Transition Metal Switchable Mirror

ScienceCinema

None

2017-12-29

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft. More information at: http://windows.lbl.gov/materials/chromogenics/default.htm

Transition Metal Switchable Mirror

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

None

2009-08-21

The switchable-mirrors technology was developed by Tom Richardson and Jonathan Slack of Berkeley Lab's Environmental Energy Technologies Division. By using transition metals rather than the rare earth metals used in the first metal-hydride switchable mirrors, Richardson and Slack were able to lower the cost and simplify the manufacturing process. Energy performance is improved as well, because the new windows can reflect or transmit both visible and infrared light. Besides windows for offices and homes, possible applications include automobile sunroofs, signs and displays, aircraft windows, and spacecraft. More information at: http://windows.lbl.gov/materials/chromogenics/default.htm

A miniature single element effusion cell for the vacuum deposition of transition-metal and rare-earth elements

NASA Astrophysics Data System (ADS)

Harris, V. G.; Koon, N. C.

1997-08-01

A miniature single element effusion cell has been fabricated and tested that allows for the high-vacuum deposition of a variety of transition-metal and rare-earth elements. The cell is designed to operate under high-vacuum conditions, ≈10-9 Torr, with low power demands, <200 W. The virtues of this evaporator are the simplicity of design and ease of fabrication, assembly, maintenance, and operation.

Ternary alkali-metal and transition metal or metalloid acetylides as alkali-metal intercalation electrodes for batteries

DOEpatents

Nemeth, Karoly; Srajer, George; Harkay, Katherine C; Terdik, Joseph Z

2015-02-10

Novel intercalation electrode materials including ternary acetylides of chemical formula: A.sub.nMC.sub.2 where A is alkali or alkaline-earth element; M is transition metal or metalloid element; C.sub.2 is reference to the acetylide ion; n is an integer that is 0, 1, 2, 3 or 4 when A is alkali element and 0, 1, or 2 when A is alkaline-earth element. The alkali elements are Lithium (Li), Sodium (Na), Potassium (K), Rubidium (Rb), Cesium (Cs) and Francium (Fr). The alkaline-earth elements are Berilium (Be), Magnesium (Mg), Calcium (Ca), Strontium (Sr), Barium (Ba), and Radium (Ra). M is a transition metal that is any element in groups 3 through 12 inclusive on the Periodic Table of Elements (elements 21 (Sc) to element 30 (Zn)). In another exemplary embodiment, M is a metalloid element.

Catalysts Based on Earth-Abundant Metals for Visible Light-Driven Water Oxidation Reaction.

PubMed

Lin, Junqi; Han, Qing; Ding, Yong

2018-06-04

Exploration of water oxidation catalyst (WOC) with excellent performance is the key for the overall water splitting reaction, which is a feasible strategy to convert solar energy to chemical energy. Although some compounds composed of noble metals, mainly Ru and Ir, have been reported to catalyze water oxidation with high efficiency, catalysts based on low-cost and earth-abundant transition metals are essential for realizing economical and large-scale light-driven water splitting. Various WOCs containing earth-abundant metals (mainly Mn, Fe, Co, Ni, Cu) have been utilized for visible light-driven water oxidation in recent years. In this Personal Account, we summarize our recent developments in WOCs based on earth-abundant transition metals including polyoxometalates (POMs), metal oxides or bimetal oxides, and metal complexes containing multidentate ligand scaffolds for visible light-driven water oxidation reaction. © 2018 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A liquid-liquid transition can exist in monatomic transition metals with a positive melting slope

PubMed Central

Lee, Byeongchan; Lee, Geun Woo

2016-01-01

Liquid-liquid transitions under high pressure are found in many elemental materials, but the transitions are known to be associated with either sp-valent materials or f-valent rare-earth elements, in which the maximum or a negative slope in the melting line is readily suggestive of the transition. Here we find a liquid-liquid transition with a positive melting slope in transition metal Ti from structural, electronic, and thermodynamic studies using ab-initio molecular dynamics calculations, showing diffusion anomaly, but no density anomaly. The origin of the transition in liquid Ti is a pressure-induced increase of local structures containing very short bonds with directionality in electronic configurations. This behavior appears to be characteristic of the early transition metals. In contrast, the late transition metal liquid Ni does not show the L-L transition with pressure. This result suggests that the possibility of the L-L transition decreases from early to late transition metals as electronic structures of late transition metals barely have a Jahn-Teller effect and bond directionality. Our results generalize that a phase transition in disordered materials is found with any valence band regardless of the sign of the melting slope, but related to the symmetry of electronic structures of constituent elements. PMID:27762334

A Transition to Metallic Hydrogen: Evidence of the Plasma Phase Transition

NASA Astrophysics Data System (ADS)

Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

The insulator-metal transition in hydrogen is one of the most outstanding problems in condensed matter physics. The high-pressure metallic phase is now predicted to be liquid atomic from T =0 K to very high temperatures. We have conducted measurements of optical properties of hot dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K in a diamond anvil cell using pulsed laser heating of the sample. We present evidence in two forms: a plateau in the heating curves (average laser power vs temperature) characteristic of a first-order phase transition with latent heat, and changes in transmittance and reflectance characteristic of a metal for temperatures above the plateau temperature. For thick films the reflectance saturates at ~0.5. The phase line of this transition has a negative slope in agreement with theories of the so-called plasma phase transition. The NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H supported this research.

Transition-Metal Decorated Aluminum Nanocrystals.

PubMed

Swearer, Dayne F; Leary, Rowan K; Newell, Ryan; Yazdi, Sadegh; Robatjazi, Hossein; Zhang, Yue; Renard, David; Nordlander, Peter; Midgley, Paul A; Halas, Naomi J; Ringe, Emilie

2017-10-24

Recently, aluminum has been established as an earth-abundant alternative to gold and silver for plasmonic applications. Particularly, aluminum nanocrystals have shown to be promising plasmonic photocatalysts, especially when coupled with catalytic metals or oxides into "antenna-reactor" heterostructures. Here, a simple polyol synthesis is presented as a flexible route to produce aluminum nanocrystals decorated with eight varieties of size-tunable transition-metal nanoparticle islands, many of which have precedence as heterogeneous catalysts. High-resolution and three-dimensional structural analysis using scanning transmission electron microscopy and electron tomography shows that abundant nanoparticle island decoration in the catalytically relevant few-nanometer size range can be achieved, with many islands spaced closely to their neighbors. When coupled with the Al nanocrystal plasmonic antenna, these small decorating islands will experience increased light absorption and strong hot-spot generation. This combination makes transition-metal decorated aluminum nanocrystals a promising material platform to develop plasmonic photocatalysis, surface-enhanced spectroscopies, and quantum plasmonics.

Coercivity of domain wall motion in thin films of amorphous rare earth-transition metal alloys

NASA Technical Reports Server (NTRS)

Mansuripur, M.; Giles, R. C.; Patterson, G.

1991-01-01

Computer simulations of a two dimensional lattice of magnetic dipoles are performed on the Connection Machine. The lattice is a discrete model for thin films of amorphous rare-earth transition metal alloys, which have application as the storage media in erasable optical data storage systems. In these simulations, the dipoles follow the dynamic Landau-Lifshitz-Gilbert equation under the influence of an effective field arising from local anisotropy, near-neighbor exchange, classical dipole-dipole interactions, and an externally applied field. Various sources of coercivity, such as defects and/or inhomogeneities in the lattice, are introduced and the subsequent motion of domain walls in response to external fields is investigated.

The Visibility of Earth Transits

NASA Technical Reports Server (NTRS)

Castellano, Timothy P.; Doyle, Laurance; McIntosh, Dawn; DeVincenzi, Donald (Technical Monitor)

2000-01-01

The recent photometric detection of planetary transits of the solar-like star HD 209458 at a distance of 47 parsecs suggest that transits can reveal the presence of Jupiter-size planetary companions in the solar neighborhood. Recent space-based transit searches have achieved photometric precision within an order of magnitude of that required to detect the much smaller transit signal of an earth-size planet across a solar-size star. Laboratory experiments in the presence of realistic noise sources have shown that CCDs can achieve photometric precision adequate to detect the 9.6 E-5 dimming of the Sun due to a transit of the Earth. Space-based solar irradiance monitoring has shown that the intrinsic variability of the Sun would not preclude such a detection. Transits of the Sun by the Earth would be detectable by observers that reside within a narrow band of sky positions near the ecliptic plane, if the observers possess current Earth epoch levels of technology and astronomical expertise. A catalog of solar-like stars that satisfy the geometric condition for Earth transit visibility are presented.

The Visibility of Earth Transits

NASA Technical Reports Server (NTRS)

Castellano, Tim; DeVincenzi, Donald L. (Technical Monitor)

2000-01-01

The recent detection of planetary transits of the solar-like star HD 209458 at a distance of 47 parsecs suggest that transits can reveal the presence of Jupiter-size planetary companions in the solar neighborhood. Recent space-based transit searches have achieved photometric precision within an order of magnitude of that required to detect the much smaller transit signal of an earth-size planet around a solar-size star. Laboratory experiments in the presence of realistic noise sources have shown that CCDs can achieve photometric precision adequate to detect the 9.6 E-5 dimming, of the Sun due to a transit of the Earth. Space-based solar irradiance monitoring has shown that the intrinsic variability of the Sun would not preclude such a detection. Transits of the Sun by the Earth would be detectable by observers that reside within a narrow band of sky positions near the ecliptic plane, if the observers possess current Earth epoch levels of technology and astronomical expertise. A catalog of candidate target stars, their properties, and simulations of the photometric Earth transit signal detectability at each target is presented.

Origin of Transitions between Metallic and Insulating States in Simple Metals

DOE PAGES

Naumov, Ivan I.; Hemley, Russell J.

2015-04-17

Unifying principles that underlie recently discovered transitions between metallic and insulating states in elemental solids under pressure are developed. Using group theory arguments and first principles calculations, we show that the electronic properties of the phases involved in these transitions are controlled by symmetry principles not previously recognized. The valence bands in these systems are described by simple and composite band representations constructed from localized Wannier functions centered on points unoccupied by atoms, and which are not necessarily all symmetrical. The character of the Wannier functions is closely related to the degree of s-p(-d) hybridization and reflects multi-center chemical bondingmore » in these insulating states. The conditions under which an insulating state is allowed for structures having an integer number of atoms per primitive unit cell as well as re-entrant (i.e., metal-insulator-metal) transition sequences are detailed, resulting in predictions of novel behavior such as phases having three-dimensional Dirac-like points. The general principles developed are tested and applied to the alkali and alkaline earth metals, including elements where high-pressure insulating phases have been identified or reported (e.g., Li, Na, and Ca).« less

High pressure phase transitions in the rare earth metal erbium to 151 GPa.

PubMed

Samudrala, Gopi K; Thomas, Sarah A; Montgomery, Jeffrey M; Vohra, Yogesh K

2011-08-10

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence hcp → Sm type → dhcp → distorted fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

High pressure phase transitions in the rare earth metal erbium to 151 GPa

NASA Astrophysics Data System (ADS)

Samudrala, Gopi K.; Thomas, Sarah A.; Montgomery, Jeffrey M.; Vohra, Yogesh K.

2011-08-01

High pressure x-ray diffraction studies have been performed on the heavy rare earth metal erbium (Er) in a diamond anvil cell at room temperature to a pressure of 151 GPa and Er has been compressed to 40% of its initial volume. The rare earth crystal structure sequence {hcp} \\to {Sm}~ {type} \\to {dhcp} \\to {distorted} fcc (hcp: hexagonal close packed; fcc: face centered cubic; dhcp: double hcp) is observed in Er below 58 GPa. We have carried out Rietveld refinement of crystal structures in the pressure range between 58 GPa and 151 GPa. We have examined various crystal structures that have been proposed for the distorted fcc (dfcc) phase and the post-dfcc phase in rare earth metals. We find that the hexagonal hR 24 structure is the best fit between 58 and 118 GPa. Above 118 GPa, a structural transformation from hR 24 phase to a monoclinic C 2/m phase is observed with a volume change of - 1.9%. We have also established a clear trend for the pressure at which a post-dfcc phase is formed in rare earth metals and show that there is a monotonic increase in this pressure with the filling of 4f shell.

Biomass transition metal hydrogen-evolution electrocatalysts and electrodes

DOEpatents

Chen, Wei-Fu; Iyer, Shweta; Iyer, Shilpa; Sasaki, Kotaro; Muckerman, James T.; Fujita, Etsuko

2017-02-28

A catalytic composition from earth-abundant transition metal salts and biomass is disclosed. A calcined catalytic composition formed from soybean powder and ammonium molybdate is specifically exemplified herein. Methods for making the catalytic composition are disclosed as are electrodes for hydrogen evolution reactions comprising the catalytic composition.

Peruvian perovskite Between Transition-metal to PGM/PlatinumGroupMetal Catalytic Fusion

NASA Astrophysics Data System (ADS)

Maksoed, Wh-

2016-11-01

Strongly correlated electronic materials made of simple building blocks, such as a transition-metal ion in an octahedral oxygen cage forming a perovskite structure- Dagotto & Tokura for examples are the high-temperature superconductivity & the CMR/Colossal Magnetoresistance . Helium-4 denotes from LC Case,ScD: "Catalytic Fusion of Deuterium into Helium-4"- 1998 dealt with gaseous D2- "contacted with a supported metallic catalyst at superatmospheric pressure". The catalyst is a platinum-group metal, at about 0.5% - 1% by weight, on activated C. Accompanies Stephen J Geier, 2010 quotes "transition metal complexes", the Energy thus produced is enormous, and because the deuterium is very cheap in the form of heavy water (less than US 1/g), the fuel cost is very low (<<1 %/KwH). "The oceans contain enough deuterium to satisfy the Earth's energy needs for many millions of year" to keep "maria"/Latin name of seas &Deuteronomy to be eternally preserves. Heartfelt Gratitudes to HE. Mr. Prof. Ir. HANDOJO.

Compositional dependence of elastic moduli for transition-metal oxide spinels

NASA Astrophysics Data System (ADS)

Reichmann, H. J.; Jacobsen, S. D.; Boffa Ballaran, T.

