium Ps trapping sites inside arsenicals in addition to existing ones. In fine-grained powdered β-As4S4 pellets, the positron trapping sites with characteristic free volumes close to bi- and tri-atomic vacancies were evidently dominated. These defects were supposed to originate from grain boundary regions and interfacial free volumes near aggregated β-As4S4 crystallites. Thus, the cumulative production of different positron traps with lifetimes close to defect-related lifetimes in realgar α-As4S4 polymorph was detected in fine-grained milled samples.

Modeling metal droplet sprays in spray forming

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

Muoio, N.G.; Crowe, C.T.; Fritsching, U.

1995-12-31

Spray casting is a process whereby a molten metal stream is atomized and deposited on a substrate. The rapid solidification of the metal droplets gives rise to a fine grain structure and improved material properties. This paper presents a simulation for the fluid and thermal interaction of the fluid and droplets in the spray and the effect on the droplet spray pattern. Good agreement is obtained between the measured and predicted droplet mass flux distribution in the spray.

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

Zhang, Qingfeng; Han, Lili; Jing, Hao

While great success has been achieved in fine-tuning the aspect ratios and thereby the plasmon resonances of cylindrical Au nanorods, facet control with atomic level precision on the highly curved nanorod surfaces has long been a significantly more challenging task. The intrinsic structural complexity and lack of precise facet control of the nanorod surfaces remain the major obstacles for the atomic-level elucidation of the structure–property relationships that underpin the intriguing catalytic performance of Au nanorods. Here we demonstrate that the facets of single-crystalline Au nanorods can be precisely tailored using cuprous ions and cetyltrimethylammonium bromide as a unique pair ofmore » surface capping competitors to guide the particle geometry evolution during nanorod overgrowth. By deliberately maneuvering the competition between cuprous ions and cetyltrimethylammonium bromide, we have been able to create, in a highly controllable and selective manner, an entire family of nanorod-derived anisotropic multifaceted geometries whose surfaces are enclosed by specific types of well-defined high-index and low-index facets. This facet-controlled nanorod overgrowth approach also allows us to fine-tune the particle aspect ratios while well-preserving all the characteristic facets and geometric features of the faceted Au nanorods. Furthermore, taking full advantage of the combined structural and plasmonic tunability, we have further studied the facet-dependent heterogeneous catalysis on well-faceted Au nanorods using surface-enhanced Raman spectroscopy as an ultrasensitive spectroscopic tool with unique time-resolving and molecular finger-printing capabilities.« less

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

Orfield, Noah J.; McBride, James R.; Wang, Feng

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

Scaling up the precision in a ytterbium Bose-Einstein condensate interferometer

NASA Astrophysics Data System (ADS)

McAlpine, Katherine; Plotkin-Swing, Benjamin; Gochnauer, Daniel; Saxberg, Brendan; Gupta, Subhadeep

2016-05-01

We report on progress toward a high-precision ytterbium (Yb) Bose-Einstein condensate (BEC) interferometer, with the goal of measuring h/m and thus the fine structure constant α. Here h is Planck's constant and m is the mass of a Yb atom. The use of the non-magnetic Yb atom makes our experiment insensitive to magnetic field noise. Our chosen symmetric 3-path interferometer geometry suppresses errors from vibration, rotation, and acceleration. The precision scales with the phase accrued due to the kinetic energy difference between the interferometer arms, resulting in a quadratic sensitivity to the momentum difference. We are installing and testing the laser pulses for large momentum transfer via Bloch oscillations. We will report on Yb BEC production in a new apparatus and progress toward realizing the atom optical elements for high precision measurements. We will also discuss approaches to mitigate two important systematics: (i) atom interaction effects can be suppressed by creating the BEC in a dynamically shaped optical trap to reduce the density; (ii) diffraction phase effects from the various atom-optical elements can be accounted for through an analysis of the light-atom interaction for each pulse.

Elastic scattering of X-rays and gamma rays by 2S electrons in ions and neutral atoms

NASA Astrophysics Data System (ADS)

Costescu, A.; Spânulescu, S.; Stoica, C.

2012-08-01

The nonrelativistic limit of Rayleigh scattering amplitude on 2s electrons of neutral and partially ionized atoms is obtained by making use of the Green Function method. The result takes into consideration the retardation, relativistic kinematics and screening effects. The spurious singularities introduced by the retardation in a nonrelativistic approach are cancelled by the relativistic kinematics. For neutral and partially ionized atoms, a screening model is considered with an effective charge obtained by fitting the Hartree-Fock charge distribution with pure Coulombian wave functions corresponding to a central potential of a nucleus with Zeff as the atomic number. The total cross section of the photoeffect on the 2s electrons is also calculated from the imaginary part of the forward scattering amplitude by means of the optical theorem. The numerical results obtained are in a good agreement (10%) with the ones obtained by Kissell for the Rayleigh amplitude and by Scofield for the Photoeffect total cross section on the 2s electrons, for atoms with atomic number 18 ≤ Z ≤ 92 and photon energies ω≤αZm. (α=1/137,... is the fine structure constant, m is the electron mass).

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

Ozkendir, Osman Murat, E-mail: ozkendir@gmail.com

Highlights: • Crystal and electronic structure properties of Nd{sub x}Ti{sub 1−x}BO{sub 2+d} structure were investigated. • New crystal structures for Nd–Ti complexes are determined. • Distortions in the crystal structure were observed as a result of Boron shortage. • Prominent change in electronic properties of the samples with the increasing Nd amount. - Abstract: Neodymium substituted TiBO{sub 3} samples were investigated according to their crystal, electric and electronic properties. Studies were conducted by X-ray absorption fine structure spectroscopy (XAFS) technique for the samples with different substitutions in the preparation processes. To achieve better crystal structure results during the study, XRDmore » pattern results were supported by extended-XAFS (EXAFS) analysis. The electronic structure analysis were studied by X-ray absorption near-edge structure spectroscopy (XANES) measurements at the room temperatures. Due to the substituted Nd atoms, prominent changes in crystal structure, new crystal geometries for Nd-Ti complexes, phase transitions in the crystals structure were detected according to the increasing Nd substitutions in the samples. In the entire stages of the substitutions, Nd atoms were observed as governing the whole phenomena due to their dominant characteristics in Ti geometries. Besides, electrical resistivity decay was determined in the materials with the increasing amount of Nd substitution.« less

Unraveling the atomic structure of biogenic silica: evidence of the structural association of Al and Si in diatom frustules

NASA Astrophysics Data System (ADS)

Gehlen, M.; Beck, L.; Calas, G.; Flank, A.-M.; Van Bennekom, A. J.; Van Beusekom, J. E. E.

2002-05-01

We used X-ray absorption spectroscopy at the Al K-edge to investigate the atomic structure of biogenic silica and to assess the effect of Al on its crystal chemistry. Our study provides the first direct evidence for a structural association of Al and Si in biogenic silica. In samples of cultured diatoms, Al is present exclusively in fourfold coordination. The location and relative intensity of X-ray absorption near-edge structure (XANES) features suggests the structural insertion of tetrahedral Al inside the silica framework synthesized by the organism. In diatom samples collected in the marine environment, Al is present in mixed six- and fourfold coordination. The relative intensity of XANES structures indicates the coexistence of structural Al with a clay component, which most likely reflects sample contamination by adhering mineral particles. Extended X-ray absorption fine structure spectroscopy has been used to get Al-O distances in biogenic silica of cultured diatoms, confirming a tetrahedral coordination. Because of its effect on solubility and reaction kinetics of biogenic silica, the structural association between Al and biogenic silica at the stage of biosynthesis has consequences for the use of sedimentary biogenic silica as an indicator of past environmental conditions.

Magnesium K-Edge NEXAFS Spectroscopy of Chlorophyll a in Solution.

PubMed

Witte, Katharina; Streeck, Cornelia; Mantouvalou, Ioanna; Suchkova, Svetlana A; Lokstein, Heiko; Grötzsch, Daniel; Martyanov, Wjatscheslav; Weser, Jan; Kanngießer, Birgit; Beckhoff, Burkhard; Stiel, Holger

2016-11-17

The interaction of the central magnesium atom of chlorophyll a (Chl a) with the carbon and nitrogen backbone was investigated by magnesium K near-edge X-ray absorption fine structure (NEXAFS) spectroscopy in fluorescence detection mode. A crude extract of Chl a was measured as a 1 × 10 -2 mol/L ethanol solution (which represents an upper limit of concentration without aggregation) and as dried droplets. For the first time, the investigation of Mg bound to Chl a in a liquid environment by means of X-ray absorption spectroscopy is demonstrated. A pre-edge feature in the dissolved as well as in dried Chl a NEXFAS spectra has been identified as a characteristic transition originating from Mg in the Chl a molecule. This result is confirmed by theoretical DFT calculations leading to molecular orbitals (MO) which are mainly situated on the magnesium atom and nitrogen and carbon atoms from the pyrrole rings. The description is the first referring to the MO distribution with respect to the central Mg ion of Chl a and the surrounding atoms. On this basis, new approaches for the investigations of dynamic processes of molecules in solution and structure-function relationships of photosynthetic pigments and pigment-protein complexes in their native environment can be developed.

Complexation of Uranium by Cells and S-Layer Sheets of Bacillus sphaericus JG-A12

PubMed Central

Merroun, Mohamed L.; Raff, Johannes; Rossberg, André; Hennig, Christoph; Reich, Tobias; Selenska-Pobell, Sonja

2005-01-01

Bacillus sphaericus JG-A12 is a natural isolate recovered from a uranium mining waste pile near the town of Johanngeorgenstadt in Saxony, Germany. The cells of this strain are enveloped by a highly ordered crystalline proteinaceous surface layer (S-layer) possessing an ability to bind uranium and other heavy metals. Purified and recrystallized S-layer proteins were shown to be phosphorylated by phosphoprotein-specific staining, inductive coupled plasma mass spectrometry analysis, and a colorimetric method. We used extended X-ray absorption fine-structure (EXAFS) spectroscopy to determine the structural parameters of the uranium complexes formed by purified and recrystallized S-layer sheets of B. sphaericus JG-A12. In addition, we investigated the complexation of uranium by the vegetative bacterial cells. The EXAFS analysis demonstrated that in all samples studied, the U(VI) is coordinated to carboxyl groups in a bidentate fashion with an average distance between the U atom and the C atom of 2.88 ± 0.02 Å and to phosphate groups in a monodentate fashion with an average distance between the U atom and the P atom of 3.62 ± 0.02 Å. Transmission electron microscopy showed that the uranium accumulated by the cells of this strain is located in dense deposits at the cell surface. PMID:16151146

Highly Scalable Matching Pursuit Signal Decomposition Algorithm

NASA Technical Reports Server (NTRS)

Christensen, Daniel; Das, Santanu; Srivastava, Ashok N.

2009-01-01

Matching Pursuit Decomposition (MPD) is a powerful iterative algorithm for signal decomposition and feature extraction. MPD decomposes any signal into linear combinations of its dictionary elements or atoms . A best fit atom from an arbitrarily defined dictionary is determined through cross-correlation. The selected atom is subtracted from the signal and this procedure is repeated on the residual in the subsequent iterations until a stopping criterion is met. The reconstructed signal reveals the waveform structure of the original signal. However, a sufficiently large dictionary is required for an accurate reconstruction; this in return increases the computational burden of the algorithm, thus limiting its applicability and level of adoption. The purpose of this research is to improve the scalability and performance of the classical MPD algorithm. Correlation thresholds were defined to prune insignificant atoms from the dictionary. The Coarse-Fine Grids and Multiple Atom Extraction techniques were proposed to decrease the computational burden of the algorithm. The Coarse-Fine Grids method enabled the approximation and refinement of the parameters for the best fit atom. The ability to extract multiple atoms within a single iteration enhanced the effectiveness and efficiency of each iteration. These improvements were implemented to produce an improved Matching Pursuit Decomposition algorithm entitled MPD++. Disparate signal decomposition applications may require a particular emphasis of accuracy or computational efficiency. The prominence of the key signal features required for the proper signal classification dictates the level of accuracy necessary in the decomposition. The MPD++ algorithm may be easily adapted to accommodate the imposed requirements. Certain feature extraction applications may require rapid signal decomposition. The full potential of MPD++ may be utilized to produce incredible performance gains while extracting only slightly less energy than the standard algorithm. When the utmost accuracy must be achieved, the modified algorithm extracts atoms more conservatively but still exhibits computational gains over classical MPD. The MPD++ algorithm was demonstrated using an over-complete dictionary on real life data. Computational times were reduced by factors of 1.9 and 44 for the emphases of accuracy and performance, respectively. The modified algorithm extracted similar amounts of energy compared to classical MPD. The degree of the improvement in computational time depends on the complexity of the data, the initialization parameters, and the breadth of the dictionary. The results of the research confirm that the three modifications successfully improved the scalability and computational efficiency of the MPD algorithm. Correlation Thresholding decreased the time complexity by reducing the dictionary size. Multiple Atom Extraction also reduced the time complexity by decreasing the number of iterations required for a stopping criterion to be reached. The Course-Fine Grids technique enabled complicated atoms with numerous variable parameters to be effectively represented in the dictionary. Due to the nature of the three proposed modifications, they are capable of being stacked and have cumulative effects on the reduction of the time complexity.

Kernel Tuning and Nonuniform Influence on Optical and Electrochemical Gaps of Bimetal Nanoclusters.

PubMed

He, Lizhong; Yuan, Jinyun; Xia, Nan; Liao, Lingwen; Liu, Xu; Gan, Zibao; Wang, Chengming; Yang, Jinlong; Wu, Zhikun

2018-03-14

Fine tuning nanoparticles with atomic precision is exciting and challenging and is critical for tuning the properties, understanding the structure-property correlation and determining the practical applications of nanoparticles. Some ultrasmall thiolated metal nanoparticles (metal nanoclusters) have been shown to be precisely doped, and even the protecting staple metal atom could be precisely reduced. However, the precise addition or reduction of the kernel atom while the other metal atoms in the nanocluster remain the same has not been successful until now, to the best of our knowledge. Here, by carefully selecting the protecting ligand with adequate steric hindrance, we synthesized a novel nanocluster in which the kernel can be regarded as that formed by the addition of two silver atoms to both ends of the Pt@Ag 12 icosohedral kernel of the Ag 24 Pt(SR) 18 (SR: thiolate) nanocluster, as revealed by single crystal X-ray crystallography. Interestingly, compared with the previously reported Ag 24 Pt(SR) 18 nanocluster, the as-obtained novel bimetal nanocluster exhibits a similar absorption but a different electrochemical gap. One possible explanation for this result is that the kernel tuning does not essentially change the electronic structure, but obviously influences the charge on the Pt@Ag 12 kernel, as demonstrated by natural population analysis, thus possibly resulting in the large electrochemical gap difference between the two nanoclusters. This work not only provides a novel strategy to tune metal nanoclusters but also reveals that the kernel change does not necessarily alter the optical and electrochemical gaps in a uniform manner, which has important implications for the structure-property correlation of nanoparticles.

A New Maraging Stainless Steel with Excellent Strength-Toughness-Corrosion Synergy.

PubMed

Tian, Jialong; Wang, Wei; Babar Shahzad, M; Yan, Wei; Shan, Yiyin; Jiang, Zhouhua; Yang, Ke

2017-11-10

A new maraging stainless steel with superior strength-toughness-corrosion synergy has been developed based on an innovative concept of alloy design. The high strength-toughness combination is achieved by forming dispersive nano-sized intermetallic compounds in the soft lath martensitic matrix with a slight amount of residual austenite. The good corrosion resistance is guaranteed by exactly controlling the Co content based on understanding the synergistic effect between Co and Cr. The fine structure characteristics of two dominant strengthening precipitations including Ni₃Ti and Mo-rich phases were finely characterized associated with transmission electron microscope (TEM) and atom probe tomography (APT) analyses. The relationship among microstructure, strength and toughness is discussed. The precipitation mechanism of different precipitates in the new maraging stainless steel is revealed based on the APT analysis.

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

DOE PAGES

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun; ...

2017-04-27

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

X-ray absorption investigation of local structural disorder in Ni 1-xFe x (x=0.10, 0.20, 0.35, and 0.50) alloys

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

Zhang, Fuxiang X.; Jin, Ke; Zhao, Shijun

Defect energetics in structural materials has long been recognized to be affected by specific alloy compositions. Significantly enhanced radiation resistance has recently been observed in concentrated solid-solution alloys. However, the link between local structural disorder and modified defect dynamics in solid solutions remains unclear. To reveal the atomic-level lattice distortion, the local structures of Ni and Fe in Ni 1-xFe x (x=0.1, 0.2, 0.35 and 0.5) solid solution alloys were measured with extended X-ray absorption fine structure (EXAFS) technique. The lattice constant and the first-neighbor distances increase with the increase of Fe content in the solid solutions. EXAFS measurements havemore » revealed that the bond length of Fe with surrounding atoms is 0.01-0.03 larger than that of Ni in the alloy systems. Debye-Waller factor of the Fe-Fe bonds in all the systems is also slightly larger than that of the Ni-Ni bond. EXAFS fitting suggests that the local structural disorder is enhanced with the addition of Fe elements in the solid solution. The local bonding environments from ab initio calculation are in good agreement with the experimental results, which suggest that the Fe has a larger first-neighbor bonding distance than that of Ni, and thus Ni atom inside the Ni-Fe solid solution alloys undergoes compressive strain.« less

Influence of 300°C thermal conversion of Fe-Ce hydrous oxides prepared by hydrothermal precipitation on the adsorptive performance of five anions: Insights from EXAFS/XANES, XRD and FTIR (companion paper).

PubMed

Chubar, Natalia; Gerda, Vasyl; Banerjee, Dipanjan

2017-04-01

In this work, we report atomic-scale reconstruction processes in Fe-Ce oxide-based composites (hydrothermally precipitated at Fe-to-Ce dosage ratios of 1:0, 2:1, 1:1, 1:2, and 0:1), upon treatment at 300°C. The structural changes are correlated with the adsorptive removal of arsenate, phosphate, fluoride, bromide, and bromate. The presence of the carbonate-based Ce-component and surface sulfate in precursor samples creates favorable conditions for phase transformation, resulting in the formation of novel (unknown) layered compounds of Fe and Ce. These compounds are of the layered double hydroxide type, with sulfate in the interlayer space. In spite of general awareness of the importance of surface area in adsorptive removal, the increase in surface area upon thermal treatment did not increase adsorption of the studied anions. However, EXAFS simulations and the adsorption tests provided evidence of regularities between local structures of Fe in composites obtained at 80 and 300°C and adsorption performance of most studied anions. The best adsorption of tetrahedral anions was demonstrated by samples whose simulated outer Fe shells resulted from oscillations from both O and Fe atoms. In contrast, the loss of extended x-ray absorption fine structure was correlated with the decrease of adsorptive removal. Both Fe K-edge and Ce L 3 -edge EXAFS suggested the formation of solid solutions. For the first time, the utilization of extended x-ray absorption fine structure is suggested as a methodological approach (first expressed in the companion paper) to estimate the surface reactivity of inorganic materials intended for use as anion exchange adsorbents. Copyright © 2016 Elsevier Inc. All rights reserved.

Surface and local electronic structure modification of MgO film using Zn and Fe ion implantation

NASA Astrophysics Data System (ADS)

Singh, Jitendra Pal; Lim, Weon Cheol; Lee, Jihye; Song, Jonghan; Lee, Ik-Jae; Chae, Keun Hwa

2018-02-01

Present work is motivated to investigate the surface and local electronic structure modifications of MgO films implanted with Zn and Fe ions. MgO film was deposited using radio frequency sputtering method. Atomic force microscopy measurements exhibit morphological changes associated with implantation. Implantation of Fe and Zn ions leads to the reduction of co-ordination geometry of Mg2+ ions in host lattice. The effect is dominant at bulk of film rather than surface as the large concentration of implanted ions resides inside bulk. Moreover, the evidences of interaction among implanted ions and oxygen are not being observed using near edge fine structure measurements.

Effective collision strengths for fine-structure forbidden transitions among the 3s^23p^3 levels of K V

NASA Astrophysics Data System (ADS)

Bell, Kenneth; Wilson, Nigel

2001-05-01

Electron temperatures and densities are difficult to determine in many astrophysical plasmas. However, it is well known that diagnostics on forbidden line intensity ratios for ions in the phosphorous isoelectronic sequence are of great importance in astrophysics, particularly for nebulae. A key element in the analysis is highly accurate atomic data. In this work we extend the earlier calculations of Butler, Zeippen and Le Bourlot (Astron. Astrophys. 203 189 (1988)) on electron scattering by K v. We have obtained effective collision strengths for a wide range of electron temperatures using the R-matrix method. Twenty-two LS target eigenstates are included in the expansion of the total wavefunction, consisting of the seven n=3 states with configuration 3s^23p^3 and 3s3p^4, twelve n=3 states with configuration 3s^23p^23d, and three n=4 states with configuration 3s^23p^24s. The fine-structure collision strengths have been obtained by transforming to a jj-coupling scheme using the JAJOM program of Saraph (Comp. Phys. Commun. 15 247 (1978)) and have been determined at a sufficiently fine energy mesh to delineate properly the resonance structure. Results for both collision strengths and for effective collision strengths will be presented at the conference and comparison will be made with the earlier work.

The Orion Nebula in the Far-Infrared: High-J CO and fine-structure lines mapped by FIFI-LS/SOFIA

NASA Astrophysics Data System (ADS)

Klein, Randolf; Looney, Leslie W.; Cox, Erin; Fischer, Christian; Iserlohe, Christof; Krabbe, Alfred

2017-03-01

The Orion Nebula is the closest massive star forming region allowing us to study the physical conditions in such a region with high spatial resolution. We used the far infrared integral-field spectrometer, FIFI-LS, on-board the airborne observatory SOFIA to study the atomic and molecular gas in the Orion Nebula at medium spectral resolution. The large maps obtained with FIFI-LS cover the nebula from the BN/KL-object to the bar in several fine structure lines. They allow us to study the conditions of the photon-dominated region and the interface to the molecular cloud with unprecedented detail. Another investigation targeted the molecular gas in the BN/KL region of the Orion Nebula, which is stirred up by a violent explosion about 500 years ago. The explosion drives a wide angled molecular outflow. We present maps of several high-J CO observations, allowing us to analyze the heated molecular gas.

Single Cobalt Atoms with Precise N-Coordination as Superior Oxygen Reduction Reaction Catalysts.

PubMed

Yin, Peiqun; Yao, Tao; Wu, Yuen; Zheng, Lirong; Lin, Yue; Liu, Wei; Ju, Huanxin; Zhu, Junfa; Hong, Xun; Deng, Zhaoxiang; Zhou, Gang; Wei, Shiqiang; Li, Yadong

2016-08-26

A new strategy for achieving stable Co single atoms (SAs) on nitrogen-doped porous carbon with high metal loading over 4 wt % is reported. The strategy is based on a pyrolysis process of predesigned bimetallic Zn/Co metal-organic frameworks, during which Co can be reduced by carbonization of the organic linker and Zn is selectively evaporated away at high temperatures above 800 °C. The spherical aberration correction electron microscopy and extended X-ray absorption fine structure measurements both confirm the atomic dispersion of Co atoms stabilized by as-generated N-doped porous carbon. Surprisingly, the obtained Co-Nx single sites exhibit superior ORR performance with a half-wave potential (0.881 V) that is more positive than commercial Pt/C (0.811 V) and most reported non-precious metal catalysts. Durability tests revealed that the Co single atoms exhibit outstanding chemical stability during electrocatalysis and thermal stability that resists sintering at 900 °C. Our findings open up a new routine for general and practical synthesis of a variety of materials bearing single atoms, which could facilitate new discoveries at the atomic scale in condensed materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cytochrome C in a dry trehalose matrix: structural and dynamical effects probed by x-ray absorption spectroscopy.

PubMed

Giachini, Lisa; Francia, Francesco; Cordone, Lorenzo; Boscherini, Federico; Venturoli, Giovanni

2007-02-15

We report on the structure and dynamics of the Fe ligand cluster of reduced horse heart cytochrome c in solution, in a dried polyvinyl alcohol (PVA) film, and in two trehalose matrices characterized by different contents of residual water. The effect of the solvent/matrix environment was studied at room temperature using Fe K-edge x-ray absorption fine structure (XAFS) spectroscopy. XAFS data were analyzed by combining ab initio simulations and multi-parameter fitting in an attempt to disentangle structural from disorder parameters. Essentially the same structural and disorder parameters account adequately for the XAFS spectra measured in solution, both in the absence and in the presence of glycerol, and in the PVA film, showing that this polymer interacts weakly with the embedded protein. Instead, incorporation in trehalose leads to severe structural changes, more prominent in the more dried matrix, consisting of 1), an increase up to 0.2 A of the distance between Fe and the imidazole N atom of the coordinating histidine residue and 2), an elongation up to 0.16 A of the distance between Fe and the fourth-shell C atoms of the heme pyrrolic units. These structural distortions are accompanied by a substantial decrease of the relative mean-square displacements of the first ligands. In the extensively dried trehalose matrix, extremely low values of the Debye Waller factors are obtained for the pyrrolic and for the imidazole N atoms. This finding is interpreted as reflecting a drastic hindering in the relative motions of the Fe ligand cluster atoms and an impressive decrease in the static disorder of the local Fe structure. It appears, therefore, that the dried trehalose matrix dramatically perturbs the energy landscape of cytochrome c, giving rise, at the level of local structure, to well-resolved structural distortions and restricting the ensemble of accessible conformational substates.

Electron impact excitation of N IV: calculations with the DARC code and a comparison with ICFT results

NASA Astrophysics Data System (ADS)

Aggarwal, K. M.; Keenan, F. P.; Lawson, K. D.

2016-10-01

There have been discussions in the recent literature regarding the accuracy of the available electron impact excitation rates (equivalently effective collision strengths Υ) for transitions in Be-like ions. In the present paper we demonstrate, once again, that earlier results for Υ are indeed overestimated (by up to four orders of magnitude), for over 40 per cent of transitions and over a wide range of temperatures. To do this we have performed two sets of calculations for N IV, with two different model sizes consisting of 166 and 238 fine-structure energy levels. As in our previous work, for the determination of atomic structure the GRASP (General-purpose Relativistic Atomic Structure Package) is adopted and for the scattering calculations (the standard and parallelised versions of) the Dirac Atomic R-matrix Code (DARC) are employed. Calculations for collision strengths and effective collision strengths have been performed over a wide range of energy (up to 45 Ryd) and temperature (up to 2.0 × 106 K), useful for applications in a variety of plasmas. Corresponding results for energy levels, lifetimes and A-values for all E1, E2, M1 and M2 transitions among 238 levels of N IV are also reported.

Investigation of gamma radiation induced changes in local structure of borosilicate glass by TDPAC and EXAFS

NASA Astrophysics Data System (ADS)

Kumar, Ashwani; Nayak, C.; Rajput, P.; Mishra, R. K.; Bhattacharyya, D.; Kaushik, C. P.; Tomar, B. S.

2016-12-01

Gamma radiation induced changes in local structure around the probe atom (Hafnium) were investigated in sodium barium borosilicate (NBS) glass, used for immobilization of high level liquid waste generated from the reprocessing plant at Trombay, Mumbai. The (NBS) glass was doped with 181Hf as a probe for time differential perturbed angular correlation (TDPAC) spectroscopy studies, while for studies using extended X-ray absorption fine structure (EXAFS) spectroscopy, the same was doped with 0.5 and 2 % (mole %) hafnium oxide. The irradiated as well as un-irradiated glass samples were studied by TDPAC and EXAFS techniques to obtain information about the changes (if any) around the probe atom due to gamma irradiation. TDPAC spectra of unirradiated and irradiated glasses were similar and reminescent of amorphous materials, indicating negligible effect of gamma radiation on the microstructure around Hafnium probe atom, though the quaqdrupole interaction frequency ( ω Q) and asymmetry parameter ( η) did show a marginal decrease in the irradiated glass compared to that in the unirradiated glass. EXAFS measurements showed a slight decrease in the Hf-O bond distance upon gamma irradiation of Hf doped NBS glass indicating densification of the glass matrix, while the cordination number around hafnium remains unchanged.

Dirac R-matrix calculations of photoionization cross sections of Ni XII and atomic structure data of Ni XIII

NASA Astrophysics Data System (ADS)

Nazir, R. T.; Bari, M. A.; Bilal, M.; Sardar, S.; Nasim, M. H.; Salahuddin, M.

2017-02-01

We performed R-matrix calculations for photoionization cross sections of the two ground state configuration 3s23p5 (^2P^o3/2,1/2) levels and 12 excited states of Ni XII using relativistic Dirac Atomic R-matrix Codes (DARC) across the photon energy range between the ionizations thresholds of the corresponding states and well above the thresholds of the last level of the Ni XIII target ion. Generally, a good agreement is obtained between our results and the earlier theoretical photoionization cross sections. Moreover, we have used two independent fully relativistic GRASP and FAC codes to calculate fine-structure energy levels, wavelengths, oscillator strengths, transitions rates among the lowest 48 levels belonging to the configuration (3s23p4, 3s3p5, 3p6, 3s23p33d) in Ni XIII. Additionally, radiative lifetimes of all the excited states of Ni XIII are presented. Our results of the atomic structure of Ni XIII show good agreement with other theoretical and experimental results available in the literature. A good agreement is found between our calculated lifetimes and the experimental ones. Our present results are useful for plasma diagnostic of fusion and astrophysical plasmas.

New Quasar Studies Keep Fundamental Physical Constant Constant

NASA Astrophysics Data System (ADS)

2004-03-01

Very Large Telescope sets stringent limit on possible variation of the fine-structure constant over cosmological time Summary Detecting or constraining the possible time variations of fundamental physical constants is an important step toward a complete understanding of basic physics and hence the world in which we live. A step in which astrophysics proves most useful. Previous astronomical measurements of the fine structure constant - the dimensionless number that determines the strength of interactions between charged particles and electromagnetic fields - suggested that this particular constant is increasing very slightly with time. If confirmed, this would have very profound implications for our understanding of fundamental physics. New studies, conducted using the UVES spectrograph on Kueyen, one of the 8.2-m telescopes of ESO's Very Large Telescope array at Paranal (Chile), secured new data with unprecedented quality. These data, combined with a very careful analysis, have provided the strongest astronomical constraints to date on the possible variation of the fine structure constant. They show that, contrary to previous claims, no evidence exist for assuming a time variation of this fundamental constant. PR Photo 07/04: Relative Changes with Redshift of the Fine Structure Constant (VLT/UVES) A fine constant To explain the Universe and to represent it mathematically, scientists rely on so-called fundamental constants or fixed numbers. The fundamental laws of physics, as we presently understand them, depend on about 25 such constants. Well-known examples are the gravitational constant, which defines the strength of the force acting between two bodies, such as the Earth and the Moon, and the speed of light. One of these constants is the so-called "fine structure constant", alpha = 1/137.03599958, a combination of electrical charge of the electron, the Planck constant and the speed of light. The fine structure constant describes how electromagnetic forces hold atoms together and the way light interacts with atoms. But are these fundamental physical constants really constant? Are those numbers always the same, everywhere in the Universe and at all times? This is not as naive a question as it may seem. Contemporary theories of fundamental interactions, such as the Grand Unification Theory or super-string theories that treat gravity and quantum mechanics in a consistent way, not only predict a dependence of fundamental physical constants with energy - particle physics experiments have shown the fine structure constant to grow to a value of about 1/128 at high collision energies - but allow for their cosmological time and space variations. A time dependence of the fundamental constants could also easily arise if, besides the three space dimensions, there exist more hidden dimensions. Already in 1955, the Russian physicist Lev Landau considered the possibility of a time dependence of alpha. In the late 1960s, George Gamow in the United States suggested that the charge of the electron, and therefore also alpha, may vary. It is clear however that such changes, if any, cannot be large or they would already have been detected in comparatively simple experiments. Tracking these possible changes thus requires the most sophisticated and precise techniques. Looking back in time In fact, quite strong constraints are already known to exist for the possible variation of the fine structure constant alpha. One such constraint is of geological nature. It is based on measures taken in the ancient natural fission reactor located near Oklo (Gabon, West Africa) and which was active roughly 2,000 million years ago. By studying the distribution of a given set of elements - isotopes of the rare earths, for example of samarium - which were produced by the fission of uranium, one can estimate whether the physical process happened at a faster or slower pace than we would expect it nowadays. Thus we can measure a possible change of the value of the fundamental constant at play here, alpha. However, the observed distribution of the elements is consistent with calculations assuming that the value of alpha at that time was precisely the same as the value today. Over the 2 billion years, the change of alpha has therefore to be smaller than about 2 parts per 100 millions. If present at all, this is a rather small change indeed. But what about changes much earlier in the history of the Universe? To measure this we must find means to probe still further into the past. And this is where astronomy can help. Because, even though astronomers can't generally do experiments, the Universe itself is a huge atomic physics laboratory. By studying very remote objects, astronomers can look back over a long time span. In this way it becomes possible to test the values of the physical constants when the Universe had only 25% of is present age, that is, about 10,000 million years ago. Very far beacons To do so, astronomers rely on spectroscopy - the measurement of the properties of light emitted or absorbed by matter. When the light from a flame is observed through a prism, a rainbow is visible. When sprinkling salt on the flame, distinct yellow lines are superimposed on the usual colours of the rainbow, so-called emission lines. Putting a gas cell between the flame and the prism, one sees however dark lines onto the rainbow: these are absorption lines. The wavelength of these emission and absorption lines is directly related to the energy levels of the atoms in the salt or in the gas. Spectroscopy thus allows us to study atomic structure. The fine structure of atoms can be observed spectroscopically as the splitting of certain energy levels in those atoms. So if alpha were to change over time, the emission and absorption spectra of these atoms would change as well. One way to look for any changes in the value of alpha over the history of the Universe is therefore to measure the spectra of distant quasars, and compare the wavelengths of certain spectral lines with present-day values. Quasars are here only used as a beacon - the flame - in the very distant Universe. Interstellar clouds of gas in galaxies, located between the quasars and us on the same line of sight and at distances varying from six to eleven thousand of million light years, absorb parts of the light emitted by the quasars. The resulting spectrum consequently presents dark "valleys" that can be attributed to well-known elements. If the fine-structure constant happens to change over the duration of the light's journey, the energy levels in the atoms would be affected and the wavelengths of the absorption lines would be shifted by different amounts. By comparing the relative gaps between the valleys with the laboratory values, it is possible to calculate alpha as a function of distance from us, that is, as a function of the age of the Universe. These measures are however extremely delicate and require a very good modelling of the absorption lines. They also put exceedingly strong requirements on the quality of the astronomical spectra. They must have enough resolution to allow very precise measurement of minuscule shifts in the spectra. And a sufficient number of photons must be captured in order to provide a statistically unambiguous result. For this, astronomers have to turn to the most advanced spectral instruments on the largest telescopes. This is where the Ultra-violet and Visible Echelle Spectrograph (UVES) and ESO's Kueyen 8.2-m telescope at the Paranal Observatory is unbeatable, thanks to the unequalled spectral quality and large collecting mirror area of this combination. Constant or not? ESO PR Photo 07/04 ESO PR Photo 07/04 Relative Changes with Redshift of the Fine Structure Constant [Preview - JPEG: 496 x 400 pix - 36k] [Normal - JPEG: 991 x 800 pix - 320k] Captions: ESO PR Photo 07/04 shows measured values of the relative change of alpha from the sample of absorption systems studied by Hum Chand and his colleagues, plotted as a function of the redshift and the corresponding look-back time. The open circle is the measurement from the Oklo natural reactor. The horizontal long dashed lines show the area of the previous claim of variation of the fine structure constant. Clearly, the new UVES data are inconsistent with this range. A team of astronomers [1], led by Patrick Petitjean (Institut d'Astrophysique de Paris and Observatoire de Paris, France) and Raghunathan Srianand (IUCAA Pune, India) very carefully studied a homogeneous sample of 50 absorption systems observed with UVES and Kueyen along 18 distant quasars lines of sight. They recorded the spectra of quasars over a total of 34 nights to achieve the highest possible spectral resolution and the best signal-to-noise ratio. Sophisticated automatic procedures specially designed for this programme were applied. In addition, the astronomers used extensive simulations to show that they can correctly model the line profiles to recover a possible variation of alpha. The result of this extensive study is that over the last 10,000 million years, the relative variation of alpha must be less than 0.6 part per million. This is the strongest constraint from quasar absorption lines studies to date. More importantly, this new result does not support previous claims of a statistically significant change of alpha with time. Interestingly, this result is supported by another - less extensive - analysis, also conducted with the UVES spectrometer on the VLT [2]. Even though those observations were only concerned with one of the brightest known quasar HE 0515-4414, this independent study lends further support to the hypothesis of no variation of alpha. Even though these new results represent a significant improvement in our knowledge of the possible (non-) variation of one of the fundamental physical constants, the present set of data would in principle still allow variations that are comparatively large compared to those resulting from the measurements from the Oklo natural reactor. Nevertheless, further progress in this field is expected with the new very-high-accuracy radial velocity spectrometer HARPS on ESO's 3.6-m telescope at the La Silla Observatory (Chile). This spectrograph works at the limit of modern technology and is mostly used to detect new planets around stars other than the Sun - it may provide an order of magnitude improvement on the determination of the variation of alpha. Other fundamental constants can be probed using quasars. In particular, by studying the wavelengths of molecular hydrogen in the remote Universe, one can probe the variations of the ratio between the masses of the proton and the electron. The same team is now engaged in such a large survey with the Very Large Telescope that should lead to unprecedented constraints on this ratio. More Information The research presented in this Press Release is based on papers published in Physical Review Letters ("Limits on the time variation of the electromagnetic fine-structure constant in the low energy limit from absorption lines in the spectra of distant quasars" by Raghunathan Srianand, Hum Chand, Patrick Petitjean, and Bastien Aracil) and in the leading European astronomy journal Astronomy & Astrophysics ("Probing the cosmological variation of the fine-structure constant: Results based on VLT-UVES sample" by Hum Chand, Raghunathan Srianand, Patrick Petitjean, and Bastien Aracil).

