Analysis of the Atomic-Scale Defect Chemistry at Interfaces in Fluorite Structured Oxides by Electron Energy Loss Spectroscopy

DTIC Science & Technology

2001-11-01

electronic properties, i.e. oxygen coordination and cation valence at grain boundaries of the fluorite structured Gdo]2Ceo.gO 2_x ceramic membrane material...required to obtain a detailed understanding of the atomic scale phenomena in ceramics, as the polycrystalline nature of Gdo.2Ceo.802- ceramic membrane material

Activation volumes of oxygen self-diffusion in fluorite structured oxides

DOE PAGES

Christopoulos, S-R G.; Kordatos, A.; Cooper, Michael William D.; ...

2016-10-27

In this study, fluorite structured oxides are used in numerous applications and as such it is necessary to determine their materials properties over a range of conditions. In the present study we employ molecular dynamics calculations to calculate the elastic and expansivity data, which are then used in a thermodynamic model (the cBΩ model) to calculate the activation volumes of oxygen self-diffusion coefficient in ThO 2, UO 2 and PuO 2 fluorite structured oxides over a wide temperature range. We present relations to calculate the activation volumes of oxygen self-diffusion coefficient in ThO 2, UO 2 and PuO 2 formore » a wide range of temperature (300–1700 K) and pressure (–7.5 to 7.5 GPa).« less

A new anion-deficient fluorite-related superstructure of Bi{sub 28}V{sub 8}O{sub 62}

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

Đorđević, T., E-mail: tamara.djordjevic@univie.ac.at; Karanović, Lj., E-mail: ljika2002@yahoo.com

2014-12-15

New hydrothermally synthesized Bi{sub 28}V{sub 8}O{sub 62} was structurally characterized using single-crystal X-ray diffraction data. Bi{sub 28}V{sub 8}O{sub 62} crystallizes in the novel type of defect fluorite structure related to the face-centered cubic δ-Bi{sub 2}O{sub 3}. It is monoclinic, s. g. P2{sub 1}/c, and the relation to the fluorite subcell is given as a∼(3/2)a{sub F}+(3/2)c{sub F}; b∼ −b{sub F}; c∼2a{sub F} −4c{sub F} (F in subscript indicate the unit cell parameter of fluorite). Its structure is characterized by slabs of edge sharing OBi{sub 4} tetrahedra surrounded by the OBi{sub 3} triangles. As a part of these OBi{sub 3} triangles, twomore » positionally disordered Bi{sup 3+} cations were observed in the marginal part of the slabs. The slabs are extending along b axis and are linked by inter-slab portion of the structure composed of VO{sub 4} tetrahedra and BiO{sub 6−x} coordination polyhedra, where x is a number of vacant oxygen sites. Raman spectra verified the coordination environment of vanadium atoms in the structure. - Graphical abstract: The [4{sup ¯}01] projection of two slabs and inter-slab part of the structure in one layer parallel to the (3{sup ¯}08)=(002{sup ¯}){sub F} plane (F in subscript indicate a fluorite type structure). The large green circles are Bi atoms. Small blue circles represent partly and fully occupied O sites, respectively. Pink (hatched black) are V1O{sub 4} and blue (hatched white) are V2O{sub 4} coordination tetrahedra. - Highlights: • Single crystals of Bi{sub 28}V{sub 8}O{sub 62} were grown using hydrothermal technique. • The crystal structure of Bi{sub 28}V{sub 8}O{sub 62} was solved using single-crystal XRD method. • Bi{sub 28}V{sub 8}O{sub 62} has an anion-deficient fluorite-related superstructure. • Raman spectrum confirmed the coordination environment of vanadium atoms. • Relation to the structurally related compound was discussed.« less

Structure reconstruction of TiO2-based multi-wall nanotubes: first-principles calculations.

PubMed

Bandura, A V; Evarestov, R A; Lukyanov, S I

2014-07-28

A new method of theoretical modelling of polyhedral single-walled nanotubes based on the consolidation of walls in the rolled-up multi-walled nanotubes is proposed. Molecular mechanics and ab initio quantum mechanics methods are applied to investigate the merging of walls in nanotubes constructed from the different phases of titania. The combination of two methods allows us to simulate the structures which are difficult to find only by ab initio calculations. For nanotube folding we have used (1) the 3-plane fluorite TiO2 layer; (2) the anatase (101) 6-plane layer; (3) the rutile (110) 6-plane layer; and (4) the 6-plane layer with lepidocrocite morphology. The symmetry of the resulting single-walled nanotubes is significantly lower than the symmetry of initial coaxial cylindrical double- or triple-walled nanotubes. These merged nanotubes acquire higher stability in comparison with the initial multi-walled nanotubes. The wall thickness of the merged nanotubes exceeds 1 nm and approaches the corresponding parameter of the experimental patterns. The present investigation demonstrates that the merged nanotubes can integrate the two different crystalline phases in one and the same wall structure.

Density functional theory calculations of UO2 oxidation: evolution of UO(2+x), U4O(9-y), U3O7, and U3O8.

PubMed

Andersson, D A; Baldinozzi, G; Desgranges, L; Conradson, D R; Conradson, S D

2013-03-04

Formation of hyperstoichiometric uranium dioxide, UO2+x, derived from the fluorite structure was investigated by means of density functional theory (DFT) calculations. Oxidation was modeled by adding oxygen atoms to UO2 fluorite supercells. For each compound ab initio molecular dynamics simulations were performed to allow the ions to optimize their local geometry. A similar approach was used for studying the reduction of U3O8. In agreement with the experimental phase diagram we identify stable line compounds at the U4O9-y and U3O7 stoichiometries. Although the transition from fluorite to the layered U3O8 structure occurs at U3O7 (UO2.333) or U3O7.333 (UO2.444), our calculated low temperature phase diagram indicates that the fluorite derived compounds are favored up to UO2.5, that is, as long as the charge-compensation for adding oxygen atoms occurs via formation of U(5+) ions, after which the U3O8-y phase becomes more stable. The most stable fluorite UO2+x phases at low temperature (0 K) are based on ordering of split quad-interstitial oxygen clusters. Most existing crystallographic models of U4O9 and U3O7, however, apply the cuboctahedral cluster. To better understand these discrepancies, the new structural models are analyzed in terms of existing neutron diffraction data. DFT calculations were also performed on the experimental cuboctahedral based U4O9-y structure, which enable comparisons between the properties of this phase with the quad-interstitial ones in detail.

Structural, electronic, and thermodynamic properties of curium dioxide: Density functional theory calculations

NASA Astrophysics Data System (ADS)

Hou, Ling; Li, Wei-Dong; Wang, Fangwei; Eriksson, Olle; Wang, Bao-Tian

2017-12-01

We present a systematic investigation of the structural, magnetic, electronic, mechanical, and thermodynamic properties of CmO2 with the local density approximation (LDA)+U and the generalized gradient approximation (GGA)+U approaches. The strong Coulomb repulsion and the spin-orbit coupling (SOC) effects on the lattice structures, electronic density of states, and band gaps are carefully studied, and compared with other A O2 (A =U , Np, Pu, and Am). The ferromagnetic configuration with half-metallic character is predicted to be energetically stable while a charge-transfer semiconductor is predicted for the antiferromagnetic configuration. The elastic constants and phonon spectra show that the fluorite structure is mechanically and dynamically stable. Based on the first-principles phonon density of states, the lattice vibrational energy is calculated using the quasiharmonic approximation. Then, the Gibbs free energy, thermal expansion coefficient, specific heat, and entropy are obtained and compared with experimental data. The mode Grüneisen parameters are presented to analyze the anharmonic properties. The Slack relation is applied to obtain the lattice thermal conductivity in temperature range of 300-1600 K. The phonon group velocities are also calculated to investigate the heat transfer. For all these properties, if available, we compare the results of CmO2 with other A O2 .

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La).

PubMed

Solomon, Jonathan M; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-12-12

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2 Zr 2 O 7 . In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2 Th 2 O 7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

NASA Astrophysics Data System (ADS)

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-12-01

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.

Transmission electron microscopic study of pyrochlore to defect-fluorite transition in rare-earth pyrohafnates

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

Karthik, Chinnathambi, E-mail: Karthikchinnathambi@boisestate.edu; Center for Advanced Energy Studies, 995 University Blvd, Idaho Falls, ID 83415; Anderson, Thomas J.

2012-10-15

A structural transition in rare earth pyrohafnates, Ln{sub 2}Hf{sub 2}O{sub 7} (Ln=Y, La, Pr, Nd, Tb, Dy, Yb and Lu), has been identified. Neutron diffraction showed that the structure transforms from well-ordered pyrochloric to fully fluoritic through the lanthanide series from La to Lu with a corresponding increase in the position parameter x of the 48f (Fd3{sup Macron }m) oxygen site from 0.330 to 0.375. As evidenced by the selected area electron diffraction, La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} exhibited a well-ordered pyrocholoric structure with the presence of intense superlattice spots, which becamemore » weak and diffuse (in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}) before disappearing completely as the series progressed towards the Lu end. High resolution electron microscopic studies showed the breakdown of the pyrochlore ordering in the form of antiphase domains resulting in diffused smoke-like superlattice spots in the case of Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. - Graphical abstract: Transmission electron microscopic studies showed the ordered pyrochlore to defect fluorite transition in rare-earth pyrohafnates to occur via the formation of anti-phase domains to start with. Highlights: Black-Right-Pointing-Pointer Pyrochlore to fluorite structural transition in rare earth pyrohafnates. Black-Right-Pointing-Pointer La{sub 2}Hf{sub 2}O{sub 7}, Pr{sub 2}Hf{sub 2}O{sub 7} and Nd{sub 2}Hf{sub 2}O{sub 7} showed well ordered pyrochlore structure. Black-Right-Pointing-Pointer Short range ordering in Dy{sub 2}Hf{sub 2}O{sub 7} and Tb{sub 2}Hf{sub 2}O{sub 7}. Black-Right-Pointing-Pointer Break down of pyrochlore ordering due to antiphase boundaries. Black-Right-Pointing-Pointer Rest of the series showed fluoritic structure.« less

The crystal structures of BiTeO 3I, NdTeO 3X (X=Cl, Br) and Bi 5TeO 8.5I 2: some crystal chemistry peculiarities of layered Bi(Ln)Te oxyhalides

NASA Astrophysics Data System (ADS)

Berdonosov, Peter S.; Charkin, Dmitry O.; Kusainova, Ardak M.; Hervoches, Charles H.; Dolgikh, Valeriy A.; Lightfoot, Philip

2000-09-01

Four new layered oxyhalides related to the Sillen family have been prepared and characterized by Rietveld refinement of powder X-ray and neutron diffraction data. BiTeO 3I and NdTeO 3Br both adopt tetragonal symmetry, space group P4/ nmm (for BiTeO 3I, a=4.10811(8), c=27.988(1) Å; NdTeO 3Br, a=4.06603(7), c=26.922(1) Å, at 25°C). The structures are composed of triple and double fluorite-related mixed metal oxide layers separated by single and double halogen layers, in the sequence MTe 2O 5XXMTe 2O 5XM 2O 2X, which may be represented by the symbol X 13X 13X 22, where the subscript signifies the number of halogen layers and the superscript the number of metal sublayers within the fluorite block, by analogy with Sillen's notation. The double fluorite layers are occupied exclusively by Bi, whereas there is an ordered arrangement of Bi/Te within the triple fluorite layers, with Te exclusively occupying the outer sublayers of the block. NdTeO 3Cl adopts an orthorhombically distorted form of this structure type, space group Pmmn, a=4.08096(8), b=4.03441(8), c=25.7582(7) Å at 25°C. Bi 5TeO 8.5I 2 adopts a distorted, non-centrosymmetric version of the simpler X 13 structure type, space group Cmm2, a=5.6878(3), b=5.7230(3), c=9.7260(6) Å, consisting of single halogen layers sandwiched between triple fluorite layers, in which there is partial ordering of the Bi/Te cations.

Structure and cation ordering in La 2UO 6, Ce 2UO 6, LaUO 4, and CeUO 4 by first principles calculations

DOE PAGES

Casillas-Trujillo, Luis; Xu, H.; McMurray, Jake W.; ...

2016-07-06

In the present work, we have used density functional theory (DFT) and DFT+U to investigate the crystal structure and phase stability of four model compounds in the Ln 2O 3-UO 2-UO 3 ternary oxide system: La2UO 6, Ce 2UO 6, LaUO 4, CeUO 4, due to the highly-correlated nature of the f-electrons in uranium. We have considered both hypothetical ordered compounds and compounds in which the cations randomly occupy atomic sites in a fluorite-like lattice. We determined that ordered compounds are stable and are energetically favored compared to disordered configurations, though the ordering tendencies are weak. To model and analyzemore » the structures of these complex oxides, we have used supercells based on a layered atomic model. In the layer model, the supercell is composed of alternating planes of anions and cations. We have considered two different ordering motifs for the cations, namely single species (isoatomic) cation layers versus mixed species cation layers. Energy differences between various ordered cationic arrangements were found to be small. This may have implications regarding radiation stability, since cationic arrangements should be able to change under irradiation with little cost in energy.« less

Chemical thermodynamic representations of and

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

Besmann, T.M.; Lindemer, T.B.

1984-01-01

All available oxygen potential-temperature-composition data for the calcium fluorite-structure phase were retrieved from the literature and utilized in the development of a binary solid solution representation of the phase. The data and phase relations are found to be best described by a solution of (Pu/sub 4/3/O/sub 2/) and (PuO/sub 2/) with a temperature dependent interaction energy. The fluorite-structure is assumed to be represented by a combination of the binaries and , and thus treated as a solution of (Pu/sub 4/3/O/sub 2/), (PuO/sub 2/), (UO/sub 2/), and either (U/sub 2/O/sub 4/./sub 5/) or (U/sub 3/O/sub 7/). The resulting equations wellmore » reproduce the large amount of oxygen potential-temperature-composition data for the mixed oxide system, all of which were also retrieved from the literature. These models are the first that appear to display the appropriate oxygen potential-temperature-composition and phase relation behavior over the entire range of existence for the phases. 39 refs., 10 figs., 3 tabs.« less

Nature of the chemical bond and prediction of radiation tolerance in pyrochlore and defect fluorite compounds

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

Lumpkin, Gregory R.; Institute of Materials and Engineering Science, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234; Pruneda, Miguel

2007-04-15

The radiation tolerance of synthetic pyrochlore and defect fluorite compounds has been studied using ion irradiation. We show that the results can be quantified in terms of the critical temperature for amorphization, structural parameters, classical Pauling electronegativity difference, and disorder energies. Our results demonstrate that radiation tolerance is correlated with a change in the structure from pyrochlore to defect fluorite, a smaller unit cell dimension, and lower cation-anion disorder energy. Radiation tolerance is promoted by an increase in the Pauling cation-anion electronegativity difference or, in other words, an increase in the ionicity of the chemical bonds. A further analysis ofmore » the data indicates that, of the two possible cation sites in ideal pyrochlore, the smaller B-site cation appears to play the major role in bonding. This result is supported by ab initio calculations of the structure and bonding, showing a correlation between the Mulliken overlap populations of the B-site cation and the critical temperature. - Graphical abstract: Three-dimensional representation of the predicted critical amorphization temperature in pyrochlores.« less

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho 2Zr 2O 7 and RE 2Th 2O 7 (RE=Ho, Y, Gd, Nd, La)

DOE PAGES

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; ...

2016-12-12

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2Zr 2O 7. In a recentmore » neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2Th 2O 7'' fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. Finally, the results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.« less

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

DOE PAGES

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin; ...

2018-04-26

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Chemical ordering in substituted fluorite oxides: a computational investigation of Ho2Zr2O7 and RE2Th2O7 (RE=Ho, Y, Gd, Nd, La)

PubMed Central

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik; Navrotsky, Alexandra; Asta, Mark

2016-01-01

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho2Zr2O7. In a recent neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE2Th2O7 fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. The results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination. PMID:27941870

Sculpting Nanoscale Functional Channels in Complex Oxides Using Energetic Ions and Electrons

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

Sachan, Ritesh; Zarkadoula, Eva; Ou, Xin

The formation of metastable phases has attracted significant attention because of their unique properties and potential functionalities. In the present study, we demonstrate the phase conversion of energetic-ion-induced amorphous nanochannels/tracks into a metastable defect fluorite in A 2B 2O 7 structured complex oxides by electron irradiation. Through in situ electron irradiation experiments in a scanning transmission electron microscope, we observe electron-induced epitaxial crystallization of the amorphous nanochannels in Yb 2Ti 2O 7 into the defect fluorite. This energetic-electron-induced phase transformation is attributed to the coupled effect of ionization-induced electronic excitations and local heating, along with subthreshold elastic energy transfers. Wemore » also show the role of ionic radii of A-site cations (A = Yb, Gd, and Sm) and B-site cations (Ti and Zr) in facilitating the electron-beam-induced crystallization of the amorphous phase to the defect-fluorite structure. The formation of the defect-fluorite structure is eased by the decrease in the difference between ionic radii of A- and B-site cations in the lattice. Molecular dynamics simulations of thermal annealing of the amorphous phase nanochannels in A 2B 2O 7 draw parallels to the electron-irradiation-induced crystallization and confirm the role of ionic radii in lowering the barrier for crystallization. Furthermore, these results suggest that employing guided electron irradiation with atomic precision is a useful technique for selected area phase formation in nanoscale printed devices.« less

Selective adsorption of benzhydroxamic acid on fluorite rendering selective separation of fluorite/calcite

NASA Astrophysics Data System (ADS)

Jiang, Wei; Gao, Zhiyong; Khoso, Sultan Ahmed; Gao, Jiande; Sun, Wei; Pu, Wei; Hu, Yuehua

2018-03-01

Fluorite, a chief source of fluorine in the nature, usually coexists with calcite mineral in ore deposits. Worldwide, flotation techniques with a selective collector and/or a selective depressant are commonly preferred for the separation of fluorite from calcite. In the present study, an attempt was made to use benzhydroxamic acid (BHA) as a collector for the selective separation of fluorite from calcite without using any depressant. Results obtained from the flotation experiments for single mineral and mixed binary minerals revealed that the BHA has a good selective collecting ability for the fluorite when 50 mg/L of BHA was used at pH of 9. The results from the zeta potential and X-ray photoelectron spectroscopy (XPS) indicated that the BHA easily chemisorbs onto the fluorite as compared to calcite. Crystal chemistry calculations showed the larger Ca density and the higher Ca activity on fluorite surface mainly account for the selective adsorption of BHA on fluorite, leading to the selective separation of fluorite from calcite. Moreover, a stronger hydrogen bonding with BHA and the weaker electrostatic repulsion with BHA- also contribute to the stronger interaction of BHA species with fluorite surface.

Ab-initio calculation for cation vacancy formation energy in anti-fluorite structure

NASA Astrophysics Data System (ADS)

Saleel, V. P. Saleel Ahammad; Chitra, D.; Veluraja, K.; Eithiraj, R. D.

2018-04-01

Lithium oxide (Li2O) has been suggested as a suitable breeder blanket material for fusion reactors. Li+ vacancies are created by neutron irradiation, forming bulk defect complex whose extra character is experimentally unclear. We present a theoretical study of Li2O using density functional theory (DFT) with a plane-wave basis set. The generalized gradient approximation (GGA) and local-density approximation (LDA) were used for exchange and correlation. Here we address the total energy for defect free, cation defect, cation vacancy and vacancy formation energy in Li2O crystal in anti-fluorite structure.

Structural mechanism of the formation of mineral Na-tveitite-a new type of phase with a fluorite-derivative structure-in the NaF-CaF{sub 2}-(Y,Ln)F{sub 3} natural system

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

Golubev, A. M., E-mail: fluorides@ns.crys.ras.ru; Otroshchenko, L. P.; Sobolev, B. P.

2012-03-15

Relationships between the chemical compositions and structures of the mineral tveitite from the southern Norway pegmatites (with the idealized formula Ca{sub 14}Y{sub 5}F{sub 43}) and Na-tveitite from the Rov mountain (Keivy, Kola Peninsula) Na{sub 2.5}Ca{sub 10}Ln{sub 1.5}Y{sub 5}F{sub 42} are considered. According to the structural mechanism of its formation, Na-tveitite is a nanocomposite crystal based on the crystalline matrix Ca{sub 14}Y{sub 5}F{sub 43} with the ordered arrangement of {l_brace}Ca{sub 8}[CaY{sub 5}]F{sub 69}{r_brace} clusters which contain anionic {l_brace}F{sub 13}{r_brace} cuboctahedra with F{sup 1-} at the center. When Na-tveitite is formed, 29% of these clusters are statistically replaced by Na-'Y' clusters {l_brace}[Na{submore » 0.5}(Y,Ln){sub 0.5}]{sub 14}F{sub 64}{r_brace} with {l_brace}F{sub 8}{r_brace} cubes at the center (analogs of matrix fluorite groups {l_brace}Ca{sub 14}F{sub 64}{r_brace}). This replacement gives rise to composition-imperfect (Na, Ca, 'Y') cationic positions and occupancy-deficient F positions, which correspond to {l_brace}F{sub 13}{r_brace} cuboctahedra and the {l_brace}F{sub 8}{r_brace} cubes that replace them. The difference between Na-tveitite and fluorite phases M{sub 1-x}R{sub x}F{sub 2+x} is as follows: its matrix is the structure of the ordered phase (tveitite) into which Na-containing rare earth fragments of fluorite-type structure are incorporated instead of ordered-phase structural blocks (clusters).« less

Electronic and transport properties of fluorite structure of La2Ce2O7

NASA Astrophysics Data System (ADS)

Mahida, H. R.; Singh, Deobrat; Gupta, Sanjeev K.; Sonvane, Yogesh; Thakor, P. B.

2017-05-01

In this paper, we have symmetrically investigated the structural, electronic and transport properties of fluorite structure of lanthanum cerate oxide (La2Ce2O7) using density functional theory (DFT). The electronic band structure of La2Ce2O7 show semiconducting in nature with band gap of 1.54 eV (indirect at R-X points) and 1.71 eV (direct at R points). We have also calculated the susceptibility, hall resistance, electrical, and thermal conductivity by using Boltztrap equation. The electrical conductivity decreases where as thermal conductivity increases with increase in the temperature. Our result shows that La2Ce2O7 has application in Proton exchange membrane (PEM) fuel cells applications.

Strain-induced phase and oxygen-vacancy stability in ionic interfaces from first-principles calculations

DOE PAGES

Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; ...

2014-12-03

Understanding interfacial chemistry is becoming crucial in materials design for heterointerfaces. Using density functional theory, we elucidate the effect of strained interfaces on phase and oxygen-vacancy stability for CeO2 | ZrO2, ThO2 | ZrO2 and CeO2 | ThO2 interfaces. The calculations show that ZrO2 transforms from cubic fluorite to the orthorhombic columbite under tensile strain providing evidence of a previous experimental speculation of an unrecognized ZrO2 phase. We also show that oxygen vacancies could be preferably stabilized on either side of the interface by manipulating strain. We predict that they are stable in tensile-strain, and unstable in compressivestrained materials.

Electronic structure and energetics of the tetragonal distortion for TiH2, ZrH2 and HfH2: a first principles study

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

Quijano, Ramiro; DeCoss, Romeo; Singh, David J

2009-01-01

The electronic structure and energetics of the tetragonal distortion for the fluorite-type dihydrides TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} are studied by means of highly accurate first-principles total-energy calculations. For HfH{sub 2}, in addition to the calculations using the scalar relativistic (SR) approximation, calculations including the spin-orbit coupling have also been performed. The results show that TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} in the cubic phase are unstable against tetragonal strain. For the three systems, the total energy shows two minima as a function of the c/a ratio with the lowest-energy minimum at c/a < 1 in agreementmore » with the experimental observations. The band structure of TiH{sub 2}, ZrH{sub 2}, and HfH{sub 2} (SR) around the Fermi level shows two common features along the two major symmetry directions of the Brillouin zone, {Lambda}?L and {Lambda}?K, a nearly flat doubly degenerate band, and a van Hove singularity, respectively. In cubic HfH{sub 2} the spin-orbit coupling lifts the degeneracy of the partially filled bands in the {Lambda}?L path, while the van Hove singularity in the {Lambda}?K path remains unchanged. The density of states of the three systems in the cubic phase shows a sharp peak at the Fermi level. We found that the tetragonal distortion produces a strong reduction in the density of states at the Fermi level resulting mainly from the splitting of the doubly-degenerate bands in the {Lambda}?L direction and the shift of the van Hove singularity to above the Fermi level. The validity of the Jahn-Teller model in explaining the tetragonal distortion in this group of dihydrides is discussed.« less

The Pressure-Induced Structural Response of A2Hf2O7 (A=Y, Sm, Eu, Gd, Dy, Yb) Compounds from 0.1-50 GPa

NASA Astrophysics Data System (ADS)

Turner, K. M.; Rittman, D.; Heymach, R.; Turner, M.; Tracy, C.; Mao, W. L.; Ewing, R. C.

2016-12-01

A2B2O7 (A, B= cations) compounds have structures that make their properties conducive to many applications; for example they are a proposed waste-form for actinides generated in the nuclear fuel cycle. This interest in part is due to their structural responses to extreme environments of high P, T, or under intense irradiation. Depending on their cationic radius ratio, ra/rb, A2B2O7 compounds either crystallize as pyrochlore (ra/rb=1.46-1.7) or "defect fluorite" (ra/rb>1.46). The structure types are similar: they are derivatives of ideal fluorite with two cations and 1/8 missing anions. In pyrochlore, the cations and anion vacancy are ordered. In "defect fluorite"-structured oxides, the cations and anion vacancies are random. A2B2O7 compounds rarely amorphize in extreme environments. Rather, they disorder and undergo phase transitions; this resistance to amorphization contributes to the durability of this potential actinide waste-form. Under high-pressure, A2B2O7 compounds are known to disorder or form a cottunite-like phase. Their radius ratio affects their response to extreme environments; "defect fluorite" type compounds tend to disorder, and pyrochlore type compounds tend to form the cottunite-like phase. We have examined six A2Hf2O7 compounds (A=Y, Sm, Eu, Gd, Dy, Yb) in situ to 50 GPa. By keeping the B-site constant (Hf), we examined the effect of a changing radius ratio on the pressure-induced structural response of hafnates. We used symmetric DACs, ruby fluorescence, stainless steel gaskets, and methanol: ethanol (4:1 by volume) pressure medium. We characterized these materials with in situ Raman spectroscopy at Stanford University, and synchrotron X-Ray Diffraction (XRD) at APS 16 BM-D and ALS 12.2.2. The compounds were pyrochlore structured (Sm, Eu, Gd) and "defect-fluorite" structured (Y, Dy, Yb) hafnates . These compounds undergo a slow phase transition to a high-pressure cotunnite-like phase between 18-30 GPa. They undergo disordering of their cation and anionic sites as pressure is increased. The pressure of their phase transitions correlates directly with their radius ratio. Our results are comparable to many high-pressure studies of rare earth zirconates and titanates, but contrast from previous experiments performed on rare earth hafnates, specifically La2Hf2O7.

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

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

Method of forming a joint

DOEpatents

Butt, Darryl Paul; Cutler, Raymond Ashton; Rynders, Steven Walton; Carolan, Michael Francis

2006-08-22

A method of joining at least two sintered bodies to form a composite structure, including providing a first multicomponent metallic oxide having a perovskitic or fluorite crystal structure; providing a second sintered body including a second multicomponent metallic oxide having a crystal structure of the same type as the first; and providing at an interface a joint material containing at least one metal oxide containing at least one metal identically contained in at least one of the first and second multicomponent metallic oxides. The joint material is free of cations of Si, Ge, Sn, Pb, P and Te and has a melting point below the sintering temperatures of both sintered bodies. The joint material is heated to a temperature above the melting point of the metal oxide(s) and below the sintering temperatures of the sintered bodies to form the joint. Structures containing such joints are also disclosed.

Direct Observations of a Dynamically Driven Phase Transition with in situ X-Ray Diffraction in a Simple Ionic Crystal

NASA Astrophysics Data System (ADS)

Kalita, Patricia; Specht, Paul; Root, Seth; Sinclair, Nicholas; Schuman, Adam; White, Melanie; Cornelius, Andrew L.; Smith, Jesse; Sinogeikin, Stanislav

2017-12-01

We report real-time observations of a phase transition in the ionic solid CaF2 , a model A B2 structure in high-pressure physics. Synchrotron x-ray diffraction coupled with dynamic loading to 27.7 GPa, and separately with static compression, follows, in situ, the fluorite to cotunnite structural phase transition, both on nanosecond and on minute time scales. Using Rietveld refinement techniques, we examine the kinetics and hysteresis of the transition. Our results give insight into the kinetic time scale of the fluorite-cotunnite phase transition under shock compression, which is relevant to a number of isomorphic compounds.

Direct Observations of a Dynamically Driven Phase Transition with in situ X-Ray Diffraction in a Simple Ionic Crystal

DOE PAGES

Kalita, Patricia E.; Specht, Paul Elliot; Root, Seth; ...

2017-12-21

Here, we report real-time observations of a phase transition in the ionic solid CaF 2, a model AB 2 structure in high-pressure physics. Synchrotron x-ray diffraction coupled with dynamic loading to 27.7 GPa, and separately with static compression, follows, in situ, the fluorite to cotunnite structural phase transition, both on nanosecond and on minute time scales. Using Rietveld refinement techniques, we examine the kinetics and hysteresis of the transition. Our results give insight into the kinetic time scale of the fluorite-cotunnite phase transition under shock compression, which is relevant to a number of isomorphic compounds.

High pressure phase transitions and compressibilities of Er2Zr2O7 and Ho2Zr2O7

NASA Astrophysics Data System (ADS)

Zhang, F. X.; Lang, M.; Becker, U.; Ewing, R. C.; Lian, J.

2008-01-01

Phase stability and compressibility of rare earth zirconates with the defect-fluorite structure were investigated by in situ synchrotron x-ray diffraction. A sluggish defect-fluorite to a cotunnitelike phase transformation occurred at pressures of ˜22 and ˜30GPa for Er2Zr2O7 and Ho2Zr2O7, respectively. Enhanced compressibility was found for the high pressure phase as a result of increasing cation coordination number and cation-anion bond length.

Lattice Parameter Behavior with Different Nd and O Concentrations in (U 1-yNd y)O 2±x Solid Solution

DOE PAGES

Lee, Seung Min; Knight, Travis W.; Voit, Stwart L.; ...

2016-02-02

The solid solution of (U1-yFPy)O- 2±x, has the same fluorite structure as UO 2±x lambda, and the lattice parameter is affected by dissolved fission product and oxygen concentrations. We investigated the relation between the lattice parameter and the concentrations of neodymium and oxygen in the fluorite structure of (U 1-yNd y)O 2±x using X-ray diffraction. Moreover, the lattice parameter behavior in the (U 1-yNd y)O 2±x, solid solution shows a linear change as a function of the oxygen-to-metal ratio and solubility of neodymium. The lattice parameter depends on the radii of ions forming the fluorite structure and also can bemore » expressed by a particular rule (modified Vegard's law). Furthermore, the numerical analyses of the lattice parameters for the stoichiometric and nonstoichionietric solid solutions were conducted, and the lattice parameter model for the (U1-yNdy)O 2±x, solid solution was assessed. There is a very linear relationship between the lattice parameter and the Nd and O concentration for the stoichiometry and nonstoichiometry of the (U 1-yNd y)O 2±x solid solution was verified.« less

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

Solomon, Jonathan M.; Shamblin, Jacob; Lang, Maik

Fluorite-structured oxides find widespread use for applications spanning nuclear energy and waste containment, energy conversion, and sensing. In such applications the host tetravalent cation is often partially substituted by trivalent cations, with an associated formation of charge-compensating oxygen vacancies. The stability and properties of such materials are known to be influenced strongly by chemical ordering of the cations and vacancies, and the nature of such ordering and associated energetics are thus of considerable interest. Here we employ density-functional theory (DFT) calculations to study the structure and energetics of cation and oxygen-vacancy ordering in Ho 2Zr 2O 7. In a recentmore » neutron total scattering study, solid solutions in this system were reported to feature local chemical ordering based on the fluorite-derivative weberite structure. The calculations show a preferred chemical ordering qualitatively consistent with these findings, and yield values for the ordering energy of 9.5 kJ/mol-cation. Similar DFT calculations are applied to additional RE 2Th 2O 7'' fluorite compounds, spanning a range of values for the ratio of the tetravalent and trivalent (RE) cation radii. Finally, the results demonstrate that weberite-type order becomes destabilized with increasing values of this size ratio, consistent with an increasing energetic preference for the tetravalent cations to have higher oxygen coordination.« less

Magnetic properties and structural transitions of fluorite-related rare earth osmates Ln3OsO7 (Ln=Pr, Tb)

NASA Astrophysics Data System (ADS)

Hinatsu, Yukio; Doi, Yoshihiro

2013-02-01

Ternary rare-earth osmates Ln3OsO7 (Ln=Pr, Tb) have been prepared. They crystallize in an ortho-rhombic superstructure of cubic fluorite with space group Cmcm. Both of these compounds undergo a structural phase transition at 130 K (Ln=Pr) and 580 K (Ln=Tb). These compounds show complex magnetic behavior at low temperatures. Pr3OsO7 exhibits magnetic transitions at 8 and 73 K, and Tb3OsO7 magnetically orders at 8 and 60 K. The Os moments become one-dimensionally ordered, and when the temperature is furthermore decreased, it provokes the ordering in the Ln3+ sublattice that simultaneously becomes three-dimensionally ordered with the Os sublattice.

Magnetic Studies on Eu3MO7 (M = Nb, Ta, Ir) with Fluorite-related Structure by 151Eu Mössbauer Spectroscopy and Magnetic Susceptibility Measurements

NASA Astrophysics Data System (ADS)

Hinatsu, Yukio; Doi, Yoshihiro; Wakeshima, Makoto

2018-06-01

Magnetic properties of europium-containing compounds Eu3MO7 (M = Nb, Ta, Ir) with fluorite-related structure have been investigated. Magnetic susceptibility measurements show that all these compounds are paramagnetic and have no magnetic ordering down to 1.8 K. At very low temperatures (T<50 K), the susceptibilities of each compound attain constant values, which is characteristic of the ground state for Eu3+ ions. The results of 151Eu Mössbauer spectroscopic measurements show that the asymmetric parameter for Eu(2) in seven-coordination is much larger than that for Eu(1) in cubic environment, which in accordance with the crystallographic result.

In-situ x-ray diffraction of a shock-induced phase transition in fluorite, CaF2

NASA Astrophysics Data System (ADS)

Glam, Benny; June Tracy, Sally; Turneaure, Stefan; Duffy, Thomas

2017-06-01

The difluorides are an important class of ionic compounds that show extensive polymorphism under both static and dynamic loading. In this study, the shock-induced phase transitions in CaF2 were investigated by in situ x-ray diffraction measurements in plate impact experiments carried out with the two-stage gas gun at the Dynamic Compression Sector of Argonne National Laboratory. Single-crystal samples in (100) and (111) orientations were shock loaded to pressures between 32 GPa to 70 GPa. The particle velocities at the interface between the sample and a LiF window were measured by VISAR and PDV. Synchrotron x-ray diffraction data were recorded at 153.4 ns intervals using a four-frame detector. The measured diffraction patterns show a high degree of sample texturing at all pressures. We observe evidence for a transition to a high-pressure phase followed by reverse transformation at late times during release. This study provides the first direct constraints on the high-pressure lattice structure of fluorite under shock compression.

Shock Compression Response of Calcium Fluoride (CaF2)

NASA Astrophysics Data System (ADS)

Root, Seth

2017-06-01

The fluorite crystal structure is a textbook lattice that is observed for many systems, such as CaF2, Mg2 Si, and CeO2. Specifically, CaF2 is a useful material for studying the fluorite system because it is readily available as a single crystal. Under static compression, CaF2 is known to have at least three solid phases: fluorite, cotunnite, and a Ni2 In phase. Along the Hugoniot CaF2 undergoes a fluorite to cotunnite phase transition, however, at higher shock pressures it is unknown whether CaF2 undergoes another solid phase transition or melts directly from the cotunnite phase. In this work, we conducted planar shock compression experiments on CaF2 using Sandia's Z-machine and a two-stage light gun up to 900 GPa. In addition, we use density functional theory (DFT) based quantum molecular dynamics (QMD) simulations to provide insight into the CaF2 state along the Hugoniot. In collaboration with: Michael Desjarlais, Ray Lemke, Patricia Kalita, Scott Alexander, Sandia National Laboratories. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL850.

[Analysis of color regulation of Fluoritum in Chinese Pharmacopoeia based on the coloration mechanism of Fluorite].

PubMed

Han, Ting; Jia, Zhe; Zhang, Hui; Liu, Huan; Gao, Yan; Zhang, Ying; Lin, Qing-Hua; Xu, Shu-Ya; Xu, Xin-Fang; Li, Xiang-Ri

2016-12-01

The fluoritum is used for gynecology frequently and it's for those diseases: kidney yang deficiency, Gong cold sterility, palpitation due to fright, insomnia and dreaminess and cold cough. It's ruled in Chinese Pharmacopoeia (1985 edition) that the fluoritum originates from fluorite which belongs to fluoride minerals. Its main content is CaF2. The colors are of differents grades with purple or green. In the market, there are large differences in quality and it has various colors. Besides of the ruled color of purple and green, white and yellow are also common colors. By digging into and analysis the relevant research literature of fluorite which belongs to fluoride minerals, colors and coloration mechanism of fluorite are summarized in this paper.Natural fluorite is the mineral which has the most species of colors in nature. The different colors of fluorite are mainly caused by the impurity elements. At present, there are mainly about the coloration mechanism of fluorite: rare earth ions (4fN ions), color center, inclusions, crystalline domains or sub microscopic inclusions. The green of fluorite is produced by 570 nm and 305 nm absorption peaks which are caused by Sm2+ and compensated ions Na+ centers generated color center. The yellow of fluorite is produced by the joining of transition element, resulting in the formation of charge transfer between the crystal ions and the formation of O2-O32- ion molecule.The black of fluorite, mainly was attributed to the existence of a higher degree of evolution of organic matter. In this passage,suggestions for modification of the properties of fluoritum in Chinese Pharmacopoeia are put forward. Copyright© by the Chinese Pharmaceutical Association.

Radiation-induced disorder in compressed lanthanide zirconates.

PubMed

Park, Sulgiye; Tracy, Cameron L; Zhang, Fuxiang; Park, Changyong; Trautmann, Christina; Tkachev, Sergey N; Lang, Maik; Mao, Wendy L; Ewing, Rodney C

2018-02-28

The effects of swift heavy ion irradiation-induced disordering on the behavior of lanthanide zirconate compounds (Ln 2 Zr 2 O 7 where Ln = Sm, Er, or Nd) at high pressures are investigated. After irradiation with 2.2 GeV 197 Au ions, the initial ordered pyrochlore structure (Fd3[combining macron]m) transformed to a defect-fluorite structure (Fm3[combining macron]m) in Sm 2 Zr 2 O 7 and Nd 2 Zr 2 O 7 . For irradiated Er 2 Zr 2 O 7 , which has a defect-fluorite structure, ion irradiation induces local disordering by introducing Frenkel defects despite retention of the initial structure. When subjected to high pressures (>29 GPa) in the absence of irradiation, all of these compounds transform to a cotunnite-like (Pnma) phase, followed by sluggish amorphization with further compression. However, if these compounds are irradiated prior to compression, the high pressure cotunnite-like phase is not formed. Rather, they transform directly from their post-irradiation defect-fluorite structure to an amorphous structure upon compression (>25 GPa). Defects and disordering induced by swift heavy ion irradiation alter the transformation pathways by raising the energetic barriers for the transformation to the high pressure cotunnite-like phase, rendering it inaccessible. As a result, the high pressure stability field of the amorphous phase is expanded to lower pressures when irradiation is coupled with compression. The responses of materials in the lanthanide zirconate system to irradiation and compression, both individually and in tandem, are strongly influenced by the specific lanthanide composition, which governs the defect energetics at extreme conditions.

Method of joining ITM materials using a partially or fully-transient liquid phase

DOEpatents

Butt, Darryl Paul; Cutler, Raymond Ashton; Rynders, Steven Walton; Carolan, Michael Francis

2006-03-14

A method of forming a composite structure includes: (1) providing first and second sintered bodies containing first and second multicomponent metallic oxides having first and second identical crystal structures that are perovskitic or fluoritic; (2) providing a joint material containing at least one metal oxide: (a) containing (i) at least one metal of an identical IUPAC Group as at least one sintered body metal in one of the multicomponent metallic oxides, (ii) a first row D-Block transition metal not contained in the multicomponent metallic oxides, and/or (iii) a lanthanide not contained in the multicomponent metallic oxides; (b) free of metals contained in the multicomponent metallic oxides; (c) free of cations of boron, silicon, germanium, tin, lead, arsenic, antimony, phosphorus and tellurium; and (d) having a melting point below the sintering temperatures of the sintered bodies; and (3) heating to a joining temperature above the melting point and below the sintering temperatures.

Nonstoichiometric fluorides—Solid electrolytes for electrochemical devices: A review

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Sobolev, B. P.

2007-09-01

The solid electrolytes with fluorine-ion conductivity that were revealed during the analysis of the phase diagrams of the MF m - RF n systems within the program of search for new multicomponent fluoride crystalline materials carried out at the Shubnikov Institute of Crystallography, Russian Academy of Sciences, are described. The most widespread and promising materials are the nonstoichiometric phases with fluorite (CaF2) and tysonite (LaF3) structures, which are formed in the MF2- RF3 systems ( M = Ca, Sr, Ba, Cd, or Pb; R = Sc, Y, or La-Lu). These phases have superionic fluorine conductivity due to the anion sublattice disorder. The ionic conductivity of crystals of both structure types has been studied and the limits of its change with composition and temperature are determined. Nonstoichiometric fluorides are used as solid electrolytes in chemical sensors, fluorine sources, and batteries. The prospects of the use of fluorine-ion conductors in solid-state electrochemical devices, principles of their operation, and the problems of optimization of their composition are discussed.

Nanostructured Crystals of Fluorite Phases Sr1 - x R x F2 + x and Their Ordering: 12. Influence of Structural Ordering on the Fluorine-Ion Conductivity of Sr0.667 R 0.333F2.333 Alloys ( R = Tb or Tm) at Their Annealing

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Karimov, D. N.; Sul'yanova, E. A.; Sobolev, B. P.

2018-01-01

The ionic conductivity of Sr0.667 R 0.333F2.333 alloys (rational Sr2 RF7 compositions) in SrF2- RF3 systems ( R = Tb or Tm), prepared by spontaneous crystallization, has been investigated for the "as-grown" state and after annealing in CF4 at 900 ± 20°C for 96 h. As-grown samples of both compositions, prepared by fast (200°C/min) melt crystallization, exhibit partial (nonequilibrium) ordering, which increases from Tb to Tm. Annealing of Sr0.667 R 0.333F2.333 alloys yields strong ordering (equilibrium for the annealing temperatures) of the fluorite structure (CaF2 type, sp. gr. Fm3̅ m, Z = 4) at the formation of t-Sr2 RF7 tetragonal compound (sp. gr. I4/ m, Z = 30). It is established that ordering of the alloy fluorite structure reduces the fluorine-ion conductivity. After the annealing, the conductivity of Sr0.667R0.333F2.333 alloys with the initial (nonequilibrium) ordering stage of t-Sr2 RF7 phases with almost complete (equilibrium) ordering decreases by a factor of 3-4.5.

Damage evolution of ion irradiated defected-fluorite La 2 Zr 2 O 7 epitaxial thin films

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

Kaspar, Tiffany C.; Gigax, Jonathan G.; Shao, Lin

2017-05-01

Pyrochlore-structure oxides, A2B2O7, may exhibit remarkable radiation tolerance due to the ease with which they can accommodate disorder by transitioning to a defected fluorite structure. The mechanism of defect formation was explored by evaluating the radiation damage behavior of high quality epitaxial La2Zr2O7 thin films with the defected fluorite structure, irradiated with 1 MeV Zr+ at doses up to 10 displacements per atom (dpa). The level of film damage was evaluated as a function of dose by Rutherford backscattering spectrometry in the channeling geometry (RBS/c) and scanning transmission electron microscopy (STEM). At lower doses, the surface of the La2Zr2O7 filmmore » amorphized, and the amorphous fraction as a function of dose fit well to a stimulated amorphization model. As the dose increased, the surface amorphization slowed, and amorphization appeared at the interface. Even at a dose of 10 dpa, the core of the film remained crystalline, despite the prediction of amorphization from the model. To inform future ab initio simulations of La2Zr2O7, the bandgap of a thick La2Zr2O7 film was measured to be indirect at 4.96 eV, with a direct transition at 5.60 eV.« less

Damage evolution of ion irradiated defected-fluorite La 2 Zr 2 O 7 epitaxial thin films

DOE PAGES

Kaspar, Tiffany C.; Gigax, Jonathan G.; Shao, Lin; ...

2017-05-01

Pyrochlore-structure oxides, A 2B 2O 7, may exhibit remarkable radiation tolerance due to the ease with which they can accommodate disorder by transitioning to a defected fluorite structure. In this paper, the mechanism of defect formation was explored by evaluating the radiation damage behavior of high quality epitaxial La 2Zr 2O 7 thin films with the defected fluorite structure, irradiated with 1 MeV Zr + at doses up to 10 displacements per atom (dpa). The level of film damage was evaluated as a function of dose by Rutherford backscattering spectrometry in the channeling geometry (RBS/c) and scanning transmission electron microscopymore » (STEM). At lower doses, the surface of the La 2Zr 2O 7 film amorphized, and the amorphous fraction as a function of dose fit well to a stimulated amorphization model. As the dose increased, the surface amorphization slowed, and amorphization appeared at the interface. Even at a dose of 10 dpa, the core of the film remained crystalline, despite the prediction of amorphization from the model. To inform future ab initio simulations of La 2Zr 2O 7, the bandgap of a thick La 2Zr 2O 7 film was measured to be indirect at 4.96 eV, with a direct transition at 5.60 eV.« less

Mineralogical, textural, geochemical and thermometric characteristics of Central Anatolian fluorites (Turkey): Tracing the origin of post-magmatic fluids

NASA Astrophysics Data System (ADS)

Cosanay, Pelin; Mutlu, Halim; Koc, Sükrü; Cevik, Nihal; Oztürk, Ceyda; Varol, Ece

2016-04-01

In this study, we investigate the spatial distribution of fluorite veins in Central Anatolia with emphasis on mineralogical, textural, geochemical and thermometric variations. The studied fluorite mineralizations (Kaman, Akçakent, Pöhrenk and Şefaatli mineralizations from west to east) are located on northern part of Kırşehir Massif which is a part of Central Anatolian Crystalline Complex that is bordered by the İzmir-Ankara-Erzincan Suture Zone. The Kaman, Akçakent and Şefaatli fluorite deposits are formed in association with magmatic rocks such as syenite and monzonite / monzodiorite in composition which are of Upper Cretaceous age. Fluorite in these deposits occurs as purple- and green-colored stockwork veins and/or disseminations along fault/fracture systems and is accompanied by quartz and rare pyrite. The Pöhrenk ore, however, is precipitated as space filling-breccia type within karstic voids of Eocene limestones and marl levels. The silicification/carbonatization and barite occurrences are found as the main alteration and secondary products of mineralization. Thickness of fluorite veins is between 2 and 30 cm. ΣREE contents of host rocks and fluorite veins are in the range of 2-806 ppm and 20-390 ppm, respectively. In element variation diagrams constructed for both host rocks and fluorite mineralizations, LREE concentrations are found to be greater than HREEs. REE contents of green-colored fluorites are about 10-fold higher than those of purple-colored ones. Negative Ce and Eu anomalies indicate high oxygen fugacity for the mineralizing fluids. Fluid inclusion studies indicated three different types of inclusions: 1) two-phase (liquid-vapor) primary and secondary inclusions, 2) single-phase (liquid) primary and secondary inclusions and 3) two-phase (liquid-vapor) and single-phase (liquid) pseudo-secondary inclusions. Results of homogenization temperatures from a number of about 200 measurements chiefly on fluorite and less often quartz and barite crystals point to a temperature range of 90-210°C and a salinity range of 0.2 to 23.0 NaCl equivalent wt%. Our ongoing survey which has been further focused on the time of mineralization and Sr-Nd isotope compositions of fluorites and host rocks as well as stable isotope systematics of accessory minerals will lead to a better understanding of the origin of mineralizing fluids that precipitated Central Anatolian fluorites.

Variable helium diffusion characteristics in fluorite

NASA Astrophysics Data System (ADS)

Wolff, R.; Dunkl, I.; Kempe, U.; Stockli, D.; Wiedenbeck, M.; von Eynatten, H.

2016-09-01

Precise analysis of the diffusion characteristics of helium in fluorite is crucial for establishing the new fluorite (U-Th-Sm)/He thermochronometer (FHe), which potentially provides a powerful tool for dating ore deposits unsuitable for the application of conventional geochronometers. Incremental helium outgassing experiments performed on fluorites derived from a spectrum of geological environments suggest a thermally activated volume diffusion mechanism. The diffusion behaviour is highly variable and the parameters range between log D0/a2 = 0.30 ± 0.27-7.27 ± 0.46 s-1 and Ea = 96 ± 3.5-182 ± 3.8 kJ/mol. Despite the fact that the CaF2 content of natural fluorites in most cases exceeds 99 weight percent, the closure temperature (Tc) of the fluorite (U-Th-Sm)/He thermochronometer as calculated from these diffusion parameters varies between 46 ± 14 °C and 169 ± 9 °C, considering a 125 μm fragment size. Here we establish that minor substitutions of calcium by rare earth elements and yttrium (REE + Y) and related charge compensation by sodium, fluorine, oxygen and/or vacancies in the fluorite crystal lattice have a significant impact on the diffusivity of helium in the mineral. With increasing REE + Y concentrations F vacancies are reduced and key diffusion pathways are narrowed. Consequently, a higher closure temperature is to be expected. An empirical case study confirms this variability: two fluorite samples from the same deposit (Horni Krupka, Czech Republic) with ca. 170 °C and ca. 43 °C Tc yield highly different (U-Th-Sm)/He ages of 290 ± 10 Ma and 79 ± 10 Ma, respectively. Accordingly, the fluorite sample with the high Tc could have quantitatively retained helium since the formation of the fluorite-bearing ores in the Permian, despite subsequent Mesozoic burial and associated regional hydrothermal heating. In contrast, the fluorite with the low Tc yields a Late Cretaceous age close to the apatite fission track (AFT) and apatite (U-Th)/He ages (AHe) from the same locality. Remarkably, thermal modelling of FHe yields comparable results to the well-established modelling based on AFT and AHe.

Methods of capturing and immobilizing radioactive nuclei with metal fluorite-based inorganic materials

DOEpatents

Wang, Yifeng; Miller, Andy; Bryan, Charles R.; Kruichak, Jessica Nicole

2015-11-17

Methods of capturing and immobilizing radioactive nuclei with metal fluorite-based inorganic materials are described. For example, a method of capturing and immobilizing radioactive nuclei includes flowing a gas stream through an exhaust apparatus. The exhaust apparatus includes a metal fluorite-based inorganic material. The gas stream includes a radioactive species. The radioactive species is removed from the gas stream by adsorbing the radioactive species to the metal fluorite-based inorganic material of the exhaust apparatus.

Geochemical associations between fluorite mineralization and A-type shoshonitic magmatism in the Keban-Elazig area, East Anatolia, Turkey

NASA Astrophysics Data System (ADS)

Akgul, Bunyamin

2015-11-01

Keban fluorite mineralizations are closely related Coniacian-Campanian subvolcanics intruded into Permian-Triassic Keban metamorphites; this event caused pyrometasomatic, porphyry, and vein-type Pb-Zn-Ag, Cu, W, and Pb-Zn-Ag-Mo-F mineralizations. These rocks are syenitic and syenomonzonitic in composition and have high Al2O3, alkali (Na2O + K2O), FeO*/MgO, Zr, Nb, Ta, Ga, Rb, Y, and rare earth element (REE) contents. They are A-type, metaluminous, and all fall in the shoshonitic series field in K2O vs SiO2 and Th/Yb vs Ta/Yb diagrams. The trace element contents and discriminations indicate that the Keban syenitoids were derived from lithospheric mantle metasomatized by oceanic-crust/sediment fluids. The metal and halogen contents of the Keban mineralizations apparently originated from metasomatized mantle and were transported to the crust by syenitoid magmas. Clear resemblances in chondrite-normalized REE patterns, LREE-HREE partionation, and high LILE contents of the magmatics and fluorites indicate a close kinship between the syenitoids and fluorite mineralizations. The HFSE contents of the fluorites are lower than those of the magmatics, as HFSEs are not soluble in aqueous fluids. The fluorites are products of early-phase alkali magmatism (LREE > HREE). The high contents of Rb, Sr, and Ba of fluorites are inherited from the magma, which also has very high contents of these elements. In Sc-∑REE, (La/Yb)n-(Eu/Eu*)n and (Tb/La)n-(Tb/Ca)n diagrams, Keban fluorites fall into distinct areas from Akcakisla-Akdagmadeni and Celikhan-Adiyaman fluorites.

Probing disorder in isometric pyrochlore and related complex oxides

NASA Astrophysics Data System (ADS)

Shamblin, Jacob; Feygenson, Mikhail; Neuefeind, Joerg; Tracy, Cameron L.; Zhang, Fuxiang; Finkeldei, Sarah; Bosbach, Dirk; Zhou, Haidong; Ewing, Rodney C.; Lang, Maik

2016-05-01

There has been an increased focus on understanding the energetics of structures with unconventional ordering (for example, correlated disorder that is heterogeneous across different length scales). In particular, compounds with the isometric pyrochlore structure, A2B2O7, can adopt a disordered, isometric fluorite-type structure, (A, B)4O7, under extreme conditions. Despite the importance of the disordering process there exists only a limited understanding of the role of local ordering on the energy landscape. We have used neutron total scattering to show that disordered fluorite (induced intrinsically by composition/stoichiometry or at far-from-equilibrium conditions produced by high-energy radiation) consists of a local orthorhombic structural unit that is repeated by a pseudo-translational symmetry, such that orthorhombic and isometric arrays coexist at different length scales. We also show that inversion in isometric spinel occurs by a similar process. This insight provides a new basis for understanding order-to-disorder transformations important for applications such as plutonium immobilization, fast ion conduction, and thermal barrier coatings.

Energetics of defects formation and oxygen migration in pyrochlore compounds from first principles calculations

NASA Astrophysics Data System (ADS)

Li, Yan; Kowalski, Piotr M.

2018-07-01

In order to get better understanding of the selective order-disorder transition in pyrochlore compounds, using ab initio methods we calculated the formation energies of coupled cation anti-site and anion Frenkel pair defects and the energy barriers for the oxygen migration for number of families of A2B2 O7 pyrochlore-type compounds. While these parameters have been previously computed with force field-based methods, the ab initio results provide more reliable values that can be confidently used in subsequent analysis. We found a fairly good correlation between the formation energies of the coupled defects and the stability field of pyrochlores. In line with previous studies, the compounds that crystallize in defect fluorite structure are found to have smaller values of coupled defect formation energies than those crystallizing in the pyrochlore phase, although the correlation is not that sharp as in the case of isolated anion Frenkel pair defect. The investigation of the energy barriers for the oxygen migration shows that it is not a good, sole indicator of the tendency of the order-disorder phase transition in pyrochlores. However, we found that the oxygen migration barrier is reduced in the presence of the cation antisite defect. This points at disordering-induced enhancement of oxygen diffusion in pyrochlore compounds.

Pressure-induced photoluminescence in Mn2+-doped BaF2 and SrF2 fluorites

NASA Astrophysics Data System (ADS)

Hernández, Ignacio; Rodríguez, Fernando

2003-01-01

This work reports an effective way for inducing room temperature photoluminescence (PL) in Mn2+-doped BaF2 and SrF2 using high-pressure techniques. The aim is to understand the surprising PL behavior exhibited by Mn2+ at the cubal site of the fluorite structure. While Mn2+-doped CaF2 shows a green PL with quantum yield close to 1 at room temperature, Mn2+-doped MF2 (M=Ba,Sr) is not PL either at room temperature (SrF2) or at any temperature (BaF2) at ambient pressure. We associate the loss of Mn2+ PL on passing from CaF2 to SrF2 or BaF2 with nonradiative multiphonon relaxation whose thermal activation energy decreases along the series CaF2→SrF2→BaF2. A salient feature of this work deals with the increase of activation energy induced by pressure. It leads to a quantum yield enhancement, which favors PL recovery. Furthermore, the activation energy mainly depends on the crystal volume per molecule irrespective of the crystal structure or the local symmetry around the impurity. In this way, the relevance of the fluorite-to-cotunnite phase transition is analyzed in connection with the PL properties of the investigated compounds. The PL spectrum and the corresponding lifetime are reported for both structural phases as a function of pressure.

Synchrotron X-ray diffraction and Raman spectroscopy of Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm-Lu) ceramics obtained by molten-salt synthesis

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

Siqueira, K.P.F.; Soares, J.C.; Granado, E.

2014-01-15

Ln{sub 3}NbO{sub 7} (Ln=La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu) ceramics were obtained by molten-salt synthesis and their structures were systematically investigated by synchrotron X-ray diffraction (SXRD), second harmonic generation (SHG) and Raman spectroscopy. It was observed that ceramics with the largest ionic radii (La, Pr, Nd) crystallized into the Pmcn space group, while the ceramics with intermediate ionic radii (Sm-Gd) exhibited a different crystal structure belonging to the Ccmm space group. For this last group of ceramics, this result was corroborated by SHG and Raman scattering and ruled out any possibility formore » the non-centrosymmetric C 222{sub 1} space group, solving a recent controversy in the literature. Finally, according to SXRD, Tb-Lu containing samples exhibited an average defect fluorite structure (Fm3{sup ¯}m space group). Nonetheless, broad scattering at forbidden Bragg reflections indicates the presence of short-range domains with lower symmetry. Vibrational spectroscopy showed the presence of six Raman-active modes, inconsistent with the average cubic fluorite structure, and in line with the existence of lower-symmetry nano-domains immersed in the average fluorite structure of these ceramics. - Graphical abstract: Raman spectrum for Sm{sub 3}NbO{sub 7} ceramics showing their 27 phonon modes adjusted through Lorentzian lines. According to synchrotron X-ray diffraction and Raman scattering, this material belongs to the space group Cmcm. Display Omitted - Highlights: • Ln{sub 3}NbO{sub 7} ceramics were obtained by molten-salt synthesis. • SXRD, SHG and Raman scattering confirmed orthorhombic and cubic structures. • Ccmm instead of C222{sub 1} is the correct structure for Sm–Gd ceramics. • Pmcn space group was confirmed for La-, Pr- and Nd-based ceramics. • For Tb–Lu ceramics, ordered domains of a pyrochlore structure were observed.« less

The reasons for the color green fluorite Mehmandooye cover using UV spectroscopy and XRF results

NASA Astrophysics Data System (ADS)

Pirzadeh, Sara; Zahiri, Reza

2016-04-01

Fluorite mineral or fluorine with chemical formula CaF2 is most important mineralfluor in nature. This mineral crystallization to colors yellow, green, pink, blue, purple, colorless and sometimes black andin cubic system crystallized.assemi transparent and glass with polished.fluoritethe purity include 48/9% fluoreand 51/9% calcium. How the creation colors in minerals different greatly indebted to Kurt Nassau research from Bell Labs, Murray Hill, New Jersey.almostall the mechanisms that cause color in minerals, are the result of the interaction of light waves with the electrons The main factors affecting the color generation include the following: 1)the presence of a constructive element inherent (essential ingredient mineral composition) 2)The presence of a minor impurities (such a element as involved in latticesolid solution) 3) appearancedefects in the crystal structure 4) There are some physical boundaries with distances very small and delicate, like blades out of the solution (which may be the play of colors or Chatvyansy) 5) Mixing mechanical impurities dispersed in a host mineral Based on the results of the analysis, XRF and UV spectrum and also based on the results of ICP, because the color green fluorite examined, the focus color (F_center) and also the presence of some elementsintermediate (such as Y (yttrium). [1] Bill, H., Calas, G. Color centres associated rare earth ions and the origin of coloration in natural fluorites// PhysChem Min, (1978), v 3, pp. 117-131.

Fluoride enrichment in groundwater of semi-arid urban area: Khan Younis City, southern Gaza Strip (Palestine)

NASA Astrophysics Data System (ADS)

Abu Jabal, Mohamed Shaban; Abustan, Ismail; Rozaimy, Mohd Remy; Al-Najar, Hussam

2014-12-01

The aim of this study is to determine fluoride enhancement in the groundwater of semi-arid urban area of Khan Younis City, southern Gaza Strip. Physicochemical data for a total of 200 groundwater samples were analyzed. The fluoride concentrations were varied from 0.3 to 6.45 mg/L with average value of 2.87 mg/L. Correlations between fluorides with other measured ions were relatively observed, negative correlation with calcium and the positive correlation with pH, bicarbonate and sodium increase the dissolution/solubility of fluoride bearing minerals, leading to fluoride leaching into the groundwater. Fluoride enrichment in the groundwater of the area is due to water hydrochemistry, mineral-water interaction (mainly calcite and fluorite), fluorite resulted from fluorapatite dissolution. The saturation indexes evaluation indicated that 42% of the samples are over saturated with respect to calcite and 35.5% under saturated with respect to fluorite, while 40.5% approached equilibrium with respect to both calcite and fluorite. At fluoride concentrations of less than 2.2 mg/L fluorite saturation indexes show under-saturation condition for fluorite and at higher fluoride concentrations show near saturation condition.

Ae2Sb2X4F2 (Ae = Sr, Ba): new members of the homologous series Ae2M(1+n)X(3+n)F2 designed from rock salt and fluorite 2D building blocks.

PubMed

Kabbour, Houria; Cario, Laurent

2006-03-20

We have designed new compounds within the homologous series Ae2F2M(1+n)X(3+n) (Ae = Sr, Ba; M = main group metal; n = integer) built up from the stacking of 2D building blocks of rock salt and fluorite types. By incrementally increasing the size of the rock salt 2D building blocks, we have obtained two new n = 1 members of this homologous series, namely, Sr2F2Sb2Se4 and Ba2F2Sb2Se4. We then succeeded in synthesizing these compounds using a high-temperature ceramic method. The structure refinements from the powder or single-crystal X-ray diffraction data confirmed presence of the expected alternating stacking of fluorite [Ae2F2] (Ae = Sr, Ba) and rock salt [Sb2Se4] 2D building blocks. However the Ba derivative shows a strong distortion of the [Sb2Se4] block and a concomitant change of the Sb atom coordination likely related to the lone-pair activity.