2012-12-01

Spinel phases (AB2O4) are common non-silicate oxides in the Earth's crust and upper mantle. A characteristic of this mineral group is the ability to host a wide range of transition metals. Here we summarize the influence of transition metals (Fe, Zn, and Mn) on the pressure dependence of elastic moduli of related spinels (magnetite, gahnite, and franklinite) using GHz-ultrasonic interferometry. Measurements were carried out up to 10 GPa in diamond-anvil cells using hydrostatic pressure media. Transition metals with unfilled 3d orbitals strongly influence the elastic properties of spinels. Franklinite (Zn,Mn)Fe2O4 and magnetite Fe3O4 with transition metals on both A and B cation sites exhibit pressure-induced mode softening of C44, whereas C44 of gahnite(ZnAl2O4) and spinel (MgAl2O4) exhibit positive pressure derivatives of the shear moduli. Spinels with two transition elements tend to undergo phase changes at a lower pressure than those with none or only one transition metal. Along the Mn-Zn solid solution, the variation of moduli with composition is non-linear, and a mid-range franklinite composition studied here shows a minimum in C44 compared with either end-member: MnFe2O 4 or ZnFe2O4. In general, the linear variation of sound velocity with density (Birch's Law) is followed by spinels, however spinels containing only one or no transition metals follow a distinct slope from those containing transition metals on both A and B sites. The Cauchy relation, 0.5(C12 - C44) = P is fulfilled by spinels with only one or no transition metals, suggesting that that Coulomb interactions dominate. Spinels with two transition metals fail to meet the Cauchy relation, indicating strong directional dependence and covalent character of bonding. The bonding character of transition metals is crucial to understanding the elastic behavior of natural and synthetic spinel solid solutions containing transition metals.

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni.

PubMed

Higgs, T D C; Bonetti, S; Ohldag, H; Banerjee, N; Wang, X L; Rosenberg, A J; Cai, Z; Zhao, J H; Moler, K A; Robinson, J W A

2016-07-22

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

DOE PAGES

Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; ...

2016-07-22

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using themore » element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. In conclusion, the results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.« less

Magnetic coupling at rare earth ferromagnet/transition metal ferromagnet interfaces: A comprehensive study of Gd/Ni

NASA Astrophysics Data System (ADS)

Higgs, T. D. C.; Bonetti, S.; Ohldag, H.; Banerjee, N.; Wang, X. L.; Rosenberg, A. J.; Cai, Z.; Zhao, J. H.; Moler, K. A.; Robinson, J. W. A.

2016-07-01

Thin film magnetic heterostructures with competing interfacial coupling and Zeeman energy provide a fertile ground to study phase transition between different equilibrium states as a function of external magnetic field and temperature. A rare-earth (RE)/transition metal (TM) ferromagnetic multilayer is a classic example where the magnetic state is determined by a competition between the Zeeman energy and antiferromagnetic interfacial exchange coupling energy. Technologically, such structures offer the possibility to engineer the macroscopic magnetic response by tuning the microscopic interactions between the layers. We have performed an exhaustive study of nickel/gadolinium as a model system for understanding RE/TM multilayers using the element-specific measurement technique x-ray magnetic circular dichroism, and determined the full magnetic state diagrams as a function of temperature and magnetic layer thickness. We compare our results to a modified Stoner-Wohlfarth-based model and provide evidence of a thickness-dependent transition to a magnetic fan state which is critical in understanding magnetoresistance effects in RE/TM systems. The results provide important insight for spintronics and superconducting spintronics where engineering tunable magnetic inhomogeneity is key for certain applications.

Recovering heavy rare earth metals from magnet scrap

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

Ott, Ryan T.; McCallum, Ralph W.; Jones, Lawrence L.

A method of treating rare earth metal-bearing permanent magnet scrap, waste or other material in a manner to recover the heavy rare earth metal content separately from the light rare earth metal content. The heavy rare earth metal content can be recovered either as a heavy rare earth metal-enriched iron based alloy or as a heavy rare earth metal based alloy.

Metal-insulator transitions

NASA Astrophysics Data System (ADS)

Imada, Masatoshi; Fujimori, Atsushi; Tokura, Yoshinori

1998-10-01

Metal-insulator transitions are accompanied by huge resistivity changes, even over tens of orders of magnitude, and are widely observed in condensed-matter systems. This article presents the observations and current understanding of the metal-insulator transition with a pedagogical introduction to the subject. Especially important are the transitions driven by correlation effects associated with the electron-electron interaction. The insulating phase caused by the correlation effects is categorized as the Mott Insulator. Near the transition point the metallic state shows fluctuations and orderings in the spin, charge, and orbital degrees of freedom. The properties of these metals are frequently quite different from those of ordinary metals, as measured by transport, optical, and magnetic probes. The review first describes theoretical approaches to the unusual metallic states and to the metal-insulator transition. The Fermi-liquid theory treats the correlations that can be adiabatically connected with the noninteracting picture. Strong-coupling models that do not require Fermi-liquid behavior have also been developed. Much work has also been done on the scaling theory of the transition. A central issue for this review is the evaluation of these approaches in simple theoretical systems such as the Hubbard model and t-J models. Another key issue is strong competition among various orderings as in the interplay of spin and orbital fluctuations. Experimentally, the unusual properties of the metallic state near the insulating transition have been most extensively studied in d-electron systems. In particular, there is revived interest in transition-metal oxides, motivated by the epoch-making findings of high-temperature superconductivity in cuprates and colossal magnetoresistance in manganites. The article reviews the rich phenomena of anomalous metallicity, taking as examples Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Ru compounds. The diverse phenomena include strong spin and

Rare Earth Metals: Resourcefulness and Recovery

NASA Astrophysics Data System (ADS)

Wang, Shijie

2013-10-01

When we appreciate the digital revolution carried over from the twentieth century with mobile communication and the Internet, and when we enjoy our high-tech lifestyle filled with iDevices, hybrid cars, wind turbines, and solar cells in this new century, we should also appreciate that all of these advanced products depend on rare earth metals to function. Although there are only 136,000 tons of annual worldwide demand, (Cho, Rare Earth Metals, Will We Have Enough?)1 rare earth metals are becoming such hot commodities on international markets, due to not only to their increasing uses, including in most critical military hardware, but also to Chinese growth, which accounts for 95% of global rare earth metal production. Hence, the 2013 technical calendar topic, planned by the TMS/Hydrometallurgy and Electrometallurgy Committee, is particularly relevant, with four articles (including this commentary) contributed to the JOM October Issue discussing rare earth metals' resourcefulness and recovery.

Role of thermal heating on the voltage induced insulator-metal transition in VO2.

PubMed

Zimmers, A; Aigouy, L; Mortier, M; Sharoni, A; Wang, Siming; West, K G; Ramirez, J G; Schuller, Ivan K

2013-02-01

We show that the main mechanism for the dc voltage or dc current induced insulator-metal transition in vanadium dioxide VO(2) is due to local Joule heating and not a purely electronic effect. This "tour de force" experiment was accomplished by using the fluorescence spectra of rare-earth doped micron sized particles as local temperature sensors. As the insulator-metal transition is induced by a dc voltage or dc current, the local temperature reaches the transition temperature indicating that Joule heating plays a predominant role. This has critical implications for the understanding of the dc voltage or dc current induced insulator-metal transition and has a direct impact on applications which use dc voltage or dc current to externally drive the transition.

Understanding Metal-Insulator transitions in ultra-thin films of LaNiO3

NASA Astrophysics Data System (ADS)

Ravichandran, Jayakanth; King, Philip D. C.; Schlom, Darrell G.; Shen, Kyle M.; Kim, Philip

2014-03-01

LaNiO3 (LNO) is a bulk paramagnetic metal and a member of the family of RENiO3 Nickelates (RE = Rare Earth Metals), which is on the verge of the metal-insulator transition. Ultra-thin films of LNO has been studied extensively in the past and due to its sensitivity to disorder, the true nature of the metal-insulator transition in these films have been hard to decipher. We grow high quality ultra-thin films of LNO using reactive molecular beam epitaxy (MBE) and use a combination of ionic liquid gating and magneto-transport measurements to understand the nature and tunability of metal-insulator transition as a function of thickness for LNO. The underlying mechanisms for the transition are discussed in the framework of standard transport models. These results are discussed in the light of other Mott insulators such as Sr2IrO4, where we have performed similar measurements around the insulating state.

Band gap tuning in transition metal oxides by site-specific substitution

DOEpatents

Lee, Ho Nyung; Chisholm, Jr., Matthew F; Jellison, Jr., Gerald Earle; Singh, David J; Choi, Woo Seok

2013-12-24

A transition metal oxide insulator composition having a tuned band gap includes a transition metal oxide having a perovskite or a perovskite-like crystalline structure. The transition metal oxide includes at least one first element selected form the group of Bi, Ca, Ba, Sr, Li, Na, Mg, K, Pb, and Pr; and at least one second element selected from the group of Ti, Al, V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Nb, Mo, Ru, Rh, Hf, Ta, W, Re, Os, Ir, and Pt. At least one correlated insulator is integrated into the crystalline structure, including REMO.sub.3, wherein RE is at least one Rare Earth element, and wherein M is at least one element selected from the group of Co, V, Cr, Ni, Mn, and Fe. The composition is characterized by a band gap of less of 4.5 eV.

Density functional plus dynamical mean-field theory of the metal-insulator transition in early transition-metal oxides

NASA Astrophysics Data System (ADS)

Dang, Hung T.; Ai, Xinyuan; Millis, Andrew J.; Marianetti, Chris A.

2014-09-01

The combination of density functional theory and single-site dynamical mean-field theory, using both Hartree and full continuous-time quantum Monte Carlo impurity solvers, is used to study the metal-insulator phase diagram of perovskite transition-metal oxides of the form ABO3 with a rare-earth ion A =Sr, La, Y and transition metal B =Ti, V, Cr. The correlated subspace is constructed from atomiclike d orbitals defined using maximally localized Wannier functions derived from the full p-d manifold; for comparison, results obtained using a projector method are also given. Paramagnetic DFT + DMFT computations using full charge self-consistency along with the standard "fully localized limit" (FLL) double counting are shown to incorrectly predict that LaTiO3, YTiO3, LaVO3, and SrMnO3 are metals. A more general examination of the dependence of physical properties on the mean p-d energy splitting, the occupancy of the correlated d states, the double-counting correction, and the lattice structure demonstrates the importance of charge-transfer physics even in the early transition-metal oxides and elucidates the factors underlying the failure of the standard approximations. If the double counting is chosen to produce a p-d splitting consistent with experimental spectra, single-site dynamical mean-field theory provides a reasonable account of the materials properties. The relation of the results to those obtained from "d-only" models in which the correlation problem is based on the frontier orbital p-d antibonding bands is determined. It is found that if an effective interaction U is properly chosen the d-only model provides a good account of the physics of the d1 and d2 materials.

K2-155: A Bright Metal-poor M Dwarf with Three Transiting Super-Earths

NASA Astrophysics Data System (ADS)

Hirano, Teruyuki; Dai, Fei; Livingston, John H.; Fujii, Yuka; Cochran, William D.; Endl, Michael; Gandolfi, Davide; Redfield, Seth; Winn, Joshua N.; Guenther, Eike W.; Prieto-Arranz, Jorge; Albrecht, Simon; Barragan, Oscar; Cabrera, Juan; Cauley, P. Wilson; Csizmadia, Szilard; Deeg, Hans; Eigmüller, Philipp; Erikson, Anders; Fridlund, Malcolm; Fukui, Akihiko; Grziwa, Sascha; Hatzes, Artie P.; Korth, Judith; Narita, Norio; Nespral, David; Niraula, Prajwal; Nowak, Grzegorz; Pätzold, Martin; Palle, Enric; Persson, Carina M.; Rauer, Heike; Ribas, Ignasi; Smith, Alexis M. S.; Van Eylen, Vincent

2018-03-01

We report on the discovery of three transiting super-Earths around K2-155 (EPIC 210897587), a relatively bright early M dwarf (V = 12.81 mag) observed during Campaign 13 of the NASA K2 mission. To characterize the system and validate the planet candidates, we conducted speckle imaging and high-dispersion optical spectroscopy, including radial velocity measurements. Based on the K2 light curve and the spectroscopic characterization of the host star, the planet sizes and orbital periods are {1.55}-0.17+0.20 {R}\\oplus and 6.34365 ± 0.00028 days for the inner planet; {1.95}-0.22+0.27 {R}\\oplus and 13.85402 ± 0.00088 days for the middle planet; and {1.64}-0.17+0.18 {R}\\oplus and 40.6835 ± 0.0031 days for the outer planet. The outer planet (K2-155d) is near the habitable zone, with an insolation 1.67 ± 0.38 times that of the Earth. The planet’s radius falls within the range between that of smaller rocky planets and larger gas-rich planets. To assess the habitability of this planet, we present a series of three-dimensional global climate simulations, assuming that K2-155d is tidally locked and has an Earth-like composition and atmosphere. We find that the planet can maintain a moderate surface temperature if the insolation proves to be smaller than ∼1.5 times that of the Earth. Doppler mass measurements, transit spectroscopy, and other follow-up observations should be rewarding, as K2-155 is one of the optically brightest M dwarfs known to harbor transiting planets.

Production method for making rare earth compounds

DOEpatents

McCallum, R.W.; Ellis, T.W.; Dennis, K.W.; Hofer, R.J.; Branagan, D.J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g., a transition metal and optional boron), and a carbide-forming element (e.g., a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g., Nd{sub 2}Fe{sub 14}B or LaNi{sub 5}) and a carbide of the carbide-forming element are formed.

Production method for making rare earth compounds

DOEpatents

McCallum, R. William; Ellis, Timothy W.; Dennis, Kevin W.; Hofer, Robert J.; Branagan, Daniel J.

1997-11-25

A method of making a rare earth compound, such as a earth-transition metal permanent magnet compound, without the need for producing rare earth metal as a process step, comprises carbothermically reacting a rare earth oxide to form a rare earth carbide and heating the rare earth carbide, a compound-forming reactant (e.g. a transition metal and optional boron), and a carbide-forming element (e.g. a refractory metal) that forms a carbide that is more thermodynamically favorable than the rare earth carbide whereby the rare earth compound (e.g. Nd.sub.2 Fe.sub.14 B or LaNi.sub.5) and a carbide of the carbide-forming element are formed.