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

Levin, I.; Krayzman, V.; Woicik, J. C.

Local structures in cubic perovskite-type (Ba 0.6Bi 0.4)(Ti 0.6Sc 0.4)O 3 solid solutions that exhibit reentrant dipole glass behavior have been studied with variable-temperature x-ray/neutron total scattering, extended x-ray absorption fine structure, and electron diffraction methods. Simultaneous fitting of these data using a reverse Monte Carlo algorithm provided instantaneous atomic configurations, which have been used to extract local displacements of the constituent species. The smaller Bi and Ti atoms exhibit probability density distributions that consist of 14 and 8 split sites, respectively. In contrast, Ba and Sc feature single-site distributions. The multisite distributions arise from large and strongly anisotropic off-centermore » displacements of Bi and Ti. The cation displacements are correlated over a short range, with a correlation length limited by chemical disorder. The magnitudes of these displacements and their anisotropy, which are largely determined by local chemistry, change relatively insignificantly on cooling from room temperature. The structure features a nonrandom distribution of local polarization with low-dimensional polar clusters that are several unit cells in size. In situ measurements of atomic pair-distribution function under applied electric field were used to study field-induced changes in the local structure; however, no significant effects besides lattice expansion in the direction of the field could be observed up to electric-field values of 4 kVmm -1.« less

Disentangling neighbors and extended range density oscillations in monatomic amorphous semiconductors.

PubMed

Roorda, S; Martin, C; Droui, M; Chicoine, M; Kazimirov, A; Kycia, S

2012-06-22

High energy x-ray diffraction measurements of pure amorphous Ge were made and its radial distribution function (RDF) was determined at high resolution, revealing new information on the atomic structure of amorphous semiconductors. Fine structure in the second peak in the RDF provides evidence that a fraction of third neighbors are closer than some second neighbors; taking this into account leads to a narrow distribution of tetrahedral bond angles, (8.5 ± 0.1)°. A small peak which appears near 5 Å upon thermal annealing shows that some ordering in the dihedral bond-angle distribution takes place during structural relaxation. Extended range order is detected (in both a-Ge and a-Si) which persists to beyond 20 Å, and both the periodicity and its decay length increase upon thermal annealing. Previously, the effect of structural relaxation was only detected at intermediate range, involving reduced tetrahedral bond-angle distortions. These results enhance our understanding of the atomic order in continuous random networks and place significantly more stringent requirements on computer models intending to describe these networks, or their alternatives which attempt to describe the structure in terms of an arrangement of paracrystals.

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

Tian, Liang; Ames Lab. and Iowa State Univ., Ames, IA; Anderson, Iver

Recently, a novel Al/Ca composite was produced by severe plastic deformation of Al powders and Ca granules for possible use as a high-voltage power transmission conductor. Since the strength of such composites is inversely proportional to the Ca filament size, fine Ca powders (less than ~250 μm) are needed to achieve the desired high strength for the powder metallurgy production of an Al-matrix composite reinforced by nano-scale Ca filaments. However, fine Ca powders are not commercially available. Therefore, we have developed a method to produce fine Ca powders via centrifugal atomization to supply Ca powder for prototype development of Al/Camore » composite conductor. A secondary goal of the project was to demonstrate that Ca powder can be safely prepared, stored, and handled and could potentially be scaled for commercial production. Our results showed that centrifugal atomization can yield as much as 83 vol. % Ca powder particles smaller than 250 μm. The mean particle size sometimes matches, sometimes deviates substantially from the predictions of the Champagne & Anger equation likely due to unexpected secondary atomization. The particle size distribution is typical for a ligament-disintegration atomization mode. Scanning electron micrographs showed that the morphology of these Ca powders varied with powder size. Spark testing and auto-ignition tests indicated that the atomized powders were difficult to ignite, providing confidence that this material can be handled safely in air.« less

Modern steels at atomic and nanometre scales

DOE PAGES

Caballero, F. G.; Garcia-Mateo, C.; Miller, M. K.

2014-10-10

Processing bulk nanocrystalline materials for structural applications still poses a difficult challenge, particularly in achieving an industrially viable process. Recent work in ferritic steels has proved that it is possible to move from ultrafine to nanoscale by exploiting the bainite reaction without the use of severe deformation, rapid heat treatment or mechanical processing. This new generation of steels has been designed in which transformation at low temperature leads to a nanoscale structure consisting of extremely fine, 20–40 nm thick plates of bainitic ferrite and films of retained austenite. Finally, a description of the characteristics and significance of this remarkable microstructuremore » is provided here.« less

Atomistic Model of Physical Ageing in Se-rich As-Se Glasses

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

Golovchak,R.; Shpotyuk, O.; Kozdras, A.

2007-01-01

Thermal, optical, X-ray excited and magnetic methods were used to develop a microstructural model of physical ageing in Se-rich glasses. The glass composition As10Se90, possessing a typical cross-linked chain structure, was chosen as a model object for the investigations. The effect of physical ageing in this glass was revealed by differential scanning calorimetry, whereas the corresponding changes in its atomic arrangement were studied by extended X-ray absorption fine structure, Raman and solid-state 77Se nuclear magnetic resonance spectroscopy. Straightening-shrinkage processes are shown to be responsible for the physical ageing in this Se-rich As-Se glass.

Local structure in BaTi O 3 - BiSc O 3 dipole glasses

DOE PAGES

Levin, I.; Krayzman, V.; Woicik, J. C.; ...

2016-03-14

Local structures in cubic perovskite-type (Ba 0.6Bi 0.4)(Ti 0.6Sc 0.4)O 3 solid solutions that exhibit reentrant dipole glass behavior have been studied with variable-temperature x-ray/neutron total scattering, extended x-ray absorption fine structure, and electron diffraction methods. Simultaneous fitting of these data using a reverse Monte Carlo algorithm provided instantaneous atomic configurations, which have been used to extract local displacements of the constituent species. The smaller Bi and Ti atoms exhibit probability density distributions that consist of 14 and 8 split sites, respectively. In contrast, Ba and Sc feature single-site distributions. The multisite distributions arise from large and strongly anisotropic off-centermore » displacements of Bi and Ti. The cation displacements are correlated over a short range, with a correlation length limited by chemical disorder. The magnitudes of these displacements and their anisotropy, which are largely determined by local chemistry, change relatively insignificantly on cooling from room temperature. The structure features a nonrandom distribution of local polarization with low-dimensional polar clusters that are several unit cells in size. In situ measurements of atomic pair-distribution function under applied electric field were used to study field-induced changes in the local structure; however, no significant effects besides lattice expansion in the direction of the field could be observed up to electric-field values of 4 kVmm -1.« less

Atomization of liquid fuels. Part I

NASA Technical Reports Server (NTRS)

Kuehn,

1925-01-01

In the present treatise we will consider chiefly the problem of solid injection in comparison with air injection. On leaving the valve or nozzle through one or more small openings, the fuel is split up into innumerable fine drops, which penetrate the combustion chamber in divergent directions in the form of a conical jet. The efficiency of this jet is judged from the following three viewpoints: 1) with respect to the fineness of atomization; 2) with respect to the direction or distribution of sprayed particles; 3) with respect to the penetration of the particles.

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

NASA Astrophysics Data System (ADS)

McBriarty, Martin E.

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

Widths of atomic 4s and 4p vacancy states, 46 less than or equal to Z less than or equal to 50

NASA Technical Reports Server (NTRS)

Hsiungchen, M.; Crasemann, B.; Yin, L. I.; Tsang, T.; Adler, I.

1975-01-01

Auger and X-ray photoelectron spectra involving N1, N2, and N3 vacancy states of Pd, Ag, Cd, In, and Sn were measured and compared with results of free atom calculations. As previously observed in Cu and Zn Auger spectra that involve 3d-band electrons, free-atom characteristics with regard to widths and structure were found in the Ag and Cd M4-N4,5N4,5 and M5-N4,5N4,5 Auger spectra that arise from transitions of 4d-band electrons. Theoretical N1 widths computed with calculated free-atom Auger energies agree well with measurements. Theory however predicts wider N2 than N3 vacancy states (as observed for Xe), while the measured N2 and N3 widths are nearly equal to each other and to the average of the calculated N2 and N3 widths. The calculations are made difficult by the exceedingly short lifetime of some 4p vacancies and by the extreme sensitivity of super-Coster-Kronig rates, which dominate the deexcitation, to the transition energy and to the fine details of the atomic potential.

Atomic layer confined vacancies for atomic-level insights into carbon dioxide electroreduction

NASA Astrophysics Data System (ADS)

Gao, Shan; Sun, Zhongti; Liu, Wei; Jiao, Xingchen; Zu, Xiaolong; Hu, Qitao; Sun, Yongfu; Yao, Tao; Zhang, Wenhua; Wei, Shiqiang; Xie, Yi

2017-02-01

The role of oxygen vacancies in carbon dioxide electroreduction remains somewhat unclear. Here we construct a model of oxygen vacancies confined in atomic layer, taking the synthetic oxygen-deficient cobalt oxide single-unit-cell layers as an example. Density functional theory calculations demonstrate the main defect is the oxygen(II) vacancy, while X-ray absorption fine structure spectroscopy reveals their distinct oxygen vacancy concentrations. Proton transfer is theoretically/experimentally demonstrated to be a rate-limiting step, while energy calculations unveil that the presence of oxygen(II) vacancies lower the rate-limiting activation barrier from 0.51 to 0.40 eV via stabilizing the formate anion radical intermediate, confirmed by the lowered onset potential from 0.81 to 0.78 V and decreased Tafel slope from 48 to 37 mV dec-1. Hence, vacancy-rich cobalt oxide single-unit-cell layers exhibit current densities of 2.7 mA cm-2 with ca. 85% formate selectivity during 40-h tests. This work establishes a clear atomic-level correlation between oxygen vacancies and carbon dioxide electroreduction.

Ethene adsorption and dehydrogenation on clean and oxygen precovered Ni(111) studied by high resolution x-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Lorenz, M. P. A.; Fuhrmann, T.; Streber, R.; Bayer, A.; Bebensee, F.; Gotterbarm, K.; Kinne, M.; Tränkenschuh, B.; Zhu, J. F.; Papp, C.; Denecke, R.; Steinrück, H.-P.

2010-07-01

The adsorption and thermal evolution of ethene (ethylene) on clean and oxygen precovered Ni(111) was investigated with high resolution x-ray photoelectron spectroscopy using synchrotron radiation at BESSY II. The high resolution spectra allow to unequivocally identify the local environment of individual carbon atoms. Upon adsorption at 110 K, ethene adsorbs in a geometry, where the two carbon atoms within the intact ethene molecule occupy nonequivalent sites, most likely hollow and on top; this new result unambiguously solves an old puzzle concerning the adsorption geometry of ethene on Ni(111). On the oxygen precovered surface a different adsorption geometry is found with both carbon atoms occupying equivalent hollow sites. Upon heating ethene on the clean surface, we can confirm the dehydrogenation to ethine (acetylene), which adsorbs in a geometry, where both carbon atoms occupy equivalent sites. On the oxygen precovered surface dehydrogenation of ethene is completely suppressed. For the identification of the adsorbed species and the quantitative analysis the vibrational fine structure of the x-ray photoelectron spectra was analyzed in detail.

Fine structural features of nanoscale zero-valent iron characterized by spherical aberration corrected scanning transmission electron microscopy (Cs-STEM).

PubMed

Liu, Airong; Zhang, Wei-xian

2014-09-21

An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI.

Spontaneous formation of suboxidic coordination around Co in ferromagnetic rutile Ti 0.95Co 0.5O 2 film

DOE PAGES

Hu, Wen; Hayaski, Kouichi; Fukumura, Tomoteru; ...

2015-06-02

To evaluate local atomic structures around Co in high temperature diluted ferromagnetic semiconductor Co-doped TiO 2, x-ray fluorescence holography and x-ray absorption fine structure experiments were carried out on rutile paramagnetic Ti 0.99Co 0.01O 2 and ferromagnetic Ti 0.95Co 0.05O 2 films. The Co atoms in the Ti 0.99Co 0.01O 2 simply substituted for Ti sites in the rutile structure, whereas a suboxidic arrangement of CoO 2Ti 4 formed around Co in the Ti 0.95Co 0.05O 2 films. A theoretical investigation based on a series of first-principles calculations indicated the stability of the aggregated suboxidic clusters in the rutile TiOmore » 2, supporting our hypothesis for the formation of suboxidic coordination in the highly Co-doped sample. As a result, the suboxidic coordination may be the source of strong exchange interaction, resulting in the high Curie temperature in Co-doped TiO 2.« less

Atomizing nozzle and process

DOEpatents

Anderson, I.E.; Figliola, R.S.; Molnar, H.M.

1993-07-20

High pressure atomizing nozzle includes a high pressure gas manifold having a divergent expansion chamber between a gas inlet and arcuate manifold segment to minimize standing shock wave patterns in the manifold and thereby improve filling of the manifold with high pressure gas for improved melt atomization. The atomizing nozzle is especially useful in atomizing rare earth-transition metal alloys to form fine powder particles wherein a majority of the powder particles exhibit particle sizes having near-optimum magnetic properties.

Atomizing nozzle and process

DOEpatents

Anderson, Iver E.; Figliola, Richard S.; Molnar, Holly M.

1992-06-30

High pressure atomizing nozzle includes a high pressure gas manifold having a divergent expansion chamber between a gas inlet and arcuate manifold segment to minimize standing shock wave patterns in the manifold and thereby improve filling of the manifold with high pressure gas for improved melt atomization. The atomizing nozzle is especially useful in atomizing rare earth-transition metal alloys to form fine powder particles wherein a majority of the powder particles exhibit particle sizes having near-optimum magnetic properties.

Facet control of gold nanorods

DOE PAGES

Zhang, Qingfeng; Han, Lili; Jing, Hao; ...

2016-01-21

While great success has been achieved in fine-tuning the aspect ratios and thereby the plasmon resonances of cylindrical Au nanorods, facet control with atomic level precision on the highly curved nanorod surfaces has long been a significantly more challenging task. The intrinsic structural complexity and lack of precise facet control of the nanorod surfaces remain the major obstacles for the atomic-level elucidation of the structure–property relationships that underpin the intriguing catalytic performance of Au nanorods. Here we demonstrate that the facets of single-crystalline Au nanorods can be precisely tailored using cuprous ions and cetyltrimethylammonium bromide as a unique pair ofmore » surface capping competitors to guide the particle geometry evolution during nanorod overgrowth. By deliberately maneuvering the competition between cuprous ions and cetyltrimethylammonium bromide, we have been able to create, in a highly controllable and selective manner, an entire family of nanorod-derived anisotropic multifaceted geometries whose surfaces are enclosed by specific types of well-defined high-index and low-index facets. This facet-controlled nanorod overgrowth approach also allows us to fine-tune the particle aspect ratios while well-preserving all the characteristic facets and geometric features of the faceted Au nanorods. Furthermore, taking full advantage of the combined structural and plasmonic tunability, we have further studied the facet-dependent heterogeneous catalysis on well-faceted Au nanorods using surface-enhanced Raman spectroscopy as an ultrasensitive spectroscopic tool with unique time-resolving and molecular finger-printing capabilities.« less

Atomic Processes and Diagnostics of Low Pressure Krypton Plasma

NASA Astrophysics Data System (ADS)

Srivastava, Rajesh; Goyal, Dipti; Gangwar, Reetesh; Stafford, Luc

2015-03-01

Optical emission spectroscopy along with suitable collisional-radiative (CR) model is used in plasma diagnostics. Importance of reliable cross-sections for various atomic processes is shown for low pressure argon plasma. In the present work, radially-averaged Kr emission lines from the 2pi --> 1sj were recorded as a function of pressure from 1 to 50mTorr. We have developed a CR model using our fine-structure relativistic-distorted wave cross sections. The various processes considered are electron-impact excitation, ionization and their reverse processes. The required rate coefficients have been calculated from these cross-sections assuming Maxwellian energy distribution. Electron temperature obtained from the CR model is found to be in good agreement with the probe measurements. Work is supported by IAEA Vienna, DAE-BRNS Mumbai and CSIR, New Delhi.

Fine-grained BaZr0.2Ti0.8O3 thin films for tunable device applications

NASA Astrophysics Data System (ADS)

Ying, Z.; Yun, P.; Wang, D. Y.; Zhou, X. Y.; Song, Z. T.; Feng, S. L.; Wang, Y.; Chan, H. L. W.

2007-04-01

A study of the structure and in-plane dielectric properties of BaZr0.2Ti0.8O3 thin film epitaxially grown on (LaAlO3)0.3(Sr2AlTaO6)0.35 (001) single-crystal substrates through pulsed-laser deposition has been carried out. X-ray diffraction measurements revealed a good crystallinity and tensile in-plane stress in the film. Fine grains with an average size of ˜20 nm were observed using atomic force microscopy. Curie temperature of the film was found to be ˜120 °C, which is 100 °C higher than that of the ceramic. Butterfly-shaped C-V curve confirmed the in-plane ferroelectric state in the film. A large dielectric tunability of ˜50% was found in the film.

A New Maraging Stainless Steel with Excellent Strength–Toughness–Corrosion Synergy

PubMed Central

Tian, Jialong; Wang, Wei; Babar Shahzad, M.; Yan, Wei; Shan, Yiyin; Jiang, Zhouhua; Yang, Ke

2017-01-01

A new maraging stainless steel with superior strength–toughness–corrosion synergy has been developed based on an innovative concept of alloy design. The high strength–toughness combination is achieved by forming dispersive nano-sized intermetallic compounds in the soft lath martensitic matrix with a slight amount of residual austenite. The good corrosion resistance is guaranteed by exactly controlling the Co content based on understanding the synergistic effect between Co and Cr. The fine structure characteristics of two dominant strengthening precipitations including Ni3Ti and Mo-rich phases were finely characterized associated with transmission electron microscope (TEM) and atom probe tomography (APT) analyses. The relationship among microstructure, strength and toughness is discussed. The precipitation mechanism of different precipitates in the new maraging stainless steel is revealed based on the APT analysis. PMID:29125550

Atomic-scale observation of structural and electronic orders in the layered compound α-RuCl3

NASA Astrophysics Data System (ADS)

Ziatdinov, M.; Banerjee, A.; Maksov, A.; Berlijn, T.; Zhou, W.; Cao, H. B.; Yan, J.-Q.; Bridges, C. A.; Mandrus, D. G.; Nagler, S. E.; Baddorf, A. P.; Kalinin, S. V.

2016-12-01

A pseudospin-1/2 Mott phase on a honeycomb lattice is proposed to host the celebrated two-dimensional Kitaev model which has an elusive quantum spin liquid ground state, and fascinating physics relevant to the development of future templates towards topological quantum bits. Here we report a comprehensive, atomically resolved real-space study by scanning transmission electron and scanning tunnelling microscopies on a novel layered material displaying Kitaev physics, α-RuCl3. Our local crystallography analysis reveals considerable variations in the geometry of the ligand sublattice in thin films of α-RuCl3 that opens a way to realization of a spatially inhomogeneous magnetic ground state at the nanometre length scale. Using scanning tunnelling techniques, we observe the electronic energy gap of ~0.25 eV and intra-unit cell symmetry breaking of charge distribution in individual α-RuCl3 surface layer. The corresponding charge-ordered pattern has a fine structure associated with two different types of charge disproportionation at Cl-terminated surface.

Radiation damage free ghost diffraction with atomic resolution

DOE PAGES

Li, Zheng; Medvedev, Nikita; Chapman, Henry N.; ...

2017-12-21

The x-ray free electron lasers can enable diffractive structural determination of protein nanocrystals and single molecules that are too small and radiation-sensitive for conventional x-ray diffraction. However the electronic form factor may be modified during the ultrashort x-ray pulse due to photoionization and electron cascade caused by the intense x-ray pulse. For general x-ray imaging techniques, the minimization of the effects of radiation damage is of major concern to ensure reliable reconstruction of molecular structure. Here in this paper, we show that radiation damage free diffraction can be achieved with atomic spatial resolution by using x-ray parametric down-conversion and ghostmore » diffraction with entangled photons of x-ray and optical frequencies. We show that the formation of the diffraction patterns satisfies a condition analogous to the Bragg equation, with a resolution that can be as fine as the crystal lattice length scale of several Ångstrom. Since the samples are illuminated by low energy optical photons, they can be free of radiation damage.« less

Radiation damage free ghost diffraction with atomic resolution

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

Li, Zheng; Medvedev, Nikita; Chapman, Henry N.

The x-ray free electron lasers can enable diffractive structural determination of protein nanocrystals and single molecules that are too small and radiation-sensitive for conventional x-ray diffraction. However the electronic form factor may be modified during the ultrashort x-ray pulse due to photoionization and electron cascade caused by the intense x-ray pulse. For general x-ray imaging techniques, the minimization of the effects of radiation damage is of major concern to ensure reliable reconstruction of molecular structure. Here in this paper, we show that radiation damage free diffraction can be achieved with atomic spatial resolution by using x-ray parametric down-conversion and ghostmore » diffraction with entangled photons of x-ray and optical frequencies. We show that the formation of the diffraction patterns satisfies a condition analogous to the Bragg equation, with a resolution that can be as fine as the crystal lattice length scale of several Ångstrom. Since the samples are illuminated by low energy optical photons, they can be free of radiation damage.« less

Structure and magnetic properties of Sm{sub 3}(Fe{sub 0.85}Cr{sub 0.15}){sub 29}N{sub y} alloys

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

Suzuki, Shunji; Suzuki, Shinya; Kawasaki, Masahito

1995-11-01

The structure and magnetic properties of Sm{sub 3}(Fe{sub 0.85}Cr{sub 0.15}){sub 29}N{sub y} alloy were investigated. It was found that the alloy had the R{sub 3}(Fe,M){sub 29}-type structure and absorbed 4--5 wt.% of nitrogen which exceeds 4 nitrogen atoms per unit formula. The coercivity of the powder was greatly influenced by the nitrogen content and annealing. The Sm{sub 3}(Fe{sub 0.85}Cr{sub 0.15}){sub 29}N{sub y} alloy powder with 4.1 wt.% of nitrogen showed a high coercivity of 552 kA/m without fine grinding.

Preface -2017EMRS-Fall-symposium W: Stress, structure and stoichiometry effects on the properties of nanomaterials IV

NASA Astrophysics Data System (ADS)

Sánchez, Florencio; Craciun, Valentin

2018-07-01

Research on nanomaterials and nanostructures is continuing to grow at a rapid pace as they are used in many important devices like transistors, sensors, MEMS or components of modern tools for diagnosis and treatment in medicine. The functional properties of the materials used in these devices depend on their microstructure, and can be finely tuned using physical and chemical synthesis or various processing techniques that change the structure, composition, morphology and defects type and concentration. The investigation of stress, stoichiometry, phase structure and defects at atomic level is necessary to understand, model and further optimize the electric, magnetic, optical and mechanical properties of the nanosystems and for engineers to design new, better and more reliable devices.

Hyperfine structure in 229gTh3+ as a probe of the 229gTh→ 229mTh nuclear excitation energy.

PubMed

Beloy, K

2014-02-14

We identify a potential means to extract the 229gTh→ 229mTh nuclear excitation energy from precision microwave spectroscopy of the 5F(5/2,7/2) hyperfine manifolds in the ion 229gTh3+. The hyperfine interaction mixes this ground fine structure doublet with states of the nuclear isomer, introducing small but observable shifts to the hyperfine sublevels. We demonstrate how accurate atomic structure calculations may be combined with the measurement of the hyperfine intervals to quantify the effects of this mixing. Further knowledge of the magnetic dipole decay rate of the isomer, as recently reported, allows an indirect determination of the nuclear excitation energy.

On the role of atomic metastability in the production of Balmer line radiation from ‘cold’ atomic hydrogen, deuterium and hydrogenic ion impurities in fusion edge plasmas

NASA Astrophysics Data System (ADS)

Hey, J. D.

2012-03-01

Published arguments, which assign an important role to atomic metastability in the production of ‘narrow’ Zeeman component radiation from the boundary region of fusion plasmas, are examined critically in relation to l-redistribution by proton and electron collisions, and mixing of unperturbed atomic states by the ion microfield and microfield gradient. It is concluded that these important processes indeed severely constrain the contribution from ‘metastable’ states to the generation of the hydrogen Balmer spectra, for electron concentrations above 1012 cm-3, as pointed out before by the present author (Hey et al 1999 J. Phys. B: At. Mol. Opt. Phys. 32 3555). The analysis of collision-induced l-redistribution represents an extension of that used previously (Hey et al 1996 Contrib. Plasma Phys. 36 583), applicable up to higher electron densities. For comparison purposes, we also consider the question of metastability of ionized helium in a low-temperature plasma, and that of some common hydrogenic impurities (C5+ and Ne9+) in a hydrogen (deuterium) fusion plasma. While for low nuclear charge Z the metastability of 2s1/2 levels is quenched by the plasma environment, it is much reduced in high-Z ions owing to the rapid increase with Z of the two-photon electric dipole (2E1) and magnetic dipole (M1) spontaneous transition rates to the ground state, whereas the role of the plasma in these cases is less important. The main new principle elaborated in this work is the sensitivity of atomic line strengths, and hence collision strengths, to perturbation by the plasma environment for transitions between fine-structure sublevels of the same principal quantum number. As the plasma microfield strength grows, ‘allowed’ transitions diminish in strength, while ‘forbidden’ transitions grow. However, owing to violation of the parity selection rule, there is an overall loss of collision strength available to transitions, resulting from the appearance of significant ‘self-strength’ contributions, in accord with the sum rules for the line strengths, which remain valid over the range of fields considered. Thus, the relative effectiveness per perturber of both electron and ion collisions, for inducing population transfer between fine-structure sublevels, diminishes as the sublevels evolve from a fine-structure dominated to a Stark-effect-dominated regime. In the concluding discussion, we mention that this finding may have a bearing on discrepancies claimed between Stark broadening theory developed by Griem (1967 Astrophys. J. 148 547) and by Watson (2006 J. Phys.B: At. Mol. Opt. Phys. 39 1889), and the measurements of Bell and co-workers (2000 Publ. Astron. Soc. Pac. 112 1236; 2011 Astrophys. Space Sci. 335 451) for high-n radio recombination lines from galactic H II regions. In the absence of detailed modelling to test this suggestion, however, it would be premature to attempt to draw any firm conclusions along these lines. This manuscript is dedicated to the memory of my esteemed colleague Dr. rer. nat. Manfred Korten (1940-2010).

Structural Characterization of Sm(III)(EDTMP).

PubMed

Yang, Y; Pushie, M J; Cooper, D M L; Doschak, M R

2015-11-02

Samarium-153 ethylenediamine-N,N,N',N'-tetrakis(methylenephosphonic acid) ((153)Sm-EDTMP, or samarium lexidronam), also known by its registered trademark name Quadramet, is an approved therapeutic radiopharmaceutical used in the palliative treatment of painful bone metastases. Typically, patients with prostate, breast, or lung cancer are most likely to go on to require bone pain palliation treatment due to bone metastases. Sm(EDTMP) is a bone-seeking drug which accumulates on rapidly growing bone, thereby delivering a highly region-specific dose of radiation, chiefly through β particle emission. Even with its widespread clinical use, the structure of Sm(EDTMP) has not yet been characterized at atomic resolution, despite attempts to crystallize the complex. Herein, we prepared a 1:1 complex of the cold (stable isotope) of Sm(EDTMP) under alkaline conditions and then isolated and characterized the complex using conventional spectroscopic techniques, as well as with extended X-ray absorption fine structure (EXAFS) spectroscopy and density functional structure calculations, using natural abundance Sm. We present the atomic resolution structure of [Sm(III)(EDTMP)-8H](5-) for the first time, supported by the EXAFS data and complementary spectroscopic techniques, which demonstrate that the samarium coordination environment in solution is in agreement with the structure that has long been conjectured.

Pulsed high energy synthesis of fine metal powders

NASA Technical Reports Server (NTRS)

Witherspoon, F. Douglas (Inventor); Massey, Dennis W. (Inventor)

1999-01-01

Repetitively pulsed plasma jets generated by a capillary arc discharge at high stagnation pressure (>15,000 psi) and high temperature (>10,000 K) are utilized to produce 0.1-10 .mu.m sized metal powders and decrease cost of production. The plasma jets impact and atomize melt materials to form the fine powders. The melt can originate from a conventional melt stream or from a pulsed arc between two electrodes. Gas streams used in conventional gas atomization are replaced with much higher momentum flux plasma jets. Delivering strong incident shocks aids in primary disintegration of the molten material. A series of short duration, high pressure plasma pulses fragment the molten material. The pulses introduce sharp velocity gradients in the molten material which disintegrates into fine particles. The plasma pulses have peak pressures of approximately one kilobar. The high pressures improve the efficiency of disintegration. High gas flow velocities and pressures are achieved without reduction in gas density. Repetitively pulsed plasma jets will produce powders with lower mean size and narrower size distribution than conventional atomization techniques.

Fe Isolated Single Atoms on S, N Codoped Carbon by Copolymer Pyrolysis Strategy for Highly Efficient Oxygen Reduction Reaction.

PubMed

Li, Qiheng; Chen, Wenxing; Xiao, Hai; Gong, Yue; Li, Zhi; Zheng, Lirong; Zheng, Xusheng; Yan, Wensheng; Cheong, Weng-Chon; Shen, Rongan; Fu, Ninghua; Gu, Lin; Zhuang, Zhongbin; Chen, Chen; Wang, Dingsheng; Peng, Qing; Li, Jun; Li, Yadong

2018-06-01

Heteroatom-doped Fe-NC catalyst has emerged as one of the most promising candidates to replace noble metal-based catalysts for highly efficient oxygen reduction reaction (ORR). However, delicate controls over their structure parameters to optimize the catalytic efficiency and molecular-level understandings of the catalytic mechanism are still challenging. Herein, a novel pyrrole-thiophene copolymer pyrolysis strategy to synthesize Fe-isolated single atoms on sulfur and nitrogen-codoped carbon (Fe-ISA/SNC) with controllable S, N doping is rationally designed. The catalytic efficiency of Fe-ISA/SNC shows a volcano-type curve with the increase of sulfur doping. The optimized Fe-ISA/SNC exhibits a half-wave potential of 0.896 V (vs reversible hydrogen electrode (RHE)), which is more positive than those of Fe-isolated single atoms on nitrogen codoped carbon (Fe-ISA/NC, 0.839 V), commercial Pt/C (0.841 V), and most reported nonprecious metal catalysts. Fe-ISA/SNC is methanol tolerable and shows negligible activity decay in alkaline condition during 15 000 voltage cycles. X-ray absorption fine structure analysis and density functional theory calculations reveal that the incorporated sulfur engineers the charges on N atoms surrounding the Fe reactive center. The enriched charge facilitates the rate-limiting reductive release of OH* and therefore improved the overall ORR efficiency. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-dimensional nanowires on homoepitaxial interfaces: Atomic-scale mechanism of breakdown and disintegration

NASA Astrophysics Data System (ADS)

Michailov, Michail; Ranguelov, Bogdan

2018-03-01

We present a model for hole-mediated spontaneous breakdown of ahomoepitaxial two-dimensional (2D) flat nanowire based exclusively on random, thermally-activated motion of atoms. The model suggests a consecutive three-step mechanism driving the rupture and complete disintegration of the nanowire on a crystalline surface. The breakdown scenario includes: (i) local narrowing of a part of the stripe to a monatomic chain, (ii) formation of a recoverable single vacancy or a 2D vacancy cluster that causes temporary nanowire rupture, (iii) formation of a non-recoverable 2D hole leading to permanent nanowire breakdown. These successive events in the temporal evolution of the nanowire morphology bring the nanowire stripe into an irreversible unstable state, leading to a dramatic change in its peculiar physical properties and conductivity. The atomistic simulations also reveal a strong increase of the nanowire lifetime with an enlargement of its width and open up a way for a fine atomic-scale control of the nanowire lifetime and structural, morphological and thermodynamic stability.

Tunable Spin-orbit Coupling and Quantum Phase Transition in a Trapped Bose-Einstein Condensate

PubMed Central

Zhang, Yongping; Chen, Gang; Zhang, Chuanwei

2013-01-01

Spin-orbit coupling (SOC), the intrinsic interaction between a particle spin and its motion, is responsible for various important phenomena, ranging from atomic fine structure to topological condensed matter physics. The recent experimental breakthrough on the realization of SOC for ultra-cold atoms provides a completely new platform for exploring spin-orbit coupled superfluid physics. However, the SOC strength in the experiment is not tunable. In this report, we propose a scheme for tuning the SOC strength through a fast and coherent modulation of the laser intensities. We show that the many-body interaction between atoms, together with the tunable SOC, can drive a quantum phase transition (QPT) from spin-balanced to spin-polarized ground states in a harmonic trapped Bose-Einstein condensate (BEC), which resembles the long-sought Dicke QPT. We characterize the QPT using the periods of collective oscillations of the BEC, which show pronounced peaks and damping around the quantum critical point. PMID:23727689

MCDF calculations of Auger cascade processes

NASA Astrophysics Data System (ADS)

Beerwerth, Randolf; Fritzsche, Stephan

2017-10-01

We model the multiple ionization of near-neutral core-excited atoms where a cascade of Auger processes leads to the emission of several electrons. We utilize the multiconfiguration Dirac-Fock (MCDF) method to generate approximate wave functions for all fine-structure levels and to account for all decays between them. This approach allows to compute electron spectra, the population of final-states and ion yields, that are accessible in many experiments. Furthermore, our approach is based on the configuration interaction method. A careful treatment of correlation between electronic configurations enables one to model three-electron processes such as an Auger decay that is accompanied by an additional shake-up transition. Here, this model is applied to the triple ionization of atomic cadmium, where we show that the decay of inner-shell 4p holes to triply-charged final states is purely due to the shake-up transition of valence 5s electrons. Contribution to the Topical Issue "Atomic and Molecular Data and their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, Grzegorz Karwasz.

Intramolecular energy transfer and the driving mechanisms for large-amplitude collective motions of clusters

NASA Astrophysics Data System (ADS)

Yanao, Tomohiro; Koon, Wang Sang; Marsden, Jerrold E.

2009-04-01

This paper uncovers novel and specific dynamical mechanisms that initiate large-amplitude collective motions in polyatomic molecules. These mechanisms are understood in terms of intramolecular energy transfer between modes and driving forces. Structural transition dynamics of a six-atom cluster between a symmetric and an elongated isomer is highlighted as an illustrative example of what is a general message. First, we introduce a general method of hyperspherical mode analysis to analyze the energy transfer among internal modes of polyatomic molecules. In this method, the (3n-6) internal modes of an n-atom molecule are classified generally into three coarse level gyration-radius modes, three fine level twisting modes, and (3n-12) fine level shearing modes. We show that a large amount of kinetic energy flows into the gyration-radius modes when the cluster undergoes structural transitions by changing its mass distribution. Based on this fact, we construct a reactive mode as a linear combination of the three gyration-radius modes. It is shown that before the reactive mode acquires a large amount of kinetic energy, activation or inactivation of the twisting modes, depending on the geometry of the isomer, plays crucial roles for the onset of a structural transition. Specifically, in a symmetric isomer with a spherical mass distribution, activation of specific twisting modes drives the structural transition into an elongated isomer by inducing a strong internal centrifugal force, which has the effect of elongating the mass distribution of the system. On the other hand, in an elongated isomer, inactivation of specific twisting modes initiates the structural transition into a symmetric isomer with lower potential energy by suppressing the elongation effect of the internal centrifugal force and making the effects of the potential force dominant. This driving mechanism for reactions as well as the present method of hyperspherical mode analysis should be widely applicable to molecular reactions in which a system changes its overall mass distribution in a significant way.