Genesis of rare-metal pegmatites and alkaline apatite-fluorite rocks of Burpala massi, Northern Baikal folded zone

NASA Astrophysics Data System (ADS)

Sotnikova, Irina; Vladykin, Nikolai

2015-04-01

Burpalinsky rare metal alkaline massif in the Northern Baikal folded zone in southern margin of Siberian Platform, is a of intrusion central type, created 287 Ma covering area of about 250 km2. It is composed of nepheline syenites and pulaskites grading to quartz syenites in the contacts. Veines and dykes are represented by shonkinites, sodalite syenite, leucocratic granophyres, alkali granites and numerous rare metal alkaline syenite pegmatites and two dykes of carbonatites. All rocks except for granites are cut by a large apatite-fluorite dyke rocks with mica and magnetite, which in turn is cut by alaskite granites dyke. The massif has been studied by A.M. Portnov, A.A. Ganzeev et al. (1992) Burpalinsky massif is highly enriched with trace elements, which are concentrated in pegmatite dykes. About 70 rare-metal minerals we found in massif. Zr-silicates: zircon, eudialyte, lovenite, Ti-lovenite, velerite, burpalite, seidozerite, Ca- seidozerite, Rosenbuschite, vlasovite, katapleite, Ca-katapleite, elpidite. Ti- minerals:- sphene, astrophyllite, ramsaite, Mn-neptunite bafertisite, chevkinite, Mn-ilmenite, pirofanite, Sr-perrerit, landauite, rutile, anatase, brookite; TR- minerals - loparite, metaloparite, britolite, rinkolite, melanocerite, bastnesite, parisite, ankilite, monazite, fluocerite, TR-apatite; Nb- minerals - pyrochlore, loparite. Other rare minerals leucophanite, hambergite, pyrochlore, betafite, torite, thorianite, tayniolite, brewsterite, cryolite and others. We have proposed a new scheme massif: shonkinites - nepheline syenites - alkaline syenite - quartz syenites - veined rocks: mariupolites, rare-metal pegmatites, apatite, fluorite rock alyaskite and alkaline granites and carbonatites (Sotnikova, 2009). Apatite-fluorite rocks are found in the central part of massif. This is a large vein body of 2 km length and a 20 m width cutting prevailing pulaskites. Previously, these rocks were regarded as hydrothermal low-temperature phase. New geological and thermobarometric evidence suggests that apatite-fluorite rocks were formed from the residual fluid-melt, separated after crystallization of rare-metal pegmatites. Petrochemical and geochemical data Burpalinsky are in accord of general trend of crystal differentiation of alkaline magma containing small concentrations of CO2 and higher P2O5 and F, which accumulated significantly separated from the pegmatite melts. In some pegmatites fluorite with rare-metal minerals (flyuocerit etc) are separating in schlieren. Apatite-fluorite rocks are cut by leucogranite dyke, having genetic connection with rare-metal pegmatites. Late granitic phases has its own association of rare-metal minerals described by A.A. Ganzeev (1972). Thermobarometric geochemical study of apatite-fluorite rocks Burpala massif found a large number of primary fluid inclusions (15-50 micrometers). Thermal and cryometric research of 60 individual fluid inclusions in fluorite showed the domination of Na, Ca, Mg chlorides and high temperatures salt inclusions in fluorites (above 550C) and melt inclusions in apatites (800C). Apatite-fluorite rocks in massif are similar to foskorites in carbonatite complexes, with similar high Ca content, but instead fluorite, together with other "foskoritovymi" minerals - apatite, magnetite, mica, and pyroxene were formed instead for calcite. Isotopic studies (Sr-Nd) indicate the mantle source of primary magma Burpala massif close to EM-2, which is characteristic of alkaline intrusions in the folded belts (Vladykin 2009). RBRF grant 14-45-04057

Polyphase vein mineralization in the Fennoscandian Shield at Åkerlandet, Järvsand, and Laisvall along the erosional front of the Caledonian orogen, Sweden

NASA Astrophysics Data System (ADS)

Saintilan, Nicolas J.; Stephens, Michael B.; Spikings, Richard; Schneider, Jens; Chiaradia, Massimo; Spangenberg, Jorge E.; Ulianov, Alexey; Fontboté, Lluís

2017-08-01

The Åkerlandet, Järvsand, and Laisvall deposits in Sweden are calcite-fluorite-sulfide vein deposits and occurrences located close to the current erosional front of the Caledonian orogen and hosted by crystalline basement rocks in the Fennoscandian Shield. At Laisvall, basement-hosted veinlets occur beneath Ediacaran to Cambrian sandstones that host a strata-bound Pb-Zn deposit. The mineralized fractures at Åkerlandet and Järvsand occur along fault systems oriented N-S to NNW-SSE. Veins or veinlets strike NNW-SSE and NW-SE at Åkerlandet, NNE-SSW at Järvsand, and NNW-SSE and NNE-SSW to NE-SW at Laisvall. At Åkerlandet and Järvsand, fractures acted as conduits for hydrothermal fluids of variable composition and formed during separate tectonic events. At Åkerlandet, the fault zone with NNW-SSE strike shows kinematic indicators consistent with NE-SW bulk horizontal extension. At Järvsand, the calcite-fluorite-galena veins formed along R-Riedel shears related to the host N-S to NNW-SSE fault system. The kinematic indicators are consistent with NW-SE bulk horizontal extension, similar to the extensional deformation during the later part of the Caledonian orogeny (Silurian to Devonian). At Åkerlandet, adularia-quartz deposition was followed by sphalerite ± galena and finally by precipitation of fluorite and calcite. 40Ar-39Ar thermochronology of a single adularia sample did not yield a well-defined plateau age but the gas released at higher temperatures suggests an early Tonian (980 to 950 Ma) crystallization age, i.e., during the later part of the Sveconorwegian orogeny, although the data do not exclude other less likely interpretations. Previous fluid inclusion microthermometry and geochronological studies and new petrographic and geochemical results suggest that sphalerite ± galena mineralization formed from saline, relatively oxidizing, moderate-temperature, and slightly acidic hydrothermal fluids, either during the Ediacaran or the Middle Ordovician. Metals and H2S were derived from local basement rocks. Based on petrographic evidence, rare earth element composition, and S, C, and O isotope data, fluorite and calcite precipitated under near neutral and relatively reducing conditions. Occurrence of solid bitumen in veins at Åkerlandet and C and O isotope data of calcite at Åkerlandet and in the Laisvall basement veinlets suggest that the precipitation of calcite and fluorite was triggered by interaction of hot and evolved hydrothermal fluids (87Sr/86Sr = 0.718-0.732) with organic matter. Structural, petrographic, and geochemical data at Laisvall suggest that the basement structures hosting calcite-fluorite ± pyrite veinlets were utilized in the Middle Ordovician as the plumbing system for the oxidizing, slightly acidic, metal-bearing brines that caused the economic Pb-Zn mineralization in the overlying sandstones.

Superhyperfine Structure of the EPR Spectra of Nd3+ Impurity Ions in Fluorite CaF2

NASA Astrophysics Data System (ADS)

Aminov, L. K.; Gafurov, M. R.; Kurkin, I. N.; Malkin, B. Z.; Rodionov, A. A.

2018-05-01

EPR spectra of a CaF2 single crystal that was grown from melt containing a small addition of NdF3 were studied. Signals corresponding to tetragonal centers of Nd3+ ions and cubic centers of Er3+ and Yb3+ ions were found. Superhyperfine structure (SHFS) in the spectra of the Nd3+ ions was observed for the first time in this crystal; parameters of the superhyperfine interaction of the Nd3+ ions with the nearest nine fluorine ions were determined. The dependence of the resolution of the Nd3+ EPR spectrum SHFS on the incident microwave power at the temperature of T ≈ 6 K was studied. Obtained results are discussed and compared with the literature data.

Fluid inclusion study of some Sarrabus fluorite deposits, Sardinia, Italy.

USGS Publications Warehouse

Belkin, H.E.; de Vivo, B.; Valera, R.

1984-01-01

Fluid inclusions in six deposits of fluorite fracture fillings associated with Hercynian (Carboniferous) cycle magmatism were studied by microthermometric techniques. All the inclusions were liquid dominated, aqueous, and homogenized in the liquid phase. One-phase (liquid), two-phase (liquid + vapour) and three-phase (liquid, vapour, and solid NaCl daughter mineral) fluid inclusions were noted. This study indicates that five of the fluorite deposits formed from 95o-125oC fluids with approx 15 wt.% NaCl. One other deposit appears to have been formed by very dilute solutions at approx 125oC. It is suggested that the local fluorite-forming process was the formation of fracture-localized hydrothermal systems in which magmatic water interaction with some other fluid-connate, meteoric, or marine.-G.J.N.

A hydrothermal system associated with the Siljan impact structure, Sweden--implications for the search for fossil life on Mars.

PubMed

Hode, Tomas; von Dalwigk, Ilka; Broman, Curt

2003-01-01

The Siljan ring structure (368 +/- 1.1 Ma) is the largest known impact structure in Europe. It isa 65-km-wide, eroded, complex impact structure, displaying several structural units, including a central uplifted region surrounded by a ring-shaped depression. Associated with the impact crater are traces of a post-impact hydrothermal system indicated by precipitated and altered hydrothermal mineral assemblages. Precipitated hydrothermal minerals include quartz veins and breccia fillings associated with granitic rocks at the outer margin of the central uplift, and calcite, fluorite, galena, and sphalerite veins associated with Paleozoic carbonate rocks located outside the central uplift. Two-phase water/gas and oil/gas inclusions in calcite and fluorite display homogenization temperatures between 75 degrees C and 137 degrees C. With an estimated erosional unloading of approximately 1 km, the formation temperatures were probably not more than 10-15 degrees C higher. Fluid inclusion ice-melting temperatures indicate a very low salt content, reducing the probability that the mineralization was precipitated during the Caledonian Orogeny. Our findings suggest that large impacts induce low-temperature hydrothermal systems that may be habitats for thermophilic organisms. Large impact structures on Mars may therefore be suitable targets in the search for fossil thermophilic organisms.

Surface-structure-controlled sectoral zoning of the rare earth elements in fluorite from Long Lake, New York, and Bingham, New Mexico, USA

NASA Astrophysics Data System (ADS)

Bosze, Stephanie; Rakovan, John

2002-03-01

The concentration and distribution of rare earth elements (REE) in sectorally zoned fluorite crystals from Long Lake, New York, and the Hansonburg Mining District, Bingham, New Mexico, have been studied using cathodoluminescence and synchrotron X-ray fluorescence microanalysis (SXRFMA). In cubo-octahedral samples from Long Lake, New York, Ce, Nd, Gd, Dy, Ho, Er, and Tm are preferentially partitioned into the |111| sector relative to the |100| sector. Partition coefficients (K d = concentration in |111| sector/concentration in |100| sector) range between 3.5 for Ce, to 1.4 for Tm, with a general decrease in K d as elements deviated from the ionic radius of Ca 2+, for which REE substitute in fluorite. Diffusion of the REE has occurred, as evidenced by gradual changes in composition over distances of 0.2 to 0.3 mm at sector boundaries. In Bingham samples, three different partition coefficients were determined for Dy: K d|100|/|111| = 2.83, K d |100|/|110| = 1.77, and K d |110|/|111| = 1.60. These are mean K d values for a 95% confidence interval. In another sample from the same deposit, Dy, Er, and Gd were found to be preferentially incorporated into the |100| sector relative to the |210| sector with average K d |100|/|210| of 3.1, 2.4, and 2.9, respectively. In a third sample, Nd was found to be preferentially incorporated into the |110| sector relative to the |321| sector with an average K d |110|/|321| value of 2.3. Compositional heterogeneities in a given sector (concentric zoning) have been resolved using SXRFMA but are significantly less than the concentration difference across sector boundaries. Often fluorite exists in a wide variety of morphologies, as is the case in the Hansonburg Mining District of Bingham. We suggest caution when using the REE as petrogenetic indicators because fluorite trace element chemistry can vary greatly among crystals within a deposit depending on the internal morphology of a particular crystal.

Phase Behavior and Equations of State of the Actinide Oxides

NASA Astrophysics Data System (ADS)

Chidester, B.; Pardo, O. S.; Panero, W. R.; Fischer, R. A.; Thompson, E. C.; Heinz, D. L.; Prescher, C.; Prakapenka, V. B.; Campbell, A.

2017-12-01

The distribution of the long-lived heat-producing actinide elements U and Th in the deep Earth has important implications for the dynamics of the mantle and possibly the energy budget of Earth's core. The low shear velocities of the Large Low-Shear Velocity Provinces (LLSVPs) on the core-mantle boundary suggests that these regions are at least partially molten and may contain concentrated amounts of the radioactive elements, as well as other large cations such as the rare Earth elements. As such, by exploring the phase behavior of actinide-bearing minerals at extreme conditions, some insight into the mineralogy, formation, and geochemical and geodynamical effects of these regions can be gained. We have performed in situ high-pressure, high-temperature synchrotron X-ray diffraction experiments and calculations on two actinide oxide materials, UO2 and ThO2, to determine their phase behavior at the extreme conditions of the lower mantle. Experiments on ThO2 reached 60 GPa and 2500 K, and experiments on UO2 reached 95 GPa and 2500 K. We find that ThO2 exists in the fluorite-type structure to 20 GPa at high temperatures, at which point it transforms to the high-pressure cotunnite-type structure and remains thus up to 60 GPa. At room temperature, an anomalous expansion of the fluorite structure is observed prior to the transition, and may signal anion sub-lattice disorder. Similarly, UO2 exists in the fluorite-type structure at ambient conditions and up to 28 GPa at high temperatures. Above these pressures, we have observed a previously unidentified phase of UO2 with a tetragonal structure as the lower-temperature phase and the cotunnite-type phase at higher temperatures. Above 78 GPa, UO2 undergoes another transition or possible dissociation into two separate oxide phases. These phase diagrams suggest that the actinides could exist as oxides in solid solution with other analogous phases (e.g. ZrO2) in the cotunnite-type structure throughout much of Earth's lower mantle.

Accelerator-based analytical technique in the evaluation of some Nigeria’s natural minerals: Fluorite, tourmaline and topaz

NASA Astrophysics Data System (ADS)

Olabanji, S. O.; Ige, O. A.; Mazzoli, C.; Ceccato, D.; Akintunde, J. A.; De Poli, M.; Moschini, G.

2005-10-01

For the first time, the complementary accelerator-based analytical technique of PIXE and electron microprobe analysis (EMPA) were employed for the characterization of some Nigeria's natural minerals namely fluorite, tourmaline and topaz. These minerals occur in different areas in Nigeria. The minerals are mainly used as gemstones and for other scientific and technological applications and therefore are very important. There is need to characterize them to know the quality of these gemstones and update the geochemical data on them geared towards useful applications. PIXE analysis was carried out using the 1.8 MeV collimated proton beam from the 2.5 MV AN 2000 Van de Graaff accelerator at INFN, LNL, Legnaro, Padova, Italy. The novel results which show many elements at different concentrations in these minerals are presented and discussed.

Studies on phase transition temperature of rare earth niobates Ln3NbO7 (Ln = Pr, Sm, Eu) with orthorhombic fluorite-related structure

NASA Astrophysics Data System (ADS)

Hinatsu, Yukio; Doi, Yoshihiro

2017-06-01

The phase transition of ternary rare earth niobates Ln3NbO7 (Ln = Pr, Sm, Eu) was investigated by the measurements of high-temperature and low-temperature X-ray diffraction, differential scanning calorimetry (DSC) and differential thermal analysis (DTA). These compounds crystallize in an orthorhombic superstructure derived from the structure of cubic fluorite (space group Pnma for Ln = Pr; C2221 for Ln = Sm, Eu). Sm3NbO7 undergoes the phase transition when the temperature is increased through ca. 1080 K and above the transition temperature, its structure is well described with space group Pnma. For Eu3NbO7, the phase transition was not observed up to 1273 K Pr3NbO7 indicates the phase transition when the temperature is increased through ca. 370 K. The change of the phase transition temperature against the Ln ionic radius for Ln3NbO7 is quite different from those for Ln3MO7 (M = Mo, Ru, Re, Os, or Ir), i.e., no systematic relationship between the phase transition temperature and the Ln ionic radius has been observed for Ln3NbO7 compounds.

Decomposition of L a2 -xS rxCu O4 into several L a2O3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

NASA Astrophysics Data System (ADS)

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; Yu, Guichuan; Sasagawa, Takao; Greven, Martin; Mkhoyan, K. Andre

2018-05-01

We report the decomposition of L a2 -xS rxCu O4 into L a2O3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150 °C and is considerably expedited in the temperature range of 350 °C-450 °C. Two major resultant solid phases are identified as metallic Cu and L a2O3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, L a2O3 phases are further identified to be derivatives of a fluorite structure—fluorite, pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and La M4 ,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and L a2O3 phases remain unchanged after cooling to room temperature.

Fluorite solubility equilibria in selected geothermal waters

USGS Publications Warehouse

Nordstrom, D. Kirk; Jenne, E.A.

1977-01-01

Calculation of chemical equilibria in 351 hot springs and surface waters from selected geothermal areas in the western United States indicate that the solubility of the mineral fluorite, CaF2, provides an equilibrium control on dissolved fluoride activity. Waters that are undersaturated have undergone dilution by non-thermal waters as shown by decreased conductivity and temperature values, and only 2% of the samples are supersaturated by more than the expected error. Calculations also demonstrate that simultaneous chemical equilibria between the thermal waters and calcite as well as fluorite minerals exist under a variety of conditions. Testing for fluorite solubility required a critical review of the thermodynamic data for fluorite. By applying multiple regression of a mathematical model to selected published data we have obtained revised estimates of the pK (10,96), ??Gof (-280.08 kcal/mole), ??Hof (-292.59 kcal/mole), S?? (16.39 cal/deg/mole) and CoP (16.16 cal/deg/mole) for CaF2 at 25??C and 1 atm. Association constants and reaction enthalpies for fluoride complexes with boron, calcium and iron are included in this review. The excellent agreement between the computer-based activity products and the revised pK suggests that the chemistry of geothermal waters may also be a guide to evaluating mineral solubility data where major discrepancies are evident. ?? 1977.

Oxygen disorder, a way to accommodate large epitaxial strains in oxides

DOE PAGES

Zhang, Yu Yang; Mishra, Rohan; Pennycook, Timothy J.; ...

2015-09-22

Density-functional calculations (total-energy comparisons) and checks for negative-frequency phonon modes are employed as a stability indicator to show that, in rutile- and fluorite-structure oxides, e.g., zirconia strained by a strontium titanate substrate, oxygen-sublattice disorder can be the energetically preferred way to accommodate strain.

XRD monitoring of α self-irradiation in uranium-americium mixed oxides.

PubMed

Horlait, Denis; Lebreton, Florent; Roussel, Pascal; Delahaye, Thibaud

2013-12-16

The structural evolution under (241)Am self-irradiation of U(1-x)Am(x)O(2±δ) transmutation fuels (with x ≤ 0.5) was studied by X-ray diffraction (XRD). Samples first underwent a preliminary heat treatment performed under a reducing atmosphere (Ar/H2(4%)) aiming to recover the previously accumulated structural defects. Over all measurements (carried out over up to a full year and for integrated doses up to 1.5 × 10(18) α-decay events·g(-1)), only fluorite U(1-x)Am(x)O(2±δ) solid solutions were observed. Within a few days after the end of the heat treatment, each of the five studied samples was slowly oxidized as a consequence of their move to air atmosphere, which is evidenced by XRD by an initial sharp decrease of the unit cell parameter. For the compounds with x ≤ 0.15, this oxidation occurred without any phase transitions, but for U0.6Am0.4O(2±δ) and U0.5Am0.5O(2±δ), this process is accompanied by a transition from a first fluorite solid solution to a second oxidized one, as the latter is thermodynamically stable in ambient conditions. In the meantime and after the oxidation process, (241)Am α self-irradiation caused a structural swelling up to ∼0.8 vol %, independently of the sample composition. The kinetic constants of swelling were also determined by regression of experimental data and are, as expected, dependent on x and thus on the dose rate. The normalization of these kinetic constants by sample α-activity, however, leads to very close swelling rates among the samples. Finally, evolutions of microstrain and crystallite size were also monitored, but for the considered dose rates and cumulated doses, α self-irradiation was found, within the limits of the diffractometer used, to have almost no impact on these characteristics. Microstrain was found to be influenced instead by the americium content in the materials (i.e., by the impurities associated with americium starting material and the increase of cationic charge heterogeneity with increasing americium content).

Fast oxygen diffusion in bismuth oxide probed by quasielastic neutron scattering

DOE PAGES

Mamontov, Eugene

2016-09-24

In this paper, we present the first, to our knowledge, study of solid state oxygen translational diffusion by quasielastic neutron scattering. Such studies in the past might have been precluded by relatively low diffusivities of oxygen anions in the temperature range amenable to neutron scattering experiments. To explore the potential of the quasielastic scattering technique, which can deduce atomic diffusion jump length of oxygen anions through the momentum transfer dependence of the scattering signal, we have selected the fastest known oxygen conductor, bismuth oxide. Finally, we have found the oxygen anion jump length in excellent agreement with the nearest oxygen-vacancymore » distance in the anion sublattice of the fluorite-related structure of bismuth oxide.« less

Preparation and characterization of a possible topological insulator BiYO3: experiment versus theory.

PubMed

Zhang, Y; Deng, S; Pan, M; Lei, M; Kan, X; Ding, Y; Zhao, Y; Köhler, J

2016-03-21

The Bi-Y-O system has been investigated by X-ray powder diffraction, electron diffraction, UV-vis and IR experiments. A metastable cubic high temperature phase of BiYO3 with fluorite-type structure has been structurally characterized for the first time and shows a large band gap of ∼ 5.9 eV. A unified description for the numerous structural variants discovered in the Bi-Y-O system is established within the symmetry breaking approach. This rich structural phenomenon makes the Bi-Y-O system a promising candidate in the search for new topological insulators for applications. On this basis, a long standing controversy on the phase diagram of the Bi-Y-O system has been solved. Our DFT calculations predict a high pressure phase for BiYO3 with perovskite (ABO3) structure and ordering of Bi and Y on the A and B sites, respectively. However, our analysis of the nature of the low energy electronic structure shows that this phase is not a suitable candidate for a topological insulator.

Mechanical, lattice dynamical and electronic properties of CeO2 at high pressure: First-principles studies

NASA Astrophysics Data System (ADS)

Li, Mei; Jia, Huiling; Li, Xueyan; Liu, Xuejie

2016-01-01

The elastic constants (Cij), bulk modulus (B), shear modulus (G) and elastic modulus (E) of cubic fluorite CeO2 under high pressure have been studied using the plane-wave pseudopotential method based on density functional theory. The calculated results show that the mechanical properties (Cij, B, G and E) of CeO2 increase with increasing pressure, and the phase transition of CeO2 occurs beyond the pressure of 130 GPa. From the calculated phonon spectrum using Parlinsk-Li-Kawasoe method, we found that CeO2 appears imaginary frequency at 140 GPa, which indicates phase transition. The energy band, density of states and charge density of CeO2 under high pressure are calculated using GGA+U method. It is found that the high pressure makes the electron delocalization and Ce-O covalent bonding enhanced. As pressure increases, the band gap between O2p and Ce4f states near the Fermi level increases, and CeO2 nonmetallic nature promotes. The present research results in a better understanding of how CeO2 responds to compression.

Synthesis, crystal structures and ionic conductivities of Bi{sub 14}P{sub 4}O{sub 31} and Bi{sub 50}V{sub 4}O{sub 85}. Two members of the series Bi{sub 18-4m}M{sub 4m}O{sub 27+4m} (M=P, V) related to the fluorite-type structure

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

Mauvy, F.; Launay, J.C.; Darriet, J.

2005-06-15

The two hitherto unknown compounds Bi{sub 14}P{sub 4}O{sub 31} and Bi{sub 50}V{sub 4}O{sub 85} were prepared by the direct solid-state reaction of Bi{sub 2}O{sub 3} and (NH{sub 4})H{sub 2}PO{sub 4} or V{sub 2}O{sub 5}, respectively. Bi{sub 14}P{sub 4}O{sub 31} crystallizes in a C-centred monoclinic symmetry (C2/c space group) with the unit-cell parameters: a=19.2745(2)A, b=11.3698(1)A, c=52.4082(2)A and {beta}=93.63(1){sup o} (Z=16). The symmetry of Bi{sub 50}V{sub 4}O{sub 85} is also monoclinic (I2/m space group) with lattice parameters of a=11.8123(3)A, b=11.7425(2)A, c=16.5396(2)A and {beta}=90.14(1){sup o} (Z=2). Both structures correspond to a fluorite-type superstructure where the Bi and P or V atoms are orderedmore » in the framework. An idealized structural model is proposed where the structures result of the stacking of mixed atomic layers of composition [Bi{sub 14}M{sub 4}O{sub 31}] and [Bi{sub 18}O{sub 27}] respectively. This new family can be formulated Bi{sub 18-4m}M{sub 4m}O{sub 27+4m} with M=P, V and where the parameter m (0=

Decomposition of L a 2 – x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

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

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet

Here, we report the decomposition of La 2–xSr xCuO 4 into La 2O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2O 3 phases are further identified to be derivatives of a fluorite structure—fluorite,more » pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2O 3 phases remain unchanged after cooling to room temperature.« less

Decomposition of L a 2 – x S r x Cu O 4 into several L a 2 O 3 phases at elevated temperatures in ultrahigh vacuum inside a transmission electron microscope

DOE PAGES

Jeong, Jong Seok; Wu, Wangzhou; Topsakal, Mehmet; ...

2018-05-15

Here, we report the decomposition of La 2–xSr xCuO 4 into La 2O 3 and Cu nanoparticles in ultrahigh vacuum, observed by in situ heating experiments in a transmission electron microscope. The analysis of electron diffraction data reveals that the phase decomposition process starts at about 150°C and is considerably expedited in the temperature range of 350°C–450°C. Two major resultant solid phases are identified as metallic Cu and La 2O 3 by electron diffraction, simulation, and electron energy-loss spectroscopy (EELS) analyses. With the aid of calculations, La 2O 3 phases are further identified to be derivatives of a fluorite structure—fluorite,more » pyrochlore, and (distorted) bixbyite—characterized by different oxygen-vacancy order. Additionally, the bulk plasmon energy and the fine structures of the O K and LaM 4,5 EELS edges are reported for these structures, along with simulated O K x-ray absorption near-edge structure. The resultant Cu nanoparticles and La 2O 3 phases remain unchanged after cooling to room temperature.« less

Polyphase enrichment and redistribution processes in silver-rich mineral associations of the hydrothermal fluorite-barite-(Ag-Cu) Clara deposit, SW Germany

NASA Astrophysics Data System (ADS)

Keim, Maximilian F.; Walter, Benjamin F.; Neumann, Udo; Kreissl, Stefan; Bayerl, Richard; Markl, Gregor

2018-03-01

The silver-copper sulfide mineralization associated with the fluorite-barite vein system at the Clara deposit in SW Germany shows large scale vertical zoning. Low to moderate silver contents prevail in the upper 350 m, whereas high silver contents occur in the subsequent 450 m of the currently known vein system. This change in Ag tenor is related to conspicuous mineralogical changes with depth. A detailed petrographic and fluid inclusion study identifies evidence for five subsequent hydrothermal and one alteration stage—all contributing to mineralogical diversity. The vertical Ag zoning, however, is attributed only to the first of these stages. During this first stage, increasing oxidation of ascending hydrothermal fluids (90-160 °C, 24.2-26.7 wt% NaCl+CaCl2) led to the formation of high-Ag tetrahedrite-tennantite in the lower parts and basically Ag-free enargite in the upper parts of the vein system. The subsequent hydrothermal stage led to significant mineralogical changes, but inherited the pre-existing Ag zonation. In this second hydrothermal stage, which was related to fluids similar in composition to those of the first stage (70-125 °C, 23.1-26.5 wt% NaCl+CaCl2), dissolution of high Ag-tetrahedrite-tennantite resulted in the formation of complex Ag-sulfosalts together with moderately Ag-bearing tetrahedrite-tennantite and chalcopyrite. The first two stages were formed by fluid mixing of a sedimentary and a hot basement fluid. The influx of fluids with high Ag, Bi and Pb activity during stage 3 and 5 resulted in the local replacement of earlier Ag-sulfosalts by galena and Ag-(Bi)-sulfosalts. The fourth stage is marked by partial dissolution of sulfides and sulfosalts by a late, hot, undiluted basement fluid (250 °C, 18.7-20.9 wt% NaCl+CaCl2) precipitating fluorite, barite and quartz. Finally, supergene alteration lead to the dissolution of silver-bearing phases and the precipitation of acanthite and native silver. The study illustrates, how metal tenor and mineralogy are decoupled in vertically extensive, polyphase hydrothermal vein systems. This may be pertinent to similarly zoned polymetallic vein systems.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, W.; Flytzani-Stephanopoulos, M.

1996-03-19

A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Composite catalyst for carbon monoxide and hydrocarbon oxidation

DOEpatents

Liu, Wei; Flytzani-Stephanopoulos, Maria

1996-01-01

A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

Unusual behavior of uranium dioxide at high magnetic fields. Part I

NASA Astrophysics Data System (ADS)

Gofryk, K.; Jaime, M.; Zapf, V.; Harrison, N.; Saul, A.; Radtke, G.; Lashley, J. C.; Salamon, M.; Andersson, A. D.; Stanek, C.; Durakiewicz, T.; Smith, J. L.

UO2 is a Mott-Hubbard insulator with well-localized 5 f-electrons and its crystal structure is the face-centered-cubic fluorite. It experiences a first-order antiferromagnetic phase transition at 30.8 K to a non-collinear antiferromagnetic structure that remains a topic of debate. It is believed that the first order nature of the transition results from the competition between the exchange interaction and the Jahn-Teller distortion of oxygen atoms. Despite extensive experimental and theoretical efforts the nature of the competing degrees of freedom and their couplings (such as spin-phonon coupling) are still unclear. Here we present results of our extensive thermodynamic investigations, on well-characterized and oriented single crystals of UO2, focusing on magnetization M(T,H) measurements in DC and pulsed magnetic fields to up 65 T at the NHMFL. Work supported by the Department of Energy, Office of Basic Energy Sciences, Materials Sciences, and Engineering Division. The NHMFL Pulsed Field Facility is supported by the NSF, the U.S. D.O.E., and the State of Florida through NSF cooperative Grant DMR.

Single crystals of the fluorite nonstoichiometric phase Eu{0.916/2+}Eu{0.084/3+}F2.084 (conductivity, transmission, and hardness)

NASA Astrophysics Data System (ADS)

Sobolev, B. P.; Turkina, T. M.; Sorokin, N. I.; Karimov, D. N.; Komar'kova, O. N.; Sulyanova, E. A.

2010-07-01

The nonstoichiometric phase EuF2+ x has been obtained via the partial reduction of EuF3 by elementary Si at 900-1100°C. Eu{0.916/2+}Eu{0.084/3+}F2.084 (EuF2.084) single crystals have been grown from melt by the Bridgman method in a fluorinating atmosphere. These crystals belong to the CaF2 structure type (sp. gr. Fm bar 3 m) with the cubic lattice parameter a = 5.8287(2) Å, are transparent in the spectral range of 0.5-11.3 μm, and have microhardness H μ = 3.12 ± 0.13 GPa and ionic conductivity σ = 1.4 × 10-5 S/cm at 400°C with the ion transport activation energy E a = 1.10 ± 0.05 eV. The physicochemical characteristics of the fluorite phases in the EuF2 - EuF3 systems are similar to those of the phases in the SrF2 - EuF3 and SrF2 - GdF3 systems due to the similar lattice parameters of the EuF2 and SrF2 components. Europium difluoride supplements the list of fluorite components MF2 ( M = Ca, Sr, Ba, Cd, Pb), which are crystal matrices for nonstoichiometric (nanostructured) fluoride materials M 1 - x R x F2 + x ( R are rare earth elements).

Dependences of the density of M 1- x R x F2 + x and R 1- y M y F3- y single crystals ( M = Ca, Sr, Ba, Cd, Pb; R means rare earth elements) on composition

NASA Astrophysics Data System (ADS)

Sorokin, N. I.; Krivandina, E. A.; Zhmurova, Z. I.

2013-11-01

The density of single crystals of nonstoichiometric phases Ba1 - x La x F2 + x (0 ≤ x ≤ 0.5) and Sr0.8La0.2 - x Lu x F2.2 (0 ≤ x ≤ 0.2) with the fluorite (CaF2) structure type and R 1 - y Sr y F3 - y ( R = Pr, Nd; 0 ≤ y ≤ 0.15) with the tysonite (LaF3) structure type has been measured. Single crystals were grown from a melt by the Bridgman method. The measured concentration dependences of single crystal density are linear. The interstitial and vacancy models of defect formation in the fluorite and tysonite phases, respectively, are confirmed. To implement the composition control of single crystals of superionic conductors M 1 - x R x F2 + x and R 1 - y M y F3 - y in practice, calibration graphs of X-ray density in the MF2- RF3 systems ( M = Ca, Sr, Ba, Cd, Pb; R = La-Lu, Y) are plotted.

A geochemical study of the Sweet Home Mine, Colorado Mineral Belt, USA: hydrothermal fluid evolution above a hypothesized granite cupola

NASA Astrophysics Data System (ADS)

Lüders, Volker; Romer, Rolf L.; Gilg, H. Albert; Bodnar, Robert J.; Pettke, Thomas; Misantoni, Dean

2009-05-01

Deposition of quartz-molybdenite-pyrite-topaz-muscovite-fluorite and subsequent hübnerite and sulfide-fluorite-rhodochrosite mineralization at the Sweet Home Mine occurred coeval with the final stage of magmatic activity and ore formation at the nearby world-class Climax molybdenum deposit about 26 to 25 m.y. ago. The mineralization occurred at depths of about 3,000 m and is related to at least two major fluid systems: (1) one dominated by magmatic fluids, and (2) another dominated by meteoric water. The sulfur isotopic composition of pyrite, strontium isotopes and REY distribution in fluorite suggest that the early-stage quartz-molybdenite-pyrite-topaz-muscovite-fluorite mineral assemblage was deposited from magmatic fluids under a fluctuating pressure regime at temperatures of about 400°C as indicated by CO2-bearing, moderately saline (7.5-12.5 wt.% NaCl equiv.) fluid inclusions. LA-ICPMS analyses of fluid inclusions in quartz demonstrate that fluids from the Sweet Home Mine are enriched in incompatible elements but have considerably lower metal contents than those reported from porphyry-Cu-Au-Mo or Climax-type deposits. The ore-forming fluid exsolved from a highly differentiated magma possibly related to the deep-seated Alma Batholith or distal porphyry stock(s). Sulfide mineralization, marking the periphery of Climax-type porphyry systems, with fluorite and rhodochrosite as gangue minerals was deposited under a hydrostatic pressure regime from low-salinity ± CO2-bearing fluids with low metal content at temperatures below 400°C. The sulfide mineralization is characterized by mostly negative δ34S values for sphalerite, galena, chalcopyrite, and tetrahedrite, highly variable δ18O values for rhodochrosite, and low REE contents in fluorite. The Pb isotopic composition of galena as well as the highly variable 87Sr/86Sr ratios of fluorite, rhodochrosite, and apatite indicates that at least part of the Pb and Sr originated from a much more radiogenic source than Climax-type granites. It is suggested that the sulfide mineralization at the Sweet Home Mine formed from magmatic fluids that mixed with variable amounts of externally derived fluids. The migration of the latter fluids, that were major components during late-stage mineralization at the Sweet Home Mine, was probably driven by a buried magmatic intrusion.

Swift-heavy ion irradiation response and annealing behavior of A2TiO5 (A = Nd, Gd, and Yb)

NASA Astrophysics Data System (ADS)

Park, Sulgiye; Tracy, Cameron L.; Zhang, Fuxiang; Palomares, Raul I.; Park, Changyong; Trautmann, Christina; Lang, Maik; Mao, Wendy L.; Ewing, Rodney C.

2018-02-01

The structural responses of A2BO5 (A = Nd, Gd, and Yb; B = Ti) compositions irradiated by high-energy Au ions (2.2 GeV) were investigated using transmission electron microscopy, synchrotron X-ray diffraction and Raman spectroscopy. The extent of irradiation-induced amorphization depends on the size of the A-site cation, with smaller lanthanides having less susceptibility to the accumulation of radiation damage. In the track-overlapping regime, complete amorphization is observed in all three compounds, despite the ability of Yb2TiO5 to incorporate a great deal of structural disorder into its initial defect-fluorite structure (Fm-3m). This is attributed to the high cation radius ratio (A:B = 2:1), which reduces the stability of the structure upon ion irradiation. The fully-amorphized samples were subsequently isochronally heated at temperature intervals from 100 °C to 850 °C. X-ray diffraction analysis indicated a similar damage recovery process in Nd2TiO5 and Gd2TiO5, where both compositions recover their original structures (Pnma) at 850 °C. In contrast, Yb2TiO5 exhibited recrystallization of a metastable, non-equilibrium orthorhombic phase at 550 °C, prior to a transformation to the stable defect-fluorite phase (Fm-3m) at 625 °C. These compositional variations in radiation tolerance and thermal recovery processes are described in terms of the energetics of disordering during the damage and recrystallization processes.

C60 and U ion irradiation of Gd 2Ti xZr 2-xO 7 pyrochlore

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

Zhang, Jiaming; Toulemonde, Marcel; Lang, Maik

2015-08-01

Gd 2Ti xZr 2-xO 7 (x = 0 to 2) pyrochlore was irradiated by 30 MeV C 60 clusters, which provide an extremely high ionizing energy density. Here, high-resolution transmission electron microscopy revealed a complex ion-track structure in Gd 2Ti 2O 7 and Gd 2TiZrO 7, consisting of an amorphous core and a shell of a disordered, defect-fluorite structure.

Rietveld analysis of the cubic crystal structure of Na-stabilized zirconia

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

Fagherazzi, G.; Canton, P.; Benedetti, A.

Using x-ray Rietveld analysis the fcc (fluorite-type) structure of a Na-containing nanocrystalline zirconia powder (9.5 nm estimated of crystallite size) obtained by precipitation and subsequent calcination has been confirmed. The result shows that using conventional x-ray diffraction techniques the cubic crystallographic form of ZrO{sub 2} from the tetragonal one in nanosized powders. These conclusions are supported by the findings of independent Raman scattering experiments. {copyright} {ital 1997 Materials Research Society.}

The Crystal Structure of Thorium and Zirconium Dihydrides by X-ray and Neutron Diffraction

DOE R&D Accomplishments Database

Rundle, R.E.; Shull, C.G.; Wollan, E.O.

1951-04-20

Thorium forms a tetragonal lower hydride of composition ThH{sub 2}. The hydrides ThH{sub 2}, ThD{sub 2}, and ZrD{sub 2} have been studied by neutron diffraction in order that hydrogen positions could be determined. The hydrides are isomorphous, and have a deformed fluorite structure. Metal-hydrogen distances in thorium hydride are unusually large, as in UH{sub 3}. Thorium and zirconium scattering amplitudes and a revised scattering amplitude for deuterium are reported.

First-principles Calculations of Equilibrium Calcium Isotope Fractionation among Ca-bearing Minerals

NASA Astrophysics Data System (ADS)

Zhou, C.; Wang, W.; Kang, J.; Wu, Z.; Huang, F.

2016-12-01

Calcium isotope fractionation factors of Ca-bearing minerals are investigated with the first principle calculations based on density functional theory (DFT). The sequence of heavy Ca isotope enrichment is forsterite > grossular > butschliite > lime > fluorite > tremolite diopside > anhydrite dolomite titanite > anorthite > perovskite gehlenite aragonite richterite > akermanite > oldhamite. This order is consistent with variation of Ca-O bond lengths, indicating that Ca-O bond energy plays an overwhelming role on the fractionations of Ca isotopes. Our study provides important insights into the Ca isotopic data of meteorites. Our calculation predicts that oldhamites (CaS) are enriched in light Ca isotopes relative to silicate phase if they are in equilibrium, contrast with the observations in Valdes et al (2014). Therefore, oldhamite and silicate phase in the meteorites should be in disequilibrium for Ca isotopes. Our results can also be used to understand Ca isotopic composition of the Moon. Δ44/40Ca between olivine (with CaO content of 2.48 wt%) and diopside is up to 0.41‰ and Δ44/40Cagrossular-diopside is 0.26‰ at 1500K. Feng et al. (2014) calculated that Δ44/40Ca between opx with CaO content of 1.74 wt% and cpx is about 0.27‰ at 1500 K. According to the Lunar Magma Ocean (LMO) model, the modern Moon is chemically stratified (Snyder et al., 1992; Elardo et al., 2011). Assuming that the lower cumulate and upper residual melt are in isotopic equilibrium during the evolution of Lunar Magma Ocean where the cumulate may be mainly composed of olivine and orthopyroxene or garnet/spinel, δ44/40Ca of the Moon could be underestimated by 0.05‰ to 0.25‰ if the shallow lunar samples are used to represent the bulk Moon.

Optimization of ionic conductivity in doped ceria

PubMed Central

Andersson, David A.; Simak, Sergei I.; Skorodumova, Natalia V.; Abrikosov, Igor A.; Johansson, Börje

2006-01-01

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy–dopant interactions, represented by association (binding) energies of vacancy–dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately. PMID:16478802

Optimization of ionic conductivity in doped ceria.

PubMed

Andersson, David A; Simak, Sergei I; Skorodumova, Natalia V; Abrikosov, Igor A; Johansson, Börje

2006-03-07

Oxides with the cubic fluorite structure, e.g., ceria (CeO2), are known to be good solid electrolytes when they are doped with cations of lower valence than the host cations. The high ionic conductivity of doped ceria makes it an attractive electrolyte for solid oxide fuel cells, whose prospects as an environmentally friendly power source are very promising. In these electrolytes, the current is carried by oxygen ions that are transported by oxygen vacancies, present to compensate for the lower charge of the dopant cations. Ionic conductivity in ceria is closely related to oxygen-vacancy formation and migration properties. A clear physical picture of the connection between the choice of a dopant and the improvement of ionic conductivity in ceria is still lacking. Here we present a quantum-mechanical first-principles study of the influence of different trivalent impurities on these properties. Our results reveal a remarkable correspondence between vacancy properties at the atomic level and the macroscopic ionic conductivity. The key parameters comprise migration barriers for bulk diffusion and vacancy-dopant interactions, represented by association (binding) energies of vacancy-dopant clusters. The interactions can be divided into repulsive elastic and attractive electronic parts. In the optimal electrolyte, these parts should balance. This finding offers a simple and clear way to narrow the search for superior dopants and combinations of dopants. The ideal dopant should have an effective atomic number between 61 (Pm) and 62 (Sm), and we elaborate that combinations of Nd/Sm and Pr/Gd show enhanced ionic conductivity, as compared with that for each element separately.

Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

NASA Astrophysics Data System (ADS)

Zhan, Chun; Yao, Zhenpeng; Lu, Jun; Ma, Lu; Maroni, Victor A.; Li, Liang; Lee, Eungje; Alp, Esen E.; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Johnson, Christopher; Thackeray, Michael M.; Chan, Maria K. Y.; Wolverton, Chris; Amine, Khalil

2017-12-01

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

[Assessment of Soil Fluorine Pollution in Jinhua Fluorite Ore Areas].

PubMed

Ye, Qun-feng; Zhou, Xiao-ling

2015-07-01

The contents of. soil total fluorine (TF) and water-soluble fluorine (WF) were measured in fluorite ore areas located in Jinhua City. The single factor index, geoaccumulation index and health risk assessment were used to evaluate fluorine pollution in soil in four fluorite ore areas and one non-ore area, respectively. The results showed that the TF contents in soils were 28. 36-56 052. 39 mg.kg-1 with an arithmetic mean value of 8 325.90 mg.kg-1, a geometric mean of 1 555. 94 mg.kg-1, and a median of 812. 98 mg.kg-1. The variation coefficient of TF was 172. 07% . The soil WF contents ranged from 0. 83 to 74. 63 mg.kg-1 with an arithmetic mean value of 16. 94 mg.kg-1, a geometric mean of 10. 59 mg.kg-1, and a median of 10. 17 mg.kg-1. The variation coefficient of WF was 100. 10%. The soil TF and WF contents were far higher than the national average level of the local fluorine epidemic occurrence area. The fluoride pollution in soil was significantly affected by human factors. Soil fluorine pollution in Yangjia, Lengshuikeng and Huajie fluorite ore areas was the most serious, followed by Daren fluorite ore area, and in non-ore area there was almost no fluorine pollution. Oral ingestion of soils was the main exposure route. Sensitivity analysis of model parameters showed that children's weight exerted the largest influence over hazard quotient. Furthermore, a significant positive correlation was found among the three kinds of evaluation methods.

Laser-excited fluorescence of rare earth elements in fluorite: Initial observations with a laser Raman microprobe

USGS Publications Warehouse

Burruss, R.C.; Ging, T.G.; Eppinger, R.G.; Samson, a.M.

1992-01-01

Fluorescence emission spectra of three samples of fluorite containing 226-867 ppm total rare earth elements (REE) were excited by visible and ultraviolet wavelength lines of an argon ion laser and recorded with a Raman microprobe spectrometer system. Narrow emission lines ( 0.9 for Eu2+ and 0.99 for Er3+. Detection limits for three micrometer spots are about 0.01 ppm Eu2+ and 0.07 ppm Er3+. These limits are less than chondrite abundance for Eu and Er, demonstrating the potential microprobe analytical applications of laser-excited fluorescence of REE in fluorite. However, application of this technique to common rock-forming minerals may be hampered by competition between fluorescence emission and radiationless energy transfer processes involving lattice phonons. ?? 1992.

Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah

USGS Publications Warehouse

Cunningham, C.G.; Rasmussen, J.D.; Steven, T.A.; Rye, R.O.; Rowley, P.D.; Romberger, S.B.; Selverstone, J.

1998-01-01

Uranium deposits containing molybdenum and fluorite occur in the Central Mining Area, near Marysvale, Utah, and formed in an epithermal vein system that is part of a volcanic/hypabyssal complex. They represent a known, but uncommon, type of deposit; relative to other commonly described volcanic-related uranium deposits, they are young, well-exposed and well-documented. Hydrothermal uranium-bearing quartz and fluorite veins are exposed over a 300 m vertical range in the mines. Molybdenum, as jordisite (amorphous MoS2, together with fluorite and pyrite, increase with depth, and uranium decreases with depth. The veins cut 23-Ma quartz monzonite, 20-Ma granite, and 19-Ma rhyolite ash-flow tuff. The veins formed at 19-18 Ma in a 1 km2 area, above a cupola of a composite, recurrent, magma chamber at least 24 ?? 5 km across that fed a sequence of 21- to 14-Ma hypabyssal granitic stocks, rhyolite lava flows, ash-flow tuffs, and volcanic domes. Formation of the Central Mining Area began when the intrusion of a rhyolite stock, and related molybdenite-bearing, uranium-rich, glassy rhyolite dikes, lifted the fractured roof above the stock. A breccia pipe formed and relieved magmatic pressures, and as blocks of the fractured roof began to settle back in place, flat-lying, concave-downward, 'pull-apart' fractures were formed. Uranium-bearing, quartz and fluorite veins were deposited by a shallow hydrothermal system in the disarticulated carapace. The veins, which filled open spaces along the high-angle fault zones and flat-lying fractures, were deposited within 115 m of the ground surface above the concealed rhyolite stock. Hydrothermal fluids with temperatures near 200??C, ??18OH2O ~ -1.5, ?? -1.5, ??DH2O ~ -130, log fO2 about -47 to -50, and pH about 6 to 7, permeated the fractured rocks; these fluids were rich in fluorine, molybdenum, potassium, and hydrogen sulfide, and contained uranium as fluoride complexes. The hydrothermal fluids reacted with the wallrock resulting in precipitation of uranium minerals. At the deepest exposed levels, wall-rocks were altered to sericite; and uraninite, coffinite, jordisite, fluorite, molybdenite, quartz, and pyrite were deposited in the veins. The fluids were progressively oxidized and cooled at higher levels in the system by boiling and degassing; iron-bearing minerals in wall rocks were oxidized to hematite, and quartz, fluorite, minor siderite, and uraninite were deposited in the veins. Near the ground surface, the fluids were acidified by condensation of volatiles and oxidation of hydrogen sulfide in near-surface, steam-heated, ground waters; wall rocks were altered to kaolinite, and quartz fluorite, and uraninite were deposited in veins. Secondary uranium minerals, hematite, and gypsum formed during supergene alteration later in the Cenozoic when the upper part of the mineralized system was exposed by erosion.

The use of fluoride as a natural tracer in water and the relationship to geological features: Examples from the Animas River Watershed, San Juan Mountains, Silverton, Colorado

USGS Publications Warehouse

Bove, D.J.; Walton-Day, K.; Kimball, B.A.

2009-01-01

Investigations within the Silverton caldera, in southwestern Colorado, used a combination of traditional geological mapping, alteration-assemblage mapping, and aqueous geochemical sampling that showed a relationship between geological and hydrologic features that may be used to better understand the provenance and evolution of the water. Veins containing fluorite, huebnerite, and elevated molybdenum concentrations are temporally and perhaps genetically associated with the emplacement of high-silica rhyolite intrusions. Both the rhyolites and the fluorite-bearing veins produce waters containing elevated concentrations of F-, K and Be. The identification of water samples with elevated F/Cl molar ratios (> 10) has also aided in the location of water draining F-rich sources, even after these waters have been diluted substantially. These unique aqueous geochemical signatures can be used to relate water chemistry to key geological features and mineralized source areas. Two examples that illustrate this relationship are: (1) surface-water samples containing elevated F-concentrations (> 1.8 mg/l) that closely bracket the extent of several small high-silica rhyolite intrusions; and (2) water samples containing elevated concentrations of F-(> 1.8 mg/ l) that spatially relate to mines or areas that contain late-stage fluorite/huebnerite veins. In two additional cases, the existence of high F-concentrations in water can be used to: (1) infer interaction of the water with mine waste derived from systems known to contain the fluorite/huebnerite association; and (2) relate changes in water quality over time at a high elevation mine tunnel to plugging of a lower elevation mine tunnel and the subsequent rise of the water table into mineralized areas containing fluorite/huebnerite veining. Thus, the unique geochemical signature of the water produced from fluorite veins indicates the location of high-silica rhyolites, mines, and mine waste containing the veins. Existence of high F-concentrations along with K and Be in water in combination with other geological evidence may be used to better understand the provenance of the water. ?? 2009 AAG/Geological Society of London.

Elasticity of fluorite at high temperatures

NASA Astrophysics Data System (ADS)

Eke, J.; Tennakoon, S.; Mookherjee, M.

2017-12-01

Fluorite (CaF2) is a simple halide with cubic space group symmetry (Fm-3m) and is often used as an internal pressure calibrant in moderate high-pressure/high-temperature experiments [1]. In order to gain insight into the elastic behavior of fluorite, we have conducted Resonant Ultrasound Spectroscopy (RUS) on a single crystal of fluorite with rectangular parallelepiped geometry. Using single crystal X-ray diffraction, we aligned the edges of the rectangular parallelepiped with [-1 1 1], [-1 1 -2], and [-1 -1 0] crystallographic directions. We conducted the RUS measurements up to 620 K. RUS spectra are influenced by the geometry, density, and the full elastic moduli tensor of the material. In our high-temperature RUS experiments, the geometry and density were constrained using thermal expansion from previous studies [2]. We determined the elasticity by minimizing the difference between observed resonance and calculated Eigen frequency using Rayleigh-Ritz method [3]. We found that at room temperature, the single crystal elastic moduli for fluorite are 170, 49, and 33 GPa for C11, C12, and C44 respectively. At room temperatures, the aggregate bulk modulus (K) is 90 GPa and the shear modulus (G) is 43 GPa. We note that the elastic moduli and sound wave velocities decrease linearly as a function of temperature with dVP /dT and dVS /dT being -9.6 ×10-4 and -5.0 ×10-4 km/s/K respectively. Our high-temperature RUS results are in good agreement with previous studies on fluorite using both Ultrasonic methods and Brillouin scattering [4,5]. Acknowledgement: This study is supported by US NSF awards EAR-1639552 and EAR-1634422. References: [1] Speziale, S., Duffy, T. S. 2002, Phys. Chem. Miner., 29, 465-472; [2] Roberts, R. B., White, G. K., 1986, J. Phys. C: Solid State Phys., 19, 7167-7172. [3] Migliori, A., Maynard, J. D., 2005, Rev. Sci. Instrum., 76, 121301. [4] Catlow, C. R. A., Comins, J. D., Germano, F. A., Harley, R. T., Hayes, W., 1978, J. Phys. C Solid State Phys., 11, 3197; [5] Jones, L. E. A., 1977, Phys. Earth Planet. Inter., 15(1), 77-89.

Swift-heavy ion irradiation response and annealing behavior of A 2TiO 5 (A = Nd, Gd, and Yb)

DOE PAGES

Park, Sulgiye; Tracy, Cameron L.; Zhang, Fuxiang; ...

2017-09-28

The structural responses of A 2BO 5 (A = Nd, Gd, and Yb; B = Ti) compositions irradiated by high-energy Au ions (2.2 GeV) were investigated using transmission electron microscopy, synchrotron X-ray diffraction and Raman spectroscopy. The extent of irradiation-induced amorphization depends on the size of the A-site cation, with smaller lanthanides having less susceptibility to the accumulation of radiation damage. In the track-overlapping regime, complete amorphization is observed in all three compounds, despite the ability of Yb 2TiO 5 to incorporate a great deal of structural disorder into its initial defect-fluorite structure (Fm-3m). This is attributed to the highmore » cation radius ratio (A:B = 2:1), which reduces the stability of the structure upon ion irradiation. The fully-amorphized samples were subsequently isochronally heated at temperature intervals from 100 °C to 850 °C. X-ray diffraction analysis indicated a similar damage recovery process in Nd 2TiO 5 and Gd 2TiO 5, where both compositions recover their original structures (Pnma) at 850 °C. In contrast, Yb2TiO5 exhibited recrystallization of a metastable, non-equilibrium orthorhombic phase at ~ 550 °C, prior to a transformation to the stable defect-fluorite phase (Fm-3m) at 625 °C. In conclusion, these compositional variations in radiation tolerance and thermal recovery processes are described in terms of the energetics of disordering during the damage and recrystallization processes.« less

Swift-heavy ion irradiation response and annealing behavior of A 2TiO 5 (A = Nd, Gd, and Yb)

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

Park, Sulgiye; Tracy, Cameron L.; Zhang, Fuxiang

The structural responses of A 2BO 5 (A = Nd, Gd, and Yb; B = Ti) compositions irradiated by high-energy Au ions (2.2 GeV) were investigated using transmission electron microscopy, synchrotron X-ray diffraction and Raman spectroscopy. The extent of irradiation-induced amorphization depends on the size of the A-site cation, with smaller lanthanides having less susceptibility to the accumulation of radiation damage. In the track-overlapping regime, complete amorphization is observed in all three compounds, despite the ability of Yb 2TiO 5 to incorporate a great deal of structural disorder into its initial defect-fluorite structure (Fm-3m). This is attributed to the highmore » cation radius ratio (A:B = 2:1), which reduces the stability of the structure upon ion irradiation. The fully-amorphized samples were subsequently isochronally heated at temperature intervals from 100 °C to 850 °C. X-ray diffraction analysis indicated a similar damage recovery process in Nd 2TiO 5 and Gd 2TiO 5, where both compositions recover their original structures (Pnma) at 850 °C. In contrast, Yb2TiO5 exhibited recrystallization of a metastable, non-equilibrium orthorhombic phase at ~ 550 °C, prior to a transformation to the stable defect-fluorite phase (Fm-3m) at 625 °C. In conclusion, these compositional variations in radiation tolerance and thermal recovery processes are described in terms of the energetics of disordering during the damage and recrystallization processes.« less

Homogeneously dispersed CeO2 nanoparticles on exfoliated hexaniobate nanosheets

NASA Astrophysics Data System (ADS)

Marques, Thalles M. F.; Strayer, Megan E.; Ghosh, Anupama; Silva, Alexandre; Ferreira, Odair P.; Fujisawa, Kazunori; Alves da Cunha, Jose R.; Abreu, Guilherme J. P.; Terrones, Mauricio; Mallouk, Thomas E.; Viana, Bartolomeu C.

2017-12-01

Hexaniobate nanosheets derived from the parent compound K4Nb6O17 have been decorated with CeO2 nanoparticles by ion exchange with aqueous cerium (IV) solution. Very homogeneous CeO2 nanoparticle decoration of the hexaniobate sheets can be achieved by this method and the resulting composites may absorb visible light. HRTEM images show that ∼3.0 nm diameter CeO2 nanoparticles adhere to hexaniobate nanosheets that are exfoliated and then restacked prior to Ce deposition. The interfacial interaction between CeO2 nanoparticles and nanosheets would be due to an electrostatic attraction mechanism. Raman and XRD measurements have given strong evidence that CeO2 nanoparticles have fluorite structure. EDS, FTIR and XPS results suggest almost complete exchange of TBA+ and K+ by Ce4+. Cerium ion exchange on the acid exchanged parent compound, H2.9K1.1Nb6O17, revealed that the extent of Ce ion exchange is much greater in case of nanosheets, which may be rationalized by the larger surface area available after exfoliation. XPS measurements show that the ratio of Ce4+/Ce3+ is around 4.4, in agreement with the formation of fluorite structure (CeO2). Thus, these CeO2 nanoparticle/nanosheet composites may be useful for catalytic processes.

The potential role of magmatic gases in the genesis of Illinois- Kentucky fluorspar deposits: implications from chemical reaction path modeling

USGS Publications Warehouse

Plumlee, G.S.; Goldhaber, M.B.; Rowan, E.L.

1995-01-01

Presents results of reaction path calculations using the chemical speciation and reaction path program SOLVEQ and CHILLER to model possible fluorite deposition mechanisms in the Illinois-Kentucky fluorspar district. The results indicate that the fluids responsible for Illinois-Kentucky fluorspar mineralization were most likely quite acidic (pH < 4) and rich in fluorine in order to produce the fluorite-rich, dolomite-poor mineral assemblages and extensive dissolution of host limestones. A possible source for the acid and fluorine may have been HF-rich gases which were expelled from alkalic magmas and then incorporated by migrating basinal brines. An analysis of the geologic setting of other fluorite deposits and districts worldwide suggests that involvement of magmatic gases is probable for many of these districts as well. -from Authors

A charge-optimized many-body potential for the U-UO2-O2 system

NASA Astrophysics Data System (ADS)

Li, Yangzhong; Liang, Tao; Sinnott, Susan B.; Phillpot, Simon R.

2013-12-01

Building on previous charge-optimized many-body (COMB) potentials for metallic α-U and gaseous O2, we have developed a new potential for UO2, which also allows the simulation of U-UO2-O2 systems. The UO2 lattice parameter, elastic constants and formation energies of stoichiometric and non-stoichiometric intrinsic defects are well reproduced. Moreover, this is the first rigid-ion potential that produces the correct deviation of the Cauchy relation, as well as the first classical interatomic potential that is able to determine the defect energies of non-stoichiometric intrinsic point defects in UO2 with an appropriate reference state. The oxygen molecule interstitial in the α-U structure is shown to decompose, with some U-O bonds approaching the natural bond length of perfect UO2. Finally, we demonstrate the capability of this COMB potential to simulate a complex system by performing a simulation of the α-U + O2 → UO2 phase transformation. We also identify a possible mechanism for uranium oxidation and the orientation of the resulting fluorite UO2 structure relative to the coordinate system of orthorhombic α-U.

Structural and electronic phase transitions of ThS 2 from first-principles calculations

DOE PAGES

Guo, Yongliang; Wang, Changying; Qiu, Wujie; ...

2016-10-07

Performed a systematic study using first-principles methods of the pressure-induced structural and electronic phase transitions in ThS 2, which may play an important role in the next generation nuclear energy fuel technology.

Some physical properties of naturally irradiated fluorite

USGS Publications Warehouse

Berman, Robert

1955-01-01

Five samples of purple fluorite found in association with radioactive, materials, and a synthetic colorless control sample were studied and compared.  Before and after heating, observations were made on specific gravity, index of refraction, unit-cell size, breadth of X-ray diffraction lines, and fluorescence.  The purple samples became colorless on heating above 175° C.  During the process, observations were made on color, thermoluminescence, and differential thermal analysis curves.  There were strong correlations between the various physical properties, and it was found possible to arrange the samples in order of increasing difference in their physical properties from the control sample. This order apparently represents increasing structural damage by radiation; if so, it correlates with decreasing specific gravity, increasing index of refraction, broadening of X-ray lines, and increasingly strong exothermic reactions on annealing. The differences between the samples in index of refraction and X-ray pattern are largely eliminated on annealing.  Annealing begins at 1750 C; thermoluminescence at lower temperatures is due to electrons escaping from the metastable potential traps, not the destruction of those traps which takes place on annealing.

Chemical solution route to self-assembled epitaxial oxide nanostructures.

PubMed

Obradors, X; Puig, T; Gibert, M; Queraltó, A; Zabaleta, J; Mestres, N

2014-04-07

Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials.

Review of A 2B 2O 7 Pyrochlore Response to Irradiation and Pressure

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

Lang, Maik; Zhang, Fuxiang; Zhang, Jiaming

2010-10-01

This article reviews recent research on swift heavy-ion irradiations and high-pressure studies on pyrochlores of the Gd 2Zr 2-xTi xO 7 binary. Applying three complementary analytical techniques (synchrotron X-ray diffraction, Raman spectroscopy and transmission electron microscopy) allowed for the investigation of the response of pyrochlore to irradiation and/or pressure. The chemical composition of pyrochlore has a strong effect on the character and energetics of the type of structural modifications that can be obtained under pressure or irradiation: For Ti-rich pyrochlores, the crystalline-to-amorphous transition is the dominant process. When Zr is substituted for Ti, an order–disorder transformation to the defect-fluorite structuremore » becomes the increasingly dominant process. Except for Gd 2Zr 2O 7, single ion tracks in pyrochlore consist of an amorphous core, surrounded by a crystalline, but disordered, defect-fluorite shell. This shell is surrounded by a defect-rich pyrochlore region. In contrast to similar effects observed when pressure or irradiation are applied separately, the response of the pyrochlore structure is significantly different when it is exposed simultaneously to pressure and irradiation. The combination of relativistic heavy ions with high pressure results in the formation of a new metastable pyrochlore phase. TEM and quantum–mechanical calculations suggest that these novel structural modifications are caused by the formation of nanocrystals and the modified energetics of nanomaterials.« less

Review of A2B2O7 Pyrochlore Response to Irradiation and Pressure

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

Lang, M.; Zhang, F; Zhang, J

2010-01-01

This article reviews recent research on swift heavy-ion irradiations and high-pressure studies on pyrochlores of the Gd{sub 2}Zr{sub 2-x}Ti{sub x}O{sub 7} binary. Applying three complementary analytical techniques (synchrotron X-ray diffraction, Raman spectroscopy and transmission electron microscopy) allowed for the investigation of the response of pyrochlore to irradiation and/or pressure. The chemical composition of pyrochlore has a strong effect on the character and energetics of the type of structural modifications that can be obtained under pressure or irradiation: For Ti-rich pyrochlores, the crystalline-to-amorphous transition is the dominant process. When Zr is substituted for Ti, an order-disorder transformation to the defect-fluorite structuremore » becomes the increasingly dominant process. Except for Gd{sub 2}Zr{sub 2}O{sub 7}, single ion tracks in pyrochlore consist of an amorphous core, surrounded by a crystalline, but disordered, defect-fluorite shell. This shell is surrounded by a defect-rich pyrochlore region. In contrast to similar effects observed when pressure or irradiation are applied separately, the response of the pyrochlore structure is significantly different when it is exposed simultaneously to pressure and irradiation. The combination of relativistic heavy ions with high pressure results in the formation of a new metastable pyrochlore phase. TEM and quantum-mechanical calculations suggest that these novel structural modifications are caused by the formation of nanocrystals and the modified energetics of nanomaterials.« less

Interplay of structural, optical and magnetic properties in Gd doped CeO{sub 2}

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

Soni, S.; Dalela, S., E-mail: sdphysics@rediffmail.com; Kumar, Sudish

In this research wok systematic investigation on the synthesis, characterization, optical and magnetic properties of Ce{sub 1-x}Gd{sub x}O{sub 2} (where x=0.02, 0.04, 0.06, and 0.10) synthesized using the Solid-state method. Structural, Optical and Magnetic properties of the samples were investigated by X-ray diffraction (XRD), UV-VIS-NIR spectroscopy and VSM. Fluorite structure is confirmed from the XRD measurement on Gd doped CeO{sub 2} samples. Magnetic studies showed that the Gd doped polycrystalline samples display room temperature ferromagnetism and the ferromagnetic ordering strengthens with the Gd concentration.

Radiation-induced amorphization resistance and radiation tolerance in structurally related oxides.

PubMed

Sickafus, Kurt E; Grimes, Robin W; Valdez, James A; Cleave, Antony; Tang, Ming; Ishimaru, Manabu; Corish, Siobhan M; Stanek, Christopher R; Uberuaga, Blas P

2007-03-01

Ceramics destined for use in hostile environments such as nuclear reactors or waste immobilization must be highly durable and especially resistant to radiation damage effects. In particular, they must not be prone to amorphization or swelling. Few ceramics meet these criteria and much work has been devoted in recent years to identifying radiation-tolerant ceramics and the characteristics that promote radiation tolerance. Here, we examine trends in radiation damage behaviour for families of compounds related by crystal structure. Specifically, we consider oxides with structures related to the fluorite crystal structure. We demonstrate that improved amorphization resistance characteristics are to be found in compounds that have a natural tendency to accommodate lattice disorder.

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

Morris, J.R.; Lu, Z.; Ring, D.M.

We have examined a variety of structures for the {l_brace}510{r_brace} symmetric tilt boundary in Si and Ge, using tight-binding and first-principles calculations. These calculations show that the observed structure in Si is the lowest-energy structure, despite the fact that it is more complicated than what is necessary to preserve fourfold coordination. Contrary to calculations using a Tersoff potential, first-principles calculations show that the energy depends strongly upon the structure. A recently developed tight-binding model for Si produces results in very good agreement with the first-principles calculations. Electronic density of states calculations based upon this model show no evidence of midgapmore » states and little evidence of electronic states localized to the grain boundary. {copyright} {ital 1998} {ital The American Physical Society}« less

Magnetic interactions in new fluorite-related rare earth oxides LnLn’{sub 2}RuO{sub 7} (Ln, Ln’=rare earths)

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

Hinatsu, Yukio, E-mail: hinatsu@sci.hokudai.ac.jp; Doi, Yoshihiro

2016-07-15

New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. They crystallize in an orthorhombic superstructure of cubic fluorite with space group Cmcm. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K, which is considerably lowered compared with that for Pr{sub 3}RuO{sub 7}. Analysis of the magnetic specific heat indicates that the magnetic behavior observed at 27 K for Pr{sub 2}YRuO{sub 7} is predominantly due to the magnetic interactions between Ru ions, and that the interactions between the Pr{sup 3+} and Ru{sup 5+} ions are alsomore » important. La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K, which is ascribed to the magnetic ordering between Ru{sup 5+} ions from the analysis of the magnetic specific heat data. - Graphical abstract: New fluorite-related quaternary rare earth oxides Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} have been prepared. Through magnetic susceptibility and specific heat measurements, Pr{sub 2}YRuO{sub 7} and La{sub 2}TbRuO{sub 7} show an antiferromagnetic transition at 27 and 9.0 K, respectively. Display Omitted - Highlights: • New fluorite-related quaternary rare earth oxides LnLn’{sub 2}RuO{sub 7} have been prepared. • Pr{sub 2}YRuO{sub 7} shows an antiferromagnetic transition at 27 K. • La{sub 2}TbRuO{sub 7} shows magnetic ordering at 9.0 K. • Their magnetic exchange mechanism has been elucidated by the magnetic entropy change.« less

Dependences of the density of M{sub 1-x}R{sub x}F{sub 2+x} and R{sub 1-y}M{sub y}F{sub 3-y} single crystals (M = Ca, Sr, Ba, Cd, Pb; R means rare earth elements) on composition

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

Sorokin, N. I., E-mail: sorokin@ns.crys.ras.ru; Krivandina, E. A.; Zhmurova, Z. I.