First-principles simulations of transition metal ions in silicon as potential quantum bits

NASA Astrophysics Data System (ADS)

Ma, He; Seo, Hosung; Galli, Giulia

Optically active spin defects in semiconductors have gained increasing attention in recent years for use as potential solid-state quantum bits (or qubits). Examples include the nitrogen-vacancy center in diamond, transition metal impurities, and rare earth ions. In this talk, we present first-principles theoretical results on group 6 transition metal ion (Chromium, Molybdenum and Tungsten) impurities in silicon, and we investigate their potential use as qubits. We used density functional theory (DFT) to calculate defect formation energies and we found that transition metal ions have lower formation energies at interstitial than substitutional sites. We also computed the electronic structure of the defects with particular attention to the position of the defect energy levels with respect to the silicon band edges. Based on our results, we will discuss the possibility of implementing qubits in silicon using group 6 transition metal ions. This work is supported by the National Science Foundation (NSF) through the University of Chicago MRSEC under Award Number DMR-1420709.

Heterobimetallic transition metal/rare earth metal bifunctional catalysis: a Cu/Sm/Schiff base complex for syn-selective catalytic asymmetric nitro-Mannich reaction.

PubMed

Handa, Shinya; Gnanadesikan, Vijay; Matsunaga, Shigeki; Shibasaki, Masakatsu

2010-04-07

The full details of a catalytic asymmetric syn-selective nitro-Mannich reaction promoted by heterobimetallic Cu/Sm/dinucleating Schiff base complexes are described, demonstrating the effectiveness of the heterobimetallic transition metal/rare earth metal bifunctional catalysis. The first-generation system prepared from Cu(OAc)(2)/Sm(O-iPr)(3)/Schiff base 1a = 1:1:1 with an achiral phenol additive was partially successful for achieving the syn-selective catalytic asymmetric nitro-Mannich reaction. The substrate scope and limitations of the first-generation system remained problematic. After mechanistic studies on the catalyst prepared from Sm(O-iPr)(3), we reoptimized the catalyst preparation method, and a catalyst derived from Sm(5)O(O-iPr)(13) showed broader substrate generality as well as higher reactivity and stereoselectivity compared to Sm(O-iPr)(3). The optimal system with Sm(5)O(O-iPr)(13) was applicable to various aromatic, heteroaromatic, and isomerizable aliphatic N-Boc imines, giving products in 66-99% ee and syn/anti = >20:1-13:1. Catalytic asymmetric synthesis of nemonapride is also demonstrated using the catalyst derived from Sm(5)O(O-iPr)(13).

Solvo-thermal synthesis of a unique alkaline earth-transition Ba-Cd micro-porous coordination framework as hetero-metallic luminescent sensor for Cu2+ and real-time detection of benzaldehyde

NASA Astrophysics Data System (ADS)

Ding, Bin; Ma, Dian Xue; Zhang, Hui Min; Meng, Xin; Qiu, Rong Rong; Ren, Rong; Wu, Jie; Wu, Xiang Xia; Huo, Jian Zhong; Liu, Yuan Yuan; Shi, Xue Fang

2018-06-01

In this work a unique hetero-metallic alkaline earth-transition Ba-Cd luminescent micro-porous metal-organic framework {[BaCd(μ6-tp)1.5(μ2-Cl)(H2O) (DMF)2]·0.75H2O}n (H2tp = terephthalic acid) (1) has been prepared under solvo-thermal conditions. In 1 infinite 1D {Ba-X-Cd} (X = O, Cl) inorganic chains are linked via these full de-pronated tp2- ligands forming a unique 3D I1O2 type micro-porous coordination framework. PXRD patterns of 1 have been determined confirming pure phases of 1. Luminescence investigations suggested that 1 exhibits highly selective and sensitive sensing for trace amounts of benzaldehyde in ethanol, which provides a facile method for real-time detection of benzaldehyde. Meanwhile 1 also exhibits highly selective and sensitive sensing for Cu2+ over other cations with high quenching efficiency Ksv value 1.15 × 104 L·mol-1. As far as we know, 1 represents the first example of alkaline earth-transition hetero-metallic Ba-Cd micro-porous coordination framework as bi-functional luminescent probes for Cu2+ and benzaldehyde.

Temperate Earth-sized planets transiting a nearby ultracool dwarf star

PubMed Central

Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M.; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam; Triaud, Amaury H. M. J.; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K.; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

2017-01-01

Stellar-like objects with effective temperatures of 2700K and below are referred to as “ultracool dwarfs”1. This heterogeneous group includes both extremely low-mass stars and brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15% of the stellar-like objects in the vicinity of the Sun2. Based on the small masses and sizes of their protoplanetary disks3,4, core-accretion theory for ultracool dwarfs predicts a large, but heretofore undetected population of close-in terrestrial planets5, ranging from metal-rich Mercury-sized planets6 to more hospitable volatile-rich Earth-sized planets7. Here we report the discovery of three short-period Earth-sized planets transiting an ultracool dwarf star 12 parsecs away using data collected by the TRAPPIST8 telescope as part of an ongoing prototype transit survey9. The inner two planets receive four and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star10. Eleven orbits remain possible for the third planet based on our data, the most likely resulting in an irradiation significantly smaller than Earth's. The infrared brightness of the host star combined with its Jupiter-like size offer the possibility of thoroughly characterizing the components of this nearby planetary system. PMID:27135924

Ultrafast Transient Absorption Spectroscopy of Polymer-Based Organophotoredox Catalysts Mimicking Transition-Metal Complexes

NASA Astrophysics Data System (ADS)

Jamhawi, Abdelqader; Paul, Anam C.; Smith, Justin D.; Handa, Sachin; Liu, Jinjun

2017-06-01

Transition-metal complexes of rare earth metals including ruthenium and iridium are most commonly employed as visible-light photocatalysts. Despite their highly important and broad applications, they have many disadvantages including high cost associated with low abundance in earth crust, potential toxicity, requirement of specialized ligands for desired activity, and difficulty in recycling of metal contents as well as associated ligands. Polymer-based organophotoredox catalysts are promising alternatives and possess unique advantages such as easier synthesis from inexpensive starting material, longer excited state life time, broad range of activity, sustainability, and recyclability. In this research talk, time-resolved photoluminescence and femtosecond transient absorption (TA) spectroscopy measurements of three novel polymer-based organophotoredox catalysts will be presented. By our synthetic team, their catalytic activity has been proven in some highly valuable chemical transformations, that otherwise require transition metal complexes. Time-resolved spectroscopic investigations have demonstrated that photoinduced processes in these catalysts are similar to the transition metal complexes. Especially, intramolecular vibrational relaxation, internal conversion, and intersystem crossing from the S1 state to the T1 state all occur on a sub-picosecond timescale. The long lifetime of the T1 state ( 2-3 microsecond) renders these polymers potent oxidizing and reducing agents. A spectroscopic and kinetic model has been developed for global fitting of TA spectra in both the frequency and time domains. Implication of the current ultrafast spectroscopy studies of these novel molecules to their roles in photocatalysis will be discussed.

Light-induced metal-insulator transition in a switchable mirror.

PubMed

Hoekstra, A F; Roy, A S; Rosenbaum, T F; Griessen, R; Wijngaarden, R J; Koeman, N J

2001-06-04

Rare earth hydride films can be converted reversibly from metallic mirrors to insulating windows simply by changing the surrounding hydrogen gas pressure at room temperature. At low temperatures, in situ doping is not possible in this way as hydrogen cannot diffuse. However, our finding of persistent photoconductivity under ultraviolet illumination offers an attractive possibility to tune yttrium hydride through the T = 0 metal-insulator transition. Conductivity and Hall measurements are used to determine critical exponents. The unusually large value for the product of the static and dynamical critical exponents appears to signify the important role played by electron-electron interactions.

Metal–insulator transition in a transition metal dichalcogenide: Dependence on metal contacts

NASA Astrophysics Data System (ADS)

Shimazu, Y.; Arai, K.; Iwabuchi, T.

2018-03-01

Transition metal dichalcogenides are promising layered materials for realizing novel nanoelectronic and nano-optoelectronic devices. Molybdenum disulfide (MoS2), a typical transition metal dichalcogenide, has been extensively investigated due to the presence of a sizable band gap, which enables the use of MoS2 as a channel material in field-effect transistors (FET). The gate-voltage-tunable metal–insulator transition and superconductivity using MoS2 have been demonstrated in previous studies. These interesting phenomena can be considered as quantum phase transitions in two-dimensional systems. In this study, we observed that the transport properties of thin MoS2 flakes in FET geometry significantly depend on metal contacts. On comparing Ti/Au with Al contacts, it was found that the threshold voltages for FET switching and metal–insulator transition were considerably lower for the device with Al contacts. This result indicated the significant influence of the Al contacts on the properties of MoS2 devices.

K2-111 b - a short period super-Earth transiting a metal poor, evolved old star

NASA Astrophysics Data System (ADS)

Fridlund, Malcolm; Gaidos, Eric; Barragán, Oscar; Persson, Carina M.; Gandolfi, Davide; Cabrera, Juan; Hirano, Teruyuki; Kuzuhara, Masayuki; Csizmadia, Sz.; Nowak, Grzegorz; Endl, Michael; Grziwa, Sascha; Korth, Judith; Pfaff, Jeremias; Bitsch, Bertram; Johansen, Anders; Mustill, Alexander J.; Davies, Melvyn B.; Deeg, Hans J.; Palle, Enric; Cochran, William D.; Eigmüller, Philipp; Erikson, Anders; Guenther, Eike; Hatzes, Artie P.; Kiilerich, Amanda; Kudo, Tomoyuki; MacQueen, Phillip; Narita, Norio; Nespral, David; Pätzold, Martin; Prieto-Arranz, Jorge; Rauer, Heike; Van Eylen, Vincent

2017-07-01

Context. From a light curve acquired through the K2 space mission, the star K2-111(EPIC 210894022) has been identified as possibly orbited by a transiting planet. Aims: Our aim is to confirm the planetary nature of the object and derive its fundamental parameters. Methods: We analyse the light curve variations during the planetary transit using packages developed specifically for exoplanetary transits. Reconnaissance spectroscopy and radial velocity observations have been obtained using three separate telescope and spectrograph combinations. The spectroscopic synthesis package SME has been used to derive the stellar photospheric parameters that were used as input to various stellar evolutionary tracks in order to derive the parameters of the system. The planetary transit was also validated to occur on the assumed host star through adaptive imaging and statistical analysis. Results: The star is found to be located in the background of the Hyades cluster at a distance at least 4 times further away from Earth than the cluster itself. The spectrum and the space velocities of K2-111 strongly suggest it to be a member of the thick disk population. The co-added high-resolution spectra show that that it is a metal poor ([Fe/H] = - 0.53 ± 0.05 dex) and α-rich somewhat evolved solar-like star of spectral type G3. We find Teff = 5730 ± 50 K, log g⋆ = 4.15 ± 0.1 cgs, and derive a radius of R⋆ = 1.3 ± 0.1 R⊙ and a mass of M⋆ = 0.88 ± 0.02 M⊙. The currently available radial velocity data confirms a super-Earth class planet with a mass of 8.6 ± 3.9 M⊕ and a radius of 1.9 ± 0.2 R⊕. A second more massive object with a period longer than about 120 days is indicated by a long-term radial velocity drift. Conclusions: The radial velocity detection together with the imaging confirms with a high level of significance that the transit signature is caused by a planet orbiting the star K2-111. This planet is also confirmed in the radial velocity data. A second more

Interplay of rare-earth and transition-metal subsystems in C u3Yb (SeO3) 2O2Cl

NASA Astrophysics Data System (ADS)

Markina, M. M.; Zakharov, K. V.; Ovchenkov, E. A.; Berdonosov, P. S.; Dolgikh, V. A.; Kuznetsova, E. S.; Olenev, A. V.; Klimin, S. A.; Kashchenko, M. A.; Budkin, I. V.; Yatsyk, I. V.; Demidov, A. A.; Zvereva, E. A.; Vasiliev, A. N.

2017-10-01

We present the synthesis and the experimental and theoretical study of the new member of the francisite family, C u3Yb (SeO3) 2O2Cl . The compound reaches an antiferromagnetic order at TN=36.7 K and experiences first-order spin-reorientation transition to weakly ferromagnetic phase at TR=8.7 K evidenced in specific heat Cp and magnetic susceptibility χ measurements. Distinctly different magnetization loops in T earth and transition-metal subsystems. At low temperatures, the saturation magnetization Ms˜5.2 μB is reached in pulsed magnetic-field measurements. The electron spin resonance data reveal the complicated character of the absorption line attributed to response from both copper and ytterbium ions. Critical broadening of the linewidth at the phase transitions points to quasi-two-dimensional character of the magnetic correlations. The spectroscopy of Y b3 + ions evidences splitting of the lowest-energy Kramers doublet of 2F5 /2 excited multiplet at TRtransition in the framework of a unified approach based on the mean-field approximation and crystal-field calculations.

Solvo-thermal synthesis of a unique alkaline earth-transition Ba-Cd micro-porous coordination framework as hetero-metallic luminescent sensor for Cu2+ and real-time detection of benzaldehyde.

PubMed

Ding, Bin; Ma, Dian Xue; Zhang, Hui Min; Meng, Xin; Qiu, Rong Rong; Ren, Rong; Wu, Jie; Wu, Xiang Xia; Huo, Jian Zhong; Liu, Yuan Yuan; Shi, Xue Fang

2018-06-15

In this work a unique hetero-metallic alkaline earth-transition Ba-Cd luminescent micro-porous metal-organic framework {[BaCd(μ 6 -tp) 1.5 (μ 2 -Cl)(H 2 O) (DMF) 2 ]·0.75H 2 O} n (H 2 tp=terephthalic acid) (1) has been prepared under solvo-thermal conditions. In 1 infinite 1D {Ba-X-Cd} (X=O, Cl) inorganic chains are linked via these full de-pronated tp 2- ligands forming a unique 3D I 1 O 2 type micro-porous coordination framework. PXRD patterns of 1 have been determined confirming pure phases of 1. Luminescence investigations suggested that 1 exhibits highly selective and sensitive sensing for trace amounts of benzaldehyde in ethanol, which provides a facile method for real-time detection of benzaldehyde. Meanwhile 1 also exhibits highly selective and sensitive sensing for Cu 2+ over other cations with high quenching efficiency K sv value 1.15×10 4 L·mol -1 . As far as we know, 1 represents the first example of alkaline earth-transition hetero-metallic Ba-Cd micro-porous coordination framework as bi-functional luminescent probes for Cu 2+ and benzaldehyde. Copyright © 2018 Elsevier B.V. All rights reserved.