Predictions of thermomagnetic properties of Laves phase compounds: TbAl2, GdAl2 and SmAl2 performed with ATOMIC MATTERS MFA computation system

NASA Astrophysics Data System (ADS)

Michalski, Rafał; Zygadło, Jakub

2018-04-01

Recent calculations of properties of TbAl2 GdAl2 and SmAl2 single crystals, performed with our new computation system called ATOMIC MATTERS MFA are presented. We applied localized electron approach to describe the thermal evolution of Fine Electronic Structure of Tb3+, Gd3+ and Sm3+ ions over a wide temperature range and estimate Magnetocaloric Effect (MCE). Thermomagnetic properties of TbAl2, GdAl2 and SmAl2 were calculated based on the fine electronic structure of the 4f8, 4f7 and 4f5 electronic configuration of the Tb3+ and Gd3+ and Sm3+ ions, respectively. Our calculations yielded: magnetic moment value and direction; single-crystalline magnetization curves in zero field and in external magnetic field applied in various directions m(T,Bext); the 4f-electronic components of specific heat c4f(T,Bext); and temperature dependence of the magnetic entropy and isothermal entropy change with external magnetic field - ΔS(T,Bext). The cubic universal CEF parameters values used for all CEF calculations was taken from literature and recalculated for universal cubic parameters set for the RAl2 series: A4 = +7.164 Ka04 and A6 = -1.038 Ka06. Magnetic properties were found to be anisotropic due to cubic Laves phase C15 crystal structure symmetry. These studies reveal the importance of multipolar charge interactions when describing thermomagnetic properties of real 4f electronic systems and the effectiveness of an applied self-consistent molecular field in calculations for magnetic phase transition simulation.

From Supercomputer Modeling to Highest Mass Resolution in FT-ICR.

PubMed

N Nikolaev, Evgene; N Vladimirov, Gleb; Jertz, Roland; Baykut, Gökhan

2013-01-01

Understanding of behavior of ion ensembles inside FT-ICR cell based on the computer simulation of ion motion gives rise to the new ideas of cell designs. The recently introduced novel FT-ICR cell based on a Penning ion trap with specially shaped excitation and detection electrodes prevents distortion of ion cyclotron motion phases (normally caused by non-ideal electric trapping fields) by averaging the trapping DC electric field during the ion motion in the ICR cell. Detection times of 5 min resulting in resolving power close to 40,000,000 have been reached for reserpine at m/z 609 at a magnetic field of only 7 Tesla. Fine structures of resolved 13Cn isotopic cluster groups could be measured for molecular masses up to 5.7 kDa (insulin) with resolving power of 4,000,000 at 7 Tesla. Based on resolved fine structure patterns atomic compositions can be directly determined using a new developed algorithm for fine structure processing. Mass spectra of proteins and multimers of proteins reaching masses up to 186 kDa (enolase tetramer) could be measured with isotopic resolution. For instance, at 7 Tesla resolving power of 800,000 was achieved for enolase dimer (96 kDa) and 500,000 for molecular masses above 100 kDa. Experimental data indicate that there is practically no limit for the resolving power of this ICR cell except by collisional damping in the ultrahigh vacuum chamber.

Hyperfine excitation of OH+ by H

NASA Astrophysics Data System (ADS)

Lique, François; Bulut, Niyazi; Roncero, Octavio

2016-10-01

The OH+ ions are widespread in the interstellar medium and play an important role in the interstellar chemistry as they act as precursors to the H2O molecule. Accurate determination of their abundance rely on their collisional rate coefficients with atomic hydrogen and electrons. In this paper, we derive OH+-H fine and hyperfine-resolved rate coefficients by extrapolating recent quantum wave packet calculations for the OH+ + H collisions, including inelastic and exchange processes. The extrapolation method used is based on the infinite order sudden approach. State-to-state rate coefficients between the first 22 fine levels and 43 hyperfine levels of OH+ were obtained for temperatures ranging from 10 to 1000 K. Fine structure-resolved rate coefficients present a strong propensity rule in favour of Δj = ΔN transitions. The Δj = ΔF propensity rule is observed for the hyperfine transitions. The new rate coefficients will help significantly in the interpretation of OH+ spectra from photon-dominated region (PDR), and enable the OH+ molecule to become a powerful astrophysical tool for studying the oxygen chemistry.

Modern trends in increasing the quality of the steels intended for cutting and metal-working tools: I. Improvement of granule metallurgy processes

NASA Astrophysics Data System (ADS)

Belyanchikov, L. N.

2008-12-01

The following new technological processes for producing fine gas-atomized powders of tool and high-speed steels with a low content of nonmetallic inclusions are considered: the process designed by Böhler Uddeholm Powder Technology (Austria) and processes involving a heated gas. In the former process, a metal is poured from a ladle with electroslag heating, and the atomizing unit consists of three injectors. A new process of producing tools from fine powders by three-dimensional printing, i.e., so-called 3D-printing, is described.

Long- and Short-Range Structure of Ferrimagnetic Iron-Chromium Maghemites.

PubMed

García-Guaderrama, Marco; Montero-Cabrera, María E; Morán, Emilio; Alario-Franco, Miguel A; Fuentes-Cobas, Luis E; Macías-Ríos, Edgar; Esparza-Ponce, Hilda E; Fuentes-Montero, María E

2015-12-07

Maghemite-like materials containing Fe(3+) and Cr(3+) in comparable amounts have been prepared by solution-combustion synthesis. The conditions of synthesis and the magnetic properties are described. These materials are ferrimagnetic and are much more stable than pure iron maghemite since their maghemite-hematite transformation takes place at about ∼ 700 °C instead of ∼ 300 °C, as usually reported. These materials were studied by synchrotron radiation X-ray diffraction (XRD) and by X-ray absorption fine structure (XAFS) of the K-absorption edge of two elements. High-resolution XRD patterns were processed by means of the Rietveld method. Thus, maghemites were studied by XAFS in both Fe and Cr K-edges to clarify the short-range structure of the investigated systems. Pre-edge decomposition and theoretical modeling of X-ray absorption near edge structure transitions were performed. The extended X-ray absorption fine structure (EXAFS) spectra were fitted considering the facts that the central atom of Fe is able to occupy octahedral and tetrahedral sites, each with a weight adjustment, while Cr occupies only octahedral sites. Interatomic distances were determined for x = 1, by fitting simultaneously both Fe and Cr K-edges average EXAFS spectra. The results showed that the cation vacancies tend to follow a regular pattern within the structure of the iron-chromium maghemite (FeCrO3).

An extended X-Ray absorption fine structure (exafs) study of copper (II) sulphate pentahydrate

NASA Astrophysics Data System (ADS)

Joyner, Richard W.

1980-05-01

The EXAFS spectrum of copper (II) sulphate pentahydrate has been measured using synchrotron radiation. Comparison with the results of ab initio calculation gives a mean copper-oxygen distance of 1.95 Å, in reasonable agreement with the known value of 1.97 Å. The relation between the EXAFS Debye-Waller factor and thermal parameters measured by neutron diffraction is discussed. Absence in the EXAFS spectrum of evidence for the second-nearest neighbour oxygen atoms, at Cu-O ≈ 2.4 Å, is discussed.

Optimizing soft X-ray NEXAFS spectroscopy in the laboratory

NASA Astrophysics Data System (ADS)

Mantouvalou, I.; Jonas, A.; Witte, K.; Jung, R.; Stiel, H.; Kanngießer, B.

2017-05-01

Near edge X-ray absorption fine structure (NEXAFS) spectroscopy in the soft X-ray range is feasible in the laboratory using laser-produced plasma sources. We present a study using seven different target materials for optimized data analysis. The emission spectra of the materials with atomic numbers ranging from Z = 6 to Z = 79 show distinct differences, rendering the adapted selection of a suitable target material for specialized experiments feasible. For NEXAFS spectroscopy a 112.5 nm thick polyimide film is investigated as a reference exemplifying the superiority of quasi-continuum like emission spectra.

Local atomic and electronic structure of LaCoO3 /SrTiO3 thin films by HAADF STEM and EELS

NASA Astrophysics Data System (ADS)

Borisevich, Albina; Hyuck Jang, Jae; Kim, Young-Min; Qiao, Liang; Biegalski, Michael

2013-03-01

For perovskite films with several competing functionalities, magnetic and electronic properties can be affected both by structural order parameters and chemical factors. For example, in LaCoO3 (LCO) thin films, magnetic and transport properties are strongly dependent on strain state and oxygen content. For this study, LCO thin films were deposited by pulsed laser deposition method with different thicknesses (2, 5, 15 unit cell and 20 nm thickness) on SrTiO3 substrate. X-ray photoelectron spectroscopy studies of the grown films have demonstrated that Co 3p edges shift up to 2 eV for 15 u.c. and 20 nm films, indicating possible presence of 2D electron gas. The structure of the 5 u.c and 15 u.c LCO films was examined. Atomic position mapping from STEM HAADF and BF images can reveal lattice parameter and octahedral tilt behavior with atomic resolution. BF STEM imaging showed that octahedral tilts were active in the 15 u.c. film but not in the 5 u.c. film. A complex pattern of O K fine structure evolution at the interface was observed; results of the deconvolution of different contributions to this behavior using advanced simulations, as well as data on oxygen vacancy mapping, will be presented. Research supported by the US DOE-BES, Materials Sciences and Engineering Division, and through a user project supported by ORNL's ShaRE User Program.

In-situ crystallization of GeTe\\GaSb phase change memory stacked films

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

Velea, A., E-mail: alin.velea@psi.ch; National Institute of Materials Physics, RO-077125 Magurele, Ilfov; Borca, C. N.

2014-12-21

Single and double layer phase change memory structures based on GeTe and GaSb thin films were deposited by pulsed laser deposition (PLD). Their crystallization behavior was studied using in-situ synchrotron techniques. Electrical resistance vs. temperature investigations, using the four points probe method, showed transition temperatures of 138 °C and 198 °C for GeTe and GaSb single films, respectively. It was found that after GeTe crystallization in the stacked films, Ga atoms from the GaSb layer diffused in the vacancies of the GeTe crystalline structure. Therefore, the crystallization temperature of the Sb-rich GaSb layer is decreased by more than 30 °C. Furthermore, at 210 °C,more » the antimony excess from GaSb films crystallizes as a secondary phase. At higher annealing temperatures, the crystalline Sb phase increased on the expense of GaSb crystalline phase which was reduced. Extended X-ray absorption fine structure (EXAFS) measurements at the Ga and Ge K-edges revealed changes in their local atomic environments as a function of the annealing temperature. Simulations unveil a tetrahedral configuration in the amorphous state and octahedral configuration in the crystalline state for Ge atoms, while Ga is four-fold coordinated in both as-deposited and annealed samples.« less

GAS-ATOMIZED SPRAY SCRUBBER EVALUATION

EPA Science Inventory

The report gives results of fine particle collection efficiency measurements of a gas-atomized spray scrubber, cleaning effluent gas from a No. 7 gray iron cupola. Tests were made at several levels of pressure drop and liquid/gas ratio. Particle size measurements on inlet and out...

Grain Refinement by Authigenic Inoculation Inherited from the Medium-Range Order Structure of Ni-Cr-W Superalloy

NASA Astrophysics Data System (ADS)

Gao, Zhongtang; Hu, Rui; Guo, Wei; Zhang, Chuanwei

2018-04-01

The combination of liquidus casting and thermal control solidification furnace was applied to obtain a fine-grained ingot. A rapid quenching method and x-ray diffraction measurement were used to investigate the effect of authigenic inoculation on grain refinement. The structure factor S(Q) of liquid Ni-Cr-W superalloy at 1400 °C (Liquidus temperature) and bright-field image of the microstructures quenched from 1400 °C have been measured by the high-temperature x-ray diffractometer and the transmission electron microscopy (TEM), respectively. The results show that a pre-peak exists on a S(Q) curve at the liquidus temperature. The clusters of atom in rapidly quenched microstructures obtained by isothermal heat treatment at 1400 °C were studied using TEM. Meanwhile, the effect of isothermal different temperatures on rapidly quenched microstructures was studied. The results also show that there are only the globular, equiaxed grains distributed in the solidification structure. These particles are inherited from the medium-range order structure, which is beneficial for grain refinement. The normalized work-hardening rate-strain curve indicates the work-hardening rate of fine grain is higher than that of conventional grain at the same temperature and the same deformation.

Grain Refinement by Authigenic Inoculation Inherited from the Medium-Range Order Structure of Ni-Cr-W Superalloy

NASA Astrophysics Data System (ADS)

Gao, Zhongtang; Hu, Rui; Guo, Wei; Zhang, Chuanwei

2018-05-01

The combination of liquidus casting and thermal control solidification furnace was applied to obtain a fine-grained ingot. A rapid quenching method and x-ray diffraction measurement were used to investigate the effect of authigenic inoculation on grain refinement. The structure factor S( Q) of liquid Ni -Cr-W superalloy at 1400 °C (Liquidus temperature) and bright-field image of the microstructures quenched from 1400 °C have been measured by the high-temperature x-ray diffractometer and the transmission electron microscopy (TEM), respectively. The results show that a pre-peak exists on a S( Q) curve at the liquidus temperature. The clusters of atom in rapidly quenched microstructures obtained by isothermal heat treatment at 1400 °C were studied using TEM. Meanwhile, the effect of isothermal different temperatures on rapidly quenched microstructures was studied. The results also show that there are only the globular, equiaxed grains distributed in the solidification structure. These particles are inherited from the medium-range order structure, which is beneficial for grain refinement. The normalized work-hardening rate-strain curve indicates the work-hardening rate of fine grain is higher than that of conventional grain at the same temperature and the same deformation.

Effect of elastic collisions and electronic excitation on lattice structure of NiTi bulk intermetallic compound irradiated with energetic ions

NASA Astrophysics Data System (ADS)

Ochi, M.; Kojima, H.; Hori, F.; Kaneno, Y.; Semboshi, S.; Saitoh, Y.; Okamoto, Y.; Ishikawa, N.; Iwase, A.

2018-07-01

NiTi bulk intermetallic compound with the B19‧ structure was irradiated with 1 MeV He, 5 MeV Al, 16 MeV Au and 200 MeV Xe ions, and the change in lattice structure near the surface by the ion bombardment was investigated by using the grazing incidence X-ray diffraction (GIXD) and the extended X-ray absorption fine structure (EXAFS). The lattice structure transformation by the irradiation strongly depends on ion species and/or energies. For the 1 MeV He irradiation, the lattice structure changed from B19‧ to the A2 structure, but did not show an amorphization even after the high fluence irradiation. For the 5 MeV Al irradiation, the samples are partially amorphized. For the 16 MeV Au irradiation, the lattice structure of the NiTi samples changed nearly completely from the B19‧ structure to the amorphous state via the A2 structure. The value of dpa (displacement per atom) which is needed for the amorphization is, however, much smaller than the case of the Al ion irradiation. For the 200 MeV Xe ion irradiation, the lattice structure completely changed to the A2 structure even by a small ion fluence. The dependence of the lattice structure transformation on elastic collisions (dpa), the spectrum of the primary knock-on (PKA) atoms and the density of energy deposited through electronic excitation was discussed.

Effective adsorption and collection of cesium from aqueous solution using graphene oxide grown on porous alumina

NASA Astrophysics Data System (ADS)

Entani, Shiro; Honda, Mitsunori; Shimoyama, Iwao; Li, Songtian; Naramoto, Hiroshi; Yaita, Tsuyoshi; Sakai, Seiji

2018-04-01

Graphene oxide (GO) with a large surface area was synthesized by the direct growth of GO on porous alumina using chemical vapor deposition to study the Cs adsorption mechanism in aqueous solutions. Electronic structure analysis employing in situ near-edge X-ray absorption fine structure spectroscopy and X-ray photoelectron spectroscopy measurements clarifies the Cs atoms bond via oxygen functional groups on GO in the aqueous solution. The Cs adsorption capacity was found to be as high as 650-850 mg g-1, which indicates that the GO/porous alumina acts as an effective adsorbent with high adsorption efficiency for radioactive nuclides in aqueous solutions.

Planar Lattice Instability in LA2CUO4.1 across the Superconducting Transition

NASA Astrophysics Data System (ADS)

Acosta-Alejandro, Manuel; Mustre-de Leon, Jose; Conradson, Steven

2001-03-01

The local atomic structure of La2CuO4.1 around Cu K-edge is analyzed for 10

Strain induced atomic structure at the Ir-doped LaAlO3/SrTiO3 interface.

PubMed

Lee, M; Arras, R; Warot-Fonrose, B; Hungria, T; Lippmaa, M; Daimon, H; Casanove, M J

2017-11-01

The structure of Ir-doped LaAlO 3 /SrTiO 3 (001) interfaces was investigated on the atomic scale using probe-corrected transmission electron microscopy in high-angle annular dark-field scanning mode (HAADF-STEM) and electron energy loss spectroscopy (EELS), combined with first-principles calculations. We report the evolution of the strain state experimentally measured in a 5 unit-cell thick LaAlO 3 film as a function of the Ir concentration in the topmost SrTiO 3 layer. It is shown that the LaAlO 3 layers remain fully elastically strained up to 3% of Ir doping, whereas a higher doping level seems to promote strain relaxation through enhanced cationic interdiffusion. The observed differences between the energy loss near edge structure (ELNES) of Ti-L 2,3 and O-K edges at non-doped and Ir-doped interfaces are consistent with the location of the Ir dopants at the interface, up to 3% of Ir doping. These findings, supported by the results of density functional theory (DFT) calculations, provide strong evidence that the effect of dopant concentrations on the properties of this kind of interface should not be analyzed without obtaining essential information from the fine structural and chemical analysis of the grown structures.

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

DOE PAGES

Zhao, Shen; Li, Yuanyuan; Liu, Deyu; ...

2017-08-07

In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

Multimodal Study of the Speciations and Activities of Supported Pd Catalysts During the Hydrogenation of Ethylene

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

Zhao, Shen; Li, Yuanyuan; Liu, Deyu

In this paper we describe a multimodal exploration of the atomic structure and chemical state of silica-supported palladium nanocluster catalysts during the hydrogenation of ethylene in operando conditions that variously transform the metallic phases between hydride and carbide speciations. The work exploits a microreactor that allows combined multiprobe investigations by high-resolution transmission electron microscopy (HR-TEM), X-ray absorption fine structure (XAFS), and microbeam IR (μ-IR) analyses on the catalyst under operando conditions. The work specifically explores the reaction processes that mediate the interconversion of hydride and carbide phases of the Pd clusters in consequence to changes made in the composition ofmore » the gas-phase reactant feeds, their stability against coarsening, the reversibility of structural/compositional transformations, and the role that oligomeric/waxy byproducts (here forming under hydrogen-limited reactant compositions) might play in modifying activity. The results provide new insights into structural features of the chemistry/mechanisms of Pd catalysis during the selective hydrogenation of acetylene in ethylene—a process simplified here in the use of binary ethylene/hydrogen mixtures. Finally, these explorations, performed in operando conditions, provide new understandings of structure–activity relationships for Pd catalysis in regimes that actively transmute important attributes of electronic and atomic structures.« less

Microstructure, Morphology, and Nanomechanical Properties Near Fine Holes Produced by Electro-Discharge Machining

NASA Astrophysics Data System (ADS)

Blau, P. J.; Howe, J. Y.; Coffey, D. W.; Trejo, R. M.; Kenik, E. D.; Jolly, B. C.; Yang, N.

2012-08-01

Fine holes in metal alloys are employed for many important technological purposes, including cooling and the precise atomization of liquids. For example, they play an important role in the metering and delivery of fuel to the combustion chambers in energy-efficient, low-emission diesel engines. Electro-discharge machining (EDM) is one process employed to produce such holes. Since the hole shape and bore morphology can affect fluid flow, and holes also represent structural discontinuities in the tips of the spray nozzles, it is important to understand the microstructures adjacent to these holes, the features of the hole walls, and the nanomechanical properties of the material that was in some manner altered by the EDM hole-making process. Several techniques were used to characterize the structure and properties of spray-holes in a commercial injector nozzle. These include scanning electron microscopy, cross sectioning and metallographic etching, bore surface roughness measurements by optical interferometry, scanning electron microscopy, and transmission electron microscopy of recast EDM layers extracted with the help of a focused ion beam.

Precision atomic spectroscopy for improved limits on variation of the fine structure constant and local position invariance.

PubMed

Fortier, T M; Ashby, N; Bergquist, J C; Delaney, M J; Diddams, S A; Heavner, T P; Hollberg, L; Itano, W M; Jefferts, S R; Kim, K; Levi, F; Lorini, L; Oskay, W H; Parker, T E; Shirley, J; Stalnaker, J E

2007-02-16

We report tests of local position invariance and the variation of fundamental constants from measurements of the frequency ratio of the 282-nm 199Hg+ optical clock transition to the ground state hyperfine splitting in 133Cs. Analysis of the frequency ratio of the two clocks, extending over 6 yr at NIST, is used to place a limit on its fractional variation of <5.8x10(-6) per change in normalized solar gravitational potential. The same frequency ratio is also used to obtain 20-fold improvement over previous limits on the fractional variation of the fine structure constant of |alpha/alpha|<1.3x10(-16) yr-1, assuming invariance of other fundamental constants. Comparisons of our results with those previously reported for the absolute optical frequency measurements in H and 171Yb+ vs other 133Cs standards yield a coupled constraint of -1.5x10(-15)

Dark energy and equivalence principle constraints from astrophysical tests of the stability of the fine-structure constant

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

Martins, C.J.A.P.; Pinho, A.M.M.; Alves, R.F.C.

2015-08-01

Astrophysical tests of the stability of fundamental couplings, such as the fine-structure constant α, are becoming an increasingly powerful probe of new physics. Here we discuss how these measurements, combined with local atomic clock tests and Type Ia supernova and Hubble parameter data, constrain the simplest class of dynamical dark energy models where the same degree of freedom is assumed to provide both the dark energy and (through a dimensionless coupling, ζ, to the electromagnetic sector) the α variation. Specifically, current data tightly constrains a combination of ζ and the present dark energy equation of state w{sub 0}. Moreover, inmore » these models the new degree of freedom inevitably couples to nucleons (through the α dependence of their masses) and leads to violations of the Weak Equivalence Principle. We obtain indirect bounds on the Eötvös parameter η that are typically stronger than the current direct ones. We discuss the model-dependence of our results and briefly comment on how the forthcoming generation of high-resolution ultra-stable spectrographs will enable significantly tighter constraints.« less

A wavelet analysis for the X-ray absorption spectra of molecules

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

Penfold, T. J.; Ecole polytechnique Federale de Lausanne, Laboratoire de chimie et biochimie computationnelles, ISIC, FSB-BCH, CH-1015 Lausanne; SwissFEL, Paul Scherrer Inst, CH-5232 Villigen

2013-01-07

We present a Wavelet transform analysis for the X-ray absorption spectra of molecules. In contrast to the traditionally used Fourier transform approach, this analysis yields a 2D correlation plot in both R- and k-space. As a consequence, it is possible to distinguish between different scattering pathways at the same distance from the absorbing atom and between the contributions of single and multiple scattering events, making an unambiguous assignment of the fine structure oscillations for complex systems possible. We apply this to two previously studied transition metal complexes, namely iron hexacyanide in both its ferric and ferrous form, and a rheniummore » diimine complex, [ReX(CO){sub 3}(bpy)], where X = Br, Cl, or ethyl pyridine (Etpy). Our results demonstrate the potential advantages of using this approach and they highlight the importance of multiple scattering, and specifically the focusing phenomenon to the extended X-ray absorption fine structure (EXAFS) spectra of these complexes. We also shed light on the low sensitivity of the EXAFS spectrum to the Re-X scattering pathway.« less

Quantum coherent control of the photoelectron angular distribution in bichromatic-field ionization of atomic neon

NASA Astrophysics Data System (ADS)

Gryzlova, E. V.; Grum-Grzhimailo, A. N.; Staroselskaya, E. I.; Douguet, N.; Bartschat, K.

2018-01-01

We investigate the coherent control of the photoelectron angular distribution in bichromatic atomic ionization. Neon is selected as target since it is one of the most popular systems in current gas-phase experiments with free-electron lasers (FELSs). In particular, we tackle practical questions, such as the role of the fine-structure splitting, the pulse length, and the intensity. Time-dependent and stationary perturbation theory are employed, and we also solve the time-dependent Schrödinger equation in a single-active electron model. We consider neon ionized by a FEL pulse whose fundamental frequency is in resonance with either 2 p -3 s or 2 p -4 s excitation. The contribution of the nonresonant two-photon process and its potential constructive or destructive role for quantum coherent control is investigated.

Energy levels and radiative rates for Ne-like ions from Cu to Ga

NASA Astrophysics Data System (ADS)

Singh, Narendra; Aggarwal, Sunny

2017-11-01

Energy levels, lifetimes and wave function compositions are computed for 127 fine structural levels in Ne-like ions (Z=29{-}31). Configuration interaction has been included among 51 configurations (generating 1016 levels) and multiconfigurational Dirac-Fock method is used to generate the wave functions. Similar calculations have also been performed using the fully relativistic flexible atomic code (FAC). Transition wavelength, oscillator strength, transition probabilities and line strength are reported for electric dipole (E1), electric quadrupole (E2), magnetic dipole (M1) and magnetic quadrupole (M2) transitions from the ground level. We compared our calculated results with the available data in the literature. The calculated results are found to be in close agreement with the previous results. Further, we predict some new atomic data which may be important for plasma diagnostics.

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

DOE PAGES

Zhang, Chenhao; Yang, Shize; Wu, Jingjie; ...

2018-03-25

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Electrochemical CO 2 Reduction with Atomic Iron-Dispersed on Nitrogen-Doped Graphene

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

Zhang, Chenhao; Yang, Shize; Wu, Jingjie

Electrochemical reduction of CO 2 provides an opportunity to reach a carbon-neutral energy recycling regime, in which CO 2 emissions from fuel use are collected and converted back to fuels. The reduction of CO 2 to CO is the first step toward the synthesis of more complex carbon-based fuels and chemicals. Therefore, understanding this step is crucial for the development of high-performance electrocatalyst for CO 2 conversion to higher order products such as hydrocarbons. In this paper, atomic iron dispersed on nitrogen-doped graphene (Fe/NG) is synthesized as an efficient electrocatalyst for CO 2 reduction to CO. Fe/NG has a lowmore » reduction overpotential with high Faradic efficiency up to 80%. The existence of nitrogen-confined atomic Fe moieties on the nitrogen-doped graphene layer is confirmed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure analysis. The Fe/NG catalysts provide an ideal platform for comparative studies of the effect of the catalytic center on the electrocatalytic performance. Finally, the CO 2 reduction reaction mechanism on atomic Fe surrounded by four N atoms (Fe–N 4) embedded in nitrogen-doped graphene is further investigated through density functional theory calculations, revealing a possible promotional effect of nitrogen doping on graphene.« less

Probing the influence of the center atom coordination structure in iron phthalocyanine multi-walled carbon nanotube-based oxygen reduction reaction catalysts by X-ray absorption fine structure spectroscopy

NASA Astrophysics Data System (ADS)

Peng, Yingxiang; Li, Zhipan; Xia, Dingguo; Zheng, Lirong; Liao, Yi; Li, Kai; Zuo, Xia

2015-09-01

Three different pentacoordinate iron phthalocyanine (FePc) electrocatalysts with an axial ligand (pyridyl group, Py) anchored to multi-walled carbon nanotubes (MWCNTs) are prepared by a microwave method as high performance composite electrocatalysts (FePc-Py/MWCNTs) for the oxygen reduction reaction (ORR). For comparison, tetracoordinate FePc electrocatalysts without an axial ligand anchored to MWCNTs (FePc/MWCNTs) are assembled in the same way. Ultraviolet-visible spectrophotometry (UV-Vis), Raman spectroscopy (RS), and high-resolution transmission electron microscopy (HRTEM) are used to characterize the obtained electrocatalysts. The electrocatalytic activity of the samples is measured by linear sweep voltammetry (LSV), and the onset potential of all of the FePc-Py/MWCNTs electrocatalysts is found to be more positive than that of their FePc/MWCNTs counterparts. X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy are employed to elucidate the relationship between molecular structure and electrocatalytic activity. XPS indicates that higher concentrations of Fe3+ and pyridine-type nitrogen play critical roles in determining the electrocatalytic ORR activity of the samples. XAFS spectroscopy reveals that the FePc-Py/MWCNTs electrocatalysts have a coordination geometry around Fe that is closer to the square pyramidal structure, a higher concentration of Fe3+, and a smaller phthalocyanine ring radius compared with those of FePc/MWCNTs.

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

Nahar, Sultana N., E-mail: nahar@astronomy.ohio-state.edu

The atomic parameters–oscillator strengths, line strengths, radiative decay rates (A), and lifetimes–for fine structure transitions of electric dipole (E1) type for the astrophysically abundant ion Ne IV are presented. The results include 868 fine structure levels with n≤ 10, l≤ 9, and 1/2≤J≤ 19/2 of even and odd parities, and the corresponding 83,767 E1 transitions. The calculations were carried out using the relativistic Breit–Pauli R-matrix method in the close coupling approximation. The transitions have been identified spectroscopically using an algorithm based on quantum defect analysis and other criteria. The calculated energies agree with the 103 observed and identified energies to withinmore » 3% or better for most of the levels. Some larger differences are also noted. The A-values show good to fair agreement with the very limited number of available transitions in the table compiled by NIST, but show very good agreement with the latest published multi-configuration Hartree–Fock calculations. The present transitions should be useful for diagnostics as well as for precise and complete spectral modeling in the soft X-ray to infra-red regions of astrophysical and laboratory plasmas. -- Highlights: •The first application of BPRM method for accurate E1 transitions in Ne IV is reported. •Amount of atomic data (n going up to 10) is complete for most practical applications. •The calculated energies are in very good agreement with most observed levels. •Very good agreement of A-values and lifetimes with other relativistic calculations. •The results should provide precise nebular abundances, chemical evolution etc.« less

A triple-bridged azido-Cu(II) chain compound fine-tuned by mixed carboxylate/ethanol linkers displays slow-relaxation and ferromagnetic order: synthesis, crystal structure, magnetic properties and DFT calculations.

PubMed

Liu, Xiangyu; Chen, Sanping; Grancha, Thais; Pardo, Emilio; Ke, Hongshan; Yin, Bing; Wei, Qing; Xie, Gang; Gao, Shengli

2014-11-07

A new azido-Cu(II) compound, [Cu(4-fba)(N3)(C2H5OH)] (4-fba = 4-fluorobenzoic acid) (1), has been synthesized and characterized. The X-ray crystal structure analysis demonstrates that only one crystallographically independent Cu(II) ion in the asymmetric unit of 1 exhibits a stretched octahedral geometry in which two azido N atoms and two carboxylic O atoms locate in the equatorial square, while two ethanol O atoms occupy the apical positions, forming a 1D Cu(II) chain with an alternating triple-bridge of EO-azido, syn,syn-carboxylate, and μ2-ethanol. The title compound consists of ferromagnetically interacting ferromagnetic chains, which exhibit ferromagnetic order (T(c) = 7.0 K). The strong ferromagnetic coupling between adjacent Cu(II) ions within each chain is due to the countercomplementarity of the super-exchange pathways, whereas the ferromagnetic interchain interactions--responsible for the long-range magnetic ordering--are most likely due to the presence of coordinated ethanol molecules establishing hydrogen bonds with neighboring chains. DFT calculations have been performed on compound 1 to offer a qualitative theoretical explanation of the magnetic behavior.

Magnetizabilities of relativistic hydrogenlike atoms in some arbitrary discrete energy eigenstates

NASA Astrophysics Data System (ADS)

Stefańska, Patrycja

2016-03-01

We present the results of numerical calculations of magnetizability (χ) of the relativistic one-electron atoms with a pointlike, spinless and motionless nuclei of charge Ze. Exploiting the analytical formula for χ recently derived by us Stefańska (2015), valid for an arbitrary discrete energy eigenstate, we have found the values of the magnetizability for the ground state and for the first and the second set of excited states (i.e.: 2s1/2, 2p1/2, 2p3/2, 3s1/2, 3p1/2, 3p3/2, 3d3/2, and 3d5/2) of the Dirac one-electron atom. The results for ions with the atomic number 1 ⩽ Z ⩽ 137 are given in 14 tables. The comparison of the numerical values of magnetizabilities for the ground state and for each state belonging to the first set of excited states of selected hydrogenlike ions, obtained with the use of two different values of the fine-structure constant, i.e.: α-1 = 137.035 999 139 (CODATA 2014) and α-1 = 137.035 999 074 (CODATA 2010), is also presented.

Atom Interferometry with Ultracold Quantum Gases in a Microgravity Environment

NASA Astrophysics Data System (ADS)

Williams, Jason; D'Incao, Jose; Chiow, Sheng-Wey; Yu, Nan

2015-05-01

Precision atom interferometers (AI) in space promise exciting technical capabilities for fundamental physics research, with proposals including unprecedented tests of the weak equivalence principle, precision measurements of the fine structure and gravitational constants, and detection of gravity waves and dark energy. Consequently, multiple AI-based missions have been proposed to NASA, including a dual-atomic-species interferometer that is to be integrated into the Cold Atom Laboratory (CAL) onboard the International Space Station. In this talk, I will discuss our plans and preparation at JPL for the proposed flight experiments to use the CAL facility to study the leading-order systematics expected to corrupt future high-precision measurements of fundamental physics with AIs in microgravity. The project centers on the physics of pairwise interactions and molecular dynamics in these quantum systems as a means to overcome uncontrolled shifts associated with the gravity gradient and few-particle collisions. We will further utilize the CAL AI for proof-of-principle tests of systematic mitigation and phase-readout techniques for use in the next-generation of precision metrology experiments based on AIs in microgravity. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

Efficient simultaneous reverse Monte Carlo modeling of pair-distribution functions and extended x-ray-absorption fine structure spectra of crystalline disordered materials.

PubMed

Németh, Károly; Chapman, Karena W; Balasubramanian, Mahalingam; Shyam, Badri; Chupas, Peter J; Heald, Steve M; Newville, Matt; Klingler, Robert J; Winans, Randall E; Almer, Jonathan D; Sandi, Giselle; Srajer, George

2012-02-21

An efficient implementation of simultaneous reverse Monte Carlo (RMC) modeling of pair distribution function (PDF) and EXAFS spectra is reported. This implementation is an extension of the technique established by Krayzman et al. [J. Appl. Cryst. 42, 867 (2009)] in the sense that it enables simultaneous real-space fitting of x-ray PDF with accurate treatment of Q-dependence of the scattering cross-sections and EXAFS with multiple photoelectron scattering included. The extension also allows for atom swaps during EXAFS fits thereby enabling modeling the effects of chemical disorder, such as migrating atoms and vacancies. Significant acceleration of EXAFS computation is achieved via discretization of effective path lengths and subsequent reduction of operation counts. The validity and accuracy of the approach is illustrated on small atomic clusters and on 5500-9000 atom models of bcc-Fe and α-Fe(2)O(3). The accuracy gains of combined simultaneous EXAFS and PDF fits are pointed out against PDF-only and EXAFS-only RMC fits. Our modeling approach may be widely used in PDF and EXAFS based investigations of disordered materials. © 2012 American Institute of Physics

Fine tuning and MOND in a metamaterial "multiverse".

PubMed

Smolyaninov, Igor I; Smolyaninova, Vera N

2017-08-14

We consider the recently suggested model of a multiverse based on a ferrofluid. When the ferrofluid is subjected to a modest external magnetic field, the nanoparticles inside the ferrofluid form small hyperbolic metamaterial domains, which from the electromagnetic standpoint behave as individual "Minkowski universes" exhibiting different "laws of physics", such as different strength of effective gravity, different versions of modified Newtonian dynamics (MOND) and different radiation lifetimes. When the ferrofluid "multiverse" is populated with atomic or molecular species, and these species are excited using an external laser source, the radiation lifetimes of atoms and molecules in these "universes" depend strongly on the individual physical properties of each "universe" via the Purcell effect. Some "universes" are better fine-tuned than others to sustain the excited states of these species. Thus, the ferrofluid-based metamaterial "multiverse" may be used to study models of MOND and to illustrate the fine-tuning mechanism in cosmology.

X-ray absorption spectroscopy: EXAFS (Extended X-ray Absorption Fine Structure) and XANES (X-ray Absorption Near Edge Structure)

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

Alp, E.E.; Mini, S.M.; Ramanathan, M.

1990-04-01

The x-ray absorption spectroscopy (XAS) had been an essential tool to gather spectroscopic information about atomic energy level structure in the early decades of this century. It has also played an important role in the discovery and systematization of rare-earth elements. The discovery of synchrotron radiation in 1952, and later the availability of broadly tunable synchrotron based x-ray sources have revitalized this technique since the 1970's. The correct interpretation of the oscillatory structure in the x-ray absorption cross-section above the absorption edge by Sayers et. al. has transformed XAS from a spectroscopic tool to a structural technique. EXAFS (Extended X-raymore » Absorption Fine Structure) yields information about the interatomic distances, near neighbor coordination numbers, and lattice dynamics. An excellent description of the principles and data analysis techniques of EXAFS is given by Teo. XANES (X-ray Absorption Near Edge Structure), on the other hand, gives information about the valence state, energy bandwidth and bond angles. Today, there are about 50 experimental stations in various synchrotrons around the world dedicated to collecting x-ray absorption data from the bulk and surfaces of solids and liquids. In this chapter, we will give the basic principles of XAS, explain the information content of essentially two different aspects of the absorption process leading to EXAFS and XANES, and discuss the source and samples limitations.« less

Unexpectedly large difference of the electron density at the nucleus in the 4p ^2{P}_{{1}/{2},{3}/{2}} fine-structure doublet of Ca^+

NASA Astrophysics Data System (ADS)

Shi, C.; Gebert, F.; Gorges, C.; Kaufmann, S.; Nörtershäuser, W.; Sahoo, B. K.; Surzhykov, A.; Yerokhin, V. A.; Berengut, J. C.; Wolf, F.; Heip, J. C.; Schmidt, P. O.