2013-11-15

The density of single crystals of nonstoichiometric phases Ba{sub 1-x}La{sub x}F{sub 2+x} (0 {<=} x {<=} 0.5) and Sr{sub 0.8}La{sub 0.2-x}Lu{sub x}F{sub 2.2} (0 {<=} x {<=} 0.2) with the fluorite (CaF{sub 2}) structure type and R{sub 1-y}Sr{sub y}F{sub 3-y} (R = Pr, Nd; 0 {<=} y {<=} 0.15) with the tysonite (LaF{sub 3}) structure type has been measured. Single crystals were grown from a melt by the Bridgman method. The measured concentration dependences of single crystal density are linear. The interstitial and vacancy models of defect formation in the fluorite and tysonite phases, respectively, are confirmed. To implement themore » composition control of single crystals of superionic conductors M{sub 1-x}R{sub x}F{sub 2+x} and R{sub 1-y}M{sub y}F{sub 3-y} in practice, calibration graphs of X-ray density in the MF{sub 2}-RF{sub 3} systems (M = Ca, Sr, Ba, Cd, Pb; R = La-Lu, Y) are plotted.« less

Comparative XRPD and XAS study of the impact of the synthesis process on the electronic and structural environments of uranium–americium mixed oxides

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

Prieur, D., E-mail: dam.prieur@gmail.com; Lebreton, F.; Martin, P.M.

2015-10-15

Uranium–americium mixed oxides are potential compounds to reduce americium inventory in nuclear waste via a partitioning and transmutation strategy. A thorough assessment of the oxygen-to-metal ratio is paramount in such materials as it determines the important underlying electronic structure and phase relations, affecting both thermal conductivity of the material and its interaction with the cladding and coolant. In 2011, various XAS experiments on U{sub 1−x}Am{sub x}O{sub 2±δ} samples prepared by different synthesis methods have reported contradictory results on the charge distribution of U and Am. This work alleviates this discrepancy. The XAS results confirm that, independently of the synthesis process,more » the reductive sintering of U{sub 1−x}Am{sub x}O{sub 2±δ} leads to the formation of similar fluorite solid solution indicating the presence of Am{sup +III} and U{sup +V} in equimolar proportions. - Graphical abstract: Formation of (U{sup IV/V},Am{sup III})O{sup 2} solid solution by sol–gel and by powder metallurgy. - Highlights: • Uranium–americium mixed oxides were synthesized by sol–gel and powder metallurgy. • Fluorite solid solutions with similar local environment have been obtained. • U{sup V} and Am{sup III} are formed in equimolar proportions.« less

TEM and HRTEM study of oxide particles in an Al-alloyed high-Cr oxide dispersion strengthened ferritic steel with Hf addition

NASA Astrophysics Data System (ADS)

Dou, Peng; Kimura, Akihiko; Kasada, Ryuta; Okuda, Takanari; Inoue, Masaki; Ukai, Shigeharu; Ohnuki, Somei; Fujisawa, Toshiharu; Abe, Fujio; Jiang, Shan; Yang, Zhigang

2017-03-01

The nanoparticles in an Al-alloyed high-Cr oxide dispersion strengthened (ODS) ferritic steel with Hf addition, i.e., SOC-16 (Fe-15Cr-2W-0.1Ti-4Al-0.62Hf-0.35Y2O3), have been examined by transmission electron microscopy (TEM) and high resolution transmission electron microscopy (HRTEM). Relative to an Al-alloyed high-Cr ODS ferritic steel without Hf addition, i.e., SOC-9 (Fe-15.5Cr-2W-0.1Ti-4Al-0.35Y2O3), the dispersion morphology and coherency of the oxide nanoparticles in SOC-16 were significantly improved. Almost all the small nanoparticles (diameter <10 nm) in SOC-16 were found to be consistent with cubic Y2Hf2O7 oxides with the anion-deficient fluorite structure and coherent with the bcc steel matrix. The larger particles (diameter >10 nm) were also mainly identified as cubic Y2Hf2O7 oxides with the anion-deficient fluorite structure. The results presented here are compared with those of SOC-9 with a brief discussion of the underlying mechanisms of the unusual thermal and irradiation stabilities of the oxides as well as the superior strength, excellent irradiation tolerance and extraordinary corrosion resistance of SOC-16.

Radiation coloring of nonstoichiometric M(1-x)R(x)F(2+x) single crystals with a fluorite defect structure

NASA Astrophysics Data System (ADS)

Rustamov, Ia.; Tavshunskii, G. A.; Khabibullaev, P. K.; Bessonova, T. S.; Sobolev, B. P.

1985-06-01

Experimental results are reported concerning the radiation coloring of nonstoichiometric crystals of the M(1-x)R(x)F(2+x) type in the presence of fluorite defects. Samples of the crystals are cut using the Stockbarger technique in a chemically active fluoridating atmosphere generated by pyrolysis of tetrafluoroethylene. The samples were irradiated at 77 and 300 K using a Co-60 gamma-ray source and the total doses were in the range 10 to the 6th to 10 to the 7th roentgen. Absorption spectra of the crystals were analogous spectra for MF2-RF3 single crystals with RF 3 contents of less than 1 mole percent. It is shown that the properties of radiation coloring of the two types of crystal are very different: F-centers formed at 300 K in Ca(1-x)R(x) F(2+x), but not at 77 K. Complex color centers were observed at 77 K in Ca(1-x)R(x)F(2+x) single crystals and the intensity of the centers was determined by the competition among the electron trapping processes involving the r3(+) ions. It is concluded that the coloring characteristics of the M(1-x)R(x)F(2+x) crystals are related to their structural characteristics as compared with the MF2-RF3 crystals.

Remarkable changes in the photoluminescent properties of Y2Ce2O7:Eu(3+) red phosphors through modification of the cerium oxidation states and oxygen vacancy ordering.

PubMed

Raj, Athira K V; Prabhakar Rao, P; Sreena, T S; Sameera, S; James, Vineetha; Renju, U A

2014-11-21

A new series of red phosphors based on Eu(3+)-doped yttrium cerate [Y1.9Ce2O7:0.1Eu(3+), Y2Ce1.9O7:0.1Eu(3+) and Y2Ce2-xO7:xEu(3+) (x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.50)] was prepared via a conventional solid-state method. The influence of the substitution of Eu(3+) at the aliovalent site on the photoluminescent properties was determined by powder X-ray diffraction, FT Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy with energy-dispersive spectroscopy, UV-visible absorption spectroscopy, photoluminescence spectroscopy and lifetime measurements. The substitution of Eu(3+) at the Ce(4+) site induces a structural transition from a defect fluorite to a C-type structure, which increases the oxygen vacancy ordering and the distortion of the Eu(3+) environment, and decreases the formation of Ce(3+) states. In contrast, phosphors with isovalent substitution at the Y(3+) site exhibit the biphasic nature of defect fluorite and a C-type structure, thereby increasing the number of Ce(3+) oxidation states. These modifications resulted in remarkable changes in the photoluminescent properties of Y2Ce1.9O7:0.1Eu(3+) red phosphors, with emission intensities 3.8 times greater than those of the Ce0.9O2:0.1Eu(3+) and Y1.9Ce2O7:0.1Eu(3+). The photoluminescent properties of Y2Ce2-xO7:xEu(3+) were studied at different Eu(3+) concentrations under excitation with blue light. These phosphors emit intense red light due to the (5)D0-(7)F2 transition under excitation at 466 nm and no concentration quenching is observed with up to 50 mol% Eu(3+). They show increased lifetimes in the range 0.62-0.72 ms at Eu(3+) concentrations. The cation ordering linked to the oxygen vacancy ordering led to the uniform distribution of Eu(3+) ions in the lattice, thus allowing higher doping concentrations without quenching and consequently increasing the lifetime of the (5)D0 states. Our results demonstrate that significant improvements in the photoluminescence properties can be achieved by the structural alteration of a fluorite CeO2 to a C-type lattice.

First principles and experimental study of the electronic structure and phase stability of bulk thallium bromide

NASA Astrophysics Data System (ADS)

Smith, Holland M.; Zhou, Yuzhi; Ciampi, Guido; Kim, Hadong; Cirignano, Leonard J.; Shah, Kanai S.; Haller, E. E.; Chrzan, D. C.

2013-08-01

We apply state-of-art first principle calculations to study the polymorphism and electronic structure of three previously reported phases of TlBr. The calculated band structures of NaCl-structure phase and orthorhombic-structure phase have different features than that of commonly observed CsCl-structure phase. We further interpret photoluminescence spectra based on our calculations. Several peaks close to calculated band gap values of the NaCl-structure phase and the orthorhombic-structure phase are found in unpolished TlBr samples.

Epitaxial crystals of Bi₂Pt₂O₇ pyrochlore through the transformation of δ–Bi₂O₃ fluorite

DOE PAGES

Gutiérrez–Llorente, Araceli; Joress, Howie; Woll, Arthur; ...

2015-03-01

Bi₂Pt₂O₇ pyrochlore is thought to be one of the most promising oxide catalysts for application in fuel cell technology. Unfortunately, direct film growth of Bi₂Pt₂O₇ has not yet been achieved, owing to the difficulty of oxidizing platinum metal in the precursor material to Pt⁴⁺. In this work, in order to induce oxidation of the platinum, we annealed pulsed laser deposited films consisting of epitaxial δ–Bi₂O₃ and co-deposited, comparatively disordered platinum. We present synchrotron x-ray diffraction results that show the nonuniform annealed films contain the first epitaxial crystals of Bi₂Pt₂O₇. We also visualized the pyrochlore structure by scanning transmission electron microscopy,more » and observed ordered cation vacancies in the epitaxial crystals formed in a bismuth-rich film but not in those formed in a platinum-rich film. The similarity between the δ–Bi₂O₃ and Bi₂Pt₂O₇ structures appears to facilitate the pyrochlore formation. These results provide the only route to date for the formation of epitaxial Bi₂Pt₂O₇.« less

Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ: a first-principles investigation

Treesearch

ShunLi Shang; Louis G. Hector Jr.; Paul Saxe; Zi-Kui Liu; Robert J. Moon; Pablo D. Zavattieri

2014-01-01

Anisotropy and temperature dependence of structural, thermodynamic and elastic properties of crystalline cellulose Iβ were computed with first-principles density functional theory (DFT) and a semi-empirical correction for van der Waals interactions. Specifically, we report the computed temperature variation (up to 500...

Systematics of stretching of fluid inclusions I: fluorite and sphalerite at 1 atmosphere confining pressure.

USGS Publications Warehouse

Bodnar, R.J.; Bethke, P.M.

1984-01-01

Measured homogenization T of fluid inclusions in fluorite and sphalerite may be higher than the true homogenization T of samples that have been previously heated in the laboratory or naturally in post-entrapment events. As T and with it internal P is increased, the resulting volume increase may become inelastic. If the volume increase exceeds the precision of T measurement, the inclusion is said to have stretched. More than 1300 measurements on fluid inclusions in fluorite and sphalerite indicate that stretching is systematically related to P-V-T-X properties of the fluid, inclusion size and shape, physical properties of the host mineral, and the confining P. Experimental methods are detailed in an appendix. The mechanism of stretching is probably plastic deformation or - not observed - microfracturing. The systematic relationship between the internal P necessary to initiate stretching and the inclusion volume provides a means of recognizing previously stretched inclusions and estimating the magnitude of post-entrapment thermal events. -G.J.N.

Thermodynamics of fission products in dispersion fuel designs - first principles modeling of defect behavior in bulk and at interfaces

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

Liu, Xiang-yand; Uberuaga, Blas P; Nerikar, Pankaj

2009-01-01

Density functional theory (DFT) calculations of fission product (Xe, Sr, and Cs) incorporation and segregation in alkaline earth metal oxides, HfO{sub 2} and UO{sub 2} oxides, and the MgO/(U, Hf, Ce)O{sub 2} interfaces have been carried out. In the case of UO{sub 2}, the calculations were performed using spin polarization and with a Hubbard U term characterizing the on-sit Coulomb repulsion between the localized 5f electrons. The fission product solution energies in bulk UO{sub 2{+-}x} have been calculated as a function of non-stoichiometry x, and were compared to that in MgO. These calculations demonstrate that the fission product incorporation energiesmore » in MgO are higher than in HfO{sub 2}. However, this trend is reversed or reduced for alkaline earth oxides with larger cation sizes. The solution energies of fission products in MgO are substantially higher than in UO{sub 2{+-}x}, except for the case of Sr in the hypostoichiometric case. Due to size effects, the thermodynamic driving force of segregation for Xe and Cs from bulk MgO to the MgO/fluorite interface is strong. However, this driving force is relatively weak for Sr.« less

The influence of crystal structure on ion-irradiation tolerance in the Sm(x)Yb(2-x)TiO5 series

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

Aughterson, R. D.; Lumpkin, G. R.; de los Reyes, M.

2016-04-01

his ion-irradiation study covers the four major crystal structure types in the Ln(2)TiO(5) series (Ln = lanthanide), namely orthorhombic Pnma, hexagonal P63/mmc, cubic (pyrochlore-like) Fd-3m and cubic (fluorite-like) Fm-3m. This is the first systematic examination of the complete Ln(2)TiO(5) crystal system and the first reported examination of the hexagonal structure. A series of samples, based on the stoichiometry Sm(x)Yb(2-x)TiO5 (where x = 2, 1.4, 1, 0.6, and 0) have been irradiated using 1 MeV Kr2+ ions and characterised in-situ using a transmission electron microscope. Two quantities are used to define ion-irradiation tolerance: critical dose of amorphisation (D-c), which is themore » irradiating ion dose required for a crystalline to amorphous transition, and the critical temperature (T-c), above which the sample cannot be rendered amorphous by ion irradiation. The structure type plus elements of bonding are correlated to ion-irradiation tolerance. The cubic phases, Yb2TiO5 and Sm0.6Yb1.4TiO5, were found to be the most radiation tolerant, with Tc values of 479 and 697 K respectively. The improved radiation tolerance with a change in symmetry to cubic is consistent with previous studies of similar compounds.« less

Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces: Implications for catalysis and energy applications

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

Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi

The structures and properties of Ce 1–xZr xO 2 (x = 0–1) solid solutions, selected Ce 1–xZr xO 2 surfaces, and Ce 1–xZr xO 2/CeO 2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+ U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O 2 phases, indicating a significant rise in microhardness from CeO 2 to ZrO 2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO 2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energymore » of Ce 1–xZr xO 2(111)/CeO 2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce 1–xZr xO 2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce 1–xZr xO 2/CeO 2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce 0.25Zr 0.75O 2/CeO 2 interfaces.« less

Effect of synthesis conditions on the nanopowder properties of Ce{sub 0.9}Zr{sub 0.1}O{sub 2}

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

Zimicz, M.G.; Fabregas, I.O.; Lamas, D.G.

Graphical abstract: . The synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{sub 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. Research highlights: {yields} All samples exhibited the fluorite-type crystal structure, nanometric average crystallite size and negligible carbon content. {yields} Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. {yields} Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties. -- Abstract: In this work, the synthesis of nanocrystalline Ce{sub 0.9}Zr{sub 0.1}O{submore » 2} powders via the gel-combustion method, using different fuels, and following either stoichiometric or non-stoichiometric pH-controlled routes is investigated. The objective is to evaluate the effect of synthesis conditions on the textural and morphological properties, and the crystal structure of the synthesized materials. The solids were characterized by nitrogen physisorption, Scanning Electron Microscopy (SEM), X-ray powder diffraction (XPD), and Carbon-Hydrogen-Nitrogen Elemental Analysis (CHN). All the powders exhibited nanometric crystallite size, fluorite-type structure and negligible carbon content. Synthesis conditions strongly affect the average crystallite size, the degree of agglomeration, the specific surface area and the pore volume. Our results indicate that, by controlling the synthesis conditions it is possible to obtain solids with custom-made morphological properties.« less

Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces [Density functional analysis of fluorite-structured (Ce, Zr)O 2/CeO 2 interfaces: Implications for catalysis and energy applications

DOE PAGES

Weck, Philippe F.; Juan, Pierre -Alexandre; Dingreville, Remi; ...

2017-06-21

The structures and properties of Ce 1–xZr xO 2 (x = 0–1) solid solutions, selected Ce 1–xZr xO 2 surfaces, and Ce 1–xZr xO 2/CeO 2 interfaces were computed within the framework of density functional theory corrected for strong electron correlation (DFT+ U). The calculated Debye temperature increases steadily with Zr content in (Ce, Zr)O 2 phases, indicating a significant rise in microhardness from CeO 2 to ZrO 2, without appreciable loss in ductility as the interfacial stoichiometry changes. Surface energy calculations for the low-index CeO 2(111) and (110) surfaces show limited sensitivity to strong 4f-electron correlation. The fracture energymore » of Ce 1–xZr xO 2(111)/CeO 2(111) increases markedly with Zr content, with a significant decrease in energy for thicker Ce 1–xZr xO 2 films. These findings suggest the crucial role of Zr acting as a binder at the Ce 1–xZr xO 2/CeO 2 interfaces, due to the more covalent character of Zr–O bonds compared to Ce–O. Finally, the impact of surface relaxation upon interface cracking was assessed and found to reach a maximum for Ce 0.25Zr 0.75O 2/CeO 2 interfaces.« less

A kinetic study of the replacement of calcite marble by fluorite

NASA Astrophysics Data System (ADS)

Trindade Pedrosa, Elisabete; Boeck, Lena; Putnis, Christine V.; Putnis, Andrew

2016-04-01

Replacement reactions are relevant in any situation that involves the reequilibration between a solid and an aqueous fluid phase and are commonly controlled by an interface-coupled dissolution-precipitation mechanism (Putnis and Putnis, 2007). These reactions control many large-scale Earth processes whenever aqueous fluids are available, such as during metamorphism, metasomatism, and weathering. An important consequence of coupled dissolution-precipitation is the generation of porosity in the product phase that then allows the infiltration of the fluid within the mineral being replaced. Understanding the mechanism and kinetics of the replacement of carbonates by fluorite has application in earth sciences and engineering. Fluorite (CaF2) occurs in all kinds of rocks (igneous, sedimentary, and metamorphic) and its origin is commonly associated with hydrothermal fluids. Moreover, calcium carbonate has been suggested as a successful seed material for the sequestration of fluoride from contaminated waters (Waghmare and Arfin, 2015). The aim of the present work is to investigate aspects of the replacement of calcium carbonate by fluorite to better understand the mechanism and kinetics of this reaction. Small cubes (˜ 3 × 3 × 3 mm) of Carrara marble (CaCO3 > 99 %) were cut and reacted with a 4 M ammonium fluoride (NH4F) solution for different times (1 to 48 hours) and temperatures (60, 80, 100, and 140 ° C). The microstructure of the product phases was analysed using SEM. The kinetics of replacement was monitored from the Rietveld analysis of X-ray powder diffraction patterns of the products as a function of temperature and reaction time. After reaction, all samples preserved their size and external morphology (a pseudomorphic replacement) and the product phase (fluorite) was highly porous. The activation energy Ea (kJ/mol) of the replacement reaction was empirically determined by both model-fitting and model-free methods. The isoconversional method yielded an empirical activation energy of 41 kJ/mol, and a statistical approach applied to the model-fitting method revealed that the replacement of Carrara marble by fluorite is better fitted to a diffusion-controlled process. This is consistent with ion diffusion through the fluid phase. These results suggest that the replacement reaction is dependent on the fluid migration rate through the newly formed porosity. Putnis, A., Putnis C.V., 2007. The mechanism of reequilibration of solids in the presence of a fluid phase. Journal of Solid State Chemistry, 180, 1783-1786. Waghmare, S.S., Arfin, T. (2015). Fluoride removal from water by calcium materials: A state-of-the-art review. Int. J. Innov. Res. Sci. Eng. Technol. 4, 8090-8102.

Gradient composite metal-ceramic foam as supportive component for planar SOFCs and MIEC membranes

NASA Astrophysics Data System (ADS)

Smorygo, Oleg; Mikutski, Vitali; Marukovich, Alexander; Sadykov, Vladislav; Usoltsev, Vladimir; Mezentseva, Natalia; Borodinecs, Anatolijs; Bobrenok, Oleg

2011-06-01

A novel approach to the design of planar gradient porous supports for the thin-film SOFCs and MIEC membranes is described. The support's thermal expansion is controlled by the creation of a two-component composite metal-ceramic foam structure. Thin MIEC membranes and SOFCs were prepared on the composite supports by the layerwise deposition of composite functional layers including complex fluorites and perovskites. Lab-scale studies demonstrated promising performance of both MIEC membrane and SOFC.

The Crystal-Chemical Effect of REE Separation in Minerals: Causes and Practical Values

NASA Astrophysics Data System (ADS)

Vinokurov, S. F.

2018-03-01

Contrast variations in the type of REE distribution from a distinctly negative mode to a positive mode is revealed in zonal fluorites of Eastern Transbaikal, with a pronounced decrease in the Ce/Y ratios in successive zones of increasing Y accompanied by a gradual decrease in the temperature and salinity of fluid inclusions in the fluorites. It is assumed that these facts are caused by the appearance of nm-size phases of REE minerals characterized by various crystalline structures and demonstrating selective concentrations of lanthanides, i.e., exhibiting a crystal-chemical differentiation of REEs that is widespread in the processes of mineral formation. Based on this natural mechanism, the development of a procedure of selective REE extraction from the concentrates is proposed. The primary laboratory experiments resulted in the discovery of the difference in REE concentrations in the sediment and filtrate with the separation coefficient varying by a factor of 76. The results obtained allow one to expect a true separation possibility for Nd along with the medium and heavy REEs. In view of the data obtained, the crystalline-chemical separation of REEs has some advantages compared to the processes currently used, especially extraction.

First-principles study of low-spin LaCoO3 with structurally consistent Hubbard U

NASA Astrophysics Data System (ADS)

Hsu, H.; Umemoto, K.; Cococcioni, M.; Wentzcovitch, R.

2008-12-01

We use the local density approximation + Hubbard U (LDA+U) method to calculate the structural and electronic properties of low-spin LaCoO3. The Hubbard U is obtained by first principles and consistent with each fully-optimized atomic structure at different pressures. With structurally consistent U, the fully-optimized atomic structure agrees with experimental data better than the calculations with fixed or vanishing U. A discussion on how the Hubbard U affects the electronic and atomic structure of LaCoO3 is also given.

Fraction of boroxol rings in vitreous boron oxide from a first-principles analysis of Raman and NMR spectra.

PubMed

Umari, P; Pasquarello, Alfredo

2005-09-23

We determine the fraction f of B atoms belonging to boroxol rings in vitreous boron oxide through a first-principles analysis. After generating a model structure of vitreous B2O3 by first-principles molecular dynamics, we address a large set of properties, including the neutron structure factor, the neutron density of vibrational states, the infrared spectra, the Raman spectra, and the 11B NMR spectra, and find overall good agreement with corresponding experimental data. From the analysis of Raman and 11B NMR spectra, we yield consistently for both probes a fraction f of approximately 0.75. This result indicates that the structure of vitreous boron oxide is largely dominated by boroxol rings.

Conformational structures of a decapeptide validated by first principles calculations and cold ion spectroscopy.

PubMed

Roy, Tapta Kanchan; Kopysov, Vladimir; Nagornova, Natalia S; Rizzo, Thomas R; Boyarkin, Oleg V; Gerber, R Benny

2015-05-18

Calculated structures of the two most stable conformers of a protonated decapeptide gramicidin S in the gas phase have been validated by comparing the vibrational spectra, calculated from first- principles and measured in a wide spectral range using infrared (IR)-UV double resonance cold ion spectroscopy. All the 522 vibrational modes of each conformer were calculated quantum mechanically and compared with the experiment without any recourse to an empirical scaling. The study demonstrates that first-principles calculations, when accounting for vibrational anharmonicity, can reproduce high-resolution experimental spectra well enough for validating structures of molecules as large as of 200 atoms. The validated accurate structures of the peptide may serve as templates for in silico drug design and absolute calibration of ion mobility measurements. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Multigrid based First-Principles Molecular Dynamics

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

Fattebert, Jean-Luc; Osei-Kuffuor, Daniel; Dunn, Ian

2017-06-01

MGmol ls a First-Principles Molecular Dynamics code. It relies on the Born-Oppenheimer approximation and models the electronic structure using Density Functional Theory, either LDA or PBE. Norm-conserving pseudopotentials are used to model atomic cores.

Ceria-Based Anodes for Next Generation Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Mirfakhraei, Behzad

Mixed ionic and electronic conducting materials (MIECs) have been suggested to represent the next generation of solid oxide fuel cell (SOFC) anodes, primarily due to their significantly enhanced active surface area and their tolerance to fuel components. In this thesis, the main focus has been on determining and tuning the physicochemical and electrochemical properties of ceria-based MIECs in the versatile perovskite or fluorite crystal structures. In one direction, BaZr0.1Ce0.7Y0.1 M0.1O3-delta (M = Fe, Ni, Co and Yb) (BZCY-M) perovskites were synthesized using solid-state or wet citric acid combustion methods and the effect of various transition metal dopants on the sintering behavior, crystal structure, chemical stability under CO2 and H 2S, and electrical conductivity, was investigated. BZCY-Ni, synthesized using the wet combustion method, was the best performing anode, giving a polarization resistance (RP) of 0.4 O.cm2 at 800 °C. Scanning electron microscopy and X-ray diffraction analysis showed that this was due to the exsolution of catalytic Ni nanoparticles onto the oxide surface. Evolving from this promising result, the effect of Mo-doped CeO 2 (nCMO) or Ni nanoparticle infiltration into a porous Gd-doped CeO 2 (GDC) anode (in the fluorite structure) was studied. While 3 wt. % Ni infiltration lowered RP by up to 90 %, giving 0.09 O.cm2 at 800 °C and exhibiting a ca. 5 times higher tolerance towards 10 ppm H2, nCMO infiltration enhanced the H2 stability by ca. 3 times, but had no influence on RP. In parallel work, a first-time study of the Ce3+ and Ce 4+ redox process (pseudocapacitance) within GDC anode materials was carried out using cyclic voltammetry (CV) in wet H2 at high temperatures. It was concluded that, at 500-600 °C, the Ce3+/Ce 4+ reaction is diffusion controlled, probably due to O2- transport limitations in the outer 5-10 layers of the GDC particles, giving a very high capacitance of ca. 70 F/g. Increasing the temperature ultimately diminished the observed capacitance, likely as the chemical reduction of GDC at high temperatures is irreversible.

An Ultrastable Heterobimetallic Uranium(IV)/Vanadium(III) Solid Compound Protected by a Redox-Active Phosphite Ligand: Crystal Structure, Oxidative Dissolution, and First-Principles Simulation.

PubMed

Gui, Daxiang; Dai, Xing; Zheng, Tao; Wang, Xiangxiang; Silver, Mark A; Chen, Lanhua; Zhang, Chao; Diwu, Juan; Zhou, Ruhong; Chai, Zhifang; Wang, Shuao

2018-02-05

The first heterobimetallic uranium(IV)/vanadium(III) phosphite compound, Na 2 UV 2 (HPO 3 ) 6 (denoted as UVP), was synthesized via an in situ redox-active hydrothermal reaction. It exhibits superior hydrolytic and antioxidant stability compared to the majority of structures containing low-valent uranium or vanadium, further elucidated by first-principles simulations, and therefore shows potential applications in nuclear waste management.

Regional stratigraphy and distribution of epigenetic stratabound celestine, fluorite, barite and Pb-Zn deposits in the MVT province of northeastern Mexico

NASA Astrophysics Data System (ADS)

González-Sánchez, Francisco; Camprubí, Antoni; González-Partida, Eduardo; Puente-Solís, Rafael; Canet, Carles; Centeno-García, Elena; Atudorei, Viorel

2009-04-01

Northeastern Mexico hosts numerous epigenetic stratabound carbonate-hosted low-temperature hydrothermal deposits of celestine, fluorite, barite and zinc-lead, which formed by replacement of Mesozoic evaporites or carbonate rocks. Such deposits can be permissively catalogued as Mississippi Valley-type (MVT) deposits. The deposits studied in the state of Coahuila are associated with granitic and metasedimentary basement highs (horsts) marginal or central to the Mesozoic Sabinas Basin. These horsts controlled the stratigraphy of the Mesozoic basins and subsequently influenced the Laramide structural pattern. The Sabinas Basin consists of ~6,000-m-thick Jurassic to Cretaceous siliciclastic, carbonate and evaporitic series. The MVT deposits are mostly in Barremian and in Aptian-Albian to Cenomanian formations and likely formed from basinal brines that were mobilized during the Laramide orogeny, although earlier diagenetic replacement of evaporite layers (barite and celestine deposits) and lining of paleokarstic cavities in reef carbonates (Zn-Pb deposits) is observed. Fluid inclusion microthermometry and isotopic studies suggest ore formation due to mixing of basinal brines and meteoric water. Homogenization temperatures of fluid inclusions range from 45°C to 210°C; salinities range from 0 to 26 wt.% NaCl equiv., and some inclusions contain hydrocarbons or bitumen. Sulfur isotope data suggest that most of the sulfur in barite and celestine is derived from Barremian to Cenomanian evaporites. Regional geology and a compilation of metallogenic features define the new MVT province of northeastern Mexico, which comprises most of the state of Coahuila and portions of the neighboring states of Nuevo León, Durango and, perhaps extends into Zacatecas and southern Texas. This province exhibits a regional metal zonation, with celestine deposits to the south, fluorite deposits to the north and barite and Zn-Pb deposits mostly in the central part.

Crystal structure and chemical bonding in the mixed anion compound BaSF.

PubMed

Driss, D; Cadars, S; Deniard, P; Mevellec, J-Y; Corraze, B; Janod, E; Cario, L

2017-11-28

BaSF was synthesised by a solid state reaction at high temperature and its crystal structure was determined thanks to X-ray diffraction on a single crystal. This transparent yellow fluorochalcogenide has an intergrowth structure built from the stacking of fluorite type layers and sulfur layers. In BaSF sulfur atoms form dimers with interatomic distances as short as 2.1074(10) Å. DFT calculations confirm that this compound is a band insulator with the Fermi level lying in between the antibonding π* and σ* molecular orbitals of the sulfur dimers. Reflectance measurements show that the optical band gap of BaSF is about 2.7 eV in good agreement with the value found from DFT calculations.

Novel Natural Convection Heat Sink Design Concepts From First Principles

DTIC Science & Technology

2016-06-01

NAVAL POSTGRADUATE SCHOOL MONTEREY, CALIFORNIA THESIS Approved for public release; distribution is unlimited NOVEL NATURAL ...COVERED Master’s Thesis 4. TITLE AND SUBTITLE NOVEL NATURAL CONVECTION HEAT SINK DESIGN CONCEPTS FROM FIRST PRINCIPLES 5. FUNDING NUMBERS 6...geometric structures that incorporate the principles of the stack effect to improve the heat transfer capability of a heat sink under natural convection

Investigation of structural stability and elastic properties of CrH and MnH: A first principles study

NASA Astrophysics Data System (ADS)

Kanagaprabha, S.; Rajeswarapalanichamy, R.; Sudhapriyanga, G.; Murugan, A.; Santhosh, M.; Iyakutti, K.

2015-06-01

The structural and mechanical properties of CrH and MnH are investigated using first principles calculation based on density functional theory as implemented in VASP code with generalized gradient approximation. The calculated ground state properties are in good agreement with previous experimental and other theoretical results. A structural phase transition from NaCl to NiAs phase at a pressure of 76 GPa is predicted for both CrH and MnH.

First principle study of structural, electronic and fermi surface properties of aluminum praseodymium

NASA Astrophysics Data System (ADS)

Shugani, Mani; Aynyas, Mahendra; Sanyal, S. P.

2018-05-01

We present a structural, Electronic and Fermi surface properties of Aluminum Praseodymium (AlPr) using First-principles density functional calculation by using full potential linearized augmented plane wave (FP-LAPW) method within generalized gradient approximation (GGA). The ground state properties along with electronic and Fermi surface properties are studied. It is found that AlPr is metallic and the bonding between Al and Pr is covalent.

On the nature of the phase transition in uranium dioxide

NASA Astrophysics Data System (ADS)

Gofryk, K.; Mast, D.; Antonio, D.; Shrestha, K.; Andersson, D.; Stanek, C.; Jaime, M.

Uranium dioxide (UO2) is by far the most studied actinide material as it is a primary fuel used in light water nuclear reactors. Its thermal and magnetic properties remain, however, a puzzle resulting from strong couplings between magnetism and lattice vibrations. UO2 crystalizes in the face-centered-cubic fluorite structure and is a Mott-Hubbard insulator with well-localized uranium 5 f-electrons. In addition, below 30 K, a long range antiferromagnetic ordering of the electric-quadrupole of the uranium moments is observed, forming complex non-collinear 3-k magnetic structure. This transition is accompanied by Jahn-Teller distortion of oxygen atoms. It is believed that the first order nature of the transition results from the competition between the exchange interaction and the Jahn-Teller distortion. Here we present results of our extensive thermodynamic investigations on well-characterized and oriented single crystals of UO2+x (x = 0, 0.033, 0.04, and 0.11). By focusing on the transition region under applied magnetic field we are able to study the interplay between different competing interactions (structural, magnetic, and electrical), its dynamics, and relationship to the oxygen content. We will discuss implications of these results. Work supported by the Department of Energy, Office of Basic Energy Sciences, Materials Sciences, and Engineering Division.

Shallow Acceptor State in Mg-Doped CuAlO2 and Its Effect on Electrical and Optical Properties: An Experimental and First-Principles Study.

PubMed

Liu, Ruijian; Li, Yongfeng; Yao, Bin; Ding, Zhanhui; Jiang, Yuhong; Meng, Lei; Deng, Rui; Zhang, Ligong; Zhang, Zhenzhong; Zhao, Haifeng; Liu, Lei

2017-04-12

Shallow acceptor states in Mg-doped CuAlO 2 and their effect on structural, electrical, and optical properties are investigated by combining first-principles calculations and experiments. First-principles calculations demonstrate that Mg substituting at the Al site in CuAlO 2 plays the role of shallow acceptor and has a low formation energy, suggesting that Mg doping can increase hole concentration and improve the conductivity of CuAlO 2 . Hall effect measurements indicate that the hole concentration of the Mg-doped CuAlO 2 thin film is 2 orders of magnitude higher than that of undoped CuAlO 2 . The best room temperature conductivity of 8.0 × 10 -2 S/cm is obtained. A band gap widening is observed in the optical absorption spectra of Mg-doped CuAlO 2 , which is well supported by the results from first-principles electronic structure calculations.

Site-specific electronic structure analysis by channeling EELS and first-principles calculations.

PubMed

Tatsumi, Kazuyoshi; Muto, Shunsuke; Yamamoto, Yu; Ikeno, Hirokazu; Yoshioka, Satoru; Tanaka, Isao

2006-01-01

Site-specific electronic structures were investigated by electron energy loss spectroscopy (EELS) under electron channeling conditions. The Al-K and Mn-L(2,3) electron energy loss near-edge structure (ELNES) of, respectively, NiAl2O4 and Mn3O4 were measured. Deconvolution of the raw spectra with the instrumental resolution function restored the blunt and hidden fine features, which allowed us to interpret the experimental spectral features by comparing with theoretical spectra obtained by first-principles calculations. The present method successfully revealed the electronic structures specific to the differently coordinated cationic sites.

First-principles investigation of mechanical properties of silicene, germanene and stanene

NASA Astrophysics Data System (ADS)

Mortazavi, Bohayra; Rahaman, Obaidur; Makaremi, Meysam; Dianat, Arezoo; Cuniberti, Gianaurelio; Rabczuk, Timon

2017-03-01

Two-dimensional allotropes of group-IV substrates including silicene, germanene and stanene have recently attracted considerable attention in nanodevice fabrication industry. These materials involving the buckled structure have been experimentally fabricated lately. In this study, first-principles density functional theory calculations were utilized to investigate the mechanical properties of single-layer and free-standing silicene, germanene and stanene. Uniaxial tensile and compressive simulations were carried out to probe and compare stress-strain properties; such as the Young's modulus, Poisson's ratio and ultimate strength. We evaluated the chirality effect on the mechanical response and bond structure of the 2D substrates. Our first-principles simulations suggest that in all studied samples application of uniaxial loading can alter the electronic nature of the buckled structures into the metallic character. Our investigation provides a general but also useful viewpoint with respect to the mechanical properties of silicene, germanene and stanene.

Band Structures and Transport Properties of High-Performance Half-Heusler Thermoelectric Materials by First Principles.

PubMed

Fang, Teng; Zhao, Xinbing; Zhu, Tiejun

2018-05-19

Half-Heusler (HH) compounds, with a valence electron count of 8 or 18, have gained popularity as promising high-temperature thermoelectric (TE) materials due to their excellent electrical properties, robust mechanical capabilities, and good high-temperature thermal stability. With the help of first-principles calculations, great progress has been made in half-Heusler thermoelectric materials. In this review, we summarize some representative theoretical work on band structures and transport properties of HH compounds. We introduce how basic band-structure calculations are used to investigate the atomic disorder in n-type M NiSb ( M = Ti, Zr, Hf) compounds and guide the band engineering to enhance TE performance in p-type Fe R Sb ( R = V, Nb) based systems. The calculations on electrical transport properties, especially the scattering time, and lattice thermal conductivities are also demonstrated. The outlook for future research directions of first-principles calculations on HH TE materials is also discussed.

Computational study of Li2OHCl as a possible solid state battery material

NASA Astrophysics Data System (ADS)

Howard, Jason; Holzwarth, N. A. W.

Preparations of Li2OHCl have recently been experimentally studied as solid state Li ion electrolytes. A disordered cubic phase is known to be stable at temperatures T >35o C. Following previous ideas, first principles supercells are constructed with up to 320 atoms to model the cubic phase. First principles molecular dynamics simulations of the cubic phase show Li ion diffusion occuring on the t =10-12 s time scale, at temperatures as low as T = 400 K. The structure of the lower temperature phase (T <35o C) is not known in detail. A reasonable model of this structure is developed by using the tetragonal ideal structure found by first principles simulations and a model Hamiltonian to account for alternative orientations of the OH groups. Supported by NSF Grant DMR-1507942. Thanks to Zachary D. Hood of GaTech and ORNL for introducing these materials to us.

Band Structures and Transport Properties of High-Performance Half-Heusler Thermoelectric Materials by First Principles

PubMed Central

Fang, Teng; Zhao, Xinbing

2018-01-01

Half-Heusler (HH) compounds, with a valence electron count of 8 or 18, have gained popularity as promising high-temperature thermoelectric (TE) materials due to their excellent electrical properties, robust mechanical capabilities, and good high-temperature thermal stability. With the help of first-principles calculations, great progress has been made in half-Heusler thermoelectric materials. In this review, we summarize some representative theoretical work on band structures and transport properties of HH compounds. We introduce how basic band-structure calculations are used to investigate the atomic disorder in n-type MNiSb (M = Ti, Zr, Hf) compounds and guide the band engineering to enhance TE performance in p-type FeRSb (R = V, Nb) based systems. The calculations on electrical transport properties, especially the scattering time, and lattice thermal conductivities are also demonstrated. The outlook for future research directions of first-principles calculations on HH TE materials is also discussed. PMID:29783759

Mineral saturation states in natural waters and their sensitivity to thermodynamic and analytical errors

USGS Publications Warehouse

Nordstrom, D. Kirk; Ball, James W.

1989-01-01

Saturation indices computed with WATEQ4F chemical analyses from a groundwater in crystalline bedrock and a surface water receiving acid mine drainage are frequently at or above saturation with respect to calcite, fluorite, barite, gibbsite and ferrihydrite. Deep granitic groundwaters from Stripa, Sweden, are supersaturated with respect to calcite and fluorite. Acid mine waters from the Leviathan Mine drainage basin in California are supersaturated with respect to barite by about a factor of three. These mine waters also are 10 times supersaturated with respect to the most soluble form of ferric hydroxide but are near saturation with respect to microcrystalline gibbsite. A sensitivity analysis has been performed by varying the analytic and thermodynamic parameters for which the saturation indices are most sensitive. For calcite, fluorite and barite, the supersaturation effect appears to be real because it is only slightly decreased by sources of uncertainty. Apparent supersaturation for gibbsite is most likely caused by the degree of crystallinity on solubility behavior. Apparent supersaturation for ferric hydroxide is likely caused by small colloidal particles (< 0.1 µm) in the water sample that cannot be removed by standard field filtration, although several other possible explanations cannot be easily excluded.

Adsorption of organic molecules on mineral surfaces studied by first-principle calculations: A review.

PubMed

Zhao, Hongxia; Yang, Yong; Shu, Xin; Wang, Yanwei; Ran, Qianping

2018-04-09

First-principle calculations, especially by the density functional theory (DFT) methods, are becoming a power technique to study molecular structure and properties of organic/inorganic interfaces. This review introduces some recent examples on the study of adsorption models of organic molecules or oligomers on mineral surfaces and interfacial properties obtained from first-principles calculations. The aim of this contribution is to inspire scientists to benefit from first-principle calculations and to apply the similar strategies when studying and tailoring interfacial properties at the atomistic scale, especially for those interested in the design and development of new molecules and new products. Copyright © 2017. Published by Elsevier B.V.

A comparative first-principles study of structural and electronic properties among memantine, amantadine and rimantadine

NASA Astrophysics Data System (ADS)

Middleton, Kirsten; Zhang, G. P.; Nichols, Michael R.; George, Thomas F.

2012-05-01

Memantine, amantadine and rimantadine are structurally derived from the same diamondoid, adamantane. These derivatives demonstrate therapeutic efficacy in human diseases: memantine for Alzheimer's disease and amantadine and rimantadine for influenza. In order to better understand some of the properties that distinguish these three compounds, we conduct first-principles calculations on their structure and electronic properties. Our results indicate that protonation has a significant effect on the dipole moment, where the dipole moment in protonated memantine is over eight times larger than in the deprotonated form.

Clapeyron slope reversal in the melting curve of AuGa2 at 5.5 GPa.

PubMed

Geballe, Z M; Raju, S V; Godwal, B K; Jeanloz, R

2013-10-16

We use x-ray diffraction in a resistively heated diamond anvil cell to extend the melting curve of AuGa2 beyond its minimum at 5.5 GPa and 720 K, and to constrain the high-temperature phase boundaries between cubic (fluorite structure), orthorhombic (cottunite structure) and monoclinic phases. We document a large change in Clapeyron slope that coincides with the transitions from cubic to lower symmetry phases, showing that a structural transition is the direct cause of the change in slope. In addition, moderate (~30 K) to large (90 K) hysteresis is detected between melting and freezing, from which we infer that at high pressures, AuGa2 crystals can remain in a metastable state at more than 5% above the thermodynamic melting temperature.

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor-Liquid Equilibrium

NASA Astrophysics Data System (ADS)

Yamamoto, Hideki; Sumoge, Iwao

2011-03-01

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor-liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor-liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor-liquid equilibrium of the hydrofluoric acid-water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid-water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm-3) and hydrofluoric acid (5.0 mol · dm-3) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm-3 to 1.13 mol · dm-3, and the concentration of hydrofluoric acid increased to 5.41 mol · dm-3. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm-3 and 0.46 mol · dm-3, respectively. It was thus found that the salt effect on vapor-liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.

Efficient Predictions of Excited State for Nanomaterials Using Aces 3 and 4

DTIC Science & Technology

2017-12-20

by first-principle methods in the software package ACES by using large parallel computers, growing tothe exascale. 15. SUBJECT TERMS Computer...modeling, excited states, optical properties, structure, stability, activation barriers first principle methods , parallel computing 16. SECURITY...2 Progress with new density functional methods

Constructing first-principles phase diagrams of amorphous LixSi using machine-learning-assisted sampling with an evolutionary algorithm

NASA Astrophysics Data System (ADS)

Artrith, Nongnuch; Urban, Alexander; Ceder, Gerbrand

2018-06-01

The atomistic modeling of amorphous materials requires structure sizes and sampling statistics that are challenging to achieve with first-principles methods. Here, we propose a methodology to speed up the sampling of amorphous and disordered materials using a combination of a genetic algorithm and a specialized machine-learning potential based on artificial neural networks (ANNs). We show for the example of the amorphous LiSi alloy that around 1000 first-principles calculations are sufficient for the ANN-potential assisted sampling of low-energy atomic configurations in the entire amorphous LixSi phase space. The obtained phase diagram is validated by comparison with the results from an extensive sampling of LixSi configurations using molecular dynamics simulations and a general ANN potential trained to ˜45 000 first-principles calculations. This demonstrates the utility of the approach for the first-principles modeling of amorphous materials.

The Baby Care Questionnaire: A measure of parenting principles and practices during infancy☆

PubMed Central

Winstanley, Alice; Gattis, Merideth

2013-01-01

The current report provides a new framework to explore the role of parenting practices and principles during infancy. We identify structure and attunement as key parenting principles during infancy. Structure represents reliance on regularity and routines in daily life. Attunement represents reliance on infant cues and close physical contact. We suggest parents’ relative endorsement of these parenting principles is related to their choices about practices such as feeding, holding and night-time sleeping. We designed the Baby Care Questionnaire to measure parents’ endorsement of structure and attunement, as well as their daily parenting practices. We report data demonstrating the factor structure, reliability and validity of the BCQ. The BCQ, to our knowledge, is the first comprehensive measure of parenting practices and principles during infancy. We conclude with a discussion of future directions for the measure. PMID:24050932

Perspective: Role of structure prediction in materials discovery and design

NASA Astrophysics Data System (ADS)

Needs, Richard J.; Pickard, Chris J.

2016-05-01

Materials informatics owes much to bioinformatics and the Materials Genome Initiative has been inspired by the Human Genome Project. But there is more to bioinformatics than genomes, and the same is true for materials informatics. Here we describe the rapidly expanding role of searching for structures of materials using first-principles electronic-structure methods. Structure searching has played an important part in unraveling structures of dense hydrogen and in identifying the record-high-temperature superconducting component in hydrogen sulfide at high pressures. We suggest that first-principles structure searching has already demonstrated its ability to determine structures of a wide range of materials and that it will play a central and increasing part in materials discovery and design.

First principles molecular dynamics of molten NaCl

NASA Astrophysics Data System (ADS)

Galamba, N.; Costa Cabral, B. J.

2007-03-01

First principles Hellmann-Feynman molecular dynamics (HFMD) results for molten NaCl at a single state point are reported. The effect of induction forces on the structure and dynamics of the system is studied by comparison of the partial radial distribution functions and the velocity and force autocorrelation functions with those calculated from classical MD based on rigid-ion and shell-model potentials. The first principles results reproduce the main structural features of the molten salt observed experimentally, whereas they are incorrectly described by both rigid-ion and shell-model potentials. Moreover, HFMD Green-Kubo self-diffusion coefficients are in closer agreement with experimental data than those predicted by classical MD. A comprehensive discussion of MD results for molten NaCl based on different ab initio parametrized polarizable interionic potentials is also given.

Structure and properties of microporous titanosilicate determined by first-principles calculations

NASA Astrophysics Data System (ADS)

Ching, W. Y.; Xu, Yong-Nian; Gu, Zong-Quan

1996-12-01

The structure of EST-10, a member of synthetic microporous titanosilicates, was recently determined by an ingenious combination of experimental and simulational techniques. However, the locations of the alkali atoms in the framework remain elusive and its electronic structure is totally unknown. Based on first-principles local density calculations, the possible locations of the alkali atoms are identified and its electronic structure and bonding fully elucidated. ETS-10 is a semiconductor with a direct band gap of 2.33 eV. The Na atoms are likely to locate inside the seven-member ring pore adjacent to the one-dimensional Ti-O-Ti-O- chain.

Structural electronic and mechanical properties of YM2 (M=Mn, Fe, Co) laves phase compounds: First principle calculations analyzed with datamining approach

NASA Astrophysics Data System (ADS)

Saidi, F.; Sebaa, N.; Mahmoudi, A.; Aourag, H.; Merad, G.; Dergal, M.

2018-06-01

We performed first-principle calculations to investigate structural, phase stability, electronic and mechanical properties for the Laves phases YM2 (M = Mn, Fe, Co) with C15, C14 and C36 structures. We used the density functional theory within the framework of both pseudo-potentials and plane wave basis using VASP (Vienna Ab Initio Software Package). The calculated equilibrium structural parameters are in accordance with available theoretical values. Mechanical properties were calculated, discussed, and analyzed with data mining approach in terms of structure stability. The results reveal that YCo2 is harder than YFe2 and YMn2.

Stable isotope study of fluid inclusions in fluorite from Idaho: implications for continental climates during the Eocene

USGS Publications Warehouse

Seal, R.R.; Rye, R.O.

1993-01-01

Isotopic studies of fluid inclusions from meteoric water-dominated epithermal ore deposits offer a unique opportunity to study paleoclimates because the fluids can provide direct samples of ancient waters. Fluorite-hosted fluid inclusions from the Eocene (51-50 Ma) epithermal deposits of the Bayhorse mining district, have low salinities and low to moderate homogenization temperatures indicating meteoric origins for the fluids. Oxygen and hydrogen isotope data on inclusion fluids are almost identical to those of modern meteoric waters in the area. The equivalence of the isotope composition of the Eocene inclusion fluids and modern meteoric waters indicates that the Eocene climatic conditions were similar to those today. -from Authors

First-principles molecular dynamics simulation study on electrolytes for use in redox flow battery

NASA Astrophysics Data System (ADS)

Choe, Yoong-Kee; Tsuchida, Eiji; Tokuda, Kazuya; Ootsuka, Jun; Saito, Yoshihiro; Masuno, Atsunobu; Inoue, Hiroyuki

2017-11-01

Results of first-principles molecular dynamics simulations carried out to investigate structural aspects of electrolytes for use in a redox flow battery are reported. The electrolytes studied here are aqueous sulfuric acid solutions where its property is of importance for dissolving redox couples in redox flow battery. The simulation results indicate that structural features of the acid solutions depend on the concentration of sulfuric acid. Such dependency arises from increase of proton dissociation from sulfuric acid.

Electronic structure and microscopic model of CoNb2O6

NASA Astrophysics Data System (ADS)

Molla, Kaimujjaman; Rahaman, Badiur

2018-05-01

We present the first principle density functional calculations to figure out the underlying spin model of CoNb2O6. The first principles calculations define the main paths of superexchange interaction between Co spins in this compound. We discuss the nature of the exchange paths and provide quantitative estimates of magnetic exchange couplings. A microscopic modeling based on analysis of the electronic structure of this system puts it in the interesting class of weakly couple geometrically frustrated isosceles triangular Ising antiferromagnet.

Structural Polymorphism in “Kesterite” Cu 2ZnSnS 4 : Raman Spectroscopy and First-Principles Calculations Analysis

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

Dimitrievska, Mirjana; Boero, Federica; Litvinchuk, Alexander P.

This work presents detailed structural and vibrational characterization of different Cu 2ZnSnS 4 (CZTS) polymorphs (space groups: Imore » $$\\bar{4}$$, P$$\\bar{4}$$2c, and P$$\\bar{4}$$2m), using Raman spectroscopy and first-principles calculations. Multiwavelength Raman measurements on bulk crystalline CZTS samples permitted determination of the vibrational modes of each polymorph structure, with frequencies matching well with the results obtained from simulations. Lastly, the results present Raman spectra fingerprints as well as experimental references for the different polymorph modifications.« less

Structural Polymorphism in “Kesterite” Cu 2ZnSnS 4 : Raman Spectroscopy and First-Principles Calculations Analysis

DOE PAGES

Dimitrievska, Mirjana; Boero, Federica; Litvinchuk, Alexander P.; ...

2017-03-06

This work presents detailed structural and vibrational characterization of different Cu 2ZnSnS 4 (CZTS) polymorphs (space groups: Imore » $$\\bar{4}$$, P$$\\bar{4}$$2c, and P$$\\bar{4}$$2m), using Raman spectroscopy and first-principles calculations. Multiwavelength Raman measurements on bulk crystalline CZTS samples permitted determination of the vibrational modes of each polymorph structure, with frequencies matching well with the results obtained from simulations. Lastly, the results present Raman spectra fingerprints as well as experimental references for the different polymorph modifications.« less

A first principles prediction of the crystal structure of C6Br2ClFH2

NASA Astrophysics Data System (ADS)

Misquitta, Alston J.; Welch, Gareth W. A.; Stone, Anthony J.; Price, Sarah L.

2008-04-01

We have constructed an intermolecular potential for the 1,3-dibromo-2-chloro-5-fluorobenzene molecule from first principles using SAPT(DFT) interaction energy calculations and the Williams-Stone-Misquitta method for obtaining molecular properties in distributed form. This molecule was included in the fourth Blind Test of crystal structure prediction organised by the Cambridge Crystallographic Data Centre. Using our potential, we have predicted the crystal structure of CBrClFH and found the lowest energy solution to be in excellent agreement with the experimentally observed crystal when it was subsequently revealed.

In-situ X-ray diffraction study of phase transformations in the Am-O system

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

Lebreton, Florent, E-mail: florent.lebreton@cea.fr; GEMH, ENSCI, 87065 Limoges; Belin, Renaud C., E-mail: renaud.belin@cea.fr

2012-12-15

In the frame of minor actinides recycling, americium can be transmuted by adding it in UO{sub 2} or (U, Pu)O{sub 2} fuels. Americium oxides exhibiting a higher oxygen potential than U or Pu oxides, its addition alters the fuel properties. To comprehend its influence, a thorough knowledge of the Am-O phase equilibria diagram and of thermal expansion behavior is of main interest. Due to americium scarcity and high radiotoxicity, few experimental reports on this topic are available. Here we present in-situ high-temperature XRD results on the reduction from AmO{sub 2} to Am{sub 2}O{sub 3}. We show that fluorite (Fm-3m) AmO{submore » 2} is reduced to cubic (Ia-3) C Prime -type Am{sub 2}O{sub 3+{delta}}, and then into hexagonal (P6{sub 3}/mmc) A-type Am{sub 2}O{sub 3}, which remains stable up to 1840 K. We also demonstrate the transitional existence of the monoclinic (C2/m) B-type Am{sub 2}O{sub 3}. At last, we describe, for the first time, the thermal expansion behavior of the hexagonal Am{sub 2}O{sub 3} between room temperature and 1840 K. - Graphical abstract: Americium dioxide was in situ studied by high-temperature X-ray diffraction. First, fluorite AmO{sub 2} is reduced to cubic C Prime -type Am{sub 2}O{sub 3+{delta}} and then transforms into hexagonal A-type Am{sub 2}O{sub 3}, which remains stable up to 1840 K. Then, we demonstrate the transitional existence of monoclinic B-type Am{sub 2}O{sub 3}. At last, we describe, for the first time, the thermal expansion of A-type Am{sub 2}O{sub 3} between room temperature and 1840 K. This work may contribute to a better understanding of Am oxide behavior. Highlights: Black-Right-Pointing-Pointer We realize an in-situ high-temperature X-ray diffraction study on an AmO{sub 2} sample. Black-Right-Pointing-Pointer Fluorite AmO{sub 2} transforms to cubic Am{sub 2}O{sub 3+{delta}} and then to hexagonal Am{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Little-known monoclinic Am{sub 2}O{sub 3} is observed during the cubic-to-hexagonal transition. Black-Right-Pointing-Pointer Lattice parameter thermal expansion of hexagonal Am{sub 2}O{sub 3} is given up to 1840 K. Black-Right-Pointing-Pointer We give additional data on AmO{sub 2} lattice parameter expansion under self-irradiation.« less

Heavy ion irradiation-induced microstructural evolution in pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} at room temperature and 723 K

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

Xie, Q.R.; Zhang, J., E-mail: zhangjian@xmu.edu.cn; Dong, X.N.

Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} at room temperature and 723 K to a fluence of 4×10{sup 15} ions/cm{sup 2}, corresponding to an average ballistic damage dose of 10 displacements per atom in the peak damage region. Irradiation-induced microstructural evolution was examined by grazing incidence X-ray diffraction, and cross-sectional transmission electron microscopy. Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal which has the identical structure of pyrochlore, and the formation of nano-crystal is attributed to the mechanism of epitaxial recrystallization. However, an orderedmore » pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Graphical Abstract: Polycrystalline pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated with 600 keV Kr{sup 3+} to a fluence of 4×10{sup 15} ions/cm{sup 2} at room temperature and 723 K, Incomplete amorphization was observed in the sample irradiated at room temperature due to the formation of nano-crystal. However, an ordered pyrochlore phase to a swelling disordered fluorite phase transformation is occurred for the Lu{sub 2}Ti{sub 2}O{sub 7} sample irradiated at 723 K, which is due to the disordering of metal cations and anion vacancies. - Highlights: Pyrochlore Lu{sub 2}Ti{sub 2}O{sub 7} pellets were irradiated by heavy ions at RT and 723 K. At RT irradiation, ~75% of amorphization was achieved. The nano-crystals were formed in the damage layer at RT irradiation. The formed nano-crystals enhanced the radiation tolerance of Lu{sub 2}Ti{sub 2}O{sub 7}. A pyrochlore to fluorite phase transformation was observed at 723 K irradiation.« less

Structures and magnetic properties of Co-Zr-B magnets studied by first-principles calculations

DOE PAGES

Zhao, Xin; Ke, Liqin; Nguyen, Manh Cuong; ...

2015-06-23

The structures and magnetic properties of Co-Zr-B alloys near the composition of Co 5Zr with B at. % ≤6% were studied using adaptive genetic algorithm and first-principles calculations. The energy and magnetic moment contour maps as a function of chemical composition were constructed for the Co-Zr-B magnet alloys through extensive structure searches and calculations. We found that Co-Zr-B system exhibits the same structure motif as the “Co 11Zr 2” polymorphs, and such motif plays a key role in achieving strong magnetic anisotropy. Boron atoms were found to be able to substitute cobalt atoms or occupy the “interruption” sites. First-principles calculationsmore » showed that the magnetocrystalline anisotropy energies of the boron-doped alloys are close to that of the high-temperature rhombohedral Co 5Zr phase and larger than that of the low-temperature Co 5.25Zr phase. As a result, our calculations provide useful guidelines for further experimental optimization of the magnetic performances of these alloys.« less

Effect of structure and thermodynamic stability on the response of lanthanide stannate pyrochlores to ion beam irradiation.

PubMed

Lian, J; Helean, K B; Kennedy, B J; Wang, L M; Navrotsky, A; Ewing, R C

2006-02-09

The lanthanide stannates, Ln2Sn2O7, Ln=La-Lu and Y, have the isometric pyrochlore structure, A2B2O7, and their structural properties have been refined by Rietveld analysis of powder neutron and synchrotron X-ray diffraction data. In this study, the enthalpies of formation of selected stannate pyrochlores, Ln=La, Nd, Sm, Eu, Dy, and Yb, were measured by high-temperature oxide melt solution calorimetry. Their radiation response was determined by 1 MeV Kr2+ ion irradiation combined with in situ TEM observation over the temperature range of 25 to 1000 K. The enthalpy of formation from binary oxides of stannate pyrochlores became more endothermic (from -145 to -40 kJ/mol) as the size of the lanthanide in the A-site decreases. A more exothermic trend of the enthalpy of formation was observed in stannate pyrochlores with larger lanthanide ions, particularly La, possibly as a result of increased covalency in the Sn-O bond. In contrast to lanthanide titanate pyrochlores, Ln2Ti2O7, that are generally susceptible to radiation-induced amorphization and zirconate pyrochlores, Ln2Zr2O7, that are generally resistant to radiation-induced amorphization, the lanthanide stannate pyrochlores show a much greater variation in their response to ion irradiation. La, Nd, and Gd stannates experience the radiation-induced transformation to the aperiodic state, and the critical amorphization temperatures are approximately 960, 700, and 350 K, respectively. Y and Er stannate pyrochlores cannot be amorphized by ion beam irradiation, even at 25 K, and instead disorder to a defect fluorite structure. Comparison of the calorimetric and ion irradiation data for titanate, zirconate, and stannate pyrochlores reveals a strong correlation among subtle changes in crystal structure with changing composition, the energetics of the disordering process, and the temperature above which the material can no longer be amorphized. In summary, as the structure approaches the ideal, ordered pyrochlore structure, radiation-induced amorphization is more easily attained. This is consistent with an increasingly exothermic trend in the enthalpies of formation of pyrochlores from the oxides, that is, the greater the thermochemical stability of the pyrochlore structure, the more likely it will be amorphized upon radiation damage rather than recover to a disordered fluorite structure.

Geochemical appraisal of fluoride-laden groundwater in Suri I and II blocks, Birbhum district, West Bengal

NASA Astrophysics Data System (ADS)

Das, Shreya; Nag, S. K.

2017-09-01

The present study has been carried out covering two blocks—Suri I and II in Birbhum district, West Bengal, India. The evaluation focuses on occurrence, distribution and geochemistry in 26 water samples collected from borewells spread across the entire study area homogeneously. Quantitative chemical analysis of groundwater samples collected from the present study area has shown that samples from two locations—Gangta and Dhalla contain fluoride greater than the permissible limit prescribed by WHO during both post-monsoon and pre-monsoon sampling sessions. Significant factor controlling geochemistry of groundwater has been identified to be rock-water interaction processes during both sampling sessions based on the results of Gibb's diagrams. Geochemical modeling studies have revealed that fluorite (CaF2) is, indeed, present as a significant fluoride-bearing mineral in the groundwaters of this study area. Calcite or CaCO3 is one of the most common minerals with which fluorite remains associated, and saturation index calculations have revealed that the calcite-fluorite geochemistry is the dominant factor controlling fluoride concentration in this area during both post- and pre-monsoon. High fluoride waters have also been found to be of `bicarbonate' type showing increase of sodium in water with decrease of calcium.

The structural, electronic and optical properties of Au-ZnO interface structure from the first-principles calculation

NASA Astrophysics Data System (ADS)

Huo, Jin-Rong; Li, Lu; Cheng, Hai-Xia; Wang, Xiao-Xu; Zhang, Guo-Hua; Qian, Ping

2018-03-01

The interface structure, electronic and optical properties of Au-ZnO are studied using the first-principles calculation based on density functional theory (DFT). Given the interfacial distance, bonding configurations and terminated surface, we built the optimal interface structure and calculated the electronic and optical properties of the interface. The total density of states, partial electronic density of states, electric charge density and atomic populations (Mulliken) are also displayed. The results show that the electrons converge at O atoms at the interface, leading to a stronger binding of interfaces and thereby affecting the optical properties of interface structures. In addition, we present the binding energies of different interface structures. When the interface structure of Au-ZnO gets changed, furthermore, varying optical properties are exhibited.

A look inside epitaxial cobalt-on-fluorite nanoparticles with three-dimensional reciprocal space mapping using GIXD, RHEED and GISAXS.

PubMed

Suturin, S M; Fedorov, V V; Korovin, A M; Valkovskiy, G A; Konnikov, S G; Tabuchi, M; Sokolov, N S

2013-08-01

In this work epitaxial growth of cobalt on CaF 2 (111), (110) and (001) surfaces has been extensively studied. It has been shown by atomic force microscopy that at selected growth conditions stand-alone faceted Co nanoparticles are formed on a fluorite surface. Grazing-incidence X-ray diffraction (GIXD) and reflection high-energy electron diffraction (RHEED) studies have revealed that the particles crystallize in the face-centered cubic lattice structure otherwise non-achievable in bulk cobalt under normal conditions. The particles were found to inherit lattice orientation from the underlying CaF 2 layer. Three-dimensional reciprocal space mapping carried out using X-ray and electron diffraction has revealed that there exist long bright 〈111〉 streaks passing through the cobalt Bragg reflections. These streaks are attributed to stacking faults formed in the crystal lattice of larger islands upon coalescence of independently nucleated smaller islands. Distinguished from the stacking fault streaks, crystal truncation rods perpendicular to the {111} and {001} particle facets have been observed. Finally, grazing-incidence small-angle X-ray scattering (GISAXS) has been applied to decouple the shape-related scattering from that induced by the crystal lattice defects. Particle faceting has been verified by modeling the GISAXS patterns. The work demonstrates the importance of three-dimensional reciprocal space mapping in the study of epitaxial nanoparticles.

A look inside epitaxial cobalt-on-fluorite nanoparticles with three-dimensional reciprocal space mapping using GIXD, RHEED and GISAXS

PubMed Central

Suturin, S. M.; Fedorov, V. V.; Korovin, A. M.; Valkovskiy, G. A.; Konnikov, S. G.; Tabuchi, M.; Sokolov, N. S.

2013-01-01

In this work epitaxial growth of cobalt on CaF2(111), (110) and (001) surfaces has been extensively studied. It has been shown by atomic force microscopy that at selected growth conditions stand-alone faceted Co nanoparticles are formed on a fluorite surface. Grazing-incidence X-ray diffraction (GIXD) and reflection high-energy electron diffraction (RHEED) studies have revealed that the particles crystallize in the face-centered cubic lattice structure otherwise non-achievable in bulk cobalt under normal conditions. The particles were found to inherit lattice orientation from the underlying CaF2 layer. Three-dimensional reciprocal space mapping carried out using X-ray and electron diffraction has revealed that there exist long bright 〈111〉 streaks passing through the cobalt Bragg reflections. These streaks are attributed to stacking faults formed in the crystal lattice of larger islands upon coalescence of independently nucleated smaller islands. Distinguished from the stacking fault streaks, crystal truncation rods perpendicular to the {111} and {001} particle facets have been observed. Finally, grazing-incidence small-angle X-ray scattering (GISAXS) has been applied to decouple the shape-related scattering from that induced by the crystal lattice defects. Particle faceting has been verified by modeling the GISAXS patterns. The work demonstrates the importance of three-dimensional reciprocal space mapping in the study of epitaxial nanoparticles. PMID:24046491

Identification of F impurities in F-doped ZnO by synchrotron X-ray absorption near edge structures

NASA Astrophysics Data System (ADS)

Na-Phattalung, Sutassana; Limpijumnong, Sukit; Min, Chul-Hee; Cho, Deok-Yong; Lee, Seung-Ran; Char, Kookrin; Yu, Jaejun

2018-04-01

Synchrotron X-ray absorption near edge structure (XANES) measurements of F K-edge in conjunction with first-principles calculations are used to identify the local structure of the fluorine (F) atom in F-doped ZnO. The ZnO film was grown by pulsed laser deposition with an Nd:YAG laser, and an oxyfluoridation method was used to introduce F ions into the ZnO films. The measured XANES spectrum of the sample was compared against the first-principles XANES calculations based on various models for local atomic structures surrounding F atoms. The observed spectral features are attributed to ZnF2 and FO defects in wurtzite bulk ZnO.