Molecular precursor routes to transition metal sulfides

NASA Astrophysics Data System (ADS)

Dinnage, Christopher Walker

This thesis is primarily concerned with the synthesis of homoleptic early transition meta thiolates and the subsequent preparation of bulk and thin-film metal disulfides from these compounds. Chapter 1 gives an introduction into the properties, preparation procedures and uses of bulk and thin-film transition metal disulfides as well as giving an overview of early transition metal thiolates synthesied so far in the literature (for titanium, zirconium, tantalum and niobium). Chapter 2 is concerned with the synthesis of a number of ionic and neutral transition metal thiolates. The main synthetic methodologies discussed in this chapter include substitution reactions of transition metal amides and alkyls with thiols, salt metathesis reactions of transition metal chlorides with alkali metal thiolates or with a base / thiol and the use of Grignard reagents. Chapter 3 discusses the preparation of bulk transition metal disulfides using the thiolates prepared in the previous chapter via a thio "sol-gel" route. The preparation of a range of bulk metal and mixed-metal disulfides using transition metal chlorides and hexamethyldisilathiane is also discussed in this chapter. Finally, chapter 4 is concerned with the attempted preparation of thin-films of some transition metal disulfides. Decomposition studies of some of the thiolates prepared in chapter 2 are discussed using thermal gravimetric analysis. Vapour-phase deposition studies are also explored in order to test the potential of the transition metal thiolates as precursors to the disulfides. Experiments using low-pressure chemical vapour deposition and aerosol-assisted chemical vapour deposition are also described.

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Astrophysics Data System (ADS)

Westfall, Richard

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

Near-Earth asteroids: Metals occurrence, extraction, and fabrication

NASA Technical Reports Server (NTRS)

Westfall, Richard

1991-01-01

Near-earth asteroids occur in three principle types of orbits: Amor, Apollo, and Aten. Amor asteroids make relatively close (within 0.3 AU) approaches to the earth's orbit, but do not actually overlap it. Apollo asteroids spend most of their time outside the earth's orbital path, but at some point of close approach to the sun, they cross the orbit of the earth. Aten asteroids are those whose orbits remain inside the earth's path for the majority of their time, with semi-major axes less than 0.1 AU. Near-earth orbit asteroids include: stones, stony-irons, irons, carbonaceous, and super-carbonaceous. Metals within these asteroids include: iron, nickel, cobalt, the platinum group, aluminum, titanium, and others. Focus is on the extraction of ferrous and platinum group metals from the stony-iron asteroids, and the iron asteroids. Extraction of the metal fraction can be accomplished through the use of tunnel-boring-machines (TBM) in the case of the stony-irons. The metals within the story-iron asteroids occur as dispersed granules, which can be separated from the stony fraction through magnetic and gaseous digestion separation techniques. The metal asteroids are processes by drilling and gaseous digestion or by gaseous digestion alone. Manufacturing of structures, housings, framing networks, pressure vessels, mirrors, and other products is accomplished through the chemical vapor deposition (CVD) of metal coating on advanced composites and on the inside of contour-defining inflatables (CDI). Metal coatings on advanced composites provide: resistance to degradation in the hostile environments of space; superior optical properties; superior heat dissipation; service as wear coatings; and service as evidential coatings. Metal coatings on the inside of CDI produce metal load-bearing products. Fibers such as graphite, kevlar, glass, ceramic, metal, etc., can be incorporated in the metal coatings on the inside of CDI producing metal matrix products which exhibit high strength

Charge-separated and molecular heterobimetallic rare earth-rare earth and alkaline earth-rare earth aryloxo complexes featuring intramolecular metal-pi-arene interactions.

PubMed

Deacon, Glen B; Junk, Peter C; Moxey, Graeme J; Ruhlandt-Senge, Karin; St Prix, Courtney; Zuniga, Maria F

2009-01-01

Treatment of a rare earth metal (Ln) and a potential divalent rare earth metal (Ln') or an alkaline earth metal (Ae) with 2,6-diphenylphenol (HOdpp) at elevated temperatures (200-250 degrees C) afforded heterobimetallic aryloxo complexes, which were structurally characterised. A charge-separated species [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] was obtained for a range of metals, demonstrating the similarities between the chemistry of the divalent rare earth metals and the alkaline earth metals. The [(Ln'/Ae)(2)(Odpp)(3)](+) cation in the heterobimetallic structures is unusual in that it consists solely of bridging aryloxide ligands. A molecular heterobimetallic species [AeEu(Odpp)(4)] (Ae = Ca, Sr, Ba) was obtained by treating an alkaline earth metal and Eu metal with HOdpp at elevated temperatures. Similarly, [BaSr(Odpp)(4)] was prepared by treating Ba metal and Sr metal with HOdpp. Treatment of [Ba(2)(Odpp)(4)] with [Mg(Odpp)(2)(thf)(2)] in toluene afforded [Ba(2)(Odpp)(3)][Mg(Odpp)(3)(thf)]. Analogous solution-based syntheses were not possible for [(Ln'/Ae)(2)(Odpp)(3)][Ln(Odpp)(4)] complexes, for which the free-metal route was essential. As a result of the absence of additional donor ligands, the crystal structures of the heterobimetallic complexes feature extensive pi-Ph-metal interactions involving the pendant phenyl groups of the Odpp ligands, thus enabling the large electropositive metal atoms to attain coordination saturation. The charge-separated heterobimetallic species were purified by extraction with toluene/thf mixtures at ambient temperature (Ba-containing compounds) or by extraction with toluene under pressure above the boiling point of the solvent (other products). In donor solvents, heterobimetallic complexes other than those containing barium were found to fragment into homometallic species.

Effects of Rare Earth Metals on Steel Microstructures

PubMed Central

Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Kuo, Chia-Liang; Su, Yen-Hao; Chen, Shin-Hau; Lin, Kuan-Ju; Hsieh, Ping-Hung; Hwang, Weng-Sing

2016-01-01

Rare earth metals are used in semiconductors, solar cells and catalysts. This review focuses on the background of oxide metallurgy technologies, the chemical and physical properties of rare earth (RE) metals, the background of oxide metallurgy, the functions of RE metals in steelmaking, and the influences of RE metals on steel microstructures. Future prospects for RE metal applications in steelmaking are also presented. PMID:28773545

Microwave-assisted synthesis of transition metal phosphide

DOEpatents

Viswanathan, Tito

2014-12-30

A method of synthesizing transition metal phosphide. In one embodiment, the method has the steps of preparing a transition metal lignosulfonate, mixing the transition metal lignosulfonate with phosphoric acid to form a mixture, and subjecting the mixture to a microwave radiation for a duration of time effective to obtain a transition metal phosphide.

Rare earth metal-containing ionic liquids

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

Prodius, Denis; Mudring, Anja-Verena

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Rare earth metal-containing ionic liquids

DOE PAGES

Prodius, Denis; Mudring, Anja-Verena

2018-03-07

As an innovative tool, ionic liquids (ILs) are widely employed as an alternative, smart, reaction media (vs. traditional solvents) offering interesting technology solutions for dissolving, processing and recycling of metal-containing materials. The costly mining and refining of rare earths (RE), combined with increasing demand for high-tech and energy-related applications around the world, urgently requires effective approaches to improve the efficiency of rare earth separation and recovery. In this context, ionic liquids appear as an attractive technology solution. Finally, this paper addresses the structural and coordination chemistry of ionic liquids comprising rare earth metals with the aim to add to understandingmore » prospects of ionic liquids in the chemistry of rare earths.« less

Alkali metal and alkali earth metal gadolinium halide scintillators

DOEpatents

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Parms, Shameka; Porter-Chapman, Yetta D.; Wiggins, Latoria K.

2016-08-02

The present invention provides for a composition comprising an inorganic scintillator comprising a gadolinium halide, optionally cerium-doped, having the formula A.sub.nGdX.sub.m:Ce; wherein A is nothing, an alkali metal, such as Li or Na, or an alkali earth metal, such as Ba; X is F, Br, Cl, or I; n is an integer from 1 to 2; m is an integer from 4 to 7; and the molar percent of cerium is 0% to 100%. The gadolinium halides or alkali earth metal gadolinium halides are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

Chemical analysis of extracting transition metal oxides from polymetallic ore by sulphate process

NASA Astrophysics Data System (ADS)

Enkh-Uyanga, Otgon-Uul; Munkhtsetseg, Baatar; Urangoo, Urtnasan; Tserendulam, Enkhtur; Agiimaa, Davaadorj

2017-06-01

In this research work we attempt to improve the purity of polymetallic ores in Mongolia whilst developing practical applications of its refinement processes and this paper presents the results of chemical research of extracting transition metal titanium oxides, ferrous oxide and rare earth oxides from polymetallic ore. Thereby, chemical and mineral analysis of polymetallic ore is carried out basis of responses to the support process at various degrees of water whereas transition metal sulphates solubility differ. As a result of sulphate and resulphurization process we have extracted anatase with 62.5 percent titanium dioxide and brookite mineral with 89.6 percent of titanium dioxide as well as mineral with 83.8 percent of ferrous oxide hematite and rare earth oxides with 57.6 percent of cerium oxide. These oxides are identified under various conditions in the thermal processing. The morphology structure and chemical content compound of the mineral has been verified as a result of the XRF, XRD, SEM-EDX analysis.

Nature of the transition between a ferromagnetic metal and a spin-glass insulator in pyrochlore molybdates.

PubMed

Hanasaki, N; Watanabe, K; Ohtsuka, T; Kézsmárki, I; Iguchi, S; Miyasaka, S; Tokura, Y

2007-08-24

The metal-insulator transition has been investigated for pyrochlore molybdates R(2)Mo(2)O(7) with nonmagnetic rare-earth ions R. The dynamical scaling analysis of ac susceptibility reveals that the geometrical frustration causes the atomic spin-glass state. The reentrant spin-glass phase exists below the ferromagnetic transition. The electronic specific heat is enhanced as compared to the band calculation result, perhaps due to the orbital fluctuation in the half-metallic ferromagnetic state. The large specific heat is rather reduced upon the transition, likely because the short-range antiferromagnetic fluctuation shrinks the Fermi surface.

Effect of patch borders on coercivity in amorphous rare earth-transition metal thin films

NASA Technical Reports Server (NTRS)

Patterson, G.; Fu, H.; Giles, R. C.; Mansuripur, M.

1991-01-01

The coercivity at the micron scale is a very important property of magneto-optical media. It is a key factor that determines the magnetic domain wall movement and domain reversal. How the coercivity is influenced by a special type of patch borders is discussed. Patch formation is a general phenomenon in growth processes of amorphous rare earth transition metal thin films. Different patches may stem from different seeds and the patch borders are formed when they merge. Though little is known about the exact properties of the borders, we may expect that the exchange interaction at the patch border is weaker than that within a patch, since there is usually a spatial gap between two patches. Computer simulations were performed on a 2-D hexagonal lattice consisting of 37 complete patches with random shape and size. From the series of simulations we may conclude that the domain in the patch with borders of 30 percent exchange strength can expand most easily to the whole lattice, because the exchange strength can expand most easily to the whole lattice, because the exchange strength of the border is not too high to prevent the domain from growing within the patch and it is not too low to prevent the domain from expanding beyond the patch.

Transition Metal Compounds Towards Holography

PubMed Central

Dieckmann, Volker; Eicke, Sebastian; Springfeld, Kristin; Imlau, Mirco

2012-01-01

We have successfully proposed the application of transition metal compounds in holographic recording media. Such compounds feature an ultra-fast light-induced linkage isomerization of the transition-metal–ligand bond with switching times in the sub-picosecond regime and lifetimes from microseconds up to hours at room temperature. This article highlights the photofunctionality of two of the most promising transition metal compounds and the photophysical mechanisms that are underlying the hologram recording. We present the latest progress with respect to the key measures of holographic media assembled from transition metal compounds, the molecular embedding in a dielectric matrix and their impressive potential for modern holographic applications. PMID:28817028

Method for dry etching of transition metals

DOEpatents

Ashby, Carol I. H.; Baca, Albert G.; Esherick, Peter; Parmeter, John E.; Rieger, Dennis J.; Shul, Randy J.

1998-01-01

A method for dry etching of transition metals. The method for dry etching of a transition metal (or a transition metal alloy such as a silicide) on a substrate comprises providing at least one nitrogen- or phosphorous-containing .pi.-acceptor ligand in proximity to the transition metal, and etching the transition metal to form a volatile transition metal/.pi.-acceptor ligand complex. The dry etching may be performed in a plasma etching system such as a reactive ion etching (RIE) system, a downstream plasma etching system (i.e. a plasma afterglow), a chemically-assisted ion beam etching (CAIBE) system or the like. The dry etching may also be performed by generating the .pi.-acceptor ligands directly from a ligand source gas (e.g. nitrosyl ligands generated from nitric oxide), or from contact with energized particles such as photons, electrons, ions, atoms, or molecules. In some preferred embodiments of the present invention, an intermediary reactant species such as carbonyl or a halide ligand is used for an initial chemical reaction with the transition metal, with the intermediary reactant species being replaced at least in part by the .pi.-acceptor ligand for forming the volatile transition metal/.pi.-acceptor ligand complex.

Recognition- and reactivity-based fluorescent probes for studying transition metal signaling in living systems.

PubMed

Aron, Allegra T; Ramos-Torres, Karla M; Cotruvo, Joseph A; Chang, Christopher J

2015-08-18

Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed "recognition" and "reactivity". Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give three recent

Transition Metals and Virulence in Bacteria.

PubMed

Palmer, Lauren D; Skaar, Eric P

2016-11-23

Transition metals are required trace elements for all forms of life. Due to their unique inorganic and redox properties, transition metals serve as cofactors for enzymes and other proteins. In bacterial pathogenesis, the vertebrate host represents a rich source of nutrient metals, and bacteria have evolved diverse metal acquisition strategies. Host metal homeostasis changes dramatically in response to bacterial infections, including production of metal sequestering proteins and the bombardment of bacteria with toxic levels of metals. In response, bacteria have evolved systems to subvert metal sequestration and toxicity. The coevolution of hosts and their bacterial pathogens in the battle for metals has uncovered emerging paradigms in social microbiology, rapid evolution, host specificity, and metal homeostasis across domains. This review focuses on recent advances and open questions in our understanding of the complex role of transition metals at the host-pathogen interface.