2017-01-01

We measured the isotope shift in the ^2{S}_{{1}/{2}} → ^2{P}_{{3}/{2}} (D2) transition in singly ionized calcium ions using photon recoil spectroscopy. The high accuracy of the technique enables us to compare the difference between the isotope shifts of this transition to the previously measured isotopic shifts of the ^2{S}_{{1}/{2}} → ^2{P}_{{1}/{2}} (D1) line. This so-called splitting isotope shift is extracted and exhibits a clear signature of field shift contributions. From the data, we were able to extract the small difference of the field shift coefficient and mass shifts between the two transitions with high accuracy. This J-dependence is of relativistic origin and can be used to benchmark atomic structure calculations. As a first step, we use several ab initio atomic structure calculation methods to provide more accurate values for the field shift constants and their ratio. Remarkably, the high-accuracy value for the ratio of the field shift constants extracted from the experimental data is larger than all available theoretical predictions.

Optical and electrical properties of polycrystalline and amorphous Al-Ti thin films

NASA Astrophysics Data System (ADS)

Canulescu, S.; Borca, C. N.; Rechendorff, K.; Davidsdóttir, S.; Pagh Almtoft, K.; Nielsen, L. P.; Schou, J.

2016-04-01

The structural, optical, and transport properties of sputter-deposited Al-Ti thin films have been investigated as a function of Ti alloying with a concentration ranging from 2% to 46%. The optical reflectivity of Al-Ti films at visible and near-infrared wavelengths decreases with increasing Ti content. X-ray absorption fine structure measurements reveal that the atomic ordering around Ti atoms increases with increasing Ti content up to 20% and then decreases as a result of a transition from a polycrystalline to amorphous structure. The transport properties of the Al-Ti films are influenced by electron scattering at the grain boundaries in the case of polycrystalline films and static defects, such as anti-site effects and vacancies in the case of the amorphous alloys. The combination of Ti having a real refractive index (n) comparable with the extinction coefficient (k) and Al with n much smaller than k allows us to explore the parameter space for the free-electron behavior in transition metal-Al alloys. The free electron model, applied for the polycrystalline Al-Ti films with Ti content up to 20%, leads to an optical reflectance at near infrared wavelengths that scales linearly with the square root of the electrical resistivity.

Spectroscopic diagnostics of NIF ICF implosions using line ratios of Kr dopant in the ignition capsule

NASA Astrophysics Data System (ADS)

Dasgupta, Arati; Ouart, Nicholas; Giuiani, John; Clark, Robert; Schneider, Marilyn; Scott, Howard; Chen, Hui; Ma, Tammy

2017-10-01

X ray spectroscopy is used on the NIF to diagnose the plasma conditions in the ignition target in indirect drive ICF implosions. A platform is being developed at NIF where small traces of krypton are used as a dopant to the fuel gas for spectroscopic diagnostics using krypton line emissions. The fraction of krypton dopant was varied in the experiments and was selected so as not to perturb the implosion. Our goal is to use X-ray spectroscopy of dopant line ratios produced by the hot core that can provide a precise measurement of electron temperature. Simulations of the krypton spectra using a 1 in 104 atomic fraction of krypton in direct-drive exploding pusher with a range of electron temperatures and densities show discrepancies when different atomic models are used. We use our non-LTE atomic model with a detailed fine-structure level atomic structure and collisional-radiative rates to investigate the krypton spectra at the same conditions. Synthetic spectra are generated with a detailed multi-frequency radiation transport scheme from the emission regions of interest to analyze the experimental data with 0.02% Kr concentration and compare and contrast with the existing simulations at LLNL. Work supported by DOE/NNSA; Part of this work was also done under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract No. DE-AC52-07NA27344.

Analytical SuperSTEM for extraterrestrial materials research

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

Bradley, J P; Dai, Z R

2009-09-08

Electron-beam studies of extraterrestrial materials with significantly improved spatial resolution, energy resolution and sensitivity are enabled using a 300 keV SuperSTEM scanning transmission electron microscope with a monochromator and two spherical aberration correctors. The improved technical capabilities enable analyses previously not possible. Mineral structures can be directly imaged and analyzed with single-atomic-column resolution, liquids and implanted gases can be detected, and UV-VIS optical properties can be measured. Detection limits for minor/trace elements in thin (<100 nm thick) specimens are improved such that quantitative measurements of some extend to the sub-500 ppm level. Electron energy-loss spectroscopy (EELS) can be carried outmore » with 0.10-0.20 eV energy resolution and atomic-scale spatial resolution such that variations in oxidation state from one atomic column to another can be detected. Petrographic mapping is extended down to the atomic scale using energy-dispersive x-ray spectroscopy (EDS) and energy-filtered transmission electron microscopy (EFTEM) imaging. Technical capabilities and examples of the applications of SuperSTEM to extraterrestrial materials are presented, including the UV spectral properties and organic carbon K-edge fine structure of carbonaceous matter in interplanetary dust particles (IDPs), x-ray elemental maps showing the nanometer-scale distribution of carbon within GEMS (glass with embedded metal and sulfides), the first detection and quantification of trace Ti in GEMS using EDS, and detection of molecular H{sub 2}O in vesicles and implanted H{sub 2} and He in irradiated mineral and glass grains.« less

Copernicus observations of C I: pressures and carbon abundances in diffuse interstellar clouds

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

Jenkins, E.B.; Jura, M.; Loewenstein, M.

1983-07-01

Using the Copernicus satellite, we observed ultraviolet absorption lines of interstellar neutral carbon atoms toward 27 stars. In addition to deriving column densities of C I (both in its ground state and the two excited fine-structure levels), we used our equivalent widths to revise the f-values of some of the C I transitions measured by other investigators. We also observed H/sub 2/ from the J = 4 level so that we could compare the rotational excitation of H/sub 2/ with the fine-structure excitation of C I. From the amount of fine-structure excitation of C I in each case, we havemore » derived information on the thermal gas pressures within the diffuse clouds. Most clouds have p/k between 10/sup 3/ cm/sup -3/ K and 10/sup 4/ cm/sup -3/ K, but we found that at least 6% of the C I-bearing material is at p/k>10/sup 4/ cm/sup -3/ K, and one-third of the gas has upper limits for pressure below 10/sup 3/ cm/sup -3/ K, assuming temperatures are not appreciably below 20 K. An analysis of radial velocities for the absorption lines showed no distinctive trends for the kinematics of high- or low-pressure gas components. From the apparent lack of acceleration of high-pressure clouds, we conclude that it is unlikely that streaming intercloud material is causing significant ram pressurization. We have compared our results with the predictions for pressure fluctuations caused by supernova explosions in the theory of McKee and Ostriker.« less

Structure, electronic properties, and aggregation behavior of hydroxylated carbon nanotubes

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

López-Oyama, A. B.; Silva-Molina, R. A.; Ruíz-García, J.

2014-11-07

We present a combined experimental and theoretical study to analyze the structure, electronic properties, and aggregation behavior of hydroxylated multiwalled carbon nanotubes (OH–MWCNT). Our MWCNTs have average diameters of ∼2 nm, lengths of approximately 100–300 nm, and a hydroxyl surface coverage θ∼0.1. When deposited on the air/water interface the OH–MWCNTs are partially soluble and the floating units interact and link with each other forming extended foam-like carbon networks. Surface pressure-area isotherms of the nanotube films are performed using the Langmuir balance method at different equilibration times. The films are transferred into a mica substrate and atomic force microscopy images showmore » that the foam like structure is preserved and reveals fine details of their microstructure. Density functional theory calculations performed on model hydroxylated carbon nanotubes show that low energy atomic configurations are found when the OH groups form molecular islands on the nanotube's surface. This patchy behavior for the OH species is expected to produce nanotubes having reduced wettabilities, in line with experimental observations. OH doping yields nanotubes having small HOMO–LUMO energy gaps and generates a nanotube → OH direction for the charge transfer leading to the existence of more hole carriers in the structures. Our synthesized OH–MWCNTs might have promising applications.« less

Structure, electronic properties, and aggregation behavior of hydroxylated carbon nanotubes.

PubMed

López-Oyama, A B; Silva-Molina, R A; Ruíz-García, J; Gámez-Corrales, R; Guirado-López, R A

2014-11-07

We present a combined experimental and theoretical study to analyze the structure, electronic properties, and aggregation behavior of hydroxylated multiwalled carbon nanotubes (OH-MWCNT). Our MWCNTs have average diameters of ~2 nm, lengths of approximately 100-300 nm, and a hydroxyl surface coverage θ~0.1. When deposited on the air/water interface the OH-MWCNTs are partially soluble and the floating units interact and link with each other forming extended foam-like carbon networks. Surface pressure-area isotherms of the nanotube films are performed using the Langmuir balance method at different equilibration times. The films are transferred into a mica substrate and atomic force microscopy images show that the foam like structure is preserved and reveals fine details of their microstructure. Density functional theory calculations performed on model hydroxylated carbon nanotubes show that low energy atomic configurations are found when the OH groups form molecular islands on the nanotube's surface. This patchy behavior for the OH species is expected to produce nanotubes having reduced wettabilities, in line with experimental observations. OH doping yields nanotubes having small HOMO-LUMO energy gaps and generates a nanotube → OH direction for the charge transfer leading to the existence of more hole carriers in the structures. Our synthesized OH-MWCNTs might have promising applications.

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

Liu Chao; Hong Fashui; Wu Kang

Neodymium (Nd), as a member of rare earth elements, proved to enhance the photosynthesis rate and organic substance accumulation of spinach through the increase in carboxylation activity of Rubisco. Although the oxygenase activity of spinach Rubisco was slightly changed with the Nd{sup 3+} treatment, the specific factor of Rubisco was greatly increased. It was partially due to the promotion of Rubisco activase (R-A) activity but mainly to the formation of Rubisco-Rubisco activase super-complex, a heavier molecular mass protein (about 1200 kD) comprising both Rubisco and Rubisco activase. This super-complex was found during the extraction procedure of Rubisco by the gelmore » electrophoresis and Western-blot studies. The formation of Rubisco-R-A super-complex suggested that the secondary structure of the protein purified from the Nd{sup 3+}-treated spinach was different from that of the control. Extended X-ray absorption fine structure study of the 'Rubisco' purified from the Nd{sup 3+}-treated spinach revealed that Nd was bound with four oxygen atoms and two sulfur atoms of amino acid residues at the Nd-O and Nd-S bond lengths of 2.46 and 2.89 A, respectively.« less

Fabrication of GaN doped ZnO nanocrystallines by laser ablation.

PubMed

Gopalakrishnan, N; Shin, B C; Bhuvana, K P; Elanchezhiyan, J; Balasubramanian, T

2008-08-01

Here, we present the fabrication of pure and GaN doped ZnO nanocrystallines on Si(111) substrates by KrF excimer laser. The targets for the ablation have been prepared by conventional ceramic method. The fabricated nanocrystallines have been investigated by X-ray diffraction, photoluminescence and atomic force microscopy. The X-ray diffraction analysis shows that the crystalline size of pure ZnO is 36 nm and it is 41 nm while doped with 0.8 mol% of GaN due to best stoichiometry between Zn and O. Photoluminescence studies reveal that intense deep level emissions have been observed for pure ZnO and it has been suppressed for the GaN doped ZnO structures. The images of atomic force microscope show that the rms surface roughness is 27 nm for pure ZnO and the morphology is improved with decrease in rms roughness, 18 nm with fine crystallines while doped with 1 mol% GaN. The improved structural, optical and morphological properties of ZnO nanocrystalline due to GaN dopant have been discussed in detail.

Atomic-scale observation of structural and electronic orders in the layered compound α-RuCl3

PubMed Central

Ziatdinov, M.; Banerjee, A.; Maksov, A.; Berlijn, T.; Zhou, W.; Cao, H. B.; Yan, J.-Q.; Bridges, C. A.; Mandrus, D. G.; Nagler, S. E.; Baddorf, A. P.; Kalinin, S. V.

2016-01-01

A pseudospin-1/2 Mott phase on a honeycomb lattice is proposed to host the celebrated two-dimensional Kitaev model which has an elusive quantum spin liquid ground state, and fascinating physics relevant to the development of future templates towards topological quantum bits. Here we report a comprehensive, atomically resolved real-space study by scanning transmission electron and scanning tunnelling microscopies on a novel layered material displaying Kitaev physics, α-RuCl3. Our local crystallography analysis reveals considerable variations in the geometry of the ligand sublattice in thin films of α-RuCl3 that opens a way to realization of a spatially inhomogeneous magnetic ground state at the nanometre length scale. Using scanning tunnelling techniques, we observe the electronic energy gap of ≈0.25 eV and intra-unit cell symmetry breaking of charge distribution in individual α-RuCl3 surface layer. The corresponding charge-ordered pattern has a fine structure associated with two different types of charge disproportionation at Cl-terminated surface. PMID:27941761

Atomic-scale observation of structural and electronic orders in the layered compound α-RuCl3.

PubMed

Ziatdinov, M; Banerjee, A; Maksov, A; Berlijn, T; Zhou, W; Cao, H B; Yan, J-Q; Bridges, C A; Mandrus, D G; Nagler, S E; Baddorf, A P; Kalinin, S V

2016-12-12

A pseudospin-1/2 Mott phase on a honeycomb lattice is proposed to host the celebrated two-dimensional Kitaev model which has an elusive quantum spin liquid ground state, and fascinating physics relevant to the development of future templates towards topological quantum bits. Here we report a comprehensive, atomically resolved real-space study by scanning transmission electron and scanning tunnelling microscopies on a novel layered material displaying Kitaev physics, α-RuCl 3 . Our local crystallography analysis reveals considerable variations in the geometry of the ligand sublattice in thin films of α-RuCl 3 that opens a way to realization of a spatially inhomogeneous magnetic ground state at the nanometre length scale. Using scanning tunnelling techniques, we observe the electronic energy gap of ≈0.25 eV and intra-unit cell symmetry breaking of charge distribution in individual α-RuCl 3 surface layer. The corresponding charge-ordered pattern has a fine structure associated with two different types of charge disproportionation at Cl-terminated surface.

On the fine structure of meteoritical taenite/tetrataenite and its interpretation

NASA Astrophysics Data System (ADS)

Albertsen, J. F.; Nielsen, H. P.; Buchwald, V. F.

1983-04-01

TEM, electron microprobe, and Moessbauer spectroscopy are used in investigating taenite fields from several meteorites. A delicate pattern of antiphase domains is revealed in the tetrataenite, as is the presence of low-Ni taenite at the antiphase boundaries in what was hitherto believed to be pure tetrataenite. The observations suggest that the 'cloudy taenite' (cloudy zone II) was formed by a magnetically induced spinodal decomposition of the metastable taenite during slow cooling below 400 C. It is thought likely that decompositin occurs when the Curie temperature of the alloy changes rapidly with composition, as it does in f.c.c. iron-nickel alloys containing approximately 28-43 percent Ni (wt pct). The large contribution to Gibbs free energy from magnetic ordering leads to inflections in the Gibbs free energy curve, making the alloy unstable with regard to decomposition, in this case into a magnetically and atomically ordered Ni-rich alloy plus a magnetically and atomically disordered Ni-poor alloy. The model accounts well for the structure and composition of the two phases in the cloudy taenite.

Atomic-scale observation of structural and electronic orders in the layered compound α-RuCl 3

DOE PAGES

Ziatdinov, Maxim A.; Banerjee, Arnab; Maksov, Artem B.; ...

2016-12-12

A pseudospin-1/2 Mott phase on a honeycomb lattice is proposed to host the celebrated two-dimensional Kitaev model which has an elusive quantum spin liquid ground state, and fascinating physics relevant to the development of future templates towards topological quantum bits. Here we report a comprehensive, atomically resolved real-space study by scanning transmission electron and scanning tunnelling microscopies on a novel layered material displaying Kitaev physics, -RuCl3. Our local crystallography analysis reveals considerable variations in the geometry of the ligand sublattice in thin films of -RuCl3 that opens a way to realization of a spatially inhomogeneous magnetic ground state at themore » nanometre length scale. Using scanning tunnelling techniques, we observe the electronic energy gap of 0.25 eV and intra-unit cell symmetry breaking of charge distribution in individual -RuCl3 surface layer. The corresponding charge-ordered pattern has a fine structure associated with two different types of charge disproportionation at Cl-terminated surface.« less

Localized Symmetry Breaking for Tuning Thermal Expansion in ScF 3 Nanoscale Frameworks

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

Hu, Lei; Qin, Feiyu; Sanson, Andrea

The local symmetry, beyond the averaged crystallographic structure, tends to bring unu-sual performances. Negative thermal expansion is a peculiar physical property of solids. Here, we report the delicate design of the localized symmetry breaking to achieve the controllable thermal expansion in ScF3 nano-scale frameworks. Intriguingly, an isotropic zero thermal expansion is concurrently engi-neered by localized symmetry breaking, with a remarkably low coefficient of thermal expansion of about +4.0×10-8/K up to 675K. This mechanism is investigated by the joint analysis of atomic pair dis-tribution function of synchrotron X-ray total scattering and extended X-ray absorption fine structure spectra. A localized rhombohedral distortionmore » presumably plays a critical role in stiffening ScF3 nano-scale frameworks and concomitantly suppressing transverse thermal vibrations of fluorine atoms. This physical scenario is also theoretically corroborated by the extinction of phonon modes with negative Grüneisen parameters in the rhombohedral ScF3. The present work opens an untraditional chemical modification to achieve controllable thermal expansion by breaking local symmetries of materials.« less

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

PubMed

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

Relativistic opacities for astrophysical applications

DOE PAGES

Fontes, Christopher John; Fryer, Christopher Lee; Hungerford, Aimee L.; ...

2015-06-29

Here, we report on the use of the Los Alamos suite of relativistic atomic physics codes to generate radiative opacities for the modeling of astrophysically relevant plasmas under local thermodynamic equilibrium (LTE) conditions. The atomic structure calculations are carried out in fine-structure detail, including full configuration interaction. Three example applications are considered: iron opacities at conditions relevant to the base of the solar convection zone, nickel opacities for the modeling of stellar envelopes, and samarium opacities for the modeling of light curves produced by neutron star mergers. In the first two examples, comparisons are made between opacities that are generatedmore » with the fully and semi-relativistic capabilities in the Los Alamos suite of codes. As expected for these highly charged, iron-peak ions, the two methods produce reasonably similar results, providing confidence that the numerical methods have been correctly implemented. However, discrepancies greater than 10% are observed for nickel and investigated in detail. In the final application, the relativistic capability is used in a preliminary investigation of the complicated absorption spectrum associated with cold lanthanide elements.« less

Ultrahigh resolution drug design I: details of interactions in human aldose reductase-inhibitor complex at 0.66 A.

PubMed

Howard, E I; Sanishvili, R; Cachau, R E; Mitschler, A; Chevrier, B; Barth, P; Lamour, V; Van Zandt, M; Sibley, E; Bon, C; Moras, D; Schneider, T R; Joachimiak, A; Podjarny, A

2004-06-01

The first subatomic resolution structure of a 36 kDa protein [aldose reductase (AR)] is presented. AR was cocrystallized at pH 5.0 with its cofactor NADP+ and inhibitor IDD 594, a therapeutic candidate for the treatment of diabetic complications. X-ray diffraction data were collected up to 0.62 A resolution and treated up to 0.66 A resolution. Anisotropic refinement followed by a blocked matrix inversion produced low standard deviations (<0.005 A). The model was very well ordered overall (CA atoms' mean B factor is 5.5 A2). The model and the electron-density maps revealed fine features, such as H-atoms, bond densities, and significant deviations from standard stereochemistry. Other features, such as networks of hydrogen bonds (H bonds), a large number of multiple conformations, and solvent structure were also better defined. Most of the atoms in the active site region were extremely well ordered (mean B approximately 3 A2), leading to the identification of the protonation states of the residues involved in catalysis. The electrostatic interactions of the inhibitor's charged carboxylate head with the catalytic residues and the charged coenzyme NADP+ explained the inhibitor's noncompetitive character. Furthermore, a short contact involving the IDD 594 bromine atom explained the selectivity profile of the inhibitor, important feature to avoid toxic effects. The presented structure and the details revealed are instrumental for better understanding of the inhibition mechanism of AR by IDD 594, and hence, for the rational drug design of future inhibitors. This work demonstrates the capabilities of subatomic resolution experiments and stimulates further developments of methods allowing the use of the full potential of these experiments. Copyright 2004 Wiley-Liss, Inc.

ANTIHYDROGEN PRODUCTION AND PRECISION SPECTROSCOPY WITH ATHENA/AD-1

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

M. HOLZSCHEITER; C. AMSLER; ET AL

2000-11-01

CPT invariance is a fundamental property of quantum field theories in flat space-time. Principal consequences include the predictions that particles and their antiparticles have equal masses and lifetimes, and equal and opposite electric charges and magnetic moments. It also follows that the fine structure, hyperfine structure, and Lamb shifts of matter and antimatter bound systems should be identical. It is proposed to generate new stringent tests of CPT using precision spectroscopy on antihydrogen atoms. An experiment to produce antihydrogen at rest has been approved for running at the Antiproton Decelerator (AD) at CERN. We describe the fundamental features of thismore » experiment and the experimental approach to the first phase of the program, the formation and identification of low energy antihydrogen.« less

Two phase titanium aluminide alloy

DOEpatents

Deevi, Seetharama C.; Liu, C. T.

2001-01-01

A two-phase titanic aluminide alloy having a lamellar microstructure with little intercolony structures. The alloy can include fine particles such as boride particles at colony boundaries and/or grain boundary equiaxed structures. The alloy can include alloying additions such as .ltoreq.10 at % W, Nb and/or Mo. The alloy can be free of Cr, V, Mn, Cu and/or Ni and can include, in atomic %, 45 to 55% Ti, 40 to 50% Al, 1 to 5% Nb, 0.3 to 2% W, up to 1% Mo and 0.1 to 0.3% B. In weight %, the alloy can include 57 to 60% Ti, 30 to 32% Al, 4 to 9% Nb, up to 2% Mo, 2 to 8% W and 0.02 to 0.08% B.

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural using ALD overcoating

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

Zhang, Hongbo; Lei, Yu; Kropf, A. Jeremy

2014-08-01

The stability of a gas-phase furfural hydrogenation catalyst (CuCr2O4 center dot CuO) was enhanced by depositing a thin Al2O3 layer using atomic layer deposition (ALD). Based on temperature-programed reduction (TPR) measurements, the reduction temperature of Cu was raised significantly, and the activation energy for furfural reduction was decreased following the ALD treatment. Thinner ALD layers yielded higher furfural hydrogenation activities. X-ray absorption fine structure (XAFS) spectroscopy studies indicated that Cu1+/Cu-0 are the active species for furfural reduction.

Biexciton emission from single isoelectronic traps formed by nitrogen-nitrogen pairs in GaAs

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

Takamiya, Kengo; Fukushima, Toshiyuki; Yagi, Shuhei

2013-12-04

We have studied photoluminescence (PL) from individual isoelectronic traps formed by nitrogen-nitrogen (NN) pairs in GaAs. Sharp emission lines due to exciton and biexciton were observed from individual isoelectronic traps in nitrogen atomic-layer doped (ALD) GaAs. The binding energy of biexciton bound to individual isoelectronic traps was approximately 8 meV. Both the exciton and biexciton luminescence lines show completely random polarization and no fine-structure splitting. These results are desirable to the application to the quantum cryptography used in the field of quantum information technology.

40 CFR 63.5935 - What definitions apply to this subpart?

Code of Federal Regulations, 2011 CFR

2011-07-01

... defined in the CAA, in 40 CFR 63.2, and in this section as follows: Atomized mechanical application means application of resin or gel coat with spray equipment that separates the liquid into a fine mist. This fine... equivalent material) prior to resin application, and the resin is injected into the covered mold are also...

Carbon Dioxide Electroreduction into Syngas Boosted by a Partially Delocalized Charge in Molybdenum Sulfide Selenide Alloy Monolayers.

PubMed

Xu, Jiaqi; Li, Xiaodong; Liu, Wei; Sun, Yongfu; Ju, Zhengyu; Yao, Tao; Wang, Chengming; Ju, Huanxin; Zhu, Junfa; Wei, Shiqiang; Xie, Yi

2017-07-24

Structural parameters of ternary transition-metal dichalcogenide (TMD) alloy usually obey Vegard law well, while interestingly it often exhibits boosted electrocatalytic performances relative to its two pristine binary TMDs. To unveil the underlying reasons, we propose an ideal model of ternary TMDs alloy monolayer. As a prototype, MoSeS alloy monolayers are successfully synthesized, in which X-ray absorption fine structure spectroscopy manifests their shortened Mo-S and lengthened Mo-Se bonds, helping to tailor the d-band electronic structure of Mo atoms. Density functional theory calculations illustrate an increased density of states near their conduction band edge, which ensures faster electron transfer confirmed by their lower work function and smaller charge-transfer resistance. Energy calculations show the off-center charge around Mo atoms not only benefits for stabilizing COOH* intermediate confirmed by its most negative formation energy, but also facilitates the rate-limiting CO desorption step verified by CO temperature programmed desorption and electro-stripping tests. As a result, MoSeS alloy monolayers attain the highest 45.2 % Faradaic efficiency for CO production, much larger than that of MoS 2 monolayers (16.6 %) and MoSe 2 monolayers (30.5 %) at -1.15 V vs. RHE. This work discloses how the partially delocalized charge in ternary TMDs alloys accelerates electrocatalytic performances at atomic level, opening new horizons for manipulating CO 2 electroreduction properties. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temperature-dependent local structural properties of redox Pt nanoparticles on TiO 2 and ZrO 2 supports

DOE PAGES

Jeong, Eun -Suk; Park, Chang -In; Jin, Zhenlan; ...

2015-01-21

This paper examined the local structural properties of Pt nanoparticles on SiO 2, TiO 2–SiO 2, and ZrO 2–SiO 2 supports to better understand the impact of oxide-support type on the performance of Pt-based catalysts. In situ X-ray absorption fine structure (XAFS) measurements were taken for the Pt L3-edge in a temperature range from 300 to 700 K in He, H 2, and O 2 gas environments. The XAFS measurements demonstrated that Pt atoms were highly dispersed on TiO 2–SiO 2 and ZrO 2–SiO 2 forming pancake-shaped nanoparticles, whereas Pt atoms formed larger particles of hemispherical shapes on SiO 2more » supports. Contrary to the SiO 2 case, the coordination numbers for Pt, Ti, and Zr around Pt atoms on the TiO 2–SiO 2 and ZrO 2–SiO 2 supports were nearly constant from 300 to 700 K under the different gas environments. These results are consistent with the improvements in thermal stability of Pt nanoparticles achieved by incorporating TiO 2 or ZrO 2 on the surface of SiO 2 supports. XAFS analysis further indicated that the enhanced dispersion and stability of Pt were a consequence of the strong metal support interaction via Pt–Ti and Pt–Zr bonds.« less

Laser Spectroscopy of Highly-Charged Ions in an Electron Beam Ion Trap

NASA Astrophysics Data System (ADS)

Hosaka, K.; Crosby, D. N.; Gaarde-Widdowson, K.; Smith, C. J.; Silver, J. D.; Kinugawa, T.; Ohtani, S.; Myers, E. G.

2002-05-01

Using a ^14C^16O2 carbon-dioxide laser the 2s_1/2 - 2p_3/2 (fine structure - Lamb shift) transition has been induced in hydrogen-like nitrogen ions produced and trapped in the Oxford EBIT [1]. The transition was observed using a Si(Li) x-ray detector as a small increase in x-rays at the energy of the 2p - 1s transition as the laser wavelength was line-tuned across the resonance. A corresponding reduction in x-rays near the peak of the two-photon 2s - 1s energy spectrum was also seen. The method will be compared with the fast-beam laser technique [2]. [1] J.D. Silver et al., Rev. Sci. Instrum. 65, 1072 (1994). [2] E.G. Myers and M.R. Tarbutt, in The Hydrogen Atom, Precision Physics of Simple Atomic Systems, ed. S.G. Karshenboim et al., Springer 2001, p 688.

Biomimetic whisker-shaped apatite coating of titanium powder.

PubMed

Sim, Young Uk; Kim, Jong Hee; Yang, Tae Young; Yoon, Seog Young; Park, Hong Chae

2010-05-01

Biomimetic apatite coatings on chemically modified titanium powder have been processed and the resulting coating layers evaluated in terms of morphology, composition and structure, using TF-XRD, XPS, SEM, TEM and FTIR analysis. After 7 days immersion in a simulated body fluid (SBF), nanometer-sized fine precipitates with an amorphous whisker-like phase and a Ca/P atomic ratio of 1.94 were obtained on the external surface of the titanium particles. When the immersion time in SBF was extended to 16 days, the coating layer consisted of the whisker-like nanostructured crystals of carbonated hydroxyapatite with a atomic ratio of 3; in such a case, a double coating layer was developed. The double layer could be divided into two regions and could be clearly distinguished: an inner dense region (approximately 200 nm in thickness) which may include hard agglomerated crystals and an outer less dense region (> 500 nm in thickness) in which crystals are loosely distributed.

Recent Progresses and Development of Advanced Atomic Layer Deposition towards High-Performance Li-Ion Batteries

PubMed Central

Lu, Wei; Liang, Longwei; Sun, Xuan; Sun, Xiaofei; Wu, Chen; Hou, Linrui; Sun, Jinfeng

2017-01-01

Electrode materials and electrolytes play a vital role in device-level performance of rechargeable Li-ion batteries (LIBs). However, electrode structure/component degeneration and electrode-electrolyte sur-/interface evolution are identified as the most crucial obstacles in practical applications. Thanks to its congenital advantages, atomic layer deposition (ALD) methodology has attracted enormous attention in advanced LIBs. This review mainly focuses upon the up-to-date progress and development of the ALD in high-performance LIBs. The significant roles of the ALD in rational design and fabrication of multi-dimensional nanostructured electrode materials, and finely tailoring electrode-electrolyte sur-/interfaces are comprehensively highlighted. Furthermore, we clearly envision that this contribution will motivate more extensive and insightful studies in the ALD to considerably improve Li-storage behaviors. Future trends and prospects to further develop advanced ALD nanotechnology in next-generation LIBs were also presented. PMID:29036916

Inorganic and Organometallic Molecular Wires for Single-Molecule Devices.

PubMed

Tanaka, Yuya; Kiguchi, Manabu; Akita, Munetaka

2017-04-06

Recent developments of single-molecule conductance measurements allow us to understand fundamental conducting properties of molecular wires. While a wide variety of organic molecular wires have been studied so far, inorganic and organometallic molecular wires have received much less attention. However, molecular wires with transition-metal atoms show interesting features and functions distinct from those of organic wires. These properties originate mainly from metal-ligand dπ-pπ interactions and metal-metal d-d interactions. Thanks to the rich combination of metal atoms and supporting ligands, frontier orbital energies of the molecular wires can be finely tuned to lead to highly conducting molecular wires. Moreover, the unique electronic structures of metal complexes are susceptible to subtle environmental changes, leading to potential functional molecular devices. This article reviews recent advances in the single-molecule conductance study of inorganic and organometallic molecular wires. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantum optics in a high impedance environment

NASA Astrophysics Data System (ADS)

Puertas, Javier; Gheeraert, Nicolas; Krupko, Yuriy; Dassonneville, Remy; Planat, Luca; Foroughui, Farshad; Naud, Cecile; Guichard, Wiebke; Buisson, Olivier; Florens, Serge; Roch, Nicolas; Snyman, Izak

Understanding light matter interaction remains a key topic in fundamental physics. Its strength is imposed by the fine structure constant, α. For most atomic and molecular systems α =e2/ℏc 4 πɛo = 1 / 137 << 1 , giving weak interactions. When dealing with superconducting artificial atoms, α is either proportional to 1 /Zc (magnetic coupling) or Zc (electric coupling), where Zc is the characteristic impedance of the environment. Recent experiments followed the first approach, coupling a flux qubit to a low impedance environment, demonstrating strong interaction (α 1). In our work, we reached the large α regime, following a complementary approach: we couple electrically a transmon qubit to an array of 5000 SQUIDs. This metamaterial provides high characteristic impedance ( 3 kΩ), in-situ flux tunability and full control over its dispersion relation. In this new regime, all usual approximations break down and new phenomena such as frequency conversion at the single photon level are expected.

Extended X-ray Absorption Fine Structure (EXAFS) Analysis of Vitreous Rare Earth Sodium Phosphates

NASA Astrophysics Data System (ADS)

Yoo, Changhyeon; Marasinghe, Kanishka; Segre, Carlo; Shibata, Tomohiro

2015-03-01

The local structure around rare-earth ions (RE3+) in rare-earth ultraphosphate (REUP) glasses has been studied using RE LIII edge (RE = Nd, Er, Dy, and Eu) and K edge (RE = Nd, Pr, Dy, and Eu) extended X-ray absorption fine structure (EXAFS) spectroscopy. (RE2O3)x (Na2O)y(P2O5) 1 - x - y glasses in the compositional range 0 <= x <= 0.14 and x + y = 0.3 and 0.4 were studied. RE-oxygen (RE-O) coordination number decreases from ~ 10 to ~ 7.5 with increasing RE-content for Nd, Pr, Eu, and Dy. For Er, RE-O coordination number increases from ~ 8.7 to ~ 10 with increasing RE-content. For the first oxygen shell, the RE-O distance ranges between 2.41-2.43 Å, 2.44-2.46 Å, 2.24-2.26 Å, 2.28-2.32 Å, and 2.32-2.36 Å for Nd, Pr, Er, Dy, and EU glasses, respectively. Second shell around RE ions consists of phosphorus atoms, with RE-P distance about 3.0-3.5 Å and coordination number ranging from 1 to 3. The third shell primarily contains oxygen and is at a distance about 4.0-4.1 Å from RE ions.

Sub-Doppler infrared spectroscopy of propargyl radical (H{sub 2}CCCH) in a slit supersonic expansion

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

Chang, Chih-Hsuan; Nesbitt, David J.

The acetylenic CH stretch mode (ν{sub 1}) of propargyl (H{sub 2}CCCH) radical has been studied at sub-Doppler resolution (∼60 MHz) via infrared laser absorption spectroscopy in a supersonic slit-jet discharge expansion, where low rotational temperatures (T{sub rot} = 13.5(4) K) and lack of spectral congestion permit improved determination of band origin and rotational constants for the excited state. For the lowest J states primarily populated in the slit jet cooled expansion, fine structure due to the unpaired electron spin is resolved completely, which permits accurate analysis of electron spin-rotation interactions in the vibrationally excited states (ε{sub aa} = − 518.1(1.8),more » ε{sub bb} = − 13.0(3), ε{sub cc} = − 1.8(3) MHz). In addition, hyperfine broadening in substantial excess of the sub-Doppler experimental linewidths is observed due to nuclear spin–electron spin contributions at the methylenic (—CH{sub 2}) and acetylenic (—CH) positions, which permits detailed modeling of the fine/hyperfine structure line contours. The results are consistent with a delocalized radical spin density extending over both methylenic and acetylenic C atoms, in excellent agreement with simple resonance structures as well as ab initio theoretical calculations.« less

Chaotic behavior of channeling particles.

PubMed

Chen, Ling; Kaloyeros, Alain E.; Wang, Guang-Hou

1994-03-01

Channeling describes the collimated motion of energetic charged particles along the lattice plane or axis in a crystal. The energetic particles are steered through the channels formed by strings of atomic constituents in the lattice. In the case of planar channeling, the motion of a charged particle between the atomic planes can be periodic or quasiperiodic, such as a simple oscillatory motion in the transverse direction. In practice, however, the periodic motion of the channeling particles can be accompanied by an irregular, chaotic behavior. In this paper, the Moliere potential, which is considered as a good analytical approximation for the interaction of channeling particles with the rows of atoms in the lattice, is used to simulate the channeling behavior of positively charged particles in a tungsten (100) crystal plane. By appropriate selection of channeling parameters, such as the projectile energy E(0) and incident angle psi(0), the transition of channeling particles from regular to chaotic motion is demonstrated. It is argued that the fine structures that appear in the angular scan channeling experiments are due to the particles' chaotic motion.

Atomic and Molecular Spectroscopic Studies of the DIII-D Neutral Beam Ion Source and Neutralizer

NASA Astrophysics Data System (ADS)

Crowley, B.; Rauch, J.; Scoville, J. T.; Sharma, S. K.; Choksi, B.

2015-11-01

The neutral beam system is interesting in that it comprises two distinct low temperature plasmas. Firstly, the ion source is typically a filament or RF driven plasma from which ions are extracted by a high voltage accelerator grid system. Secondly the neutralizer is essentially a low temperature plasma system with the beam serving as the primary ionization source and the neutralizer walls serving as conducting boundaries. Atomic spectroscopy of Doppler shifted D-alpha light emanating from the fast atoms is studied to determine the composition of the source and the divergence of the beam. Molecular spectroscopy involves measuring fine structure in electron-vibrational rotational bands. The technique has applications in low temperature plasmas and here it is used to determine gas temperature in the neutralizer. We describe the experimental set-up and the physics model used to relate the spectroscopic data to the plasma parameters and we present results of recent experiments exploring how to increase neutralization efficiency. Supported by the US DOE under DE-FC02-04ER54698.