First-principles study of structural and electronic properties of Be0.25Zn0.75S mixed compound

NASA Astrophysics Data System (ADS)

Paliwal, U.; Joshi, K. B.

2018-05-01

In this work the first-principles study of structural and electronic properties of Be0.25Zn0.75S mixed compound is presented. The calculations are performed applying the QUANTUM ESPRESSO code utilizing the Perdew, Becke, Ernzerhof generalized gradient approximation in the framework of density functional theory. Adopting standard optimization strategy, the ground state equilibrium lattice constant and bulk modulus are calculated. After settling the structure the electronic band structure, bandgap and static dielectric constant are evaluated. In absence of any experimental work on this system our findings are compared with the available theoretical calculations which are found to follow well anticipated general trends.

Structure and properties of microporous titanosilicate determined by first-principles calculations

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

Ching, W.Y.; Xu, Y.; Gu, Z.

1996-12-01

The structure of EST-10, a member of synthetic microporous titanosilicates, was recently determined by an ingenious combination of experimental and simulational techniques. However, the locations of the alkali atoms in the framework remain elusive and its electronic structure is totally unknown. Based on first-principles local density calculations, the possible locations of the alkali atoms are identified and its electronic structure and bonding fully elucidated. ETS-10 is a semiconductor with a direct band gap of 2.33 eV. The Na atoms are likely to locate inside the seven-member ring pore adjacent to the one-dimensional Ti-O-Ti-O- chain. {copyright} {ital 1996 The American Physicalmore » Society.}« less

Lithium halide monolayers: Structural, electronic and optical properties by first principles study

NASA Astrophysics Data System (ADS)

Safari, Mandana; Maskaneh, Pegah; Moghadam, Atousa Dashti; Jalilian, Jaafar

2016-09-01

Using first principle study, we investigate the structural, electronic and optical properties of lithium halide monolayers (LiF, LiCl, LiBr). In contrast to graphene and other graphene-like structures that form hexagonal rings in plane, these compounds can form and stabilize in cubic shape interestingly. The type of band structure in these insulators is identified as indirect type and ionic nature of their bonds are illustrated as well. The optical properties demonstrate extremely transparent feature for them as a result of wide band gap in the visible range; also their electron transitions are indicated for achieving a better vision on the absorption mechanism in these kinds of monolayers.

First principles calculation of material properties of group IV elements and III-V compounds

NASA Astrophysics Data System (ADS)

Malone, Brad Dean

This thesis presents first principles calculations on the properties of group IV elements and group III-V compounds. It includes investigations into what structure a material is likely to form in, and given that structure, what are its electronic, optical, and lattice dynamical properties as well as what are the properties of defects that might be introduced into the sample. The thesis is divided as follows: • Chapter 1 contains some of the conceptual foundations used in the present work. These involve the major approximations which allow us to approach the problem of systems with huge numbers of interacting electrons and atomic cores. • Then, in Chapter 2, we discuss one of the major limitations to the DFT formalism introduced in Chapter 1, namely its inability to predict the quasiparticle spectra of materials and in particular the band gap of a semiconductor. We introduce a Green's function approach to the electron self-energy Sigma known as the GW approximation and use it to compute the quasiparticle band structures of a number of group IV and III-V semiconductors. • In Chapter 3 we present a first-principles study of a number of high-pressure metastable phases of Si with tetrahedral bonding. The phases studied include all experimentally determined phases that result from decompression from the metallic beta-Sn phase, specifically the BC8 (Si-III), hexagonal diamond (Si-IV), and R8 (Si-XII). In addition to these, we also study the hypothetical ST12 structure found upon decompression from beta-Sn in germanium. • Our attention is then turned to the first principles calculations of optical properties in Chapter 4. The Bethe-Salpeter equation is then solved to obtain the optical spectrum of this material including electron-hole interactions. The calculated optical spectrum is compared with experimental data for other forms of silicon commonly used in photovoltaic devices, namely the cubic, polycrystalline, and amorphous forms. • In Chapter 5 we present first principles calculations of the quasiparticle and optical excitation spectra of recently predicted silicon and germanium polytypes in the body-centered-tetragonal (bct) structure. The quasiparticle spectra calculated within the GW approximation predict that both silicon and germanium in the bct structure are small band gap materials. The optical spectra are then evaluated by solving the Bethe-Salpeter equation taking into account. • We examine the low-pressure phases of Ge in Chapter 6 by performing first principles calculations of the electronic structure and lattice dynamics of the R8, BC8, ST12, and hexagonal diamond structures of Ge. To aid future experimental investigation, we include predictions of the Raman-active frequencies of these phases as well as present the full phonon dispersion throughout the zone. • In Chapter 7 we demonstrate how first principles calculations can be used to predict new structures. In a study aimed at finding new useful forms of silicon, we use an ab initio random structure searching (AIRSS) method to identify a new phase of silicon in the Ibamstructure. The Ibam phase is found to be semimetallic within density functional theory with a small band overlap, and it is expected that quasiparticle corrections using the GW approximation would yield a semiconducting state with a small band gap. • We present a first-principles study of boron and phosphorus substitutional defects in Si-XII in Chapter 8. Recent result from nanoindentation experiments reveal that the Si-XII phase is semiconducting and has the interesting property that it can be doped n- and p-type at room temperature without an annealing step. Using the hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE), we examine the formation energies of the B and P defects at the two distinct atomic sites in Si-XII to find on which site the substitutional defects are more easily accommodated. We also estimate the thermodynamic transition levels of each defect in its relevant charge states. (Abstract shortened by UMI.).

Hydrogen separation through tailored dual phase membranes with nominal composition BaCe0.8Eu0.2O3-δ:Ce0.8Y0.2O2-δ at intermediate temperatures

NASA Astrophysics Data System (ADS)

Ivanova, Mariya E.; Escolástico, Sonia; Balaguer, Maria; Palisaitis, Justinas; Sohn, Yoo Jung; Meulenberg, Wilhelm A.; Guillon, Olivier; Mayer, Joachim; Serra, Jose M.

2016-11-01

Hydrogen permeation membranes are a key element in improving the energy conversion efficiency and decreasing the greenhouse gas emissions from energy generation. The scientific community faces the challenge of identifying and optimizing stable and effective ceramic materials for H2 separation membranes at elevated temperature (400-800 °C) for industrial separations and intensified catalytic reactors. As such, composite materials with nominal composition BaCe0.8Eu0.2O3-δ:Ce0.8Y0.2O2-δ revealed unprecedented H2 permeation levels of 0.4 to 0.61 mL·min-1·cm-2 at 700 °C measured on 500 μm-thick-specimen. A detailed structural and phase study revealed single phase perovskite and fluorite starting materials synthesized via the conventional ceramic route. Strong tendency of Eu to migrate from the perovskite to the fluorite phase was observed at sintering temperature, leading to significant Eu depletion of the proton conducing BaCe0.8Eu0.2O3-δ phase. Composite microstructure was examined prior and after a variety of functional tests, including electrical conductivity, H2-permeation and stability in CO2 containing atmospheres at elevated temperatures, revealing stable material without morphological and structural changes, with segregation-free interfaces and no further diffusive effects between the constituting phases. In this context, dual phase material based on BaCe0.8Eu0.2O3-δ:Ce0.8Y0.2O2-δ represents a very promising candidate for H2 separating membrane in energy- and environmentally-related applications.

Fluorine, fluorite, and fluorspar in central Colorado

USGS Publications Warehouse

Wallace, Alan R.

2010-01-01

Fluorine (F) is a widespread element that was deposited in a variety of rocks, minerals, and geologic environments in central Colorado. It occurs as a trace element, as a major component of the mineral fluorite (CaFs), and as a major economic source of fluorine in fluorspar deposits, which are massive concentrations of fluorite. This study has compiled available geochemical analyses of rocks, both unmineralized and mineralized, to determine the distribution of fluorine in specific age-lithologic categories, ranging from 1.8-giga-annum (Ga) metamorphic rocks to modern soils, throughout central Colorado. It also draws upon field studies of fluorine-rich mineral deposits, including fluorspar deposits, to decipher the nearly two-billion-year-long geologic history of fluorine in the study area, with implications for mineral-resource evaluations and exploration. The resulting compilation provides an important inventory of the naturally occurring levels and sources of fluorine that ultimately weather, erode, and become part of surface waters that are used for domestic water supplies in densely populated areas along the Colorado Front Range. Most commonly, fluorine is a trace element in virtually all rocks in the region. In the 3,798 unmineralized rocks that were analyzed for fluorine in the study area, the average fluorine content was 1,550 parts per million (ppm). The median was 640 ppm, nearly identical to the average crustal abundance of 650 ppm, and some high-fluorine rocks in the Pikes Peak area skewed the average to a value much greater than the median. Most unmineralized age-lithologic rock suites, including Proterozoic metamorphic rocks, 1.7- and 1.4-Ga granitic batholiths, Cambrian igneous rocks, Phanerozoic sedimentary rocks, and Laramide and Tertiary igneous rocks, had median fluorine values of 400 to 740 ppm fluorine. In all suites, however, a small number of analyzed samples contained more than 1 percent (10,000 ppm) fluorine. The 1.1-Ga plutonic rocks related to the Pikes Peak batholith had a mean fluorine content of 1,700 ppm, and primary magmatic fluorite and fluorite-bearing pegmatites are common throughout that igneous mass. Fluorine was deposited in many types of economic mineral deposits in central Colorado, and it currently is a significant trace element in some thermal springs. In the fluorspar deposits, fluorine contents were as high as 37 percent. Some fluorine-rich porphyry systems, such as Jamestown, had fluorine values that ranged from 200 ppm to nearly 37 percent fluorine, and veins in other deposits contained hydrothermal fluorite, although it was not ubiquitous. For the 495 samples from non-fluorspar mining districts (and excluding Jamestown), however, the median fluorine content was 990 ppm. This is above the crustal average but still relatively modest compared to the fluorspar deposits, and it indicates that the majority of the mineralizing systems in central Colorado did not deposit large amounts of fluorine. Nevertheless, the fluorine- and fluorite-rich mineral deposits could be used as guides for the evaluation and discovery of related but concealed porphyry and epithermal base- and precious-metal deposits. The Cenozoic geologic history of central Colorado included multiple periods during which fluorine-bearing rocks and mineral deposits were exposed, weathered, and eroded. This protracted history has released fluorine into soils and regoliths, and modern rainfall and snowmelt interact with these substrates to add fluorine to the hydrosphere. This study did not evaluate the fluorine contents of water or make any predictions about what areas might be major sources for dissolved fluorine. However, the abundant data that are available on fluorine in surface water and ground water can be coupled with the results of this study to provide additional insight into natural sources of fluorine in domestic drinking water.

Concentration of small ring structures in vitreous silica from a first-principles analysis of the Raman spectrum.

PubMed

Umari, P; Gonze, Xavier; Pasquarello, Alfredo

2003-01-17

Using a first-principles approach, we calculate Raman spectra for a model structure of vitreous silica. We develop a perturbational method for calculating the dielectric tensor in an ultrasoft pseudopotential scheme and obtain Raman coupling tensors by finite differences with respect to atomic displacements. For frequencies below 1000 cm(-1), the parallel-polarized Raman spectrum of vitreous silica is dominated by oxygen bending motions, showing a strong sensitivity to the intermediate range structure. By modeling the Raman coupling, we derive estimates for the concentrations of three- and four-membered rings from the experimental intensities of the Raman defect lines.

First principles investigation of structural, vibrational and thermal properties of black and blue phosphorene

NASA Astrophysics Data System (ADS)

Arif Khalil, R. M.; Ahmad, Javed; Rana, Anwar Manzoor; Bukhari, Syed Hamad; Tufiq Jamil, M.; Tehreem, Tuba; Nissar, Umair

2018-05-01

In this investigation, structural, dynamical and thermal properties of black and blue phosphorene (P) are presented through the first principles calculations based on the density functional theory (DFT). These DFT calculations depict that due to the approximately same values of ground state energy at zero Kelvin and Helmholtz free energy at room-temperature, it is expected that both structures can coexist at transition temperature. Lattice dynamics of both phases were investigated by using the finite displacement supercell approach. It is noticed on the basis of harmonic approximation thermodynamic calculations that the blue phase is thermodynamically more stable than the black phase above 155 K.

THE STRUCTURE, MAGNETISM AND CONDUCTIVITY OF Li3V2(PO4)3: A THEORETICAL AND EXPERIMENTAL STUDY

NASA Astrophysics Data System (ADS)

Lin, Zhi-Ping; Zhao, Yu-Jun; Zhao, Yan-Ming

2013-10-01

In this paper, we present a combination of first-principles and experimental investigations on the structural, magnetic and electronic properties of monoclinic Li3V2(PO4)3. The change of dielectric constant indicates that the structural phase transition appear around the temperature 120°C. The first-principles calculation and magnetic measurement display that Li3V2(PO4)3 is a compound with weak ferromagnetism, with Curie constant of C = 0.004 and Curie temperature of 140 K. The experimental and theoretical results demonstrated that the Li3V2(PO4)3 is a typical semiconductor.

Lattice distortions and local compressibility around trivalent rare-earth impurities in fluorites

NASA Astrophysics Data System (ADS)

Tovar, M.; Ramos, C. A.; Fainstein, C.

1983-10-01

We have calculated the lattice distortions around trivalent rare-earth dilute impurities, occupying substitutionally metal sites in fluorites. Explicit results are given for the equilibrium positions of the nearest fluorine ligands, R, the induced electric dipole moments, and the local hydrostatic strains for MF2 (M=Cd, Ca, Sr, Pb, and Ba). These results are used to study the impurity-ligand distance dependence of the fourth-order cubic-crystal-field parameter, b4, for Gd3+ and the isoelectronic ion Eu2+. Comparison is made with the change of b4 with hydrostatic stress using the calculated local compressibility of the lattice. A consistent description of the experimental data is obtained assuming b4~R-m with m~10.

First-principles phase stability at high temperatures and pressure in Nb 90Zr 10 alloy

DOE PAGES

Landa, A.; Soderlind, P.

2016-08-18

The phase stability of Nb 90Zr 10 alloy at high temperatures and compression is explored by means of first-principles electronic-structure calculations. Utilizing the self-consistent ab initio lattice dynamics (SCAILD) approach in conjunction with density-functional theory, we show that pressure-induced mechanical instability of the body-centered cubic phase, which results in formation of a rhombohedral phase at around 50 GPa, will prevail significant heating. As a result, the body-centered cubic structure will recover before melting at ~1800 K.

Ba2F2Fe2+ 0.5Fe3+ S3: a two-dimensional inhomogeneous mixed valence iron compound.

PubMed

Kabbour, Houria; Cario, Laurent

2008-03-03

The structure of the new mixed valence compound Ba2F2Fe1.5S3 was solved by means of single crystal X-ray analysis. It crystallizes in an orthorhombic cell, in the Pnma space group with the cell parameters a = 12.528(3) A, b = 18.852(4) A, and c = 6.0896(12) A. The structure is formed by the alternated stacking of fluorite type [Ba2F2]2+ blocks and the newly discovered [Fe1.5S3]2- blocks. This [Fe1.5S3]2- block exhibits a mixed valence of iron with Fe(+II) located in octahedrons and Fe(+III) in tetrahedrons. Preliminary susceptibility measurements suggest a low dimensional antiferromagnetic behavior.

Ba2F2Fe(1.5)Se3: An Intergrowth Compound Containing Iron Selenide Layers.

PubMed

Driss, Dalel; Janod, Etienne; Corraze, Benoit; Guillot-Deudon, Catherine; Cario, Laurent

2016-03-21

The iron selenide compound Ba2F2Fe(1.5)Se3 was synthesized by a high-temperature ceramic method. The single-crystal X-ray structure determination revealed a layered-like structure built on [Ba2F2](2+) layers of the fluorite type and iron selenide layers [Fe(1.5)Se3](2-). These [Fe1.5Se3](2-) layers contain iron in two valence states, namely, Fe(II+) and Fe(III+) located in octahedral and tetrahedral sites, respectively. Magnetic measurements are consistent with a high-spin state for Fe(II+) and an intermediate-spin state for Fe(III+). Moreover, susceptibility and resistivity measurements demonstrate that Ba2F2Fe(1.5)Se3 is an antiferromagnetic insulator.

Novel carbon-ion fuel cells. Quarterly technical report, April--June 1996

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

Cocks, F.H.

1996-11-01

This report presents research to develop a new type of of fuel cell using a solid electrolyte that transports carbon ions. This new class of fuel cell would use solid C dissolved in molten metal (carbide) as a fuel reservoir and anode; thus expensive gas or liquid fuel would not be required. Thermodynamic efficiency of carbon-ion fuel cells is reviewed, as are electrolyte crystal structures (oxide and fluorite carbides). The sequence of laboratory research procedures for developing a solid C-ion electrolyte and to determine the ionic conductivity of C ions therein is outlined; results of the laboratory research to datemore » are summarized, including XRD analysis of crystal structures and transition temperatures of carbides (La, Ce, Be, Al) and SIMS of carbon isotopes.« less

Occurrence model for volcanogenic beryllium deposits: Chapter F in Mineral deposit models for resource assessment

USGS Publications Warehouse

Foley, Nora K.; Hofstra, Albert H.; Lindsey, David A.; Seal, Robert R.; Jaskula, Brian W.; Piatak, Nadine M.

2012-01-01

Current global and domestic mineral resources of beryllium (Be) for industrial uses are dominated by ores produced from deposits of the volcanogenic Be type. Beryllium deposits of this type can form where hydrothermal fluids interact with fluorine and lithophile-element (uranium, thorium, rubidium, lithium, beryllium, cesium, tantalum, rare earth elements, and tin) enriched volcanic rocks that contain a highly reactive lithic component, such as carbonate clasts. Volcanic and hypabyssal high-silica biotite-bearing topaz rhyolite constitutes the most well-recognized igneous suite associated with such Be deposits. The exemplar setting is an extensional tectonic environment, such as that characterized by the Basin and Range Province, where younger topaz-bearing igneous rock sequences overlie older dolomite, quartzite, shale, and limestone sequences. Mined deposits and related mineralized rocks at Spor Mountain, Utah, make up a unique economic deposit of volcanogenic Be having extensive production and proven and probable reserves. Proven reserves in Utah, as reported by the U.S. Geological Survey National Mineral Information Center, total about 15,900 tons of Be that are present in the mineral bertrandite (Be4Si2O7(OH)2). At the type locality for volcanogenic Be, Spor Mountain, the tuffaceous breccias and stratified tuffs that host the Be ore formed as a result of explosive volcanism that brought carbonate and other lithic fragments to the surface through vent structures that cut the underlying dolomitic Paleozoic sedimentary rock sequences. The tuffaceous sediments and lithic clasts are thought to make up phreatomagmatic base surge deposits. Hydrothermal fluids leached Be from volcanic glass in the tuff and redeposited the Be as bertrandite upon reaction of the hydrothermal fluid with carbonate clasts in lithic-rich sections of tuff. The localization of the deposits in tuff above fluorite-mineralized faults in carbonate rocks, together with isotopic evidence for the involvement of magmatic water in an otherwise meteoric water-dominated hydrothermal system, indicate that magmatic volatiles contributed to mineralization. At the type locality, hydrothermal alteration of dolomite clasts formed layered nodules of calcite, opal, fluorite, and bertrandite, the latter occurring finely intergrown with fluorite. Alteration assemblages and elemental enrichments in the tuff and surrounding volcanic rocks include regional diagenetic clays and potassium feldspar and distinctive hydrothermal halos of anomalous fluorine, lithium, molybdenum, niobium, tin, and tantalum, and intense potassium feldspathization with sericite and lithium-smectite in the immediate vicinity of Be ore. Formation of volcanogenic Be deposits is due to the coincidence of multiple factors that include an appropriate Be-bearing source rock, a subjacent pluton that supplied volatiles and heat to drive convection of meteoric groundwater, a depositional site characterized by the intersection of normal faults with permeable tuff below a less permeable cap rock, a fluorine-rich ore fluid that facilitated Be transport (for example, BeF42- complex), and the existence of a chemical trap that caused fluorite and bertrandite to precipitate at the former site of carbonate lithic clasts in the tuff.

Columnar epitaxy of hexagonal and orthorhombic silicides on Si(111)

NASA Technical Reports Server (NTRS)

Fathauer, R. W.; Nieh, C. W.; Xiao, Q. F.; Hashimoto, Shin

1990-01-01

Columnar grains of PtSi and CrSi2 surrounded by high-quality epitaxial silicon are obtained by ultrahigh vacuum codeposition of Si and metal in an approximately 10:1 ratio on Si(111) substrates heated to 610-840 C. This result is similar to that found previously for CoSi2 (a nearly-lattice-matched cubic-fluorite crystal) on Si(111), in spite of the respective orthorhombic and hexagonal structures of PtSi and CrSi2. The PtSi grains are epitaxial and have one of three variants of the relation defined by PtSi(010)/Si(111), with PtSi 001 line/Si 110 line type.

The structural and electronic properties of amorphous HgCdTe from first-principles calculations

NASA Astrophysics Data System (ADS)

Zhao, Huxian; Chen, Xiaoshuang; Lu, Jianping; Shu, Haibo; Lu, Wei

2014-01-01

Amorphous mercury cadmium telluride (a-MCT) model structures, with x being 0.125 and 0.25, are obtained from first-principles calculations. We generate initial structures by computation alchemy method. It is found that most atoms in the network of amorphous structures tend to be fourfold and form tetrahedral structures, implying that the chemical ordered continuous random network with some coordination defects is the ideal structure for a-MCT. The electronic structure is also concerned. The gap is found to be 0.30 and 0.26 eV for a-Hg0.875Cd0.125Te and a-Hg0.75Cd0.25Te model structures, independent of the composition. By comparing with the properties of crystalline MCT with the same composition, we observe a blue-shift of energy band gap. The localization of tail states and its atomic origin are also discussed.

Site preference of alloying elements in DO22-Ni3V phase: Phase-field and first-principles study

NASA Astrophysics Data System (ADS)

Zhang, Ding-Ni; Shangguan, Qian-Qian; Liu, Fu; Zhang, Ming-Yi

2015-07-01

Site preference of alloying elements in DO22-Ni3V phase was investigated using phase-field and first-principles method. The concentrations of alloying elements on sublattices of DO22-Ni3V phase were quantitatively studied using phase-field model based on microscopic diffusion equations. The phase-field computation results demonstrate that the concentration differences of alloying elements on the NiI and NiII site are attributed to the coordination environment difference. Host atoms Ni and substitutional ternary additions Al prefer to occupy NiI site. Antisite atoms V show site preference on the NiII site. Further reason of site preference of alloying elements on the two different Ni sites were studied using first-principles method to calculate the electronic structure of DO22-Ni3V phase. Calculation of density of states, orbitals population and charge population of the optimized Ni3V structure found that the electronic structures of NiI and NiII sites are different. Electronic structure difference, which is caused by coordination environment difference, is the essential reason for site selectivity behaviors of alloying elements on NiI and NiII sites.

Ab-initio study on the absorption spectrum of color change sapphire based on first-principles calculations with considering lattice relaxation-effect

NASA Astrophysics Data System (ADS)

Novita, Mega; Nagoshi, Hikari; Sudo, Akiho; Ogasawara, Kazuyoshi

2018-01-01

In this study, we performed an investigation on α-Al2O3: V3+ material, or the so-called color change sapphire, based on first-principles calculations without referring to any experimental parameter. The molecular orbital (MO) structure was estimated by the one-electron MO calculations using the discrete variational-Xα (DV-Xα) method. Next, the absorption spectra were estimated by the many-electron calculations using the discrete variational multi-electron (DVME) method. The effect of lattice relaxation on the crystal structures was estimated based on the first-principles band structure calculations. We performed geometry optimizations on the pure α-Al2O3 and with the impurity V3+ ion using Cambridge Serial Total Energy Package (CASTEP) code. The effect of energy corrections such as configuration dependence correction and correlation correction was also investigated in detail. The results revealed that the structural change on the α-Al2O3: V3+ resulted from the geometry optimization improved the calculated absorption spectra. By a combination of both the lattice relaxation-effect and the energy correction-effect improve the agreement to the experiment fact.

Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

PubMed Central

Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A.; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E.

2015-01-01

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. These results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives. PMID:26510750

Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores

DOE PAGES

Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; ...

2015-10-29

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinelmore » that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. Furthermore, these results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.« less

Opposite correlations between cation disordering and amorphization resistance in spinels versus pyrochlores.

PubMed

Uberuaga, Blas Pedro; Tang, Ming; Jiang, Chao; Valdez, James A; Smith, Roger; Wang, Yongqiang; Sickafus, Kurt E

2015-10-29

Understanding and predicting radiation damage evolution in complex materials is crucial for developing next-generation nuclear energy sources. Here, using a combination of ion beam irradiation, transmission electron microscopy and X-ray diffraction, we show that, contrary to the behaviour observed in pyrochlores, the amorphization resistance of spinel compounds correlates directly with the energy to disorder the structure. Using a combination of atomistic simulation techniques, we ascribe this behaviour to structural defects on the cation sublattice that are present in spinel but not in pyrochlore. Specifically, because of these structural defects, there are kinetic pathways for the relaxation of disorder in spinel that are absent in pyrochlore. This leads to a direct correlation between amorphization resistance and disordering energetics in spinel, the opposite of that observed in pyrochlores. These results provide new insight into the origins of amorphization resistance in complex oxides beyond fluorite derivatives.

Structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 phases from first-principles calculations

NASA Astrophysics Data System (ADS)

Li, X. D.; Li, K.; Wei, C. H.; Han, W. D.; Zhou, N. G.

2018-06-01

The structural, electronic, elastic, and thermodynamic properties of CaSi, Ca2Si, and CaSi2 are systematically investigated by using first-principles calculations method based on density functional theory (DFT). The calculated formation enthalpies and cohesive energies show that CaSi2 possesses the greatest structural stability and CaSi has the strongest alloying ability. The structural stability of the three phases is compared according to electronic structures. Further analysis on electronic structures indicates that the bonding of these phases exhibits the combinations of metallic, covalent, and ionic bonds. The elastic constants are calculated, and the bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and anisotropy factor of polycrystalline materials are deduced. Additionally, the thermodynamic properties were theoretically predicted and discussed.

Effects of firing schedule on solubility limits and transport properties of ZrO 2-TiO 2-Y 2O 3 fluorites

NASA Astrophysics Data System (ADS)

Fagg, D. P.; Frade, J. R.; Mogensen, M.; Irvine, J. T. S.

2007-08-01

The low Y/high Zr edge of the cubic defect fluorite solid solution in the system ZrO 2-TiO 2-Y 2O 3 in air is reassessed, as it is these compositions which have been suggested to offer the highest levels of mixed conductivity. Vegard's law is obeyed for values of x which lie within the cubic defect fluorite phase in Zr 1-x-yY yTi xO 2-δ for values of y=0.2 and 0.25. Measured lattice parameters show good agreement with those calculated from the Kim relation. Deviation from Vegard's law places the limit of the solid solution at x=0.18 and 0.20 for values of y=0.2 and 0.25, respectively, at 1500 °C. Discrepancies in current literature data can be shown to be due to differences in firing schedule such as slight temperature fluctuations and/or different cooling rates. A high level of care of sintering temperature and cooling profile is essential to form the most promising single-phase materials which contain maximum Ti-contents with low Y-contents. Contraction of the phase limit as a result of poor synthesis control leads to erroneously high values of bulk ionic conductivity while values of electronic conductivity are shown to be less affected.

Oxysulfide LiAlSO: A Lithium Superionic Conductor from First Principles.

PubMed

Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan

2017-05-12

Through first-principles calculations and crystal structure prediction techniques, we identify a new layered oxysulfide LiAlSO in orthorhombic structure as a novel lithium superionic conductor. Two kinds of stacking sequences of layers of AlS_{2}O_{2} are found in different temperature ranges. Phonon and molecular dynamics simulations verify their dynamic stabilities, and wide band gaps up to 5.6 eV are found by electronic structure calculations. The lithium migration energy barrier simulations reveal the collective interstitial-host ion "kick-off" hopping mode with barriers lower than 50 meV as the dominating conduction mechanism for LiAlSO, indicating it to be a promising solid-state electrolyte in lithium secondary batteries with fast ionic conductivity and a wide electrochemical window. This is a first attempt in which the lithium superionic conductors are designed by the crystal structure prediction method and may help explore other mixed-anion battery materials.

Oxysulfide LiAlSO: A Lithium Superionic Conductor from First Principles

NASA Astrophysics Data System (ADS)

Wang, Xuelong; Xiao, Ruijuan; Li, Hong; Chen, Liquan

2017-05-01

Through first-principles calculations and crystal structure prediction techniques, we identify a new layered oxysulfide LiAlSO in orthorhombic structure as a novel lithium superionic conductor. Two kinds of stacking sequences of layers of AlS2O2 are found in different temperature ranges. Phonon and molecular dynamics simulations verify their dynamic stabilities, and wide band gaps up to 5.6 eV are found by electronic structure calculations. The lithium migration energy barrier simulations reveal the collective interstitial-host ion "kick-off" hopping mode with barriers lower than 50 meV as the dominating conduction mechanism for LiAlSO, indicating it to be a promising solid-state electrolyte in lithium secondary batteries with fast ionic conductivity and a wide electrochemical window. This is a first attempt in which the lithium superionic conductors are designed by the crystal structure prediction method and may help explore other mixed-anion battery materials.

A salt diapir-related Mississippi Valley-type deposit: the Bou Jaber Pb-Zn-Ba-F deposit, Tunisia: fluid inclusion and isotope study

NASA Astrophysics Data System (ADS)

Bouhlel, Salah; Leach, David L.; Johnson, Craig A.; Marsh, Erin; Salmi-Laouar, Sihem; Banks, David A.

2016-08-01

The Bou Jaber Ba-F-Pb-Zn deposit is located at the edge of the Bou Jaber Triassic salt diapir in the Tunisia Salt Diapir Province. The ores are unconformity and fault-controlled and occur as subvertical column-shaped bodies developed in dissolution-collapse breccias and in cavities within the Late Aptian platform carbonate rocks, which are covered unconformably by impermeable shales and marls of the Fahdene Formation (Late Albian-Cenomanian age). The host rock is hydrothermally altered to ankerite proximal to and within the ore bodies. Quartz, as fine-grained bipyramidal crystals, formed during hydrothermal alteration of the host rocks. The ore mineral assemblage is composed of barite, fluorite, sphalerite, and galena in decreasing abundance. The ore zones outline distinct depositional events: sphalerite-galena, barite-ankerite, and fluorite. Fluid inclusions, commonly oil-rich, have distinct fluid salinities and homogenization temperatures for each of these events: sphalerite-galena (17 to 24 wt% NaCl eq., and Th from 112 to 136 °C); ankerite-barite (11 to 17 wt% NaCl eq., and Th from 100 to 130 °C); fluorite (19 to 21 wt% NaCl eq., Th from 140 to 165 °C). The mean temperature of the ore fluids decreased from sphalerite (125 °C) to barite (115 °C) and increased during fluorite deposition (152 °C); then decreased to ˜110 °C during late calcite precipitation. Laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) analyses of fluid inclusions in fluorite are metal rich (hundreds to thousands ppm Pb, Zn, Cu, Fe) but the inclusions in barite are deficient in Pb, Zn, Cu, Fe. Inclusions in fluorite have Cl/Br and Na/Br ratios of several thousand, consistent with dissolution of halite while the inclusions analysed in barite have values lower than seawater which are indicative of a Br-enriched brine derived from evaporation plus a component of halite dissolution. The salinity of the barite-hosted fluid inclusions is less than obtained simply by the evaporation of seawater to halite saturation and requires a dilution of more than two times by meteoric water. The higher K/Na values in fluid inclusions from barite suggest that the brines interacted with K-rich rocks in the basement or siliciclastic sediments in the basin. Carbonate gangue minerals (ankerite and calcite) have δ13C and δ18O values that are close to the carbonate host rock and indicate fluid equilibrium between carbonate host rocks and hydrothermal brines. The δ34S values for sphalerite and galena fall within a narrow range (1 to 10 ‰) with a bulk value of 7.5 ‰, indicating a homogeneous source of sulfur. The δ34S values of barite are also relatively homogeneous (22 ‰), with 6 ‰ higher than the δ34S of local and regional Triassic evaporites (15 ‰). The latter are believed to be the source of sulfate. Temperature of deposition together with sulfur isotope data indicate that the reduced sulfur in sulfides was derived through thermochemical sulfate reduction of Triassic sulfate via hydrocarbons produced probably from Late Cretaceous source rocks. The 87Sr/86Sr ratio in the Bou Jaber barite (0.709821 to 0.711408) together with the lead isotope values of Bou Jaber galena (206Pb/204Pb = 18.699 to 18.737; 207Pb/204Pb = 15.635 to 15.708 and 208Pb/204Pb = 38.321 to 38.947) show that metals were extracted from homogeneous crustal source(s). The tectonic setting of the Bou Jaber ore deposit, the carbonate nature of the host rocks, the epigenetic style of the mineralization and the mineral associations, together with sulfur and oxygen isotope data and fluid inclusion data show that the Bou Jaber lead-zinc mineralization has the major characteristics of a salt diapir-related Mississippi Valley-type (MVT) deposit with superimposed events of fluorite and of barite deposition. Field relations are consistent with mineral deposition during the Eocene-Miocene Alpine orogeny from multiple hydrothermal events: (1) Zn-Pb sulfides formed by mixing of two fluids: one fluid metal-rich but reduced sulfur-poor and a second fluid reduced sulfur-rich; (2) barite precipitation involved the influx of a meteoric water component that mixed with a barium-rich fluid; and (3) fluorite precipitated from a highly saline fluid with higher temperatures.

Exploiting periodic first-principles calculations in NMR spectroscopy of disordered solids.

PubMed

Ashbrook, Sharon E; Dawson, Daniel M

2013-09-17

Much of the information contained within solid-state nuclear magnetic resonance (NMR) spectra remains unexploited because of the challenges in obtaining high-resolution spectra and the difficulty in assigning those spectra. Recent advances that enable researchers to accurately and efficiently determine NMR parameters in periodic systems have revolutionized the application of density functional theory (DFT) calculations in solid-state NMR spectroscopy. These advances are particularly useful for experimentalists. The use of first-principles calculations aids in both the interpretation and assignment of the complex spectral line shapes observed for solids. Furthermore, calculations provide a method for evaluating potential structural models against experimental data for materials with poorly characterized structures. Determining the structure of well-ordered, periodic crystalline solids can be straightforward using methods that exploit Bragg diffraction. However, the deviations from periodicity, such as compositional, positional, or temporal disorder, often produce the physical properties (such as ferroelectricity or ionic conductivity) that may be of commercial interest. With its sensitivity to the atomic-scale environment, NMR provides a potentially useful tool for studying disordered materials, and the combination of experiment with first-principles calculations offers a particularly attractive approach. In this Account, we discuss some of the issues associated with the practical implementation of first-principles calculations of NMR parameters in solids. We then use two key examples to illustrate the structural insights that researchers can obtain when applying such calculations to disordered inorganic materials. First, we describe an investigation of cation disorder in Y2Ti(2-x)Sn(x)O7 pyrochlore ceramics using (89)Y and (119)Sn NMR. Researchers have proposed that these materials could serve as host phases for the encapsulation of lanthanide- and actinide-bearing radioactive waste. In a second example, we discuss how (17)O NMR can be used to probe the dynamic disorder of H in hydroxyl-humite minerals (nMg2SiO4·Mg(OH)2), and how (19)F NMR can be used to understand F substitution in these systems. The combination of first-principles calculations and multinuclear NMR spectroscopy facilitates the investigation of local structure, disorder, and dynamics in solids. We expect that applications will undoubtedly become more widespread with further advances in computational and experimental methods. Insight into the atomic-scale environment is a crucial first step in understanding the structure-property relationships in solids, and it enables the efficient design of future materials for a range of end uses.

Electronic and crystal structure of NiTi martensite

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

Sanati, M.; Albers, R.C.; Pinski, F.J.

1998-11-01

All of the first-principles electronic-structure calculations for the martensitic structure of NiTi have used the experimental atomic parameters reported by Michal and Sinclair [Acta Crystallogr., Sect. B: Struct. Crystallogr. Cryst. Chem. {bold B37}, 1803 (1981)]. We have used first-principles, full-potential, linear muffin-tin orbital calculations to examine the total energy of all the experimental martensitic structures reported in the literature. We find that another crystal structure, that of Kudoh {ital et al.} [Acta Metall. Mater. {bold 33}, 2049 (1985)], has the lowest total energy at zero temperature. Ground-state and formation energies were calculated for all of the experimental structures. Total andmore » local densities of states were calculated and compared with each other for the structures of both Kudoh {ital et al.} and Michal and Sinclair thinsp {copyright} {ital 1998} {ital The American Physical Society}« less

First principles study of structural stability, electronic structure and mechanical properties of ReN and TcN

NASA Astrophysics Data System (ADS)

Rajeswarapalanichamy, R.; Kavitha, M.; Sudha Priyanga, G.; Iyakutti, K.

2015-03-01

The crystal structure, structural stability, electronic and mechanical properties of ReN and TcN are investigated using first principles calculations. We have considered five different crystal structures: NaCl, zinc blende (ZB), NiAs, tungsten carbide (WC) and wurtzite (WZ). Among these ZB phase is found to be the lowest energy phase for ReN and TcN at normal pressure. Pressure induced structural phase transitions from ZB to WZ phase at 214 GPa in ReN and ZB to NiAs phase at 171 GPa in TcN are predicted. The electronic structure reveals that both ReN and TcN are metallic in nature. The computed elastic constants indicate that both the nitrides are mechanically stable. As ReN in NiAs phase has high bulk and shear moduli and low Poisson's ratio, it is found to be a potential ultra incompressible super hard material.

First-principles study of graphene under c-HfO{sub 2}(111) layers: Electronic structures and transport properties

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

Kaneko, Tomoaki, E-mail: kaneko@flex.phys.tohoku.ac.jp; Materials Research Consortium for Energy Efficient Electronic Devices; Ohno, Takahisa, E-mail: OHNO.Takahisa@nims.go.jp

2016-08-22

We investigated the electronic properties, stability, and transport of graphene under c-HfO{sub 2}(111) layers by performing first-principles calculations with special attention to the chemical bonding between graphene and HfO{sub 2} surfaces. When the interface of HfO{sub 2}/graphene is terminated by an O layer, the linear dispersion of graphene is preserved and the degradation of transport is suppressed. For other interface structures, HfO{sub 2} is tightly adsorbed on graphene and the transport is strictly limited. In terms of the stability of the interface structures, an O-terminated interface is preferable, which is achieved under an O-deficient condition.

First principle study of transport properties of a graphene nano structure

NASA Astrophysics Data System (ADS)

Kumar, Naveen; Sharma, Munish; Sharma, Jyoti Dhar; Ahluwalia, P. K.

2013-06-01

The first principle quantum transport calculations have been performed for graphene using Tran SIESTA which calculates transport properties using nonequilibrium Green's function method in conjunction with density-functional theory. Transmission functions, electron density of states and current-voltage characteristic have been calculated for a graphene nano structure using graphene electrodes. Transmission function, density of states and projected density of states show a discrete band structure which varies with applied voltage. The value of current is very low for applied voltage between 0.0 V to 5.0 V and lies in the range of pico ampere. In the V-I characteristic current shows non-linear fluctuating pattern with increase in voltage.

Identification and properties of the non-cubic phases of Mg 2Pb

DOE PAGES

Li, Yuwei; Bian, Guang; Singh, David J.

2016-12-20

Mg 2Pb occurs in the cubic fluorite structure and is a semimetal with a band structure strongly affected by spin-orbit interaction on the Pb p states. Its properties are therefore of interest in the context of topological materials. In addition a different phase of Mg 2Pb was experimentally reported, but its crystal structure and properties remain unknown. Here we determine the structure of this phase using ab initio evolutionary methods and report its properties. The energy of one tetragonal phase, space group P4/ nmm, is 2 meV per atom higher than that of the ground state structure supporting the experimentalmore » observation. We find this tetragonal phase to be a compenstated anisotropic metal with strong spin orbit effects. As a result, many other metastable structures have also been identified, especially one orthorhombic structure, space group Pnma, of which energy is 17 meV per atom higher than that of ground state structure and which perhaps could be the phase that was reported based on similarity of lattice parameters.« less

First principle calculation in FeCo overlayer on GaAs substrate

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

Jain, Vishal, E-mail: vjain045@gmail.com; Lakshmi, N.; Jain, Vivek Kumar

In this work the first principle electronic structure calculation is reported for FeCo/GaAs thin film system to investigate the effect of orientation on the electronic structural properties. A unit cell describing FeCo layers and GaAs layers is constructed for (100), (110), (111) orientation with vacuum of 30Å to reduce dimensions. It is found that although the (110) orientation is energetically more favorable than others, the magnetic moment is quite large in (100) and (111) system compared to the (110) and is due to the total DOS variation with orientation.

First-principles study of giant thermoelectric power in incommensurate TlInSe2

NASA Astrophysics Data System (ADS)

Ishikawa, M.; Nakayama, T.; Wakita, K.; Shim, Y. G.; Mamedov, N.

2018-04-01

Ternary thallium compound TlInSe2 exhibits a giant Seebeck effect below around 410 K, where Tl atoms form one dimensional incommensurate (IC) arrays. To clarify the origin of large thermoelectric power in the IC phase, the electronic properties of Tl-atom super-structured TlInSe2 were studied using the first-principles calculations. It was shown that the super-structures induce strong binding states between Se-p orbitals in the nearest neighboring layers and produce large density of states near lower conduction bands, which might be one of the origins to produce large thermoelectric power.

First-principles study on the phase transitions, crystal stabilities and thermodynamic properties of TiN under high pressure

NASA Astrophysics Data System (ADS)

Sun, Xinjun; Liu, Changdong; Guo, Yongliang; Sun, Deyan; Ke, Xuezhi

2018-03-01

The structural and thermodynamic properties of titanium nitride (TiN) have been investigated by merging first-principles calculations and particle-swarm algorithm. The three phases are identified for TiN, including the B1, the P63 / mmc, and the B2 phases. A new phase of anti-TiP structure with the space group P63 / mmc has been predicted. The calculated phase transition from the B1 to the P63 / mmc occurs at 270 GPa. The vibrational, elastic, and thermodynamic properties for the three phases have been calculated and discussed.

Synthesis of nano-sized crystalline oxide ion conducting fluorite-type Y 2O 3-doped CeO 2 using perovskite-like BaCe 0.9Y 0.1O 2.95 (BCY) and study of CO 2 capture properties of BCY

NASA Astrophysics Data System (ADS)

Sneha, B. R.; Thangadurai, V.

2007-10-01

Formation of nano-sized Y 2O 3-doped CeO 2 (YCO) was observed in the chemical reaction between proton conducting Y 2O 3-doped BaCeO 3 (BCY) and CO 2 in the temperature range 700-1000 °C, which is generally prepared by wet-chemical methods that include sol-gel, hydrothermal, polymerization, combustion, and precipitation reactions. BCY can capture CO 2 of 0.13 g per ceramic gram at 700 °C, which is comparable to that of the well-known Li 2ZrO 3 (0.15 g per ceramic gram at 600 °C). Powder X-ray diffraction (PXRD), energy dispersive X-ray analysis (EDX), laser particle size analysis (LPSA), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ac impedance spectroscopy were employed to characterize the reaction product obtained from reaction between BCY and CO 2 and subsequent acid washing. PXRD study reveals presence of fluorite-like CeO 2 ( a=5.410 (1) Å) structure and BaCO 3 in reaction products. TEM investigation of the acid washed product showed the formation of nano-sized material with particle sizes of about 50 nm. The electrical conductivity of acid washed product (YCO) in air was found to be about an order higher than the undoped CeO 2 reported in the literature.

Fluid inclusion studies of the Rodeo de Los Molles REE and Th deposit, Las Chacras Batholith, Central Argentina

NASA Astrophysics Data System (ADS)

Lira, Raul; Ripley, Edward M.

1990-03-01

The Rodeo de Los Molles rare earth element (REE) and thorium deposit is located in granitic rocks of the Las Chacras-Piedras Coloradas Batholith, in the southern block of the Eastern Pampean Ranges, Central Argentina. Mineralization occurs within an elongate (2 km × 0.6 km) body of alkalifeldspar granite (alaskite) localized along the northeastern edge of a composite batholith. The surrounding lithology is predominantly a biotite monzogranite. Both the alaskite and localized areas of quartz alkalifeldspar syenite within the alaskite have been produced by hydrothermal alteration of a late-crystallizing phase of the monzogranite. REE minerals are primarily of the cerium group and include britholite and allanite, both partially replaced by bastnaesite or thorbastnaesite. These minerals occur as nodules with quartz, fluorite, aegirine-augite, sphene, and Fe-Ti oxides within aplitic to pegmatoidal quartz alkalifeldspar syenite. Uranothorite, along with a second generation of fluorite and minor amounts of MnBa oxides, occurs in the alaskite as nodules, or within quartz-lined miarolitic cavities, but is not found with the Ce-mineralization. Studies of fluid inclusions contained in quartz and fluorite indicate a complex history of open-system fluid migration and interaction with monzogranite host rocks. Fluids responsible for REE mineralization and quartz deposition, along with initial alteration of the monzogranite to alaskite and quartz alkalifeldspar syenite, were of relatively high temperature (T h of fluid inclusions in quartz = 356-535°C) and moderate salinity (15-25 eq. wt% NaCl). Mixed CO 2H 2O fluids (XCO 2 = .13-.07) found as both primary and secondary inclusions within fluorite are representative of fluids involved in the replacement of britholite-allanite by bastnaesite and sphene, aegirine-augite, and plagioclase by calcite. Minimum pressures of mineral deposition estimated from H 2OCO 2NaCl phase relations range from 1 to 2 kbars. Secondary aqueous fluid inclusions in quartz define a trend of low salinity-high temperature to high salinity-low temperature, thought to be a result of hydration reactions occurring in alaskite and quartz alkali-feldspar syenite. The highest salinity fluids (35-37 eq. wt% NaCl) detected in the area are associated with the formation of uranothorite and late fluorite. Multiple periods of hydrothermal fluid introduction are consistent with recent geological data that indicate that the batholith is composed of several stock-like bodies. The location of the mineralized area near the top of the magma chamber, the presence of numerous miarolitic cavities, and the bulk composition of inclusion fluids (Na ≥ K > Ca) suggest that the fluids responsible for REE and Th mineralization were of magmatic origin.

First principle investigation of electronic structure, chemical bonding and optical properties of tetrabarium gallium trinitride oxide single crystal

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

Khan, Saleem Ayaz, E-mail: sayaz_usb@yahoo.com; Azam, Sikander

The electronic band structure, valence electron charge density and optical susceptibilities of tetrabarium gallium trinitride (TGT) were calculated via first principle study. The electronic band structure calculation describes TGT as semiconductor having direct band gap of 1.38 eV. The valence electronic charge density contour verified the non-polar covalent nature of the bond. The absorption edge and first peak of dielectric tensor components showed electrons transition from N-p state to Ba-d state. The calculated uniaxial anisotropy (0.4842) and birefringence (−0.0061) of present paper is prearranged as follow the spectral components of the dielectric tensor. The first peak in energy loss functionmore » (ELOS) shows the energy loss of fast traveling electrons in the material. The first sharp peak produced in ELOS around 10.5 eV show plasmon loss having plasma frequencies 0.1536, 0.004 and 0.066 of dielectric tensor components. This plasmon loss also cause decrease in reflectivity spectra.« less

A first principles study on newly proposed (Ca/Sr/Ba)Fe2Bi2 compounds with their parent compounds

NASA Astrophysics Data System (ADS)

Sundareswari, M.; Jayalakshmi, D. S.; Viswanathan, E.

2016-02-01

The structural, electronic, bonding and magnetic properties of newly proposed iron-based compounds viz., CaFe2Bi2, SrFe2Bi2, BaFe2Bi2 with their Fermi surface topology are reported here for the first time by means of first principles calculation. All these properties of newly proposed compounds are compared and analysed along with their respective parent compounds namely (Ca,Sr,Ba)Fe2As2.

Structural and electronic properties of LaPd2As2 superconductor: First-principle calculations

NASA Astrophysics Data System (ADS)

Singh, Birender; Kumar, Pradeep

2017-05-01

In present work we have studied electronic and structural properties of superconducting LaPd2As2 compound having collapsed tetragonal structure using first-principle calculations. The band structure calculations show that the LaPd2As2 is metallic consistent with the reported experimental observation, and the density of states plots clearly shows that at the Fermi level major contribution to density of states arises from Pd 4d and As 4p states, unlike the Fe-based superconductors where major contribution at the Fermi level comes from Fe 3d states. The estimated value of electron-phonon coupling is found to be 0.37, which gives the upper bound of superconducting transition temperature of 5K, suggesting the conventional nature of this superconductor.

First-principles study of high-pressure structural phase transitions of magnesium

NASA Astrophysics Data System (ADS)

Liu, Qiuxiang; Fan, Changzeng; Zhang, Ruijun

2009-06-01

The structural phase transitions for the hcp, bcc, dhcp, and fcc of magnesium at hydrostatic pressures larger than about 200 GPa at zero temperature are studied by first-principles total energy calculations. The plane-wave basis pseudopotential method has been adopted, in which the generalized gradient approximation implanted in the CASTEP code is employed. By comparing the enthalpy differences of the hcp structure with other three structures under different pressures, it can be seen that when the pressure becomes higher than about 65, 130, and 190 GPa, the bcc, dhcp, and fcc structures become more stable relative to the hcp structure, respectively. Due to the lowest enthalpy value of the bcc structure above 65 GPa, it can be deduced that magnesium may transform to the bcc structure from the ground state hcp structure around 65 GPa, but no further phase transitions occur without additionally applying high temperature. In addition, the equation of state of magnesium is calculated, indicating that bcc structure is the softest phase.

Transferable atomistic model to describe the energetics of zirconia

NASA Astrophysics Data System (ADS)

Wilson, Mark; Schönberger, Uwe; Finnis, Michael W.

1996-10-01

We have investigated the energies of a number of phases of ZrO2 using models of an increasing degree of sophistication: the simple ionic model, the polarizable ion model, the compressible ion model, and finally a model including quadrupole polarizability of the oxygen ions. The three structures which are observed with increasing temperatures are monoclinic, tetragonal, and cubic (fluorite). Besides these we have studied some hypothetical structures which certain potentials erroneously predict or which occur in other oxides with this stoichiometry, e.g., the α-PbO2 structure and rutile. We have also performed ab initio density functional calculations with the full-potential linear combination of muffin-tin orbitals method to investigate the cubic-tetragonal distortion. A detailed comparison is made between the results using classical potentials, the experimental data, and our own and other ab initio results. The factors which stabilize the various structure are analyzed. We find the only genuinely transferable model is the one including compressible ions and anion polarizability to the quadrupole level.

Short-term Rn-222 concentration changes in underground spaces with limited air exchange

NASA Astrophysics Data System (ADS)

Fijałkowska-Lichwa, Lidia; Przylibski, Tadeusz A.

2010-05-01

Authors conducted research on radon concentration in two underground structures located in the vicinity of Kletno (Sudety Mts., SW Poland), which are accessible for visitors. One of these structures is Niedźwiedzia (Bear) Cave, and the second one is the part of former uranium mine - Fluorite Adit. Both selected underground structures are characterized by almost constant temperature, changing within the range from +5 to +7° C and also constant relative humidity, close to 100%. Both these parameters testify that air exchange with the atmosphere is very limited. Air exchange is limited particularly in Niedźwiedzia Cave, which microclimate is protected i.e. by applying of locks at the entrance and exit of tourist route. The measurements were conducted between 16.05.2008. and 15.11.2009., by the use of a new Polish equipment - SRDN-3 devices with semiconductor detector. SRDN-3 device records every hour radon concentration as well as atmospheric parameters - relative humidity and temperature. At the same time authors conducted measurements of basic parameters in the open atmosphere close to Niedźwiedzia Cave. Obtained results of atmospheric parameters measurements may be used for both underground structures; because they are located within the distance of about 1 km. Atmospheric parameters were measured by the use of automatic weather station VantagePro2. On the base of conducted research authors corroborate, that the differences of radon concentration in both underground structures reach three orders of magnitude during a year. In Niedźwiedzia Cave these values are in the range from below 88 Bq/m3 (detection limit of the SRDN-3 device) up to 12 kBq/m3. Related values in Fluorite Adit are between < 88 Bq/m3 and 35 kBq/m3. It was observed also the different course of daily radon concentration changes in both structures. Additionally, authors registered that daily course of radon concentration changes differs due to season of the year. Such changes are observed in both structures. The reasons of these changes are probably connected with the way of air exchange between interior of the structure and the atmosphere. In both cases they are determined by atmospheric air temperature changes in relation with the temperature of the air inside the cave or adit. Authors have been still working on this problem. We can also say, that the character of daily radon concentration changes inside both examined structures differ from typical changes noted in dwelling houses.

Magnetic interactions in praseodymium ruthenate Pr{sub 3}RuO{sub 7} with fluorite-related structure

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

Inabayashi, Masaki; Doi, Yoshihiro; Wakeshima, Makoto

2017-06-15

Solid solutions Pr{sub 3}(Ru{sub 1-x}Ta{sub x})O{sub 7} (0≤x≤1.0) and (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7} (0≤x≤0.7) were obtained as a single phase compound. They crystallize in an orthorhombic superstructure derived from that of the cubic fluorite with space group Cmcm. The results of the Rietveld analysis for X-ray diffraction profiles of Pr{sub 3}(Ru{sub 1-x}Ta{sub x})O{sub 7} showed that Ru and Ta atoms are randomly situated at the six-coordinate 4b site. For (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7}, with increasing the concentration of Y ions (x value), the smaller Y ions occupy selectively the seven-coordinate 8g site rather than the eight-coordinate 4a site.more » Through magnetic susceptibility measurements for Pr{sub 3}(Ru{sub 1-x}Ta{sub x})O{sub 7}, the antiferromagnetic transition temperatures decrease linearly with increasing x value, and at x=0.75 no magnetic ordering was found down to 1.8 K, indicating the magnetic interaction is not one-dimensional, but three-dimensional. On the other hand, the antiferromagnetic transition temperature for (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7} decreases with increasing x value, but above x≥0.50 it becomes constant (~12 K). This result indicates that Pr{sup 3+} ions at the seven-coordinate site greatly contribute to the antiferromagnetic interactions observed in (Pr{sub 1-x}Y{sub x}){sub 3}RuO{sub 7}. Density functional calculations of Pr{sub 3}RuO{sub 7} demonstrate that the electronic structure gives insulating character and that oxygen 2p orbitals hybridize strongly with Ru 4d orbitals in the valence band (VB). Near the top of VB, the Pr 4 f orbitals at the seven-coordinated site also show a weak hybridization with the O(1) 2p orbitals. The Ru-O(1)-Pr superexchange pathway take part in three-dimensional magnetic interaction and play an important role in an enhancement of long-range magnetic ordering. - Graphical abstract: The spin densities and the spin polarization of Pr{sub 3}RuO{sub 7} are shown. Significant spin polarization is seen on the magnetic Pr and Ru ions, but there is also some on the O(1), (3) ligands of Ru. - Highlights: • New fluorite-related quaternary praseodymium ruthenates were prepared. • Pr{sub 3}RuO{sub 7} shows an antiferromagnetic transition at 55 K. • The Ru-O-Pr superexchange interactions are three-dimensional.« less

Achieving accuracy in first-principles calculations for EOS: basis completeness at high temperatures

NASA Astrophysics Data System (ADS)

Wills, John; Mattsson, Ann

2013-06-01

First-principles electronic structure calculations can provide EOS data in regimes of pressure and temperature where accurate experimental data is difficult or impossible to obtain. This lack, however, also precludes validation of calculations in those regimes. Factors that influence the accuracy of first-principles data include (1) theoretical approximations and (2) computational approximations used in implementing and solving the underlying equations. In the first category are the approximate exchange/correlation functionals and approximate wave equations approximating the Dirac equation; in the second are basis completeness, series convergence, and truncation errors. We are using two rather different electronic structure methods (VASP and RSPt) to make definitive the requirements for accuracy of the second type, common to both. In this talk, we discuss requirements for converged calculation at high temperature and moderated pressure. At convergence we show that both methods give identical results. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

High-pressure structural study of MnF 2

DOE PAGES

Stavrou, Elissaios; Yao, Yansun; Goncharov, Alexander F.; ...

2015-02-01

In this study, manganese fluoride (MnF 2) with the tetragonal rutile-type structure has been studied using a synchrotron angle-dispersive powder x-ray diffraction and Raman spectroscopy in a diamond anvil cell up to 60 GPa at room temperature combined with first-principles density functional calculations. The experimental data reveal two pressure-induced structural phase transitions with the following sequence: rutile → SrI 2 type (3 GPa)→ α–PbCl 2 type (13 GPa). Complete structural information, including interatomic distances, has been determined in the case of MnF 2 including the exact structure of the debated first high-pressure phase. First-principles density functional calculations confirm this phasemore » transition sequence, and the two calculated transition pressures are in excellent agreement with the experiment. Lattice dynamics calculations also reproduce the experimental Raman spectra measured for the ambient and high-pressure phases. The results are discussed in line with the possible practical use of rutile-type fluorides in general and specifically MnF 2 as a model compound to reveal the HP structural behavior of rutile-type SiO 2 (Stishovite).« less

Taolin Zn-Pb-fluorite deposit, People's Republic of China: an example of some problems in fluid inclusion research on mineral deposits.

USGS Publications Warehouse

Roedder, E.; Howard, K.W.

1988-01-01

The ore in this large Zn-Pb-fluorite deposit in NE Hunan Province occurs as open space-filling in a major fault zone between granite and metasedimentary rocks. Following barren, pre-ore quartz, three stages of ore deposition are recognized. Studies on 400 fluid inclusions from all four stages show homogenization T of 120-200oC (av. approx 160o) and salinities of 0-14 wt.% equiv. NaCl (av. 7.7) . These results differ considerably from some previously published sulphur isotopic T (221-344oC), and data for five inclusions that are more saline (9.0-7.7 wt.% equiv. NaCl) and hotter (up to 345oC) (M.A. 85M/2835, 87M/0888).-R.A.H.

A hybrid computational-experimental approach for automated crystal structure solution

NASA Astrophysics Data System (ADS)

Meredig, Bryce; Wolverton, C.

2013-02-01

Crystal structure solution from diffraction experiments is one of the most fundamental tasks in materials science, chemistry, physics and geology. Unfortunately, numerous factors render this process labour intensive and error prone. Experimental conditions, such as high pressure or structural metastability, often complicate characterization. Furthermore, many materials of great modern interest, such as batteries and hydrogen storage media, contain light elements such as Li and H that only weakly scatter X-rays. Finally, structural refinements generally require significant human input and intuition, as they rely on good initial guesses for the target structure. To address these many challenges, we demonstrate a new hybrid approach, first-principles-assisted structure solution (FPASS), which combines experimental diffraction data, statistical symmetry information and first-principles-based algorithmic optimization to automatically solve crystal structures. We demonstrate the broad utility of FPASS to clarify four important crystal structure debates: the hydrogen storage candidates MgNH and NH3BH3; Li2O2, relevant to Li-air batteries; and high-pressure silane, SiH4.

A first-principles study on second-order ferroelectric phase transition in two-dimensional puckered group V materials

NASA Astrophysics Data System (ADS)

Lee, Sang-Hoon; Jhi, Seung-Hoon

We study two-dimensional group V materials (P, As, Sb, and Bi) in puckered honeycomb structure using first-principles calculations. Two factors, the degree of puckering and buckling characterize not only the atomic structure but also the electronic structure and its topological phase. By analyzing the lone-pair character of constituent elements and the softening of the phonon mode, we clarify the origin of the buckling. We show that the phonon softening leads the second-order type structural phase transition from a flat to a buckled configuration. The inversion symmetry breaking associated with the structural transition induces the spontaneous polarization in these homogenous materials. Our calculations suggest that external strains or n-type doping are effective methods to control the degree of buckling. We find that the ferroelectric and non-trivial topological phase can coexist in puckered Bi when tensile strains are applied.

Modeling the structural, dynamical, and magnetic properties of liquid Al1-xMnx ( x=0.14 , 0.2, and 0.4): A first-principles investigation

NASA Astrophysics Data System (ADS)

Jakse, N.; Pasturel, A.

2007-07-01

We report the results of first-principles molecular dynamics simulations of liquid Al1-xMnx alloys at three different compositions. The local structure as defined by the Bhatia-Thornton partial structure factors is found to display significant changes at x=0.4 . In addition, a structural analysis using three-dimensional pair-analysis techniques evidences a fivefold symmetry around x=0.14 , in agreement with the experimental quasicrystal-forming range, and an increasing complexity of the Frank-Kasper polytetrahedral symmetry around Mn atoms at x=0.4 . We also examine the time evolution of the configurations at the three compositions in terms of the mean-square displacements and self-diffusion coefficients. Finally, we show a strong interplay between the structural changes and the evolution of the magnetic properties of the Mn atoms as a function of composition.

Pressure-induced phase transition of KTa1/2Nb1/2O3 solid solutions: A first-principles study

NASA Astrophysics Data System (ADS)

Zhang, Huadi; Liu, Bing; Zhang, Cong; Qiu, Chengcheng; Wang, Xuping; Zhang, Yuanyuan; Lv, Xianshun; Wei, Lei; Li, Qinggang

2018-05-01

The structures and electronic properties of KTa1/2Nb1/2O3 under high pressures have been investigated using the first-principles calculations. Three candidates with B site cation ordered along the [1 0 0], [1 1 0] and [1 1 1] directions are found stable under different pressures by thermodynamics, mechanics and dynamics stability criteria. Further electronic analysis indicates that three structures are semiconductors with different band-gap characteristics. The peculiar chemical bonds of Nb-O and Ta-O are expected to be related to the different electronegativity of the corresponding cations.

Molecular adsorption study of nicotine and caffeine on single-walled carbon nanotubes from first principles

NASA Astrophysics Data System (ADS)

Lee, Hyung-June; Kim, Gunn; Kwon, Young-Kyun

2013-08-01

Using first-principles calculations, we investigate the electronic structures and binding properties of nicotine and caffeine adsorbed on single-walled carbon nanotubes to determine whether CNTs are appropriate for filtering or sensing nicotine and caffeine molecules. We find that caffeine adsorbs more strongly than nicotine. The different binding characteristics are discussed by analyzing the modification of the electronic structure of the molecule-adsorbed CNTs. We also calculate the quantum conductance of the CNTs in the presence of nicotine or caffeine adsorbates and demonstrate that the influence of caffeine is stronger than nicotine on the conductance of the host CNT.

GMR in magnetic multilayers from a first principles band structure Kubo-Greenwood approach

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

Rao, F.; Freeman, A.J.

1998-07-01

The authors employ the Kubo-Greenwood formula to investigate from first-principles the giant magnetoresistance in Fe{sub m}M{sub n} (M = V, Cr, Mn and Cu) superlattices. The results indicate that MR can arise from band structure changes from ferromagnetic to anti-ferromagnetic alignments. Quantum confinement in the perpendicular direction is induced by the potential steps between the Fe and spacer layers and causes a much larger MR in the current-perpendicular-to-the-plane (CPP) geometry than in the current-in-plane (CIP) geometry. In the presence of the spin-orbit coupling interaction, MR is found to be reduced by spin-channel mixing.

Si-centered capped trigonal prism ordering in liquid Pd 82Si 18 alloy study by first-principles calculations

DOE PAGES

Dong, F.; Yue, G. Q.; Ames Lab. and Iowa State Univ., Ames, IA; ...

2017-03-24

First-principles molecular dynamic (MD) simulation and X-ray diffraction were employed to study the local structures of Pd–Si liquid at the eutectic composition (Pd 82Si 18). Here, a strong repulsion is found between Si atoms, and Si atoms prefer to be evenly distributed in the liquid. The dominate local structures around Si atoms are found to be with of a trigonal prism capped by three half-octahedra and an archimedean anti-prism. The populations of these clusters increase significantly upon cooling, and may play an important role in the formation of Pd 82Si 18 alloy glass.

Si-centered capped trigonal prism ordering in liquid Pd 82Si 18 alloy study by first-principles calculations

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

Dong, F.; Yue, G. Q.; Ames Lab. and Iowa State Univ., Ames, IA

First-principles molecular dynamic (MD) simulation and X-ray diffraction were employed to study the local structures of Pd–Si liquid at the eutectic composition (Pd 82Si 18). Here, a strong repulsion is found between Si atoms, and Si atoms prefer to be evenly distributed in the liquid. The dominate local structures around Si atoms are found to be with of a trigonal prism capped by three half-octahedra and an archimedean anti-prism. The populations of these clusters increase significantly upon cooling, and may play an important role in the formation of Pd 82Si 18 alloy glass.