Tailoring transition-metal hydroxides and oxides by photon-induced reactions

DOE PAGES

Niu, Kai -Yang; Fang, Liang; Ye, Rong; ...

2016-10-18

Controlled synthesis of transition-metal hydroxides and oxides with earth-abundant elements have attracted significant interest because of their wide applications, for example as battery electrode materials or electrocatalysts for fuel generation. Here, we report the tuning of the structure of transition-metal hydroxides and oxides by controlling chemical reactions using an unfocused laser to irradiate the precursor solution. A Nd:YAG laser with wavelengths of 532 nm or 1064 nm was used. The Ni 2+, Mn 2+, and Co 2+ ion-containing aqueous solution undergoes photo-induced reactions and produces hollow metal-oxide nanospheres (Ni 0.18Mn 0.45Co 0.37O x) or core–shell metal hydroxide nanoflowers ([Ni 0.15Mnmore » 0.15Co 0.7(OH) 2](NO 3) 0.2•H 2O), depending on the laser wavelengths. We propose two reaction pathways, either by photo-induced redox reaction or hydrolysis reaction, which are responsible for the formation of distinct nanostructures. As a result, the study of photon-induced materials growth shines light on the rational design of complex nanostructures with advanced functionalities.« less

Spin crossover and Mott—Hubbard transition under high pressure and high temperature in the low mantle of the Earth

NASA Astrophysics Data System (ADS)

Ovchinnikov, S. G.; Ovchinnikova, T. M.; Plotkin, V. V.; Dyad'kov, P. G.

2015-11-01

Effect of high pressure induced spin crossover on the magnetic, electronic and structural properties of the minerals forming the Earth's low mantle is discussed. The low temperature P, T phase diagram of ferropericlase has the quantum phase transition point Pc = 56 GPa at T = 0 confirmed recently by the synchrotron Mössbauer spectroscopy. The LDA+GTB calculated phase diagram describes the experimental data. Its extension to the high temperature resulted earlier in prediction of the metallic properties of the Earth's mantle at the depth 1400 km < h < 1800 km. Estimation of the electrical conductivity based on the percolation theory is given. We discuss also the thermodynamic properties and structural anomalies resulting from the spin crossover and metal-insulator transition and compare them with the experimental seismic and geomagnetic field data.

Metal-insulator and charge ordering transitions in oxide nanostructures

NASA Astrophysics Data System (ADS)

Singh, Sujay Kumar

Strongly correlated oxides are a class of materials wherein interplay of various degrees of freedom results in novel electronic and magnetic phenomena. Vanadium oxides are widely studied correlated materials that exhibit metal-insulator transitions (MIT) in a wide temperature range from 70 K to 380 K. In this Thesis, results from electrical transport measurements on vanadium dioxide (VO2) and vanadium oxide bronze (MxV 2O5) (where M: alkali, alkaline earth, and transition metal cations) are presented and discussed. Although the MIT in VO2 has been studied for more than 50 years, the microscopic origin of the transition is still debated since a slew of external parameters such as light, voltage, and strain are found to significantly alter the transition. Furthermore, recent works on electrically driven switching in VO2 have shown that the role of Joule heating to be a major cause as opposed to electric field. We explore the mechanisms behind the electrically driven switching in single crystalline nanobeams of VO2 through DC and AC transport measurements. The harmonic analysis of the AC measurement data shows that non-uniform Joule heating causes electronic inhomogeneities to develop within the nanobeam and is responsible for driving the transition in VO2. Surprisingly, field assisted emission mechanisms such as Poole-Frenkel effect is found to be absent and the role of percolation is also identified in the electrically driven transition. This Thesis also provides a new insight into the mechanisms behind the electrolyte gating induced resistance modulation and the suppression of MIT in VO2. We show that the metallic phase of VO2 induced by electrolyte gating is due to an electrochemical process and can be both reversible and irreversible under different conditions. The kinetics of the redox processes increase with temperature; a complete suppression of the transition and the stabilization of the metallic phase are achievable by gating in the rutile metallic phase

Method for dry etching of transition metals

DOEpatents

Ashby, C.I.H.; Baca, A.G.; Esherick, P.; Parmeter, J.E.; Rieger, D.J.; Shul, R.J.

1998-09-29

A method for dry etching of transition metals is disclosed. The method for dry etching of a transition metal (or a transition metal alloy such as a silicide) on a substrate comprises providing at least one nitrogen- or phosphorus-containing {pi}-acceptor ligand in proximity to the transition metal, and etching the transition metal to form a volatile transition metal/{pi}-acceptor ligand complex. The dry etching may be performed in a plasma etching system such as a reactive ion etching (RIE) system, a downstream plasma etching system (i.e. a plasma afterglow), a chemically-assisted ion beam etching (CAIBE) system or the like. The dry etching may also be performed by generating the {pi}-acceptor ligands directly from a ligand source gas (e.g. nitrosyl ligands generated from nitric oxide), or from contact with energized particles such as photons, electrons, ions, atoms, or molecules. In some preferred embodiments of the present invention, an intermediary reactant species such as carbonyl or a halide ligand is used for an initial chemical reaction with the transition metal, with the intermediary reactant species being replaced at least in part by the {pi}-acceptor ligand for forming the volatile transition metal/{pi}-acceptor ligand complex.

Transition Metals and Virulence in Bacteria

PubMed Central

Palmer, Lauren D.; Skaar, Eric P.

2016-01-01

Transition metals are required trace elements for all forms of life. Due to their unique inorganic and redox properties, transition metals serve as cofactors for enzymes and other proteins. In bacterial pathogenesis, the vertebrate host represents a rich source of nutrient metals, and bacteria have evolved diverse metal acquisition strategies. Host metal homeostasis changes dramatically in response to bacterial infections, including production of metal sequestering proteins and the bombardment of bacteria with toxic levels of metals. Presumably, in response, bacteria have evolved systems to subvert metal sequestration and toxicity. The coevolution of hosts and their bacterial pathogens in the battle for metals has uncovered emerging paradigms in social microbiology, rapid evolution, host specificity, and metal homeostasis across domains. This review focuses on recent advances and open questions in our understanding of the complex role of transition metals at the host-pathogen interface. PMID:27617971

Determination of Thermodynamic Properties of Alkaline Earth-liquid Metal Alloys Using the Electromotive Force Technique

PubMed Central

Nigl, Thomas P.; Smith, Nathan D.; Lichtenstein, Timothy; Gesualdi, Jarrod; Kumar, Kuldeep; Kim, Hojong

2017-01-01

A novel electrochemical cell based on a CaF2 solid-state electrolyte has been developed to measure the electromotive force (emf) of binary alkaline earth-liquid metal alloys as functions of both composition and temperature in order to acquire thermodynamic data. The cell consists of a chemically stable solid-state CaF2-AF2 electrolyte (where A is the alkaline-earth element such as Ca, Sr, or Ba), with binary A-B alloy (where B is the liquid metal such as Bi or Sb) working electrodes, and a pure A metal reference electrode. Emf data are collected over a temperature range of 723 K to 1,123 K in 25 K increments for multiple alloy compositions per experiment and the results are analyzed to yield activity values, phase transition temperatures, and partial molar entropies/enthalpies for each composition. PMID:29155770

Half-Metallic Ferromagnetism and Stability of Transition Metal Pnictides and Chalcogenides

NASA Astrophysics Data System (ADS)

Liu, Bang-Gui

It is highly desirable to explore robust half-metallic ferromagnetic materials compatible with important semiconductors for spintronic applications. A state-of-the-art full potential augmented plane wave method within the densityfunctional theory is reliable enough for this purpose. In this chapter we review theoretical research on half-metallic ferromagnetism and structural stability of transition metal pnictides and chalcogenides. We show that some zincblende transition metal pnictides are half-metallic and the half-metallic gap can be fairly wide, which is consistent with experiment. Systematic calculations reveal that zincblende phases of CrTe, CrSe, and VTe are excellent half-metallic ferromagnets. These three materials have wide half-metallic gaps, are low in total energy with respect to the corresponding ground-state phases, and, importantly, are structurally stable. Halfmetallic ferromagnetism is also found in wurtzite transition metal pnictides and chalcogenides and in transition-metal doped semiconductors as well as deformed structures. Some of these half-metallic materials could be grown epitaxially in the form of ultrathin .lms or layers suitable for real spintronic applications.

Recognition- and Reactivity-Based Fluorescent Probes for Studying Transition Metal Signaling in Living Systems

PubMed Central

2015-01-01

Conspectus Metals are essential for life, playing critical roles in all aspects of the central dogma of biology (e.g., the transcription and translation of nucleic acids and synthesis of proteins). Redox-inactive alkali, alkaline earth, and transition metals such as sodium, potassium, calcium, and zinc are widely recognized as dynamic signals, whereas redox-active transition metals such as copper and iron are traditionally thought of as sequestered by protein ligands, including as static enzyme cofactors, in part because of their potential to trigger oxidative stress and damage via Fenton chemistry. Metals in biology can be broadly categorized into two pools: static and labile. In the former, proteins and other macromolecules tightly bind metals; in the latter, metals are bound relatively weakly to cellular ligands, including proteins and low molecular weight ligands. Fluorescent probes can be useful tools for studying the roles of transition metals in their labile forms. Probes for imaging transition metal dynamics in living systems must meet several stringent criteria. In addition to exhibiting desirable photophysical properties and biocompatibility, they must be selective and show a fluorescence turn-on response to the metal of interest. To meet this challenge, we have pursued two general strategies for metal detection, termed “recognition” and “reactivity”. Our design of transition metal probes makes use of a recognition-based approach for copper and nickel and a reactivity-based approach for cobalt and iron. This Account summarizes progress in our laboratory on both the development and application of fluorescent probes to identify and study the signaling roles of transition metals in biology. In conjunction with complementary methods for direct metal detection and genetic and/or pharmacological manipulations, fluorescent probes for transition metals have helped reveal a number of principles underlying transition metal dynamics. In this Account, we give

Neutron diffraction studies of some rare earth-transition metal deuterides

NASA Astrophysics Data System (ADS)

James, W. J.

1984-04-01

Neutron diffraction studies of the ternary alloy system Y6(Fel-xMnx)23 reveal that the unusual magnetic behavior upon substitution of Mn or Fe into the end members, is a consequence of atomic ordering wherein there is strong site preference of Mn for the f sub 2 sites and of Fe for the f sub 1 sites. In the Mn-rich compositions, Fe is found to have no spontaneous moments. Therefore, the long range magnetic ordering arises solely from Mn-Mn interactions. Upon substitution of Mn into the Fe-rich ternaries, the Fe moments are considerably reduced. Neutron diffraction studies of Y6Mn23D23 show that a transition occurs below 180K from a fcc structure to a primitive tetragonal structure, space group P4/mmm with the onset of antiferromagnetic ordering. The Mn moments are directed along the c-axis. The transition probably results from atomic ordering of the D atoms at low temperature which induces c axis magnetic ordering. The question of the appropriate space group of LaNi4.5Al0.5D4.5, P6/mmm or P3/m has been resolved by a careful refinement and analysis of neutron diffraction data. The preferred space group is P6/mmm. Neutron powder diffraction and thermal magnetization measurements on small single crystals of ErNi3, ErCo3, and ErFe3 (space group R3m) show that the magnetocrystalline properties are a consequence of competing local site anisotropies between the two non-equivalent crystallographic sites of Er and two of the three non-equivalent sites of the 3d-transition metal.

Temperate Earth-sized planets transiting a nearby ultracool dwarf star

NASA Astrophysics Data System (ADS)

Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M.; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam J.; Triaud, Amaury H. M. J.; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K.; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

2016-05-01

Star-like objects with effective temperatures of less than 2,700 kelvin are referred to as ‘ultracool dwarfs’. This heterogeneous group includes stars of extremely low mass as well as brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15 per cent of the population of astronomical objects near the Sun. Core-accretion theory predicts that, given the small masses of these ultracool dwarfs, and the small sizes of their protoplanetary disks, there should be a large but hitherto undetected population of terrestrial planets orbiting them—ranging from metal-rich Mercury-sized planets to more hospitable volatile-rich Earth-sized planets. Here we report observations of three short-period Earth-sized planets transiting an ultracool dwarf star only 12 parsecs away. The inner two planets receive four times and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Our data suggest that 11 orbits remain possible for the third planet, the most likely resulting in irradiation significantly less than that received by Earth. The infrared brightness of the host star, combined with its Jupiter-like size, offers the possibility of thoroughly characterizing the components of this nearby planetary system.

Temperate Earth-sized planets transiting a nearby ultracool dwarf star.

PubMed

Gillon, Michaël; Jehin, Emmanuël; Lederer, Susan M; Delrez, Laetitia; de Wit, Julien; Burdanov, Artem; Van Grootel, Valérie; Burgasser, Adam J; Triaud, Amaury H M J; Opitom, Cyrielle; Demory, Brice-Olivier; Sahu, Devendra K; Bardalez Gagliuffi, Daniella; Magain, Pierre; Queloz, Didier

2016-05-12

Star-like objects with effective temperatures of less than 2,700 kelvin are referred to as 'ultracool dwarfs'. This heterogeneous group includes stars of extremely low mass as well as brown dwarfs (substellar objects not massive enough to sustain hydrogen fusion), and represents about 15 per cent of the population of astronomical objects near the Sun. Core-accretion theory predicts that, given the small masses of these ultracool dwarfs, and the small sizes of their protoplanetary disks, there should be a large but hitherto undetected population of terrestrial planets orbiting them--ranging from metal-rich Mercury-sized planets to more hospitable volatile-rich Earth-sized planets. Here we report observations of three short-period Earth-sized planets transiting an ultracool dwarf star only 12 parsecs away. The inner two planets receive four times and two times the irradiation of Earth, respectively, placing them close to the inner edge of the habitable zone of the star. Our data suggest that 11 orbits remain possible for the third planet, the most likely resulting in irradiation significantly less than that received by Earth. The infrared brightness of the host star, combined with its Jupiter-like size, offers the possibility of thoroughly characterizing the components of this nearby planetary system.