Shell- and subshell-resolved projectile excitation of hydrogenlike Au{sup 78+} ions in relativistic ion-atom collisions

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

Gumberidze, A.; Frankfurt Institute for Advanced Studies FIAS, D-60438 Frankfurt am Main; Fritzsche, S.

2010-11-15

The projectile excitation of high-Z ions has been investigated in relativistic ion-atoms collisions by observing the subsequent x-ray emission. The x-ray spectra from the projectile excitation have been separated from the x-ray emission following electron capture into the excited states using a novel anticoincidence technique. For the particular case of hydrogenlike Au{sup 78+} ions colliding with Ar atoms, Coulomb excitation from the ground state into the fine-structure-resolved n=2 levels as well as into levels with principal quantum number n{>=}3 has been measured with excellent statistics. The observed spectra agree well with simulated spectra that are based on Dirac's relativistic equationmore » and the proper inclusion of the magnetic interaction into the amplitudes for projectile excitation. It is shown that a coherent inclusion of the magnetic part of the Lienard-Wiechert potential leads to the lowering of the excitation cross section by up to 35%. This effect is more pronounced for excitation into states with high angular momentum and is confirmed by our experimental data.« less

Role of the local structure in superconductivity of LaO0.5F0.5BiS2-x Se x system

NASA Astrophysics Data System (ADS)

Paris, E.; Mizuguchi, Y.; Hacisalihoglu, M. Y.; Hiroi, T.; Joseph, B.; Aquilanti, G.; Miura, O.; Mizokawa, T.; Saini, N. L.

2017-04-01

We have studied the local structure of LaO0.5F0.5BiS2-x Se x by Bi L1-edge extended x-ray absorption fine structure (EXAFS). We find a significant effect of Se substitution on the local atomic correlations with a gradual elongation of average in-plane Bi-S bondlength. The associated mean square relative displacement, measuring average local distortions in the BiS2 plane, hardly shows any change for small Se substitution, but decreases significantly for x≥slant 0.6 . The Se substitution appears to suppress the local distortions within the BiS2 plane that may optimize in-plane orbital hybridization and hence the superconductivity. The results suggest that the local structure of the BiS2-layer is one of the key ingredients to control the physical properties of the BiS2-based dichalcogenides.

Pore radius fine tuning of a silica matrix (MCM-41) based on the synthesis of alumina nanolayers with different thicknesses by atomic layer deposition

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

Zemtsova, Elena G., E-mail: ezimtsova@yandex.ru; Arbenin, Andrei Yu.; Plotnikov, Alexander F.

2015-03-15

The authors investigated a new approach to modify the surface of the mesoporous silica matrix MCM-41. This approach is based on manipulating the chemical composition of the porous surface layer and also on fine tuning the pore radius by applying the atomic layer deposition (ALD) technique. The synthesis of alumina nanolayers was performed on the planar and the porous matrix (MCM-41) by the ALD technique using aluminum tri-sec-butoxide and water as precursors. The authors show that one cycle on silicon, using aluminum tri-sec-butoxide and water as precursors, results in a 1–1.2 Å increase in alumina nanolayer thickness. This is comparable tomore » the increase in thickness per cycle for other precursors such as trimethylaluminum and aluminum chloride. The authors show that the synthesis of an Al{sub 2}O{sub 3} nanolayer on the pore surface of the mesoporous silica matrix MCM-41 by the ALD technique results in a regular change in the porous structure of the samples. The specific porosity (ml/g) of the MCM-41 was 0.95 and that of MCM-41 after 5 ALD cycles was 0.39. The pore diameter (nm) of MCM-41 was 3.3 and that of MCM-41 after 5 ALD cycles was 2.3.« less

Complex polarization propagator approach in the restricted open-shell, self-consistent field approximation: the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine.

PubMed

Linares, Mathieu; Stafström, Sven; Rinkevicius, Zilvinas; Ågren, Hans; Norman, Patrick

2011-05-12

A presentation of the complex polarization propagator in the restricted open-shell self-consistent field approximation is given. It rests on a formulation of a resonant-convergent, first-order polarization propagator approach that makes it possible to directly calculate the X-ray absorption cross section at a particular frequency without explicitly addressing the excited states. The quality of the predicted X-ray spectra relates only to the type of density functional applied without any separate treatment of dynamical relaxation effects. The method is applied to the calculation of the near K-edge X-ray absorption fine structure spectra of allyl and copper phthalocyanine. Comparison is made between the spectra of the radicals and those of the corresponding cations and anions to assess the effect of the increase of electron charge in the frontier orbital. The method offers the possibility for unique assignment of symmetry-independent atoms. The overall excellent spectral agreement motivates the application of the method as a routine precise tool for analyzing X-ray absorption of large systems of technological interest.

High Electrochemical Sensitivity of TiO2- x Nanosheets and an Electron-Induced Mutual Interference Effect toward Heavy Metal Ions Demonstrated Using X-ray Absorption Fine Structure Spectra.

PubMed

Zhou, Wen-Yi; Li, Shan-Shan; Song, Jie-Yao; Jiang, Min; Jiang, Tian-Jia; Liu, Jin-Yun; Liu, Jin-Huai; Huang, Xing-Jiu

2018-04-03

Mutual interference is a severe issue that occurs during the electrochemical detection of heavy metal ions. This limitation presents a notable drawback for its high sensitivity to specific targets. Here, we present a high electrochemical sensitivity of ∼237.1 μA cm -2 μM -1 toward copper(II) [Cu(II)] based on oxygen-deficient titanium dioxide (TiO 2- x ) nanosheets. We fully demonstrated an atomic-level relationship between electrochemical behaviors and the key factors, including the high-energy (001) facet percentage, oxygen vacancy concentration, surface -OH content, and charge carrier density, is fully demonstrated. These four factors were quantified using Raman, electron spin resonance, X-ray photoelectron spectroscopy spectra, and Mott-Schottky plots. In the mutual interference investigation, we selected cadmium(II) [Cd(II)] as the target ion because of the significant difference in its stripping potential (∼700 mV). The results show that the Cd(II) can enhance the sensitivity of TiO 2- x nanosheets toward Cu(II), exhibiting an electron-induced mutual interference effect, as demonstrated by X-ray absorption fine structure spectra.

Quantitative Phase Composition of TiO 2-Coated Nanoporous-Au Monoliths by X-ray Absorption Spectroscopy and Correlations to Catalytic

DOE PAGES

Bagge-Hansen, Michael; Wichmann, Andre; Wittstock, Arne; ...

2014-02-03

Porous titania/metal composite materials have many potential applications in the fields of green catalysis, energy harvesting, and storage in which both the overall morphology of the nanoporous host material and the crystallographic phase of the titania (TiO 2) guest determine the material’s performance. New insights into the structure–function relationships of these materials were obtained by near-edge X-ray absorption fine structure (NEXAFS) spectroscopy that, for example, provides quantitative crystallographic phase composition from ultrathin, nanostructured titania films, including sensitivity to amorphous components. We demonstrate that crystallographic phase, morphology, and catalytic activity of TiO 2-functionalized nanoporous gold (np-Au) can be controlled by amore » simple annealing procedure (T < 1300 K). The material was prepared by atomic layer deposition of ~2 nm thick TiO 2 on millimeter-sized samples of np-Au (40–50 nm mean ligament size) and catalytically investigated with respect to aerobic CO oxidation. Moreover, the annealing-induced changes in catalytic activity are correlated with concurrent morphology and phase changes as provided by cross-sectional scanning electron microscopy, transmission electron microscopy, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy.« less

Structural Characterization of Poorly-Crystalline Scorodite, Iron (III)-arsenate Co-precipitates and Uranium Millneutralized Raffinate Solids using X-ray Absorption Fine Structure Spectroscopy

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

Chen, N.; Jiang, D; Cutler, J

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Femore » K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 {+-} 0.02 A and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 {+-} 0.02 A and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 {+-} 0.03 A and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 {+-} 0.03 A and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 {+-} 0.03 A and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As-Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.« less

Structural characterization of poorly-crystalline scorodite, iron(III)-arsenate co-precipitates and uranium mill neutralized raffinate solids using X-ray absorption fine structure spectroscopy

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

Chen, N; Jiang, D T; Cutler, J

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Femore » K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 ± 0.02 Å and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 ± 0.02 Å and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 ± 0.03 Å and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 ± 0.03 Å and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 ± 0.03 Å and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As-Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.« less

High rotational CO lines in post-AGB stars and PNe

NASA Technical Reports Server (NTRS)

Justtanont, K.; Tielens, Alexander G. G. M.; Skinner, C. J.; Haas, Michael R.

1995-01-01

A significant fraction of a star's initial mass is lost while it is on the Asymptotic Giant Branch (AGB). Mass loss rates range from 10(exp -7) solar mass/yr for early AGB stars to a few 10(exp -4) solar mass/yr for stars at the tip of the AGB. Dust grains condense from the outflow as the gas expands and form a dust shell around the central star. A superwind (approximately 10(exp -4) to 10(exp -3) solar mass/yr) is thought to terminate the AGB phase. In the post-AGB phase, the star evolves to a higher effective temperature, the mass loss decreases (approximately 10(exp -8) solar mass/yr), but the wind velocity increases (approximately 1000 km/s). During this evolution, dust and gas are exposed to an increasingly harsher radiation field and when T(sub eff) reaches about 30,000 K, the nebula is ionized and becomes a planetary nebula (PN). Photons from the central star can create a photodissociation region (PDR) in the expanding superwind. Gas can be heated through the photoelectric effect working on small grains and polycyclic aromatic hydrocarbons (PAH's). This gas can cool via the atomic fine structure lines of O I (63 microns and 145 microns) and C II (158 microns), as well as the rotational lines of CO. In the post-AGB phase, the fast wind from the central star will interact with the material ejected during the AGB phase. The shock caused by this interaction will dissociate and heat the gas. This warm gas will cool through atomic fine structure lines of O I and the rotational lines of (newly formed) CO.

Electron impact excitation rate coefficients for P-like Ni XIV

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

Wang, K.; Shanghai EBIT Lab, Institute of Modern Physics, Department of Nuclear Science and Technology, Fudan University, Shanghai 200433; Yan, J.

2012-07-15

We have calculated the atomic data including electron impact excitations and radiative decays among the lowest 143 fine-structure levels arising from 3s{sup 2}3p{sup 3}, 3s3p{sup 4}, 3s{sup 2}3p{sup 2}3d, 3p{sup 5}, 3s3p{sup 3}3d, and 3s{sup 2}3p3d{sup 2} configurations in P-like Ni XIV. Direct excitation collision strengths are calculated employing the relativistic distorted-wave method. Resonances are included via the isolated resonance approximation using distorted-waves. Resonance contributions from S-like [3s{sup 2}3p{sup 3}, 3s3p{sup 4}, 3s{sup 2}3p{sup 2}3d,3p{sup 5}, 3s3p{sup 3}3d,3s{sup 2}3p3d{sup 2}, 3p{sup 4}3d,3s3p{sup 2}3d{sup 2},3s{sup 2}3d{sup 3}]n{sup Prime }l{sup Prime} complex series are taken into account. Effective collision strengths are reportedmore » over an electron temperature range of 1.0 Multiplication-Sign 10{sup 5}-1.0 Multiplication-Sign 10{sup 8} K. -- Highlights: Black-Right-Pointing-Pointer Radiative and collisional atomic data are presented for the lowest 143 fine-structure levels in P-like Ni XIV. Black-Right-Pointing-Pointer Calculations are performed using the FAC package. Black-Right-Pointing-Pointer Resonances enhance significantly a large amount of transitions. Black-Right-Pointing-Pointer Resonances play an important role of level population and line intensity ratios.« less

Acoustic fine structure may encode biologically relevant information for zebra finches.

PubMed

Prior, Nora H; Smith, Edward; Lawson, Shelby; Ball, Gregory F; Dooling, Robert J

2018-04-18

The ability to discriminate changes in the fine structure of complex sounds is well developed in birds. However, the precise limit of this discrimination ability and how it is used in the context of natural communication remains unclear. Here we describe natural variability in acoustic fine structure of male and female zebra finch calls. Results from psychoacoustic experiments demonstrate that zebra finches are able to discriminate extremely small differences in fine structure, which are on the order of the variation in acoustic fine structure that is present in their vocal signals. Results from signal analysis methods also suggest that acoustic fine structure may carry information that distinguishes between biologically relevant categories including sex, call type and individual identity. Combined, our results are consistent with the hypothesis that zebra finches can encode biologically relevant information within the fine structure of their calls. This study provides a foundation for our understanding of how acoustic fine structure may be involved in animal communication.

Precipitation Behavior During Aging in α Phase Titanium Supersaturated with Cu

NASA Astrophysics Data System (ADS)

Mitsuhara, Masatoshi; Masuda, Tomoya; Nishida, Minoru; Kunieda, Tomonori; Fujii, Hideki

2016-04-01

Age hardening of Ti-2.3 mass pct Cu (Ti-2.3Cu) at 673 K to 873 K (400 °C to 600 °C) after solution treatment at 1063 K (790 °C) was observed. The relationship between precipitates formed during aging and changes in hardness was investigated. During aging at 673 K (400 °C), the hardness increased rapidly up to 200 hours, and subsequently increased more slowly up to 1000 hours. At 873 K (600 °C), the hardness began to decrease immediately. Transmission electron microscopy showed that fine disk-shaped precipitates of 20 to 40 nm in diameter grew in the α phase. It is concluded that these precipitates interacted with dislocations and increased the hardness. At 873 K (600 °C), precipitates of 1 µm in length and Ti2Cu particles of 200 nm in length were observed. The decrease in hardness may have resulted from the precipitate formation decreasing the concentration of Cu in the α phase. Bright/dark contrast of the three atomic layers and small atomic shift of the hcp structure were observed in the atomic resolution imaging of the precipitates. This suggests that the precipitates are not just Cu-enriched zones and have structures with similar periodicity to the Ti2Cu phase, which is thermally stable at those aging temperatures.

The Influence of Milling and Spark Plasma Sintering on the Microstructure and Properties of the Al7075 Alloy

PubMed Central

Málek, Přemysl; Minárik, Peter; Novák, Pavel; Průša, Filip

2018-01-01

The compact samples of an Al7075 alloy were prepared by a combination of gas atomization, high energy milling, and spark plasma sintering. The predominantly cellular morphology observed in gas atomized powder particles was completely changed by mechanical milling. The continuous-like intermetallic phases present along intercellular boundaries were destroyed; nevertheless, a small amount of Mg(Zn,Cu,Al)2 phase was observed also in the milled powder. Milling resulted in a severe plastic deformation of the material and led to a reduction of grain size from several µm into the nanocrystalline region. The combination of these microstructural characteristics resulted in abnormally high microhardness values exceeding 300 HV. Consolidation through spark plasma sintering (SPS) resulted in bulk samples with negligible porosity. The heat exposition during SPS led to precipitation of intermetallic phases from the non-equilibrium microstructure of both gas atomized and milled powders. SPS of the milled powder resulted in a recrystallization of the severely deformed structure. An ultra-fine grained structure (grain size close to 500 nm) with grains divided primarily by high-angle boundaries was formed. A simultaneous release of stored deformation energy and an increase in the grain size caused a drop of microhardness to values close to 150 HV. This value was retained even after annealing at 425 °C. PMID:29614046

Recent progress on the cold atoms clocks at BNM-LPTF

NASA Astrophysics Data System (ADS)

Abgrall, M.; Lemonde, P.; Bize, S.; Sortais, Y.; Zhang, S.; Santarelli, G.; Laurent, P.; Clairon, A.; Salomon, C.

We present recent results on microwave frequency standards using cold atoms. Two cesium fountains have been built and exhibit a frequency accuracy of 1×10-15. Though quite different in their design, both fountains are found to give the same frequency within the error bars of the measurements. One of the fountains is transportable. It was moved to Germany and used as a reference for a phase coherent measurement of the 1S-2S transition of hydrogen with a 2×10-14 accuracy. When using a cryogenic sapphire oscillator as an interrogation oscillator, the frequency stability reaches the fundamental limit set by the quantum projection noise. A short term stability of 4×10-14 τ-1/2 has been obtained. One limitation to the performances of cesium fountains is the frequency shift due to collisions between cold atoms. We show that with rubidium atoms, this effect can be decreased by two orders of magnitude. This feature should allow to vastly improve both the stability and accuracy of microwave fountains. Finally by tracking the frequency between rubidium and cesium fountains, we test the stability of the fine structure constant α with a few 10-15 resolution. We also present the status of the ACES space project.

Magnetic-dipole-to-electric-quadrupole cross-susceptibilities for relativistic hydrogenlike atoms in some low-lying discrete energy eigenstates

NASA Astrophysics Data System (ADS)

Stefańska, Patrycja

2017-01-01

In this paper we present tabulated data for magnetic-dipole-to-electric-quadrupole cross-susceptibilities (χ M 1 →E 2) for Dirac one-electron atoms with a pointlike, spinless and motionless nucleus of charge Ze. Numerical values of this susceptibility for the hydrogen atom (Z = 1) and for hydrogenic ions with 2 ⩽ Z ⩽ 137 are computed from the general analytical formula, recently derived by us (Stefanska, 2016), valid for an arbitrary discrete energy eigenstate. In this work we provide 30 tables with the values of χ M 1 →E 2 for the ground state, and also for the first, the second and the third set of excited states (i.e.: 2s1/2, 2p1/2, 2p3/2, 3s1/2, 3p1/2, 3p3/2, 3d3/2, 3d5/2, 4s1/2, 4p1/2, 4p3/2, 4d3/2, 4d5/2, 4f5/2 and 4f7/2) of the relativistic hydrogenlike atoms. The value of the inverse of the fine-structure constant used in the calculations is α-1 = 137.035999139, and was taken from CODATA 2014.

Complex vibrations in arsenide skutterudites and oxyskutterudites

NASA Astrophysics Data System (ADS)

Bridges, F.; Car, B.; Sutton, L.; Hoffman-Stapleton, M.; Keiber, T.; Baumbach, R. E.; Maple, M. B.; Henkie, Z.; Wawryk, R.

2015-01-01

The local structure of two skutterudite families—Ce M4As12 (M =Fe , Ru, Os) and L n Cu3Ru4O12 (L n =La , Pr, and Nd)—have been studied using the extended x-ray absorption fine structure (EXAFS) technique with a focus on the lattice vibrations about the rare-earth "rattler atoms" and the extent to which these vibrations can be considered local modes, with the rattler vibrating inside a nearly rigid cage. X-ray absorption data at all the metal edges were collected over a temperature range of 4 to 300 K and analyzed using standard procedures. The pair distances from EXAFS results agree quite well with the average structure obtained from diffraction. The cage structure is formed by the M and As atoms in Ce M4As12 and by Cu, O, and Ru atoms in L n Cu3Ru4O12 . Although some of the bonds within the cage are quite stiff (correlated Debye temperatures, θcD, are ˜500 K for Ce M4As12 and above 800 K for L n Cu3Ru4O12 ), we show that the structure is not completely rigid. For the rattler atom the nearest-neighbor pairs have a relatively low Einstein temperature, θE:˜100 - 120 K for Ce-As and ˜130 K for L n -O . Surprisingly, the behaviors of the second-neighbor pairs are quite different: for Ce M4As12 the second-neighbor pairs (Ce -M ) have a weaker bond while for L n Cu3Ru4O12 the L n -Ru second-neighbor pair has a stiffer effective spring constant than the first-neighbor pair. In addition, we show that the As4 or CuO4 rings are relatively rigid units and that their vibrations are anisotropic within these cubic structures, with stiff restoring forces perpendicular to the rings and much weaker restoring forces in directions parallel to the rings. Consequently vibrations of the rings may also act as "rattlers" and help suppress thermal conductivity. In general neither the rigid-cage approximation nor the simple reduced-mass approximation are sufficient for describing rattler behavior.

Collisional radiative model for Ar-O2 mixture plasma with fully relativistic fine structure cross sections

NASA Astrophysics Data System (ADS)

Priti, Gangwar, Reetesh Kumar; Srivastava, Rajesh

2018-04-01

A collisional radiative (C-R) model has been developed to diagnose the rf generated Ar-O2 (0%-5%) mixture plasma at low temperatures. Since in such plasmas the most dominant process is an electron impact excitation process, we considered several electron impact fine structure transitions in an argon atom from its ground as well as excited states. The cross-sections for these transitions have been obtained using the reliable fully relativistic distorted wave theory. Processes which account for the coupling of argon with the oxygen molecules have been further added to the model. We couple our model to the optical spectroscopic measurements reported by Jogi et al. [J. Phys. D: Appl. Phys. 47, 335206 (2014)]. The plasma parameters, viz. the electron density (ne) and the electron temperature (Te) as a function of O2 concentration have been obtained using thirteen intense emission lines out of 3p54p → 3p54s transitions observed in their spectroscopic measurements. It is found that as the content of O2 in Ar increases from 0%-5%, Te increases in the range 0.85-1.7 eV, while the electron density decreases from 2.76 × 1012-2.34 × 1011 cm-3. The Ar-3p54s (1si) fine-structure level populations at our extracted plasma parameters are found to be in very good agreement with those obtained from the measurements. Furthermore, we have estimated the individual contributions coming from the ground state, 1si manifolds and cascade contributions to the population of the radiating Ar-3p54p (2pi) states as a function of a trace amount of O2. Such information is very useful to understand the importance of various processes occurring in the plasma.

Herschel Galactic Plane Survey of [NII] Fine Structure Emission

NASA Astrophysics Data System (ADS)

Goldsmith, Paul F.; Yıldız, Umut A.; Langer, William D.; Pineda, Jorge L.

2015-12-01

We present the first large-scale high angular resolution survey of ionized nitrogen in the Galactic Plane through emission of its two fine structure transitions ([N ii]) at 122 and 205 μm. The observations were largely obtained with the PACS instrument onboard the Herschel Space Observatory. The lines of sight were in the Galactic plane, following those of the Herschel OTKP project GOT C+. Both lines are reliably detected at the 10-8-10-7 Wm-2 sr-1 level over the range -60° ≤ l ≤ 60°. The rms of the intensity among the 25 PACS spaxels of a given pointing is typically less than one third of the mean intensity, showing that the emission is extended. [N ii] is produced in gas in which hydrogen is ionized, and collisional excitation is by electrons. The ratio of the two fine structure transitions provides a direct measurement of the electron density, yielding n(e) largely in the range 10-50 cm-3 with an average value of 29 cm-3 and N+ column densities 1016-1017 cm-2. [N ii] emission is highly correlated with that of [C ii], and we calculate that between 1/3 and 1/2 of the [C ii] emission is associated with the ionized gas. The relatively high electron densities indicate that the source of the [N ii] emission is not the warm ionized medium (WIM), which has electron densities more than 100 times smaller. Possible origins of the observed [N ii] include the ionized surfaces of dense atomic and molecular clouds, the extended low-density envelopes of H ii regions, and low-filling factor high-density fluctuations of the WIM.

Fine-structure calculations of energy levels, oscillator strengths, and transition probabilities for sulfur-like iron, Fe XI

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

Abou El-Maaref, A., E-mail: aahmh@hotmail.com; Ahmad, Mahmoud; Allam, S.H.

Energy levels, oscillator strengths, and transition probabilities for transitions among the 14 LS states belonging to configurations of sulfur-like iron, Fe XI, have been calculated. These states are represented by configuration interaction wavefunctions and have configurations 3s{sup 2}3p{sup 4}, 3s3p{sup 5}, 3s{sup 2}3p{sup 3}3d, 3s{sup 2}3p{sup 3}4s, 3s{sup 2}3p{sup 3}4p, and 3s{sup 2}3p{sup 3}4d, which give rise to 123 fine-structure energy levels. Extensive configuration interaction calculations using the CIV3 code have been performed. To assess the importance of relativistic effects, the intermediate coupling scheme by means of the Breit–Pauli Hamiltonian terms, such as the one-body mass correction and Darwin term,more » and spin–orbit, spin–other-orbit, and spin–spin corrections, are incorporated within the code. These incorporations adjusted the energy levels, therefore the calculated values are close to the available experimental data. Comparisons between the present calculated energy levels as well as oscillator strengths and both experimental and theoretical data have been performed. Our results show good agreement with earlier works, and they might be useful in thermonuclear fusion research and astrophysical applications. -- Highlights: •Accurate atomic data of iron ions are needed for identification of solar corona. •Extensive configuration interaction wavefunctions including 123 fine-structure levels have been calculated. •The relativistic effects by means of the Breit–Pauli Hamiltonian terms are incorporated. •This incorporation adjusts the energy levels, therefore the calculated values are close to experimental values.« less

Modeling the Influence of Injection Modes on the Evolution of Solution Sprays in a Plasma Jet

NASA Astrophysics Data System (ADS)

Shan, Y.; Coyle, T. W.; Mostaghimi, J.

2010-01-01

Solution precursor plasma spraying (SPPS) is a novel technology with great potential for depositing finely structured ceramic coatings with nano- and sub-micrometric features. The solution is injected into the plasma jet either as a liquid stream or gas atomized droplets. Solution droplets or the stream interact with the plasma jet and break up into fine droplets. The solvent vaporizes very fast as the droplets travel downstream. Solid particles are finally formed, and the particle are heated up and accelerated to the substrate to generate the coating. The deposition process and the properties of coatings obtained are extremely sensitive to the process parameters, such as torch operating conditions, injection modes, injection parameters, and substrate temperatures. This article numerically investigates the effect of injection modes, a liquid stream injection and a gas-blast injection, on the size distribution of injected droplets. The particle/droplet size, temperature, and position distributions on the substrate are predicted for different injection modes.

Network topology for the formation of solvated electrons in binary CaO–Al2O3 composition glasses

PubMed Central

Akola, Jaakko; Kohara, Shinji; Ohara, Koji; Fujiwara, Akihiko; Watanabe, Yasuhiro; Masuno, Atsunobu; Usuki, Takeshi; Kubo, Takashi; Nakahira, Atsushi; Nitta, Kiyofumi; Uruga, Tomoya; Weber, J. K. Richard; Benmore, Chris J.

2013-01-01

Glass formation in the CaO–Al2O3 system represents an important phenomenon because it does not contain typical network-forming cations. We have produced structural models of CaO–Al2O3 glasses using combined density functional theory–reverse Monte Carlo simulations and obtained structures that reproduce experiments (X-ray and neutron diffraction, extended X-ray absorption fine structure) and result in cohesive energies close to the crystalline ground states. The O–Ca and O–Al coordination numbers are similar in the eutectic 64 mol % CaO (64CaO) glass [comparable to 12CaO·7Al2O3 (C12A7)], and the glass structure comprises a topologically disordered cage network with large-sized rings. This topologically disordered network is the signature of the high glass-forming ability of 64CaO glass and high viscosity in the melt. Analysis of the electronic structure reveals that the atomic charges for Al are comparable to those for Ca, and the bond strength of Al–O is stronger than that of Ca–O, indicating that oxygen is more weakly bound by cations in CaO-rich glass. The analysis shows that the lowest unoccupied molecular orbitals occurs in cavity sites, suggesting that the C12A7 electride glass [Kim SW, Shimoyama T, Hosono H (2011) Science 333(6038):71–74] synthesized from a strongly reduced high-temperature melt can host solvated electrons and bipolarons. Calculations of 64CaO glass structures with few subtracted oxygen atoms (additional electrons) confirm this observation. The comparable atomic charges and coordination of the cations promote more efficient elemental mixing, and this is the origin of the extended cage structure and hosted solvated (trapped) electrons in the C12A7 glass. PMID:23723350

Network topology for the formation of solvated electrons in binary CaO-Al2O3 composition glasses.

PubMed

Akola, Jaakko; Kohara, Shinji; Ohara, Koji; Fujiwara, Akihiko; Watanabe, Yasuhiro; Masuno, Atsunobu; Usuki, Takeshi; Kubo, Takashi; Nakahira, Atsushi; Nitta, Kiyofumi; Uruga, Tomoya; Weber, J K Richard; Benmore, Chris J

2013-06-18

Glass formation in the CaO-Al2O3 system represents an important phenomenon because it does not contain typical network-forming cations. We have produced structural models of CaO-Al2O3 glasses using combined density functional theory-reverse Monte Carlo simulations and obtained structures that reproduce experiments (X-ray and neutron diffraction, extended X-ray absorption fine structure) and result in cohesive energies close to the crystalline ground states. The O-Ca and O-Al coordination numbers are similar in the eutectic 64 mol % CaO (64CaO) glass [comparable to 12CaO·7Al2O3 (C12A7)], and the glass structure comprises a topologically disordered cage network with large-sized rings. This topologically disordered network is the signature of the high glass-forming ability of 64CaO glass and high viscosity in the melt. Analysis of the electronic structure reveals that the atomic charges for Al are comparable to those for Ca, and the bond strength of Al-O is stronger than that of Ca-O, indicating that oxygen is more weakly bound by cations in CaO-rich glass. The analysis shows that the lowest unoccupied molecular orbitals occurs in cavity sites, suggesting that the C12A7 electride glass [Kim SW, Shimoyama T, Hosono H (2011) Science 333(6038):71-74] synthesized from a strongly reduced high-temperature melt can host solvated electrons and bipolarons. Calculations of 64CaO glass structures with few subtracted oxygen atoms (additional electrons) confirm this observation. The comparable atomic charges and coordination of the cations promote more efficient elemental mixing, and this is the origin of the extended cage structure and hosted solvated (trapped) electrons in the C12A7 glass.

Interfaces in Heterogeneous Catalysts: Advancing Mechanistic Understanding through Atomic-Scale Measurements.

PubMed

Gao, Wenpei; Hood, Zachary D; Chi, Miaofang

2017-04-18

Developing novel catalysts with high efficiency and selectivity is critical for enabling future clean energy conversion technologies. Interfaces in catalyst systems have long been considered the most critical factor in controlling catalytic reaction mechanisms. Interfaces include not only the catalyst surface but also interfaces within catalyst particles and those formed by constructing heterogeneous catalysts. The atomic and electronic structures of catalytic surfaces govern the kinetics of binding and release of reactant molecules from surface atoms. Interfaces within catalysts are introduced to enhance the intrinsic activity and stability of the catalyst by tuning the surface atomic and chemical structures. Examples include interfaces between the core and shell, twin or domain boundaries, or phase boundaries within single catalyst particles. In supported catalyst nanoparticles (NPs), the interface between the metallic NP and support serves as a critical tuning factor for enhancing catalytic activity. Surface electronic structure can be indirectly tuned and catalytically active sites can be increased through the use of supporting oxides. Tuning interfaces in catalyst systems has been identified as an important strategy in the design of novel catalysts. However, the governing principle of how interfaces contribute to catalyst behavior, especially in terms of interactions with intermediates and their stability during electrochemical operation, are largely unknown. This is mainly due to the evolving nature of such interfaces. Small changes in the structural and chemical configuration of these interfaces may result in altering the catalytic performance. These interfacial arrangements evolve continuously during synthesis, processing, use, and even static operation. A technique that can probe the local atomic and electronic interfacial structures with high precision while monitoring the dynamic interfacial behavior in situ is essential for elucidating the role of interfaces and providing deeper insight for fine-tuning and optimizing catalyst properties. Scanning transmission electron microscopy (STEM) has long been a primary characterization technique used for studying nanomaterials because of its exceptional imaging resolution and simultaneous chemical analysis. Over the past decade, advances in STEM, that is, the commercialization of both aberration correctors and monochromators, have significantly improved the spatial and energy resolution. Imaging atomic structures with subangstrom resolution and identifying chemical species with single-atom sensitivity are now routine for STEM. These advancements have greatly benefitted catalytic research. For example, the roles of lattice strain and surface elemental distribution and their effect on catalytic stability and reactivity have been well documented in bimetallic catalysts. In addition, three-dimensional atomic structures revealed by STEM tomography have been integrated in theoretical modeling for predictive catalyst NP design. Recent developments in stable electronic and mechanical devices have opened opportunities to monitor the evolution of catalysts in operando under synthesis and reaction conditions; high-speed direct electron detectors have achieved sub-millisecond time resolutions and allow for rapid structural and chemical changes to be captured. Investigations of catalysts using these latest microscopy techniques have provided new insights into atomic-level catalytic mechanisms. Further integration of new microscopy methods is expected to provide multidimensional descriptions of interfaces under relevant synthesis and reaction conditions. In this Account, we discuss recent insights on understanding catalyst activity, selectivity, and stability using advanced STEM techniques, with an emphasis on how critical interfaces dictate the performance of precious metal-based heterogeneous catalysts. The role of extended interfacial structures, including those between core and shell, between separate phases and twinned grains, between the catalyst surface and gas, and between metal and support are discussed. We also provide an outlook on how emerging electron microscopy techniques, such as vibrational spectroscopy and electron ptychography, will impact future catalysis research.

Specific features of the atomic structure of metallic layers of multilayered (CoFeZr/SiO2)32 and (CoFeZr/ a-Si)40 nanostructures with different interlayers

NASA Astrophysics Data System (ADS)

Domashevskaya, E. P.; Guda, A. A.; Chernyshev, A. V.; Sitnikov, V. G.

2017-02-01

Multilayered nanostructures (MN) were prepared by ion-beam successive sputtering from two targets, one of which was a metallic Co45Fe45Zr10 alloy plate and another target was a quartz (SiO2) or silicon plate on the surface of a rotating glass-ceramic substrate in an argon atmosphere. The Co and Fe K edges X-ray absorption fine structure of XANES in the (CoFeZr/SiO2)32 sample with oxide interlayers was similar to XANES of metallic Fe foil. This indicated the existence in metallic layers of multilayered CoFeZr nanocrystals with a local environment similar to the atomic environment in solid solutions on the base of bcc Fe structure, which is also confirmed by XRD data. XANES near the Co and Fe K edges absorption in another multilayered nanostructure with silicon interlayers (CoFeZr/ a-Si)40 differs from XANES of MN with dielectric SiO2 interlayer, which demonstrates a dominant influence of the Fe-Si and Co-Si bonds in the local environment of 3 d Co and Fe metals when they form CoFeSi-type silicide phases in thinner bilayers of this MN.

Electronic properties of B and Al doped graphane: A hybrid density functional study

NASA Astrophysics Data System (ADS)

Mapasha, R. E.; Igumbor, E.; Andriambelaza, N. F.; Chetty, N.

2018-04-01

Using a hybrid density functional theory approach parametrized by Heyd, Scuseria and Ernzerhof (HSE06 hybrid functional), we study the energetics, structural and electronic properties of a graphane monolayer substitutionally doped with the B (BCH) and Al (AlCH) atoms. The BCH defect can be integrated within a graphane monolayer at a relative low formation energy, without major structural distortions and symmetry breaking. The AlCH defect relaxes outward of the monolayer and breaks the symmetry. The density of states plots indicate that BCH doped graphane monolayer is a wide band gap semiconductor, whereas the AlCH defect introduces the spin dependent mid gap states at the vicinity of the Fermi level, revealing a metallic character with the pronounced magnetic features. We further examine the response of the Al dependent spin states on the multiple charge states doping. We find that the defect formation energy, structural and electronic properties can be altered via charge state modulation. The +1 charge doping opens an energy band gap of 1.75 eV. This value corresponds to the wavelength in the visible spectrum, suggesting an ideal material for solar cell absorbers. Our study fine tunes the graphane band gap through the foreign atom doping as well as via defect charge state modulation.

Bayes-Turchin analysis of x-ray absorption data above the Fe L{sub 2,3}-edges

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

Rossner, H. H.; Schmitz, D.; Imperia, P.

2006-10-01

Extended x-ray absorption fine structure (EXAFS) data and magnetic EXAFS (MEXAFS) data were measured at two temperatures (180 and 296 K) in the energy region of the overlapping L-edges of bcc Fe grown on a V(110) crystal surface. In combination with a Bayes-Turchin data analysis procedure these measurements enable the exploration of local crystallographic and magnetic structures. The analysis determined the atomic-like background together with the EXAFS parameters which consisted of ten shell radii, the Debye-Waller parameters, separated into structural and vibrational components, and the third cumulant of the first scattering path. The vibrational components for 97 different scattering pathsmore » were determined by a two parameter force-field model using a priori values adjusted to Born-von Karman parameters of inelastic neutron scattering data. The investigations of the system Fe/V(110) demonstrate that the simultaneous fitting of atomic background parameters and EXAFS parameters can be performed reliably. Using the L{sub 2}- and L{sub 3}-components extracted from the EXAFS analysis and the rigid-band model, the MEXAFS oscillations can only be described when the sign of the exchange energy is changed compared to the predictions of the Hedin Lundquist exchange and correlation functional.« less

Nuclear Physics Around the Unitarity Limit.

PubMed

König, Sebastian; Grießhammer, Harald W; Hammer, H-W; van Kolck, U

2017-05-19

We argue that many features of the structure of nuclei emerge from a strictly perturbative expansion around the unitarity limit, where the two-nucleon S waves have bound states at zero energy. In this limit, the gross features of states in the nuclear chart are correlated to only one dimensionful parameter, which is related to the breaking of scale invariance to a discrete scaling symmetry and set by the triton binding energy. Observables are moved to their physical values by small perturbative corrections, much like in descriptions of the fine structure of atomic spectra. We provide evidence in favor of the conjecture that light, and possibly heavier, nuclei are bound weakly enough to be insensitive to the details of the interactions but strongly enough to be insensitive to the exact size of the two-nucleon system.