First-principles calculations of the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2)

NASA Astrophysics Data System (ADS)

Wen, Xiangli; Liang, Yuxuan; Bai, Pengpeng; Luo, Bingwei; Fang, Teng; Yue, Luo; An, Teng; Song, Weiyu; Zheng, Shuqi

2017-11-01

The thermodynamic properties of Fe-S compounds with different crystal structure are very different. In this study, the structural, elastic and thermodynamic properties of mackinawite (FeS) and pyrite (FeS2) were investigated by first-principles calculations. Examination of the electronic density of states shows that mackinawite (FeS) is metallic and that pyrite (FeS2) is a semiconductor with a band gap of Eg = 1.02 eV. Using the stress-strain method, the elastic properties including the bulk modulus and shear modulus were derived from the elastic Cij data. Density functional perturbation theory (DFPT) calculations within the quasi-harmonic approximation (QHA) were used to calculate the thermodynamic properties, and the two Fe-S compounds are found to be dynamically stable. The isothermal bulk modulus, thermal expansion coefficient, heat capacities, Gibbs free energy and entropy of the Fe-S compounds are obtained by first-principles phonon calculations. Furthermore, the temperature of the mackinawite (FeS) ⟶ pyrite (FeS2) phase transition at 0 GPa was predicted. Based on the calculation results, the model for prediction of Fe-S compounds in the Fe-H2S-H2O system was improved.

Vibrational and mechanical properties of single layer MXene structures: a first-principles investigation

NASA Astrophysics Data System (ADS)

Yorulmaz, Uğur; Özden, Ayberk; Perkgöz, Nihan K.; Ay, Feridun; Sevik, Cem

2016-08-01

MXenes, carbides, nitrides and carbonitrides of early transition metals are the new members of two dimensional materials family given with a formula of {{{M}}}n+1 X n . Recent advances in chemical exfoliation and CVD growth of these crystals together with their promising performance in electrochemical energy storage systems have triggered the interest in these two dimensional structures. In this work, we employ first principles calculations for n = 1 structures of Sc, Ti, Zr, Mo and Hf pristine MXenes and their fully surface terminated forms with F and O. We systematically investigated the dynamical and mechanical stability of both pristine and fully terminated MXene structures to determine the possible MXene candidates for experimental realization. In conjunction with an extensive stability analysis, we report Raman and infrared active mode frequencies for the first time, providing indispensable information for the experimental elaboration of MXene field. After determining dynamically stable MXenes, we provide their phonon dispersion relations, electronic and mechanical properties.

Vibrational and mechanical properties of single layer MXene structures: a first-principles investigation.

PubMed

Yorulmaz, Uğur; Özden, Ayberk; Perkgöz, Nihan K; Ay, Feridun; Sevik, Cem

2016-08-19

MXenes, carbides, nitrides and carbonitrides of early transition metals are the new members of two dimensional materials family given with a formula of [Formula: see text] X n . Recent advances in chemical exfoliation and CVD growth of these crystals together with their promising performance in electrochemical energy storage systems have triggered the interest in these two dimensional structures. In this work, we employ first principles calculations for n = 1 structures of Sc, Ti, Zr, Mo and Hf pristine MXenes and their fully surface terminated forms with F and O. We systematically investigated the dynamical and mechanical stability of both pristine and fully terminated MXene structures to determine the possible MXene candidates for experimental realization. In conjunction with an extensive stability analysis, we report Raman and infrared active mode frequencies for the first time, providing indispensable information for the experimental elaboration of MXene field. After determining dynamically stable MXenes, we provide their phonon dispersion relations, electronic and mechanical properties.

First-principles theory of cation- and intercalation-ordering in Li_xCoO_2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

1998-03-01

Using a combination of first-principles total energies, a cluster expansion technique, and Monte Carlo simulations, we present a first-principles theory which can predict both cation- and intercalation-ordering patterns at both zero and finite temperatures, and can provide first-principles predictions of battery voltages of Li_xCoO_2/Li cells. The classes of ordering problems that we study are the following: (i) The LiMO2 oxides (M=3d metal) form a series of structures based on an octahedrally-coordinated network with anions (O) on one fcc sublattice and cations (Li and M) on the other, leading to Li/Co ordering in LiCoO2 (x=1). We find the ground state is the CuPt or (111)-layered cation arrangment, in agreement with the observed structure. (ii) In battery applications, Li is (de)intercalated from the compound, creating a vacancy (denoted Box) that can be positioned in different lattice locations; Thus, Box/Co ordering in BoxCoO2 (x=0) is also of interest. We find the ground state for BoxCoO2 is also a (111)-layered structure, although a different stacking sequence (AAA) of close-packed layers is preferred. (iii) The vacancies left behind by Li extraction can form ordered vacancy compounds in partially de-lithiated Li_xCoO_2, leading to a Box/Li ordering problem (0<=x<=1). Our calculations agree with the observed voltage profiles in these systems, and predict the existence of new intercalation-ordered compounds. Supported by BES/OER/DMS under contract DE-AC36-83CH10093.

Vivek S. Bharadwaj | NREL

Science.gov Websites

Interests Vivek's interests broadly span across protein structure and dynamics, reaction mechanisms, and energetics and kinetics from first principles Protein structure prediction and docking Education PhD structure on the fumarate addition mechanism - a gas-phase ab initio study," Physical Chemistry

Role of composition, bond covalency, and short-range order in the disordering of stannate pyrochlores by swift heavy ion irradiation

NASA Astrophysics Data System (ADS)

Tracy, Cameron L.; Shamblin, Jacob; Park, Sulgiye; Zhang, Fuxiang; Trautmann, Christina; Lang, Maik; Ewing, Rodney C.

2016-08-01

A2S n2O7 (A =Nd ,Sm,Gd,Er,Yb,and Y) materials with the pyrochlore structure were irradiated with 2.2 GeV Au ions to systematically investigate disordering of this system in response to dense electronic excitation. Structural modifications were characterized, over multiple length scales, by transmission electron microscopy, x-ray diffraction, and Raman spectroscopy. Transformations to amorphous and disordered phases were observed, with disordering dominating the structural response of materials with small A -site cation ionic radii. Both the disordered and amorphous phases were found to possess weberite-type local ordering, differing only in that the disordered phase exhibits a long-range, modulated arrangement of weberite-type structural units into an average defect-fluorite structure, while the amorphous phase remains fully aperiodic. Comparison with the behavior of titanate and zirconate pyrochlores showed minimal influence of the high covalency of the Sn-O bond on this phase behavior. An analytical model of damage accumulation was developed to account for simultaneous amorphization and recrystallization of the disordered phase during irradiation.

First-principles approach to calculating energy level alignment at aqueous semiconductor interfaces.

PubMed

Kharche, Neerav; Muckerman, James T; Hybertsen, Mark S

2014-10-24

A first-principles approach is demonstrated for calculating the relationship between an aqueous semiconductor interface structure and energy level alignment. The physical interface structure is sampled using density functional theory based molecular dynamics, yielding the interface electrostatic dipole. The  GW approach from many-body perturbation theory is used to place the electronic band edge energies of the semiconductor relative to the occupied 1b1 energy level in water. The application to the specific cases of nonpolar (101¯0) facets of GaN and ZnO reveals a significant role for the structural motifs at the interface, including the degree of interface water dissociation and the dynamical fluctuations in the interface Zn-O and O-H bond orientations. These effects contribute up to 0.5 eV.

In and Si adatoms on Si(111)5×2-Au : Scanning tunneling microscopy and first-principles density functional calculations

NASA Astrophysics Data System (ADS)

Stępniak, A.; Nita, P.; Krawiec, M.; Jałochowski, M.

2009-09-01

Structural properties of monatomic indium chains on Si(111)5×2-Au surface are investigated by scanning tunneling microscopy (STM) and first-principles density functional calculations (DFT). The STM topography data show that submonolayer coverage of indium leads to a well-ordered chain structure with the same periodicity as the Si adatoms form on Si(111)5×2-Au surface. Bias-dependent STM topography and spectroscopy reveal two different mechanisms of In-atoms adsorption on the surface: bonding to Si adatoms and substitution for Si atoms in the adatom positions. Those mechanisms are further corroborated by DFT calculations. The obtained structural model of In-modified Si(111)5×2-Au surface remains in good agreement with the experimental data.

First principles predictions of electronic and elastic properties of BaPb2As2 in the ThCr2Si2-type structure

NASA Astrophysics Data System (ADS)

Bourourou, Y.; Amari, S.; Yahiaoui, I. E.; Bouhafs, B.

2018-01-01

A first-principles approach is used to predicts the electronic and elastic properties of BaPb2As2 superconductor compound, using full-potential linearized augmented plane wave plus local orbitals (FP-L/APW+lo) scheme within the local density approximation LDA. The calculated equilibrium structural parameter a agree well with the experiment while the c/a ratio is far away from the experimental result. The band structure, density of states, together with the charge density and chemical bonding are discussed. The calculated elastic constants for our compound indicate that it is mechanically stable at ambient pressure. Polycrystalline elastic moduli (Young's, Bulk, shear Modulus and the Poisson's ratio) were calculated according to the Voigte-Reusse-Hill (VRH) average.

Theoretical study of band gap in CuAlO2: Pressure dependence and self-interaction correction

NASA Astrophysics Data System (ADS)

Nakanishi, Akitaka; Katayama-Yoshida, Hiroshi

2012-08-01

By using first-principles calculations, we studied the energy gaps of delafossite CuAlO2: (1) pressure dependence and (2) self-interaction correction (SIC). Our simulation shows that CuAlO2 transforms from a delafossite structure to a leaning delafossite structure at 60 GPa. The energy gap of CuAlO2 increases through the structural transition due to the enhanced covalency of Cu 3d and O 2p states. We implemented a self-interaction correction (SIC) into first-principles calculation code to go beyond local density approximation and applied it to CuAlO2. The energy gap calculated within the SIC is close to experimental data while one calculated without the SIC is about 1 eV smaller than the experimental data.

Ion mobility and conductivity in the M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (M=K, Rb) solid solutions with fluorite structure

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

Kavun, V. Ya., E-mail: kavun@ich.dvo.ru; Uvarov, N.F.; Slobodyuk, A.B.

Ionic mobility and conductivity in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} and Rb{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} (x=0.05, 0.09) solid solutions with the fluorite structure have been investigated using the methods of {sup 19}F NMR, X-ray diffraction and impedance spectroscopy. Types of ionic motions in the fluoride sublattice of solid solutions have been established and temperature ranges of their realization have been determined (150–450 K). Diffusion of fluoride ions is a dominating type of ionic motions in the fluoride sublattice of solid solutions under study above 350 K. Due to high ionic conductivity, above 10{sup –3} S/cm at 450 K,more » these solid solutions can be used as solid electrolytes in various electrochemical devices and systems. - Graphical abstract: Temperature dependence of the concentration of mobile (2, 4) and immobile (1, 3) F ions in the K{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions. - Highlights: • Studied the ion mobility, conductivity in M{sub 0.5–x}Pb{sub x}Bi{sub 0.5}F{sub 2+x} solid solutions (M=K, Rb). • An analysis of {sup 19}F NMR spectra made it possible to identify types of ion mobility. • The main type of ion motion above 300 K in solid solutions is a diffusion of ions F{sup –}. • The ionic conductivity of the solid solutions studied more than 10{sup –3} S/cm at 450 K.« less

Experimental observation of charge-shift bond in fluorite CaF2.

PubMed

Stachowicz, Marcin; Malinska, Maura; Parafiniuk, Jan; Woźniak, Krzysztof

2017-08-01

On the basis of a multipole refinement of single-crystal X-ray diffraction data collected using an Ag source at 90 K to a resolution of 1.63 Å -1 , a quantitative experimental charge density distribution has been obtained for fluorite (CaF 2 ). The atoms-in-molecules integrated experimental charges for Ca 2+ and F - ions are +1.40 e and -0.70 e, respectively. The derived electron-density distribution, maximum electron-density paths, interaction lines and bond critical points along Ca 2+ ...F - and F - ...F - contacts revealed the character of these interactions. The Ca 2+ ...F - interaction is clearly a closed shell and ionic in character. However, the F - ...F - interaction has properties associated with the recently recognized type of interaction referred to as `charge-shift' bonding. This conclusion is supported by the topology of the electron localization function and analysis of the quantum theory of atoms in molecules and crystals topological parameters. The Ca 2+ ...F - bonded radii - measured as distances from the centre of the ion to the critical point - are 1.21 Å for the Ca 2+ cation and 1.15 Å for the F - anion. These values are in a good agreement with the corresponding Shannon ionic radii. The F - ...F - bond path and bond critical point is also found in the CaF 2 crystal structure. According to the quantum theory of atoms in molecules and crystals, this interaction is attractive in character. This is additionally supported by the topology of non-covalent interactions based on the reduced density gradient.

The interfacial orientation relationship of oxide nanoparticles in a hafnium-containing oxide dispersion-strengthened austenitic stainless steel

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

Miao, Yinbin, E-mail: miao2@illinois.edu; Mo, Kun; Cui, Bai

2015-03-15

This work reports comprehensive investigations on the orientation relationship of the oxide nanoparticles in a hafnium-containing austenitic oxide dispersion-strengthened 316 stainless steel. The phases of the oxide nanoparticles were determined by a combination of scanning transmission electron microscopy–electron dispersive X-ray spectroscopy, atom probe tomography and synchrotron X-ray diffraction to be complex Y–Ti–Hf–O compounds with similar crystal structures, including bixbyite Y{sub 2}O{sub 3}, fluorite Y{sub 2}O{sub 3}–HfO{sub 2} solid solution and pyrochlore (or fluorite) Y{sub 2}(Ti,Hf){sub 2−x}O{sub 7−x}. High resolution transmission electron microscopy was used to characterize the particle–matrix interfaces. Two different coherency relationships along with one axis-parallel relation between themore » oxide nanoparticles and the steel matrix were found. The size of the nanoparticles significantly influences the orientation relationship. The results provide insight into the relationship of these nanoparticles with the matrix, which has implications for interpreting material properties as well as responses to radiation. - Highlights: • The oxide nanoparticles in a hafnium-containing austenitic ODS were characterized. • The nanoparticles are Y–Hf–Ti–O enriched phases according to APT and STEM–EDS. • Two coherency and an axis-parallel orientation relationships were found by HR-TEM. • Particle size has a prominent effect on the orientation relationship (OR). • Formation mechanism of the oxide nanoparticles was discussed based on the ORs.« less

A combined experimental and computational thermodynamic investigation of the U-Th-O system

DOE PAGES

McMurray, Jake Wesley; Voit, Stewart L.; Besmann, Theodore M.

2016-03-21

Here, the thermodynamics of the U–Th–O system have been assessed using the Calphad method. The compound energy formalism (CEF) and a partially ionic two-sublattice liquid model (TSLM) were used for the fluorite U 1–yTh yO 2±x, γ-(U,Th) 4O 9, and the U–Th–O melt. The O 2 activity of fluorite U 1–yTh yO 2±x with temperature and composition was determined by thermogravimetric analysis. Thermodynamic studies for the Th–O binary and U–Th–O ternary available in the open literature were critically reviewed. A self-consistent data set was selected and compiled with the equilibrium oxygen pressures determined by thermogravimetry in order to optimize themore » adjustable parameters of models selected to represent the phases in the Th–O and U–Th–O systems.« less

Solid iron-hydrogen alloys under high pressure by first principles

NASA Astrophysics Data System (ADS)

Umemoto, K.; Hirose, K.

2016-12-01

Hydrogen and iron are two of major constituents of the Earth and planetary interiors. The crystal structure of solid FeHx is one of the most fundamental information in order to understand properties of planetary cores. It is well known that FeH takes closed-packed structures: dhcp, hcp, and fcc. Recently, hydrogen-rich phases, FeH2 and FeH3, were experimentally synthesized [1]. Although a tetragonal structure of FeH2 was proposed, it could not explain experimental observations, energetic stability and compression curve. Here we propose a new crystal structure of FeH2. The symmetry of the new structure is completely identical to that in originally proposed one, but the hydrogen sublattice which cannot be directly determined by XRD experiments is different. It will be demonstrated by first principles that the new structure can be fully consistent with experimental observations. [1] C. M. Pépin, A. Dewaele, G. Geneste, P. Loubeyre, and M. Mezouar, Phys. Rev. Lett. 113, 265504 (2014).

M3Ag17(SPh)12 Nanoparticles and Their Structure Prediction.

PubMed

Wickramasinghe, Sameera; Atnagulov, Aydar; Conn, Brian E; Yoon, Bokwon; Barnett, Robert N; Griffith, Wendell P; Landman, Uzi; Bigioni, Terry P

2015-09-16

Although silver nanoparticles are of great fundamental and practical interest, only one structure has been determined thus far: M4Ag44(SPh)30, where M is a monocation, and SPh is an aromatic thiolate ligand. This is in part due to the fact that no other molecular silver nanoparticles have been synthesized with aromatic thiolate ligands. Here we report the synthesis of M3Ag17(4-tert-butylbenzene-thiol)12, which has good stability and an unusual optical spectrum. We also present a rational strategy for predicting the structure of this molecule. First-principles calculations support the structural model, predict a HOMO-LUMO energy gap of 1.77 eV, and predict a new "monomer mount" capping motif, Ag(SR)3, for Ag nanoparticles. The calculated optical absorption spectrum is in good correspondence with the measured spectrum. Heteroatom substitution was also used as a structural probe. First-principles calculations based on the structural model predicted a strong preference for a single Au atom substitution in agreement with experiment.

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

Nelson, Nicholas C.; Wang, Zhuoran; Naik, Pranjali

Deposition of trimethylphosphate onto ceria followed by thermal treatment resulted in the formation of surface phosphates with retention of the ceria fluorite structure. The structural and chemical properties of the phosphate-functionalized ceria were studied using 31P solid-state NMR, XPS, zeta titration, ammonia thermal desorption, pyridine adsorption, and model reactions. The introduction of phosphates generated Brønsted acid sites and decreased the number of Lewis acid sites on the surface. The relative amount of Lewis and Brønsted acids can be controlled by the amount of trimethylphosphate used in the synthesis. Upon deposition of Pd, the multifunctional material showed enhanced activity for themore » hydrogenolysis of eugenol and guaiacol compared to Pd on the unmodified ceria support. As a result, this was attributed to the cooperativity between the Lewis acid sites, which activate the substrate for dearomatization, and the redox/Brønsted acid properties, which catalyze hydrogenolysis.« less

A stable compound of helium and sodium at high pressure

DOE PAGES

Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.; ...

2017-02-06

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na 2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes thismore » material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na 8 cubes. As a result, we also predict the existence of Na 2HeO with a similar structure at pressures above 15 GPa.« less

Phage-directed synthesis of copper sulfide: structural and optical characterization

NASA Astrophysics Data System (ADS)

Shahriar Zaman, Mohammed; Moon, Chung Hee; Bozhilov, Krassimir N.; Haberer, Elaine D.

2013-08-01

The growth of crystalline copper sulfide using a viral template was investigated using sequential incubation in CuCl2 and Na2S precursors. Non-specific electrostatic attraction between a genetically-modified M13 bacteriophage and copper cations in the CuCl2 precursor caused phage agglomeration and bundle formation. Following the addition of Na2S, polydisperse nanocrystals 2-7 nm in size were found along the length of the viral scaffold. The structure of the copper sulfide material was identified as cubic anti-fluorite type Cu1.8S, space group F m\\bar {3}m. Strong interband absorption was observed within the ultraviolet to visible range with an onset near 800 nm. Furthermore, free carrier absorption, associated with the localized surface plasmon resonance of the copper sulfide nanocrystals, was seen in the near infrared with absorbance maxima at 1060 nm and 3000 nm, respectively.

Stereochemistry of silicon in oxygen-containing compounds

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

Serezhkin, V. N., E-mail: Serezhkin@samsu.ru; Urusov, V. S.

2017-01-15

Specific stereochemical features of silicon in oxygen-containing compounds, including hybrid silicates with all oxygen atoms of SiO{sub n} groups ({sub n} = 4, 5, or 6) entering into the composition of organic anions or molecules, are described by characteristics of Voronoi—Dirichlet polyhedra. It is found that in rutile-like stishovite and post-stishovite phases with the structures similar to those of СаСl{sub 2}, α-PbO{sub 2}, or pyrite FeS{sub 2}, the volume of Voronoi—Dirichlet polyhedra of silicon and oxygen atoms decreases linearly with pressure increasing to 268 GPa. Based on these results, the possibility of formation of new post-stishovite phases is shown, namely,more » the fluorite-like structure (transition predicted at ~400 GPa) and a body-centered cubic lattice with statistical arrangement of silicon and oxygen atoms (~900 GPa).« less

Raman spectroscopy and electron-phonon coupling in Eu3+ doped Gd2Zr2O7 nanopowders

NASA Astrophysics Data System (ADS)

Krizan, G.; Gilic, M.; Ristic-Djurovic, J. L.; Trajic, J.; Romcevic, M.; Krizan, J.; Hadzic, B.; Vasic, B.; Romcevic, N.

2017-11-01

The Raman spectra of Eu3+ doped Gd2Zr2O7 nanopowders were measured. We registered three phonons at 177 cm-1, 268 cm-1, and 592 cm-1, as well as their overtones at 354 cm-1, 445 cm-1, 708 cm-1, 1062 cm-1, 1184 cm-1, ∼1530 cm-1, and ∼1720 cm-1. The phonon at 592 cm-1 is known to be characteristic for Gd2Zr2O7 fluorite-type structure; however, the other two have not been registered so far. We found that the position of the newly detected phonons agrees well with the observed electron-phonon interaction. On the other hand, the registered multiphonon processes were a consequence of miniaturization that further induced changes in electronic structure of Eu3+ doped Gd2Zr2O7 nanopowders.

A stable compound of helium and sodium at high pressure

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

Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na 2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes thismore » material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na 8 cubes. We also predict the existence of Na 2HeO with a similar structure at pressures above 15 GPa.« less

A stable compound of helium and sodium at high pressure

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

Dong, Xiao; Oganov, Artem R.; Goncharov, Alexander F.

Helium is generally understood to be chemically inert and this is due to its extremely stable closed-shell electronic configuration, zero electron affinity and an unsurpassed ionization potential. It is not known to form thermodynamically stable compounds, except a few inclusion compounds. Here, using the ab initio evolutionary algorithm USPEX and subsequent high-pressure synthesis in a diamond anvil cell, we report the discovery of a thermodynamically stable compound of helium and sodium, Na 2He, which has a fluorite-type structure and is stable at pressures >113 GPa. We show that the presence of He atoms causes strong electron localization and makes thismore » material insulating. This phase is an electride, with electron pairs localized in interstices, forming eight-centre two-electron bonds within empty Na 8 cubes. As a result, we also predict the existence of Na 2HeO with a similar structure at pressures above 15 GPa.« less

Enhanced superconductivity in the high pressure phase of SnAs studied from first principles

NASA Astrophysics Data System (ADS)

Sreenivasa Reddy, P. V.; Kanchana, V.; Millichamp, T. E.; Vaitheeswaran, G.; Dugdale, S. B.

2017-01-01

First principles calculations are performed using density functional theory and density functional perturbation theory for SnAs. Total energy calculations show the first order phase transition from an NaCl structure to a CsCl one at around 37 GPa, which is also confirmed from enthalpy calculations and agrees well with experimental work. Calculations of the phonon structure and hence the electron-phonon coupling, λep, and superconducting transition temperature, Tc, across the phase diagram are performed. These calculations give an ambient pressure Tc, in the NaCl structure, of 3.08 K, in good agreement with experiment whilst at the transition pressure, in the CsCl structure, a drastically increased value of Tc = 12.2 K is found. Calculations also show a dramatic increase in the electronic density of states at this pressure. The lowest energy acoustic phonon branch in each structure also demonstrates some softening effects. Electronic structure calculations of the Fermi surface in both phases are presented for the first time as well as further calculations of the generalised susceptibility with the inclusion of matrix elements. These calculations indicate that the softening is not derived from Fermi surface nesting and it is concluded to be due to a wavevector-dependent enhancement of the electron-phonon coupling.

Irradiation effects in UO2 and CeO2

NASA Astrophysics Data System (ADS)

Ye, Bei; Oaks, Aaron; Kirk, Mark; Yun, Di; Chen, Wei-Ying; Holtzman, Benjamin; Stubbins, James F.

2013-10-01

Single crystal CeO2, as a surrogate material to UO2, was irradiated with 500 keV xenon ions at 800 °C while being observed using in situ transmission electron microscopy (TEM). Experimental results show the formation and growth of defect clusters including dislocation loops and cavities as a function of increasing atomic displacement dose. At high dose, the dislocation loop structure evolves into an extended dislocation line structure, which appears to remain stable to the high dose levels examined in this study. A high concentration of cavities was also present in the microstructure. Despite high atomic displacement doses, the specimen remained crystalline to a cumulated dose of 5 × 1015 ions/cm2, which is consistent with the known stability of the fluorite structure under high dose irradiation. Kinetic Monte Carlo calculations show that oxygen mobility is substantially higher in hypo-stoichiometric UO2/CeO2 than hyper-stoichiometric systems. This result is consistent with the ability of irradiation damage to recover even at intermediate irradiation temperatures.

Structures, phase transitions, and magnetic properties of C o3Si from first-principles calculations

NASA Astrophysics Data System (ADS)

Zhao, Xin; Yu, Shu; Wu, Shunqing; Nguyen, Manh Cuong; Wang, Cai-Zhuang; Ho, Kai-Ming

2017-07-01

C o3Si was recently reported to exhibit remarkable magnetic properties in the nanoparticle form [B. Balasubramanian et al., Appl. Phys. Lett. 108, 152406 (2016)], 10.1063/1.4945987, yet better understanding of this material should be promoted. Here we report a study on the crystal structures of C o3Si using an adaptive genetic algorithm and discuss its electronic and magnetic properties from first-principles calculations. Several competing phases of C o3Si have been revealed from our calculations. We show that the hexagonal C o3Si structure reported in experiments has lower energy in the nonmagnetic state than in the ferromagnetic state at zero temperature. The ferromagnetic state of the hexagonal structure is dynamically unstable with imaginary phonon modes and transforms into a new orthorhombic structure, which is confirmed by our structure searches to have the lowest energy for both C o3Si and C o3Ge . Magnetic properties of the experimental hexagonal structure and the lowest-energy structures obtained from our structure searches are investigated in detail.

Electronic structure and mechanical properties of osmium borides, carbides and nitrides from first principles

NASA Astrophysics Data System (ADS)

Liang, Yongcheng; Zhao, Jianzhi; Zhang, Bin

2008-06-01

The stabilities, mechanical properties and electronic structures of osmium boride (OsB), carbide (OsC) and nitride (OsN), in the tungsten carbide (WC), rocksalt (NaCl), cesium chloride (CsCl) and zinc blende (ZnS) structures respectively, are systematically predicted by calculations from first-principles. Only four phases, namely, OsB(WC), OsB(CsCl), OsC(WC), and OsC(ZnS), are mechanically stable, and none is a superhard compound, contrary to previous speculation. Most importantly, we find that the changing trends of bulk modulus and shear modulus are completely different for OsB, OsC and OsN in same hexagonal WC structure, which indicates that the underlying sources of hardness and incompressibility are fundamentally different: the former is determined by bonding nature while the latter is closely associated with valence electron density.

Role of zero-point effects in stabilizing the ground state structure of bulk Fe2P

NASA Astrophysics Data System (ADS)

Bhat, Soumya S.; Gupta, Kapil; Bhattacharjee, Satadeep; Lee, Seung-Cheol

2018-05-01

Structural stability of Fe2P is investigated in detail using first-principles calculations based on density functional theory. While the orthorhombic C23 phase is found to be energetically more stable, the experiments suggest it to be hexagonal C22 phase. In the present study, we show that in order to obtain the correct ground state structure of Fe2P from the first-principles based methods it is utmost necessary to consider the zero-point effects such as zero-point vibrations and spin fluctuations. This study demonstrates an exceptional case where a bulk material is stabilized by quantum effects, which are usually important in low-dimensional materials. Our results also indicate the possibility of magnetic field induced structural quantum phase transition in Fe2P, which should form the basis for further theoretical and experimental efforts.

Liquid li structure and dynamics: A comparison between OFDFT and second nearest-neighbor embedded-atom method

DOE PAGES

Chen, Mohan; Vella, Joseph R.; Panagiotopoulos, Athanassios Z.; ...

2015-04-08

The structure and dynamics of liquid lithium are studied using two simulation methods: orbital-free (OF) first-principles molecular dynamics (MD), which employs OF density functional theory (DFT), and classical MD utilizing a second nearest-neighbor embedded-atom method potential. The properties we studied include the dynamic structure factor, the self-diffusion coefficient, the dispersion relation, the viscosity, and the bond angle distribution function. Our simulation results were compared to available experimental data when possible. Each method has distinct advantages and disadvantages. For example, OFDFT gives better agreement with experimental dynamic structure factors, yet is more computationally demanding than classical simulations. Classical simulations can accessmore » a broader temperature range and longer time scales. The combination of first-principles and classical simulations is a powerful tool for studying properties of liquid lithium.« less

Compositional bowing of band energies and their deformation potentials in strained InGaAs ternary alloys: A first-principles study

NASA Astrophysics Data System (ADS)

Khomyakov, Petr A.; Luisier, Mathieu; Schenk, Andreas

2015-08-01

Using first-principles calculations, we show that the conduction and valence band energies and their deformation potentials exhibit a non-negligible compositional bowing in strained ternary semiconductor alloys such as InGaAs. The electronic structure of these compounds has been calculated within the framework of local density approximation and hybrid functional approach for large cubic supercells and special quasi-random structures, which represent two kinds of model structures for random alloys. We find that the predicted bowing effect for the band energy deformation potentials is rather insensitive to the choice of the functional and alloy structural model. The direction of bowing is determined by In cations that give a stronger contribution to the formation of the InxGa1-xAs valence band states with x ≳ 0.5, compared to Ga cations.

Atomic structure and electronic properties of MgO grain boundaries in tunnelling magnetoresistive devices

PubMed Central

Bean, Jonathan J.; Saito, Mitsuhiro; Fukami, Shunsuke; Sato, Hideo; Ikeda, Shoji; Ohno, Hideo; Ikuhara, Yuichi; McKenna, Keith P.

2017-01-01

Polycrystalline metal oxides find diverse applications in areas such as nanoelectronics, photovoltaics and catalysis. Although grain boundary defects are ubiquitous their structure and electronic properties are very poorly understood since it is extremely challenging to probe the structure of buried interfaces directly. In this paper we combine novel plan-view high-resolution transmission electron microscopy and first principles calculations to provide atomic level understanding of the structure and properties of grain boundaries in the barrier layer of a magnetic tunnel junction. We show that the highly [001] textured MgO films contain numerous tilt grain boundaries. First principles calculations reveal how these grain boundaries are associated with locally reduced band gaps (by up to 3 eV). Using a simple model we show how shunting a proportion of the tunnelling current through grain boundaries imposes limits on the maximum magnetoresistance that can be achieved in devices. PMID:28374755

Coupled structural, thermal, phase-change and electromagnetic analysis for superconductors, volume 2

NASA Technical Reports Server (NTRS)

Felippa, Carlos A.; Farhat, Charbel; Park, K. C.; Militello, Carmelo; Schuler, James J.

1993-01-01

Two families of parametrized mixed variational principles for linear electromagnetodynamics are constructed. The first family is applicable when the current density distribution is known a priori. Its six independent fields are magnetic intensity and flux density, magnetic potential, electric intensity and flux density and electric potential. Through appropriate specialization of parameters the first principle reduces to more conventional principles proposed in the literature. The second family is appropriate when the current density distribution and a conjugate Lagrange multiplier field are adjoined, giving a total of eight independently varied fields. In this case it is shown that a conventional variational principle exists only in the time-independent (static) case. Several static functionals with reduced number of varied fields are presented. The application of one of these principles to construct finite elements with current prediction capabilities is illustrated with a numerical example.

Crystal growth and electronic structure of low-temperature phase SrMgF{sub 4}

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

Atuchin, Victor V.; Functional Electronics Laboratory, Tomsk State University, Tomsk 634050; Laboratory of Semiconductor and Dielectric Materials, Novosibirsk State University, Novosibirsk 630090

2016-04-15

Using the vertical Bridgman method, the single crystal of low temperature phase SrMgF{sub 4} is obtained. The crystal is in a very good optical quality with the size of 10×7×5 mm{sup 3}. Detailed photoemission spectra of the element core levels are determined by a monochromatic AlKa (1486.6 eV) X-ray source. Moreover, the first-principles calculations are performed to investigate the electronic structure of SrMgF{sub 4}. A good agreement between experimental and calculated results is achieved. It is demonstrated that almost all the electronic orbitals are strongly localized and the hybridization with the others is very small, but the Mg–F bonds covalencymore » is relatively stronger than that of Sr–F bonds. - Graphical abstract: Large size of low-temperature phase SrMgF{sub 4} crystal was obtained (right) and its electronic structure was investigated by X-ray photoelectron spectroscopy and first-principles calculation (left). - Highlights: • Large size single crystal of low-temperature phase SrMgF{sub 4} is obtained. • Electronic structure of SrMgF{sub 4} is measured by X-ray photoelectron spectroscopy. • Partial densities of states are determined by first-principles calculation. • Good agreement between experimental and calculated results is achieved. • Strong ionic characteristics of chemical bonds are exhibited in SrMgF{sub 4}.« less

First-principles study of low compressibility osmium borides

NASA Astrophysics Data System (ADS)

Gou, Huiyang; Hou, Li; Zhang, Jingwu; Li, Hui; Sun, Guifang; Gao, Faming

2006-05-01

Using first-principles total energy calculations we investigate the structural, elastic, and electronic properties of OsB2 and OsB, respectively. The calculated equilibrium structural parameters of OsB2 are in agreement with the available experimental results. The calculations indicate that OsB in tungsten carbide is more energetically stable under the ambient condition than the metastable cesium chloride phase of OsB. Results of bulk modulus show that they are potential low compressible materials. The hardness of OsB2 is estimated by employing a semiempirical theory. The results indicate that OsB2 is an ultraincompressible material, but not a superhard material. The method designing superhard materials is different from one creating ultraincompressible materials.

First principles investigation of structural, mechanical, dynamical and thermodynamic properties of AgMg under pressure

NASA Astrophysics Data System (ADS)

Cui, Rong Hua; Chao Dong, Zheng; Gui Zhong, Chong

2017-12-01

The effects of pressure on the structural, mechanical, dynamical and thermodynamic properties of AgMg have been investigated using first principles based on density functional theory. The optimized lattice constants agree well with previous experimental and theoretical results. The bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and Debye temperature under pressures were calculated. The calculated results of Cauchy pressure and B/G ratio indicate that AgMg shows ductile nature. Phonon dispersion curves suggest the dynamical stability of AgMg. The pressure dependent behavior of thermodynamic properties are calculated, the Helmholtz free energy and internal energy increase with increase of pressure, while entropy and heat capacity decrease.

Quantum Impurity Models as Reference Systems for Strongly Correlated Materials: The Road from the Kondo Impurity Model to First Principles Electronic Structure Calculations with Dynamical Mean-Field Theory

NASA Astrophysics Data System (ADS)

Kotliar, Gabriel

2005-01-01

Dynamical mean field theory (DMFT) relates extended systems (bulk solids, surfaces and interfaces) to quantum impurity models (QIM) satisfying a self-consistency condition. This mapping provides an economic description of correlated electron materials. It is currently used in practical computations of physical properties of real materials. It has also great conceptual value, providing a simple picture of correlated electron phenomena on the lattice, using concepts derived from quantum impurity models such as the Kondo effect. DMFT can also be formulated as a first principles electronic structure method and is applicable to correlated materials.

First-principles study of crystal structure, elastic stiffness constants, piezoelectric constants, and spontaneous polarization of orthorhombic Pna21-M2O3 (M = Al, Ga, In, Sc, Y)

NASA Astrophysics Data System (ADS)

Shimada, Kazuhiro

2018-03-01

We perform first-principles calculations to investigate the crystal structure, elastic and piezoelectric properties, and spontaneous polarization of orthorhombic M2O3 (M = Al, Ga, In, Sc, Y) with Pna21 space group based on density functional theory. The lattice parameters, full elastic stiffness constants, piezoelectric stress and strain constants, and spontaneous polarization are successfully predicted. Comparison with available experimental and computational results indicates the validity of our computational results. Detailed analysis of the results clarifies the difference in the bonding character and the origin of the strong piezoelectric response and large spontaneous polarization.

Discovery of carbon-vacancy ordering in Nb4AlC3–x under the guidance of first-principles calculations

PubMed Central

Zhang, Hui; Hu, Tao; Wang, Xiaohui; Li, Zhaojin; Hu, Minmin; Wu, Erdong; Zhou, Yanchun

2015-01-01

The conventional wisdom to tailor the properties of binary transition metal carbides by order-disorder phase transformation has been inapplicable for the machinable ternary carbides (MTCs) due to the absence of ordered phase in bulk sample. Here, the presence of an ordered phase with structural carbon vacancies in Nb4AlC3–x (x ≈ 0.3) ternary carbide is predicted by first-principles calculations, and experimentally identified for the first time by transmission electron microscopy and micro-Raman spectroscopy. Consistent with the first-principles prediction, the ordered phase, o-Nb4AlC3, crystalizes in P63/mcm with a = 5.423 Å, c = 24.146 Å. Coexistence of ordered (o-Nb4AlC3) and disordered (Nb4AlC3–x) phase brings about abundant domains with irregular shape in the bulk sample. Both heating and electron irradiation can induce the transformation from o-Nb4AlC3 to Nb4AlC3–x. Our findings may offer substantial insights into the roles of carbon vacancies in the structure stability and order-disorder phase transformation in MTCs. PMID:26388153

Structure of naturally hydrated ferrihydrite revealed through neutron diffraction and first-principles modeling

NASA Astrophysics Data System (ADS)

Chappell, Helen F.; Thom, William; Bowron, Daniel T.; Faria, Nuno; Hasnip, Philip J.; Powell, Jonathan J.

2017-08-01

Ferrihydrite, with a ``two-line'' x-ray diffraction pattern (2L-Fh), is the most amorphous of the iron oxides and is ubiquitous in both terrestrial and aquatic environments. It also plays a central role in the regulation and metabolism of iron in bacteria, algae, higher plants, and animals, including humans. In this study, we present a single-phase model for ferrihydrite that unifies existing analytical data while adhering to fundamental chemical principles. The primary particle is small (20-50 Å) and has a dynamic and variably hydrated surface, which negates long-range order; collectively, these features have hampered complete characterization and frustrated our understanding of the mineral's reactivity and chemical/biochemical function. Near and intermediate range neutron diffraction (NIMROD) and first-principles density functional theory (DFT) were employed in this study to generate and interpret high-resolution data of naturally hydrated, synthetic 2L-Fh at standard temperature. The structural optimization overcomes transgressions of coordination chemistry inherent within previously proposed structures, to produce a robust and unambiguous single-phase model.

Study of the extra-ionic electron distributions in semi-metallic structures by nuclear quadrupole resonance techniques

NASA Technical Reports Server (NTRS)

Murty, A. N.

1976-01-01

A straightforward self-consistent method was developed to estimate solid state electrostatic potentials, fields and field gradients in ionic solids. The method is a direct practical application of basic electrostatics to solid state and also helps in the understanding of the principles of crystal structure. The necessary mathematical equations, derived from first principles, were presented and the systematic computational procedure developed to arrive at the solid state electrostatic field gradients values was given.

Pressure-induced structural phase transformation and superconducting properties of titanium mononitride

NASA Astrophysics Data System (ADS)

Li, Qian; Guo, Yanan; Zhang, Miao; Ge, Xinlei

2018-03-01

In this work, we have systematically performed the first-principles structure search on titanium mononitride (TiN) within Crystal Structure AnaLYsis by Particle Swarm Optimization (CALYPSO) methodology at high pressures. Here, we have confirmed a phase transition from cubic rock-salt (fcc) phase to CsCl (bcc) phase of TiN at ∼348 GPa. Further simulations reveal that the bcc phase is dynamically stable, and could be synthesized experimentally in principle. The calculated elastic anisotropy decreases with the phase transformation from fcc to bcc structure under high pressures, and the material changes from ductile to brittle simultaneously. Moreover, we found that both structures are superconductive with the superconducting critical temperature of 2-12 K.

Resolving phase stability in the Ti-O binary with first-principles statistical mechanics methods

NASA Astrophysics Data System (ADS)

Gunda, N. S. Harsha; Puchala, Brian; Van der Ven, Anton

2018-03-01

The Ti-O system consists of a multitude of stable and metastable oxides that are used in wide ranging applications. In this work we investigate phase stability in the Ti-O binary from first principles. We perform a systematic search for ground state structures as a function of oxygen concentration by considering oxygen-vacancy and/or titanium-vacancy orderings over four parent crystal structures: (i) hcp Ti, (ii) ω -Ti, (iii) rocksalt, and (iv) hcp oxygen containing interstitial titanium. We explore phase stability at finite temperature using cluster expansion Hamiltonians and Monte Carlo simulations. The calculations predict a high oxygen solubility in hcp Ti and the stability of suboxide phases that undergo order-disorder transitions upon heating. Vacancy ordered rocksalt phases are also predicted at low temperature that disorder to form an extended solid solution at high temperatures. Predicted stable and metastable phase diagrams are qualitatively consistent with experimental observations, however, important discrepancies are revealed between first-principles density functional theory predictions of phase stability and the current understanding of phase stability in this system.

A First-Principles Theoretical Study on the Thermoelectric Properties of the Compound Cu5AlSn2S8

NASA Astrophysics Data System (ADS)

Li, Weijian; Zhou, Chenyi; Li, Liangliang

2016-03-01

A new compound of Cu5AlSn2S8, which contained earth-abundant and environment-friendly elements and had a diamond-like crystal structure, was designed, and its electronic structure and thermoelectric transport properties from 300 K to 700 K were investigated by first-principles calculations, Boltzmann transport equations, and a modified Slack's model. The largest power factors of Cu5AlSn2S8 at 700 K were 47.5 × 1010 W m-1 K-2 s-1 and 14.7 × 1010 W m-1 K-2 s-1 for p- and n-type semiconductors, respectively. The lattice thermal conductivity of Cu5AlSn2S8 was calculated with its shear modulus and isothermal bulk modulus, which were also obtained by first-principles calculations. The lattice thermal conductivity was 0.9-2.2 W m-1 K-1 from 300 K to 700 K, relatively low among thermoelectric compounds. This theoretical study showed that Cu5AlSn2S8 could be a potential thermoelectric material.

Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study

NASA Astrophysics Data System (ADS)

Nam, Hyo On; Morgan, Dane

2015-10-01

Molten salts technology is of significant interest for nuclear, solar, and other energy systems. In this work, first-principles molecular dynamics (FPMD) was used to model the solute behavior in eutectic LiCl-KCl and FLiBe (Li2BeF4) melts at 773 K and 973 K, respectively. The thermo-kinetic properties for solute systems such as the redox potential, solute diffusion coefficients and structural information surrounding the solute were predicted from FPMD modeling and the calculated properties are generally in agreement with the experiments. In particular, we formulate an approach to model redox energetics vs. chlorine (or fluorine) potential from first-principles approaches. This study develops approaches for, and demonstrates the capabilities of, FPMD to model solute properties in molten salts.

Short-term 222Rn activity concentration changes in underground spaces with limited air exchange with the atmosphere

NASA Astrophysics Data System (ADS)

Fijałkowska-Lichwa, L.; Przylibski, T. A.

2011-04-01

The authors investigated short-time changes in 222Rn activity concentration occurring yearly in two underground tourist facilities with limited air exchange with the atmosphere. One of them is Niedźwiedzia (Bear) Cave in Kletno, Poland - a natural space equipped with locks ensuring isolation from the atmosphere. The other site is Fluorite Adit in Kletno, a section of a disused uranium mine. This adit is equipped with a mechanical ventilation system, operated periodically outside the opening times (at night). Both sites are situated within the same metamorphic rock complex, at similar altitudes, about 2 km apart. The measurements conducted revealed spring and autumn occurrence of convective air movements. In Bear Cave, this process causes a reduction in 222Rn activity concentration in the daytime, i.e. when tourists, guides and other staff are present in the cave. From the point of view of radiation protection, this is the best situation. For the rest of the year, daily concentrations of 222Rn activity in the cave are very stable. In Fluorite Adit, on the other hand, significant variations in daily 222Rn activity concentrations are recorded almost all year round. These changes are determined by the periods of activity and inactivity of mechanical ventilation. Unfortunately this is inactive in the daytime, which results in the highest values of 222Rn activity concentration at the times when tourists and staff are present in the adit. Slightly lower concentrations of radon in Fluorite Adit are recorded in the winter season, when convective air movements carry a substantial amount of radon out into the atmosphere. The incorrect usage of mechanical ventilation in Fluorite Adit results in the most unfavourable conditions in terms of radiation protection. The staff working in that facility are exposed practically throughout the year to the highest 222Rn activity concentrations, both at work (in the adit) and at home (outside their working hours). Therefore, not very well considered solution for the ventilation system not only does not prevent radioactive exposure of the staff, but can even increase it. The authors have also observed comparable characteristics of the annual patterns of 222Rn activity concentration changes in underground spaces and residential buildings situated in the same or similar climatic zones.

First-Principles Study on the Structural and Magnetic Properties of Iron Hydride

NASA Astrophysics Data System (ADS)

Tsumuraya, Takao; Matsuura, Yasuyuki; Shishidou, Tatsuya; Oguchi, Tamio

2012-06-01

The magnetic and structural properties of iron hydride FeH with the double hexagonal close-packed (dhcp) and hexagonal close-packed (hcp) structures are investigated by first-principles density-functional theory calculations with a spin-polarized form of generalized gradient approximation. All the calculations are performed using all-electron full-potential linearized augmented plane wave method. Both dhcp and hcp FeH are ferromagnetic at ambient pressure. The ferromagnetic ordering of the dhcp structure collapses at a pressure of 48 GPa, while that of the hcp structure vanishes gradually from 48 GPa. The modification in the density of states (DOS) due to the applied pressure causes the collapse of the magnetization. The difference in magnetic moment reduction between dhcp and hcp FeH is attributed to their DOS around the Fermi level. The calculated magnetocrystalline anisotropy energies between in-plane and out-of-plane spin orientations are found to be 124 μeV/Fe for the dhcp structure, and 100 μeV/Fe for the hcp structure. The easy axis is in-plane direction for both structures.

Zirconia and Pyrochlore Oxides for Thermal Barrier Coatings in Gas Turbine Engines

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

2014-06-01

One of the important applications of yttria-stabilized zirconia (YSZ) is as a thermal barrier coating for gas turbine engines. While YSZ performs well in this function, the need for increased operating temperatures to achieve higher energy conversion efficiencies, requires the development of improved materials. To meet this challenge, some rare-earth zirconates that form the cubic fluorite-derived pyrochlore structure are being developed for use in thermal barrier coatings due to their low thermal conductivity, excellent chemical stability, and other suitable properties. In this paper, the thermal conductivities of current and prospective oxides for use in thermal barrier coatings are reviewed. The factors affecting the variations and differences in the thermal conductivities and the degradation behaviors of these materials are discussed.

First principles determination of dislocation properties.

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

Hamilton, John C.

2003-12-01

This report details the work accomplished on first principles determination of dislocation properties. It contains an introduction and three chapters detailing three major accomplishments. First, we have used first principle calculations to determine the shear strength of an aluminum twin boundary. We find it to be remarkably small ({approx}17 mJ/m{sup 2}). This unexpected result is explained and will likely pertain for many other grain boundaries. Second, we have proven that the conventional explanation for finite grain boundary facets is wrong for a particular aluminum grain boundary. Instead of finite facets being stabilized by grain boundary stress, we find them tomore » originate from kinetic effects. Finally we report on a new application of the Frenkel-Kontorova model to understand reconstructions of (100) type surfaces. In addition to the commonly accepted formation of rectangular dislocation arrays, we find numerous other possible solutions to the model including hexagonal reconstructions and a clock-rotated structure.« less

Pressure induced structural phase transition of OsB 2: First-principles calculations

NASA Astrophysics Data System (ADS)

Ren, Fengzhu; Wang, Yuanxu; Lo, V. C.

2010-04-01

Orthorhombic OsB 2 was synthesized at 1000 °C and its compressibility was measured by using the high-pressure X-ray diffraction in a Diacell diamond anvil cell from ambient pressure to 32 GPa [R.W. Cumberland, et al. (2005)]. First-principles calculations were performed to study the possibility of the phase transition of OsB 2. An analysis of the calculated enthalpy shows that orthorhombic OsB 2 can transfer to the hexagonal phase at 10.8 GPa. The calculated results with the quasi-harmonic approximation indicate that this phase transition pressure is little affected by the thermal effect. The calculated phonon band structure shows that the hexagonal P 6 3/ mmc structure (high-pressure phase) is stable for OsB 2. We expect the phase transition can be further confirmed by the experimental work.

Pressure effects on structural, electronic, elastic and lattice dynamical properties of XSi2 (X = Cr, Mo, W) from first principles

NASA Astrophysics Data System (ADS)

Zhu, Haiyan; Shi, Liwei; Li, Shuaiqi; Zhang, Shaobo; Xia, Wangsuo

2018-04-01

First-principles calculations have been performed to study the structure, elastic and lattice dynamical properties of C40 XSi2 (X=Cr, Mo, W) under hydrostatic pressure. The obtained structural parameters are in line with existing experimental and theoretical data. The evolutions of fundamental bandgap energies, elastic moduli, IR absorption spectra with pressure have been investigated in detail. Our results indicate that the energy gaps of XSi2 (X=Cr, Mo, W) show different trends as the pressure increases. Larger BH/GH ratio and Poisson’s ratio are achieved with pressure, suggesting an improved ductility for XSi2 (X=Cr, Mo, W). Moreover, a large elastic anisotropy under pressure is exhibited in Young’s anisotropic factors. The infrared-active phonon frequencies exhibit substantial blueshifts under pressure.

First-principles approach to calculating energy level alignment at aqueous semiconductor interfaces

DOE PAGES

Kharche, Neerav; Muckerman, James T.; Hybertsen, Mark S.

2014-10-21

A first-principles approach is demonstrated for calculating the relationship between an aqueous semiconductor interface structure and energy level alignment. The physical interface structure is sampled using density functional theory based molecular dynamics, yielding the interface electrostatic dipole. The GW approach from many-body perturbation theory is used to place the electronic band edge energies of the semiconductor relative to the occupied 1 b₁ energy level in water. The application to the specific cases of nonpolar (101¯0 ) facets of GaN and ZnO reveals a significant role for the structural motifs at the interface, including the degree of interface water dissociation andmore » the dynamical fluctuations in the interface Zn-O and O-H bond orientations. As a result, these effects contribute up to 0.5 eV.« less

Density functional theory calculations of III-N based semiconductors with mBJLDA

NASA Astrophysics Data System (ADS)

Gürel, Hikmet Hakan; Akıncı, Özden; Ünlü, Hilmi

2017-02-01

In this work, we present first principles calculations based on a full potential linear augmented plane-wave method (FP-LAPW) to calculate structural and electronic properties of III-V based nitrides such as GaN, AlN, InN in a zinc-blende cubic structure. First principles calculation using the local density approximation (LDA) and generalized gradient approximation (GGA) underestimate the band gap. We proposed a new potential called modified Becke-Johnson local density approximation (MBJLDA) that combines modified Becke-Johnson exchange potential and the LDA correlation potential to get better band gap results compared to experiment. We compared various exchange-correlation potentials (LSDA, GGA, HSE, and MBJLDA) to determine band gaps and structural properties of semiconductors. We show that using MBJLDA density potential gives a better agreement with experimental data for band gaps III-V nitrides based semiconductors.

Structural studies of TiC{sub 1−x}O{sub x} solid solution by Rietveld refinement and first-principles calculations

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

Jiang, Bo, E-mail: youqin5912@yahoo.com.cn; Hou, Na; Huang, Shanyan

2013-08-15

The lattice parameters, structural stability and electronic structure of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution were investigated by Rietveld refinement and first-principles calculations. Series of TiC{sub 1−x}O{sub x} were precisely synthesized by sintering process under the vacuum. Rietveld refinement results of XRD patterns show the properties of continuous solid solution in TiC{sub 1−x}O{sub x} over the whole composition range. The lattice parameters vary from 0.4324 nm to 0.4194 nm decreasing with increasing oxygen concentration. Results of first-principles calculations reveal that the disorder C/O structure is stable than the order C/O structure. Further investigations of the vacancy in Ti{submore » 1−Va}(C{sub 1−x}O{sub x}){sub 1−Va} solid solution present that the structure of vacancy segregated in TiO-part is more stable than the disorder C/O structure, which can be ascribed to the Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy via the analysis of the electron density difference plots and PDOS. - Graphical abstract: XRD of series of titanium oxycarbides (TiC{sub 1−x}O{sub x}, 0≤x≤1) solid solution prepared by adjusting the proportion of TiO in the starting material. Highlights: • Titanium oxycarbides were obtained by sintering TiO and TiC under carefully controlled conditions. • Rietveld refinement results show continuous solid solution with FCC structure in TiC{sub 1−x}O{sub x}. • The disorder C/O structure is stable than the order C/O structure. • Introduction of vacancy segregated in TiO-part is more stable than disorder C/O structure. • Ti–Ti bond across O-vacancy and the charge redistributed around Ti-vacancy enhance structural stability.« less

Surface structures of L10-MnGa (001) by scanning tunneling microscopy and first-principles theory

NASA Astrophysics Data System (ADS)

Corbett, J. P.; Guerrero-Sanchez, J.; Richard, A. L.; Ingram, D. C.; Takeuchi, N.; Smith, A. R.

2017-11-01

We report on the surface reconstructions of L10-ordered MnGa (001) thin films grown by molecular beam epitaxy on a 50 nm Mn3N2 (001) layer freshly grown on a magnesium oxide (001) substrate. Scanning tunneling microscopy, Auger electron spectroscopy, and reflection high energy electron diffraction are combined with first-principles density functional theory calculations to determine the reconstructions of the L10-ordered MnGa (001) surface. We find two lowest energy reconstructions of the MnGa (001) face: a 1 × 1 Ga-terminated structure and a 1 × 2 structure with a Mn replacing a Ga in the 1 × 1 Ga-terminated surface. The 1 × 2 reconstruction forms a row structure along [100]. The manganese:gallium stoichiometry within the surface based on theoretical modeling is in good agreement with experiment. Magnetic moment calculations for the two lowest energy structures reveal important surface and bulk effects leading to oscillatory total magnetization for ultra-thin MnGa (001) films.

Thermoelectric properties of AgSbTe₂ from first-principles calculations

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

Rezaei, Nafiseh; Akbarzadeh, Hadi; Hashemifar, S. Javad, E-mail: hashemifar@cc.iut.ac.ir

2014-09-14

The structural, electronic, and transport properties of AgSbTe₂ are studied by using full-relativistic first-principles electronic structure calculation and semiclassical description of transport parameters. The results indicate that, within various exchange-correlation functionals, the cubic Fd3⁻m and trigonal R3⁻m structures of AgSbTe₂ are more stable than two other considered structures. The computed Seebeck coefficients at different values of the band gap and carrier concentration are accurately compared with the available experimental data to speculate a band gap of about 0.1–0.35 eV for AgSbTe₂ compound, in agreement with our calculated electronic structure within the hybrid HSE (Heyd-Scuseria-Ernzerhof) functional. By calculating the semiclassical Seebeckmore » coefficient, electrical conductivity, and electronic part of thermal conductivity, we present the theoretical upper limit of the thermoelectric figure of merit of AgSbTe₂ as a function of temperature and carrier concentration.« less

Structural phases arising from reconstructive and isostructural transitions in high-melting-point oxides under hydrostatic pressure: A first-principles study

NASA Astrophysics Data System (ADS)

Tian, Hao; Kuang, Xiao-Yu; Mao, Ai-Jie; Yang, Yurong; Xu, Changsong; Sayedaghaee, S. Omid; Bellaiche, L.

2018-01-01

High-melting-point oxides of chemical formula A B O3 with A =Ca , Sr, Ba and B =Zr , Hf are investigated as a function of hydrostatic pressure up to 200 GPa by combining first-principles calculations with a particle swarm optimization method. Ca- and Sr-based systems: (1) first undergo a reconstructive phase transition from a perovskite state to a novel structure that belongs to the post-post-perovskite family and (2) then experience an isostructural transition to a second, also new post-post-perovskite state at higher pressures, via the sudden formation of a specific out-of-plane B -O bond. In contrast, the studied Ba compounds evolve from a perovskite phase to a third novel post-post-perovskite structure via another reconstructive phase transition. The original characteristics of these three different post-post-perovskite states are emphasized. Unusual electronic properties, including significant piezochromic effects and an insulator-metal transition, are also reported and explained.

Hierarchical Coupling of First-Principles Molecular Dynamics with Advanced Sampling Methods.

PubMed

Sevgen, Emre; Giberti, Federico; Sidky, Hythem; Whitmer, Jonathan K; Galli, Giulia; Gygi, Francois; de Pablo, Juan J

2018-05-14

We present a seamless coupling of a suite of codes designed to perform advanced sampling simulations, with a first-principles molecular dynamics (MD) engine. As an illustrative example, we discuss results for the free energy and potential surfaces of the alanine dipeptide obtained using both local and hybrid density functionals (DFT), and we compare them with those of a widely used classical force field, Amber99sb. In our calculations, the efficiency of first-principles MD using hybrid functionals is augmented by hierarchical sampling, where hybrid free energy calculations are initiated using estimates obtained with local functionals. We find that the free energy surfaces obtained from classical and first-principles calculations differ. Compared to DFT results, the classical force field overestimates the internal energy contribution of high free energy states, and it underestimates the entropic contribution along the entire free energy profile. Using the string method, we illustrate how these differences lead to different transition pathways connecting the metastable minima of the alanine dipeptide. In larger peptides, those differences would lead to qualitatively different results for the equilibrium structure and conformation of these molecules.

Effects of interlayer screening and temperature on dielectric functions of graphene by first-principles

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

Yang, J. Y.; Liu, L. H., E-mail: lhliu@hit.edu.cn; Department of Physics, Harbin Institute of Technology, Harbin 150001

2016-07-21

The dielectric functions of few-layer graphene and the related temperature dependence are investigated from the atomic scale using first-principles calculations. Compared with ellipsometry experiments in the spectral range of 190–2500 nm, the normalized optical constants of mono-layer graphene demonstrate good agreement and further validate first-principles calculations. To interpret dielectric function of mono-layer graphene, the electronic band structure and density of states are analyzed. By comparing dielectric functions of mono-, bi-, and tri-layer graphene, it shows that interlayer screening strengthens intraband transition and greatly enhances the absorption peak located around 1 eV. The strengthened optical absorption is intrinsically caused by the increasing electronmore » states near the Fermi level. To investigate temperature effect, the first-principles calculations and lattice dynamics are combined. The lattice vibration enhances parallel optical absorption peak around 1 eV and induces redshift. Moreover, it is observed that the van der Waals force plays a key role in keeping the interlayer distance stable during dynamics simulations.« less

New two-dimensional V-V binary compounds with a honeycomb-like structure: a first-principles study

NASA Astrophysics Data System (ADS)

Xiao, Wen-Zhi; Xiao, Gang; Rong, Qing-Yan; Wang, Ling-Ling

2018-03-01

We systematically search for the stable structures of two-dimensional (2D) V-V binary compounds with honeycomb-like structure by using the first-principles calculation. We identify 26 stable structures out of 54 2D V-V compounds based on various assessments of stabilities: total energy, thermodynamics, and mechanics. Among them, 12 2D V-V compounds are previously unrecognized structures. For each class V-V isomer, the most stable structures are found to be β-AsP, β-SbAs, α-BiAs, α-BiSb, α 2-SbP, and α 2-BiP. For all isomers of the AsP, they are always stable, and hence PAs monolayer is most likely to be prepared experimentally. All the stable structures are semiconductors with bandgaps ranging from 0.06 eV to 2.52 eV at the Heyd-Scuseria-Ernzerhof level. Therefore, they are potential materials for versatile semiconductor devices. Our findings provide a new clue to facilitate the design of 2D materials for potential applications.

Structures, energetics, vibrational spectra of NH4+ (H2O)(n=4,6) clusters: Ab initio calculations and first principles molecular dynamics simulations.

PubMed

Karthikeyan, S; Singh, Jiten N; Park, Mina; Kumar, Rajesh; Kim, Kwang S

2008-06-28

Important structural isomers of NH(4) (+)(H(2)O)(n=4,6) have been studied by using density functional theory, Moller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH(4) (+)(H(2)O)(n=4,6) because otherwise wrong structures could be assigned for the most probable structures. For NH(4) (+)(H(2)O)(6), the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH(4) (+)(H(2)O)(4) and two lowest energy isomers of NH(4) (+)(H(2)O)(6) explains each experimental IR spectrum.

Structures, energetics, vibrational spectra of NH4+(H2O)n=4,6 clusters: Ab initio calculations and first principles molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Karthikeyan, S.; Singh, Jiten N.; Park, Mina; Kumar, Rajesh; Kim, Kwang S.

2008-06-01

Important structural isomers of NH4+(H2O)n=4,6 have been studied by using density functional theory, Møller-Plesset second order perturbation theory, and coupled-cluster theory with single, double, and perturbative triple excitations [CCSD(T)]. The zero-point energy (ZPE) correction to the complete basis set limit of the CCSD(T) binding energies and free energies is necessary to identify the low energy structures for NH4+(H2O)n=4,6 because otherwise wrong structures could be assigned for the most probable structures. For NH4+(H2O)6, the cage-type structure, which is more stable than the previously reported open structure before the ZPE correction, turns out to be less stable after the ZPE correction. In first principles Car-Parrinello molecular dynamics simulations around 100 K, the combined power spectrum of three lowest energy isomers of NH4+(H2O)4 and two lowest energy isomers of NH4+(H2O)6 explains each experimental IR spectrum.

First-principles screening of structural properties of intermetallic compounds on martensitic transformation

NASA Astrophysics Data System (ADS)

Lee, Joohwi; Ikeda, Yuji; Tanaka, Isao

2017-11-01

Martensitic transformation with good structural compatibility between parent and martensitic phases are required for shape memory alloys (SMAs) in terms of functional stability. In this study, first-principles-based materials screening is systematically performed to investigate the intermetallic compounds with the martensitic phases by focusing on energetic and dynamical stabilities as well as structural compatibility with the parent phase. The B2, D03, and L21 crystal structures are considered as the parent phases, and the 2H and 6M structures are considered as the martensitic phases. In total, 3384 binary and 3243 ternary alloys with stoichiometric composition ratios are investigated. It is found that 187 alloys survive after the screening. Some of the surviving alloys are constituted by the chemical elements already widely used in SMAs, but other various metallic elements are also found in the surviving alloys. The energetic stability of the surviving alloys is further analyzed by comparison with the data in Materials Project Database (MPD) to examine the alloys whose martensitic structures may cause further phase separation or transition to the other structures.

A Variational Principle for Reconstruction of Elastic Deformations in Shear Deformable Plates and Shells

NASA Technical Reports Server (NTRS)

Tessler, Alexander; Spangler, Jan L.

2003-01-01

A variational principle is formulated for the inverse problem of full-field reconstruction of three-dimensional plate/shell deformations from experimentally measured surface strains. The formulation is based upon the minimization of a least squares functional that uses the complete set of strain measures consistent with linear, first-order shear-deformation theory. The formulation, which accommodates for transverse shear deformation, is applicable for the analysis of thin and moderately thick plate and shell structures. The main benefit of the variational principle is that it is well suited for C(sup 0)-continuous displacement finite element discretizations, thus enabling the development of robust algorithms for application to complex civil and aeronautical structures. The methodology is especially aimed at the next generation of aerospace vehicles for use in real-time structural health monitoring systems.

Enhanced superconductivity in SnSb under pressure: a first principles study

NASA Astrophysics Data System (ADS)

Sreenivasa Reddy, P. V.; Kanchana, V.

2017-10-01

First principles electronic structure calculations reveal both SnP and SnSb to be stable in the NaCl structure. In SnSb, a first order phase transition from NaCl to CsCl type structure is observed at around 13 GPa, which is also confirmed from enthalpy calculations and agrees well with experimental and other theoretical reports. Calculations of the phonon spectra, and hence the electron-phonon coupling λep and superconducting transition temperature T c, were performed at zero pressure for both the compounds, and at high pressure for SnSb. These calculations report Tc of 0.614 K and 3.083 K for SnP and SnSb respectively, in the NaCl structure—in good agreement with experiment—whilst at the transition pressure, in the CsCl structure, a drastically increased value of T c around 9.18 K (9.74 K at 20 GPa) is found for SnSb, together with a dramatic increase in the electronic density of states at this pressure. The lowest energy acoustic phonon branches in each structure also demonstrate some softening effects, which are well addressed in this work.

Origin of structural analogies and differences between the atomic structures of GeSe4 and GeS4 glasses: A first principles study.