Site specific physics in RT5 (R = rare earths and T = transition metals) materials

NASA Astrophysics Data System (ADS)

Paudyal, Durga

Most of RT5 compounds form in hexagonal CaCu5-type structure with three non-equivalent sites: R (1a), T (2c), and T (3g). R atoms sit in the middle of the T (2c) hexagonal layers. Advanced density functional theory calculations including on-site electron correlation and spin orbit coupling show crystal field split localized R 4f states, which are responsible for the large part of the magnetic anisotropy exhibited by these systems. In addition, the hexagonal T (2c) layers help enhancing the magnetic anisotropy. Partially quenched R 4f orbital moment is the origin of magnetic anisotropy which also helps enhancing magnetic moment. The interchange of T sites by other transition metals and the partial substitution of R atoms by transition metals could optimize needed magnetic moment and magnetic anisotropy by forming a complex geometry structure favoring permanent magnetic properties. This research is supported by the Critical Materials Institute, an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Advanced Manufacturing office.

METHOD OF MAKING ALLOYS OF SECOND RARE EARTH SERIES METALS

DOEpatents

Baker, R.D.; Hayward, B.R.

1963-01-01

>This invention relates to a process for alloying the second rare earth series metals with Mo, Nb, or Zr. A halide of the rare earth metal is mixed with about 1 to 20 at.% of an oxide of Mo, Nb, or Zr. Iodine and an alkali or alkaline earth metal are added, and the resulting mixture is heated in an inert atmosphere to 350 deg C. (AEC)

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, James B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass. CA, USA, in 1949, was significant because it led to the production of commercial quantities or rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Rare-earth metal prices in the USA ca. 1960 to 1994

USGS Publications Warehouse

Hedrick, J.B.

1997-01-01

Rare-earth metal prices were compiled from the late 1950s and early 1960s through 1994. Although commercial demand for rare-earth metals began in 1908, as the alloy mischmetal, commercial quantities of a wide range of individual rare-earth metals were not available until the late 1950s. The discovery of a large, high-grade rare-earth deposit at Mountain Pass, CA, USA, in 1949, was significant because it led to the production of commercial quantities of rare-earth elements that reduced prices and encouraged wider application of the materials. The availability of ore from Mountain Pass, and other large rare-earth deposits, especially those in Australia and China, has provided the world with abundant resources for rare-earth metal production. This availability, coupled with improved technology from Government and private-sector metallurgical research, has resulted in substantial decreases in rare-earth metal prices since the late 1950s and early 1960s. Price series for the individual rare-earth metals (except promethium) are quoted on a kilogram basis from the late 1950s and early 1960s through 1994. Prices are given in US dollars on an actual and constant dollar basis. Industrial and economic factors affecting prices during this time period are examined.

Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates

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

Bisogni, Valentina; Catalano, Sara; Green, Robert J.

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. However, a complete understanding of these materials remains elusive. Here, taking a NdNiO 3 thin film as a representative example, we utilize a combination of x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculationsmore » and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d 8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a “conventional” positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation.« less

Ground-state oxygen holes and the metal–insulator transition in the negative charge-transfer rare-earth nickelates

DOE PAGES

Bisogni, Valentina; Catalano, Sara; Green, Robert J.; ...

2016-10-11

The metal-insulator transitions and the intriguing physical properties of rare-earth perovskite nickelates have attracted considerable attention in recent years. However, a complete understanding of these materials remains elusive. Here, taking a NdNiO 3 thin film as a representative example, we utilize a combination of x-ray absorption (XAS) and resonant inelastic x-ray scattering (RIXS) spectroscopies to resolve important aspects of the complex electronic structure of the rare-earth nickelates. The unusual coexistence of bound and continuum excitations observed in the RIXS spectra provides strong evidence for the abundance of oxygen 2p holes in the ground state of these materials. Using cluster calculationsmore » and Anderson impurity model interpretation, we show that these distinct spectral signatures arise from a Ni 3d 8 configuration along with holes in the oxygen 2p valence band, confirming suggestions that these materials do not obey a “conventional” positive charge-transfer picture, but instead exhibit a negative charge-transfer energy, in line with recent models interpreting the metal to insulator transition in terms of bond disproportionation.« less

Atomically thin transition metal layers: Atomic layer stabilization and metal-semiconductor transition

NASA Astrophysics Data System (ADS)

Hwang, Jeongwoon; Oh, Young Jun; Kim, Jiyoung; Sung, Myung Mo; Cho, Kyeongjae

2018-04-01

We have performed first-principle calculations to explore the possibility of synthesizing atomically thin transition metal (TM) layers. Buckled structures as well as planar structures of elemental 2D TM layers result in significantly higher formation energies compared with sp-bonded elemental 2D materials with similar structures, such as silicene and phosphorene. It is shown that the TM layers can be stabilized by surface passivation with HS, C6H5S2, or O, and O passivation is most effective. The surface oxygen passivation can improve stability leading to thermodynamically stable TM monolayers except Au, which is the most non-reactive metal element. Such stabilized TM monolayers also show an electronic structure transition from metallic state of free-standing TM layer to semiconducting O-passivated Mo and W monolayers with band gaps of 0.20-1.38 eV.

Syntheses and structures of alkaline earth metal bis(diphenylamides).

PubMed

Gärtner, Martin; Fischer, Reinald; Langer, Jens; Görls, Helmar; Walther, Dirk; Westerhausen, Matthias

2007-06-11

Various preparative procedures are employed in order to synthesize alkaline earth metal bis(diphenylamides) such as (i) metalation of HNPh2 with the alkaline earth metal M, (ii) metalation of HNPh2 with MPh2, (iii) metathesis reaction of MI2 with KNPh2, (iv) metalation of HNPh2 with PhMI in THF, and (v) metathesis reaction of PhMI with KNPh2 followed by a dismutation reaction yielding MPh2 and M(NPh2)2. The magnesium compounds [(diox)MgPh2]infinity (1) and (thf)2Mg(NPh2)2 (2) show tetracoordinate metal atoms, whereas in (dme)2Ca(NPh2)2 (3), (thf)4Sr(NPh2)2 (4), and (thf)4Ba(NPh2)2 (5) the metals are 6-fold coordinated. Additional agostic interactions between an ipso-carbon of one of the phenyl groups of the amide ligand and the alkaline earth metal atom lead to unsymmetric coordination of the NPh2 anions with two strongly different M-N-C angles in 3-5.

The Search for Extraterrestrial Intelligence in Earth's Solar Transit Zone.

PubMed

Heller, René; Pudritz, Ralph E

2016-04-01

Over the past few years, astronomers have detected thousands of planets and candidate planets by observing their periodic transits in front of their host stars. A related method, called transit spectroscopy, might soon allow studies of the chemical imprints of life in extrasolar planetary atmospheres. Here, we address the reciprocal question, namely, from where is Earth detectable by extrasolar observers using similar methods. We explore Earth's transit zone (ETZ), the projection of a band around Earth's ecliptic onto the celestial plane, where observers can detect Earth transits across the Sun. ETZ is between 0.520° and 0.537° wide due to the noncircular Earth orbit. The restricted Earth transit zone (rETZ), where Earth transits the Sun less than 0.5 solar radii from its center, is about 0.262° wide. We first compile a target list of 45 K and 37 G dwarf stars inside the rETZ and within 1 kpc (about 3260 light-years) using the Hipparcos catalogue. We then greatly enlarge the number of potential targets by constructing an analytic galactic disk model and find that about 10(5) K and G dwarf stars should reside within the rETZ. The ongoing Gaia space mission can potentially discover all G dwarfs among them (several 10(4)) within the next 5 years. Many more potentially habitable planets orbit dim, unknown M stars in ETZ and other stars that traversed ETZ thousands of years ago. If any of these planets host intelligent observers, they could have identified Earth as a habitable, or even as a living, world long ago, and we could be receiving their broadcasts today. The K2 mission, the Allen Telescope Array, the upcoming Square Kilometer Array, or the Green Bank Telescope might detect such deliberate extraterrestrial messages. Ultimately, ETZ would be an ideal region to be monitored by the Breakthrough Listen Initiatives, an upcoming survey that will constitute the most comprehensive search for extraterrestrial intelligence so far.

The Search for Extraterrestrial Intelligence in Earth's Solar Transit Zone

NASA Astrophysics Data System (ADS)

Heller, René; Pudritz, Ralph E.

2016-04-01

Over the past few years, astronomers have detected thousands of planets and candidate planets by observing their periodic transits in front of their host stars. A related method, called transit spectroscopy, might soon allow studies of the chemical imprints of life in extrasolar planetary atmospheres. Here, we address the reciprocal question, namely, from where is Earth detectable by extrasolar observers using similar methods. We explore Earth's transit zone (ETZ), the projection of a band around Earth's ecliptic onto the celestial plane, where observers can detect Earth transits across the Sun. ETZ is between 0.520° and 0.537° wide due to the noncircular Earth orbit. The restricted Earth transit zone (rETZ), where Earth transits the Sun less than 0.5 solar radii from its center, is about 0.262° wide. We first compile a target list of 45 K and 37 G dwarf stars inside the rETZ and within 1 kpc (about 3260 light-years) using the Hipparcos catalogue. We then greatly enlarge the number of potential targets by constructing an analytic galactic disk model and find that about 105 K and G dwarf stars should reside within the rETZ. The ongoing Gaia space mission can potentially discover all G dwarfs among them (several 104) within the next 5 years. Many more potentially habitable planets orbit dim, unknown M stars in ETZ and other stars that traversed ETZ thousands of years ago. If any of these planets host intelligent observers, they could have identified Earth as a habitable, or even as a living, world long ago, and we could be receiving their broadcasts today. The K2 mission, the Allen Telescope Array, the upcoming Square Kilometer Array, or the Green Bank Telescope might detect such deliberate extraterrestrial messages. Ultimately, ETZ would be an ideal region to be monitored by the Breakthrough Listen Initiatives, an upcoming survey that will constitute the most comprehensive search for extraterrestrial intelligence so far.

Superconductivity in transition metals.

PubMed

Slocombe, Daniel R; Kuznetsov, Vladimir L; Grochala, Wojciech; Williams, Robert J P; Edwards, Peter P

2015-03-13

A qualitative account of the occurrence and magnitude of superconductivity in the transition metals is presented, with a primary emphasis on elements of the first row. Correlations of the important parameters of the Bardeen-Cooper-Schrieffer theory of superconductivity are highlighted with respect to the number of d-shell electrons per atom of the transition elements. The relation between the systematics of superconductivity in the transition metals and the periodic table high-lights the importance of short-range or chemical bonding on the remarkable natural phenomenon of superconductivity in the chemical elements. A relationship between superconductivity and lattice instability appears naturally as a balance and competition between localized covalent bonding and so-called broken covalency, which favours d-electron delocalization and superconductivity. In this manner, the systematics of superconductivity and various other physical properties of the transition elements are related and unified. © 2015 The Author(s) Published by the Royal Society. All rights reserved.

Method of boronizing transition metal surfaces

DOEpatents

Koyama, Koichiro; Shimotake, Hiroshi.

1983-08-16

A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB[sub 2], or CrB[sub 2]. A transition metal to be coated is immersed in the melt at a temperature of no more than 700 C and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface. 4 figs.

Method of boronizing transition metal surfaces

DOEpatents

Koyama, Koichiro; Shimotake, Hiroshi

1983-01-01

A method is presented for preparing a boride layer on a transition metal substrate for use in corrosive environments or as a harden surface in machine applications. This method is particularly useful in treating current collectors for use within a high temperature and corrosive electrochemical cell environment. A melt of a alkali metal boride tetrafluoride salt including such as KF to lower its melting point is prepared including a dissolved boron containing material, for instance NiB, MnB.sub.2, or CrB.sub.2. A transition metal to be coated is immersed in the melt at a temperature of no more than 700.degree. C. and a surface boride layer of that transition metal is formed within a period of about 24 hours on the substrate surface.

Nucleic acid-functionalized transition metal nanosheets for biosensing applications

PubMed Central

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-01-01

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. PMID:27020066

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2016-06-28

The present invention provides a method of producing a crystalline rare earth phosphate nanostructure. The method comprising: providing a rare earth metal precursor solution and providing a phosphate precursor solution; placing a porous membrane between the metal precursor solution and the phosphate precursor solution, wherein metal cations of the metal precursor solution and phosphate ions of the phosphate precursor solution react, thereby producing a crystalline rare earth metal phosphate nanostructure.

Mesoporous Transition Metal Oxides for Supercapacitors.

PubMed

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Transition metal catalysis in the generation of petroleum and natural gas. Final report

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

Mango, F.D.

1997-01-21

This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalyticallymore » robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process: The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.« less

Thermophysical properties of liquid rare earth metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Patel, H. P.; Jani, A. R.

2013-06-01

The thermodynamical properties like long wavelength limit S(0), iso-thermal compressibility (χT), thermal expansion coefficient (αV), thermal pressure coefficient (γV), specific heat at constant volume (CV) and specific heat at constant pressure (CP) are calculated for liquid rare earth metals. Our newly constructed parameter free model potential is used to describe the electron ion interaction due to Sarkar et al (S) local field correction function. Lastly, we conclude that our newly constructed model potential is capable to explain the thermophysical properties of liquid rare earth metals.

Mass fractionation processes of transition metal isotopes

NASA Astrophysics Data System (ADS)

Zhu, X. K.; Guo, Y.; Williams, R. J. P.; O'Nions, R. K.; Matthews, A.; Belshaw, N. S.; Canters, G. W.; de Waal, E. C.; Weser, U.; Burgess, B. K.; Salvato, B.

2002-06-01

Recent advances in mass spectrometry make it possible to utilise isotope variations of transition metals to address some important issues in solar system and biological sciences. Realisation of the potential offered by these new isotope systems however requires an adequate understanding of the factors controlling their isotope fractionation. Here we show the results of a broadly based study on copper and iron isotope fractionation during various inorganic and biological processes. These results demonstrate that: (1) naturally occurring inorganic processes can fractionate Fe isotope to a detectable level even at temperature ˜1000°C, which challenges the previous view that Fe isotope variations in natural system are unique biosignatures; (2) multiple-step equilibrium processes at low temperatures may cause large mass fractionation of transition metal isotopes even when the fractionation per single step is small; (3) oxidation-reduction is an importation controlling factor of isotope fractionation of transition metal elements with multiple valences, which opens a wide range of applications of these new isotope systems, ranging from metal-silicate fractionation in the solar system to uptake pathways of these elements in biological systems; (4) organisms incorporate lighter isotopes of transition metals preferentially, and transition metal isotope fractionation occurs stepwise along their pathways within biological systems during their uptake.