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

Friebel, Daniel

In situ x-ray absorption spectroscopy (XAS) at the Pt L{sub 3} edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard x-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF8 code and complementary extended x-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at highmore » electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.« less

Low-energy Scattering of Positronium by Atoms

NASA Technical Reports Server (NTRS)

Ray, Hasi

2007-01-01

The survey reports theoretical studies involving positronium (Ps) - atom scattering. Investigations carried out in last few decades have been briefly reviewed in this article. A brief description of close-coupling approximation (CCA), the first-Born approximation (FBA) and the Born-Oppenheimer approximation (BOA) for Ps-Atom systems are made. The CCA codes of Ray et a1 [1-6] are reinvestigated using very fine mesh-points to search for resonances. The article advocates the need for an extended basis set & a systematic study using CCAs.

Spray forming process for producing molds, dies and related tooling

DOEpatents

McHugh, Kevin M.; Key, James F.

1998-01-01

A method for spray forming manufacturing of near-net-shape molds, dies and related toolings, wherein liquid material such as molten metal, metallic alloys, or polymers are atomized into fine droplets by a high temperature, high velocity gas and deposited onto a pattern. Quenching of the atomized droplets provides a heat sink, thereby allowing undercooled and partially solidified droplets to be formed in-flight. Composites can be formed by combining the atomized droplets with solid particles such as whiskers or fibers.

Spray forming system for producing molds, dies and related tooling

DOEpatents

McHugh, Kevin M.

2000-01-01

A system for the spray forming manufacturing of near-net-shape molds, dies and related toolings, wherein liquid material such as molten metal, metallic alloys, or polymers are atomized into fine droplets by a high temperature, high velocity gas and deposited onto a pattern. Quenching of the atomized droplets provides a heat sink, thereby allowing undercooled and partially solidified droplets to be formed in-flight. Composites can be formed by combining the atomized droplets with solid particles such as powders, whiskers or fibers.

Spray forming process for producing molds, dies and related tooling

DOEpatents

McHugh, K.M.; Key, J.F.

1998-02-17

A method is disclosed for spray forming manufacturing of near-net-shape molds, dies and related toolings, wherein liquid material such as molten metal, metallic alloys, or polymers are atomized into fine droplets by a high temperature, high velocity gas and deposited onto a pattern. Quenching of the atomized droplets provides a heat sink, thereby allowing undercooled and partially solidified droplets to be formed in-flight. Composites can be formed by combining the atomized droplets with solid particles such as whiskers or fibers. 17 figs.

Glass-wool study of laser-induced spin currents en route to hyperpolarized Cs salt

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

Ishikawa, Kiyoshi

2011-07-15

The nuclear spin polarization of optically pumped Cs atoms flows to the surface of Cs hydride in a vapor cell. A fine glass wool lightly coated with the salt helps greatly increase the surface area in contact with the pumped atoms and enhance the spin polarization of the salt nuclei. Even though the glass wool randomly scatters the pump light, the atomic vapor can be polarized with unpolarized light in a magnetic field. The measured enhancement in the salt enables study of the polarizations of light and atomic nuclei very near the salt surface.

EXAFS: New tool for study of battery and fuel cell materials

NASA Technical Reports Server (NTRS)

Mcbreen, James; Ogrady, William E.; Pandya, Kaumudi I.

1987-01-01

Extended X ray absorption fine structure (EXAFS) is a powerful technique for probing the local atomic structure of battery and fuel cell materials. The major advantages of EXAFS are that both the probe and the signal are X rays and the technique is element selective and applicable to all states of matter. This permits in situ studies of electrodes and determination of the structure of single components in composite electrodes, or even complete cells. EXAFS specifically probes short range order and yields coordination numbers, bond distances, and chemical identity of nearest neighbors. Thus, it is ideal for structural studies of ions in solution and the poorly crystallized materials that are often the active materials or catalysts in batteries and fuel cells. Studies on typical battery and fuel cell components are used to describe the technique and the capability of EXAFS as a structural tool in these applications. Typical experimental and data analysis procedures are outlined. The advantages and limitations of the technique are also briefly discussed.

Electron impact excitation of tin

NASA Astrophysics Data System (ADS)

Sharma, Lalita; Bharti, Swati; Srivastava, Rajesh

2017-05-01

We study the electron impact excitation of the fine-structure levels of the ground state configuration 5p2 to the excited states of the configuration 5p6s in tin atom. These calculations have been carried out in the jj coupling scheme using the relativistic distorted-wave method. Results for differential cross section are reported at incident electron energies 20, 50, 80 and 100 eV while integrated cross sections are presented in the incident electron energy range of 5 to 100 eV. Contribution to the Topical Issue: "Low-Energy Interactions related to Atmospheric and Extreme Conditions", edited by S. Ptasinska, M. Smialek-Telega, A. Milosavljevic and B. Sivaraman.

Method and apparatus for atomization and spraying of molten metals

DOEpatents

Hobson, David O.; Alexeff, Igor; Sikka, Vinod K.

1990-01-01

A method and device for dispersing molten metal into fine particulate spray, the method comprises applying an electric current through the molten metal and simultaneously applying a magnetic field to the molten metal in a plane perpendicular to the electric current, whereby the molten metal is caused to form into droplets at an angle perpendicular to both the electric current and the magnetic field. The device comprises a structure for providing a molten metal, appropriately arranged electrodes for applying an electric current through the molten metal, and a magnet for providing a magnetic field in a plane perpendicular to the electric current.

Method and apparatus for atomization and spraying of molten metals

DOEpatents

Hobson, D.O.; Alexeff, I.; Sikka, V.K.

1988-07-19

A method and device for dispersing molten metal into fine particulate spray, the method comprises applying an electric current through the molten metal and simultaneously applying a magnetic field to the molten metal in a plane perpendicular to the electric current, whereby the molten metal is caused to form into droplets at an angle perpendicular to both the electric current and the magnetic field. The device comprises a structure for providing a molten metal, appropriately arranged electrodes for applying an electric current through the molten metal, and a magnet for providing a magnetic field in a plane perpendicular to the electric current. 11 figs.

Intrinsic magnetic properties of bimetallic nanoparticles elaborated by cluster beam deposition.

PubMed

Dupuis, V; Khadra, G; Hillion, A; Tamion, A; Tuaillon-Combes, J; Bardotti, L; Tournus, F

2015-11-14

In this paper, we present some specific chemical and magnetic order obtained very recently on characteristic bimetallic nanoalloys prepared by mass-selected Low Energy Cluster Beam Deposition (LECBD). We study how the competition between d-atom hybridization, complex structure, morphology and chemical affinity affects their intrinsic magnetic properties at the nanoscale. The structural and magnetic properties of these nanoalloys were investigated using various experimental techniques that include High Resolution Transmission Electron Microscopy (HRTEM), Superconducting Quantum Interference Device (SQUID) magnetometry, as well as synchrotron techniques such as Extended X-ray Absorption Fine Structure (EXAFS) and X-ray Magnetic Circular Dichroism (XMCD). Depending on the chemical nature of the nanoalloys we observe different magnetic responses compared to their bulk counterparts. In particular, we show how specific relaxation in nanoalloys impacts their magnetic anisotropy; and how finite size effects (size reduction) inversely enhance their magnetic moment.

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

Oliver, S. A.; Harris, V. G.; Hamdeh, H. H.

The cation site occupancy of a mechanically activated nanocrystalline zinc ferrite powder was determined as (Zn{sub 0.55}{sup 2+}Fe{sub 0.18}{sup 3+}){sub tet}[Zr{sub 0.45}{sup 2+}Fe{sub 1.82}{sup 3+}]{sub oct}O{sub 4} through analysis of extended x-ray absorption fine structure measurements, showing a large redistribution of cations between sites compared to normal zinc ferrite samples. The overpopulation of cations in the octahedral sites was attributed to the ascendance in importance of the ionic radii over the crystal energy and bonding coordination in determining which interstitial sites are occupied in this structurally disordered powder. Slight changes are observed in the local atomic environment about the zincmore » cations, but not the iron cations, with respect to the spinel structure. The presence of Fe{sup 3+} on both sites is consistent with the measured room temperature magnetic properties. (c) 2000 American Institute of Physics.« less

Characterization of CuHal-intercalated carbon nanotubes with x-ray absorption spectroscopy combined with x-ray photoelectron and resonant photoemission spectroscopies

NASA Astrophysics Data System (ADS)

Brzhezinskaya, M.; Generalov, A.; Vinogdradov, A.; Eliseev, A.

2013-04-01

Encapsulated single-walled carbon nanotubes (SWCNTs) with inner channels filled by different compounds present the new class of composite materials. Such CNTs give opportunity to form 1D nanocrystals as well as quantum nanowires with new physical and chemical properties inside the tubes. The present study is aimed to characterize the possible chemical interaction between CuHal (Hal=I, Cl, Br) and SWCNTs in CuHal@SWCNTs and electronic structure of the latter using high-resolution near edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with high-resolution X-ray photoelectron spectroscopy and resonant photoemission spectroscopy. The present study has shown that there is a chemical interaction between the filler and π-electron subsystem of CNTs which is accompanied by changes of the atomic and electronic structure of the filler during the encapsulating it inside CNTs.

Relativistic R -matrix calculations for the electron-impact excitation of neutral molybdenum

NASA Astrophysics Data System (ADS)

Smyth, R. T.; Johnson, C. A.; Ennis, D. A.; Loch, S. D.; Ramsbottom, C. A.; Ballance, C. P.

2017-10-01

A recent PISCES-B Mod experiment [Nishijima et al., J. Phys. B 43, 225701 (2010), 10.1088/0953-4075/43/22/225701] has revealed up to a factor of 5 discrepancy between measurement and the two existing theoretical models [Badnell et al., J. Phys. B 29, 3683 (1996), 10.1088/0953-4075/29/16/014; Bartschat et al., J. Phys. B 35, 2899 (2002), 10.1088/0953-4075/35/13/305], providing important diagnostics for Mo i. In the following paper we address this issue by employing a relativistic atomic structure and R -matrix scattering calculations to improve upon the available models for future applications and benchmark results against a recent Compact Toroidal Hybrid experiment [Hartwell et al., Fusion Sci. Technol. 72, 76 (2017), 10.1080/15361055.2017.1291046]. We determine the atomic structure of Mo i using grasp0, which implements the multiconfigurational Dirac-Fock method. Fine structure energies and radiative transition rates are presented and compared to existing experimental and theoretical values. The electron-impact excitation of Mo i is investigated using the relativistic R -matrix method and the parallel versions of the Dirac atomic R -matrix codes. Electron-impact excitation cross sections are presented and compared to the few available theoretical cross sections. Throughout, our emphasis is on improving the results for the z 1,2,3o5P →a S52,z 2,3,4o7P → a S73 and y 2,3,4o7P → a S73 electric dipole transitions of particular relevance for diagnostic work.

Multi-technology Investigation of the Atomic Structure of Calcium Silicate Hydrates

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

Geng, Guoqing; Kilcoyne, David A.; Benmore, Chris J.

2015-01-01

In this study, synthetic C-S-H samples were investigated to reveal the feature at atomic scale. Rietveld refinement was applied to high resolution X-ray scattering data, yielding the lattice constants of the pseudocrystal structure, as well as the crystallinity along three axes. Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra was collected at calcium L3,2-edge. Evolution of calcium coordination symmetry were studied by investigating spectra characteristics. Pair Distribution Function (PDF) study yields the statistics of atom pair distribution. Coordination number of Ca and Si were obtained by integrating Radial distribution function. Atomic model based on dimeric structure were discussed and comparedmore » with experimental data. Synthetic C-S-H samples with increasing Ca/Si ratio exhibit pseudo-crystal structure, resembling Dreierketten configuration similar to natural tobermorite structure. Along c-axis, the repeated structure could not survives two layers in case of low Ca/Si ratio (0.70, 1.05). But in high Ca/Si ratio (1.42) case, the crystallinity along c-axis is much bigger. The coordination number of Ca decreases with increasing Ca/Si ratio. Octahedrally coordinated Ca are observed in sample with Ca/Si ratio of 1.42. Various dimeric models are compared with experimental data. In case of Ca/Si ratio of 1.42, SiO4 tetrahedron chain needs to be shortened in linkage, most probably by substituting bridging SiO4 tetrahedron with CaO6 octahedron. These octahedrons in interlayer space act like pins to join two adjacent layer structures together. The crystallinity is thus increased along c-axis, and average coordination number is therefore reduced. In case of Ca/Si 1.05, crystallinity is low along c-axis since, indicating that not too many Ca ions exist in interlayer space to hold two layers together. Instead, negative charge of end oxygen could be balanced by proton. Ca/Si 0.70 has long tetrahedron chain linkage within layer while the linkage between adjacent layers are not strong, resulting in low crystallinity along c-axis. Neither Ca/Si ratio 0.70 nor 1.42 sample contains any Ca in octahedral symmetry, as indicated by the weak crystal field splitting of NEXAFS spectra.« less

A reactive, scalable, and transferable model for molecular energies from a neural network approach based on local information

NASA Astrophysics Data System (ADS)

Unke, Oliver T.; Meuwly, Markus

2018-06-01

Despite the ever-increasing computer power, accurate ab initio calculations for large systems (thousands to millions of atoms) remain infeasible. Instead, approximate empirical energy functions are used. Most current approaches are either transferable between different chemical systems, but not particularly accurate, or they are fine-tuned to a specific application. In this work, a data-driven method to construct a potential energy surface based on neural networks is presented. Since the total energy is decomposed into local atomic contributions, the evaluation is easily parallelizable and scales linearly with system size. With prediction errors below 0.5 kcal mol-1 for both unknown molecules and configurations, the method is accurate across chemical and configurational space, which is demonstrated by applying it to datasets from nonreactive and reactive molecular dynamics simulations and a diverse database of equilibrium structures. The possibility to use small molecules as reference data to predict larger structures is also explored. Since the descriptor only uses local information, high-level ab initio methods, which are computationally too expensive for large molecules, become feasible for generating the necessary reference data used to train the neural network.

Research investigation directed toward extending the useful range of the electromagnetic spectrum

NASA Technical Reports Server (NTRS)

Hartmann, S. R.

1971-01-01

The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

The role of ion exchange in the passivation of In(Zn)P nanocrystals with ZnS

PubMed Central

Cho, Deok-Yong; Xi, Lifei; Boothroyd, Chris; Kardynal, Beata; Lam, Yeng Ming

2016-01-01

We have investigated the chemical state of In(Zn)P/ZnS core/shell nanocrystals (NCs) for color conversion applications using hard X-ray absorption spectroscopy (XAS) and photoluminescence excitation (PLE). Analyses of the edge energies as well as the X-ray absorption fine structure (XAFS) reveal that the Zn2+ ions from ZnS remain in the shell while the S2− ions penetrate into the core at an early stage of the ZnS deposition. It is further demonstrated that for short growth times, the ZnS shell coverage on the core was incomplete, whereas the coverage improved gradually as the shell deposition time increased. Together with evidence from PLE spectra, where there is a strong indication of the presence of P vacancies, this suggests that the core-shell interface in the In(Zn)P/ZnS NCs are subject to substantial atomic exchanges and detailed models for the shell structure beyond simple layer coverage are needed. This substantial atomic exchange is very likely to be the reason for the improved photoluminescence behavior of the core-shell particles compare to In(Zn)P-only NCs as S can passivate the NCs surfaces. PMID:26972936

Core-level spectra and molecular deformation in adsorption: V-shaped pentacene on Al(001)

PubMed Central

Lin, He; Brivio, Gian Paolo; Floreano, Luca; Fratesi, Guido

2015-01-01

Summary By first-principle simulations we study the effects of molecular deformation on the electronic and spectroscopic properties as it occurs for pentacene adsorbed on the most stable site of Al(001). The rationale for the particular V-shaped deformed structure is discussed and understood. The molecule–surface bond is made evident by mapping the charge redistribution. Upon X-ray photoelectron spectroscopy (XPS) from the molecule, the bond with the surface is destabilized by the electron density rearrangement to screen the core hole. This destabilization depends on the ionized carbon atom, inducing a narrowing of the XPS spectrum with respect to the molecules adsorbed hypothetically undistorted, in full agreement to experiments. When looking instead at the near-edge X-ray absorption fine structure (NEXAFS) spectra, individual contributions from the non-equivalent C atoms provide evidence of the molecular orbital filling, hybridization, and interchange induced by distortion. The alteration of the C–C bond lengths due to the V-shaped bending decreases by a factor of two the azimuthal dichroism of NEXAFS spectra, i.e., the energy splitting of the sigma resonances measured along the two in-plane molecular axes. PMID:26734516

Investigation of the Structural Stability of Ion-Implanted Gd 2Ti 2-xSn xO 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy

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

Aluri, Esther Rani; Hayes, John R.; Walker, James D.S.

2016-03-24

Rare-earth titanate and stannate pyrochlore-type oxides have been investigated in the past for the sequestration of nuclear waste elements because of their resistance to radiation-induced structural damage. In order to enhance this property, it is necessary to understand the effect of radioactive decay of the incorporated actinide elements on the local chemical environment. In this study, Gd 2Ti 2–xSn xO 7 materials have been implanted with Au– ions to simulate radiation-induced structural damage. Glancing angle X-ray absorption near-edge spectroscopy (GA-XANES), glancing angle X-ray absorption fine structure (GA-EXAFS) analysis, and powder X-ray diffraction have been used to investigate changes in themore » local coordination environment of the metal atoms in the damaged surface layer. Examination of GA-XANES/EXAFS spectra from the implanted Gd 2Ti 2–xSn xO 7 materials collected at various glancing angles allowed for an investigation of how the local coordination environment around the absorbing atoms changed at different depths in the damaged surface layer. This study has shown the usefulness of GA-XANES to the examination of ion-implanted materials and has suggested that Gd 2Ti 2–xSn xO 7 becomes more susceptible to ion-beam-induced structural damage with increasing Sn concentration.« less

Electrochemically fabricated polypyrrole-cobalt-oxygen coordination complex as high-performance lithium-storage materials.

PubMed

Guo, Bingkun; Kong, Qingyu; Zhu, Ying; Mao, Ya; Wang, Zhaoxiang; Wan, Meixiang; Chen, Liquan

2011-12-23

Current lithium-ion battery (LIB) technologies are all based on inorganic electrode materials, though organic materials have been used as electrodes for years. Disadvantages such as limited thermal stability and low specific capacity hinder their applications. On the other hand, the transition metal oxides that provide high lithium-storage capacity by way of electrochemical conversion reaction suffer from poor cycling stability. Here we report a novel high-performance, organic, lithium-storage material, a polypyrrole-cobalt-oxygen (PPy-Co-O) coordination complex, with high lithium-storage capacity and excellent cycling stability. Extended X-ray absorption fine structure and Raman spectroscopy and other physical and electrochemical characterizations demonstrate that this coordination complex can be electrochemically fabricated by cycling PPy-coated Co(3)O(4) between 0.0 V and 3.0 V versus Li(+)/Li. Density functional theory (DFT) calculations indicate that each cobalt atom coordinates with two nitrogen atoms within the PPy-Co coordination layer and the layers are connected with oxygen atoms between them. Coordination weakens the C-H bonds on PPy and makes the complex a novel lithium-storage material with high capacity and high cycling stability. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Opportunities for Maturing Precision Metrology with Ultracold Gas Studies Aboard the ISS

NASA Astrophysics Data System (ADS)

Williams, Jason; D'Incao, Jose

2017-04-01

Precision atom interferometers (AI) in space are expected to become an enabling technology for future fundamental physics research, with proposals including unprecedented tests of the validity of the weak equivalence principle, measurements of the fine structure and gravitational constants, and detection of gravity waves and dark matter/dark energy. We will discuss our preparation at JPL to use NASA's Cold Atom Lab facility (CAL) to mature the technology of precision, space-based, AIs. The focus of our flight project is three-fold: a) study the controlled dynamics of heteronuclear Feshbach molecules, at temperatures of nano-Kelvins or below, as a means to overcome uncontrolled density-profile-dependent shifts in differential AIs, b) demonstrate unprecedented atom-photon coherence times with spatially constrained AIs, c) use the imaging capabilities of CAL to detect and analyze spatial fringe patterns written onto the clouds after AI and thereby measure the rotational noise of the ISS. The impact from this work, and potential for follow-on studies, will also be reviewed in the context of future space-based fundamental physics missions. This research was carried out at the Jet Propulsion Laboratory, California Institute of Technology, under a contract with the National Aeronautics and Space Administration.

Development of Low Cost Gas Atomization of Precursor Powders for Simplified ODS Alloy Production

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

Anderson, Iver

2014-08-05

A novel gas atomization reaction synthesis (GARS) method was developed in this project to enable production (at our partner’s facility) a precursor Ni-Cr-Y-Ti powder with a surface oxide and an internal rare earth (RE) containing intermetallic compound (IMC) phase. Consolidation and heat-treatment experiments were performed at Ames Lab to promote the exchange of oxygen from the surface oxide to the RE intermetallic to form nano-metric oxide dispersoids. Alloy selection was aided by an internal oxidation and serial grinding experiments at Ames Lab and found that Hf-containing alloys may form more stable dispersoids than Ti-containing alloy, i.e., the Hf-containing system exhibitedmore » five different oxide phases and two different intermetallics compared to the two oxide phases and one intermetallic in the Ti-containing alloys. Since the simpler Ti-containing system was less complex to characterize, and make observations on the effects of processing parameters, the Ti-containing system was selected by Ames Lab for experimental atomization trials at our partner. An internal oxidation model was developed at Ames Lab and used to predict the heat treatment times necessary for dispersoid formation as a function of powder size and temperature. A new high-pressure gas atomization (HPGA) nozzle was developed at Ames Lab with the aim of promoting fine powder production at scales similar to that of the high gas-flow and melt-flow of industrial atomizers. The atomization nozzle was characterized using schlieren imaging and aspiration pressure testing at Ames Lab to determine the optimum melt delivery tip geometry and atomization pressure to promote enhanced secondary atomization mechanisms. Six atomization trials were performed at our partner to investigate the effects of: gas atomization pressure and reactive gas concentration on the particle size distribution (PSD) and the oxygen content of the resulting powder. Also, the effect on the rapidly solidified microstructure (as a function of powder size) was investigated at Ames Lab as a function of reactive gas composition and bulk alloy composition. The results indicated that the pulsatile gas atomization mechanism and a significantly enhanced yield of fine powders reported in the literature for this type of process were not observed. Also it was determined that reactive gas may marginally improve the fine powder yield but further experiments are required. The oxygen content in the gas also did not have any detrimental effect on the microstructure (i.e. did not significantly reduce undercooling). On the contrary, the oxygen addition to the atomization gas may have mitigated some potent catalytic nucleation sites, but not enough to significantly alter the microstructure vs. particle size relationship. Overall the downstream injection of oxygen was not found to significantly affect either the particle size distribution or undercooling (as inferred from microstructure and XRD observations) but injection further upstream, including in the gas atomization nozzle, remains to be investigated in later work.« less

Grain boundaries at the surface of consolidated MgO nanocrystals and acid-base functionality.

PubMed

Vingurt, Dima; Fuks, David; Landau, Miron V; Vidruk, Roxana; Herskowitz, Moti

2013-09-21

The increase of the surface basicity-acidity of MgO material by factors of 1.8-3.0 due to consolidation of its nanocrystals was demonstrated by the indicator titration. It was shown that the parallel increase of surface acidity and basicity is attributed to the formation of grain boundaries (GB) after MgO aerogel densification. A simple model predicting the increase of surface acidity-basicity of MgO that correlates with the results of direct measurements was proposed. The model is based on the study of the fine atomic structure at GB surface areas in consolidated MgO nanocrystals in the framework of Density Functional Theory. It is found that the displacements of coordinatively unsaturated surface ions near the GB are significant at the distances ~3-4 atomic layers from the geometrical contact plane between nanocrystals. The detailed analysis of atomic positions inside GB demonstrated the coordination deficiency of surface atoms at the GB areas leading to the formation of stretched bonds and to creation of low coordinated surface ions due to splitting of coordination numbers of surface atoms belonging to GB areas. Density of states for electrons shows the existence of additional states in the band gap close to the bottom of the conduction band. The adsorption energy of CO2 molecules atop oxygen atoms exposed at surface GB areas is of the same order of magnitude as that reported for oxygen atoms at crystallographic edges and corners of MgO crystals. It provides additional options for bonding of molecules at the surface of nanocrystalline MgO increasing the adsorption capacity and catalytic activity.

Hydrothermal recrystallization of transition metal nitroprussides. Formation of the most stable phases

NASA Astrophysics Data System (ADS)

Echevarría, F.; Reguera, L.; González M, M.; Galicia, J.; Ávila, M.; Reguera, E.

2018-02-01

Hydrothermal recrystallization appears to be an appropriate treatment to explore the structural diversity of porous coordination polymers. In this contribution, such a post-synthesis treatment is applied to divalent transition metal nitroprussides, T[Fe(CN)5NO]•xH2O with T =Mn, Fe, Co, Ni, Cu, Zn, Cd. This family of compounds forms an interesting series of nanoporous coordination polymers with a wide structural diversity, related to the synthesis route used and the solid hydration degree (x). The effect of a hydrothermal recrystallization of previously prepared fine powders using the precipitation method, on their crystal structure and related properties is herein discussed. In this series of coordination polymers, for Fe, Co, Ni the precipitated powders are obtained as cubic phase, with a high porosity related to presence of systematic vacancies for building unit [Fe(CN)5NO]. For Fe and Co a structural transition, from cubic to orthorhombic, was observed, which is associated to formation of a most compact structure. The crystal structure for the new orthorhombic phases was refined from the collected powder HR-XRD patterns. For Ni, the cubic phase remains stable even for large heating time, which is ascribed to the high polarizing power of this metal. The high porosity for the cubic phase allows an easy accommodation for the local deformations around the Ni atom coordination sphere. The structural information from XRD was complemented with CO2 and H2 adsorption and TG data, IR and UV-vis spectra, and magnetic measurements. The magnetic data, through the presence of spin-orbit coupling for Fe and Co in the two phases, provide fine details on the coordination environment for the metal linked at the N ends of the CN group.

Influence of wave-packet dynamics on the medium gain of an atomic system

NASA Astrophysics Data System (ADS)

Delagnes, J. C.; Bouchene, M. A.

2007-10-01

A sequence of two femtosecond pulses—a strong driving π -polarized pulse and a weak propagating σ -polarized pulse—excites resonantly the S1/2→P1/2 transition of an atomic system. Strong interference effects take place in the system between absorption and emission paths leading to a substantial amplification of the σ pulse. We study the influence of the fine structure on the medium gain when the contribution of the off-resonant P3/2 level is taken into account. A drastic reduction of the medium gain is obtained. This effect is explained within the bright-state dark-state formalism where the strong driving pulse creates a wave packet that can be trapped in a state—the bright state—leading to a significant reduction of the gain for the σ pulse. Finally, we also show that periodical gain dependence with the driving pulse energy exhibits a significant change in its period value (compared with expected Rabi oscillations).

Synthesis and Mechanical Characterization of Binary and Ternary Intermetallic Alloys Based on Fe-Ti-Al by Resonant Ultrasound Vibrational Methods.

PubMed

Chanbi, Daoud; Ogam, Erick; Amara, Sif Eddine; Fellah, Z E A

2018-05-07

Precise but simple experimental and inverse methods allowing the recovery of mechanical material parameters are necessary for the exploration of materials with novel crystallographic structures and elastic properties, particularly for new materials and those existing only in theory. The alloys studied herein are of new atomic compositions. This paper reports an experimental study involving the synthesis and development of methods for the determination of the elastic properties of binary (Fe-Al, Fe-Ti and Ti-Al) and ternary (Fe-Ti-Al) intermetallic alloys with different concentrations of their individual constituents. The alloys studied were synthesized from high purity metals using an arc furnace with argon flow to ensure their uniformity and homogeneity. Precise but simple methods for the recovery of the elastic constants of the isotropic metals from resonant ultrasound vibration data were developed. These methods allowed the fine analysis of the relationships between the atomic concentration of a given constituent and the Young’s modulus or alloy density.

Collisional perturbation of radio-frequency E1 transitions in an atomic beam of dysprosium

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

Cingoez, A.; Lapierre, Alain; Nguyen, A.-T.

2005-12-15

We have studied collisional perturbations of radio-frequency (rf) electric-dipole (E1) transitions between the nearly degenerate opposite-parity levels in atomic dysprosium (Dy) in the presence of 10 to 80 {mu}Torr of H{sub 2}, N{sub 2}, He, Ar, Ne, Kr, and Xe. Collisional broadening and shift of the resonance, as well as the attenuation of the signal amplitude are observed to be proportional to the foreign-gas density with the exception of H{sub 2} and Ne, for which no shifts were observed. Corresponding rates and cross sections are presented. In addition, rates and cross sections for O{sub 2} are extracted from measurements usingmore » air as foreign gas. The primary motivation for this study is the need for accurate determination of the shift rates, which are needed in a laboratory search for the temporal variation of the fine-structure constant [A. T. Nguyen, D. Budker, S. K. Lamoreaux, and J. R. Torgerson, Phys. Rev. A 69, 22105 (2004)].« less

One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization.

PubMed

Ozaki, Kyohei; Kawasumi, Katsuaki; Shibata, Mari; Ito, Hideto; Itami, Kenichiro

2015-02-16

The optoelectronic nature of two-dimensional sheets of sp(2)-hydridized carbons (for example, graphenes and nanographenes) can be dramatically altered and tuned by altering the degree of π-extension, shape, width and edge topology. Among various approaches to synthesize nanographenes with atom-by-atom precision, one-shot annulative π-extension (APEX) reactions of polycyclic aromatic hydrocarbons hold significant potential not only to achieve a 'growth from template' synthesis of nanographenes, but also to fine-tune the properties of nanographenes. Here we describe one-shot APEX reactions that occur at the K-region (convex armchair edge) of polycyclic aromatic hydrocarbons by the Pd(CH3CN)4(SbF6)2/o-chloranil catalytic system with silicon-bridged aromatics as π-extending agents. Density functional theory calculations suggest that the complete K-region selectivity stems from the olefinic (decreased aromatic) character of the K-region. The protocol is applicable to multiple APEX and sequential APEX reactions, to construct various nanographene structures in a rapid and programmable manner.

The uniformity study of non-oxide thin film at device level using electron energy loss spectroscopy

NASA Astrophysics Data System (ADS)

Li, Zhi-Peng; Zheng, Yuankai; Li, Shaoping; Wang, Haifeng

2018-05-01

Electron energy loss spectroscopy (EELS) has been widely used as a chemical analysis technique to characterize materials chemical properties, such as element valence states, atoms/ions bonding environment. This study provides a new method to characterize physical properties (i.e., film uniformity, grain orientations) of non-oxide thin films in the magnetic device by using EELS microanalysis on scanning transmission electron microscope. This method is based on analyzing white line ratio of spectra and related extended energy loss fine structures so as to correlate it with thin film uniformity. This new approach can provide an effective and sensitive method to monitor/characterize thin film quality (i.e., uniformity) at atomic level for thin film development, which is especially useful for examining ultra-thin films (i.e., several nanometers) or embedded films in devices for industry applications. More importantly, this technique enables development of quantitative characterization of thin film uniformity and it would be a remarkably useful technique for examining various types of devices for industrial applications.

One-shot K-region-selective annulative π-extension for nanographene synthesis and functionalization

NASA Astrophysics Data System (ADS)

Ozaki, Kyohei; Kawasumi, Katsuaki; Shibata, Mari; Ito, Hideto; Itami, Kenichiro

2015-02-01

The optoelectronic nature of two-dimensional sheets of sp2-hydridized carbons (for example, graphenes and nanographenes) can be dramatically altered and tuned by altering the degree of π-extension, shape, width and edge topology. Among various approaches to synthesize nanographenes with atom-by-atom precision, one-shot annulative π-extension (APEX) reactions of polycyclic aromatic hydrocarbons hold significant potential not only to achieve a ‘growth from template’ synthesis of nanographenes, but also to fine-tune the properties of nanographenes. Here we describe one-shot APEX reactions that occur at the K-region (convex armchair edge) of polycyclic aromatic hydrocarbons by the Pd(CH3CN)4(SbF6)2/o-chloranil catalytic system with silicon-bridged aromatics as π-extending agents. Density functional theory calculations suggest that the complete K-region selectivity stems from the olefinic (decreased aromatic) character of the K-region. The protocol is applicable to multiple APEX and sequential APEX reactions, to construct various nanographene structures in a rapid and programmable manner.

An x-ray absorption study of the iron site in bacterial photosynthetic reaction centers.

PubMed Central

Bunker, G; Stern, E A; Blankenship, R E; Parson, W W

1982-01-01

Measurements were made of the extended x-ray absorption fine structure (EXAFS) of the iron site in photosynthetic reaction centers from the bacterium Rhodopseudomonas sphaeroides. Forms with two quinones, two quinones with added o-phenanthroline, and one quinone were studied. Only the two forms containing two quinones maintained their integrity and were analyzed. The spectra show directly that the added o-phenanthroline does not chelate the iron atom. Further analysis indicates that the iron is octahedrally coordinated by nitrogen and/or oxygen atoms located at various distances, with the average value of about 2.14 A. The analysis suggests that most of the ligands are nitrogens and that three of the nitrogen ligands belong to histidine rings. This interpretation accounts for several unusual features of the EXAFS spectrum. We speculate that the quinones are bound to the histidine rings in some manner. Qualitative features of the absorption edge spectra also are discussed and are related to the Fe-ligand distance. PMID:6977382

Synthesis and Mechanical Characterization of Binary and Ternary Intermetallic Alloys Based on Fe-Ti-Al by Resonant Ultrasound Vibrational Methods

PubMed Central

Chanbi, Daoud; Amara, Sif Eddine; Fellah, Z. E. A.

2018-01-01

Precise but simple experimental and inverse methods allowing the recovery of mechanical material parameters are necessary for the exploration of materials with novel crystallographic structures and elastic properties, particularly for new materials and those existing only in theory. The alloys studied herein are of new atomic compositions. This paper reports an experimental study involving the synthesis and development of methods for the determination of the elastic properties of binary (Fe-Al, Fe-Ti and Ti-Al) and ternary (Fe-Ti-Al) intermetallic alloys with different concentrations of their individual constituents. The alloys studied were synthesized from high purity metals using an arc furnace with argon flow to ensure their uniformity and homogeneity. Precise but simple methods for the recovery of the elastic constants of the isotropic metals from resonant ultrasound vibration data were developed. These methods allowed the fine analysis of the relationships between the atomic concentration of a given constituent and the Young’s modulus or alloy density. PMID:29735946

TRP channels in calcium homeostasis: from hormonal control to structure-function relationship of TRPV5 and TRPV6.

PubMed

van Goor, Mark K C; Hoenderop, Joost G J; van der Wijst, Jenny

2017-06-01

Maintaining plasma calcium levels within a narrow range is of vital importance for many physiological functions. Therefore, calcium transport processes in the intestine, bone and kidney are tightly regulated to fine-tune the rate of absorption, storage and excretion. The TRPV5 and TRPV6 calcium channels are viewed as the gatekeepers of epithelial calcium transport. Several calciotropic hormones control the channels at the level of transcription, membrane expression, and function. Recent technological advances have provided the first near-atomic resolution structural models of several TRPV channels, allowing insight into their architecture. While this field is still in its infancy, it has increased our understanding of molecular channel regulation and holds great promise for future structure-function studies of these ion channels. This review will summarize the mechanisms that control the systemic calcium balance, as well as extrapolate structural views to the molecular functioning of TRPV5/6 channels in epithelial calcium transport. Copyright © 2016. Published by Elsevier B.V.

Optimisation of specimen temperature and pulse fraction in atom probe microscopy experiments on a microalloyed steel.

PubMed

Yao, L; Cairney, J M; Zhu, C; Ringer, S P

2011-05-01

This paper details the effects of systematic changes to the experimental parameters for atom probe microscopy of microalloyed steels. We have used assessments of the signal-to-noise ratio (SNR), compositional measurements and field desorption images to establish the optimal instrumental parameters. These corresponded to probing at the lowest possible temperature (down to 20K) with the highest possible pulse fraction (up to 30%). A steel containing a fine dispersion of solute atom clusters was used as an archetype to demonstrate the importance of running the atom probe at optimum conditions. Crown Copyright © 2010. Published by Elsevier B.V. All rights reserved.

Structural Changes Correlated with Magnetic Spin State Isomorphism in the S2 State of the Mn4CaO5 Cluster in the Oxygen-Evolving Complex of Photosystem II

PubMed Central

Chatterjee, Ruchira; Han, Guangye; Kern, Jan; Gul, Sheraz; Fuller, Franklin D.; Garachtchenko, Anna; Young, Iris; Weng, Tsu-Chien; Nordlund, Dennis; Alonso-Mori, Roberto; Bergmann, Uwe; Sokaras, Dimosthenis; Hatakeyama, Makoto; Yachandra, Vittal K.; Yano, Junko

2016-01-01

The Mn4CaO5 cluster in Photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (Si, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in the S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. Such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis. PMID:28044099

Structural changes correlated with magnetic spin state isomorphism in the S 2 state of the Mn 4CaO 5 cluster in the oxygen-evolving complex of photosystem II

DOE PAGES

Chatterjee, Ruchira; Han, Guangye; Kern, Jan; ...