PubMed

Bouzid, Assil; Le Roux, Sébastien; Ori, Guido; Boero, Mauro; Massobrio, Carlo

2015-07-21

First-principles molecular dynamics simulations based on density functional theory are employed for a comparative study of structural and bonding properties of two stoichiometrically identical chalcogenide glasses, GeSe4 and GeS4. Two periodic cells of 120 and 480 atoms are adopted. Both glasses feature a coexistence of Ge-centered tetrahedra and Se(S) homopolar connections. Results obtained for N = 480 indicate substantial differences at the level of the Se(S) environment, since Ge-Se-Se connections are more frequent than the corresponding Ge-S-S ones. The presence of a more prominent first sharp diffraction peak in the total neutron structure factor of glassy GeS4 is rationalized in terms of a higher number of large size rings, accounting for extended Ge-Se correlations. Both the electronic density of states and appropriate electronic localization tools provide evidence of a higher ionic character of Ge-S bonds when compared to Ge-Se bonds. An interesting byproduct of these investigations is the occurrence of discernible size effects that affect structural motifs involving next nearest neighbor distances, when 120 or 480 atoms are used.

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

Morris, J.R.; Lu, Z.Y.; Xiang, J.B.

We have examined a variety of structures for the (510) symmetric tilt boundary in Si, using first-principles calculations. These calculations show that the observed structure in Si is the lowest energy structure. This structure is more complicated than what is necessary to preserve four-fold coordination. We compare the results to classical and tight-binding models, in order to test these empirical problems.

Near-infrared radiation absorption properties of covellite (CuS) using first-principles calculations

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

Xiao, Lihua, E-mail: xiaolihua@git.edu.cn; College of Physics and Information Science, Hunan Normal University, Changsha 410081; Guizhou Special Functional Materials 2011 Collaborative Innovation Center, Guizhou Institute of Technology, Guiyang 550003

2016-08-15

First-principles density functional theory was used to investigate the electronic structure, optical properties and the origin of the near-infrared (NIR) absorption of covellite (CuS). The calculated lattice constant and optical properties are found to be in reasonable agreement with experimental and theoretical findings. The electronic structure reveals that the valence and conduction bands of covellite are determined by the Cu 3d and S 3p states. By analyzing its optical properties, we can fully understand the potential of covellite (CuS) as a NIR absorbing material. Our results show that covellite (CuS) exhibits NIR absorption due to its metal-like plasma oscillation inmore » the NIR range.« less

Solid-state NMR spectroscopy and first-principles calculations: a powerful combination of tools for the investigation of polymorphism of indomethacin.

PubMed

Ukmar, Tina; Kaučič, Venčeslav; Mali, Gregor

2011-09-01

Two polymorphs of indomethacin were investigated by 1H MAS and CRAMPS, and 1H-13C CPMAS and HETCOR NMR techniques. The obtained spectra clearly elucidated the structural differences between the polymorphs, especially the different numbers of indomethacin molecules within the crystallographic asymmetric units and the different schemes of hydrogen bonding among the molecules. Known structure of indomethacin gamma was used in first-principles DFT/GIPAW calculations of 1H and 13C isotropic chemical shifts. Two packages, freely available Quantum Espresso and commercially available CASTEP, were employed. They both provided values that excellently agreed with the measured values, and thus allowed unambiguous assignment of 1H and 13C spectral lines.

First-Principles Study of Antimony Doping Effects on the Iron-Based Superconductor CaFe(SbxAs1-x)2

NASA Astrophysics Data System (ADS)

Nagai, Yuki; Nakamura, Hiroki; Machida, Masahiko; Kuroki, Kazuhiko

2015-09-01

We study antimony doping effects on the iron-based superconductor CaFe(SbxAs1-x)2 by using the first-principles calculation. The calculations reveal that the substitution of a doped antimony atom into As of the chainlike As layers is more stable than that into FeAs layers. This prediction can be checked by experiments. Our results suggest that doping homologous elements into the chainlike As layers, which only exist in the novel 112 system, is responsible for rising up the critical temperature. We discuss antimony doping effects on the electronic structure. It is found that the calculated band structures with and without the antimony doping are similar to each other within our framework.

The Global Optimization of Pt13 Cluster Using the First-Principle Molecular Dynamics with the Quenching Technique

NASA Astrophysics Data System (ADS)

Chen, Xiangping; Duan, Haiming; Cao, Biaobing; Long, Mengqiu

2018-03-01

The high-temperature first-principle molecular dynamics method used to obtain the low energy configurations of clusters [L. L. Wang and D. D. Johnson, PRB 75, 235405 (2007)] is extended to a considerably large temperature range by combination with the quenching technique. Our results show that there are strong correlations between the possibilities for obtaining the ground-state structure and the temperatures. Larger possibilities can be obtained at relatively low temperatures (as corresponds to the pre-melting temperature range). Details of the structural correlation with the temperature are investigated by taking the Pt13 cluster as an example, which suggests a quite efficient method to obtain the lowest-energy geometries of metal clusters.

Adsorption of methanol molecule on graphene: Experimental results and first-principles calculations

NASA Astrophysics Data System (ADS)

Zhao, X. W.; Tian, Y. L.; Yue, W. W.; Chen, M. N.; Hu, G. C.; Ren, J. F.; Yuan, X. B.

2018-04-01

Adsorption properties of methanol molecule on graphene surface are studied both theoretically and experimentally. The adsorption geometrical structures, adsorption energies, band structures, density of states and the effective masses are obtained by means of first-principles calculations. It is found that the electronic characteristics and conductivity of graphene are sensitive to the methanol molecule adsorption. After adsorption of methanol molecule, bandgap appears. With the increasing of the adsorption distance, the bandgap, adsorption energy and effective mass of the adsorption system decreased, hence the resistivity of the system decreases gradually, these results are consistent with the experimental results. All these calculations and experiments indicate that the graphene-based sensors have a wide range of applications in detecting particular molecules.

Prediction study of structural, elastic and electronic properties of FeMP (M = Ti, Zr, Hf) compounds

NASA Astrophysics Data System (ADS)

Tanto, A.; Chihi, T.; Ghebouli, M. A.; Reffas, M.; Fatmi, M.; Ghebouli, B.

2018-06-01

First principles calculations are applied in the study of FeMP (M = Ti, Zr, Hf) compounds. We investigate the structural, elastic, mechanical and electronic properties by combining first-principles calculations with the CASTEP approach. For ideal polycrystalline FeMP (M = Ti, Zr, Hf) the shear modulus, Young's modulus, Poisson's ratio, elastic anisotropy indexes, Pugh's criterion, elastic wave velocities and Debye temperature are also calculated from the single crystal elastic constants. The shear anisotropic factors and anisotropy are obtained from the single crystal elastic constants. The Debye temperature is calculated from the average elastic wave velocity obtained from shear and bulk modulus as well as the integration of elastic wave velocities in different directions of the single crystal.

Adsorption and Electronic Structure of Sr and Ag Atoms on Graphite Surfaces: a First-Principles Study

NASA Astrophysics Data System (ADS)

Luo, Xiao-Feng; Fang, Chao; Li, Xin; Lai, Wen-Sheng; Sun, Li-Feng; Liang, Tong-Xiang

2013-06-01

The adsorption behaviors of radioactive strontium and silver nuclides on the graphite surface in a high-temperature gas-cooled reactor are studied by first-principles theory using generalized gradient approximation (GGA) and local density approximation (LDA) pseudo-potentials. It turns out that Sr prefers to be absorbed at the hollow of the carbon hexagonal cell by 0.54 eV (GGA), while Ag likes to sit right above the carbon atom with an adsorption energy of almost zero (GGA) and 0.45 eV (LDA). Electronic structure analysis reveals that Sr donates its partial electrons of the 4p and 5s states to the graphite substrate, while Ag on graphite is a physical adsorption without any electron transfer.

Diagnosis: Reasoning from first principles and experiential knowledge

NASA Technical Reports Server (NTRS)

Williams, Linda J. F.; Lawler, Dennis G.

1987-01-01

Completeness, efficiency and autonomy are requirements for suture diagnostic reasoning systems. Methods for automating diagnostic reasoning systems include diagnosis from first principles (i.e., reasoning from a thorough description of structure and behavior) and diagnosis from experiential knowledge (i.e., reasoning from a set of examples obtained from experts). However, implementation of either as a single reasoning method fails to meet these requirements. The approach of combining reasoning from first principles and reasoning from experiential knowledge does address the requirements discussed above and can possibly ease some of the difficulties associated with knowledge acquisition by allowing developers to systematically enumerate a portion of the knowledge necessary to build the diagnosis program. The ability to enumerate knowledge systematically facilitates defining the program's scope, completeness, and competence and assists in bounding, controlling, and guiding the knowledge acquisition process.

Crystal structure of Earth's inner core: A first-principles study

NASA Astrophysics Data System (ADS)

Moustafa, S. G.; Schultz, A. J.; Zurek, E.; Kofke, D. A.

2017-12-01

Since the detection of the Earth's solid inner core (IC) by Lehmann in 1936, its composition and crystal structure (which are essential to understand Earth's evolution) have been controversial. While seismological measurements (e.g. PREM) can give a robust estimation of the density, pressure, and elasticity of the IC, they cannot be directly used to determine its composition and/or crystal structure. Experimentally, reaching the extreme IC conditions ( 330 GPa and 6000 K) and getting reliable measurements is very challenging. First-principles calculations provide a viable alternative that can work as a powerful investigative tool. Although several attempts have been made to assess phase stability at IC conditions computationally, they often use a low level of theory for electronic structure (e.g., classical force-field), adopt approximate methods (e.g., quasiharmonic approximation, fixed hcp-c/a), or do not consider finite-size effects. The study of phase stability using accurate first-principles methods is hampered in part by the difficulty of computing the free energy (FE), the central thermodynamic quantity that determines stability, while including anharmonic and finite-size effects. Additional difficulty related to the IC in particular is introduced by the dynamical instability of one of the IC candidate structures (bcc) at low temperature. Recently [1-3], we introduced a novel method (denoted as "harmonically mapped averaging", or HMA) to efficiently measure anharmonic properties (e.g. FE, pressure, elastic modulus) by molecular simulation, yielding orders of magnitude CPU speedup compared to conventional methods. We have applied this method to the hcp candidate phase of iron at the IC conditions, obtaining first-principles anharmonic FE values with unprecedented accuracy and precision [4]. We have now completed and report HMA calculations to assess the phase stability of all IC candidate phases (fcc/hcp/bcc). This knowledge is the prerequisite for interpreting the geophysical and geochemical constraints of the IC (e.g. anisotropy and low rigidity); which should be a key ingredient in the longstanding debate about the nature of the Earth's IC. References[1] 10.1103/PhysRevE.92.043303[2] 10.1021/acs.jctc.6b00018[3] 10.1021/acs.jctc.6b01082[4] 10.1103/PhysRevB.96.014117

Consistency of maternal cognitions and principles across the first five months following preterm and term deliveries

PubMed Central

Winstanley, A.; Sperotto, R.G.; Putnick, D.L.; Cherian, S.; Bornstein, M.H.; Gattis, M.

2014-01-01

The aims of this study were to examine and compare the development of parenting cognitions and principles in mothers following preterm and term deliveries. Parenting cognitions about child development, including thinking that is restricted to single causes and single outcomes (categorical thinking) and thinking that takes into account multiple perspectives (perspectivist thinking), have been shown to relate to child outcomes. Parenting principles about using routines (structure) or infant cues (attunement) to guide daily caregiving have been shown to relate to caregiving practices. We investigated the continuity and stability of parenting cognitions and principles in the days following birth to 5 months postpartum for mothers of infants born term and preterm. All parenting cognitions were stable across time. Categorical thinking increased at a group level across time in mothers of preterm, but not term, infants. Perspectivist thinking increased at a group level for first-time mothers (regardless of birth status) and tended to be lower in mothers of preterm infants. Structure at birth did not predict later structure (and so was unstable) in mothers of preterm, but not term, infants and neither group changed in mean level across time. Attunement was consistent across time in both groups of mothers. These results indicate that prematurity has multiple, diverse effects on parenting beliefs, which may in turn influence maternal behavior and child outcomes. PMID:25459794

First-principles investigations into the thermodynamics of cation disorder and its impact on electronic structure and magnetic properties of spinel Co(Cr1-x Mn x )2O4.

PubMed

Das, Debashish; Ghosh, Subhradip

2017-02-08

Cation disorder over different crystallographic sites in spinel oxides is known to affect their properties. Recent experiments on Mn doped multiferroic [Formula: see text] indicate that a possible distribution of Mn atoms among tetrahedrally and octahedrally coordinated sites in the spinel lattice give rise to different variations in the structural parameters and saturation magnetisations in different concentration regimes of Mn atoms substituting the Cr. A composition dependent magnetic compensation behaviour points to the role conversions of the magnetic constituents. In this work, we have investigated the thermodynamics of cation disorder in [Formula: see text] system and its consequences on the structural, electronic and magnetic properties, using results from first-principles electronic structure calculations. We have computed the variations in the cation-disorder as a function of Mn concentration and the temperature and found that at the annealing temperature of the experiment many of the systems exhibit cation disorder. Our results support the interpretations of the experimental results regarding the qualitative variations in the sub-lattice occupancies and the associated magnetisation behaviour, with composition. We have analysed the variations in structural, magnetic and electronic properties of this system with variations in the compositions and the degree of cation disorder from the variations in their electronic structures and by using the ideas from crystal field theory. Our study provides a complete microscopic picture of the effects that are responsible for composition dependent behavioural differences of the properties of this system. This work lays down a general framework, based upon results from first-principles calculations, to understand and analyse the substitutional magnetic spinel oxides [Formula: see text] in presence of cation disorder.

The prediction of crystal structure by merging knowledge methods with first principles quantum mechanics

NASA Astrophysics Data System (ADS)

Ceder, Gerbrand

2007-03-01

The prediction of structure is a key problem in computational materials science that forms the platform on which rational materials design can be performed. Finding structure by traditional optimization methods on quantum mechanical energy models is not possible due to the complexity and high dimensionality of the coordinate space. An unusual, but efficient solution to this problem can be obtained by merging ideas from heuristic and ab initio methods: In the same way that scientist build empirical rules by observation of experimental trends, we have developed machine learning approaches that extract knowledge from a large set of experimental information and a database of over 15,000 first principles computations, and used these to rapidly direct accurate quantum mechanical techniques to the lowest energy crystal structure of a material. Knowledge is captured in a Bayesian probability network that relates the probability to find a particular crystal structure at a given composition to structure and energy information at other compositions. We show that this approach is highly efficient in finding the ground states of binary metallic alloys and can be easily generalized to more complex systems.

First Principles Predictions of the Structure and Function of G-Protein-Coupled Receptors: Validation for Bovine Rhodopsin

PubMed Central

Trabanino, Rene J.; Hall, Spencer E.; Vaidehi, Nagarajan; Floriano, Wely B.; Kam, Victor W. T.; Goddard, William A.

2004-01-01

G-protein-coupled receptors (GPCRs) are involved in cell communication processes and with mediating such senses as vision, smell, taste, and pain. They constitute a prominent superfamily of drug targets, but an atomic-level structure is available for only one GPCR, bovine rhodopsin, making it difficult to use structure-based methods to design receptor-specific drugs. We have developed the MembStruk first principles computational method for predicting the three-dimensional structure of GPCRs. In this article we validate the MembStruk procedure by comparing its predictions with the high-resolution crystal structure of bovine rhodopsin. The crystal structure of bovine rhodopsin has the second extracellular (EC-II) loop closed over the transmembrane regions by making a disulfide linkage between Cys-110 and Cys-187, but we speculate that opening this loop may play a role in the activation process of the receptor through the cysteine linkage with helix 3. Consequently we predicted two structures for bovine rhodopsin from the primary sequence (with no input from the crystal structure)—one with the EC-II loop closed as in the crystal structure, and the other with the EC-II loop open. The MembStruk-predicted structure of bovine rhodopsin with the closed EC-II loop deviates from the crystal by 2.84 Å coordinate root mean-square (CRMS) in the transmembrane region main-chain atoms. The predicted three-dimensional structures for other GPCRs can be validated only by predicting binding sites and energies for various ligands. For such predictions we developed the HierDock first principles computational method. We validate HierDock by predicting the binding site of 11-cis-retinal in the crystal structure of bovine rhodopsin. Scanning the whole protein without using any prior knowledge of the binding site, we find that the best scoring conformation in rhodopsin is 1.1 Å CRMS from the crystal structure for the ligand atoms. This predicted conformation has the carbonyl O only 2.82 Å from the N of Lys-296. Making this Schiff base bond and minimizing leads to a final conformation only 0.62 Å CRMS from the crystal structure. We also used HierDock to predict the binding site of 11-cis-retinal in the MembStruk-predicted structure of bovine rhodopsin (closed loop). Scanning the whole protein structure leads to a structure in which the carbonyl O is only 2.85 Å from the N of Lys-296. Making this Schiff base bond and minimizing leads to a final conformation only 2.92 Å CRMS from the crystal structure. The good agreement of the ab initio-predicted protein structures and ligand binding site with experiment validates the use of the MembStruk and HierDock first principles' methods. Since these methods are generic and applicable to any GPCR, they should be useful in predicting the structures of other GPCRs and the binding site of ligands to these proteins. PMID:15041637

Thermal and chemical variations of the Nigerian Benue trough lead-zinc-barite-fluorite deposits

NASA Astrophysics Data System (ADS)

Ogundipe, Ibukun Emmanuel

2017-08-01

The Benue trough is an intra-continental rift initiated in the Cretaceous during the opening of the South Atlantic Ocean. Lead-zinc-barite-fluorite mineralization occurs along the 600 km axis of the trough in three discrete sub-basins which coincide with the lower, middle and upper mineral districts of the Benue Valley. Lithologically these sub-basins are dominated by black carbonaceous shale in the Lower Benue, platform carbonates in the Middle Benue and sandstones in the Upper Benue. Micro-thermometric analysis of fluid inclusions in sphalerite, fluorite, barite and quartz have shown that each mineral district has its own unique thermal and chemical imprint. For example, the temperature can be bracketed between 109 °C and 160 °C for lower Benue, 89 °C-144 °C for the Middle Benue and 176 °C-254 °C for the Upper Benue. Chemical differentiation also exists between each mineral district with the Lower Benue having 22 wt % equivalent NaCl while the Middle and Upper Benue have 18 and 16 wt % equivalent NaCl respectively. This study shows that inter-district thermal and chemical variations exist between the ore-stage sulfide and post-sulfide gangue minerals of the entire Benue Valley. Similarly, intra-district thermal and chemical variations have also been observed among all the paragenetic minerals of each district. The thermal variations may be as a result of variations in the geothermal gradient accompanying continental rifting from one district to the other. The variations in the chemistry between the Lower Benue and the Upper Benue paragenic minerals may be as a result of the distinct lithological differences across the Benue Trough.

A New Superhard Phase and Physical Properties of ZrB₃ from First-Principles Calculations.

PubMed

Zhang, Gangtai; Bai, Tingting; Zhao, Yaru; Hu, Yanfei

2016-08-22

Using the first-principles particle swarm optimization algorithm for crystal structural prediction, we have predicted a novel monoclinic C 2/ m structure for ZrB₃, which is more energetically favorable than the previously proposed FeB₃-, TcP₃-, MoB₃-, WB₃-, and OsB₃-type structures in the considered pressure range. The new phase is mechanically and dynamically stable, as confirmed by the calculations of its elastic constants and phonon dispersion curve. The calculated large shear modulus (227 GPa) and high hardness (42.2 GPa) show that ZrB₃ within the monoclinic phase is a potentially superhard material. The analyses of the electronic density of states and chemical bonding reveal that the strong B-B and B-Zr covalent bonds are attributed to its high hardness. By the quasi-harmonic Debye model, the heat capacity, thermal expansion coefficient and Grüneisen parameter of ZrB₃ are also systemically investigated.

On the influence of tetrahedral covalent-hybridization on electronic band structure of topological insulators from first principles

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

Zhang, X. M.; Xu, G. Z.; Liu, E. K.

Based on first-principles calculations, we investigate the influence of tetrahedral covalent-hybridization between main-group and transition-metal atoms on the topological band structures of binary HgTe and ternary half-Heusler compounds, respectively. Results show that, for the binary HgTe, when its zinc-blend structure is artificially changed to rock-salt one, the tetrahedral covalent-hybridization will be removed and correspondingly the topologically insulating band character lost. While for the ternary half-Heusler system, the strength of covalent-hybridization can be tuned by varying both chemical compositions and atomic arrangements, and the competition between tetrahedral and octahedral covalent-hybridization has been discussed in details. As a result, we found thatmore » a proper strength of tetrahedral covalent-hybridization is probably in favor to realizing the topologically insulating state with band inversion occurring at the Γ point of the Brillouin zone.« less

Structural and electronic properties of CdSe/ZnS and ZnS/CdSe core/shell nanowires via first principles study

NASA Astrophysics Data System (ADS)

Rehman, Shafiq Ur; Li, H. M.; Ding, Z. J.

2018-05-01

First principles calculations have been performed to predict the structural stability and electronic structures of hydrogen passivated wurtzite CdSe/ZnS and ZnS/CdSe core/shell nanowires (CSNWs) in the [0001] direction. The calculated binding energy shows that ZnS/CdSe CSNWs are more stable than CdSe/ZnS CSNWs and the stability of ZnS/CdSe CSNWs increases with increasing the thickness of ZnS shell. The modulated electronic band gap demonstrates an increase when the size of both CSNWs is reduced, as a result of the quantum confinement effect. The core-to-shell chemical composition of atoms shows that a strong composition effect also exists in these CSNWs, which in turn affects their electronic properties. Our simulated results show that the photoemission spectra of the CSNWs can be significantly improved by tuning the energy gap of CSNWs.

First principles pseudopotential calculation of electron energy loss near edge structures of lattice imperfections.

PubMed

Mizoguchi, Teruyasu; Matsunaga, Katsuyuki; Tochigi, Eita; Ikuhara, Yuichi

2012-01-01

Theoretical calculations of electron energy loss near edge structures (ELNES) of lattice imperfections, particularly a Ni(111)/ZrO₂(111) heterointerface and an Al₂O₃ stacking fault on the {1100} plane, are performed using a first principles pseudopotential method. The present calculation can qualitatively reproduce spectral features as well as chemical shifts in experiment by employing a special pseudopotential designed for the excited atom with a core-hole. From the calculation, spectral changes observed in O-K ELNES from a Ni/ZrO₂ interface can be attributable to interfacial oxygen-Ni interactions. In the O-K ELNES of Al₂O₃ stacking faults, theoretical calculation suggests that the spectral feature reflects coordination environment and chemical bonding. Powerful combinations of ELNES with a pseudopotential method used to investigate the atomic and electronic structures of lattice imperfections are demonstrated. Copyright © 2011 Elsevier Ltd. All rights reserved.

First principles study of crystal Si-doped Ge2Sb2Te5

NASA Astrophysics Data System (ADS)

Yan, Beibei; Yang, Fei; Chen, Tian; Wang, Minglei; Chang, Hong; Ke, Daoming; Dai, Yuehua

2017-02-01

Ge2Sb2Te5 (GST) and Si-doped GST with hexagonal structure were investigated by means of First-principles calcucations. We performed many kinds of doping types and studied the electronic properties of Si-doped GST with various Si concentrations. The theoretical calculations show that the lowest formation energy appeared when Si atoms substitute the Sb atoms (SiSb). With the increasing of Si concentrations from 10% to 30%, the impurity states arise around the Fermi level and the band gap of the SiSb structure broadens. Meanwhile, the doping supercell has the most favorable structure when the doping concentration keeps in 20%. The Si-doped GST exhibits p-type metallic characteristics more distinctly owing to the Fermi level moves toward the valence band. The Te p, d-orbitals electrons have greater impact on electronic properties than that of Te s-orbitals.

Properties of amorphous GaN from first-principles simulations

NASA Astrophysics Data System (ADS)

Cai, B.; Drabold, D. A.

2011-08-01

Amorphous GaN (a-GaN) models are obtained from first-principles simulations. We compare four a-GaN models generated by “melt-and-quench” and the computer alchemy method. We find that most atoms tend to be fourfold, and a chemically ordered continuous random network is the ideal structure for a-GaN albeit with some coordination defects. Where the electronic structure is concerned, the gap is predicted to be less than 1.0 eV, underestimated as usual by a density functional calculation. We observe a highly localized valence tail and a remarkably delocalized exponential conduction tail in all models generated. Based upon these results, we speculate on potential differences in n- and p-type doping. The structural origin of tail and defect states is discussed. The vibrational density of states and dielectric function are computed and seem consistent with experiment.

First principles molecular dynamics study of nitrogen vacancy complexes in boronitrene

NASA Astrophysics Data System (ADS)

Ukpong, A. M.; Chetty, N.

2012-07-01

We present the results of first principles molecular dynamics simulations of nitrogen vacancy complexes in monolayer hexagonal boron nitride. The threshold for local structure reconstruction is found to be sensitive to the presence of a substitutional carbon impurity. We show that activated nitrogen dynamics triggers the annihilation of defects in the layer through formation of Stone-Wales-type structures. The lowest energy state of nitrogen vacancy complexes is negatively charged and spin polarized. Using the divacancy complex, we show that their formation induces spontaneous magnetic moments, which is tunable by electron or hole injection. The Fermi level s-resonant defect state is identified as a unique signature of the ground state of the divacancy complex. Due to their ability to enhance structural cohesion, only the divacancy and the nitrogen vacancy carbon-antisite complexes are able to suppress the Fermi level resonant defect state to open a gap between the conduction and valence bands.

Time-dependent first-principles study of angle-resolved secondary electron emission from atomic sheets

NASA Astrophysics Data System (ADS)

Ueda, Yoshihiro; Suzuki, Yasumitsu; Watanabe, Kazuyuki

2018-02-01

Angle-resolved secondary electron emission (ARSEE) spectra were analyzed for two-dimensional atomic sheets using a time-dependent first-principles simulation of electron scattering. We demonstrate that the calculated ARSEE spectra capture the unoccupied band structure of the atomic sheets. The excitation dynamics that lead to SEE have also been revealed by the time-dependent Kohn-Sham decomposition scheme. In the present study, the mechanism for the experimentally observed ARSEE from atomic sheets is elucidated with respect to both energetics and the dynamical aspects of SEE.

First-Principle Simulations of Water

NASA Astrophysics Data System (ADS)

Schwegler, Eric

2004-03-01

The structural and dynamical properties of water are investigated with a series of first-principle and classical molecular dynamics simulations. A number of effects that can influence the simulated properties of water will be discussed including temperature, intramolecular flexibility [1], and the quantum nature of protons. This work was performed under the auspices of the U.S. Dept. of Energy at the University of California/Lawrence Livermore National Laboratory under contract no. W-7405-Eng-48. [1] M. Allesch, E. Schwegler, G. Galli, F. Gygi, J. Chem. Phys. in press 2004.

First-principles study of length dependence of conductance in alkanedithiols

NASA Astrophysics Data System (ADS)

Zhou, Y. X.; Jiang, F.; Chen, H.; Note, R.; Mizuseki, H.; Kawazoe, Y.

2008-01-01

Electronic transport properties of alkanedithiols are calculated by a first-principles method based on density functional theory and nonequilibrium Green's function formalism. At small bias, the I-V characteristics are linear and the resistances conform to the Magoga's exponential law. The calculated length-dependent decay constant γ which reflects the effect of internal molecular structure is in accordance with most experiments quantitatively. Also, the calculated effective contact resistance R0 is in good agreement with the results of repeatedly measuring molecule-electrode junctions [B. Xu and N. Tao, Science 301, 1221 (2003)].

Fullerene-like CS x: A first-principles study of synthetic growth

NASA Astrophysics Data System (ADS)

Goyenola, C.; Gueorguiev, G. K.; Stafström, S.; Hultman, L.

2011-04-01

Fullerene-Like (FL) Sulpho-Carbide (CSx) compounds have been addressed by first principles calculations. Geometry optimization and cohesive energy results are presented for the relative stability of precursor species such as C2S, CS2, and C2S2 in isolated form. The energy cost for structural defects, arising from the substitution of C by S is also reported. Similar to previously synthesized FL-CNx and FL-CPx compounds, the pentagon, the double pentagon defects as well as the Stone-Wales defects are confirmed as energetically feasible in CSx compounds.

Two prospective Li-based half-Heusler alloys for spintronic applications based on structural stability and spin–orbit effect

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

Zhang, R. L.; Damewood, L.; Zeng, Y. J.

To search for half-metallic materials for spintronic applications, instead of using an expensive trial-and-error experimental scheme, it is more efficient to use first-principles calculations to design materials first, and then grow them. In particular, using a priori information of the structural stability and the effect of the spin–orbit interaction (SOI) enables experimentalists to focus on favorable properties that make growing half-metals easier. We suggest that using acoustic phonon spectra is the best way to address the stability of promising half-metallic materials. Additionally, by carrying out accurate first-principles calculations, we propose two criteria for neglecting the SOI so the half-metallicity persists.more » As a result, based on the mechanical stability and the negligible SOI, we identified two half-metals, β-LiCrAs and β-LiMnSi, as promising half-Heusler alloys worth growing.« less

Two prospective Li-based half-Heusler alloys for spintronic applications based on structural stability and spin–orbit effect

DOE PAGES

Zhang, R. L.; Damewood, L.; Zeng, Y. J.; ...

2017-07-07

To search for half-metallic materials for spintronic applications, instead of using an expensive trial-and-error experimental scheme, it is more efficient to use first-principles calculations to design materials first, and then grow them. In particular, using a priori information of the structural stability and the effect of the spin–orbit interaction (SOI) enables experimentalists to focus on favorable properties that make growing half-metals easier. We suggest that using acoustic phonon spectra is the best way to address the stability of promising half-metallic materials. Additionally, by carrying out accurate first-principles calculations, we propose two criteria for neglecting the SOI so the half-metallicity persists.more » As a result, based on the mechanical stability and the negligible SOI, we identified two half-metals, β-LiCrAs and β-LiMnSi, as promising half-Heusler alloys worth growing.« less

Structural stability and electronic properties of β-tetragonal boron: A first-principles study

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

Hayami, Wataru, E-mail: hayami.wataru@nims.go.jp

2015-01-15

It is known that elemental boron has five polymorphs: α- and β-rhombohedral, α- and β-tetragonal, and the high-pressure γ phase. β-tetragonal (β-t) boron was first discovered in 1960, but there have been only a few studies since then. We have thoroughly investigated, using first-principles calculations, the atomic and electronic structures of β-t boron, the details of which were not known previously. The difficulty of calculation arises from the fact that β-t boron has a large unit cell that contains between 184 and 196 atoms, with 12 partially-occupied interstitial sites. This makes the number of configurations of interstitial atoms too greatmore » to calculate them all. By introducing assumptions based on symmetry and preliminary calculations, the number of configurations to calculate can be greatly reduced. It was eventually found that β-t boron has the lowest total energy, with 192 atoms (8 interstitial atoms) in an orthorhombic lattice. The total energy per atom was between those of α- and β-rhombohedral boron. Another tetragonal structure with 192 atoms was found to have a very close energy. The valence bands were fully filled and the gaps were about 1.16 to 1.54 eV, making it comparable to that of β-rhombohedral boron. - Graphical abstract: Electronic density distribution for the lowest-energy configuration (N=192) viewed from the 〈1 0 0〉 direction. Left: isosurface (yellow) at d=0.09 electrons/a.u.{sup 3} Right: isosurface (orange) at d=0.12 electrons/a.u.{sup 3}. - Highlights: • β-tetragonal boron was thoroughly investigated using first-principles calculations. • The lowest energy structure contains 192 atoms in an orthorhombic lattice. • Another tetragonal structure with 192 atoms has a very close energy. • The total energy per atom is between those of α- and β-rhombohedral boron. • The band gap of the lowest energy structure is about 1.16 to 1.54 eV.« less

Gypsum under pressure: A first-principles study

NASA Astrophysics Data System (ADS)

Giacomazzi, Luigi; Scandolo, Sandro

2010-02-01

We investigate by means of first-principles methods the structural response of gypsum (CaSO4ṡ2H2O) to pressures within and above the stability range of gypsum-I (P≤4GPa) . Structural and vibrational properties calculated for gypsum-I are in excellent agreement with experimental data. Compression within gypsum-I takes place predominantly through a reduction in the volume of the CaO8 polyhedra and through a distortion of the hydrogen bonds. The distance between CaSO4 layers becomes increasingly incompressible, indicating a mechanical limit to the packing of water molecules between the layers. We find that a structure with collapsed interlayer distances becomes more stable than gypsum-I above about 5 GPa. The collapse is concomitant with a rearrangement of the hydrogen-bond network of the water molecules. Comparison of the vibrational spectra calculated for this structure with experimental data taken above 5 GPa supports the validity of our model for the high-pressure phase of gypsum.

Electronic and structural reconstruction in titanate heterostructures from first principles

NASA Astrophysics Data System (ADS)

Mulder, Andrew T.; Fennie, Craig J.

2014-03-01

Recent advances in transition metal oxide heterostructures have opened new routes to create materials with novel functionalities and properties. One direction has been to combine a Mott insulating perovskite with an electronic d1 configuration, such as LaTiO3, with a band insulating d0 perovskite, such as SrTiO3. An exciting recent development is the demonstration of interfacial conductivity in GdTiO3/SrTiO3 heterostructures that display a complex structural motif of octahedral rotations and ferromagnetic properties similar to bulk GdTiO3. In this talk we present our first principles investigation of the interplay of structural, electronic, magnetic, and orbital degrees of freedom for a wide range of d1/d0 titanate heterostructures. We find evidence for both rotation driven ferroelectricity and a symmetry breaking electronic reconstruction with a concomitant structural distortion at the interface. We argue that these materials represent an ideal platform to realize novel functionalities such as the electric field control of electronic and magnetic properties.

Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations.

PubMed

Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei

2017-02-14

Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiC x O 6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young's modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young's modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.

Modeling of amorphous SiCxO6/5 by classical molecular dynamics and first principles calculations

NASA Astrophysics Data System (ADS)

Liao, Ningbo; Zhang, Miao; Zhou, Hongming; Xue, Wei

2017-02-01

Polymer-derived silicon oxycarbide (SiCO) presents excellent performance for high temperature and lithium-ion battery applications. Current experiments have provided some information on nano-structure of SiCO, while it is very challenging for experiments to take further insight into the molecular structure and its relationship with properties of materials. In this work, molecular dynamics (MD) based on empirical potential and first principle calculation were combined to investigate amorphous SiCxO6/5 ceramics. The amorphous structures of SiCO containing silicon-centered mix bond tetrahedrons and free carbon were successfully reproduced. The calculated radial distribution, angular distribution and Young’s modulus were validated by current experimental data, and more details on molecular structure were discussed. The change in the slope of Young’s modulus is related to the glass transition temperature of the material. The proposed modeling approach can be used to predict the properties of SiCO with different compositions.

Defect formation energy and magnetic structure of shape memory alloys Ni-X-Ga (X=Mn, Fe, Co) by first principle calculation

NASA Astrophysics Data System (ADS)

Bai, J.; Raulot, J. M.; Zhang, Y. D.; Esling, C.; Zhao, X.; Zuo, L.

2010-09-01

The crystallographic and magnetic structures of the Ni2XGa (X=Mn, Fe, Co), are systematically investigated by means of the first-principles calculations within the framework of density functional theory using the VIENNA AB INITIO SOFTWARE PACKAGE. The formation energies of several kinds of defects (atomic exchange, antisite, vacancy) are estimated. The Ga atoms stabilize the cubic structure, and the effect of X atoms on the structural stability is opposite. For most cases of the site occupation, the excess atoms of the rich component directly occupy the site(s) of the deficient one(s), except for Ga-rich Ni-deficient type. The magnitude of the variation in Ni moments is much larger than that of Mn in defective Ni2XGa. The value of Ni magnetic moment sensitively depends on the distance between Ni and X. Excess Mn could be ferromagnetic or antiferromagnetic, depending on the distance between the neighboring Mn atoms.

The effect of boron concentration on the structure and elastic properties of Ru-Ir alloys: first-principles calculations

NASA Astrophysics Data System (ADS)

Li, Xiaolong; Zhou, Zhaobo; Hu, Riming; Zhou, Xiaolong; Yu, Jie; Liu, Manmen

2018-04-01

The Phase stability, electronic structure, elastic properties and hardness of Ru-Ir alloys with different B concentration were investigated by first principles calculations. The calculated formation enthaplies and cohesive energies show that these compounds are all thermodynamically stable. Information on electronic structure indicates that they possess metallic characteristic and Ru-Ir-B alloys were composed of the Ru-B and Ir-B covalent bond. The elastic properties were calculated, which included bulk modulus, shear modulus, Young’s modulus, Poisson’s ratio and hardness. The calculated results reveal that the plastic of Ru-Ir-B alloys increase with the increase of the content of B atoms, but the hardness of Ru-Ir-B alloys have no substantial progress with the increase of the content of B atoms. However, it is interesting that the hardness of the Ru-Ir-B compound was improved obviously as the B content was higher than 18 atoms because of a phase structure transition.

First-principles molecular dynamics simulation of the Ca 2UO 2(CO 3) 3 complex in water

DOE PAGES

Priest, Chad; Tian, Ziqi; Jiang, De-en

2016-01-22

Recent experiments have shown that the neutral Ca 2UO 2(CO 3) 3 complex is the dominant species of uranium in many uranyl-containing streams. However, the structure and solvation of such a species in water has not been investigated from first principles. Herein we present a first principles molecular dynamics perspective of the Ca 2UO 2(CO 3) 3 complex in water based on density functional theory and Born–Oppenheimer approximation. We find that the Ca 2UO 2(CO 3) 3 complex is very stable in our simulation timeframe for three different concentrations considered and that the key distances from our simulation are inmore » good agreement with the experimental data from extended X-ray absorption fine structure (EXAFS) spectroscopy. More important, we find that the two Ca ions bind differently in the complex, as a result of the hydrogen-bonding network around the whole complex. Furthermore, this finding invites confirmation from time-resolved EXAFS and has implications in understanding the dissociative equilibrium of the Ca 2UO 2(CO 3) 3 complex in water.« less

Structure and thermal expansion of Lu 2O 3 and Yb 2O 3 up to the melting points

DOE PAGES

Pavlik, Alfred; Ushakov, Sergey V.; Navrotsky, Alexandra; ...

2017-08-24

Knowledge of thermal expansion and high temperature phase transformations is essential for prediction and interpretation of materials behavior under the extreme conditions of high temperature and intense radiation encountered in nuclear reactors. We studied the structure and thermal expansion of Lu 2O 3 and Yb 2O 3 were studied in oxygen and argon atmospheres up to their melting temperatures using synchrotron X-ray diffraction on laser heated levitated samples. Both oxides retained the cubic bixbyite C-type structure in oxygen and argon to melting. In contrast to fluorite-type structures, the increase in the unit cell parameter of Yb 2O 3 and Lumore » 2O 33 with temperature is linear within experimental error from room temperature to the melting point, with mean thermal expansion coefficients (8.5 ± 0.6) · 10 -6 K -1 and (7.7 ± 0.6) · 10 -6 K -1, respectively. There is no indication of a superionic (Bredig) transition in the C-type structure or of a previously suggested Yb 2O 3 phase transformation to hexagonal phase prior to melting.« less

Structure and thermal expansion of Lu 2O 3 and Yb 2O 3 up to the melting points

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

Pavlik, Alfred; Ushakov, Sergey V.; Navrotsky, Alexandra

Knowledge of thermal expansion and high temperature phase transformations is essential for prediction and interpretation of materials behavior under the extreme conditions of high temperature and intense radiation encountered in nuclear reactors. We studied the structure and thermal expansion of Lu 2O 3 and Yb 2O 3 were studied in oxygen and argon atmospheres up to their melting temperatures using synchrotron X-ray diffraction on laser heated levitated samples. Both oxides retained the cubic bixbyite C-type structure in oxygen and argon to melting. In contrast to fluorite-type structures, the increase in the unit cell parameter of Yb 2O 3 and Lumore » 2O 33 with temperature is linear within experimental error from room temperature to the melting point, with mean thermal expansion coefficients (8.5 ± 0.6) · 10 -6 K -1 and (7.7 ± 0.6) · 10 -6 K -1, respectively. There is no indication of a superionic (Bredig) transition in the C-type structure or of a previously suggested Yb 2O 3 phase transformation to hexagonal phase prior to melting.« less

Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

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

Danielson, Thomas; Hin, Celine; Savara, Aditya

Lattice based kinetic Monte Carlo (KMC) simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and for estimating the coverage at a certain pressure. The generalized form has been calculatedmore » by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. Finally, the equations have been shown to be general for any value of the adsorption equilibrium constant.« less

Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

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

Danielson, Thomas; Hin, Celine; Department of Mechanical Engineering, Virginia Polytechnic Institute and State University, Blacksburg, Virginia 24061

Lattice based kinetic Monte Carlo simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and, conversely, for estimating the coverage at a certain pressure. The generalized form has been calculatedmore » by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10{sup −26} to 10{sup 13}. The equations have been shown to be general for any value of the adsorption equilibrium constant.« less

Generalized adsorption isotherms for molecular and dissociative adsorption of a polar molecular species on two polar surface geometries: Perovskite (100) (Pm-3m) and fluorite (111) (Fm-3m)

DOE PAGES

Danielson, Thomas; Hin, Celine; Savara, Aditya

2016-08-10

Lattice based kinetic Monte Carlo (KMC) simulations have been used to determine a functional form for the second order adsorption isotherms on two commonly investigated crystal surfaces: the (111) fluorite surface and the (100) perovskite surface which has the same geometric symmetry as the NaCl (100) surface. The functional form is generalized to be applicable to all values of the equilibrium constant by a shift along the pressure axis. Functions have been determined for estimating the pressure at which a desired coverage would be achieved and for estimating the coverage at a certain pressure. The generalized form has been calculatedmore » by investigating the surface adsorbate coverage across a range of thermodynamic equilibrium constants that span the range 10-26 to 1013. Finally, the equations have been shown to be general for any value of the adsorption equilibrium constant.« less

First-principles simulation and low-energy effective modeling of three-dimensional skyrmion in MnGe

NASA Astrophysics Data System (ADS)

Choi, Hongchul; Tai, Yuan-Yen; Zhu, Jian-Xin; T-4 Team

The skyrmion spin textures are mostly observed in two-dimensional (2D) space, which can be topologically mapped onto the surface of the sphere with an integer multiple of topological winding number. Recently, MnGe has been reported as a candidate of 3D skyrmion crystal, showing the variation of the skyrmion size along the z-direction. We have performed the first-principles simulation and constructed a tight-binding model with calculated electronic-structure information to investigate the 3D skyrmion phase in MnGe. Our first-principles study within density functional theory shows that the calculated magnetic moment is larger than that for MnSi (with different lattice constant), implying the possibility of a multiple magnetic transition under pressure. We have also found that the small-sized skyrmion could be stabilized in a 2D structure. Such a high density of the skyrmion is in good agreement with the experimental finding of large topological Hall effect. Finally, we will extend our study to consider the 3D skyrmion structure based on the constructed tight-binding model. This work was carried out under the auspices of the National Nuclear Security Administration of the U.S. Department of Energy at Los Alamos National Laboratory (LANL) under Contract No. DE-AC52-06NA25396, and was supported by the LANL LDRD Program.

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

Morris, J.R.; Lu, Z.Y.; Ring, D.M.

The authors have examined a variety of structures for the {l_brace}510{r_brace} symmetric tilt boundary in Si, using first-principles calculations. These calculations show that the observed structure in Si is the lowest energy structure. This structure is more complicated than what is necessary to preserve four-fold coordination. They compare the results to classical and tight-binding models, in order to test these empirical approaches.

First-principles atomistic Wulff constructions for an equilibrium rutile TiO2 shape modeling

NASA Astrophysics Data System (ADS)

Jiang, Fengzhou; Yang, Lei; Zhou, Dali; He, Gang; Zhou, Jiabei; Wang, Fanhou; Chen, Zhi-Gang

2018-04-01

Identifying the exposed surfaces of rutile TiO2 crystal is crucial for its industry application and surface engineering. In this study, the shape of the rutile TiO2 was constructed by applying equilibrium thermodynamics of TiO2 crystals via first-principles density functional theory (DFT) and Wulff principles. From the DFT calculations, the surface energies of six low-index stoichiometric facets of TiO2 are determined after the calibrations of crystal structure. And then, combined surface energy calculations and Wulff principles, a geometric model of equilibrium rutile TiO2 is built up, which is coherent with the typical morphology of fully-developed equilibrium TiO2 crystal. This study provides fundamental theoretical guidance for the surface analysis and surface modification of the rutile TiO2-based materials from experimental research to industry manufacturing.

Cesium under pressure: First-principles calculation of the bcc-to-fcc phase transition

NASA Astrophysics Data System (ADS)

Carlesi, S.; Franchini, A.; Bortolani, V.; Martinelli, S.

1999-05-01

In this paper we present the ab initio calculation of the structural properties of cesium under pressure. The calculation of the total energy is done in the local-density approximation of density-functional theory, using a nonlocal pseudopotential including the nonlinear core corrections proposed by Louie et al. The calculation of the pressure-volume diagram for both bcc and fcc structures allows us to prove that the transition from bcc to fcc structure is a first-order transition.

GPU acceleration of the Locally Selfconsistent Multiple Scattering code for first principles calculation of the ground state and statistical physics of materials

NASA Astrophysics Data System (ADS)

Eisenbach, Markus; Larkin, Jeff; Lutjens, Justin; Rennich, Steven; Rogers, James H.

2017-02-01

The Locally Self-consistent Multiple Scattering (LSMS) code solves the first principles Density Functional theory Kohn-Sham equation for a wide range of materials with a special focus on metals, alloys and metallic nano-structures. It has traditionally exhibited near perfect scalability on massively parallel high performance computer architectures. We present our efforts to exploit GPUs to accelerate the LSMS code to enable first principles calculations of O(100,000) atoms and statistical physics sampling of finite temperature properties. We reimplement the scattering matrix calculation for GPUs with a block matrix inversion algorithm that only uses accelerator memory. Using the Cray XK7 system Titan at the Oak Ridge Leadership Computing Facility we achieve a sustained performance of 14.5PFlop/s and a speedup of 8.6 compared to the CPU only code.

Electrical properties of improper ferroelectrics from first principles

NASA Astrophysics Data System (ADS)

Stengel, Massimiliano; Fennie, Craig J.; Ghosez, Philippe

2012-09-01

We study the interplay of structural and polar distortions in hexagonal YMnO3 and short-period PbTiO3/SrTiO3 (PTO/STO) superlattices by means of first-principles calculations at constrained electric displacement field D. We find that in YMnO3 the tilts of the oxygen polyhedra produce a robustly polar ground state, which persists at any choice of the electrical boundary conditions. Conversely, in PTO/STO the antiferrodistortive instabilities alone do not break inversion symmetry, and open-circuit boundary conditions restore a nonpolar state. We suggest that this qualitative difference naturally provides a route to rationalizing the concept of “improper ferroelectricity” from the point of view of first-principles theory. We discuss the implications of our arguments for the design of novel multiferroic materials with enhanced functionalities and for the symmetry analysis of the phase transitions.

First principles view on chemical compound space: Gaining rigorous atomistic control of molecular properties

DOE PAGES

von Lilienfeld, O. Anatole

2013-02-26

A well-defined notion of chemical compound space (CCS) is essential for gaining rigorous control of properties through variation of elemental composition and atomic configurations. Here, we give an introduction to an atomistic first principles perspective on CCS. First, CCS is discussed in terms of variational nuclear charges in the context of conceptual density functional and molecular grand-canonical ensemble theory. Thereafter, we revisit the notion of compound pairs, related to each other via “alchemical” interpolations involving fractional nuclear charges in the electronic Hamiltonian. We address Taylor expansions in CCS, property nonlinearity, improved predictions using reference compound pairs, and the ounce-of-gold prizemore » challenge to linearize CCS. Finally, we turn to machine learning of analytical structure property relationships in CCS. Here, these relationships correspond to inferred, rather than derived through variational principle, solutions of the electronic Schrödinger equation.« less

GPU acceleration of the Locally Selfconsistent Multiple Scattering code for first principles calculation of the ground state and statistical physics of materials

DOE PAGES

Eisenbach, Markus; Larkin, Jeff; Lutjens, Justin; ...

2016-07-12

The Locally Self-consistent Multiple Scattering (LSMS) code solves the first principles Density Functional theory Kohn–Sham equation for a wide range of materials with a special focus on metals, alloys and metallic nano-structures. It has traditionally exhibited near perfect scalability on massively parallel high performance computer architectures. In this paper, we present our efforts to exploit GPUs to accelerate the LSMS code to enable first principles calculations of O(100,000) atoms and statistical physics sampling of finite temperature properties. We reimplement the scattering matrix calculation for GPUs with a block matrix inversion algorithm that only uses accelerator memory. Finally, using the Craymore » XK7 system Titan at the Oak Ridge Leadership Computing Facility we achieve a sustained performance of 14.5PFlop/s and a speedup of 8.6 compared to the CPU only code.« less

Vibrational dynamics of rutile-type GeO2 from micro-Raman spectroscopy experiments and first-principles calculations

NASA Astrophysics Data System (ADS)

Sanson, A.; Pokrovski, G. S.; Giarola, M.; Mariotto, G.

2015-01-01

The vibrational dynamics of germanium dioxide in the rutile structure has been investigated by using polarized micro-Raman scattering spectroscopy coupled with first-principles calculations. Raman spectra were carried out in backscattering geometry at room temperature from micro-crystalline samples either unoriented or oriented by means of a micromanipulator, which enabled successful detection and identification of all the Raman active modes expected on the basis of the group theory. In particular, the Eg mode, incorrectly assigned or not detected in the literature, has been definitively observed by us and unambiguously identified at 525 \\text{cm}-1 under excitation by certain laser lines, thus revealing an unusual resonance phenomenon. First-principles calculations within the framework of the density functional theory allow quantifying both wave number and intensity of the Raman vibrational spectra. The excellent agreement between calculated and experimental data corroborates the reliability of our findings.

Zirconia and Pyrochlore Oxides for Thermal Barrier Coatings in Gas Turbine Engines

DOE PAGES

Fergus, Jeffrey W.

2014-04-12

One of the important applications of yttria stabilized zirconia is as a thermal barrier coating for gas turbine engines. While yttria stabilized zirconia performs well in this function, the need for increased operating temperatures to achieve higher energy conversion efficiencies, requires the development of improved materials. To meet this challenge, some rare-earth zirconates that form the cubic fluorite derived pyrochlore structure are being developed for use in thermal barrier coatings due to their low thermal conductivity, excellent chemical stability and other suitable properties. In this paper, the thermal conductivities of current and prospective oxides for use in thermal barrier coatingsmore » are reviewed. The factors affecting the variations and differences in the thermal conductivities and the degradation behaviors of these materials are discussed.« less

Protein Multifunctionality: Principles and Mechanisms

PubMed Central

Zaretsky, Joseph Z.; Wreschner, Daniel H.

2008-01-01

In the review, the nature of protein multifunctionality is analyzed. In the first part of the review the principles of structural/functional organization of protein are discussed. In the second part, the main mechanisms involved in development of multiple functions on a single gene product(s) are analyzed. The last part represents a number of examples showing that multifunctionality is a basic feature of biologically active proteins. PMID:21566747

Electronic structure and photoabsorption of Ti 3+ ions in reduced anatase and rutile TiO 2

DOE PAGES

Wen, Bo; Hao, Qunqing; Yin, Wen-Jin; ...

2018-01-01

We have used two-photon photoemission (2PPE) spectroscopy and first-principles density functional theory calculations to investigate the electronic structure and photoabsorption of the reduced anatase TiO 2 (101) and rutile TiO 2 (110) surfaces.

FAST TRACK COMMUNICATION: Preferential functionalization on zigzag graphene nanoribbons: first-principles calculations

NASA Astrophysics Data System (ADS)

Lee, Hoonkyung

2010-09-01

We investigate the functionalization of functional groups to graphene nanoribbons with zigzag and armchair edges using first-principles calculations. We find that the formation energy for the configuration of the functional groups functionalized to the zigzag edge is ~ 0.2 eV per functional group lower than that to the armchair edge. The formation energy difference arises from a structural deformation on the armchair edge by the functionalization whereas there is no structural deformation on the zigzag edge. Selective functionalization on the zigzag edge takes place at a condition of the temperature and the pressure of ~ 25 °C and 10 - 5 atm. Our findings show that selective functionalization can offer the opportunity for an approach to the separation of zigzag graphene nanoribbons with their solubility change.

First-principles simulations on suspended coinage-metal nanotubes composed of different atomic species.

PubMed

Fa, Wei; Zhou, Jian; Dong, Jinming

2013-04-07

Substitutional doping of gold and copper atoms in a (4, 4) silver single-wall nanotube has been investigated using first-principles simulations. It is found that the Au- and Cu-substitutional doping of the tip-suspended (4, 4) Ag tube can maintain the hollow tubular structure at different alloy compositions due to the existence of a local minimum in the string tension variation with their unit cell lengths. The bonding energy differences between the mono-elements and hetero-elements and string tension may play important roles in suppressing the "self-purification" effects so that the nanoalloy tubes can be formed. Analysis of the band structure suggests that the number of conduction channels of the Ag-Au alloy tubes may lie between the pure (4, 4) Ag and Au tubes.

Structural stability, elastic and thermodynamic properties of Au-Cu alloys from first-principles calculations

NASA Astrophysics Data System (ADS)

Kong, Ge-Xing; Ma, Xiao-Juan; Liu, Qi-Jun; Li, Yong; Liu, Zheng-Tang

2018-03-01

Using first-principles calculations method based on density functional theory (DFT) with the Perdew-Burke-Ernzerhof (PBE) implementation of the generalized gradient approximation (GGA), we investigate the structural, elastic and thermodynamic properties of gold-copper intermetallic compounds (Au-Cu ICs). The calculated lattice parameters are in excellent agreement with experimental data. The elastic constants show that all the investigated Au-Cu alloys are mechanically stable. Elastic properties, including the shear modulus, Young's modulus, Poisson's ratio and Pugh's indicator, of the intermetallic compounds are evaluated and discussed, with special attention to the remarkable anisotropy displayed by Au-Cu ICs. Thermodynamic and transport properties including the Debye temperature, thermal conductivity and melting point are predicted from the averaged sound velocity and elastic moduli, using semi-empirical formulas.

Structure and properties of CaMnO3/SrMnO3/BaMnO3 superlattices from first principles

NASA Astrophysics Data System (ADS)

Li, Shen; Oh, Seongshik; Rabe, Karin

2008-03-01

Previous theoretical and experimental studies have shown that three-component, or ``tri-color'' superlattices can exhibit intrinsic electric polarization due to inversion-symmetry breaking in the layer sequence. In ferromagnetic inversion-symmetry-breaking superlattices, controlled symmetry lowering is similarly expected to lead to interesting new and tunable properties. Here, we present results of first-principles density-functional-theory calculations for short-period CaMnO3/SrMnO3/BaMnO3 superlattices, using VASP. The ground state structure, magnetic ordering, polarization and dielectric response will be presented. The role of epitaxial strain in the individual layers and the role of layer sequence will be explored. Connections to experimental studies and prospects for future work will be discussed.

Strong interplay between structure and electronic properties in CuIn(S,Se){2}: a first-principles study.

PubMed

Vidal, Julien; Botti, Silvana; Olsson, Pär; Guillemoles, Jean-François; Reining, Lucia

2010-02-05

We present a first-principles study of the electronic properties of CuIn(S,Se){2} (CIS) using state-of-the-art self-consistent GW and hybrid functionals. The calculated band gap depends strongly on the anion displacement u, an internal structural parameter that measures lattice distortion. This contrasts with the observed stability of the band gap of CIS solar panels under operating conditions, where a relatively large dispersion of values for u occurs. We solve this apparent paradox considering the coupled effect on the band gap of copper vacancies and lattice distortions. The correct treatment of d electrons in these materials requires going beyond density functional theory, and GW self-consistency is critical to evaluate the quasiparticle gap and the valence band maximum.

Thermoelectric properties of nanocrystalline Sb2Te3 thin films: experimental evaluation and first-principles calculation, addressing effect of crystal grain size.

PubMed

Morikawa, Satoshi; Inamoto, Takuya; Takashiri, Masayuki

2018-02-16

The effect of crystal grain size on the thermoelectric properties of nanocrystalline antimony telluride (Sb 2 Te 3 ) thin films was investigated by experiments and first-principles studies using a developed relaxation time approximation. The Sb 2 Te 3 thin films were deposited on glass substrates using radio-frequency magnetron sputtering. To change the crystal grain size of the Sb 2 Te 3 thin films, thermal annealing was performed at different temperatures. The crystal grain size, lattice parameter, and crystal orientation of the thin films were estimated using XRD patterns. The carrier concentration and in-plane thermoelectric properties of the thin films were measured at room temperature. A theoretical analysis was performed using a first-principles study based on density functional theory. The electronic band structures of Sb 2 Te 3 were calculated using different lattice parameters, and the thermoelectric properties were predicted based on the semi-classical Boltzmann transport equation in the relaxation time approximation. In particular, we introduced the effect of carrier scattering at the grain boundaries into the relaxation time approximation by estimating the group velocities from the electronic band structures. Finally, the experimentally measured thermoelectric properties were compared with those obtained by calculation. As a result, the calculated thermoelectric properties were found to be in good agreement with the experimental results. Therefore, we can conclude that introducing the effect of carrier scattering at the grain boundaries into the relaxation time approximation contributes to enhance the accuracy of a first-principles calculation relating to nanocrystalline materials.

Thermoelectric properties of nanocrystalline Sb2Te3 thin films: experimental evaluation and first-principles calculation, addressing effect of crystal grain size

NASA Astrophysics Data System (ADS)

Morikawa, Satoshi; Inamoto, Takuya; Takashiri, Masayuki

2018-02-01

The effect of crystal grain size on the thermoelectric properties of nanocrystalline antimony telluride (Sb2Te3) thin films was investigated by experiments and first-principles studies using a developed relaxation time approximation. The Sb2Te3 thin films were deposited on glass substrates using radio-frequency magnetron sputtering. To change the crystal grain size of the Sb2Te3 thin films, thermal annealing was performed at different temperatures. The crystal grain size, lattice parameter, and crystal orientation of the thin films were estimated using XRD patterns. The carrier concentration and in-plane thermoelectric properties of the thin films were measured at room temperature. A theoretical analysis was performed using a first-principles study based on density functional theory. The electronic band structures of Sb2Te3 were calculated using different lattice parameters, and the thermoelectric properties were predicted based on the semi-classical Boltzmann transport equation in the relaxation time approximation. In particular, we introduced the effect of carrier scattering at the grain boundaries into the relaxation time approximation by estimating the group velocities from the electronic band structures. Finally, the experimentally measured thermoelectric properties were compared with those obtained by calculation. As a result, the calculated thermoelectric properties were found to be in good agreement with the experimental results. Therefore, we can conclude that introducing the effect of carrier scattering at the grain boundaries into the relaxation time approximation contributes to enhance the accuracy of a first-principles calculation relating to nanocrystalline materials.

Anharmonicity and atomic distribution of SnTe and PbTe thermoelectrics

DOE PAGES

Li, C. W.; Ma, J.; Cao, H. B.; ...

2014-12-29

The structure and lattice dynamics of rock-salt thermoelectric materials SnTe and PbTe are investigated with single crystal and powder neutron diffraction, inelastic neutron scattering (INS), and first-principles simulations. Our first-principles calculations of the radial distribution function (RDF) in both SnTe and PbTe show a clear asymmetry in the first nearest-neighbor (1NN) peak, which increases with temperature, in agreement with experimental reports (Ref. 1,2). We show that this peak asymmetry for the 1NN Sn–Te or Pb–Te bond results from large-amplitude anharmonic vibrations (phonons). No atomic off-centering is found in our simulations. In addition, the atomic mean square displacements derived from ourmore » diffraction data reveal stiffer bonding at the anion site, in good agreement with the partial phonon densities of states from INS, and first-principles calculations. In conclusion, these results provide clear evidence for large-amplitude anharmonic phonons associated with the resonant bonding leading to the ferroelectric instability.« less

Thermoelectric properties of bismuth telluride nanoplate thin films determined using combined infrared spectroscopy and first-principles calculation

NASA Astrophysics Data System (ADS)

Wada, Kodai; Tomita, Koji; Takashiri, Masayuki

2018-06-01

The thermoelectric properties of bismuth telluride (Bi2Te3) nanoplate thin films were estimated using combined infrared spectroscopy and first-principles calculation, followed by comparing the estimated properties with those obtained using the standard electrical probing method. Hexagonal single-crystalline Bi2Te3 nanoplates were first prepared using solvothermal synthesis, followed by preparing Bi2Te3 nanoplate thin films using the drop-casting technique. The nanoplates were joined by thermally annealing them at 250 °C in Ar (95%)–H2 (5%) gas (atmospheric pressure). The electronic transport properties were estimated by infrared spectroscopy using the Drude model, with the effective mass being determined from the band structure using first-principles calculations based on the density functional theory. The electrical conductivity and Seebeck coefficient obtained using the combined analysis were higher than those obtained using the standard electrical probing method, probably because the contact resistance between the nanoplates was excluded from the estimation procedure of the combined analysis method.

Towards Rational Design of Functional Fluoride and Oxyfluoride Materials from First Principles

NASA Astrophysics Data System (ADS)

Charles, Nenian

Complex transition metal compounds (TMCs) research has produced functional materials with a range of properties, including ferroelectricity, colossal magnetoresistance, nonlinear optical activity and high-temperature superconductivity. Conventional routes to tune properties in transition metal oxides, for example, have relied primarily on cation chemical substitution and interfacial effects in thin film heterostructures. In heteroanionic TMCs, exhibiting two chemically distinct anions coordinating the same or different cations, engineering of the anion sub-lattice for property control is a promising alternative approach. The presence of multiple anions provides additional design variables, such as anion order, that are absent in homoanionic counterparts. The more complex structural and chemical phase space of heteroanionic materials provides a unique opportunity to realize enhanced or unanticipated electronic, optical, and magnetic responses. Although there is growing interest in heteroanionic materials, and synthetic and characterization advances are occurring for these materials, the crystal-chemistry principles for realizing structural and property control are only slowing emerging. This dissertation employs anion engineering to investigate phenomena in transition metal fluorides and oxyfluorides compounds using first principles density functional theory calculations. Oxyfluorides are particularly intriguing owing their tendency to stabilize highly ordered anion sublattices as well as the potential to combine the advantageous properties of transition metal oxides and fluorides. This work 1) addresses the challenges of studying fluorides and oxyfluorides using first principles calculations; 2) evaluates the feasibility of using external stimuli, such as epitaxial strain and hydrostatic pressure, to control properties of fluorides and oxyfluorides; and 3) formulates a computational workflow based on multiple levels of theory and computation to elucidate structure-property relationships and anion-order descriptors. The insights gained in this work advance the understanding of oxide-fluoride anion engineered materials and we anticipate that it will motivate novel experimental efforts and materials by design in the future.

First-principles calculations of structural, elastic, electronic, and optical properties of perovskite-type KMgH3 crystals: novel hydrogen storage material.

PubMed

Reshak, Ali H; Shalaginov, Mikhail Y; Saeed, Yasir; Kityk, I V; Auluck, S

2011-03-31

We report a first-principles study of structural and phase stability in three different structures of perovskite-types KMgH(3) according to H position. While electronic and optical properties were measured only for stable perovskite-type KMgH(3), our calculated structural parameters are found in good agreement with experiment and other theoretical results. We also study the electronic charge density space distribution contours in the (200), (101), and (100) crystallographic planes, which gives better insight picture of chemical bonding between K-H, K-Mg-H, and Mg-H. Moreover, we have calculated the electronic band structure dispersion, total, and partial density of electron states to study the band gap origin and the contribution of s-band of H, s and p-band of Mg in the valence band, and d-band of K in the conduction band. Furthermore, optical features such as dielectric functions, refractive indices, extinction coefficient, optical reflectivity, absorption coefficients, optical conductivities, and loss functions of stable KMgH(3) were calculated for photon energies up to 40 eV.

First-principle calculation of the electronic structure, DOS and effective mass TlInSe2

NASA Astrophysics Data System (ADS)

Ismayilova, N. A.; Orudzhev, G. S.; Jabarov, S. H.

2017-05-01

The electronic structure, density of states (DOS), effective mass are calculated for tetragonal TlInSe2 from first principle in the framework of density functional theory (DFT). The electronic structure of TlInSe2 has been investigated by Quantum Wise within GGA. The calculated band structure by Hartwigsen-Goedecker-Hutter (HGH) pseudopotentials (psp) shows both the valence band maximum and conduction band minimum located at the T point of the Brillouin zone. Valence band maximum at the T point and the surrounding parts originate mainly from 6s states of univalent Tl ions. Bottom of the conduction band is due to the contribution of 6p-states of Tl and 5s-states of In atoms. Calculated DOS effective mass for holes and electrons are mDOS h∗ = 0.830m e, mDOS h∗ = 0.492m e, respectively. Electron effective masses are fairly isotropic, while the hole effective masses show strong anisotropy. The calculated electronic structure, density of states and DOS effective masses of TlInSe2 are in good agreement with existing theoretical and experimental results.

First principles examination of electronic structure and optical features of 4H-GaN1-xPx polytype alloys

NASA Astrophysics Data System (ADS)

Laref, A.; Hussain, Z.; Laref, S.; Yang, J. T.; Xiong, Y. C.; Luo, S. J.