Nucleic acid-functionalized transition metal nanosheets for biosensing applications.

PubMed

Mo, Liuting; Li, Juan; Liu, Qiaoling; Qiu, Liping; Tan, Weihong

2017-03-15

In clinical diagnostics, as well as food and environmental safety practices, biosensors are powerful tools for monitoring biological or biochemical processes. Two-dimensional (2D) transition metal nanomaterials, including transition metal chalcogenides (TMCs) and transition metal oxides (TMOs), are receiving growing interest for their use in biosensing applications based on such unique properties as high surface area and fluorescence quenching abilities. Meanwhile, nucleic acid probes based on Watson-Crick base-pairing rules are also being widely applied in biosensing based on their excellent recognition capability. In particular, the emergence of functional nucleic acids in the 1980s, especially aptamers, has substantially extended the recognition capability of nucleic acids to various targets, ranging from small organic molecules and metal ions to proteins and cells. Based on π-π stacking interaction between transition metal nanosheets and nucleic acids, biosensing systems can be easily assembled. Therefore, the combination of 2D transition metal nanomaterials and nucleic acids brings intriguing opportunities in bioanalysis and biomedicine. In this review, we summarize recent advances of nucleic acid-functionalized transition metal nanosheets in biosensing applications. The structure and properties of 2D transition metal nanomaterials are first discussed, emphasizing the interaction between transition metal nanosheets and nucleic acids. Then, the applications of nucleic acid-functionalized transition metal nanosheet-based biosensors are discussed in the context of different signal transducing mechanisms, including optical and electrochemical approaches. Finally, we provide our perspectives on the current challenges and opportunities in this promising field. Copyright © 2016 Elsevier B.V. All rights reserved.

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

40 CFR 721.4668 - Hydrated alkaline earth metal salts of metalloid oxyanions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Hydrated alkaline earth metal salts of... Specific Chemical Substances § 721.4668 Hydrated alkaline earth metal salts of metalloid oxyanions. (a... hydrated alkaline earth metal salts of metalloid oxyanions (PMN P-94-1557) is subject to reporting under...

Metal Based Synthetic Strategies and the Examination of Structure Determining Factors in Alkaline Earth Metal Compounds

NASA Astrophysics Data System (ADS)

Takahashi, Yuriko

Last decades have witnessed a large expansion of the organometallic heavier alkaline earth metal species. However, continued growth of this promising area of chemistry has been slowed by severe restrictions and limitations in viable synthetic methodologies leading to difficulties in preparing and characterizing the target compounds. There is clearly a need for the further development of synthetic methodologies and detailed structure function analysis that will promote the further advancement of organoalkaline earth metal chemistry in applications as diverse as materials chemistry and catalysis. This thesis work greatly extends the synthetic options currently available towards organoalkaline earth metal species by introducing redox transmetallation protolysis (RTP), a reaction based on the readily available Ph3Bi as a non-toxic transmetallation agent. Based on a straightforward one-pot procedure and work-up, Ph3Bi based RTP presents a powerful synthetic alternative for the facile preparation of a large variety of heavy alkaline earth metal compounds. The second part of the thesis explores the effect of secondary non covalent interactions on the coordination chemistry as well as thermal properties of a series of novel alkali, alkaline earth, rare earth as well as heterobimetallic alkali/alkaline earth fluoroalkoxides. These compounds showcase the significance of non-covalent M···F-C and agostic interactions on metal stabilization and structural features, providing critical input on ligand design for the design of advanced metal organic vapor deposition (MOCVD) precursor materials. This work also showcases the impact of M···F-C interactions over M---co-ligand coordination, a critical precursor design element as well.

Electrical Conductivity in Transition Metals

ERIC Educational Resources Information Center

Talbot, Christopher; Vickneson, Kishanda

2013-01-01

The aim of this "Science Note" is to describe how to test the electron-sea model to determine whether it accurately predicts relative electrical conductivity for first-row transition metals. In the electron-sea model, a metal crystal is viewed as a three-dimensional array of metal cations immersed in a sea of delocalised valence…

Mesoporous Transition Metal Oxides for Supercapacitors

PubMed Central

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-01-01

Recently, transition metal oxides, such as ruthenium oxide (RuO2), manganese dioxide (MnO2), nickel oxides (NiO) and cobalt oxide (Co3O4), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO2, MnO2, NiO, Co3O4 and nickel cobaltite (NiCo2O4), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors. PMID:28347088

Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

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

Ogut, Serdar

The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyesmore » and metal-organic frameworks.« less

X-ray Emission Spectroscopy in Magnetic 3d-Transition Metals

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

Iota, V; Park, J; Baer, B

2003-11-18

The application of high pressure affects the band structure and magnetic interactions in solids by modifying nearest-neighbor distances and interatomic potentials. While all materials experience electronic changes with increasing pressure, spin polarized, strongly electron correlated materials are expected to undergo the most dramatic transformations. In such materials, (d and f-electron metals and compounds), applied pressure reduces the strength of on-site correlations, leading to increased electron delocalization and, eventually, to loss of its magnetism. In this ongoing project, we study the electronic and magnetic properties of Group VIII, 3d (Fe, Co and Ni) magnetic transition metals and their compounds at highmore » pressures. The high-pressure properties of magnetic 3d-transition metals and compounds have been studied extensively over the years, because of iron being a major constituent of the Earth's core and its relevance to the planetary modeling to understand the chemical composition, internal structure, and geomagnetism. However, the fundamental scientific interest in the high-pressure properties of magnetic 3d-electron systems extends well beyond the geophysical applications to include the electron correlation-driven physics. The role of magnetic interactions in the stabilization of the ''non-standard'' ambient pressure structures of Fe, Co and Ni is still incompletely understood. Theoretical studies have predicted (and high pressure experiments are beginning to show) strong correlations between the electronic structure and phase stability in these materials. The phase diagrams of magnetic 3d systems reflect a delicate balance between spin interactions and structural configuration. At ambient conditions, the crystal structures of {alpha}-Fe(bcc) and {var_epsilon}-Co(hcp) phases depart from the standard sequence (hcp {yields} bcc{yields} hcp {yields} fcc), as observed in all other non-magnetic transition metals with increasing the d-band occupancy

How Does Boiling in the Earth's Crust Influence Metal Speciation and Transport?

NASA Astrophysics Data System (ADS)

Kam, K.; Lemke, K.

2014-12-01

The presence of large quantities of precious metals, such as gold and copper, near the Earth's surface (upper crust) is commonly attributed to transport in aqueous solution and precipitation upon variations in temperature and pressure. As a consequence, gold exploration is closely linked to solution chemistry, i.e. hydrothermal processes involving aqueous fluids with densities of around unity. However, as crustal fluids buoyantly ascend, boiling produces a coexisting low-density aqueous liquid with fundamentally different physical and chemical properties, and a, most importantly, a high affinity for coinage metals (Heinrich et al., Econ Geol., 1992, 87, 1566). From recent experimental studies of Au (Hurtig and Williams-Jones, 2014, Geochim. Cosmochim. Acta,, 127, 304), we know that metal speciation in this low-density phase differs fundamentally from that observed in bulk solution, clearly, with important implications for Au, and metal speciation in general, transport and ore concentrations processes (these processes would also be operable in industrial geothermal plants given the quite special solvent properties of steam). In brief, this study focuses on the speciation of select metal halides in bulk solution as well as in water vapor, and is driven by our need to understand the solvent properties of around 2.0x109 cubic kilometers of free water (or 2,500 times as much water as stored in all lakes and rivers) present in the Earth's crust. The scope of this study has particular applications in the geothermal and oil industries, as both deal with high temperature low-density aqueous fluids. Understanding how metal halide species behave upon boiling can also provide insight into how metals, such as copper and silver, coat turbine equipment and steam piping in geothermal plants, ultimately rendering these components inoperable. This study will also provide preliminary results from mass spectrometric experiments of transition metal halides, and will be augmented with

Spectroscopic studies of transition-metal ions in molten alkali-metal carboxylates

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

Maroni, V.A.; Maciejewski, M.L.

This paper presents the results of electronic absorption and /sup 13/C-NMR measurements on molten alkali metal formates and acetates and on solutions of selected 3d transition metal ions therein. These studies provide a unique opportunity to explore (1) the highly ordered nature of alkali carboxylates, (2) the ligand field properties of acetate and formate ions, and (3) the coordination chemistry of the 3d transition metals in molten carboxylates. 1 figure, 2 tables.

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2014 CFR

2014-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2010 CFR

2010-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2012 CFR

2012-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2011 CFR

2011-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

40 CFR 421.270 - Applicability: Description of the primary rare earth metals subcategory.

Code of Federal Regulations, 2013 CFR

2013-07-01

... primary rare earth metals subcategory. 421.270 Section 421.270 Protection of Environment ENVIRONMENTAL... CATEGORY Primary Rare Earth Metals Subcategory § 421.270 Applicability: Description of the primary rare earth metals subcategory. The provisions of this subpart are applicable to discharges resulting from the...

Environmentally relevant metal and transition metal ions enhance Fc epsilon RI-mediated mast cell activation.

PubMed Central

Walczak-Drzewiecka, Aurelia; Wyczólkowska, Janina; Dastych, Jaroslaw

2003-01-01

Upon contact with allergen, sensitized mast cells release highly active proinflammatory mediators. Allergen-mediated mast cell activation is an important mechanism in the pathogenesis of atopic asthma. Asthmatic patients are especially susceptible to air pollution. Epidemiologic studies found a positive correlation between severity of symptoms among asthmatic patients and the level of particulate matter (PM) in the air. Among the constituents of PM are metals and transition metals, which could mediate some of its adverse effects on human health. We sought to determine the effect of metal and transition metal ions on allergen-mediated mast cell activation. We observed that several metal and transition metal ions activated mast cells and enhanced allergen-mediated mast cell activation. Thus, Al(3+), Cd(2+), and Sr(2+) induced release of granule-associated N-acetyl-ss-d-hexosaminidase, and Al(3+) and Ni(2+) enhanced antigen-mediated release. Metal and transition metal ions also induced significant secretion of interleukin (IL)-4 and increased antigen-mediated IL-4 secretion in mast cells. These effects of metal and transition metal ions on mast cells were observed at concentrations that do not result in direct cytotoxicity and might be relevant for environmental exposure. Thus, metals and transition metals could increase the level of allergen-mediated mast cell activation, which might be one of the mechanisms mediating exacerbation of allergen-driven asthma symptoms by air pollution. PMID:12727598

Electronic and structural properties of Lu under pressure: Relation to structural phases of the rare-earth metals

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

Min, B.I.; Oguchi, T.; Jansen, H.J.F.

1986-07-15

Ground-state electronic and structural properties of Lu under pressure are investigated with use of the self-consistent all-electron total-energy linear muffin-tin orbital band-structure method within a local-density-functional approximation. Pressure-induced structural transitions are found to occur in the following sequence: hcp--(Sm-type)--dhcp--fcc, which is the same as that observed in the crystal structures of the trivalent rare-earth metals with decreasing atomic number. This structural transition is correlated with the increase in the number of d-italic electrons under pressure.

Rare-Earth Metals and Their Applications in Aviation

DTIC Science & Technology

1984-08-01

metals are not as common as iron and steel which are visible everywhere, yet they are not unfamiliar to us. We often encounter them in everyday life...the flint of a lighter. It is an alloy of rare-earth metal and iron . It contains about 30% iron and the remainder is a composite rare-earth alloy...used to manufacture the detonators of bullets and shells as well as the pyrophoric alloys of firing devices. This type of alloy has a 49.5% content of

Understanding topological phase transition in monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Choe, Duk-Hyun; Sung, Ha-Jun; Chang, K. J.

2016-03-01

Despite considerable interest in layered transition metal dichalcogenides (TMDs), such as M X2 with M =(Mo ,W ) and X =(S ,Se ,Te ) , the physical origin of their topological nature is still poorly understood. In the conventional view of topological phase transition (TPT), the nontrivial topology of electron bands in TMDs is caused by the band inversion between metal d - and chalcogen p -orbital bands where the former is pulled down below the latter. Here, we show that, in TMDs, the TPT is entirely different from the conventional speculation. In particular, M S2 and M S e2 exhibits the opposite behavior of TPT such that the chalcogen p -orbital band moves down below the metal d -orbital band. More interestingly, in M T e2 , the band inversion occurs between the metal d -orbital bands. Our findings cast doubts on the common view of TPT and provide clear guidelines for understanding the topological nature in new topological materials to be discovered.

Process optimization and kinetics for leaching of rare earth metals from the spent Ni-metal hydride batteries.

PubMed

Meshram, Pratima; Pandey, B D; Mankhand, T R

2016-05-01

Nickel-metal hydride batteries (Ni-MH) contain not only the base metals, but valuable rare earth metals (REMs) viz. La, Sm, Nd, Pr and Ce as well. In view of the importance of resource recycling and assured supply of the contained metals in such wastes, the present study has focussed on the leaching of the rare earth metals from the spent Ni-MH batteries. The conditions for the leaching of REMs from the spent batteries were optimized as: 2M H2SO4, 348K temperature and 120min of time at a pulp density (PD) of 100g/L. Under this condition, the leaching of 98.1% Nd, 98.4% Sm, 95.5% Pr and 89.4% Ce was achieved. Besides the rare earth metals, more than 90% of base metals (Ni, Co, Mn and Zn) were also leached out in this condition. Kinetic data for the dissolution of all the rare earth metals showed the best fit to the chemical control shrinking core model. The leaching of metals followed the mechanism involving the chemical reaction proceeding on the surface of particles by the lixiviant, which was corroborated by the XRD phase analysis and SEM-EDS studies. The activation energy of 7.6, 6.3, 11.3 and 13.5kJ/mol was acquired for the leaching of neodymium, samarium, praseodymium and cerium, respectively in the temperature range 305-348K. From the leach liquor, the mixed rare earth metals were precipitated at pH∼1.8 and the precipitated REMs was analyzed by XRD and SEM studies to determine the phases and the morphological features. Copyright © 2015. Published by Elsevier Ltd.