2016-05-09

The Mn 4CaO 5 cluster in photosystem II catalyzes the four-electron redox reaction of water oxidation in natural photosynthesis. This catalytic reaction cycles through four intermediate states (S i, i = 0 to 4), involving changes in the redox state of the four Mn atoms in the cluster. Recent studies suggest the presence and importance of isomorphous structures within the same redox/intermediate S-state. It is highly likely that geometric and electronic structural flexibility play a role in the catalytic mechanism. Among the catalytic intermediates that have been identified experimentally thus far, there is clear evidence of such isomorphism in themore » S2 state, with a high-spin (5/2) (HS) and a low spin (1/2) (LS) form, identified and characterized by their distinct electron paramagnetic resonance (EPR spectroscopy) signals. We studied these two S2 isomers with Mn extended X-ray absorption fine structure (EXAFS) and absorption and emission spectroscopy (XANES/XES) to characterize the structural and electronic structural properties. The geometric and electronic structure of the HS and LS S2 states are different as determined using Mn EXAFS and XANES/XES, respectively. The Mn K-edge XANES and XES for the HS form are different from the LS and indicate a slightly lower positive charge on the Mn atoms compared to the LS form. Based on the EXAFS results which are clearly different, we propose possible structural differences between the two spin states. As a result, such structural and magnetic redox-isomers if present at room temperature, will likely play a role in the mechanism for water-exchange/oxidation in photosynthesis.« less

Structural evidence for the sorption of Ni(II) atoms on the edges of montmorillonite clay minerals: a polarized X-ray absorption fine structure study

NASA Astrophysics Data System (ADS)

Dähn, Rainer; Scheidegger, André M.; Manceau, Alain; Schlegel, Michel L.; Baeyens, Bart; Bradbury, Michael H.; Chateigner, Daniel

The nature of surface complexes formed on Ni uptake onto montmorillonite (a dioctahedral smectite) has been investigated over an extended time period by polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Self-supporting films of Ni-sorbed montmorillonite were prepared by contacting Ni and montmorillonite at pH 7.2, high ionic strength (0.3 M NaClO 4), and low Ni concentration ([Ni] initial = 19.9 μM) for 14- and 360-d reaction time. The resulting Ni concentration on the clay varied from 4 to 7 μmol/g. Quantitative texture analysis indicates that the montmorillonite particles were well orientated with respect to the plane of the film. The full width at half maximum of the orientation distribution of the c* axes of individual clay platelets about the normal to the film plane was 44.3° (14-d reaction time) and 47.1° (360-d reaction time). These values were used to correct the coordination numbers determined by P-EXAFS for texture effects. Ni K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 10, 35, 55, and 80°. Spectral analysis led to the identification of three nearest cationic subshells containing 2.0 ± 0.5 Al at 3.0 Å and 2.0 ± 0.5 Si at 3.12 Å and 4.0 ± 0.5 Si at 3.26 Å. These distances are characteristic of edge-sharing linkages between Al and Ni octahedra and of corner-sharing linkages between Ni octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Ni-Al and Ni-Si contributions indicates that Ni-Al pairs are oriented parallel to the film plane, whereas Ni-Si pairs are not. The study reveals the formation of Ni inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and thus that heavy metals binding to edge sites is a possible sorption mechanism for dioctahedral smectites. Data analysis further suggests that either the number of neighboring Al atoms slightly increases from 1.6 to 2 or that the structural order of the observed surface complexes increases from 0.01 Å 2 to 0.005 Å 2 with increasing reaction time. On the basis of the low Ni-Al coordination numbers, it appears that over an extended reaction time period of 1 yr the diffusion of Ni atoms in the octahedral layer is not the major uptake mechanism of Ni onto montmorillonite.

Rapid solidification processing system for producing molds, dies and related tooling

DOEpatents

McHugh, Kevin M.

2004-06-08

A system for the spray forming manufacturing of near-net-shape molds, dies and related toolings, wherein liquid material such as molten metal, metallic alloys, or polymers are atomized into fine droplets by a high temperature, high velocity gas and deposited onto a pattern. Quenching of the in-flight atomized droplets provides a heat sink, thereby allowing undercooled and partially solidified droplets to be formed in-flight. Composites can be formed by combining the atomized droplets with solid particles such as powders, whiskers or fibers.

Determination of cadmium in coal using solid sampling graphite furnace high-resolution continuum source atomic absorption spectrometry.

PubMed

da Silva, Alessandra Furtado; Borges, Daniel L G; Lepri, Fábio Grandis; Welz, Bernhard; Curtius, Adilson J; Heitmann, Uwe

2005-08-01

This work describes the development of a method to determine cadmium in coal, in which iridium is used as a permanent chemical modifier and calibration is performed against aqueous standards by high-resolution continuum source atomic absorption spectrometry (HR-CS AAS). This new instrumental concept makes the whole spectral environment in the vicinity of the analytical line accessible, providing a lot more data than just the change in absorbance over time available from conventional instruments. The application of Ir (400 microg) as a permanent chemical modifier, thermally deposited on the pyrolytic graphite platform surface, allowed pyrolysis temperatures of 700 degrees C to be used, which was sufficiently high to significantly reduce the continuous background that occurred before the analyte signal at pyrolysis temperatures <700 degrees C. Structured background absorption also occurred after the analyte signal when atomization temperatures of >1600 degrees C were used, which arose from the electron-excitation spectrum (with rotational fine structure) of a diatomic molecule. Under optimized conditions (pyrolysis at 700 degrees C and atomization at 1500 degrees C), interference-free determination of cadmium in seven certified coal reference materials and two real samples was achieved by direct solid sampling and calibrating against aqueous standards, resulting in good agreement with the certified values (where available) at the 95% confidence level. A characteristic mass of 0.4 pg and a detection limit of 2 ng g(-1), calculated for a sample mass of 1.0 mg coal, was obtained. A precision (expressed as the relative standard deviation, RSD) of <10% was typically obtained when coal samples in the mass range 0.6-1.2 mg were analyzed.

Bond-strength inversion in (In,Ga)As semiconductor alloys

NASA Astrophysics Data System (ADS)

Eckner, Stefanie; Ritter, Konrad; Schöppe, Philipp; Haubold, Erik; Eckner, Erich; Rensberg, Jura; Röder, Robert; Ridgway, Mark C.; Schnohr, Claudia S.

2018-05-01

The atomic-scale structure and vibrational properties of semiconductor alloys are determined by the energy required for stretching and bending the individual bonds. Using temperature-dependent extended x-ray absorption fine-structure spectroscopy, we have determined the element-specific In-As and Ga-As effective bond-stretching force constants in (In,Ga)As as a function of the alloy composition. The results reveal a striking inversion of the bond strength where the originally stiffer bond in the parent materials becomes the softer bond in the alloy and vice versa. Our findings clearly demonstrate that changes of both the individual bond length and the surrounding matrix affect the bond-stretching force constants. We thus show that the previously used common assumptions about the element-specific force constants in semiconductor alloys do not reproduce the composition dependence determined experimentally for (In,Ga)As.

Nuclear Physics Around the Unitarity Limit

DOE PAGES

König, Sebastian; Grießhammer, Harald W.; Hammer, H. -W.; ...

2017-05-15

We argue that many features of the structure of nuclei emerge from a strictly perturbative expansion around the unitarity limit, where the two-nucleon S waves have bound states at zero energy. In this limit, the gross features of states in the nuclear chart are correlated to only one dimensionful parameter, which is related to the breaking of scale invariance to a discrete scaling symmetry and set by the triton binding energy. Observables are moved to their physical values by small perturbative corrections, much like in descriptions of the fine structure of atomic spectra. We provide evidence in favor of themore » conjecture that light, and possibly heavier, nuclei are bound weakly enough to be insensitive to the details of the interactions but strongly enough to be insensitive to the exact size of the two-nucleon system.« less

In situ X-ray probing reveals fingerprints of surface platinum oxide.

PubMed

Friebel, Daniel; Miller, Daniel J; O'Grady, Christopher P; Anniyev, Toyli; Bargar, John; Bergmann, Uwe; Ogasawara, Hirohito; Wikfeldt, Kjartan Thor; Pettersson, Lars G M; Nilsson, Anders

2011-01-07

In situ X-ray absorption spectroscopy (XAS) at the Pt L(3) edge is a useful probe for Pt-O interactions at polymer electrolyte membrane fuel cell (PEMFC) cathodes. We show that XAS using the high energy resolution fluorescence detection (HERFD) mode, applied to a well-defined monolayer Pt/Rh(111) sample where the bulk penetrating hard X-rays probe only surface Pt atoms, provides a unique sensitivity to structure and chemical bonding at the Pt-electrolyte interface. Ab initio multiple-scattering calculations using the FEFF code and complementary extended X-ray absorption fine structure (EXAFS) results indicate that the commonly observed large increase of the white-line at high electrochemical potentials on PEMFC cathodes originates from platinum oxide formation, whereas previously proposed chemisorbed oxygen-containing species merely give rise to subtle spectral changes.

Core-Shell Structure of Intermediate Precipitates in a Nb-Based Z-Phase Strengthened 12% Cr Steel.

PubMed

Rashidi, Masoud; Andrén, Hans-Olof; Liu, Fang

2017-04-01

In creep resistant Z-phase strengthened 12% Cr steels, MX (M=Nb, Ta, or V, and X=C and/or N) to Z-phase (CrMN, M=Ta, Nb, or V) transformation plays an important role in achieving a fine distribution of Z-phase precipitates for creep strengthening. Atom probe tomography was employed to investigate the phase transformation in a Nb-based Z-phase strengthened trial steel. Using iso-concentration surfaces with different concentration values, and subtracting the matrix contribution enabled us to reveal the core-shell structure of the transient precipitates between MX and Z-phase. It was shown that Z-phase forms by diffusion of Cr into NbN upon ageing, and Z-phase has a composition corresponding to Cr1+x Nb1-x N with x=0.08.

Revisiting the Bohr Atom 100 Years Later

NASA Astrophysics Data System (ADS)

Wall, Ernst

2013-03-01

We use a novel electron model wherein the electron is modeled as a point charge behaving as a trapped photon revolving in a Compton wavelength orbit at light speed. The revolving point charge gives rise to spiraling Compton wavelets around the electron, which give rise to de Broglie waves. When applied to the Bohr model, the orbital radius of the electron scales to the first Bohr orbit's radius via the fine structure constant. The orbiting electron's orbital velocity, Vb, scales to that of the electron's charge's internal velocity (the velocity of light, c) via the fine structure constant. The Compton wavelets, if they reflect off the nucleus, have a round trip time just long enough to allow the electron to move one of its diameters in distance in the first Bohr orbit. The ratio of the electron's rotational frequency, fe, to its rotational frequency in the Bohr orbit fb, is fe/fb = 1/α2, which is also the number of electron rotations in single orbit. If we scale the electron's rotational energy (h*fe) to that of the orbit using this, the orbital energy value (h*fb) would be 27.2114 eV. However, the virial theorem reduces it to 13.6057, the ground state energy of the first Bohr orbit. Ref: www.tachyonmodel.com.

Growth of Nanoscale Nickel Ferrite on Carbonaceous Matrix- A Novel Method of Turning Harmful Particulates into a Functional Nanocomposite: An XAFS Study

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

Pattanaik, S.; Huggins, F; Huffman, G

2010-01-01

Particulate matter (PM) emission from residual oil combustion typically consists of carbonaceous material accompanied by inorganic matter notably transition metal sulfates. Often a minor sulfide form is found in the coarse fraction while an oxide form is more common in the fine and ultrafine fractions. A composite comprising of nanoscale nickel ferrite dispersed on carbonaceous matrix has been obtained following liberation of metal sulfates from the fine PM - a novel method of turning harmful particulates into a functional nanocomposite without the need for elaborate preparation using expensive precursors. The nickel ferrite content in the composite varies with the Fe/Nimore » ratio in particulate, fuel type, and combustion condition. Such variation may lead to the composite exhibiting diverse physical behaviors. Detailed structure and cation distribution in dispersed ferrite have been studied using Fe and Ni K-edges XAFS spectroscopy. Peaks are identified in the radial structure function with specific atom pair correlations within the spinel ferrite from which the relative occupancy of the cations in the octahedral and tetrahedral sites can be discerned. The results show that Ni(II) has strong preference for the octahedral site, while Fe(III) prefers both sites which is consistent with that of an inverted spinel ferrite.« less

Fine-structure constant constraints on dark energy. II. Extending the parameter space

NASA Astrophysics Data System (ADS)

Martins, C. J. A. P.; Pinho, A. M. M.; Carreira, P.; Gusart, A.; López, J.; Rocha, C. I. S. A.

2016-01-01

Astrophysical tests of the stability of fundamental couplings, such as the fine-structure constant α , are a powerful probe of new physics. Recently these measurements, combined with local atomic clock tests and Type Ia supernova and Hubble parameter data, were used to constrain the simplest class of dynamical dark energy models where the same degree of freedom is assumed to provide both the dark energy and (through a dimensionless coupling, ζ , to the electromagnetic sector) the α variation. One caveat of these analyses was that it was based on fiducial models where the dark energy equation of state was described by a single parameter (effectively its present day value, w0). Here we relax this assumption and study broader dark energy model classes, including the Chevallier-Polarski-Linder and early dark energy parametrizations. Even in these extended cases we find that the current data constrains the coupling ζ at the 1 0-6 level and w0 to a few percent (marginalizing over other parameters), thus confirming the robustness of earlier analyses. On the other hand, the additional parameters are typically not well constrained. We also highlight the implications of our results for constraints on violations of the weak equivalence principle and improvements to be expected from forthcoming measurements with high-resolution ultrastable spectrographs.

Growth of nanoscale nickel ferrite on carbonaceous matrix--A novel method of turning harmful particulates into a functional nanocomposite: An XAFS study.

PubMed

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

2010-06-15

Particulate matter (PM) emission from residual oil combustion typically consists of carbonaceous material accompanied by inorganic matter notably transition metal sulfates. Often a minor sulfide form is found in the coarse fraction while an oxide form is more common in the fine and ultrafine fractions. A composite comprising of nanoscale nickel ferrite dispersed on carbonaceous matrix has been obtained following liberation of metal sulfates from the fine PM--a novel method of turning harmful particulates into a functional nanocomposite without the need for elaborate preparation using expensive precursors. The nickel ferrite content in the composite varies with the Fe/Ni ratio in particulate, fuel type, and combustion condition. Such variation may lead to the composite exhibiting diverse physical behaviors. Detailed structure and cation distribution in dispersed ferrite have been studied using Fe and Ni K-edges XAFS spectroscopy. Peaks are identified in the radial structure function with specific atom pair correlations within the spinel ferrite from which the relative occupancy of the cations in the octahedral and tetrahedral sites can be discerned. The results show that Ni(II) has strong preference for the octahedral site, while Fe(III) prefers both sites which is consistent with that of an inverted spinel ferrite. Copyright 2010 Elsevier B.V. All rights reserved.

Fine-structure relaxation of O(3P) induced by collisions with He, H and H2

NASA Astrophysics Data System (ADS)

Lique, F.; Kłos, J.; Alexander, M. H.; Le Picard, S. D.; Dagdigian, P. J.

2018-02-01

The excitation of fine-structure levels of O(3P) by collisions is an important cooling process in the interstellar medium (ISM). We investigate here spin-orbit (de-)excitation of O(3Pj, j = 0, 1, 2) induced by collisions with He, H and H2 based on quantum scattering calculations of the relevant rate coefficients in the 10-1000 K temperature range. The underlying potential energy surfaces are derived from highly correlated abinitio calculations. Significant differences were found with the rate coefficients currently used in astrophysical applications. In particular, our new rate coefficients for collisions with H are up to a factor of 5 lower. Radiative transfer computations allow the assessment of the astrophysical impact of these new rate coefficients. In the case of molecular clouds, the new data are found to increase slightly the flux of the 3P1 → 3P2, while decreasing the flux of the 3P0 → 3P1 line. In the case of atomic clouds, the flux of both lines is predicted to decrease. The new rate coefficients are expected to impact significantly the modelling of cooling in astrophysical environments while also allowing new insights into oxygen chemistry in the ISM.

The Orion Nebula in the Far-Infrared: high-J CO and fine-structure lines mapped by FIFI-LS/SOFIA

NASA Astrophysics Data System (ADS)

Klein, Randolf; Looney, Leslie; Cox, Erin; Fischer, Christian; Iserlohe, Christof; Krabbe, Alfred

2015-08-01

The Orion Nebula is the closest massive star forming region allowing us to study the physical conditions in such a region with high spatial resolution. We used the far infrared integral-field spectrometer, FIFI-LS, on-board the airborne observatory SOFIA to study the atomic and molecular gas in the Orion Nebula at medium spectral resolution.The large maps obtained with FIFI-LS cover the nebula from the BN/KL-object to the bar in several fine structure lines. These spectral maps are the largest and highest spatially resolved to date. They allow us to study the conditions of the photon-dominated region and the interface to the molecular cloud with unprecedented detail.Another investigation targeted the molecular gas in the BN/KL region of the Orion Nebula, which is stirred up by a violent explosion about 500 years ago. The explosion drives a wide angled molecular outflow. We present maps of several high-J CO observations (J in the range of 10 to 30), allowing us to analyse of the heated molecular gas.The observations were taken during the commissioning of FIFI-LS last year and as recent as this March. The results are still preliminary as the data reduction and calibration is still under development.

Ferroelectric Polarization-Modulated Interfacial Fine Structures Involving Two-Dimensional Electron Gases in Pb(Zr,Ti)O3/LaAlO3/SrTiO3 Heterostructures.

PubMed

Wang, Shuangbao; Bai, Yuhang; Xie, Lin; Li, Chen; Key, Julian D; Wu, Di; Wang, Peng; Pan, Xiaoqing

2018-01-10

Interfacial fine structures of bare LaAlO 3 /SrTiO 3 (LAO/STO) heterostructures are compared with those of LAO/STO heterostructures capped with upward-polarized Pb(Zr 0.1 ,Ti 0.9 )O 3 (PZT up ) or downward-polarized Pb(Zr 0.5 ,Ti 0.5 )O 3 (PZT down ) overlayers by aberration-corrected scanning transmission electron microscopy experiments. By combining the acquired electron energy-loss spectroscopy mapping, we are able to directly observe electron transfer from Ti 4+ to Ti 3+ and ionic displacements at the interface of bare LAO/STO and PZT down /LAO/STO heterostructure unit cell by unit cell. No evidence of Ti 3+ is observed at the interface of the PZT up /LAO/STO samples. Furthermore, the confinement of the two-dimensional electron gas (2DEG) at the interface is determined by atomic-column spatial resolution. Compared with the bare LAO/STO interface, the 2DEG density at the LAO/STO interface is enhanced or depressed by the PZT down or PZT up overlayer, respectively. Our microscopy studies shed light on the mechanism of ferroelectric modulation of interfacial transport at polar/nonpolar oxide heterointerfaces, which may facilitate applications of these materials as nonvolatile memory.

Solution structures of chloroquine-ferriheme complexes modeled using MD simulation and investigated by EXAFS spectroscopy.

PubMed

Kuter, David; Streltsov, Victor; Davydova, Natalia; Venter, Gerhard A; Naidoo, Kevin J; Egan, Timothy J

2016-01-01

The interaction of chloroquine (CQ) and the μ-oxo dimer of iron(III) protoporphyrin IX (ferriheme) in aqueous solution was modeled using molecular dynamics (MD) simulations. Two models of the CQ-(μ-oxo ferriheme) complex were investigated, one involving CQ π-stacked with an unligated porphyrin face of μ-oxo ferriheme and the other in which CQ was docked between the two porphyrin rings. The feasibility of both models was tested by fitting computed structures to the experimental extended X-ray absorption fine structure (EXAFS) spectrum of the CQ-(μ-oxo ferriheme) complex in frozen aqueous solution. The docked model produced better agreement with experimental data, suggesting that this is the more likely structure in aqueous solution. The EXAFS fit indicated a longer than expected Fe-O bond of 1.87Å, accounting for the higher than expected magnetic moment of the complex. As a consequence, the asymmetric Fe-O-Fe stretch shifts much lower in frequency and was identified in the precipitated solid at 744cm(-1) with the aid of the O(18) isomer shift. Three important CQ-ferriheme interactions were identified in the docked structure. These were a hydrogen bond between the oxide bridge of μ-oxo ferriheme and the protonated quinolinium nitrogen atom of CQ; π-stacking between the quinoline ring of CQ and the porphyrin rings; and a close contact between the 7-chloro substituent of CQ and the porphyrin methyl hydrogen atoms. These interactions can be used to rationalize previously observed structure-activity relationships for quinoline-ferriheme association. Copyright © 2015 Elsevier Inc. All rights reserved.

M553 sphere forming experiment: Pure nickel specimen evaluation

NASA Technical Reports Server (NTRS)

Johnson, P. C.; Peters, E. T.

1973-01-01

A region or cap of very fine two-dimensional surface growth structure was observed at the top of three of the six pure nickel flight specimens. Such two-dimensional surface growth structures have been observed both on the ground-based specimens and on other surface areas of the flight specimens. However, the fine structures observed on the three flight samples are at least an order of magnitude finer than those previously observed, and resemble similar localized, fine, two-dimensional surface structures observed in both ground and flight specimens for the nickel alloys. The two-dimensional growth areas consist primarily of fine equiaxed grains, specimen SL-2.6, fine dendrites, specimen SL-2.5, or a core of fine equiaxed grains surrounded by a ring of fine dendrites, specimen SL-1.9.

Fast Nitrogen Atoms from Dissociative Excitation of N2 by Electron Impact

NASA Technical Reports Server (NTRS)

Ajello, Joseph M.; Ciocca, Marco

1996-01-01

The Doppler profiles of one of the fine structure lines of the N I (1200 A) g (sup 4)S(sup 0)-(sup 4)P multiplet and of the N II (1085 A) g (sup 3)p(sup O)-(sup 3)D multiplet have been measured. Excitation of the multiplets is produced by electron impact dissociative excitation of N2. The experimental line profiles are evaluated by fast Fourier transform (FFT) techniques and analysis of the profiles yields the kinetic energy distribution of fragments. The full width at half maximum (FWHM) of N I (1200 A) increases from 27+/-6 mA at 30 eV to 37+/-4 mA at 100 eV as the emission cross section of the dissociative ionization excitation process becomes more important relative to the dissociative excitation process. The FWHM of the N II (1085 A) line is 36+/-4 mA at 100 eV. For each multiplet the kinetic energy distribution function of each of the two fragment N atoms (ions) is much broader than thermal with a mean energy above 1.0 eV. The dissociation process with the largest cross section is predissociation and predominantly produces N atoms with kinetic energy distributions having mean energies above 0.5 eV. Dissociative processes can lead to a substantial escape flux of N I atoms from the satellites, Titan and Triton of the outer planets.

Temperature dependent local atomic displacements in ammonia intercalated iron selenide superconductor

NASA Astrophysics Data System (ADS)

Paris, E.; Simonelli, L.; Wakita, T.; Marini, C.; Lee, J.-H.; Olszewski, W.; Terashima, K.; Kakuto, T.; Nishimoto, N.; Kimura, T.; Kudo, K.; Kambe, T.; Nohara, M.; Yokoya, T.; Saini, N. L.

2016-06-01

Recently, ammonia-thermal reaction has been used for molecular intercalation in layered FeSe, resulting a new Lix(NH3)yFe2Se2 superconductor with Tc ~ 45 K. Here, we have used temperature dependent extended x-ray absorption fine structure (EXAFS) to investigate local atomic displacements in single crystals of this new superconductor. Using polarized EXAFS at Fe K-edge we have obtained direct information on the local Fe-Se and Fe-Fe bondlengths and corresponding mean square relative displacements (MSRD). We find that the Se-height in the intercalated system is lower than the one in the binary FeSe, suggesting compressed FeSe4 tetrahedron in the title system. Incidentally, there is hardly any effect of the intercalation on the bondlengths characteristics, revealed by the Einstein temperatures, that are similar to those found in the binary FeSe. Therefore, the molecular intercalation induces an effective compression and decouples the FeSe slabs. Furthermore, the results reveal an anomalous change in the atomic correlations across Tc, appearing as a clear decrease in the MSRD, indicating hardening of the local lattice mode. Similar response of the local lattice has been found in other families of superconductors, e.g., A15-type and cuprates superconductors. This observation suggests that local atomic correlations should have some direct correlation with the superconductivity.

Vanadium K-edge XAS studies on the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis.

PubMed

Renirie, Rokus; Charnock, John M; Garner, C David; Wever, Ron

2010-06-01

Vanadium K-edge X-ray Absorption Spectra have been recorded for the native and peroxo-forms of vanadium chloroperoxidase from Curvularia inaequalis at pH 6.0. The Extended X-ray Absorption Fine Structure (EXAFS) regions provide a refinement of previously reported crystallographic data; one short V=O bond (1.54A) is present in both forms. For the native enzyme, the vanadium is coordinated to two other oxygen atoms at 1.69A, another oxygen atom at 1.93A and the nitrogen of an imidazole group at 2.02A. In the peroxo-form, the vanadium is coordinated to two other oxygen atoms at 1.67A, another oxygen atom at 1.88A and the nitrogen of an imidazole group at 1.93A. When combined with the available crystallographic and kinetic data, a likely interpretation of the EXAFS distances is a side-on bound peroxide involving V-O bonds of 1.67 and 1.88A; thus, the latter oxygen would be 'activated' for transfer. The shorter V-N bond observed in the peroxo-form is in line with the previously reported stronger binding of the cofactor in this form of the enzyme. Reduction of the enzyme with dithionite has a clear influence on the spectrum, showing a change from vanadium(V) to vanadium(IV).

Local Structure Analysis and Interface Layer Effect of Phase-Change Recording Material Using Actual Media

NASA Astrophysics Data System (ADS)

Nakai, Tsukasa; Yoshiki, Masahiko; Satoh, Yasuhiro; Ashida, Sumio

2008-07-01

The influences of the interface layer on crystal structure, the local atomic arrangement, and the electronic and chemical structure of a GeBiTe (GBT) phase-change recording material have been investigated using X-ray diffraction (XRD), X-ray absorption fine structure (XAFS), and hard X-ray photoelectron spectroscopy (HX-PES) methods using actual rewritable high-speed HD DVD media without special sample processing. XRD results showed that the crystal structure of laser-crystallized GBT alloy in the actual HD DVD media is the same as that of GeSbTe (GST) alloy, which has a NaCl-type structure. No differences between samples with and without interface layers were found. The lattice constant of GBT is larger than that of GST. Bi increases the lattice constant of GST with respect to the Bi substitution ratio of Sb. According to HX-PES, the DOS of in the recording film amorphous state with an interface layer is closer to that of the crystalline state than the recording film without an interface layer. From XAFS results, clear differences between amorphous (Amo.) and crystalline states (Cry.) were observed. The interatomic distance of amorphous recording material is independent of the existence of an interface layer. On the other hand, the coordination number varied slightly due to the presence of the interface layer. Therefore, the electronic state of the recording layer changes because of the interface layer, although the local structure changes only slightly except for the coordination number. Combining these results, we conclude that the interface layer changes the electronic state of the recording layer and promotes crystallization, but only affects the local structure of the atomic arrangement slightly.

Native structure of photosystem II at 1.95 Å resolution viewed by femtosecond X-ray pulses.

PubMed

Suga, Michihiro; Akita, Fusamichi; Hirata, Kunio; Ueno, Go; Murakami, Hironori; Nakajima, Yoshiki; Shimizu, Tetsuya; Yamashita, Keitaro; Yamamoto, Masaki; Ago, Hideo; Shen, Jian-Ren

2015-01-01

Photosynthesis converts light energy into biologically useful chemical energy vital to life on Earth. The initial reaction of photosynthesis takes place in photosystem II (PSII), a 700-kilodalton homodimeric membrane protein complex that catalyses photo-oxidation of water into dioxygen through an S-state cycle of the oxygen evolving complex (OEC). The structure of PSII has been solved by X-ray diffraction (XRD) at 1.9 ångström resolution, which revealed that the OEC is a Mn4CaO5-cluster coordinated by a well defined protein environment. However, extended X-ray absorption fine structure (EXAFS) studies showed that the manganese cations in the OEC are easily reduced by X-ray irradiation, and slight differences were found in the Mn-Mn distances determined by XRD, EXAFS and theoretical studies. Here we report a 'radiation-damage-free' structure of PSII from Thermosynechococcus vulcanus in the S1 state at a resolution of 1.95 ångströms using femtosecond X-ray pulses of the SPring-8 ångström compact free-electron laser (SACLA) and hundreds of large, highly isomorphous PSII crystals. Compared with the structure from XRD, the OEC in the X-ray free electron laser structure has Mn-Mn distances that are shorter by 0.1-0.2 ångströms. The valences of each manganese atom were tentatively assigned as Mn1D(III), Mn2C(IV), Mn3B(IV) and Mn4A(III), based on the average Mn-ligand distances and analysis of the Jahn-Teller axis on Mn(III). One of the oxo-bridged oxygens, O5, has significantly longer distances to Mn than do the other oxo-oxygen atoms, suggesting that O5 is a hydroxide ion instead of a normal oxygen dianion and therefore may serve as one of the substrate oxygen atoms. These findings provide a structural basis for the mechanism of oxygen evolution, and we expect that this structure will provide a blueprint for the design of artificial catalysts for water oxidation.

Multiconfiguration Dirac-Hartree-Fock calculations of energy levels and radiative rates of Fe VII

NASA Astrophysics Data System (ADS)

Li, Yang; Xu, Xiaokai; Li, Bowen; Jönsson, Per; Chen, Ximeng

2018-06-01

Detailed calculations are performed for 134 fine-structure levels of the 3p63d2, 3p63d4s, 3p53d3 and 3p63d4p configurations in Fe VII using the multiconfiguration Dirac-Hartree-Fock (MCDHF) and relativistic configuration interaction (RCI) methods. Important electron correlation effects are systematically accounted for through active space (AS) expansions. Our results compare well with experimental measurements, emphasizing the importance of a careful treatment of electron correlation, and provide some missing data in the NIST atomic database. The data obtained are expected to be useful in astrophysical applications, particularly for the research of the solar coronal plasma.

Structure and properties of a splat cooled 2024 aluminum alloy

NASA Technical Reports Server (NTRS)

Lebo, M.; Grant, N. J.

1974-01-01

In the investigation the alloy was melted, heated to 750 C, and atomized into fine droplets. The droplets were rapidly quenched against a heavy copper disk rotating at 1725 rpm. The resultant splat cooled flakes were screened. Three flake sizes were finally separated. Flakes of each size were separately processed. The characteristics of the splat cooling process and the properties of the obtained products are discussed. Splat cooling against a metallic substrate permits cooling rates up to about 1,000,000 deg C/sec. Increases in yield strength and tensile strength of 14 to 19% are observed for the splat products. Other improvements are connected with increases in fatigue life and stress rupture performance.

Crossed-Beam Spectroscopy of Hydrogen: A New Value for the Rydberg Constant

NASA Astrophysics Data System (ADS)

Amin, S. R.; Caldwell, C. D.; Lichten, W.

1981-11-01

In a crossed laser-atomic beam experiment the wavelengths of the 2s-3p transitions are measured in H and D to a precision of one part in 109. Our value for the Rydberg constant is R∞=109 737.315 21(11) cm-1. The fine-structure splittings of the 3p states in H and D are 3249.8(8) and 3251.7(7) MHz, respectively; the isotope shifts for the 2s-3p12 and 2s-3p32 transitions are 124 260.7(7) and 124 262.6(7) MHz, respectively. Our results largely agree with previous, less precise experiments and with theory.

SYNCHROTRON RADIATION, FREE ELECTRON LASER, APPLICATION OF NUCLEAR TECHNOLOGY, ETC.: A new cell for X-ray absorption spectroscopy study under high pressure

NASA Astrophysics Data System (ADS)

Zheng, Li-Rong; Che, Rong-Zheng; Liu, Jing; Du, Yong-Hua; Zhou, Ying-Li; Hu, Tian-Dou

2009-08-01

X-ray absorption fine structure (XAFS) spectroscopy is a powerful technique for the investigation of the local environment around selected atoms in condensed matter. XAFS under pressure is an important method for the synchrotron source. We design a cell for a high pressure XAFS experiment. Sintered boron carbide is used as the anvils of this high pressure cell in order to obtain a full XAFS spectrum free from diffraction peaks. In addition, a hydraulic pump was adopted to make in-suit pressure modulation. High quality XAFS spectra of ZrH2 under high pressure (up to 13 GPa) were obtained by this cell.

An XAS experimental approach to study low Pt content electrocatalysts operating in PEM fuel cells.

PubMed

Principi, Emiliano; Witkowska, Agnieszka; Dsoke, Sonia; Marassi, Roberto; Di Cicco, Andrea

2009-11-21

We present an X-ray absorption spectroscopy (XAS) study of a low Pt content catalyst layer (Pt loading 0.1 mg cm(-2)) operating at the cathode of a proton exchange membrane fuel cell (PEMFC). This catalyst is based on the use of a mesoporous inorganic matrix as a support for the catalyst Pt nanoparticles. Due to the high Pt dilution, in situ measurements of its structural properties by XAS are challenging and suitable experimental strategies must be devised for this purpose. In particular, we show that accurate XAS in situ fluorescence measurements can be obtained using an optimized fuel cell, suitable protocols for alignment of a focused X-ray beam and an appropriate filter for the background signal of the other atomic species contained in the electrodes. Details, advantages and limitations of the XAS technique for in situ measurements are discussed. Analysis of the near-edge XAS and EXAFS (extended X-ray absorption fine structure) data, corroborated by a HRTEM (high-resolution transmission electron microscopy) study, shows that the Pt particles have a local structure compatible with that of bulk Pt (fcc) and coordination numbers match those expected for particles with typical sizes in the 1.5-2.0 nm range. Substantial changes in the oxidation state and in local atomic arrangement of the Pt particles are found for different applied potentials. The catalyst support, containing W atoms, exhibits a partial reduction upon PEMFC activation, thus mimicking the catalyst behavior. This indicates a possible role of the mesoporous matrix in favouring the oxygen reduction reaction (ORR) and stimulates further research on active catalyst supports.

Conformational study of glyoxal bis(amidinohydrazone) by ab initio methods

NASA Astrophysics Data System (ADS)

Mannfors, B.; Koskinen, J. T.; Pietilä, L.-O.

1997-08-01

We report the first ab initio molecular orbital study on the ground state of the endiamine tautomer of glyoxal bis(amidinohydrazone) (or glyoxal bis(guanylhydrazone), GBG) free base. The calculations were performed at the following levels of theory: Hartree-Fock, second-order Møller-Plesset perturbation theory and density functional theory (B-LYP and B3-LYP) as implemented in the Gaussian 94 software. The standard basis set 6-31G(d) was found to be sufficient. The default fine grid of Gaussian 94 was used in the density functional calculations. Molecular properties, such as optimized structures, total energies and the electrostatic potential derived (CHELPG) atomic charges, were studied as functions of C-C and N-N conformations. The lowest energy conformation was found to be all- trans, in agreement with the experimental solid-state structure. The second conformer with respect to rotation around the central C-C bond was found to be the cis conformer with an MP2//HF energy of 4.67 kcal mol -1. For rotation around the N-N bond the energy increased monotonically from the trans conformation to the cis conformation, the cis energy being very high, 22.01 kcal mol -1 (MP2//HF). The atomic charges were shown to be conformation dependent, and the bond charge increments and especially the conformational changes of the bond charge increments were found to be easily transferable between structurally related systems.

Evolution of Defect Structures and Deep Subgap States during Annealing of Amorphous In-Ga-Zn Oxide for Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Jia, Junjun; Suko, Ayaka; Shigesato, Yuzo; Okajima, Toshihiro; Inoue, Keiko; Hosomi, Hiroyuki

2018-01-01

We investigate the evolution behavior of defect structures and the subgap states in In-Ga-Zn oxide (IGZO) films with increasing postannealing temperature by means of extended x-ray absorption fine-structure (EXAFS) measurements, positron annihilation lifetime spectroscopy (PALS), and cathodoluminescence (CL) spectroscopy, aiming to understand the relationship between defect structures and subgap states. EXAFS measurements reveal the varied oxygen coordination numbers around cations during postannealing and confirm two types of point defects, namely, excess oxygen around Ga atoms and oxygen deficiency around In and/or Zn atoms. PALS suggests the existence of cation-vacancy (VM )-related clusters with neutral or negative charge in both amorphous and polycrystalline IGZO films. CL spectra show a main emission band at approximately 1.85 eV for IGZO films, and a distinct shoulder located at about 2.15 eV for IGZO films postannealed above 600 °C . These two emission bands are assigned to a recombination between the electrons in the conduction band and/or in the shallow donor levels near the conduction band and the acceptors trapped above the valence-band maximum. The shallow donors are attributed to the oxygen deficiency, and the acceptors are thought to possibly arise from the excess oxygen or the VM-related clusters. These results open up an alternative route for understanding the device instability of amorphous IGZO-based thin-film transistors, especially the presence of the neutral or negatively charged VM-related clusters in amorphous IGZO films.

Elucidation of Hydrogen Bonding Patterns in Ligand-Free, Lactose- and Glycerol-Bound Galectin-3C by Neutron Crystallography to Guide Drug Design.