2018-04-01

By using first-principles calculations, we compute the electronic band structures and typical aspects of the optical spectra of hexagonally structured GaN1-xPx alloys. Although a type III-V semiconductor, GaP commonly possesses a zinc-blende structure with an indirect band gap; as such, it may additionally form hexagonal polytypes under specific growth conditions. The electronic structures and optical properties are calculated by combining a non-nitride III-V semiconductor and a nitride III-V semiconductor, as GaP and GaN crystallizing in a 4H polytype, with the N composition ranging between x = 0-1. For all studied materials, the energy gap is found to be direct. The optical properties of the hexagonal materials may illustrate the strong polarization dependence owing to the crystalline anisotropy. This investigation for GaN1-xPx alloys is anticipated to supply paramount information for applications in the visible/ultraviolet spectral regions. At a specific concentration, x, these alloys would be exclusively appealing candidates for solar-cell applications.

On the structure of the disordered Bi 2Te 4O 11 phase

NASA Astrophysics Data System (ADS)

Masson, O.; Thomas, P.; Durand, O.; Hansen, T.; Champarnaud, J. C.; Mercurio, D.

2004-06-01

The structure of the disordered metastable Bi 2Te 4O 11 phase has been investigated using both neutron powder diffraction and reverse Monte Carlo (RMC) modelling. The average structure, of fluorite-type (space group Fm 3¯m ), is characterized by very high Debye-Waller parameters, especially for oxygen. Whereas the cations form a fairly well-defined FCC lattice, the oxygen sublattice is very disordered. It is shown that the local order is similar to that present in the stable monoclinic Bi 2Te 4O 11 phase. Clear differences are observed for the intermediate range order. The present phase is analogous to the "anti-glass" phases reported by Trömel in other tellurium-based mixed oxides. However, whereas Trömel defines anti-glass as having long range order but no short range order, it is shown here that this phase is best described as an intermediate state between the amorphous and crystalline states, i.e. having short and medium range order similar to that of tellurite glasses and a premise of long range order with the cations only.

First-principle calculation of core level binding energies of Li{sub x}PO{sub y}N{sub z} solid electrolyte

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

Guille, Émilie; Vallverdu, Germain, E-mail: germain.vallverdu@univ-pau.fr; Baraille, Isabelle

2014-12-28

We present first-principle calculations of core-level binding energies for the study of insulating, bulk phase, compounds, based on the Slater-Janak transition state model. Those calculations were performed in order to find a reliable model of the amorphous Li{sub x}PO{sub y}N{sub z} solid electrolyte which is able to reproduce its electronic properties gathered from X-ray photoemission spectroscopy (XPS) experiments. As a starting point, Li{sub 2}PO{sub 2}N models were investigated. These models, proposed by Du et al. on the basis of thermodynamics and vibrational properties, were the first structural models of Li{sub x}PO{sub y}N{sub z}. Thanks to chemical and structural modifications appliedmore » to Li{sub 2}PO{sub 2}N structures, which allow to demonstrate the relevance of our computational approach, we raise an issue concerning the possibility of encountering a non-bridging kind of nitrogen atoms (=N{sup −}) in Li{sub x}PO{sub y}N{sub z} compounds.« less

First-principles calculation of the structural and elastic properties of ternary metal nitrides TaxMo1-xN and TaxW1-xN

NASA Astrophysics Data System (ADS)

Bouamama, Kh.; Djemia, P.; Benhamida, M.

2015-09-01

First-principles pseudo-potentials calculations of the mixing enthalpy, of the lattice constants a0 and of the single-crystal elastic constants cij for ternary metal nitrides TaxMe1-xN (Me=Mo or W) alloys considering the cubic B1-rocksalt structure is carried out. For disordered ternary alloys, we employ the virtual crystal approximation VCA in which the alloy pseudopotentials are constructed within a first-principles VCA scheme. The supercell method SC is also used for ordered structures in order to evaluate clustering effects. We find that the mixing enthalpy still remains negative for TaxMe1-xN alloys in the whole composition range which implies these cubic TaxMo1-xN and TaxW1-xN ordered solid solutions are stable. We investigate the effect of Mo and W alloying on the trend of the mechanical properties of TaN. The effective shear elastic constant c44, the Cauchy pressure (c12-c44), and the shear to bulk modulus G/B ratio are used to discuss, respectively, the mechanical stability of the ternary structure and the brittle/ductile behavior in reference to TaN, MeN alloys. We determine the onset transition from the unstable structure to the stable one B1-rocksalt from the elastic stability criteria when alloying MeN with Ta. In a second stage, in the frame of anisotropic elasticity, we estimate by one homogenization method the averaged constants of the polycrystalline TaxMe1-xN alloys considering the special case of an isotropic medium with no crystallographic texture.

Confirmation of a de novo structure prediction for an atomically precise monolayer-coated silver nanoparticle

PubMed Central

Conn, Brian E.; Atnagulov, Aydar; Yoon, Bokwon; Barnett, Robert N.; Landman, Uzi; Bigioni, Terry P.

2016-01-01

Fathoming the principles underpinning the structures of monolayer-coated molecular metal nanoparticles remains an enduring challenge. Notwithstanding recent x-ray determinations, coveted veritable de novo structural predictions are scarce. Building on recent syntheses and de novo structure predictions of M3AuxAg17−x(TBBT)12, where M is a countercation, x = 0 or 1, and TBBT is 4-tert-butylbenzenethiol, we report an x-ray–determined structure that authenticates an a priori prediction and, in conjunction with first-principles theoretical analysis, lends force to the underlying forecasting methodology. The predicted and verified Ag(SR)3 monomer, together with the recently discovered Ag2(SR)5 dimer and Ag3(SR)6 trimer, establishes a family of unique mount motifs for silver thiolate nanoparticles, expanding knowledge beyond the earlier-known Au-S staples in thiol-capped gold nanoclusters. These findings demonstrate key principles underlying ligand-shell anchoring to the metal core, as well as unique T-like benzene dimer and cyclic benzene trimer ligand bundling configurations, opening vistas for rational design of metal and alloy nanoparticles. PMID:28138537

Coulomb spin liquid in anion-disordered pyrochlore Tb 2Hf 2O 7

DOE PAGES

Sibille, Romain; Lhotel, Elsa; Hatnean, Monica Ciomaga; ...

2017-10-12

Here, the charge ordered structure of ions and vacancies characterizing rare-earth pyrochlore oxides serves as a model for the study of geometrically frustrated magnetism. The organization of magnetic ions into networks of corner-sharing tetrahedra gives rise to highly correlated magnetic phases with strong fluctuations, including spin liquids and spin ices. It is an open question how these ground states governed by local rules are affected by disorder. Here we demonstrate in the pyrochlore Tb 2Hf 2O 7, that the vicinity of the disordering transition towards a defective fluorite structure translates into a tunable density of anion Frenkel disorder while cationsmore » remain ordered. Quenched random crystal fields and disordered exchange interactions can therefore be introduced into otherwise perfect pyrochlore lattices of magnetic ions. We show that disorder can play a crucial role in preventing long-range magnetic order at low temperatures, and instead induces a strongly fluctuating Coulomb spin liquid with defect-induced frozen magnetic degrees of freedom.« less

Structure and bulk modulus of Ln-doped UO2 (Ln = La, Nd) at high pressure

NASA Astrophysics Data System (ADS)

Rittman, Dylan R.; Park, Sulgiye; Tracy, Cameron L.; Zhang, Lei; Palomares, Raul I.; Lang, Maik; Navrotsky, Alexandra; Mao, Wendy L.; Ewing, Rodney C.

2017-07-01

The structure of lanthanide-doped uranium dioxide, LnxU1-xO2-0.5x+y (Ln = La, Nd), was investigated at pressures up to ∼50-55 GPa. Samples were synthesized with different lanthanides at different concentrations (x ∼ 0.2 and 0.5), and all were slightly hyperstoichiometric (y ∼ 0.25-0.4). In situ high-pressure synchrotron X-ray diffraction was used to investigate their high-pressure phase behavior and determine their bulk moduli. All samples underwent a fluorite-to-cotunnite phase transformation with increasing pressure. The pressure of the phase transformation increased with increasing hyperstoichiometry, which is consistent with results from previous computational simulations. Bulk moduli are inversely proportional to both the ionic radius of the lanthanide and its concentration, as quantified using a weighted cationic radius ratio. This trend was found to be consistent with the behavior of other elastic properties measured for Ln-doped UO2, such as Young's modulus.

Structural defects caused by swift ions in fluorite single crystals

NASA Astrophysics Data System (ADS)

Assylbayev, Ruslan; Lushchik, Aleksandr; Lushchik, Cheslav; Kudryavtseva, Irina; Shablonin, Evgeni; Vasil'chenko, Evgeni; Akilbekov, Abdirash; Zdorovets, Maxim

2018-01-01

A comparative study of radiation damage caused by the irradiation of oxygen-free calcium fluoride single crystals with ∼GeV 132Xe or 209Bi heavy ions, 100-keV light hydrogen ions (protons) or X-rays at room temperature has been performed. Optical absorption in a wide spectral region from NIR to VUV (1.5-10.5 eV), its dependence on stepwise preheating of the irradiated CaF2 crystals to a certain temperature as well as thermally stimulated luminescence accompanying the main annealing stages have been analyzed. It is shown that in addition to different F-type aggregates, Ca colloids and trifluorine quasi-molecules, complex and temperature stable structural defects responsible for VUV absorption (in particular, the 9.8 eV band) are induced in CaF2 only after irradiation with swift heavy ions. The origin and tentative creation mechanisms of such defects as well as the features of the used irradiation types are considered.

Application of SR Methods for the Study of Nanocomposite Materials for Hydrogen Energy

NASA Astrophysics Data System (ADS)

Sadykov, V. A.; Pavlova, S. N.; Vinokurov, Z. S.; Shmakov, A. N.; Eremeev, N. F.; Fedorova, Yu. E.; Yakimchuk, E. P.; Kriventsov, V. V.; Bolotov, V. A.; Tanashev, Yu. Yu.; Sadovskaya, E. M.; Cherepanova, S. V.; Zolotarev, K. V.

This work summarizes results of synchrotron radiation (SR) studies of the real/defect structure of nanocrystalline/nanocomposite oxide materials, which determines their functional properties in hydrogen energy field as catalysts and mixed ionic electronic conductors (cathodes and anodes of solid oxide fuel cells, oxygen separation membranes). For nanocrystalline ceria-zirconia mixed oxide prepared via modified Pechini route using ethanol solution of reagents, a high spatial uniformity of cations distribution between domains along with the oxygen sublattice deficiency revealed by full-profile Rietveld refinement of SR diffraction data provide structure disordering enhancing oxygen mobility. For PrNi0.5Co0.5O3-δ - Ce0.9Y0.1O2-δ nanocomposite extensive transfer of Pr cations into fluorite domains generates a new path of fast oxygen diffusion along chains of Pr3+ - Pr4+ cations as directly proved by analysis of the unit cell relaxation after changing pO2 in perfect agreement with data obtained by oxygen isotope heteroexchange.

Polyacrylamide-hydroxyapatite composite: Preparation, characterization and adsorptive features for uranium and thorium

NASA Astrophysics Data System (ADS)

Baybaş, Demet; Ulusoy, Ulvi

2012-10-01

The composite of synthetically produced hydroxyapatite (HAP) and polyacrylamide was prepared (PAAm-HAP) and characterized by BET, FT-IR, TGA, XRD, SEM and PZC analysis. The adsorptive features of HAP and PAAm-HAP were compared for UO22+ and Th4+. The entrapment of HAP into PAAm-HAP did not change the structure of HAP. Both structures had high affinity to the studied ions. The adsorption capacity of PAAm-HAP was than that of HAP. The adsorption dependence on pH and ionic intensity provided supportive evidences for the effect of complex formation on adsorption process. The adsorption kinetics was well compatible to pseudo second order model. The values of enthalpy and entropy changes were positive. Th4+ adsorption from the leachate obtained from a regional fluorite rock confirmed the selectivity of PAAm-HAP for this ion. In consequence, PAAm-HAP should be considered amongst favorite adsorbents for especially deposition of nuclear waste containing U and Th, and radionuclide at secular equilibrium with these elements.

Study on superstructure in ion co-doped BiFeO3 by using transmission electron microscopy

NASA Astrophysics Data System (ADS)

Pu, Shi-Zhou; Guo, Chao; Li, Mei-Ya; Chen, Zhen-Lian; Zou, Hua-Min

2015-04-01

La3+ and V5+ co-doped BiFeO3 ceramics are synthesized by rapid liquid sintering technique. The modulated structure in Bi0.85La0.15Fe0.97V0.03O3 is investigated by using transmission electron microscopy (TEM). Two kinds of superstructures are observed in the samples. One is the component modulated superstructure and twin-domain, which is generated by La3+ ordered substitution for Bi3+ and frequently appears. The chemical composition of the superstructure is explored by x-ray energy dispersive spectroscopy (EDS). The model of the ordered structure is proposed. Simulation based on the model is conducted. The second is the fluorite-type δ-Bi2O3 related superstructure. The relation between the ferroelectric property and the microstructure of the sample is also discussed. Project supported by the National Natural Science Foundation of China (Grant Nos. 51372174, 11074193, and 51132001) and the Fundamental Research Funds for the Central Universities.

Fermi surfaces properties of AuAl2, AuGa2, and AuIn2 with the CaF2-type cubic structure

NASA Astrophysics Data System (ADS)

Nishimura, K.; Kakihana, M.; Suzuki, F.; Yara, T.; Hedo, M.; Nakama, T.; Ōnuki, Y.; Harima, H.

2018-05-01

We grew high-quality single crystals of AuAl2, AuGa2, and AuIn2 with the fluorite (CaF2)-type cubic structure and determined the Fermi surface properties by the de Haas-van Alphen (dHvA) experiments using full-potential LAPW bad calculations. The Fermi surface and optical properties for three compounds were once studied from an interest of colors because AuAl2 has a striking bright reddish-purple color, whereas AuGa2 and AuIn2 are, respectively, neutral and bluish. The detected dHvA frequencies in the present study are found to be in a wide range of (0.1-13)×107 Oe. The main dHvA branches for three compounds are in excellent agreement with the theoretical ones, but some dHvA branches with small dHvA frequencies are slightly deviated from the theoretical ones, especially in AuGa2 and AuIn2.

Structure and bulk modulus of Ln-doped UO 2 (Ln = La, Nd) at high pressure

DOE PAGES

Rittman, Dylan R.; Park, Sulgiye; Tracy, Cameron L.; ...

2017-04-10

The structure of lanthanide-doped uranium dioxide, Ln xU 1-xO 2-0.5x+y (Ln = La, Nd), was investigated at pressures up to ~50–55 GPa. Samples were synthesized with different lanthanides at different concentrations (x ~ 0.2 and 0.5), and all were slightly hyperstoichiometric (y ~ 0.25–0.4). In situ high-pressure synchrotron X-ray diffraction was used to investigate their high-pressure phase behavior and determine their bulk moduli. All samples underwent a fluorite-to-cotunnite phase transformation with increasing pressure. The pressure of the phase transformation increased with increasing hyperstoichiometry, which is consistent with results from previous computational simulations. Bulk moduli are inversely proportional to both themore » ionic radius of the lanthanide and its concentration, as quantified using a weighted cationic radius ratio. As a result, this trend was found to be consistent with the behavior of other elastic properties measured for Ln-doped UO 2, such as Young's modulus.« less

Phosphate modified ceria as a Brønsted acidic/redox multifunctional catalyst

DOE PAGES

Nelson, Nicholas C.; Wang, Zhuoran; Naik, Pranjali; ...

2017-01-06

Deposition of trimethylphosphate onto ceria followed by thermal treatment resulted in the formation of surface phosphates with retention of the ceria fluorite structure. The structural and chemical properties of the phosphate-functionalized ceria were studied using 31P solid-state NMR, XPS, zeta titration, ammonia thermal desorption, pyridine adsorption, and model reactions. The introduction of phosphates generated Brønsted acid sites and decreased the number of Lewis acid sites on the surface. The relative amount of Lewis and Brønsted acids can be controlled by the amount of trimethylphosphate used in the synthesis. Upon deposition of Pd, the multifunctional material showed enhanced activity for themore » hydrogenolysis of eugenol and guaiacol compared to Pd on the unmodified ceria support. As a result, this was attributed to the cooperativity between the Lewis acid sites, which activate the substrate for dearomatization, and the redox/Brønsted acid properties, which catalyze hydrogenolysis.« less

A Proposed Process for Managing the First Amendment Aspects of Campus Hate Speech.

ERIC Educational Resources Information Center

Kaplan, William A.

1992-01-01

A carefully structured process for campus administrative decision making concerning hate speech is proposed and suggestions for implementation are offered. In addition, criteria for evaluating hate speech processes are outlined, and First Amendment principles circumscribing the institution's discretion to regulate hate speech are discussed.…

First-principles study of complex material systems

NASA Astrophysics Data System (ADS)

He, Lixin

This thesis covers several topics concerning the study of complex materials systems by first-principles methods. It contains four chapters. A brief, introductory motivation of this work will be given in Chapter 1. In Chapter 2, I will give a short overview of the first-principles methods, including density-functional theory (DFT), planewave pseudopotential methods, and the Berry-phase theory of polarization in crystallines insulators. I then discuss in detail the locality and exponential decay properties of Wannier functions and of related quantities such as the density matrix, and their application in linear-scaling algorithms. In Chapter 3, I investigate the interaction of oxygen vacancies and 180° domain walls in tetragonal PbTiO3 using first-principles methods. Our calculations indicate that the oxygen vacancies have a lower formation energy in the domain wall than in the bulk, thereby confirming the tendency of these defects to migrate to, and pin, the domain walls. The pinning energies are reported for each of the three possible orientations of the original Ti--O--Ti bonds, and attempts to model the results with simple continuum models are discussed. CaCu3Ti4O12 (CCTO) has attracted a lot of attention recently because it was found to have an enormous dielectric response over a very wide temperature range. In Chapter 4, I study the electronic and lattice structure, and the lattice dynamical properties, of this system. Our first-principles calculations together with experimental results point towards an extrinsic mechanism as the origin of the unusual dielectric response.

Principles of assembly reveal a periodic table of protein complexes.

PubMed

Ahnert, Sebastian E; Marsh, Joseph A; Hernández, Helena; Robinson, Carol V; Teichmann, Sarah A

2015-12-11

Structural insights into protein complexes have had a broad impact on our understanding of biological function and evolution. In this work, we sought a comprehensive understanding of the general principles underlying quaternary structure organization in protein complexes. We first examined the fundamental steps by which protein complexes can assemble, using experimental and structure-based characterization of assembly pathways. Most assembly transitions can be classified into three basic types, which can then be used to exhaustively enumerate a large set of possible quaternary structure topologies. These topologies, which include the vast majority of observed protein complex structures, enable a natural organization of protein complexes into a periodic table. On the basis of this table, we can accurately predict the expected frequencies of quaternary structure topologies, including those not yet observed. These results have important implications for quaternary structure prediction, modeling, and engineering. Copyright © 2015, American Association for the Advancement of Science.

Achieving accuracy in first-principles calculations at extreme temperature and pressure

NASA Astrophysics Data System (ADS)

Mattsson, Ann; Wills, John

2013-06-01

First-principles calculations are increasingly used to provide EOS data at pressures and temperatures where experimental data is difficult or impossible to obtain. The lack of experimental data, however, also precludes validation of the calculations in those regimes. Factors influencing the accuracy of first-principles data include theoretical approximations, and computational approximations used in implementing and solving the underlying equations. The first category includes approximate exchange-correlation functionals and wave equations simplifying the Dirac equation. In the second category are, e.g., basis completeness and pseudo-potentials. While the first category is extremely hard to assess without experimental data, inaccuracies of the second type should be well controlled. We are using two rather different electronic structure methods (VASP and RSPt) to make explicit the requirements for accuracy of the second type. We will discuss the VASP Projector Augmented Wave potentials, with examples for Li and Mo. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

First principles calculations for interaction of tyrosine with (ZnO)3 cluster

NASA Astrophysics Data System (ADS)

Singh, Satvinder; Singh, Gurinder; Kaura, Aman; Tripathi, S. K.

2018-04-01

First Principles Calculations have been performed to study interactions of Phenol ring of Tyrosine (C6H5OH) with (ZnO)3 atomic cluster. All the calculations have been performed under the Density Functional Theory (DFT) framework. Structural and electronic properties of (ZnO)3/C6H5OH have been studied. Gaussian basis set approach has been adopted for the calculations. A ring type most stable (ZnO)3 atomic cluster has been modeled, analyzed and used for the calculations. The compatibility of the results with previous studies has been presented here.

Connecting thermoelectric performance and topological-insulator behavior: Bi 2Te 3 and Bi 2Te 2Se from first principles

DOE PAGES

Shi, Hongliang; Parker, David S.; Du, Mao-Hua; ...

2015-01-20

Thermoelectric performance is of interest for numerous applications such as waste-heat recovery and solid-state energy conversion and will be seen to be closely connected to topological-insulator behavior. In this paper, we here report first-principles transport and defect calculations for Bi 2Te 2Se in relation to Bi 2Te 3. The two compounds are found to contain remarkably different electronic structures in spite of being isostructural and isoelectronic. We also discuss these results in terms of the topological-insulator characteristics of these compounds.

Introduction to Command, Control and Communications (C3) Through Comparative Case Analysis

DTIC Science & Technology

1990-03-01

enhancing the process of learning from experience. Case study allows the student to apply concepts , theories, and techniques to an actual incident within...part of the thesis describes selected principles and concepts of 33 related to cormruication management, interoperability, command structure and...The solutions to the cases require applying the principles and concepts presented in the first rart. The four cases are: (1) the Iran hostage rescue

First-Principles Prediction of Thermodynamically Stable Two-Dimensional Electrides

DOE PAGES

Ming, Wenmei; Yoon, Mina; Univ. of Tennessee, Knoxville, TN; ...

2016-10-21

Two-dimensional (2D) electrides, emerging as a new type of layered material whose electrons are confined in interlayer spaces instead of at atomic proximities, are receiving interest for their high performance in various (opto)electronics and catalytic applications. Experimentally, however, 2D electrides have been only found in a couple of layered nitrides and carbides. We report new thermodynamically stable alkaline-earth based 2D electrides by using a first-principles global structure optimization method, phonon spectrum analysis, and molecular dynamics simulation. The method was applied to binary compounds consisting of alkaline-earth elements as cations and group VA, VIA, or VIIA nonmetal elements as anions. Wemore » also revealed that the stability of a layered 2D electride structure is closely related to the cation/anion size ratio; stable 2D electrides possess a sufficiently large cation/anion size ratio to minimize electrostatic energy among cations, anions, and anionic electrons. This work demonstrates a new avenue to the discovery of thermodynamically stable 2D electrides beyond experimental material databases and provides new insight into the principles of electride design.« less

Questa baseline and pre-mining ground-water quality investigation. 3. Historical ground-water quality for the Red River Valley, New Mexico

USGS Publications Warehouse

LoVetere, Sara H.; Nordstrom, D. Kirk; Maest, Ann S.; Naus, Cheryl A.

2003-01-01

Historical ground-water quality data for 100 wells in the Red River Valley between the U.S. Geological Survey streamflow-gaging station (08265000), near Questa, and Placer Creek east of the town of Red River, New Mexico, were compiled and reviewed. The tabulation included 608 water-quality records from 23 sources entered into an electronic database. Groundwater quality data were first collected at the Red River wastewater-treatment facility in 1982. Most analyses, however, were obtained between 1994 and 2002, even though the first wells were developed in 1962. The data were evaluated by considering (a) temporal consistency, (b) quality of sampling methods, (c) charge imbalance, and (d) replicate analyses. Analyses that qualified on the basis of these criteria were modeled to obtain saturation indices for gypsum, calcite, fluorite, gibbsite, manganite, and rhodocrosite. Plots created from the data illustrate that water chemistry in the Red River Valley is predominantly controlled by calcite dissolution, congruent gypsum dissolution, and pyrite oxidation.

Effect of Zn doping on structural, optical and thermal properties of CeO2 nanoparticles

NASA Astrophysics Data System (ADS)

Ramasamy, V.; Vijayalakshmi, G.

2015-09-01

The undoped and Zn doped CeO2 nanoparticles were synthesized by chemical precipitation method at room temperature. The undoped and Zn doped CeO2 nanoparticles have been characterized by X-ray powder diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), ultraviolet visible and photoluminescence (PL) spectroscopy, Fourier transform infrared spectroscopy (FTIR) and thermogravimetry and differential thermal analysis (TG-DTA). The cubic fluorite structures of the CeO2 nanoparticles were determined by XRD. The influence of particle size on structural parameters such as lattice parameter (a), inter planar distance (d), dislocation density (δ), microstrain (ε), lattice strain (η) and texture co-efficient (TC) were also determined. The lattice strains were determined by Williamson-Hall plot method. The effect of Zn doping with shifting of the bands were observed by UV-Vis spectroscopy and also their optical band gap were determined. The emission spectra and energy band diagram of the undoped and Zn doped samples were derived from PL spectroscopy. The structural bond vibrations of undoped and Zn doped CeO2 nanoparticles were analyzed by FTIR spectroscopy. The thermal property (weight loss and decomposition) of the sample is observed by TG-DTA curve.

First-principles study of structural, electronic, and optical properties of surface defects in GaAs(001) - β2(2x4)

NASA Astrophysics Data System (ADS)

Bacuyag, Dhonny; Escaño, Mary Clare Sison; David, Melanie; Tani, Masahiko

2018-06-01

We performed first-principles calculations based on density functional theory (DFT) to investigate the role of point defects in the structural, electronic, and optical properties of the GaAs(001)- β2(2x4). In terms of structural properties, AsGa is the most stable defect structure, consistent with experiments. With respect to the electronic structure, band structures revealed the existence of sub-band and midgap states for all defects. The induced sub-bands and midgap states originated from the redistributions of charges towards these defects and neighboring atoms. The presence of these point defects introduced deep energy levels characteristic of EB3 (0.97 eV), EL4 (0.52 eV), and EL2 (0.82 eV) for AsGa, GaAs, GaV, respectively. The optical properties are found to be strongly related to these induced gap states. The calculated onset values in the absorption spectra, corresponding to the energy gaps, confirmed the absorption below the known bulk band gap of 1.43 eV. These support the possible two-step photoabsorption mediated by midgap states as observed in experiments.

Fully integrated graphene electronic biosensor for label-free detection of lead (II) ion based on G-quadruplex structure-switching.

PubMed

Li, Yijun; Wang, Cheng; Zhu, Yibo; Zhou, Xiaohong; Xiang, Yu; He, Miao; Zeng, Siyu

2017-03-15

This work presents a fully integrated graphene field-effect transistor (GFET) biosensor for the label-free detection of lead ions (Pb 2+ ) in aqueous-media, which first implements the G-quadruplex structure-switching biosensing principle in graphene nanoelectronics. We experimentally illustrate the biomolecular interplay that G-rich DNA single-strands with one-end confined on graphene surface can specifically interact with Pb 2+ ions and switch into G-quadruplex structures. Since the structure-switching of electrically charged DNA strands can disrupt the charge distribution in the vicinity of graphene surface, the carrier equilibrium in graphene sheet might be altered, and manifested by the conductivity variation of GFET. The experimental data and theoretical analysis show that our devices are capable of the label-free and specific quantification of Pb 2+ with a detection limit down to 163.7ng/L. These results first verify the signaling principle competency of G-quadruplex structure-switching in graphene electronic biosensors. Combining with the advantages of the compact device structure and convenient electrical signal, a label-free GFET biosensor for Pb 2+ monitoring is enabled with promising application potential. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of synthesis conditions on the crystal structure of the powder formed in the “HfO2 - CeO2/Ce2O3” system

NASA Astrophysics Data System (ADS)

Popov, V. V.; Menushenkov, A. P.; Khubbutdinov, R. M.; Yastrebtsev, A. A.; Svetogorov, R. D.; Zubavichus, Ya V.; Trigub, A. L.; Sharapov, A. S.; Pisarev, A. A.; Kurilkin, V. V.; Tsarenko, N. A.; Arzhatkina, L. A.

2017-12-01

Influence of synthesis conditions (type of atmosphere: reduction or oxidation, annealing temperature) on the chemical composition and structure of the compounds formed in the “HfO2 - CeO2/Ce2O3” system has been investigated by X-ray absorption fine structure spectroscopy combined with Raman spectroscopy, X-ray diffraction and thermogravimetric analysis. It was revealed that isothermal annealing of precursor at temperatures less than 1000°C in air leads to formation of Ce0.5Hf0.5O2 powders with cubic fluorite-type structure (space group Fm-3m). Further increase of annealing temperatures above 1000°C causes decomposition of formed crystal structure into two phases: cubic and monoclinic. Annealing in reduction hydrogen atmosphere causes formation of Ce4+ 2x Ce3+ 2-2x Hf2O7+x compounds with intermediate oxidation state of cerium, where value of x depends on the reducing conditions and treatment parameters. Annealing in vacuum at 1400°C strongly reduces the content of Ce4+ in a powder samples and leads to formation of pyrochlore structure (space group Fd-3m) with predominant +3 oxidation state of cerium.

Structural, electronic, and vibrational properties of high-density amorphous silicon: a first-principles molecular-dynamics study.

PubMed

Morishita, Tetsuya

2009-05-21

We report a first-principles study of the structural, electronic, and dynamical properties of high-density amorphous (HDA) silicon, which was found to be formed by pressurizing low-density amorphous (LDA) silicon (a normal amorphous Si) [T. Morishita, Phys. Rev. Lett. 93, 055503 (2004); P. F. McMillan, M. Wilson, D. Daisenberger, and D. Machon, Nature Mater. 4, 680 (2005)]. Striking structural differences between HDA and LDA are revealed. The LDA structure holds a tetrahedral network, while the HDA structure contains a highly distorted tetrahedral network. The fifth neighboring atom in HDA tends to be located at an interstitial position of a distorted tetrahedron composed of the first four neighboring atoms. Consequently, the coordination number of HDA is calculated to be approximately 5 unlike that of LDA. The electronic density of state (EDOS) shows that HDA is metallic, which is consistent with a recent experimental measurement of the electronic resistance of HDA Si. We find from local EDOS that highly distorted tetrahedral configurations enhance the metallic nature of HDA. The vibrational density of state (VDOS) also reflects the structural differences between HDA and LDA. Some of the characteristic vibrational modes of LDA are dematerialized in HDA, indicating the degradation of covalent bonds. The overall profile of the VDOS for HDA is found to be an intermediate between that for LDA and liquid Si under pressure (high-density liquid Si).

Structures of Aln (n= 27, 28, 29, and 30) clusters with double-tetrahedron structures

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

Zhang, W.; Lu, W. C.; Sun, J.

2008-01-31

Global search for lowest-energy structures of neutral aluminum clusters Al{sub n} (n = 27, 28, 29 and 30) was performed using a genetic algorithm (GA) coupled with a tight-binding (TB) method. Structural candidates obtained from our GA search were further optimized with first-principles calculations. It is found that the medium-sized aluminum clusters Al{sub 27} to Al{sub 30} favor double-tetrahedron structures.

First principle study of structural, elastic and electronic properties of APt3 (A=Mg, Sc, Y and Zr)

NASA Astrophysics Data System (ADS)

Benamer, A.; Roumili, A.; Medkour, Y.; Charifi, Z.

2018-02-01

We report results obtained from first principle calculations on APt3 compounds with A=Mg, Sc, Y and Zr. Our results of the lattice parameter a are in good agreement with experimental data, with deviations less than 0.8%. Single crystal elastic constants are calculated, then polycrystalline elastic moduli (bulk, shear and Young moduli, Poisson ration, anisotropy factor) are presented. Based on Debye model, Debye temperature ϴD is calculated from the sound velocities Vl, Vt and Vm. Band structure results show that the studied compounds are electrical conductors, the conduction mechanism is assured by Pt-d electrons. Different hybridisation states are observed between Pt-d and A-d orbitals. The study of the charge density distribution and the population analysis shows the coexistence of ionic, covalent and metallic bonds.

First-principle study of effect of variation of `x' on the band alignment in CZTS1-xSex

NASA Astrophysics Data System (ADS)

Ghemud, Vipul; Kshirsagar, Anjali

2018-04-01

The present work concentrates on the electronic structure study of CZTS1-xSex alloy with x ranging from 0 to 1. For the alloy study, we have carried out first-principles calculations employing generalized gradient approximation for structural optimization and further hybrid functional approach to compare the optical band gap with that obtained from the experiments. A systematic increase in the lattice parameters with lowering of band gap from 1.52eV to 1.04eV is seen with increasing Se concentration from 0 to 100%, however the lowering of valence band edge and conduction band edge is not linear with the concentration variation. Our results indicate that the lowering of band gap is a result increased Cu:d and Se:p hybridization with increasing `x'.

First-principles study of Ga-vacancy induced magnetism in β-Ga2O3.

PubMed

Yang, Ya; Zhang, Jihua; Hu, Shunbo; Wu, Yabei; Zhang, Jincang; Ren, Wei; Cao, Shixun

2017-11-01

First principles calculations based on density functional theory were performed to study the electronic structure and magnetic properties of β-Ga 2 O 3 in the presence of cation vacancies. We investigated two kinds of Ga vacancies at different symmetry sites and the consequent structural distortion and defect states. We found that both the six-fold coordinated octahedral site and the four-fold coordinated tetrahedral site vacancies can lead to a spin polarized ground state. Furthermore, the calculation identified a relationship between the spin polarization and the charge states of the vacancies, which might be explained by a molecular orbital model consisting of uncompensated O 2- 2p dangling bonds. The calculations for the two vacancy systems also indicated a potential long-range ferromagnetic order which is beneficial for spintronics application.

Stability and charge separation of different CH3NH3SnI3/TiO2 interface: A first-principles study

NASA Astrophysics Data System (ADS)

Yang, Zhenzhen; Wang, Yuanxu; Liu, Yunyan

2018-05-01

Interface has an important effect on charge separation of perovskite solar cells. Using first-principles calculations, we studied several different interfaces between CH3NH3SnI3 and TiO2. The interfacial structure and electronic structure of these interfaces are thoroughly explored. We found that the SnI2/anatase (SnI2/A) system is more stable than the other three systems, because an anatase surface can make Snsbnd I bond faster restore to the pristine value than a rutile surface, and SnI2/A system has a smaller standard deviation. The calculated plane-averaged electrostatic potential and the density of states suggest that SnI2/anatase interface has a better separation of photo-generated electron-hole pairs.

Atomic-scale structural and electronic properties of SrTiO3/GaAs interfaces: A combined STEM-EELS and first-principles study

NASA Astrophysics Data System (ADS)

Hong, Liang; Bhatnagar, Kunal; Droopad, Ravi; Klie, Robert F.; Öǧüt, Serdar

2017-07-01

The electronic properties of epitaxial oxide thin films grown on compound semiconductors are largely determined by the interfacial atomic structure, as well as the thermodynamic conditions during synthesis. Ferroelectric polarization and Fermi-level pinning in SrTiO3 films have been attributed to the presence of oxygen vacancies at the oxide/semiconductor interface. Here, we present scanning transmission electron microscopy (STEM) and electron energy-loss spectroscopy analyses of GaAs films grown on SrTiO3 combined with first-principles calculations to determine the atomic and electronic structures of the SrTiO3/GaAs interfaces. An atomically abrupt SrO/As interface is observed and the interfacial SrO layer is found to be O-deficient. First-principles density functional theory (DFT) calculations show SrO/Ga and Sr/As interfaces are favorable under O-rich and O-poor conditions, respectively. The SrO/Ga interface is reconstructed via the formation of Ga-Ga dimers while the Sr/As interface is abrupt and consistent with the experiment. DFT calculations further reveal that intrinsic two-dimensional electron gas (2DEG) forms in both SrO/Ga and Sr/As interfaces, and the Fermi level is pinned to the localized 2DEG states. Interfacial O vacancies can enhance the 2DEG density while it is possible for Ga/As vacancies to unpin the Fermi level from the 2DEG states.

Hydrostatic pressure effects on the structural, elastic and thermodynamic properties of the complex transition metal hydrides A2OsH6 (A = Mg, Ca, Sr and Ba)

NASA Astrophysics Data System (ADS)

Souadia, Z.; Bouhemadou, A.; Boudrifa, O.; Bin-Omran, S.; Khenata, R.; Al-Douri, Y.

2017-10-01

We report a systematic first-principles density functional theory study on the pressure dependence of the structural parameters, elastic constants and related properties and thermodynamic properties of the complex transition metal hydrides Mg2OsH6, Ca2OsH6, Sr2OsH6 and Ba2OsH6. The calculated structural parameters are in excellent agreement with the existing data in the scientific literature. The single-crystal elastic constants and related properties were predicted using the stress-strain method. The elastic moduli of the polycrystalline aggregates were evaluated via the Voigt-Reuss-Hill approach. The dependences of the lattice parameter, bulk modulus, volume thermal expansion coefficient, isobaric and isochoric heat capacity and Debye temperature on the pressure and temperature, ranging from 0 to 15 GPa and from 0 to 1000 K, respectively, were investigated using the quasi-harmonic Debye model in combination with first-principles calculations.

Alkali-metal induced band structure deformation investigated by angle-resolved photoemission spectroscopy and first-principles calculations

NASA Astrophysics Data System (ADS)

Ito, S.; Feng, B.; Arita, M.; Someya, T.; Chen, W.-C.; Takayama, A.; Iimori, T.; Namatame, H.; Taniguchi, M.; Cheng, C.-M.; Tang, S.-J.; Komori, F.; Matsuda, I.

2018-04-01

Alkali-metal adsorption on the surface of materials is widely used for in situ surface electron doping, particularly for observing unoccupied band structures by angle-resolved photoemission spectroscopy (ARPES). However, the effects of alkali-metal atoms on the resulting band structures have yet to be fully investigated, owing to difficulties in both experiments and calculations. Here, we combine ARPES measurements on cesium-adsorbed ultrathin bismuth films with first-principles calculations of the electronic charge densities and demonstrate a simple method to evaluate alkali-metal induced band deformation. We reveal that deformation of bismuth surface bands is directly correlated with vertical charge-density profiles at each electronic state of bismuth. In contrast, a change in the quantized bulk bands is well described by a conventional rigid-band-shift picture. We discuss these two aspects of the band deformation holistically, considering spatial distributions of the electronic states and cesium-bismuth hybridization, and provide a prescription for applying alkali-metal adsorption to a wide range of materials.

From intermolecular interactions to structures and properties of a novel cocrystal explosive: a first-principles study.

PubMed

Zhang, Lei; Wu, Ji-Zhou; Jiang, Sheng-Li; Yu, Yi; Chen, Jun

2016-09-29

By employing a first-principles method, we conducted a thorough study on a novel cocrystal explosive 1 : 1 NTO : TZTN and gained insight into the interaction-structure-property interrelationship. Mulliken bond orders, Hirshfeld surfaces, intermolecular binding energies, packing coefficients, and oxygen balance were calculated to analyze the intermolecular interactions and structures of the cocrystal explosive. The cocrystallization of NTO and TZTN molecules enhances the intermolecular binding force, which drives the synthesis of the cocrystal. However, the cocrystallization decreases the molecular packing density along the closest packed directions, which reduces the density by 10.5% and deteriorates the oxygen balance. All of these lead to a reduction in the detonation performance compared to NTO explosives. We have also proposed a new method to evaluate the impact sensitivity according to the lattice dynamics calculation. The cocrystal explosive has a lower impact sensitivity than TZTN but higher than NTO, which agrees well with experiments.

Possibility of transforming the electronic structure of one species of graphene adatoms into that of another by application of gate voltage: First-principles calculations

NASA Astrophysics Data System (ADS)

Chan, Kevin T.; Lee, Hoonkyung; Cohen, Marvin L.

2011-10-01

Graphene provides many advantages for controlling the electronic structure of adatoms and other adsorbates via gating. Using the projected density of states and charge density obtained from first-principles density-functional periodic supercell calculations, we investigate the possibility of performing “alchemy” of adatoms on graphene, i.e., transforming the electronic structure of one species of adatom into that of another species by application of a gate voltage. Gating is modeled as a change in the number of electrons in the unit cell, with the inclusion of a compensating uniform background charge. Within this model and the generalized gradient approximation to the exchange-correlation functional, we find that such transformations are possible for K, Ca, and several transition-metal adatoms. Gate control of the occupation of the p states of In on graphene is also investigated. The validity of the supercell approximation with uniform compensating charge and the model for exchange and correlation is also discussed.

First-principles calculations of K-shell X-ray absorption spectra for warm dense nitrogen

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

Li, Zi; Zhang, Shen; Kang, Wei

2016-05-15

X-ray absorption spectrum is a powerful tool for atomic structure detection on warm dense matter. Here, we perform first-principles molecular dynamics and X-ray absorption spectrum calculations on warm dense nitrogen along a Hugoniot curve. From the molecular dynamics trajectory, the detailed atomic structures are examined for each thermodynamical condition. The K-shell X-ray absorption spectrum is calculated, and its changes with temperature and pressure along the Hugoniot curve are discussed. The warm dense nitrogen systems may contain isolated nitrogen atoms, N{sub 2} molecules, and nitrogen clusters, which show quite different contributions to the total X-ray spectrum due to their different electronmore » density of states. The changes of X-ray spectrum along the Hugoniot curve are caused by the different nitrogen structures induced by the temperature and the pressure. Some clear signatures on X-ray spectrum for different thermodynamical conditions are pointed out, which may provide useful data for future X-ray experiments.« less

Fe-vacancy ordering in superconducting K 1–xFe 2–ySe 2: First-principles calculations and Monte Carlo simulations

DOE PAGES

Fang, Yong; Tai, Yuan -Yen; Deng, Junkai; ...

2015-07-20

Fe vacancies in the 33 K superconductor K 1–xFe 2–ySe 2 show ordering schemes that may be correlated with its superconducting properties. First-principles calculations and kinetic Monte Carlo simulations lead to a very simple model for vacancy ordering. Repulsive dipolar interactions between Fe vacancies show three ground states: amore » $$\\sqrt{8}\\times \\sqrt{10}$$ rhombus-ordered structure for 12.5% vacancies, a $$\\sqrt{5}\\times \\sqrt{5}$$ squared lattice for 20% vacancies, and a $$\\sqrt{5}\\times \\sqrt{5}$$ rhombus-ordered structure for 25% vacancies. Other structural states are derived from these three ground states and may contain additional disordered spatial regions. As a result, the repulsive interaction between Fe vacancies arises from enhanced Fe–Se covalent bonds, which differs from the well-known attractive interaction of Fe vacancies in body-centered cubic Fe.« less

Lattice structures and electronic properties of CIGS/CdS interface: First-principles calculations

NASA Astrophysics Data System (ADS)

Tang, Fu-Ling; Liu, Ran; Xue, Hong-Tao; Lu, Wen-Jiang; Feng, Yu-Dong; Rui, Zhi-Yuan; Huang, Min

2014-07-01

Using first-principles calculations within density functional theory, we study the atomic structures and electronic properties of the perfect and defective (2VCu+InCu) CuInGaSe2/CdS interfaces theoretically, especially the interface states. We find that the local lattice structure of (2VCu+InCu) interface is somewhat disorganized. By analyzing the local density of states projected on several atomic layers of the two interfaces models, we find that for the (2VCu+InCu) interface the interface states near the Fermi level in CuInGaSe2 and CdS band gap regions are mainly composed of interfacial Se-4p, Cu-3d and S-3p orbitals, while for the perfect interface there are no clear interface states in the CuInGaSe2 region but only some interface states which are mainly composed of S-3p orbitals in the valance band of CdS region.

Direct evaluation of free energy for large system through structure integration approach.

PubMed

Takeuchi, Kazuhito; Tanaka, Ryohei; Yuge, Koretaka

2015-09-30

We propose a new approach, 'structure integration', enabling direct evaluation of configurational free energy for large systems. The present approach is based on the statistical information of lattice. Through first-principles-based simulation, we find that the present method evaluates configurational free energy accurately in disorder states above critical temperature.

The "Schema" Concept: Bartlett Till Now. No. 21.

ERIC Educational Resources Information Center

Caramelli, Nicoletta

In 1932, F. C. Bartlett first used the concept of "schema" borrowing it from Head, to suggest a unitary structure whose elements interacted in a complex way. This structure, which aimed to insure the continuity of the cognizing organism, was at the same time the expression of the functional principle responsible for the mutual…

First-principles theory of cation and intercalation ordering in Li xCoO 2

NASA Astrophysics Data System (ADS)

Wolverton, C.; Zunger, Alex

Several types of cation- and vacancy-ordering are of interest in the Li xCoO 2 battery cathode material since they can have a profound effect on the battery voltage. We present a first-principles theoretical approach which can be used to calculate both cation- and vacancy-ordering patterns at both zero and finite temperatures. This theory also provides quantum-mechanical predictions (i.e., without the use of any experimental input) of battery voltages of both ordered and disordered Li xCoO 2/Li cells from the energetics of the Li intercalation reactions. Our calculations allow us to search the entire configurational space to predict the lowest-energy ground-state structures, search for large voltage cathodes, explore metastable low-energy states, and extend our calculations to finite temperatures, thereby searching for order-disorder transitions and states of partial disorder. We present the first prediction of the stable spinel structure LiCo 2O 4 for the 50% delithiated Li 0.5CoO 2.

Rock-salt structure lithium deuteride formation in liquid lithium with high-concentrations of deuterium: a first-principles molecular dynamics study

DOE PAGES

Chen, Mohan; Abrams, T.; Jaworski, M. A.; ...

2015-12-17

Because of lithium's possible use as a first wall material in a fusion reactor, a fundamental understanding of the interactions between liquid lithium (Li) and deuterium (D) is important. Here, we predict structural and dynamical properties of liquid Li samples with high concentrations of D, as derived from first-principles molecular dynamics simulations. Liquid Li samples with four concentrations of inserted D atoms (LiDmore » $$_{\\beta}$$ , $$\\beta =0.25$$ , 0.50, 0.75, and 1.00) are studied at temperatures ranging from 470 to 1143 K. Densities, diffusivities, pair distribution functions, bond angle distribution functions, geometries, and charge transfer between Li and D atoms are calculated and analyzed. The analysis suggests liquid–solid phase transitions can occur at some concentrations and temperatures, forming rock-salt LiD within liquid Li. Finally, we observed the formation of some D 2 molecules at high D concentrations.« less

First-principles study on the structure, elastic properties, hardness and electronic structure of TMB4 (TM=Cr, Re, Ru and Os) compounds

NASA Astrophysics Data System (ADS)

Pan, Y.; Zheng, W. T.; Guan, W. M.; Zhang, K. H.; Fan, X. F.

2013-11-01

The structural formation, elastic properties, hardness and electronic structure of TMB4 (TM=Cr, Re, Ru and Os) compounds are investigated using first-principles approach. The value of C22 for these compounds is almost two times bigger than the C11 and C33. The intrinsic hardness, shear modulus and Young's modulus are calculated to be in a sequence of CrB4>ReB4>RuB4>OsB4, and the Poisson's ratio and B/G ratio of TMB4 follow the order of CrB4

Lattice thermal conductivity of monolayer AsP from first-principles molecular dynamics.

PubMed

Sun, Yajing; Shuai, Zhigang; Wang, Dong

2018-05-23

Few-layered arsenic-phosphorus alloys, AsxP(1-x), with a puckered structure have been recently synthesized and demonstrated with fully tunable band gaps and optical properties. It is predicted that the carrier mobility of monolayer AsP compounds is even higher than that of black phosphorene (b-P). The anisotropic and orthogonal electrical and thermal transport properties of the puckered group VA elements make them intriguing materials for thermoelectric applications. Herein, we investigated the thermal transport properties of AsP based on first-principles molecular dynamics and the Boltzmann transport equation. We reveal that monolayer AsP with three different chemical structures possesses thermal conductivities lower than b-P, but with increased anisotropy. Further, these structures behave profoundly different on heat conduction. This can be attributed to the distinct low-frequency optical modes associated with their bonding nature. Our results highlight the impact of atomic arrangement on the thermal conductivity of AsP, and the structure-property relationship established may guide the fabrication of thermoelectric materials via the engineered alloying method.

Structure and Magnetic Properties of Rare Earth Doped Transparent Alumina

NASA Astrophysics Data System (ADS)

Limmer, Krista; Neupane, Mahesh; Chantawansri, Tanya

Recent experimental studies of rare earth (RE) doped alumina suggest that the RE induced novel phase-dependent structural and magnetic properties. Motivated by these efforts, the effects of RE doping of alpha and theta alumina on the local structure, magnetic properties, and phase stability have been examined in this first principles study. Although a direct correlation between the magnetic field dependent materials properties observed experimentally and calculated from first principles is not feasible because of the applied field and the scale, the internal magnetic properties and other properties of the doped materials are evaluated. The RE dopants are shown to increase the substitutional site volume as well as increasingly distort the site structure as a function of ionic radii. Doping both the alpha (stable) and theta (metastable) phases enhanced the relative stability of the theta phase. The energetic doping cost and internal magnetic moment were shown to be a function of the electronic configuration of the RE-dopant, with magnetic moment directly proportional to the number of unpaired electrons and doping cost being inversely related.

First-principles calculations on slip system activation in the rock salt structure: electronic origin of ductility in silver chloride

NASA Astrophysics Data System (ADS)

Nakamura, Atsutomo; Ukita, Masaya; Shimoda, Naofumi; Furushima, Yuho; Toyoura, Kazuaki; Matsunaga, Katsuyuki

2017-06-01

First principles calculations were performed to understand an electronic origin of high ductility in silver chloride (AgCl) with the rock salt structure. From calculations of generalised stacking fault energies for different slip systems, it was found that only the {1 1 0}? slip system is favourably activated in sodium chloride (NaCl) with the same rock salt structure, whereas AgCl shows three kinds of possible slip systems along the ? direction on the {0 0 1}, {1 1 0}, and {1 1 1} planes, which is in excellent agreement with experiment. Detailed analyses of the electronic structures across slip planes showed that the more covalent character of bonding of Ag-Cl than Na-Cl tends to make the slip motion energetically favourable. It was also surprising to find out that strong Ag-Ag covalent bonds across the slip plane are formed in the {0 0 1}〈1 1 0〉 slip system in AgCl, which makes it possible to activate the multiple slip systems in AgCl.

First-principle calculations of structural, electronic, optical, elastic and thermal properties of MgXAs2 (X=Si, Ge) compounds

NASA Astrophysics Data System (ADS)

Cheddadi, S.; Boubendira, K.; Meradji, H.; Ghemid, S.; Hassan, F. El Haj; Lakel, S.; Khenata, R.

2017-12-01

First-principle calculations on the structural, electronic, optical, elastic and thermal properties of the chalcopyrite MgXAs2 (X=Si, Ge) have been performed within the density functional theory (DFT) using the full-potential linearized augmented plane wave (FP-LAPW) method. The obtained equilibrium structural parameters are in good agreement with the available experimental data and theoretical results. The calculated band structures reveal a direct energy band gap for the interested compounds. The predicted band gaps using the modified Becke-Johnson (mBJ) exchange approximation are in fairly good agreement with the experimental data. The optical constants such as the dielectric function, refractive index, and the extinction coefficient are calculated and analysed. The independent elastic parameters namely, C_{11}, C_{12}, C_{13}, C_{33}, C_{44} and C_{66 } are evaluated. The effects of temperature and pressure on some macroscopic properties of MgSiAs2 and MgGeAs2 are predicted using the quasiharmonic Debye model in which the lattice vibrations are taken into account.

First-Principles Study of the Li-Mg-N-H System: Compound Structures and Hydrogen Storage Properties

NASA Astrophysics Data System (ADS)

Michel, Kyle; Ozolins, Vidvuds

2009-03-01

The Li-Mg-N-H system is studied with the addition of the Li4Mg(NH)3, MgNH, and Li4NH compounds using first-principles density-functional theory (DFT) calculations. A structure for the mixed imide Li4Mg(NH)3 is proposed, belonging to the Imm2 space group. A new structure for Li2Mg(NH)2 is given that has Pca21 symmetry; this compound has been previously reported as having Iba2 symmetry. The stability of the Li4Mg-imide is studied with respect to its decomposition reactions. The static, zero-point (ZPE), and vibrational energies of all relevant compounds belonging to this system are reported along with their predicted lowest-energy structures. Dehydrogenation reactions are presented that involve these phases and which are found to be spontaneously occurring within 400 K of room temperature. It is predicted that mixing LiH, LiNH2, and Li2Mg(NH)2 at 505 K will form Li4Mg(NH)3 with the release of 2.04 wt. % H2.

First-principles study of native defects in bulk Sm2CuO4 and its (001) surface structure

NASA Astrophysics Data System (ADS)

Zheng, Fubao; Zhang, Qinfang; Meng, Qiangqiang; Wang, Baolin; Song, Fengqi; Yunoki, Seiji; Wang, Guanghou

2018-04-01

Using the first-principles calculations based on the density functional theory, we have studied the bulk defect formation and surface structures of Sm2CuO4. To ensure the accuracy of calculations, the spin order of Cu atoms is rechecked and it is the well-known nearest-neighbor antiferromagnetic ground state, which can be attributed to the hole-mediated superexchange through the strong pdσ hybridization interaction between Cu dx2-y2 electron and the neighboring oxygen px (or py) electron. Under each present experimental condition, the Sm vacancy has a very high formation energy and is unlikely to be stable. The Cu vacancy is a shallow acceptor, which is preferred under O-rich conditions, whereas the O vacancy is a donor and energetically favorable under O-poor conditions. To construct its (001) surface structure, CuOO, CuO, and Cu terminated surfaces are found to be most favorable under different experimental conditions. The stable surface structures are always accompanied by significant surface atomic reconstructions and electron charge redistribution, which are intimately correlated to each other.

A first principle calculation of anisotropic elastic, mechanical and electronic properties of TiB

NASA Astrophysics Data System (ADS)

Zhang, Junqin; Zhao, Bin; Ma, Huihui; Wei, Qun; Yang, Yintang

2018-04-01

The structural, mechanical and electronic properties of the NaCl-type structure TiB are theoretically calculated based on the first principles. The density of states of TiB shows obvious density peaks at -0.70eV. Furthermore, there exists a pseudogap at 0.71eV to the right of the Fermi level. The calculated structural and mechanical parameters (i.e., bulk modulus, shear modulus, Young's modulus, Poisson's ratio and universal elastic anisotropy index) were in good agreement both with the previously reported experimental values and theoretical results at zero pressure. The mechanical stability criterion proves that TiB at zero pressure is mechanistically stable and exhibits ductility. The universal anisotropic index and the 3D graphics of Young's modulus are also given in this paper, which indicates that TiB is anisotropy under zero pressure. Moreover, the effects of applied pressures on the structural, mechanical and anisotropic elastic of TiB were studied in the range from 0 to 100GPa. It was found that ductility and anisotropy of TiB were enhanced with the increase of pressure.

First-principles investigation of the structural characteristics of LiMO2 cathode materials for lithium secondary batteries

NASA Astrophysics Data System (ADS)

Kim, Yongseon

2015-11-01

The structural features related to the defects of LiMO2 (M = Ni, Co, Mn) cathode materials for lithium secondary batteries were investigated by a simulation of phase diagrams based on first-principle calculations. Crystal models with various types of point defects were designed and dealt with as independent phases, which enabled an examination of the thermodynamic stability of the defects. A perfect phase without defects appeared to be the most stable for LiCoO2, whereas the formation of Li vacancies, O vacancies, and antisites between Li and Ni was thermodynamically unavoidable for LiNiO2. The introduction of both Co and Mn in LiNiO2 was effective in reducing the formation of point defects, but increasing the relative amount of Mn was undesirable because the antisite defect remained stable with Mn doping. The simulation showed good agreement with the experimental data and previous reports. Therefore, the method and the results of this study are expected to be useful for examining the synthesis, structure and related properties of layer-structured cathode materials.

First-principles study of Al2Sm intermetallic compound on structural, mechanical properties and electronic structure

NASA Astrophysics Data System (ADS)

Lin, Jingwu; Wang, Lei; Hu, Zhi; Li, Xiao; Yan, Hong

2017-02-01

The structural, thermodynamic, mechanical and electronic properties of cubic Al2Sm intermetallic compound are investigated by the first-principles method on the basis of density functional theory. In light of the strong on-site Coulomb repulsion between the highly localized 4f electrons of Sm atoms, the local spin density approximation approach paired with additional Hubbard terms is employed to achieve appropriate results. Moreover, to examine the reliability of this study, the experimental value of lattice parameter is procured from the analysis of the TEM image and diffraction pattern of Al2Sm phase in the AZ31 alloy to verify the authenticity of the results originated from the computational method. The value of cohesive energy reveals Al2Sm to be a stable in absolute zero Kelvin. According to the stability criteria, the subject of this work is mechanically stable. Afterward, elastic moduli are deduced by performing Voigt-Reuss-Hill approximation. Furthermore, elastic anisotropy and anisotropy of sound velocity are discussed. Finally, the calculation of electronic density of states is implemented to explore the underlying mechanism of structural stability.

Theoretical investigations on diamondoids (CnHm, n = 10-41): Nomenclature, structural stabilities, and gap distributions

NASA Astrophysics Data System (ADS)

Wang, Ya-Ting; Zhao, Yu-Jun; Liao, Ji-Hai; Yang, Xiao-Bao

2018-01-01

Combining the congruence check and the first-principles calculations, we have systematically investigated the structural stabilities and gap distributions of possible diamondoids (CnHm) with the carbon numbers (n) from 10 to 41. A simple method for the nomenclature is proposed, which can be used to distinguish and screen the candidates with high efficiency. Different from previous theoretical studies, the possible diamondoids can be enumerated according to our nomenclature, without any pre-determination from experiments. The structural stabilities and electronic properties have been studied by density functional based tight binding and first-principles methods, where a nearly linear correlation is found between the energy gaps obtained by these two methods. According to the formation energy of structures, we have determined the stable configurations as a function of chemical potential. The maximum and minimum energy gaps are found to be dominated by the shape of diamondoids for clusters with a given number of carbon atoms, while the gap decreases in general as the size increases due to the quantum confinement.

Computational materials science: Think locally, act globally

NASA Astrophysics Data System (ADS)

Rabe, Karin M.

2002-11-01

New first-principles calculations reveal the range of atomic arrangements underlying the average crystallographic structure of a perovskite oxide, PZT. This work opens the door to understanding the exceptional physical behaviour of PZT and related systems.

First-principles investigations into the thermodynamics of cation disorder and its impact on electronic structure and magnetic properties of spinel Co(Cr1-x Mn x )2O4

NASA Astrophysics Data System (ADS)

Das, Debashish; Ghosh, Subhradip

2017-02-01

Cation disorder over different crystallographic sites in spinel oxides is known to affect their properties. Recent experiments on Mn doped multiferroic \\text{CoC}{{\\text{r}}2}{{\\text{O}}4} indicate that a possible distribution of Mn atoms among tetrahedrally and octahedrally coordinated sites in the spinel lattice give rise to different variations in the structural parameters and saturation magnetisations in different concentration regimes of Mn atoms substituting the Cr. A composition dependent magnetic compensation behaviour points to the role conversions of the magnetic constituents. In this work, we have investigated the thermodynamics of cation disorder in \\text{Co}{{≤ft(\\text{C}{{\\text{r}}1-x}\\text{M}{{\\text{n}}x}\\right)}2}{{\\text{O}}4} system and its consequences on the structural, electronic and magnetic properties, using results from first-principles electronic structure calculations. We have computed the variations in the cation-disorder as a function of Mn concentration and the temperature and found that at the annealing temperature of the experiment many of the systems exhibit cation disorder. Our results support the interpretations of the experimental results regarding the qualitative variations in the sub-lattice occupancies and the associated magnetisation behaviour, with composition. We have analysed the variations in structural, magnetic and electronic properties of this system with variations in the compositions and the degree of cation disorder from the variations in their electronic structures and by using the ideas from crystal field theory. Our study provides a complete microscopic picture of the effects that are responsible for composition dependent behavioural differences of the properties of this system. This work lays down a general framework, based upon results from first-principles calculations, to understand and analyse the substitutional magnetic spinel oxides A{{≤ft({{B}1-x}{{C}x}\\right)}2}{{\\text{O}}4} in presence of cation disorder.

The role of syllabic structure in French visual word recognition.

PubMed

Rouibah, A; Taft, M

2001-03-01

Two experiments are reported in which the processing units involved in the reading of French polysyllabic words are examined. A comparison was made between units following the maximal onset principle (i.e., the spoken syllable) and units following the maximal coda principle (i.e., the basic orthographic syllabic structure [BOSS]). In the first experiment, it took longer to recognize that a syllable was the beginning of a word (e.g., the FOE of FOETUS) than to make the same judgment of a BOSS (e.g., FOET). The fact that a BOSS plus one letter (e.g., FOETU) also took longer to judge than the BOSS indicated that the maximal coda principle applies to the units of processing in French. The second experiment confirmed this, using a lexical decision task with the different units being demarcated on the basis of color. It was concluded that the syllabic structure that is so clearly manifested in the spoken form of French is not involved in visual word recognition.

Physics of the gut: How polymers dynamically structure the gut environment

NASA Astrophysics Data System (ADS)

Preska Steinberg, Asher; Datta, Sujit; Bogatyrev, Said; Ismagilov, Rustem

While the gut microbiome and biological regulation of the gut environment is being exhaustively studied by the microbiology community, little is known about the rich physics that governs the macro- and microstructure of the gut environment. The mammalian gut abounds in soft materials; ranging from soluble polymers (e.g. dietary fibers, therapeutic polymers and mucins) to colloidal matter (e.g. bacteria, viruses and nanoparticles carrying drugs). We have found experimentally that soluble polymers can dynamically re-structure the colonic mucus hydrogel by modulating its degree of swelling. We implemented a mean-field Flory-Huggins model to reveal that these polymer-mucus interactions can be captured using a simple, first principles thermodynamics model. In this model, the amount of deswelling increases with polymer concentration and size. We then used these physical principles to make predictions about how different polymer solutions affect the structure of mucus. Lastly, we explore applying this framework and similar physical principles to a variety of biological problems in the gut.

Intergranular fracture in UO{sub 2}: derivation of traction-separation law from atomistic simulations

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

Zhang, Yongfeng; Millett, P.C.; Tonks, M.R.

2013-07-01

In this study, the intergranular fracture behavior of UO{sub 2} was studied by molecular dynamics simulations using the Basak potential. In addition, the constitutive traction-separation law was derived from atomistic data using the cohesive-zone model. In the simulations a bicrystal model with the (100) symmetric tilt Σ5 grain boundaries was utilized. Uniaxial tension along the grain boundary normal was applied to simulate Mode-I fracture. The fracture was observed to propagate along the grain boundary by micro-pore nucleation and coalescence, giving an overall intergranular fracture behavior. Phase transformations from the Fluorite to the Rutile and Scrutinyite phases were identified at themore » propagating crack tips. These new phases are metastable and they transformed back to the Fluorite phase at the wake of crack tips as the local stress concentration was relieved by complete cracking. Such transient behavior observed at atomistic scale was found to substantially increase the energy release rate for fracture. Insertion of Xe gas into the initial notch showed minor effect on the overall fracture behavior. (authors)« less

Intergranular fracture in UO2: derivation of traction-separation law from atomistic simulations

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

Yongfeng Zhang; Paul C Millett; Michael R Tonks

2013-10-01

In this study, the intergranular fracture behavior of UO2 was studied by molecular dynamics simulations using the Basak potential. In addition, the constitutive traction-separation law was derived from atomistic data using the cohesive-zone model. In the simulations a bicrystal model with the (100) symmetric tilt E5 grain boundaries was utilized. Uniaxial tension along the grain boundary normal was applied to simulate Mode-I fracture. The fracture was observed to propagate along the grain boundary by micro-pore nucleation and coalescence, giving an overall intergranular fracture behavior. Phase transformations from the Fluorite to the Rutile and Scrutinyite phases were identified at the propagatingmore » crack tips. These new phases are metastable and they transformed back to the Fluorite phase at the wake of crack tips as the local stress concentration was relieved by complete cracking. Such transient behavior observed at atomistic scale was found to substantially increase the energy release rate for fracture. Insertion of Xe gas into the initial notch showed minor effect on the overall fracture behavior.« less

Effect of CMAS composition on hot corrosion behavior of gadolinium zirconate thermal barrier coating materials

DOE PAGES

Deng, Wenzhuo; Fergus, Jeffrey W.

2017-07-06

The resistance of synthesized pyrochlore-type Gd 2Zr 2O 7 bulk specimens to four calcium-magnesium aluminosilicate (CMAS) compositions at different temperatures was investigated. The reaction products were identified by x-ray diffraction and penetration depths were examined using scanning electron microscopy. A dense reaction layer is comprised mainly of Ca 2Gd 8(SiO 4) 6O 2 and a cubic fluorite phase formed during the CMAS attack, and some unreacted CMAS was found in a transition layer below the reaction layer. The overall infiltration depth changed slightly with temperature, however, the thickness of the reaction layer and the morphology of the transition layer variedmore » distinctly with temperature. The sintered sample underwent the most severe degradation by the CaO-lean CMAS, whereas the effect of CaSO 4 and CaCO 3 was not significant. Furthermore, the Gd content of the ZrO 2-based cubic fluorite phase depends on the temperature and the molar ratio of Ca:Si in the CMAS.« less

Geochemical Assessment of Fluoride Pollution in Groundwater of Tribal Region in India.

PubMed

Anshumali; Kumar, Manish; Chanda, Nikki; Kumar, Abhay; Kumar, Bijendra; Venkatesh, Madavi

2018-03-01

This study assessed the fluoride (F - ) pollution in groundwater samples (n = 170) of tribal regions around Bailadila Iron Ore Mines [BIOM] Complex of Dantewada District, India. Weathering of carbonate and silicate clays were important geogenic sources of dissolved ions. A Piper diagram showed a Ca-HCO 3 water type, with positive chloro-alkaline indices illustrating the occurrence of direct base-exchange reactions. The F - concentrations varied from 0.08 to 1.95 mg L -1 with a mean value of 0.9 ± 0.3 mg L -1 . Only two groundwater samples showed F - concentrations > 1.5 mg L -1 , the drinking water guideline established by the World Health Organization (WHO) and Bureau of Indian Standards (BIS). Factor analysis showed high loadings of HCO 3 - and F - , indicating alkaline conditions, favoring the dissolution of F - in the groundwater. The K fluor value is less than 10 -10.6 , indicating that the dissociation of fluorite is very slow. As a result, groundwater locations were under-saturated with respect to fluorite.

Stress wave timing nondestructive evaluation tools for inspecting historic structures : a guide for use and interpretation.

Treesearch

Robert Ross; Roy F. Pellerin; Norbert Volny; William W. Salsig; Robert H. Falk

2000-01-01

This guide was prepared to assist inspectors in the use of stress wave timing instruments and various methods of locating and defining areas of decay in timber members in historic structures. The first two sections provide (a) background information regarding conventional methods to locate and measure decay in historic structures and (b) the principles of stress wave...

Merging first principle structure studies and few-body reaction formalism

NASA Astrophysics Data System (ADS)

Crespo, R.; Cravo, E.; Arriaga, A.; Wiringa, R.; Deltuva, A.; Diego, R.

2018-02-01

Calculations for nucleon knockout from a 7Li beam due to the collision with a proton target at 400 MeV/u are shown based on ab initio Quantum Monte Carlo (QMC) and conventional shell-model nuclear structure approaches to describe the relative motion between the knockout particle and the heavy fragment of the projectile. Structure effects on the total cross section are shown.

AB INITIO STUDY OF PHONON DISPERSION AND ELASTIC PROPERTIES OF L12 INTERMETALLICS Ti3Al AND Y3Al

NASA Astrophysics Data System (ADS)

Arikan, N.; Ersen, M.; Ocak, H. Y.; Iyigör, A.; Candan, A.; UǦUR, Ş.; UǦUR, G.; Khenata, R.; Varshney, D.

2013-12-01

In this paper, the structural, elastic and phonon properties of Ti3Al and Y3Al in L12(Cu3Al) phase are studied by performing first-principles calculations within the generalized gradient approximation. The calculated lattice constants, static bulk moduli, first-order pressure derivative of bulk moduli and elastic constants for both compounds are reported. The phonon dispersion curves along several high-symmetry lines at the Brillouin zone, together with the corresponding phonon density of states, are determined using the first-principles linear-response approach of the density functional perturbation theory. Temperature variations of specific heat in the range of 0-500 K are obtained using the quasi-harmonic model.

Property Characterization and Photocatalytic Activity Evaluation of BiGdO₃ Nanoparticles under Visible Light Irradiation.

PubMed

Luan, Jingfei; Shen, Yue; Zhang, Lingyan; Guo, Ningbin

2016-09-08

BiGdO₃ nanoparticles were prepared by a solid-state reaction method and applied in photocatalytic degradation of dyes in this study. BiGdO₃ was characterized by X-ray powder diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy, Brunauer-Emmett-Teller, UV-Vis diffuse reflectance spectroscopy and transmission electron microscopy. The results showed that BiGdO₃ crystallized well with the fluorite-type structure, a face-centered cubic crystal system and a space group Fm3m 225. The lattice parameter of BiGdO₃ was 5.465 angstrom. The band gap of BiGdO₃ was estimated to be 2.25 eV. BiGdO₃ showed a strong optical absorption during the visible light region. Moreover, the photocatalytic activity of BiGdO₃ was evaluated by photocatalytic degradation of direct dyes in aqueous solution under visible light irradiation. BiGdO₃ demonstrated excellent photocatalytic activity in degrading Direct Orange 26 (DO-26) or Direct Red 23 (DR-23) under visible light irradiation. The photocatalytic degradation of DO-26 or DR-23 followed the first-order reaction kinetics, and the first-order rate constant was 0.0046 or 0.0023 min(-1) with BiGdO₃ as catalyst. The degradation intermediates of DO-26 were observed and the possible photocatalytic degradation pathway of DO-26 under visible light irradiation was provided. The effect of various operational parameters on the photocatalytic activity and the stability of BiGdO₃ particles were also discussed in detail. BiGdO₃/(visible light) photocatalysis system was confirmed to be suitable for textile industry wastewater treatment.

First-principles study on the electronic structure and elastic properties of Mo2NiB2 doped with V

NASA Astrophysics Data System (ADS)

Li, Jinming; Li, Xiaobo; Gao, Haiyun; Peng, Dian

2018-04-01

The content of this study is to analyze the electronic structure and elastic properties that the different structures of Mo2NiB2 and doping with V of the tetragonal M3B2 (Mo2Ni1‑xVxB2 and Mo2‑yNi1‑yV2yB2) (x = 0.25, 0.5, 0.75 and y = 0.125, 0.25, 0.375) by first-principles calculations based on density functional theory (DFT) combined with the projection-plus-wave method. But the calculated formation energy shows that V atoms prefer to substitute the Mo and Ni atoms of the tetragonal Mo2NiB2. Moreover, with the increase of V content, the formation enthalpy of tetragonal Mo2NiB2 is reduced, and the formation enthalpy of Mo1.625Ni0.625V0.75B2 is the least as ‑53.23 kJ/mol. The calculated elastic constant suffices the condition of mechanical stability, indicate that they are stable. The calculated elastic modulus illustrates that Mo2NiB2 having better mechanical properties when V elements are at Mo and Ni sites instead of Ni sites. The calculated and analyzed density of states of Mo1.625Ni0.625V0.75B2 has the smallest the density of states at the Fermi level indicating that it has the more stable structure. For the theoretical analysis of the first-principles calculations, the addition of 15 atom% of the V and V doping modes of Mo and Ni are preferentially replaced by V atoms of Mo2NiB2 ternary boride has the best performance.

Electronic and thermodynamic properties of layered Hf2Sfrom first-principles calculations

NASA Astrophysics Data System (ADS)

Nandadasa, Chandani; Yoon, Mina; Kim, Seong-Gon; Erwin, Steve; Kim, Sungho; Kim, Sung Wng; Lee, Kimoon

Theoretically we explored two stable phases of inorganic fullerene-like structure of the layered dihafnium sulfide (Hf2 S) . We investigated structural and electronic properties of the two phases of Hf2 S by using first-principles calculations. Our calculation identifies experimentally observed anti-NbS2 structure of Hf2 S . Our electronic calculation results indicate that the density of states of anti- NbS2 structure of Hf2 S at fermi level is less than that of the other phase of Hf2 S . To study the relative stability of different phases at finite temperature Helmholtz free energies of two phases are obtained using density functional theory and density functional perturbation theory. The free energy of the anti-NbS2 structure of Hf2 S always lies below the free energy of the other phase by confirming the most stable structure of Hf2 S . The phonon dispersion, phonon density of states including partial density of states and total density of states are obtained within density functional perturbation theory. Our calculated zero-pressure phonon dispersion curves confirm that the thermodynamic stability of Hf2 S structures. For further investigation of thermodynamic properties, the temperature dependency of thermal expansion, heat capacities at constant pressure and volume are evaluated within the quasiharmonic approximations (QHA).

First Principles Investigation of the Geometrical and Electrochemical Properties of Na4P

NASA Astrophysics Data System (ADS)

Rush, Larry E., Jr.; Holzwarth, N. A. W.

First principles simulations are used to examine the structural and physical properties of Na4P2S6 in comparison with its Li4P2S6 analog. Four model structures are considered including the C 2 / m structure recently reported by Kuhn and co-workers from their analysis of single crystals of Na4P2S6, and three structures related to the P63 / mcm structure with P site disorder found in 1982 by Mercier and co-workers from their analysis of single crystals of Li4P2S6. The computational results indicate that both Na4P2S6 and Li4P2S6 have the same disordered ground state structures consistent with the P63 / mcm space group, while the optimized C 2 / m structures have higher energies by 0.1 eV and 0.4 eV per formula unit for Na4P2S6 and Li4P2S6, respectively. Simulations of ion migration suggest that Na4P2S6 may have more favorable ionic conductivity compared to Li4P2S6. Supported by NSF Grant DMR-1105485 and DMR-1507942.

First-principles anharmonic quantum calculations for peptide spectroscopy: VSCF calculations and comparison with experiments.

PubMed

Roy, Tapta Kanchan; Sharma, Rahul; Gerber, R Benny

2016-01-21

First-principles quantum calculations for anharmonic vibrational spectroscopy of three protected dipeptides are carried out and compared with experimental data. Using hybrid HF/MP2 potentials, the Vibrational Self-Consistent Field with Second-Order Perturbation Correction (VSCF-PT2) algorithm is used to compute the spectra without any ad hoc scaling or fitting. All of the vibrational modes (135 for the largest system) are treated quantum mechanically and anharmonically using full pair-wise coupling potentials to represent the interaction between different modes. In the hybrid potential scheme the MP2 method is used for the harmonic part of the potential and a modified HF method is used for the anharmonic part. The overall agreement between computed spectra and experiment is very good and reveals different signatures for different conformers. This study shows that first-principles spectroscopic calculations of good accuracy are possible for dipeptides hence it opens possibilities for determination of dipeptide conformer structures by comparison of spectroscopic calculations with experiment.

Polarization-dependent force driving the Eg mode in bismuth under optical excitation: comparison of first-principles theory with ultra-fast x-ray experiments

NASA Astrophysics Data System (ADS)

Fahy, Stephen; Murray, Eamonn

2015-03-01

Using first principles electronic structure methods, we calculate the induced force on the Eg (zone centre transverse optical) phonon mode in bismuth immediately after absorption of a ultrafast pulse of polarized light. To compare the results with recent ultra-fast, time-resolved x-ray diffraction experiments, we include the decay of the force due to carrier scattering, as measured in optical Raman scattering experiments, and simulate the optical absorption process, depth-dependent atomic driving forces, and x-ray diffraction in the experimental geometry. We find excellent agreement between the theoretical predictions and the observed oscillations of the x-ray diffraction signal, indicating that first-principles theory of optical absorption is well suited to the calculation of initial atomic driving forces in photo-excited materials following ultrafast excitation. This work is supported by Science Foundation Ireland (Grant No. 12/IA/1601) and EU Commission under the Marie Curie Incoming International Fellowships (Grant No. PIIF-GA-2012-329695).

First-principles simulations of shock front propagation in liquid deuterium

NASA Astrophysics Data System (ADS)

Gygi, Francois; Galli, Giulia

2001-03-01

We present large-scale first-principles molecular dynamics simulations of the formation and propagation of a shock front in liquid deuterium. Molecular deuterium was subjected to supersonic impacts at velocities ranging from 10 to 30 km/s. We used Density Functional Theory in the local density approximation, and simulation cells containing 1320 deuterium atoms. The formation of a shock front was observed and its velocity was measured and compared with the results of laser-driven shock experiments [1]. The pressure and density in the compressed fluid were also computed directly from statistical averages in appropriate regions of the simulation cell, and compared with previous first-principles calculations performed at equilibrium [2]. Details of the electronic structure at the shock front, and their influence on the properties of the compressed fluid will be discussed. [1] J.W.Collins et al. Science 281, 1178 (1998). [2] G.Galli, R.Q.Hood, A.U.Hazi and F.Gygi, Phys.Rev. B61, 909 (2000).

Grain growth in U–7Mo alloy: A combined first-principles and phase field study

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

Mei, Zhi-Gang; Liang, Linyun; Kim, Yeon Soo

2016-05-01

Grain size is an important factor in controlling the swelling behavior in irradiated U-Mo dispersion fuels. Increasing the grain size in UeMo fuel particles by heat treatment is believed to delay the fuel swelling at high fission density. In this work, a multiscale simulation approach combining first-principles calculation and phase field modeling is used to investigate the grain growth behavior in U-7Mo alloy. The density functional theory based first-principles calculations were used to predict the material properties of U-7Mo alloy. The obtained grain boundary energies were then adopted as an input parameter for mesoscale phase field simulations. The effects ofmore » annealing temperature, annealing time and initial grain structures of fuel particles on the grain growth in U-7Mo alloy were examined. The predicted grain growth rate compares well with the empirical correlation derived from experiments. (C) 2016 Elsevier B.V. All rights reserved.« less

Proton transfer from water to ketyl radical anion: Assessment of critical size of hydrated cluster and free energy barrier in solution from first principles simulations

NASA Astrophysics Data System (ADS)

Biswas, Sohag; Dasgupta, Teesta; Mallik, Bhabani S.

2016-09-01

We present the reactivity of an organic intermediate by studying the proton transfer process from water to ketyl radical anion using gas phase electronic structure calculations and the metadynamics method based first principles molecular dynamics (FPMD) simulations. Our results indicate that during the micro solvation of anion by water molecules systematically, the presence of minimum three water molecules in the gas phase cluster is sufficient to observe the proton transfer event. The analysis of trajectories obtained from initial FPMD simulation of an aqueous solution of the anion does not show any evident of complete transfer of the proton from water. The cooperativity of water molecules and the relatively weak anion-water interaction in liquid state prohibit the full release of the proton. Using biasing potential through first principles metadynamics simulations, we report the observation of proton transfer reaction from water to ketyl radical anion with a barrier height of 16.0 kJ/mol.

First-principles study on leakage current caused by oxygen vacancies at HfO2/SiO2/Si interface

NASA Astrophysics Data System (ADS)

Takagi, Kensuke; Ono, Tomoya

2018-06-01

The relationship between the position of oxygen vacancies in HfO2/SiO2/Si gate stacks and the leakage current is studied by first-principles electronic-structure and electron-conduction calculations. We find that the increase in the leakage current due to the creation of oxygen vacancies in the HfO2 layer is much larger than that in the SiO2 interlayer. According to previous first-principles total energy calculations, the formation energy of oxygen vacancies is smaller in the SiO2 interlayer than that in the HfO2 layer under the same conditions. Therefore, oxygen vacancies will be attracted from the SiO2 interlayer to minimize the energy, thermodynamically justifying the scavenging technique. Thus, the scavenging process efficiently improves the dielectric constant of HfO2-based gate stacks without increasing the number of oxygen vacancies, which cause the dielectric breakdown.

First-principles study of the stability, magnetic and electronic properties of Fe and Co monoatomic chains encapsulated into copper nanotube

NASA Astrophysics Data System (ADS)

Ma, Liang-Cai; Ma, Ling; Zhang, Jian-Min

2017-07-01

By using first-principles calculations based on density-functional theory, the stability, magnetic and electronic properties of Fe and Co monoatomic chains encapsulated into copper nanotube are systematically investigated. The binding energies of the hybrid structures are remarkably higher than those of corresponding freestanding TM chains, indicating the TM chains are significantly stabilized after encapsulating into copper nanotube. The formed bonds between outer Cu and inner TM atoms show some degree of covalent bonding character. The magnetic ground states of Fe@CuNW and Co@CuNW hybrid structures are ferromagnetic, and both spin and orbital magnetic moments of inner TM atoms have been calculated. The magnetocrystalline anisotropy energies (MAE) of the hybrid structures are enhanced by nearly fourfold compared to those of corresponding freestanding TM chains, indicating that the hybrid structures can be used in ultrahigh density magnetic storage. Furthermore, the easy magnetization axis switches from that along the axis in freestanding Fe chain to that perpendicular to the axis in Fe@CuNT hybrid structure. The large spin polarization at the Fermi level also makes the hybrid systems interesting as good potential materials for spintronic devices.

Electronic structure and magnetic anisotropy of L1{sub 0}-FePt thin film studied by hard x-ray photoemission spectroscopy and first-principles calculations

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

Ueda, S.; Synchrotron X-ray Station at SPring-8, National Institute for Materials Science, Sayo, Hyogo 679-5148; Mizuguchi, M.

2016-07-25

We have studied the electronic structure of the L1{sub 0} ordered FePt thin film by hard x-ray photoemission spectroscopy (HAXPES), cluster model, and first-principles calculations to investigate the relationship between the electronic structure and perpendicular magneto-crystalline anisotropy (MCA). The Fe 2p core-level HAXPES spectrum of the ordered film revealed the strong electron correlation in the Fe 3d states and the hybridization between the Fe 3d and Pt 5d states. By comparing the experimental valence band structure with the theoretical density of states, the strong electron correlation in the Fe 3d states modifies the valence band electronic structure of the L1{submore » 0} ordered FePt thin film through the Fe 3d-Pt 5d hybridization. These results strongly suggest that the strong electron correlation effect in the Fe 3d states and the Fe 3d-Pt 5d hybridization as well as the spin-orbit interaction in the Pt 5d states play important roles in the perpendicular MCA for L1{sub 0}-FePt.« less

Nanoscale Charge Balancing Mechanism in Calcium-Silicate-Hydrate Gels: Novel Complex Disordered Materials from First-principles

NASA Astrophysics Data System (ADS)

Ozcelik, Ongun; White, Claire

Alkali-activated materials which have augmented chemical compositions as compared to ordinary Portland cement are sustainable technologies that have the potential to lower CO2 emissions associated with the construction industry. In particular, calcium-silicate-hydrate (C-S-H) gel is altered at the atomic scale due to changes in its chemical composition. Here, based on first-principles calculations, we predict a charge balancing mechanism at the molecular level in C-S-H gels when alkali atoms are introduced into their structure. This charge balancing process is responsible for the formation of novel structures which possess superior mechanical properties compared to their charge unbalanced counterparts. Different structural representations are obtained depending on the level of substitution and the degree of charge balancing incorporated in the structures. The impact of these charge balancing effects on the structures is assessed by analyzing their formation energies, local bonding environments, diffusion barriers and mechanical properties. These results provide information on the phase stability of alkali/aluminum containing C-S-H gels, shedding light on the fundamental mechanisms that play a crucial role in these complex disordered materials. We acknowledge funding from the Princeton Center for Complex Materials, a MRSEC supported by NSF.

Dielectric properties and Raman spectra of ZnO from a first principles finite-differences/finite-fields approach

PubMed Central

Calzolari, Arrigo; Nardelli, Marco Buongiorno

2013-01-01

Using first principles calculations based on density functional theory and a coupled finite-fields/finite-differences approach, we study the dielectric properties, phonon dispersions and Raman spectra of ZnO, a material whose internal polarization fields require special treatment to correctly reproduce the ground state electronic structure and the coupling with external fields. Our results are in excellent agreement with existing experimental measurements and provide an essential reference for the characterization of crystallinity, composition, piezo- and thermo-electricity of the plethora of ZnO-derived nanostructured materials used in optoelectronics and sensor devices. PMID:24141391

Structural study of Co doped MnV2O4 from first principles

NASA Astrophysics Data System (ADS)

Krishna, Jyoti; Maitra, Tulika

2017-05-01

Inspired by the recent experiments, we have theoretically investigated the compound Mn1-xCoxV2O4 using first-principles density functional theory for x = 0.0, 0.25, 0.5, 0.75. On increasing Co doping on Mn site, chemical pressure on V-V bonds increases which make the system more itinerant as indicated by decrease in the calculated RV-V values with increasing x. The calculated band gap is also seen to decrease with increasing x. This Co-doping induced itinerancy facilitates superexchange interaction among Co and V ions leading to an increase in the magnetic transition temperature.

A first-principles study of group IV and VI atoms doped blue phosphorene

NASA Astrophysics Data System (ADS)

Bai, Ruimin; Chen, Zheng; Gou, Manman; Zhang, Yixin

2018-02-01

Using first-principles calculations, we have systematically investigated the structural, electronic and magnetic properties of blue phosphorene doped by group IV and VI atoms, including C, Si, Ge, Sn, O, S, Se and Te. All the doped systems are energetically stable. Only C, Si, Ge and O-substituted systems show the characteristics of spin polarization and the magnetic moments are all 1.0 μB. Moreover, we found that C, Si, Ge and O doped systems are indirect bandgap semiconductors, while Sn, S, Se and Te doped systems present metallic property. These results show that blue phosphorene can be used prospectively in optoelectronic and spintronic devices.

First-principles study of Ti intercalation between graphene and Au surface

NASA Astrophysics Data System (ADS)

Kaneko, T.; Imamura, H.

2011-06-01

We investigate the effects of Ti intercalation between graphene and Au surface on binding energy and charge doping by using the first-principles calculations. We show that the largest binding energy is realized by the intercalation of single mono-layer of Ti. We also show that electronic structure is very sensitive to the arrangement of metal atoms at the interface. If the composition of the interface layer is Ti0.33Au0.67 and the Ti is located at the top site, the Fermi level lies closely at the Dirac point, i.e., the Dirac cone of the ideal free-standing graphene is recovered.

First principles investigation of SiC/AlGaN(0001) band offset

NASA Astrophysics Data System (ADS)

Kojima, E.; Endo, K.; Shirakawa, H.; Chokawa, K.; Araidai, M.; Ebihara, Y.; Kanemura, T.; Onda, S.; Shiraishi, K.

2017-06-01

We are attempting to develop a new type of vertical MOSFET with SiC/AlGaN heterojunction. Toward the realization of the vertical MOSFET, the control of conduction-band offset is one of the crucial subjects. We investigated the conduction-band offset of 4H-SiC/AlxGa1-xN interface by the first-principles electronic structure calculations. We found that the offset of the interface with 40% Al content becomes almost zero. Therefore, 4H-SiC/Al0.4Ga0.6N interface is one of the most promising candidates for the vertical MOSFET in future power conversion devices.

3D Diffraction Microscope Provides a First Deep View

NASA Astrophysics Data System (ADS)

Miao, Jianwei

2005-03-01

When a coherent diffraction pattern is sampled at a spacing sufficiently finer than the Bragg peak frequency (i.e. the inverse of the sample size), the phase information is in principle encoded inside the diffraction pattern, and can be directly retrieved by using an iterative process. In combination of this oversampling phasing method with either coherent X-rays or electrons, a novel form of diffraction microscopy has recently been developed to image nanoscale materials and biological structures. In this talk, I will present the principle of the oversampling method, discuss the first experimental demonstration of this microscope, and illustrate some applications in nanoscience and biology.

Tuning topological phases in the XMnSb2 system via chemical substitution from first principles

NASA Astrophysics Data System (ADS)

Griffin, Sinead M.; Neaton, Jeffrey B.

New Dirac materials are sought for their interesting fundamental physics and for their potential technological applications. Protected symmetries offer a route to potential zero mass Dirac and Weyl fermions, and can lead unique transport properties and spectroscopic signatures. In this work, we use first-principles calculations to study the XMnSb2 family of materials and show how varying X changes the nature of bulk protected topological features in their electronic structure. We further discuss new design rules for predicting new topological materials suggested by our calculations. SG is supported by the Early Postdoc Mobility Fellowship of the SNF.

First-principles study of magnetoelastic effect in the difluoride compounds MF2 (M=Mn, Fe, Co, Ni)

NASA Astrophysics Data System (ADS)

Das, Hena; Kanungo, Sudipta; Saha-Dasgupta, T.

2012-08-01

Employing first-principles density-functional-theory-based calculations, we study the electronic structure and magnetoelastic effect in difluoride compounds MF2 (M=Mn, Fe, Co, Ni). The magnetoelastic-effect-driven cell-parameter changes across the series are found to exhibit nonmonotonic behavior in agreement with recent experimental reports. Our study reveals that this originates from the nonmonotonicity in the exchange striction of the bond-stretching phonon mode associated with the short M-F bond. Our study also uncovers the role of M-F covalency in driving the nonmonotonic behavior of the M-M exchange interaction across the series.

Automated first-principles mapping for phase-change materials.

PubMed

Esser, Marc; Maintz, Stefan; Dronskowski, Richard

2017-04-05

Plotting materials on bi-coordinate maps according to physically meaningful descriptors has a successful tradition in computational solid-state science spanning more than four decades. Equipped with new ab initio techniques introduced in this work, we generate an improved version of the treasure map for phase-change materials (PCMs) as introduced previously by Lencer et al. which, other than before, charts all industrially used PCMs correctly. Furthermore, we suggest seven new PCM candidates, namely SiSb 4 Te 7 , Si 2 Sb 2 Te 5 , SiAs 2 Te 4 , PbAs 2 Te 4 , SiSb 2 Te 4 , Sn 2 As 2 Te 5 , and PbAs 4 Te 7 , to be used as synthetic targets. To realize aforementioned maps based on orbital mixing (or "hybridization") and ionicity coordinates, structural information was first included into an ab initio numerical descriptor for sp 3 orbital mixing and then generalized beyond high-symmetry structures. In addition, a simple, yet powerful quantum-mechanical ionization measure also including structural information was introduced. Taken together, these tools allow for (automatically) generating materials maps solely relying on first-principles calculations. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Fluorine in the UK environment.

PubMed

Fuge, R; Andrews, M J

1988-12-01

Relatively low concentrations of fluorine in drinking water (≤ 1 mg F/l) have been shown to significantly reduce the degree of dental caries in children and fluorine would also appear to have a beneficial effect on bone formation in both humans and farm animals. However, it is apparent that elevated levels of fluorine in the diet have sometimes resulted in problems of increased dental caries and of the development of bone deformities. Much of the fluorine in rocks and soils occurs in apatite and hydroxysilicate minerals, fluorite being the only relatively common rock forming mineral containing fluorine as an essential constituent.Little systematic data are available on fluorine concentrations in soils, plants and natural waters in the UK. General background soil concentrations lie in the range 200 - 400 mg F/kg. For waters the average fluorine content is low, <0.1 mg F/l.In the British Isles there are several areas where there are enhanced levels of fluorine. In the northern Pennines, Derbyshire, northeast Wales and Cornwall, fluorite occurs as a significant component of mineralisation and much fluorine has been added to the environment from mining waste dumps. Soils in northeast Wales contain up to 3,650 mg F/kg and in the northern Pennines up to 20,000 mg F/kg. Waters contain up to 2.3 mg F/l. In southwest England, the granites are generally fluorine-rich with the fluorite granites of the St Austell pluton containing as much as 1 percent fluorine. These rocks are frequently kaolinised and intensively worked as a source of china clay. Soils in the vicinity of the waste tips contain up to 3,300 mg F/kg and grasses up to 2,950 mg F/kg. Surface waters in the St Austell area contain up to 1.25 mg F/l.Atmospheric fluorine pollution around brickworks in the Peterborough and Bedford areas has resulted in fluorosis in farm animals. Other sources of atmospheric fluorine pollution are aluminium smelters, steelworks and fossil fuel burning.

Rare Mineralogy in Alkaline Ultramafic Rocks, Western Kentucky Fluorspar District

NASA Astrophysics Data System (ADS)

Anderson, W.

2017-12-01

The alkaline ultramafic intrusive dike complex in the Western Kentucky Fluorspar District contains unusual mineralogy that was derived from mantle magma sources. Lamprophyre and peridotite petrologic types occur in the district where altered fractionated peridotites are enriched in Rare Earth Elements (REE) and some lamprophyre facies are depleted in incompatible elements. Unusual minerals in dikes, determined by petrography and X-ray diffraction, include schorlomite and andradite titanium garnets, astrophyllite, spodumene, niobium rutile, wüstite, fluoro-tetraferriphlogopite, villiaumite, molybdenite, and fluocerite, a REE-bearing fluoride fluorescent mineral. Mixing of MVT sphalerite ore fluids accompanies a mid-stage igneous alteration and intrusion event consistent with paragenetic studies. The presence of lithium in the spodumene and fluoro-tetraferriphlogopite suggests a lithium phase in the mineral fluids, and the presence of enriched REE in dikes and fluorite mineralization suggest a metasomatic event. Several of these rare minerals have never been described in the fluorspar district, and their occurrence suggests deep mantle metasomatism. Several REE-bearing fluoride minerals occur in the dikes and in other worldwide occurrences, they are usually associated with nepheline syenite and carbonatite differentiates. There is an early and late stage fluoride mineralization, which accompanied dike intrusion and was also analyzed for REE content. One fluorite group is enriched in LREE and another in MREE, which suggests a bimodal or periodic fluorite emplacement. Whole-rock elemental analysis was chondrite normalized and indicates that some of the dikes are slightly enriched in light REE and show a classic fractionation enrichment. Variations in major-element content; high titanium, niobium, and zirconium values; and high La/Yb, Zr/Y, Zr/Hf, and Nb/Ta ratios suggest metasomatized lithospheric-asthenospheric mantle-sourced intrusions. The high La/Yb ratios in some dikes in the titanium garnet facies suggest a magma melt trend toward the carbonation phase of a fractionated peridotite parent magma.

Solute segregation and deviation from bulk thermodynamics at nanoscale crystalline defects.

PubMed

Titus, Michael S; Rhein, Robert K; Wells, Peter B; Dodge, Philip C; Viswanathan, Gopal Babu; Mills, Michael J; Van der Ven, Anton; Pollock, Tresa M

2016-12-01

It has long been known that solute segregation at crystalline defects can have profound effects on material properties. Nevertheless, quantifying the extent of solute segregation at nanoscale defects has proven challenging due to experimental limitations. A combined experimental and first-principles approach has been used to study solute segregation at extended intermetallic phases ranging from 4 to 35 atomic layers in thickness. Chemical mapping by both atom probe tomography and high-resolution scanning transmission electron microscopy demonstrates a markedly different composition for the 4-atomic-layer-thick phase, where segregation has occurred, compared to the approximately 35-atomic-layer-thick bulk phase of the same crystal structure. First-principles predictions of bulk free energies in conjunction with direct atomistic simulations of the intermetallic structure and chemistry demonstrate the breakdown of bulk thermodynamics at nanometer dimensions and highlight the importance of symmetry breaking due to the proximity of interfaces in determining equilibrium properties.

First principles investigation of the unipolar resistive switching mechanism in an interfacial phase change memory based on a GeTe/Sb2Te3 superlattice

NASA Astrophysics Data System (ADS)

Shirakawa, Hiroki; Araidai, Masaaki; Shiraishi, Kenji

2018-04-01

The interfacial phase change memory (iPCM) based on a GeTe/Sb2Te3 superlattice is one of the candidates for future storage class memories. However, the atomic structures of the high and low resistance states (HRS/LRS) remain unclear and the resistive switching mechanism is still under debate. Clarifying the switching mechanism is essential for developing further high-reliability and low-power-consumption iPCM. We propose, on the basis of the results of first-principles molecular dynamics simulations, a mechanism for resistive switching, and describe the atomic structures of the high and low resistance states of iPCM for unipolar switching. Our simulations indicated that switching from HRS to LRS occurs with Joule heating only, while that from LRS to HRS occurs with both hole injection and Joule heating.

Theoretical Prediction of an Antimony-Silicon Monolayer (penta-Sb2Si): Band Gap Engineering by Strain Effect

NASA Astrophysics Data System (ADS)

Morshedi, Hosein; Naseri, Mosayeb; Hantehzadeh, Mohammad Reza; Elahi, Seyed Mohammad

2018-04-01

In this paper, using a first principles calculation, a two-dimensional structure of silicon-antimony named penta-Sb2Si is predicted. The structural, kinetic, and thermal stabilities of the predicted monolayer are confirmed by the cohesive energy calculation, phonon dispersion analysis, and first principles molecular dynamic simulation, respectively. The electronic properties investigation shows that the pentagonal Sb2Si monolayer is a semiconductor with an indirect band gap of about 1.53 eV (2.1 eV) from GGA-PBE (PBE0 hybrid functional) calculations which can be effectively engineered by employing external biaxial compressive and tensile strain. Furthermore, the optical characteristics calculation indicates that the predicted monolayer has considerable optical absorption and reflectivity in the ultraviolet region. The results suggest that a Sb2Si monolayer has very good potential applications in new nano-optoelectronic devices.

The electronic, structural and magnetic properties of Heusler compounds ZrCrCoZ(Z=B, Al, Ga, In): A first-principles study

NASA Astrophysics Data System (ADS)

Guo, R. K.; Liu, G. D.; Lin, T. T.; Wang, W.; Wang, L. Y.; Dai, X. F.

2018-02-01

It is predicted that the ZrCrCoZ(Z=B, Al, Ga, In) compounds with LiMnPbSn-type structure are half-metallic ferrimagnets with a large half-metallic gap by the first-principles calculations. The half-metallicity of the ZrCrCoZ(Z=B, Al, Ga, In) compounds are quite robust to the axial and uniaxial strain. The total magnetic moments in per unit cell are 4 μB for the ZrCrCoZ(Z=B, Al, Ga, In) compounds and follow the Slater-Pauling rule, which can be attributed to the great spin-splitting. The calculated formation energies are negative for all the ZrCrCoZ(Z=B, Al, Ga, In) compounds, which indicates that those compounds are in the thermodynamic stability and the possibility of synthesis in experiment.

Solute segregation and deviation from bulk thermodynamics at nanoscale crystalline defects

PubMed Central

Titus, Michael S.; Rhein, Robert K.; Wells, Peter B.; Dodge, Philip C.; Viswanathan, Gopal Babu; Mills, Michael J.; Van der Ven, Anton; Pollock, Tresa M.

2016-01-01

It has long been known that solute segregation at crystalline defects can have profound effects on material properties. Nevertheless, quantifying the extent of solute segregation at nanoscale defects has proven challenging due to experimental limitations. A combined experimental and first-principles approach has been used to study solute segregation at extended intermetallic phases ranging from 4 to 35 atomic layers in thickness. Chemical mapping by both atom probe tomography and high-resolution scanning transmission electron microscopy demonstrates a markedly different composition for the 4–atomic-layer–thick phase, where segregation has occurred, compared to the approximately 35–atomic-layer–thick bulk phase of the same crystal structure. First-principles predictions of bulk free energies in conjunction with direct atomistic simulations of the intermetallic structure and chemistry demonstrate the breakdown of bulk thermodynamics at nanometer dimensions and highlight the importance of symmetry breaking due to the proximity of interfaces in determining equilibrium properties. PMID:28028543

First-principles calculations of the thermodynamic properties of transuranium elements in a molten salt medium

NASA Astrophysics Data System (ADS)

Noh, Seunghyo; Kwak, Dohyun; Lee, Juseung; Kang, Joonhee; Han, Byungchan

2014-03-01

We utilized first-principles density-functional-theory (DFT) calculations to evaluate the thermodynamic feasibility of a pyroprocessing methodology for reducing the volume of high-level radioactive materials and recycling spent nuclear fuels. The thermodynamic properties of transuranium elements (Pu, Np and Cm) were obtained in electrochemical equilibrium with a LiCl-KCl molten salt as ionic phases and as adsorbates on a W(110) surface. To accomplish the goal, we rigorously calculated the double layer interface structures on an atomic resolution, on the thermodynamically most stable configurations on W(110) surfaces and the chemical activities of the transuranium elements for various coverages of those elements. Our results indicated that the electrodeposition process was very sensitive to the atomic level structures of Cl ions at the double-layer interface. Our studies are easily expandable to general electrochemical applications involving strong redox reactions of transition metals in non-aqueous solutions.

First-principles simulation on thermoelectric propertiesof transition metal dichalcogenide monolayers

NASA Astrophysics Data System (ADS)

Nakamura, Koichi

2018-06-01

Thermoelectric properties of transition metal dichalcogenide (TMDC) monolayer models, such as Seebeck coefficient and lattice heat capacity, were simulated on the basis of first-principles calculations. The calculated Seebeck coefficients are appropriate for the thermoelectric element of all the TMDC monolayer models introduced in this study. In the MoX2/WX2 (X = S, Se, and Te) heterojunction structure, carrier electrons and holes are respectively distributed in the MoX2 and WX2 regions by adopting a common Fermi energy for both electronic structures. In particular, in the X = Te case, the practical carrier concentration with a large Seebeck coefficient can be evaluated without doping. The lattice heat capacities and their temperature dependence tendencies can be classified on the basis of the minimum frequencies of the optical modes. The quotient of the lattice thermal conductivity over the phonon relaxation time gives the temperature-independent specific values according to the kind of TMDC monolayer.

Interplay of oxygen octahedral rotations and electronic instabilities in strontium ruthenate Ruddlesden-Poppers from first principles

NASA Astrophysics Data System (ADS)

Voss, Johannes; Fennie, Craig J.

2011-03-01

The Ruddlesden-Popper ruthenates Sr n+1 Ru n O3 n + 1 display a broad range of electronic phases including p -wave superconductivity, electronic nematicity, and ferromagnetism. Elucidating the role of the number of perovskite blocks, n , in the realization of these differently ordered electronic states remains a challenge. Additionally dramatic experimental advances now enable the atomic scale growth of these complex oxide thin films on a variety of substrates coherently, allowing for the application of tunable epitaxial strain and subsequently the ability to control structural distortions such as oxygen octahedral rotations. Here we investigate from first principles the effect of oxygen octahedral rotations on the electronic structure of Sr 2 Ru O4 and Sr 3 Ru 2 O7 . We discuss possible implications for the physics of the bulk systems and point towards new effects in thin films.

Ultrafast optically induced ferromagnetic/anti-ferromagnetic phase transition in GdTiO3 from first principles

NASA Astrophysics Data System (ADS)

Khalsa, Guru; Benedek, Nicole A.

2018-03-01

Epitaxial strain and chemical substitution have been the workhorses of functional materials design. These static techniques have shown immense success in controlling properties in complex oxides through the tuning of subtle structural distortions. Recently, an approach based on the excitation of an infrared active phonon with intense midinfrared light has created an opportunity for dynamical control of structure through special nonlinear coupling to Raman phonons. We use first-principles techniques to show that this approach can dynamically induce a magnetic phase transition from the ferromagnetic ground state to a hidden antiferromagnetic phase in the rare earth titanate GdTiO3 for realistic experimental parameters. We show that a combination of a Jahn-Teller distortion, Gd displacement, and infrared phonon motion dominate this phase transition with little effect from the octahedral rotations, contrary to conventional wisdom.

Reflector automatic acquisition and pointing based on auto-collimation theodolite.

PubMed

Luo, Jun; Wang, Zhiqian; Wen, Zhuoman; Li, Mingzhu; Liu, Shaojin; Shen, Chengwu

2018-01-01

An auto-collimation theodolite (ACT) for reflector automatic acquisition and pointing is designed based on the principle of autocollimators and theodolites. First, the principle of auto-collimation and theodolites is reviewed, and then the coaxial ACT structure is developed. Subsequently, the acquisition and pointing strategies for reflector measurements are presented, which first quickly acquires the target over a wide range and then points the laser spot to the charge coupled device zero position. Finally, experiments are conducted to verify the acquisition and pointing performance, including the calibration of the ACT, the comparison of the acquisition mode and pointing mode, and the accuracy measurement in horizontal and vertical directions. In both directions, a measurement accuracy of ±3″ is achieved. The presented ACT is suitable for automatic pointing and monitoring the reflector over a small scanning area and can be used in a wide range of applications such as bridge structure monitoring and cooperative target aiming.

First-Principle Characterization for Singlet Fission Couplings.

PubMed

Yang, Chou-Hsun; Hsu, Chao-Ping

2015-05-21

The electronic coupling for singlet fission, an important parameter for determining the rate, has been found to be too small unless charge-transfer (CT) components were introduced in the diabatic states, mostly through perturbation or a model Hamiltonian. In the present work, the fragment spin difference (FSD) scheme was generalized to calculate the singlet fission coupling. The largest coupling strength obtained was 14.8 meV for two pentacenes in a crystal structure, or 33.7 meV for a transition-state structure, which yielded a singlet fission lifetime of 239 or 37 fs, generally consistent with experimental results (80 fs). Test results with other polyacene molecules are similar. We found that the charge on one fragment in the S1 diabatic state correlates well with FSD coupling, indicating the importance of the CT component. The FSD approach is a useful first-principle method for singlet fission coupling, without the need to include the CT component explicitly.

Optical properties of group-3 metal hexaboride nanoparticles by first-principles calculations

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

Yoshio, Satoshi; Maki, Koichiro; Adachi, Kenji, E-mail: kenji-adachi@ni.smm.co.jp

2016-06-21

LaB{sub 6} nanoparticles are widely used as solar control materials for strong near-infrared absorption and high visible transparency. In order to elucidate the origin of this unique optical property, first-principles calculations have been made for the energy-band structure and dielectric functions of R{sup III}B{sub 6} (R{sup III} = Sc, Y, La, Ac). On account of the precise assessment of the energy eigenvalues of vacant states in conduction band by employing the screened exchange method, as well as to the incorporation of the Drude term, dielectric functions and various physical properties of LaB{sub 6} have been reproduced in excellent agreement withmore » experimental values. Systematic examinations of dielectric functions and electronic structures of the trivalent metal hexaborides have clarified the origin of the visible transparency and the near-infrared plasmon absorption of R{sup III}B{sub 6} nanoparticles.« less

First-principles study of nitrogen-doped CuAlO2

NASA Astrophysics Data System (ADS)

Xu, Ying; Ao, Zhi Min; Yuan, Ding Wang

2012-08-01

The electronic structure and formation energies of N-doped CuAlO2 are studied using first-principles calculations. It is found that, when a N atom is doped into CuAlO2, the N atom prefers to substitute an O atom rather than to occupy an interstitial site of the Cu layer. The NO acts as a shallow accepter while the Ni acts as a deep accepter. The results of the electronic structure show that the N-doping doesn't alter the band gap of CuAlO2 for the both cases. In the substitutional case, the N impurity states occur at the top of valance band maximum (VBM), which provides holes and increases the p-type conductivity. However, in the interstitial case, the N impurity states occur in the middle of the band gap, which are more localized and this indicates that it is not good for p-type conductivity.

First-principles study of electronic properties of Si doped FeSe{sub 0.9} alloys

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

Kumar, Sandeep, E-mail: sandeep@phy.iitb.ac.in; Singh, Prabhakar P.

2016-05-23

We have performed first-principles study of electronic and superconducting properties of FeSe{sub 0.9-x}Si{sub x} (x = 0.0, 0.05) alloys using Korringa-Kohn-Rostoker Atomic Sphere Approximation within the coherent potential approximation (KKR-ASA-CPA). In our calculations, we used the local density approximation (LDA) for the exchange correlation potential. Our calculations show that these alloys are nonmagnetic in nature. We found that the substitution of Si at Se site into FeSe{sub 0.9} made subtle affects in the electronic structure with respect to the parent FeSe. The results have been analyzed in terms of changes in the density of states (DOS), band structures, Fermi surfacesmore » and the superconducting transition temperature of FeSe{sub 0.9} and FeSe{sub 0.85}Si{sub 0.05} alloys.« less

First-principles investigation on the mechanism of photocatalytic properties for cubic and orthorhombic KNbO3

NASA Astrophysics Data System (ADS)

Xu, Yong-Qiang; Wu, Shao-Yi; Ding, Chang-Chun; Wu, Li-Na; Zhang, Gao-Jun

2018-03-01

The geometric structures, band structures, density of states and optical absorption spectra are studied for cubic and orthorhombic KNbO3 (C- and O-KNO) crystals by using first-principles calculations. Based on the above calculation results, the mechanisms of photocatalytic properties for both crystals are further theoretically investigated to deepen the understandings of their photocatalytic activity from the electronic level. Calculations for the effective masses of electron and hole are carried out to make comparison in photocatalytic performance between cubic and orthorhombic phases. Optical absorption in cubic phase is found to be stronger than that in orthorhombic phase. C-KNO has smaller electron effective mass, higher mobility of photogenerated electrons, lower electron-hole recombination rate and better light absorption capacity than O-KNO. So, the photocatalytic activity of cubic phase can be higher than orthorhombic one. The present work may be beneficial to explore the series of perovskite photocatalysts.

Landau free energy for a bcc-hcp reconstructive phase transformation

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

Sanati, Mahdi; Saxena, A.; Lookman, T.

We study the bcc-hcp phase transition in Ti and Zr with the use of first-principles calculations. We have determined the complete energy surface from the bcc to hcp structure. The results are used to find an appropriate Landau free energy density for describing this transformation. The proposed Landau free energy density has two relevant order parameters: shear and shuffle. Through first-principles calculations, we show that the bcc structure is unstable with respect to the shuffle of atoms (TA{sub 1} N-point phonon) rather than the shear. Therefore, we reduce the two order parameter Landau free energy to an effective one ordermore » parameter (shuffle) potential, which is a reasonable approximation. In general, the effective Landau free energy is a triple-well potential. From the phonon dispersion data and the change in entropy at the transition temperature we find the free energy coefficients for Ti and Zr.« less

Topological reaction coordinates to explore the structure of atomic clusters and organic molecule isomers from first principles

NASA Astrophysics Data System (ADS)

Pietrucci, Fabio; Andreoni, Wanda

2011-03-01

We introduce a simple reaction coordinate based on spectral graph theory which describes the topology of the network of chemical bonds around a given atom. We employ the reaction coordinate in combination with DFT-based first-principles metadynamics to systematically explore the possible structures of silicon and carbon clusters (including fullerene-like cages) for sizes of tens of atoms. From our extensive exploration we are able to estimate the fractal dimension of the configuration space, which both for silicon and carbon clusters turns out to be quite low. Using the same approach we simulate the interconversion among a large number of chemically relevant organic molecules which are isomers of the C4 H5 N formula unit, and we demonstrate the possibility of automatically exploring isomerisation, association, and decomposition reactions without prior knowledge of the products involved.

The effects of alloying elements Al and In on Ni-Mn-Ga shape memory alloys, from first principles.

PubMed

Chen, Jie; Li, Yan; Shang, Jia-Xiang; Xu, Hui-Bin

2009-01-28

The electronic structures and formation energies of the Ni(9)Mn(4)Ga(3-x)Al(x) and Ni(9)Mn(4)Ga(3-x)In(x) alloys have been investigated using the first-principles pseudopotential plane-wave method based on density functional theory. The results show that both the austenite and martensite phases of Ni(9)Mn(4)Ga(3) alloy are stabilized by Al alloying, while they become unstable with In alloying. According to the partial density of states and structural energy analysis, different effects of Al and In alloying on the phase stability are mainly attributed to their chemical effects. The formation energy difference between the austenite and martensite phases decreases with Al or In alloying, correlating with the experimentally reported changes in martensitic transformation temperature. The shape factor plays an important role in the decrease of the formation energy difference.

Electronic structure and equation of state of Sm2Co17 from first-principles DFT+ U

NASA Astrophysics Data System (ADS)

Huang, Patrick; Butch, Nicholas P.; Jeffries, Jason R.; McCall, Scott K.

2013-03-01

Rare-earth intermetallics have important applications as permanent magnet materials, and the rational optimization of their properties would benefit greatly from guidance from ab initio modeling. However, these systems are particularly challenging for current electronic structure methods. Here, we present an ab initio study of the prototype material Sm2Co17 and related compounds, using density functional theory with a Hubbard correction for the Sm 4 f-electrons (DFT+ U method) and ultrasoft pseudopotentials. The Hubbard U parameter is derived from first principles [Cococcioni and de Gironcoli, PRB 71, 035105 (2005)], not fit to experiment. Our calculations are in good agreement with recent photoemission measurements at ambient pressure and the equation of state up to 40 GPa, thus supporting the validity of our DFT+ U model. Prepared by LLNL under Contract DE-AC52-07NA27344.

Reflector automatic acquisition and pointing based on auto-collimation theodolite

NASA Astrophysics Data System (ADS)

Luo, Jun; Wang, Zhiqian; Wen, Zhuoman; Li, Mingzhu; Liu, Shaojin; Shen, Chengwu

2018-01-01

An auto-collimation theodolite (ACT) for reflector automatic acquisition and pointing is designed based on the principle of autocollimators and theodolites. First, the principle of auto-collimation and theodolites is reviewed, and then the coaxial ACT structure is developed. Subsequently, the acquisition and pointing strategies for reflector measurements are presented, which first quickly acquires the target over a wide range and then points the laser spot to the charge coupled device zero position. Finally, experiments are conducted to verify the acquisition and pointing performance, including the calibration of the ACT, the comparison of the acquisition mode and pointing mode, and the accuracy measurement in horizontal and vertical directions. In both directions, a measurement accuracy of ±3″ is achieved. The presented ACT is suitable for automatic pointing and monitoring the reflector over a small scanning area and can be used in a wide range of applications such as bridge structure monitoring and cooperative target aiming.

Quantum interference on electron scattering in graphene by carbon impurities in underlying h -BN

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Koshino, Mikito; Saito, Riichiro

2017-03-01

Electronic structures and transport properties of graphene on h -BN with carbon impurities are investigated by first-principles calculation and the tight-binding model. We show that the coupling between the impurity level and the graphene's Dirac cone sensitively depends on the impurity position, and in particular, it nearly vanishes when the impurity is located right below the center of the six membered ring of graphene. The Bloch phase factor at the Brillouin zone edge plays a decisive role in the cancellation of the hopping integrals. The impurity position dependence on the electronic structures of graphene on h -BN is investigated by the first-principles calculation, and its qualitative feature is well explained by a tight-binding model with graphene and a single impurity site. We also propose a simple one-dimensional chain-impurity model to analytically describe the role of the quantum interference in the position-dependent coupling.

First-principles study of direct and narrow band gap semiconducting β -CuGaO 2

DOE PAGES

Nguyen, Manh Cuong; Zhao, Xin; Wang, Cai-Zhuang; ...

2015-04-16

Semiconducting oxides have attracted much attention due to their great stability in air or water and the abundance of oxygen. Recent success in synthesizing a metastable phase of CuGaO 2 with direct narrow band gap opens up new applications of semiconducting oxides as absorber layer for photovoltaics. Using first-principles density functional theory calculations, we investigate the thermodynamic and mechanical stabilities as well as the structural and electronic properties of the β-CuGaO 2 phase. Our calculations show that the β-CuGaO 2 structure is dynamically and mechanically stable. The energy band gap is confirmed to be direct at the Γ point ofmore » Brillouin zone. In conclusion, the optical absorption occurs right at the band gap edge and the density of states near the valance band maximum is large, inducing an intense absorption of light as observed in experiment.« less

First-principles investigations on structural, elastic, electronic properties and Debye temperature of orthorhombic Ni3Ta under pressure

NASA Astrophysics Data System (ADS)

Li, Pan; Zhang, Jianxin; Ma, Shiyu; Jin, Huixin; Zhang, Youjian; Zhang, Wenyang

2018-06-01

The structural, elastic, electronic properties and Debye temperature of Ni3Ta under different pressures are investigated using the first-principles method based on density functional theory. Our calculated equilibrium lattice parameters at 0 GPa well agree with the experimental and previous theoretical results. The calculated negative formation enthalpies and elastic constants both indicate that Ni3Ta is stable under different pressures. The bulk modulus B, shear modulus G, Young's modulus E and Poisson's ratio ν are calculated by the Voigt-Reuss-Hill method. The bigger ratio of B/G indicates Ni3Ta is ductile and the pressure can improve the ductility of Ni3Ta. In addition, the results of density of states and the charge density difference show that the stability of Ni3Ta is improved by the increasing pressure. The Debye temperature ΘD calculated from elastic modulus increases along with the pressure.

First principles study of pressure induced polymorphic phase transition in trimethylamine

NASA Astrophysics Data System (ADS)

Abraham, B. Moses; Vaitheeswaran, G.

2018-04-01

The pressure induced variations on the crystal structure of various polymorphs of Trimethyamine (TMA-I, TMA-II, TMAIII) has been studied theoretically using first principles calculations up to 5 GPa. The obtained equilibrium lattice parameters using standard PBE-GGA functional for the ambient and high pressure phases are found to be in good agreement with the experimental values. We calculated the enthalpies of each phase to assess their relative stability. Our results also supports the existence of additional phase transitions of TMA into two new polymorphs under external pressure. The TMA-I to TMA-II transition is found to occur at 1.41 GPa and the TMA-II to TMA-III transition at 3.33 GPa. The electronic band structure calculations using Tran Blaha-modified Becke Johnson (TB-mBJ) potential show that these polymorphs of TMA are indirect band gap insulators.

The Distribution of Heat-Producing Radioactive Elements in the Deep Earth

NASA Astrophysics Data System (ADS)

Chidester, Bethany A.

The Earth is a heat engine, where large differences in temperature between the interior and the surface drive large-scale movement that manifests as plate tectonics and the geomagnetic field that protects us from the Sun's harmful charged particles. Decay of the long-lived radioactive elements U, Th, and K is expected to contribute as much as 45% of the current heat production in the Earth, and that heat production was five times higher early in Earth's history. It is unclear how this heat source affects the thermal and dynamic evolution of the Earth's core and mantle and how that contribution has changed over geologic time. This dissertation addresses this problem in several different ways. This work represents the first high-pressure, high-temperature metal-silicate partitioning experiments for U, Th, and K in the laser-heated diamond anvil cell at conditions relevant to core formation. A chemical model is developed using parameterization of these partitioning data to constrain the concentrations of each of these elements in the core. Using a numerical calculation, it is then determined how that radioactive heat would contribute to the core's energy and entropy budget through time. One finds that, despite its strong lithophile nature at the surface, U partitions significantly into the metallic phase at increasing temperatures. This may be due to a decrease in U valence from 4+ to 2+ in high-pressure silicate melts, which our data supports. However, K and Th do not exhibit a similar change in behavior at these conditions, and this may drive fractionation between U and Th in the deep mantle. At the most extreme conditions of core formation, enough U could exist in the core to produce up to 4.4 TW of heat 4.5 billion years ago. Potassium could produce much less heat than U early on (< 1 TW), and due to its short half-life, would have decayed away much faster. While this energy source is significantly greater than was previously thought to be possible, it is likely not enough to explain the presence of the geomagnetic field early in Earth's history. I have also completed a synchrotron-based study to determine the phase behavior and equations of state of UO2 and ThO2. ThO 2 undergoes a phase transition from the fluorite- type structure (thorianite) that is stable at ambient conditions to the previously identified cotunnite-type structure around 19 GPa and 1500 K. It remains in the cotunnite-type phase up to 60 GPa and 2500 K. UO2 undergoes several solid phase transitions at high pressure. The fluorite-type (uraninite) to cotunnite-type transition occurs around 20 GPa above 1100 K. At around 35 GPa, a new phase emerges; this phase has been indexed to a tetragonal crystal structure. Finally, at 80 GPa and above, UO2 undergoes another phase transition or dissociates into two separate oxides. This understanding of the phase behavior of the simplest actinide-bearing minerals provides insight into the mineralogical hosts for these radioactive elements, as well as other large cations, in the Earth's deep mantle.

Principles of scarce medical resource allocation in natural disaster relief: a simulation approach.

PubMed

Cao, Hui; Huang, Simin

2012-01-01

A variety of triage principles have been proposed. The authors sought to evaluate their effects on how many lives can be saved in a hypothetical disaster. To determine an optimal scarce resource-rationing principle in the emergency response domain, considering the trade-off between lifesaving efficiency and ethical issues. A discrete event simulation model is developed to examine the efficiency of four resource-rationing principles: first come-first served, random, most serious first, and least serious first. Seven combinations of available resources are examined in the simulations to evaluate the performance of the principles under different levels of resource scarcity. The simulation results indicate that the performance of the medical resource allocation principles is related to the level of the resource scarcity. When the level of the scarcity is high, the performances of the four principles differ significantly. The least serious first principle performs best, followed by the random principle; the most serious first principle acts worst. However, when the scarcity is relieved, there are no significant differences among the random, first come-first served, and least serious first principles, yet the most serious first principle still performs worst. Although the least serious first principle exhibits the highest efficiency, it is not ethically flawless. Considering the trade off between the lifesaving efficiency and the ethical issues, random selection is a relatively fair and efficient principle for allocating scarce medical resources in natural disaster responses.

Nanostructured crystals of fluorite phases Sr{sub 1−x}R{sub x}F{sub 2+x} (R Are Rare Earth Elements) and their ordering: 10. Ordering under spontaneous crystallization and annealing of Sr{sub 1−x}R{sub x}F{sub 2+x} Alloys (R = Tb-Lu, Y) with 23.8–36.1 mol % RF{sub 3}

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

Sulyanova, E. A., E-mail: sulyanova@gmail.com; Karimov, D. N.; Sulyanov, S. N.

The products of spontaneous crystallization (at a cooling rate of ∼200 K/min) of Sr{sub 1−x}R{sub x}F{sub 2+x} melts in the homogeneity range of the fluorite phase have been investigated. Thirty-two irrational compositions with 23.8–36.1 mol % RF{sub 3} and eight rational Sr{sub 2}RF{sub 7} compositions are obtained. With respect to the RF{sub 3} content, these compositions form five groups: (1) Sr{sub 0.762}R{sub 0.238}F{sub 2.238} (23.8% RF{sub 3}), (2) Sr{sub 0.744}R{sub 0.256}F{sub 2.256} (25.6%), (3) Sr{sub 0.718}R{sub 0.282}F{sub 2.282} (28.2%), (4) Sr{sub 2}RF{sub 7} (33.3%), and (5) Sr{sub 0.639}R{sub 0.361}F{sub 2.361} (36.1%). R = Tb-Lu, Y for all groups. Quenching meltsmore » of group 5 with R = Tb, Dy, and Ho leads to the formation of ordered phases with the trigonal distortion of the rhβ-Na{sub 7}Zr{sub 6}F{sub 31} type, while for melts of group 5 with R = Lu, quenching yields a phase of the trigonal rhα′-Sr{sub 4}Lu{sub 3}F{sub 17} type. In group 5 with R = Y, Er, Tm, or Yb and in groups 1–4 with all REEs, fluorite phases are formed. Annealing at 900 ± 20°C for 96 h with subsequent cooling at a rate of ∼200 K/min expands the variety of ordered phases: a phase with a new r type of orthorhombic distortion is formed in group 1 with R = Lu, in group 2 with R = Tm or Lu, and in group 3 with R = Ho-Lu, Y; a t-Sr{sub 2}RF{sub 7} phase with tetragonal distortion is formed in group 4 with R = Tb-Er, Y; and a phase of trigonal rhα′ type is formed in group 5 with R = Y, Yb, or Lu. A fluorite phase arises in group 1 with R = Tb-Lu, Y as a result of quenching and annealing. The tendency to ordering becomes more pronounced with an increase in the RF{sub 3} content and REE atomic number. The annealing conditions do not provide equilibrium or the completely ordered state of all alloys.« less

Alternative Organisational Structures in Higher and Further Education. Coombe Lodge Working Paper. Information Bank Number 1471.

ERIC Educational Resources Information Center

Ferguson, C. T.

Alternative models of organizational structure are discussed in this paper as they operate in higher and further education in Great Britain. First, the basic principles of the traditional hierarchical model of college organization are presented, and the advantages and disadvantages of this model are highlighted. Next, the paper discusses the…

Program Costing with the CAMPUS Simulation Model. Project PRIME Report, Number 5.

ERIC Educational Resources Information Center

Cordes, David C.

The first section of this report on program costing with the CAMPUS simulation discusses the structuring process of Program Planning and Budgeting (PPB) systems, and emphasizes the ideas, rules, and principles for structuring resource data that have evolved during the 10 years of PPB existence. It also discusses the WICHE-PMS program…

Similar local order in disordered fluorite and aperiodic pyrochlore structures

DOE PAGES

Shamblin, Jacob; Tracy, Cameron; Palomares, Raul; ...

2017-10-01

A major challenge to understanding the response of materials to extreme environments (e.g., nuclear fuels/waste forms and fusion materials) is to unravel the processes by which a material can incorporate atomic-scale disorder, and at the same time, remain crystalline. While it has long been known that all condensed matter, even liquids and glasses, possess short-range order, the relation between fully-ordered, disordered, and aperiodic structures over multiple length scales is not well understood. For example, when defects are introduced (via pressure or irradiation) into materials adopting the pyrochlore structure, these complex oxides either disorder over specific crystallographic sites, remaining crystalline, ormore » become aperiodic. Here we present neutron total scattering results characterizing the irradiation response of two pyrochlores, one that is known to disorder (Er2Sn2O7) and the other to amorphize (Dy2Sn2O7) under ion irradiation. The results demonstrate that in both cases, the local pyrochlore structure is transformed into similar short range configurations that are best fit by the orthorhombic weberite structure, even though the two compositions have distinctly different structures, aperiodic vs. disordered-crystalline, at longer length scales. Thus, a material's resistance to amorphization may not depend primarily on local defect formation energies, but rather on the structure's compatibility with meso-scale modulations of the local order in a way that maintains long-range periodicity.« less

Basic hydraulic principles of open-channel flow

USGS Publications Warehouse

Jobson, Harvey E.; Froehlich, David C.

1988-01-01

The three basic principles of open-channel-flow analysis--the conservation of mass, energy, and momentum--are derived, explained, and applied to solve problems of open-channel flow. These principles are introduced at a level that can be comprehended by a person with an understanding of the principles of physics and mechanics equivalent to that presented in the first college level course of the subject. The reader is assumed to have a working knowledge of algebra and plane geometry as well as some knowledge of calculus. Once the principles have been derived, a number of example applications are presented that illustrate the computation of flow through culverts and bridges, and over structures, such as dams and weirs. Because resistance to flow is a major obstacle to the successful application of the energy principle to open-channel flow, procedures are outlined for the rational selection of flow resistance coefficients. The principle of specific energy is shown to be useful in the prediction of water-surface profiles both in the qualitative and quantitative sense. (USGS)

Synthesis, characterization and antibacterial activity of hybrid chitosan-cerium oxide nanoparticles: As a bionanomaterials.

PubMed

Senthilkumar, R P; Bhuvaneshwari, V; Ranjithkumar, R; Sathiyavimal, S; Malayaman, V; Chandarshekar, B

2017-11-01

The hybrid chitosan cerium oxide nanoparticles were prepared for the first time by green chemistry approach using plant leaf extract. The intense peak observed around 292nm in the UV-vis spectrum indicate the formation of cerium oxide nanoparticles. The XRD pattern revealed that the hybrid chitosan-cerium oxide nanoparticles have a polycrystalline structure with cubic fluorite phase. The FTIR spectrum of prepared samples showed the formation of Ce-O bonds and chitosan main chains COC and CO. The FESEM image of hybrid chitosan cerium oxide nanoparticles revealed that the particles are spherical in shape with grains size varying from 23.12nm to 89.91nm. EDAX analysis confirmed the presence of Ce, O, C and N elements in the prepared sample. TEM images showed that the prepared hybrid chitosan-cerium oxide nanoparticles are predominantly uniform in size and most of the particles are spherical in shape with less agglomeration and the particles size varies from 3.61nm to 24.40nm. The prepared chitosan cerium oxide nanoparticles of 50μL concentration showed good antibacterial properties against test pathogens, which was confirmed by the FESEM analysis. The prepared small particle size facilitate that these hybrid ChiCO 2 NPs could effectively be used in biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Electronic structure of the organic semiconductor copper phthalocyanine: experiment and theory.

PubMed

Aristov, V Yu; Molodtsova, O V; Maslyuk, V V; Vyalikh, D V; Zhilin, V M; Ossipyan, Yu A; Bredow, T; Mertig, I; Knupfer, M

2008-01-21

The electronic structure of the organic semiconductor copper-phthalocyanine (CuPc) has been determined by a combination of conventional and resonant photoemission, near-edge x-ray absorption, as well as by the first-principles calculations. The experimentally obtained electronic valence band structure of CuPc is in very good agreement with the calculated density of states results, allowing the derivation of detailed site specific information.

A minimal model for the structural energetics of VO2

NASA Astrophysics Data System (ADS)

Kim, Chanul; Marianetti, Chris; The Marianetti Group Team

Resolving the structural, magnetic, and electronic structure of VO2 from the first-principles of quantum mechanics is still a forefront problem despite decades of attention. Hybrid functionals have been shown to qualitatively ruin the structural energetics. While density functional theory (DFT) combined with cluster extensions of dynamical mean-field theory (DMFT) have demonstrated promising results in terms of the electronic properties, structural phase stability has not yet been addressed. In order to capture the basic physics of the structural transition, we propose a minimal model of VO2 based on the one dimensional Peierls-Hubbard model and parameterize this based on DFT calculations of VO2. The total energy versus dimerization in the minimal mode is then solved numerically exactly using density matrix renormalization group (DMRG) and compared to the Hartree-Fock solution. We demonstrate that the Hartree-Fock solution exhibits the same pathologies as DFT+U, and spin density functional theory for that matter, while the DMRG solution is consistent with experimental observation. Our results demonstrate the critical role of non-locality in the total energy, and this will need to be accounted for to obtain a complete description of VO2 from first-principles. The authors acknowledge support from FAME, one of six centers of STARnet, a Semiconductor Research Corporation program sponsored by MARCO and DARPA.

First-principles study on structure stabilities of α-S and Na-S battery systems

NASA Astrophysics Data System (ADS)

Momida, Hiroyoshi; Oguchi, Tamio

2014-03-01

To understand microscopic mechanisms of charge and discharge reactions in Na-S batteries, there has been increasing needs to study fundamental atomic and electronic structures of elemental S as well as that of Na-S phases. The most stable form of S is known to be an orthorhombic α-S crystal at ambient temperature and pressure, and α-S consists of puckered S8 rings which crystallize in space group Fddd . In this study, the crystal structure of α-S is examined by using first-principles calculations with and without the van der Waals interaction corrections of Grimme's method, and results clearly show that the van der Waals interactions between the S8 rings have crucial roles on cohesion of α-S. We also study structure stabilities of Na2S, NaS, NaS2, and Na2S5 phases with reported crystal structures. Using calculated total energies of the crystal structure models, we estimate discharge voltages assuming discharge reactions from 2Na+ xS -->Na2Sx, and discharge reactions in Na/S battery systems are discussed by comparing with experimental results. This work was partially supported by Elements Strategy Initiative for Catalysts and Batteries (ESICB) of Ministry of Education, Culture, Sports, Science, and Technology (MEXT), Japan.