PubMed

Manzoni, Francesco; Wallerstein, Johan; Schrader, Tobias E; Ostermann, Andreas; Coates, Leighton; Akke, Mikael; Blakeley, Matthew P; Oksanen, Esko; Logan, Derek T

2018-05-24

The medically important drug target galectin-3 binds galactose-containing moieties on glycoproteins through an intricate pattern of hydrogen bonds to a largely polar surface-exposed binding site. All successful inhibitors of galectin-3 to date have been based on mono- or disaccharide cores closely resembling natural ligands. A detailed understanding of the H-bonding networks in these natural ligands will provide an improved foundation for the design of novel inhibitors. Neutron crystallography is an ideal technique to reveal the geometry of hydrogen bonds because the positions of hydrogen atoms are directly detected rather than being inferred from the positions of heavier atoms as in X-ray crystallography. We present three neutron crystal structures of the C-terminal carbohydrate recognition domain of galectin-3: the ligand-free form and the complexes with the natural substrate lactose and with glycerol, which mimics important interactions made by lactose. The neutron crystal structures reveal unambiguously the exquisite fine-tuning of the hydrogen bonding pattern in the binding site to the natural disaccharide ligand. The ligand-free structure shows that most of these hydrogen bonds are preserved even when the polar groups of the ligand are replaced by water molecules. The protonation states of all histidine residues in the protein are also revealed and correlate well with NMR observations. The structures give a solid starting point for molecular dynamics simulations and computational estimates of ligand binding affinity that will inform future drug design.

MARINE D-BLUE CLEAN™

EPA Pesticide Factsheets

Technical product bulletin: this dispersant is used in oil spill cleanups on salt water, sprayed onto slick in atomized form using moderately coarse droplets rather than fine mist. Effective with crude and residual heavy oil spills.

Even the Odd Numbers Help: Failure Modes of SAM-Based Tunnel Junctions Probed via Odd-Even Effects Revealed in Synchrotrons and Supercomputers.

PubMed

Thompson, Damien; Nijhuis, Christian A

2016-10-18

This Account describes a body of research in atomic level design, synthesis, physicochemical characterization, and macroscopic electrical testing of molecular devices made from ferrocene-functionalized alkanethiol molecules, which are molecular diodes, with the aim to identify, and resolve, the failure modes that cause leakage currents. The mismatch in size between the ferrocene headgroup and alkane rod makes waxlike highly dynamic self-assembled monolayers (SAMs) on coinage metals that show remarkable atomic-scale sensitivity in their electrical properties. Our results make clear that molecular tunnel junction devices provide an excellent testbed to probe the electronic and supramolecular structures of SAMs on inorganic substrates. Contacting these SAMs to a eutectic "EGaIn" alloy top-electrode, we designed highly stable long-lived molecular switches of the form electrode-SAM-electrode with robust rectification ratios of up to 3 orders of magnitude. The graphic that accompanies this conspectus displays a computed SAM packing structure, illustrating the lollipop shape of the molecules that gives dynamic SAM supramolecular structures and also the molecule-electrode van der Waals (vdW) contacts that must be controlled to form good SAM-based devices. In this Account, we first trace the evolution of SAM-based electronic devices and rationalize their operation using energy level diagrams. We describe the measurement of device properties using near edge X-ray absorption fine structure spectroscopy, cyclic voltammetry, and X-ray photoelectron spectroscopy complemented by molecular dynamics and electronic structure calculations together with large numbers of electrical measurements. We discuss how data obtained from these combined experimental/simulation codesign studies demonstrate control over the supramolecular and electronic structure of the devices, tuning odd-even effects to optimize inherent packing tendencies of the molecules in order to minimize leakage currents in the junctions. It is now possible, but still very costly to create atomically smooth electrodes and we discuss progress toward masking electrode imperfections using cooperative molecule-electrode contacts that are only accessible by dynamic SAM structures. Finally, the unique ability of SAM devices to achieve simultaneously high and atom-sensitive electrical switching is summarized and discussed. While putting these structures to work as real world electronic devices remains very challenging, we speculate on the scientific and technological advances that are required to further improve electronic and supramolecular structure, toward the creation of high yields of long-lived molecular devices with (very) large, reproducible rectification ratios.

Modification of Structure and Tribological Properties of the Surface Layer of Metal-Ceramic Composite under Electron Irradiation in the Plasmas of Inert Gases

NASA Astrophysics Data System (ADS)

Ovcharenko, V. E.; Ivanov, K. V.; Mohovikov, A. A.; Yu, B.; Xu, Yu; Zhong, L.

2018-01-01

Metal-ceramic composites are the main materials for high-load parts in tribomechanical systems. Modern approaches to extend the operation life of tribomechanical systems are based on increasing the strength and tribological properties of the surface layer having 100 to 200 microns in depth. The essential improvement of the properties occurs when high dispersed structure is formed in the surface layer using high-energy processing. As a result of the dispersed structure formation the more uniform distribution of elastic stresses takes place under mechanical or thermal action, the energy of stress concentrators emergence significantly increases and the probability of internal defects formation reduces. The promising method to form the dispersed structure in the surface layer is pulse electron irradiation in the plasmas of inert gases combining electron irradiation and ion bombardment in one process. The present work reports upon the effect of pulse electron irradiation in plasmas of different inert gases with different atomic mass and ionization energy on the structure and tribological properties of the surface layer of TiC/(Ni-Cr) metal-ceramic composite with the volume ratio of the component being 50:50. It is experimentally shown that high-dispersed heterophase structure with a fraction of nanosized particles is formed during the irradiation. Electron microscopy study reveals that refining of the initial coarse TiC particles occurs via their dissolution in the molten metal binder followed by the precipitation of secondary fine particles in the interparticle layers of the binder. The depth of modified layer and the fraction of nanosized particles increase when the atomic number of the plasma gas increases and ionization energy decreases. The wear resistance of metal-ceramic composite improves in accordance to the formation of nanocrystalline structure in the surface layer.

Spectral and non-spectral interferences in the determination of thallium in environmental materials using electrothermal atomization and vaporization techniques—a case study

NASA Astrophysics Data System (ADS)

Vale, Maria Goreti R.; Welz, Bernhard

2002-12-01

The literature on the determination of Tl in environmental samples using electrothermal atomization (ETA) and vaporization (ETV) techniques has been reviewed with special attention devoted to potential interferences and their control. Chloride interference, which is due to the formation of the volatile monochloride in the condensed phase, is the most frequently observed problem. Due to its high dissociation energy (88 kcal/mol), TlCl is difficult to dissociate in the gas phase and is easily lost. The best means of controlling this interference in ETA is atomization under isothermal conditions according to the stabilized temperature platform furnace concept, and the use of reduced palladium as a modifier. An alternative approach appears to be the 'fast furnace' concept, wherein both the use of a modifier and the pyrolysis stage are omitted. This concept requires an efficient background correction system, and high-resolution continuum-source atomic absorption spectrometry (HR-CS AAS) appears to offer the best results. This chloride interference can also cause significant problems when ETV techniques are used. Among the spectral interferences found in the determination of thallium are those due to Pd, the most efficient modifier, and Fe, which is frequently found at high concentrations in environmental samples. Both interferences are due to nearby atomic lines, and are observed only when deuterium background correction and relatively high atomization temperatures are used. A more serious spectral interference is that due to the molecular absorption spectrum of SO 2, which has a maximum around the Tl line and exhibits a pronounced rotational fine structure. HR-CS AAS again showed the best performance in coping with this interference.

Structural, electronic structure and antibacterial properties of graphene-oxide nano-sheets

NASA Astrophysics Data System (ADS)

Sharma, Aditya; Varshney, Mayora; Nanda, Sitansu Sekhar; Shin, Hyun Joon; Kim, Namdong; Yi, Dong Kee; Chae, Keun-Hwa; Ok Won, Sung

2018-04-01

Correlation between the structural/electronic structure properties and bio-activity of graphene-based materials need to be thoroughly evaluated before their commercial implementation in the health and environment precincts. To better investigate the local hybridization of sp2/sp3 orbitals of the functional groups of graphene-oxide (GO) and their execution in the antimicrobial mechanism, we exemplify the antibacterial activity of GO sheets towards the Escherichia coli bacteria (E. coli) by applying the field-emission scanning electron microscopy (FESEM), near edge X-ray absorption fine structure (NEXAFS) and scanning transmission X-ray microscope (STXM) techniques. C K-edge and O K-edge NEXAFS spectra have revealed lesser sp2 carbon atoms in the aromatic ring and attachment of functional oxygen groups at GO sheets. Entrapment of E. coli bacteria by GO sheets is evidenced by FESEM investigations and has also been corroborated by nano-scale imaging of bacteria using the STXM. Spectroscopy evidence of functional oxygen moieties with GO sheets and physiochemical entrapment of E. coli bacteria have assisted us to elaborate the mechanism of cellular oxidative stress-induced disruption of bacterial membrane.

Multiple-wavelength neutron holography with pulsed neutrons

PubMed Central

Hayashi, Kouichi; Ohoyama, Kenji; Happo, Naohisa; Matsushita, Tomohiro; Hosokawa, Shinya; Harada, Masahide; Inamura, Yasuhiro; Nitani, Hiroaki; Shishido, Toetsu; Yubuta, Kunio

2017-01-01

Local structures around impurities in solids provide important information for understanding the mechanisms of material functions, because most of them are controlled by dopants. For this purpose, the x-ray absorption fine structure method, which provides radial distribution functions around specific elements, is most widely used. However, a similar method using neutron techniques has not yet been developed. If one can establish a method of local structural analysis with neutrons, then a new frontier of materials science can be explored owing to the specific nature of neutron scattering—that is, its high sensitivity to light elements and magnetic moments. Multiple-wavelength neutron holography using the time-of-flight technique with pulsed neutrons has great potential to realize this. We demonstrated multiple-wavelength neutron holography using a Eu-doped CaF2 single crystal and obtained a clear three-dimensional atomic image around trivalent Eu substituted for divalent Ca, revealing an interesting feature of the local structure that allows it to maintain charge neutrality. The new holography technique is expected to provide new information on local structures using the neutron technique. PMID:28835917

Alternative difference analysis scheme combining R -space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy

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

Zhan, Fei; Tao, Ye; Zhao, Haifeng

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions.R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure changemore » in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3spin crossover complex and yielded reliable distance change and excitation population.« less

Multiple-wavelength neutron holography with pulsed neutrons.

PubMed

Hayashi, Kouichi; Ohoyama, Kenji; Happo, Naohisa; Matsushita, Tomohiro; Hosokawa, Shinya; Harada, Masahide; Inamura, Yasuhiro; Nitani, Hiroaki; Shishido, Toetsu; Yubuta, Kunio

2017-08-01

Local structures around impurities in solids provide important information for understanding the mechanisms of material functions, because most of them are controlled by dopants. For this purpose, the x-ray absorption fine structure method, which provides radial distribution functions around specific elements, is most widely used. However, a similar method using neutron techniques has not yet been developed. If one can establish a method of local structural analysis with neutrons, then a new frontier of materials science can be explored owing to the specific nature of neutron scattering-that is, its high sensitivity to light elements and magnetic moments. Multiple-wavelength neutron holography using the time-of-flight technique with pulsed neutrons has great potential to realize this. We demonstrated multiple-wavelength neutron holography using a Eu-doped CaF 2 single crystal and obtained a clear three-dimensional atomic image around trivalent Eu substituted for divalent Ca, revealing an interesting feature of the local structure that allows it to maintain charge neutrality. The new holography technique is expected to provide new information on local structures using the neutron technique.

Alternative difference analysis scheme combining R-space EXAFS fit with global optimization XANES fit for X-ray transient absorption spectroscopy.

PubMed

Zhan, Fei; Tao, Ye; Zhao, Haifeng

2017-07-01

Time-resolved X-ray absorption spectroscopy (TR-XAS), based on the laser-pump/X-ray-probe method, is powerful in capturing the change of the geometrical and electronic structure of the absorbing atom upon excitation. TR-XAS data analysis is generally performed on the laser-on minus laser-off difference spectrum. Here, a new analysis scheme is presented for the TR-XAS difference fitting in both the extended X-ray absorption fine-structure (EXAFS) and the X-ray absorption near-edge structure (XANES) regions. R-space EXAFS difference fitting could quickly provide the main quantitative structure change of the first shell. The XANES fitting part introduces a global non-derivative optimization algorithm and optimizes the local structure change in a flexible way where both the core XAS calculation package and the search method in the fitting shell are changeable. The scheme was applied to the TR-XAS difference analysis of Fe(phen) 3 spin crossover complex and yielded reliable distance change and excitation population.

Iron phosphate glasses: Bulk properties and atomic scale structure

NASA Astrophysics Data System (ADS)

Joseph, Kitheri; Stennett, Martin C.; Hyatt, Neil C.; Asuvathraman, R.; Dube, Charu L.; Gandy, Amy S.; Govindan Kutty, K. V.; Jolley, Kenny; Vasudeva Rao, P. R.; Smith, Roger

2017-10-01

Bulk properties such as glass transition temperature, density and thermal expansion of iron phosphate glass compositions, with replacement of Cs by Ba, are investigated as a surrogate for the transmutation of 137Cs to 137Ba, relevant to the immobilisation of Cs in glass. These studies are required to establish the appropriate incorporation rate of 137Cs in iron phosphate glass. Density and glass transition temperature increases with the addition of BaO indicating the shrinkage and reticulation of the iron phosphate glass network. The average thermal expansion coefficient reduces from 19.8 × 10-6 K-1 to 13.4 × 10-6 K-1, when 25 wt. % of Cs2O was replaced by 25 wt. % of BaO in caesium loaded iron phosphate glass. In addition to the above bulk properties, the role of Ba as a network modifier in the structure of iron phosphate glass is examined using various spectroscopic techniques. The FeII content and average coordination number of iron in the glass network was estimated using Mössbauer spectroscopy. The FeII content in the un-doped iron phosphate glass and barium doped iron phosphate glasses was 20, 21 and 22 ± 1% respectively and the average Fe coordination varied from 5.3 ± 0.2 to 5.7 ± 0.2 with increasing Ba content. The atomic scale structure was further probed by Fe K-edge X-ray absorption spectroscopy. The average coordination number provided by extended X-ray absorption fine structure spectroscopy and X-ray absorption near edge structure was in good agreement with that given by the Mössbauer data.

Structural Analyses of Phase Stability in Amorphous and Partially Crystallized Ge-Rich GeTe Films Prepared by Atomic Layer Deposition.

PubMed

Gwon, Taehong; Mohamed, Ahmed Yousef; Yoo, Chanyoung; Park, Eui-Sang; Kim, Sanggyun; Yoo, Sijung; Lee, Han-Koo; Cho, Deok-Yong; Hwang, Cheol Seong

2017-11-29

The local bonding structures of Ge x Te 1-x (x = 0.5, 0.6, and 0.7) films prepared through atomic layer deposition (ALD) with Ge(N(Si(CH 3 ) 3 ) 2 ) 2 and ((CH 3 ) 3 Si) 2 Te precursors were investigated using Ge K-edge X-ray absorption spectroscopy (XAS). The results of the X-ray absorption fine structure analyses show that for all of the compositions, the as-grown films were amorphous with a tetrahedral Ge coordination of a mixture of Ge-Te and Ge-Ge bonds but without any signature of Ge-GeTe decomposition. The compositional evolution in the valence band electronic structures probed through X-ray photoelectron spectroscopy suggests a substantial chemical influence of additional Ge on the nonstoichiometric GeTe. This implies that the ALD process can stabilize Ge-abundant bonding networks like -Te-Ge-Ge-Te- in amorphous GeTe. Meanwhile, the XAS results on the Ge-rich films that had undergone post-deposition annealing at 350 °C show that the parts of the crystalline Ge-rich GeTe became separated into Ge crystallites and rhombohedral GeTe in accordance with the bulk phase diagram, whereas the disordered GeTe domains still remained, consistent with the observations of transmission electron microscopy and Raman spectroscopy. Therefore, amorphousness in GeTe may be essential for the nonsegregated Ge-rich phases and the low growth temperature of the ALD enables the achievement of the structurally metastable phases.

The Antimicrobial Properties of Silver Nanoparticles in Bacillus subtilis Are Mediated by Released Ag+ Ions

PubMed Central

Hsueh, Yi-Huang; Lin, Kuen-Song; Ke, Wan-Ju; Hsieh, Chien-Te; Chiang, Chao-Lung; Tzou, Dong-Ying; Liu, Shih-Tung

2015-01-01

The superior antimicrobial properties of silver nanoparticles (Ag NPs) are well-documented, but the exact mechanisms underlying Ag-NP microbial toxicity remain the subject of intense debate. Here, we show that Ag-NP concentrations as low as 10 ppm exert significant toxicity against Bacillus subtilis, a beneficial bacterium ubiquitous in the soil. Growth arrest and chromosomal DNA degradation were observed, and flow cytometric quantification of propidium iodide (PI) staining also revealed that Ag-NP concentrations of 25 ppm and above increased membrane permeability. RedoxSensor content analysis and Phag-GFP expression analysis further indicated that reductase activity and cytosolic protein expression decreased in B. subtilis cells treated with 10–50 ppm of Ag NPs. We conducted X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) analyses to directly clarify the valence and fine structure of Ag atoms in B. subtilis cells placed in contact with Ag NPs. The results confirmed the Ag species in Ag NP-treated B. subtilis cells as Ag2O, indicating that Ag-NP toxicity is likely mediated by released Ag+ ions from Ag NPs, which penetrate bacterial cells and are subsequently oxidized intracellularly to Ag2O. These findings provide conclusive evidence for the role of Ag+ ions in Ag-NP microbial toxicity, and suggest that the impact of inappropriately disposed Ag NPs to soil and water ecosystems may warrant further investigation. PMID:26669836

The Mechanism of Atomization Accompanying Solid Injection

NASA Technical Reports Server (NTRS)

Castleman, R A , Jr

1933-01-01

A brief historical and descriptive account of solid injection is followed by a detailed review of the available theoretical and experimental data that seem to throw light on the mechanism of this form of atomization. It is concluded that this evidence indicates that (1) the atomization accompanying solid injection occurs at the surface of the liquid after it issues as a solid stream from the orifice; and (2) that such atomization has a mechanism physically identical with the atomization which takes place in an air stream, both being due merely to the formation, at the gas-liquid interface, of fine ligaments under the influence of the relative motion of gas and liquid, and to their collapse, under the influence of surface tension, to form the drops in the spray.

Polarization-dependent atomic dipole traps behind a circular aperture for neutral-atom quantum computing

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

Gillen-Christandl, Katharina; Copsey, Bert D.

2011-02-15

The neutral-atom quantum computing community has successfully implemented almost all necessary steps for constructing a neutral-atom quantum computer. We present computational results of a study aimed at solving the remaining problem of creating a quantum memory with individually addressable sites for quantum computing. The basis of this quantum memory is the diffraction pattern formed by laser light incident on a circular aperture. Very close to the aperture, the diffraction pattern has localized bright and dark spots that can serve as red-detuned or blue-detuned atomic dipole traps. These traps are suitable for quantum computing even for moderate laser powers. In particular,more » for moderate laser intensities ({approx}100 W/cm{sup 2}) and comparatively small detunings ({approx}1000-10 000 linewidths), trap depths of {approx}1 mK and trap frequencies of several to tens of kilohertz are achieved. Our results indicate that these dipole traps can be moved by tilting the incident laser beams without significantly changing the trap properties. We also explored the polarization dependence of these dipole traps. We developed a code that calculates the trapping potential energy for any magnetic substate of any hyperfine ground state of any alkali-metal atom for any laser detuning much smaller than the fine-structure splitting for any given electric field distribution. We describe details of our calculations and include a summary of different notations and conventions for the reduced matrix element and how to convert it to SI units. We applied this code to these traps and found a method for bringing two traps together and apart controllably without expelling the atoms from the trap and without significant tunneling probability between the traps. This approach can be scaled up to a two-dimensional array of many pinholes, forming a quantum memory with single-site addressability, in which pairs of atoms can be brought together and apart for two-qubit gates for quantum computing.« less

Probing of the pseudogap via thermoelectric properties in the Au-Al-Gd quasicrystal approximant

NASA Astrophysics Data System (ADS)

Ishikawa, Asuka; Takagiwa, Yoshiki; Kimura, Kaoru; Tamura, Ryuji

2017-03-01

The pseudogap of the recently discovered Au-Al-Gd quasicrystal approximant crystal (AC) is investigated over a wide electron-per-atom (e /a ) ratio of ˜0.5 using thermoelectric properties as an experimental probe. This Au-Al-Gd AC provides an ideal platform for fine probing of the pseudogap among a number of known ACs because the Au-Al-Gd AC possesses an extraordinarily wide single-phase region with respect to the variation in the electron concentration [A. Ishikawa, T. Hiroto, K. Tokiwa, T. Fujii, and R. Tamura, Phys. Rev. B 93, 024416 (2016), 10.1103/PhysRevB.93.024416], in striking contrast to, for instance, binary stoichiometric C d6R ACs. As a result, a salient peak structure is observed in the Seebeck coefficient, S , with the composition as well as that of the power factor S2σ , in addition to a gradual variation in the conductivity, σ , and S . These two features are directly associated with rapid and slow variations, respectively, of spectral conductivity σ (E ) , and hence the fine structure inside the pseudogap, in the vicinity of the Fermi level EF. Based on the observed continuous variation of the Fermi wave vector reported in the previous experimental work, fine tuning of EF toward an optimal position was attempted, which led to the successful observation of a sharp peak in S2σ with a value of ˜270 μ W /m .K2 at 873 K. This is the highest value ever reported among both Tsai-type and Bergman-type compounds. The dimensionless figure of merit was determined as 0.026 at 873 K, which is also the highest reported among both Tsai-type and Bergman-type compounds.

Experimental and theoretical studies of dipole and quadrupole contributions to the vanadium K-edge XANES for VOPO4.2H2O xerogel

NASA Astrophysics Data System (ADS)

Poumellec, B.; Kraizman, V.; Aifa, Y.; Cortès, R.; Novakovich, A.; Vedrinskii, R.

1998-09-01

Angular dependence of the vanadium K-edge x-ray appearance near-edge structure (XANES) for the VOPO4.2H2O xerogel is thoroughly studied both experimentally and theoretically. The main attention is paid to the pre-edge fine structure (PEFS) of the spectra which was shown earlier to be a useful tool for the atomic short order investigations. Good quantitative agreement between theory and experiment obtained for both dipole and quadrupole contributions to the spectra proves validity of the calculation method developed and enables us to ascertain the nature of all the features in the PEFS's. The p-d mixture effect due to distortion of the central coordination octahedron and the quadrupole transitions are proved to be the only mechanisms responsible for the PEFS formation in the case considered. We show that in order to achieve quantitative agreement between experimental and theoretical spectra, it is necessary to include the effect of atomic vibrations, which makes the forbidden transitions to molecular orbitals of the central octahedron (MOCO's) dipole allowed, and to take into account deviation of the crystal layers from the substrate plane, which is not a single crystal but a texture.

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.

Tuning the Curie temperature of L 1 0 ordered FePt thin films through site-specific substitution of Rh

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

Xu, Dongbin; Sun, Cheng-Jun; Chen, Jing-Sheng

2014-10-14

In structurally ordered magnetic thin films, the Curie temperature (TC) of ferromagnetic films depends on the exchange integral of the short range ordered neighboring atoms. The exchange integral may be adjusted by controlling elemental substitutional concentration at the lattice site of interest. We show how to control the TC in high anisotropy L10 Fe50Pt50 magnetic thin films by substituting Rh into the Pt site. Rh substitution in L10 FePt modified the local atomic environment and corresponding electronic properties while retaining the ordered L10 phase. The analysis of extended x-ray Absorption Fine Structure (EXAFS) spectra shows that Rh uniformly substitutes formore » Pt in L10 FePt. With 15 at. % of Rh substitution, temperature-dependent magnetic measurements show that the saturation magnetization (Ms) decreases from 1152 emu/cc to 670 emu/cc, the magnetocrystalline anisotropy (Ku) drops from 5×107 erg/cc to 2×107 erg/cc, and TC decreased from 750 to 500 K. A model of antiferromagnetic (AFM) defects caused by controlled Rh substitution of the Pt site, reducing the TC, is proposed to interpret this phenomenon and the validity is further examined by ab initio density functional calculations.« less

Effect Of Chromium Underlayer On The Properties Of Nano-Crystalline Diamond Films

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

Garratt, Elias; AlFaify, Salem; Yoshitake, T.

2013-01-11

This paper investigated the effect of chromium underlayer on the structure, microstructure and composition of the nano-crystalline diamond films. Nano-crystalline diamond thin films were deposited at high temperature in microwave-induced plasma diluted with nitrogen, on silicon substrate with a thin film of chromium as an underlayer. The composition, structure and microstructure of the deposited layers were analyzed using non-Rutherford Backscattering Spectrometry, Raman Spectroscopy, Near-Edge X-Ray Absorption Fine Structure, X-ray Diffraction and Atomic Force Microscopy. Nanoindentation studies showed that the films deposited on chromium underlayer have higher hardness values compared to those deposited on silicon without an underlayer. Diamond and graphiticmore » phases of the films evaluated by x-ray and optical spectroscopic analysis determined consistency between sp2 and sp3 phases of carbon in chromium sample to that of diamond grown on silicon. Diffusion of chromium was observed using ion beam analysis which was correlated with the formation of chromium complexes by x-ray diffraction.« less

Atomistic nucleation sites of Pt nanoparticles on N-doped carbon nanotubes.

PubMed

Sun, Chia-Liang; Pao, Chih-Wen; Tsai, Huang-Ming; Chiou, Jau-Wern; Ray, Sekhar C; Wang, Houng-Wei; Hayashi, Michitoshi; Chen, Li-Chyong; Lin, Hong-Ji; Lee, Jyh-Fu; Chang, Li; Tsai, Min-Hsiung; Chen, Kuei-Hsien; Pong, Way-Faung

2013-08-07

The atomistic nucleation sites of Pt nanoparticles (Pt NPs) on N-doped carbon nanotubes (N-CNTs) were investigated using C and N K-edge and Pt L3-edge X-ray absorption near-edge structure (XANES)/extended X-ray absorption fine structure (EXAFS) spectroscopy. Transmission electron microscopy and XANES/EXAFS results revealed that the self-organized Pt NPs on N-CNTs are uniformly distributed because of the relatively high binding energies of the adsorbed Pt atoms at the imperfect sites. During the atomistic nucleation process of Pt NPs on N-CNTs, stable Pt-C and Pt-N bonds are presumably formed, and charge transfer occurs at the surface/interface of the N-CNTs. The findings in this study were consistent with density functional theory calculations performed using cluster models for the undoped, substitutional-N-doped and pyridine-like-N-doped CNTs.

Pt3Co concave nanocubes: synthesis, formation understanding, and enhanced catalytic activity toward hydrogenation of styrene.

PubMed

Wang, Chenyu; Lin, Cuikun; Zhang, Lihua; Quan, Zewei; Sun, Kai; Zhao, Bo; Wang, Feng; Porter, Nathan; Wang, Yuxuan; Fang, Jiye

2014-02-03

We report a facile synthesis route to prepare high-quality Pt3Co nanocubes with a concave structure, and further demonstrate that these concave Pt3Co nanocubes are terminated with high-index crystal facets. The success of this preparation is highly dependent on an appropriate nucleation process with a successively anisotropic overgrowth and a preservation of the resultant high-index planes by control binding of oleyl-amine/oleic acid with a fine-tuned composition. Using a hydrogenation of styrene as a model reaction, these Pt3Co concave nanocubes as a new class of nanocatalysts with more open structure and active atomic sites located on their high-index crystallographic planes exhibit an enhanced catalytic activity in comparison with low-indexed surface terminated Pt3Co nanocubes in similar size. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new incorporation mechanism for trivalent actinides into bioapatite: a TRLFS and EXAFS study.

PubMed

Holliday, Kiel; Handley-Sidhu, Stephanie; Dardenne, Kathy; Renshaw, Joanna; Macaskie, Lynne; Walther, Clemens; Stumpf, Thorsten

2012-02-28

One of the most toxic byproducts of nuclear power and weapons production is the transuranics, which have a high radiotoxicity and long biological half-life due to their tendency to accumulate in the skeletal system. This accumulation is inhomogeneous and has been associated with the chemical properties and structure of the bone material rather than its location or function. This suggests a chemical driving force to incorporation and requires an atomic scale mechanistic understanding of the incorporation process. Here we propose a new incorporation mechanism for trivalent actinides and lanthanides into synthetic and biologically produced hydroxyapatite. Time-resolved laser fluorescence spectroscopy and extended X-ray absorption fine structure have been used to demonstrate that trivalent actinides and lanthanides incorporate into the amorphous grain boundaries of apatite. This incorporation site can be used to explain patterns in uptake and distribution of radionuclides in the mammalian skeletal system. © 2012 American Chemical Society

Energy levels and radiative transition rates for Ge XXXI, As XXXII, and Se XXXIII

NASA Astrophysics Data System (ADS)

Aggarwal, Sunny; Singh, J.; Jha, A. K. S.; Mohan, Man

2014-07-01

Fine-structure energies of the 67 levels belonging to the 1s2, 1s 2l, 1s3l, 1s4l, 1s5l, and 1s6l configurations of Ge XXXI, As XXXII, and Se XXXIII have been calculated using the General-Purpose Relativistic Atomic Structure Package. In addition, radiative rates, oscillator strengths, transition wavelengths, and line strengths have been calculated for all electric dipole, magnetic dipole, electric quadrupole, and magnetic quadrupole transitions among these levels. Lifetimes are also presented for all excited levels of these three ions. We have compared our results with the results available in the literature and the accuracy of the data is assessed. We predict new energy levels, oscillator strengths, and transition probabilities where no other theoretical or experimental results are available, which will form the basis for future experimental work.

Comparative NEXAFS study of the selected icefish hard tissues and hydroxyapatite

NASA Astrophysics Data System (ADS)

Petrova, O. V.; Nekipelov, S. V.; Sivkov, D. V.; Mingaleva, A. E.; Nikolaev, A.; Frank-Kamenetskaya, O. V.; Bazhenov, V. V.; Vyalikh, D. V.; Molodtsov, S. L.; Sivkov, V. N.; Ehrlich, H.

2017-11-01

The structure of native Champsocephalus gunnari icefish otoliths, scales, teeth, bones and pristine hydroxyapatite (HA) were examined using Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. NEXAFS Cls-absorption spectra of the selected icefish hard tissues indicate that otoliths contain anion [CO3]2-. NEXAFS P2p-spectra clearly indicate the absence of phosphorus atoms only within otoliths and scales samples. However, the icefish teeth and bones P2p-spectra demonstrate identical spectral feature typical for the HA. NEXAFS Ca2p-spectra of the icefish hard tissues studied also shows features, which are in good correspondence with HA spectra. Interestingly, there is a red shift ≈ 0.1 eV of the 2p1/2,3/2 → 3d transition energies in NEXAFS Ca2p-spectra of teethes and bones of the C. gunnari in comparison to HA.

Local structure and charge distribution in the UO(2)-U(4)O(9) system.

PubMed

Conradson, Steven D; Manara, Dario; Wastin, Franck; Clark, David L; Lander, Gerard H; Morales, Luis A; Rebizant, Jean; Rondinella, Vincenzo V

2004-11-01

Analysis of X-ray absorption fine structure spectra of UO(2+x) for x = 0-0.20 (UO(2)--U(4)O(9)) reveals that the adventitious O atoms are incorporated as oxo groups with U--O distances of 1.74 A, most likely associated with U(VI), that occur in clusters so that the UO(2) fraction of the material largely remains intact. In addition to the formation of some additional longer U--O bonds, the U sublattice consists of an ordered portion that displays the original U--U distance and a spectroscopically silent, glassy part. This is very different from previous models derived from neutron diffraction that maintained long U--O distances and high U--O coordination numbers. UO(2+x) also differs from PuO(2+x) in its substantially shorter An-oxo distances and no sign of stable coordination with H(2)O and its hydrolysis products.

Uric acid-derived Fe3C-containing mesoporous Fe/N/C composite with high activity for oxygen reduction reaction in alkaline medium

NASA Astrophysics Data System (ADS)

Ma, Jun; Xiao, Dejian; Chen, Chang Li; Luo, Qiaomei; Yu, Yue; Zhou, Junhao; Guo, Changding; Li, Kai; Ma, Jie; Zheng, Lirong; Zuo, Xia

2018-02-01

In this work, a category of Fe3C-containing Fe/N/C mesoporous material has been fabricated by carbonizing the mixture of uric acid, Iron (Ⅲ) chloride anhydrous and carbon support (XC-72) under different pyrolysis temperature. Of all these samples, pyrolysis temperature (800 °C) becomes the most crucial factor in forming Fe3C active sites which synergizes with high content of graphitic N to catalyze oxygen reduction reaction (ORR). X-ray absorption fine structure spectroscopy (XAFS) is used to exhibit that the space structure around Fe atoms in the catalyst. This kind of catalyst possesses comparable ORR properties with commercial 20% Pt/C (onset potential is 0 V vs. Ag/AgCl in 0.1 M KOH), the average transfer electron number is 3.84 reflecting the 4-electron process. Moreover, superior stability and methanol tolerance deserve to be mentioned.

Atomic Data for the K-vacancy States of Fe XXIV

NASA Technical Reports Server (NTRS)

Bautista, M. A.; Mendoza, C.; Kallman, T. R.; Palmeri, P.

2003-01-01

As part of a project to compute improved atomic data for the spectral modeling of iron K lines, we report extensive calculations and comparisons of atomic data for K-vacancy states in Fe XXIV. The data sets include: (i) energy levels, line wavelengths, radiative and Auger rates; (ii) inner-shell electron impact excitation rates and (iii) fine structure inner-shell photoionization cross sections. The calculations of energy levels and radiative and Auger rates have involved a detailed study of orbital representations, core relaxation, configuration interaction, relativistic corrections, cancellation effects and semi-empirical corrections. It is shown that a formal treatment of the Breit interaction is essential to render the important magnetic correlations that take part in the decay pathways of this ion. As a result, the accuracy of the present A-values is firmly ranked at better than 10% while that of the Auger rates at only 15%. The calculations of collisional excitation and photoionization cross sections take into account the effects of radiation and spectator Auger dampings. In the former, these effects cause significant attenuation of resonances leading to a good agreement with a simpler method where resonances are excluded. In the latter, resonances converging to the K threshold display symmetric profiles of constant width that causes edge smearing.

Atomic Data for the K-Vacancy States of Fe XXIV

NASA Technical Reports Server (NTRS)

Bautista, M. A.; Mendoza, C.; Kallman, T. R.; Palmeri, P.

2002-01-01

As part of a project to compute improved atomic data for the spectral modeling of iron K lines, we report extensive calculations and comparisons of atomic data for K-vacancy states in Fe XXIV. The data sets include: (i) energy levels, line wavelengths, radiative and Auger rates; (ii) inner-shell electron impact excitation rates and (iii) fine structure inner-shell photoionization cross sections. The calculations of energy levels and radiative and Auger rates have involved a detailed study of orbital representations, core relaxation, configuration interaction, relativistic corrections, cancellation effects and semi-empirical corrections. It is shown that a formal treatment of the Breit interaction is essential to render the important magnetic correlations that take part in the decay pathways of this ion. As a result, the accuracy of the present A-values is firmly ranked at better than 10% while that of the Auger rates at only 15%. The calculations of collisional excitation and photoionization cross sections take into account the effects of radiation and spectator Auger dampings. In the former, these effects cause significant attenuation of resonances leading to a good agreement with a simpler method where resonances are excluded. In the latter, resonances converging to the K threshold display symmetric profiles of constant width that causes edge smearing.

Spin-orbit coupled potential energy surfaces and properties using effective relativistic coupling by asymptotic representation.

PubMed

Ndome, Hameth; Eisfeld, Wolfgang

2012-08-14

A new method has been reported recently [H. Ndome, R. Welsch, and W. Eisfeld, J. Chem. Phys. 136, 034103 (2012)] that allows the efficient generation of fully coupled potential energy surfaces (PESs) including derivative and spin-orbit (SO) coupling. The method is based on the diabatic asymptotic representation of the molecular fine structure states and an effective relativistic coupling operator and therefore is called effective relativistic coupling by asymptotic representation (ERCAR). The resulting diabatic spin-orbit coupling matrix is constant and the geometry dependence of the coupling between the eigenstates is accounted for by the diabatization. This approach allows to generate an analytical model for the fully coupled PESs without performing any ab initio SO calculations (except perhaps for the atoms) and thus is very efficient. In the present work, we study the performance of this new method for the example of hydrogen iodide as a well-established test case. Details of the diabatization and the accuracy of the results are investigated in comparison to reference ab initio calculations. The energies of the adiabatic fine structure states are reproduced in excellent agreement with reference ab initio data. It is shown that the accuracy of the ERCAR approach mainly depends on the quality of the underlying ab initio data. This is also the case for dissociation and vibrational level energies, which are influenced by the SO coupling. A method is presented how one-electron operators and the corresponding properties can be evaluated in the framework of the ERCAR approach. This allows the computation of dipole and transition moments of the fine structure states in good agreement with ab initio data. The new method is shown to be very promising for the construction of fully coupled PESs for more complex polyatomic systems to be used in quantum dynamics studies.