First-row transition metal hydrogenation and hydrosilylation catalysts

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

Trovitch, Ryan J.; Mukhopadhyay, Tufan K.; Pal, Raja

Transition metal compounds, and specifically transition metal compounds having a tetradentate and/or pentadentate supporting ligand are described, together with methods for the preparation thereof and the use of such compounds as hydrogenation and/or hydrosilylation catalysts.

Lunar Flight Study Series: Volume 6. A Study of Geometrical and Terminal Characteristics of Earth-Moon Transits Embedded in the Earth-Moon Plane

NASA Technical Reports Server (NTRS)

Lisle, B. J.

1963-01-01

This report represents the results of a study of coplanar earth-moon transits. The study was initiated to provide information concerning coplanar geometrical characteristics of earth-moon trnasits. The geometrical aspects of transit behavior are related to variations injection conditions. The model of the earth-moon system used in this investigation is the Jacobian model of the restricted three body problem. All transits considered in this study are restricted to the moon-earth plane (MEP).

Intercalation of Transition Metals into Stacked Benzene Rings: A Model Study of the Intercalation of Transition Metals into Bilayered Graphene.

PubMed

Youn, Il Seung; Kim, Dong Young; Singh, N Jiten; Park, Sung Woo; Youn, Jihee; Kim, Kwang S

2012-01-10

Structures of neutral metal-dibenzene complexes, M(C6H6)2 (M = Sc-Zn), are investigated by using Møller-Plesset second order perturbation theory (MP2). The benzene molecules change their conformation and shape upon complexation with the transition metals. We find two types of structures: (i) stacked forms for early transition metal complexes and (ii) distorted forms for late transition metal ones. The benzene molecules and the metal atom are bound together by δ bonds which originate from the interaction of π-MOs and d orbitals. The binding energy shows a maximum for Cr(C6H6)2, which obeys the 18-electron rule. It is noticeable that Mn(C6H6)2, a 19-electron complex, manages to have a stacked structure with an excess electron delocalized. For other late transition metal complexes having more than 19 electrons, the benzene molecules are bent or stray away from each other to reduce the electron density around a metal atom. For the early transition metals, the M(C6H6) complexes are found to be more weakly bound than M(C6H6)2. This is because the M(C6H6) complexes do not have enough electrons to satisfy the 18-electron rule, and so the M(C6H6)2 complexes generally tend to have tighter binding with a shorter benzene-metal length than the M(C6H6) complexes, which is quite unusual. The present results could provide a possible explanation of why on the Ni surface graphene tends to grow in a few layers, while on the Cu surface the weak interaction between the copper surface and graphene allows for the formation of a single layer of graphene, in agreement with chemical vapor deposition experiments.

Effect of rare-earth doping on the thermoelectric and electrical transport properties of the transition metal pentatelluride hafnium pentatelluride

NASA Astrophysics Data System (ADS)

Lowhorn, Nathan Dane

The transition metal pentatellurides HfTe5 and ZrTe5 have been observed to possess interesting electrical transport properties. High thermopower and low resistivity values result in high thermoelectric power factors. In addition, they possess anomalous transport behavior. The temperature dependence of the resistivity is semimetallic except for a large resistive peak as a function of temperature at around 75 K for HfTe5 and 145 K for ZrTe5. At a temperature corresponding to this peak, the thermopower crosses zero as it moves from large positive values to large negative values. This behavior has been found to be extremely sensitive to changes in the energetics of the system through influences such as magnetic field, stress, pressure, microwave radiation, and substitutional doping. This behavior has yet to be fully explained. Previous doping studies have shown profound and varied effects on the anomalous transport behavior. In this study we investigate the effect on the electrical resistivity, thermopower, and magnetoresistance of doping HfTe5 with rare-earth elements. We have grown single crystals of nominal Hf0.75RE 0.25Te5 where RE = Ce, Pr, Nd, Sm, Gd, Tb, Dy, and Ho. Electrical resistivity and thermopower data from about 10 K to room temperature are presented and discussed in terms of the thermoelectric properties. Doping with rare-earth elements of increasing atomic number leads to a systematic suppression of the anomalous transport behavior. Rare-earth doping also leads to an enhancement of the thermoelectric power factor over that of previously studied pentatellurides and the commonly used thermoelectric material Bi2Te3. For nominal Hf0.75Nd0.25Te5 and Hf0.75 Sm0.25Te5, values more than a factor of 2 larger than that Bi2Te3 are observed. In addition, suppression of the anomalous transport behavior leads to a suppression of the large magnetoresistive effect observed in the parent compounds. Rare-earth doping of HfTe5 has a profound impact on the anomalous

A temperate rocky super-Earth transiting a nearby cool star

NASA Astrophysics Data System (ADS)

Dittmann, Jason A.; Irwin, Jonathan M.; Charbonneau, David; Bonfils, Xavier; Astudillo-Defru, Nicola; Haywood, Raphaëlle D.; Berta-Thompson, Zachory K.; Newton, Elisabeth R.; Rodriguez, Joseph E.; Winters, Jennifer G.; Tan, Thiam-Guan; Almenara, Jose-Manuel; Bouchy, François; Delfosse, Xavier; Forveille, Thierry; Lovis, Christophe; Murgas, Felipe; Pepe, Francesco; Santos, Nuno C.; Udry, Stephane; Wünsche, Anaël; Esquerdo, Gilbert A.; Latham, David W.; Dressing, Courtney D.

2017-04-01

M dwarf stars, which have masses less than 60 per cent that of the Sun, make up 75 per cent of the population of the stars in the Galaxy. The atmospheres of orbiting Earth-sized planets are observationally accessible via transmission spectroscopy when the planets pass in front of these stars. Statistical results suggest that the nearest transiting Earth-sized planet in the liquid-water, habitable zone of an M dwarf star is probably around 10.5 parsecs away. A temperate planet has been discovered orbiting Proxima Centauri, the closest M dwarf, but it probably does not transit and its true mass is unknown. Seven Earth-sized planets transit the very low-mass star TRAPPIST-1, which is 12 parsecs away, but their masses and, particularly, their densities are poorly constrained. Here we report observations of LHS 1140b, a planet with a radius of 1.4 Earth radii transiting a small, cool star (LHS 1140) 12 parsecs away. We measure the mass of the planet to be 6.6 times that of Earth, consistent with a rocky bulk composition. LHS 1140b receives an insolation of 0.46 times that of Earth, placing it within the liquid-water, habitable zone. With 90 per cent confidence, we place an upper limit on the orbital eccentricity of 0.29. The circular orbit is unlikely to be the result of tides and therefore was probably present at formation. Given its large surface gravity and cool insolation, the planet may have retained its atmosphere despite the greater luminosity (compared to the present-day) of its host star in its youth. Because LHS 1140 is nearby, telescopes currently under construction might be able to search for specific atmospheric gases in the future.

A temperate rocky super-Earth transiting a nearby cool star.

PubMed

Dittmann, Jason A; Irwin, Jonathan M; Charbonneau, David; Bonfils, Xavier; Astudillo-Defru, Nicola; Haywood, Raphaëlle D; Berta-Thompson, Zachory K; Newton, Elisabeth R; Rodriguez, Joseph E; Winters, Jennifer G; Tan, Thiam-Guan; Almenara, Jose-Manuel; Bouchy, François; Delfosse, Xavier; Forveille, Thierry; Lovis, Christophe; Murgas, Felipe; Pepe, Francesco; Santos, Nuno C; Udry, Stephane; Wünsche, Anaël; Esquerdo, Gilbert A; Latham, David W; Dressing, Courtney D

2017-04-19

M dwarf stars, which have masses less than 60 per cent that of the Sun, make up 75 per cent of the population of the stars in the Galaxy. The atmospheres of orbiting Earth-sized planets are observationally accessible via transmission spectroscopy when the planets pass in front of these stars. Statistical results suggest that the nearest transiting Earth-sized planet in the liquid-water, habitable zone of an M dwarf star is probably around 10.5 parsecs away. A temperate planet has been discovered orbiting Proxima Centauri, the closest M dwarf, but it probably does not transit and its true mass is unknown. Seven Earth-sized planets transit the very low-mass star TRAPPIST-1, which is 12 parsecs away, but their masses and, particularly, their densities are poorly constrained. Here we report observations of LHS 1140b, a planet with a radius of 1.4 Earth radii transiting a small, cool star (LHS 1140) 12 parsecs away. We measure the mass of the planet to be 6.6 times that of Earth, consistent with a rocky bulk composition. LHS 1140b receives an insolation of 0.46 times that of Earth, placing it within the liquid-water, habitable zone. With 90 per cent confidence, we place an upper limit on the orbital eccentricity of 0.29. The circular orbit is unlikely to be the result of tides and therefore was probably present at formation. Given its large surface gravity and cool insolation, the planet may have retained its atmosphere despite the greater luminosity (compared to the present-day) of its host star in its youth. Because LHS 1140 is nearby, telescopes currently under construction might be able to search for specific atmospheric gases in the future.

Electronic doping of transition metal oxide perovskites

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

Cammarata, Antonio, E-mail: cammaant@fel.cvut.cz; Rondinelli, James M.

2016-05-23

CaFeO{sub 3} is a prototypical negative charge transfer oxide that undergoes electronic metal-insulator transition concomitant with a dilation and contraction of nearly rigid octahedra. Altering the charge neutrality of the bulk system destroys the electronic transition, while the structure is significantly modified at high charge content. Using density functional theory simulations, we predict an alternative avenue to modulate the structure and the electronic transition in CaFeO{sub 3}. Charge distribution can be modulated using strain-rotation coupling and thin film engineering strategies, proposing themselves as a promising avenue for fine tuning electronic features in transition metal-oxide perovskites.

Polyoxometalate electrocatalysts based on earth-abundant metals for efficient water oxidation in acidic media

NASA Astrophysics Data System (ADS)

Blasco-Ahicart, Marta; Soriano-López, Joaquín; Carbó, Jorge J.; Poblet, Josep M.; Galan-Mascaros, J. R.

2018-01-01

Water splitting is a promising approach to the efficient and cost-effective production of renewable fuels, but water oxidation remains a bottleneck in its technological development because it largely relies on noble-metal catalysts. Although inexpensive transition-metal oxides are competitive water oxidation catalysts in alkaline media, they cannot compete with noble metals in acidic media, in which hydrogen production is easier and faster. Here, we report a water oxidation catalyst based on earth-abundant metals that performs well in acidic conditions. Specifically, we report the enhanced catalytic activity of insoluble salts of polyoxometalates with caesium or barium counter-cations for oxygen evolution. In particular, the barium salt of a cobalt-phosphotungstate polyanion outperforms the state-of-the-art IrO2 catalyst even at pH < 1, with an overpotential of 189 mV at 1 mA cm-2. In addition, we find that a carbon-paste conducting support with a hydrocarbon binder can improve the stability of metal-oxide catalysts in acidic media by providing a hydrophobic environment.

Transition metals in superheat melts

NASA Technical Reports Server (NTRS)

Jakes, Petr; Wolfbauer, Michael-Patrick

1993-01-01

A series of experiments with silicate melts doped with transition element oxides was carried out at atmospheric pressures of inert gas at temperatures exceeding liquidus. As predicted from the shape of fO2 buffer curves in T-fO2 diagrams the reducing conditions for a particular oxide-metal pair can be achieved through the T increase if the released oxygen is continuously removed. Experimental studies suggest that transition metals such as Cr or V behave as siderophile elements at temperatures exceeding liquidus temperatures if the system is not buffered by the presence of other oxide of more siderophile element. For example the presence of FeO prevents the reduction of Cr2O3. The sequence of decreasing siderophility of transition elements at superheat conditions (Mo, Ni, Fe, Cr) matches the decreasing degree of depletion of siderophile elements in mantle rocks as compared to chondrites.

Phase stability of transition metals and alloys

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

Hixson, R.S.; Schiferl, D.; Wills, J.M.

1997-06-01

This is the final report of a three-year, Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This project was focused on resolving unexplained differences in calculated and measured phase transition pressures in transition metals. Part of the approach was to do new, higher accuracy calculations of transmission pressures for group 4B and group 6B metals. Theory indicates that the transition pressures for these baseline metals should change if alloyed with a d-electron donor metal, and calculations done using the Local Density Approximation (LDA) and the Virtual Crystal Approximation (VCA) indicate that this is true. Alloymore » systems were calculated for Ti, Zr and Hf based alloys with various solute concentrations. The second part of the program was to do new Diamond Anvil Cell (DAC) measurements to experimentally verify calculational results. Alloys were prepared for these systems with grain size suitable for Diamond Anvil Cell experiments. Experiments were done on pure Ti as well as Ti-V and Ti-Ta alloys. Measuring unambiguous transition pressures for these systems proved difficult, but a new technique developed yielded good results.« less

Superconducting Metallic Glass Transition-Edge-Sensors

NASA Technical Reports Server (NTRS)

Hays, Charles C. (Inventor)

2013-01-01

A superconducting metallic glass transition-edge sensor (MGTES) and a method for fabricating the MGTES are provided. A single-layer superconducting amorphous metal alloy is deposited on a substrate. The single-layer superconducting amorphous metal alloy is an absorber for the MGTES and is electrically connected to a circuit configured for readout and biasing to sense electromagnetic radiation.

A Spitzer search for transits of radial velocity detected super-Earths

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

Kammer, J. A.; Knutson, H. A.; Desert, J.-M.

2014-02-01

Unlike hot Jupiters or other gas giants, super-Earths are expected to have a wide variety of compositions, ranging from terrestrial bodies like our own to more gaseous planets like Neptune. Observations of transiting systems, which allow us to directly measure planet masses and radii and constrain atmospheric properties, are key to understanding the compositional diversity of the planets in this mass range. Although Kepler has discovered hundreds of transiting super-Earth candidates over the past 4 yr, the majority of these planets orbit stars that are too far away and too faint to allow for detailed atmospheric characterization and reliable massmore » estimates. Ground-based transit surveys focus on much brighter stars, but most lack the sensitivity to detect planets in this size range. One way to get around the difficulty of finding these smaller planets in transit is to start by choosing targets that are already known to host super-Earth sized bodies detected using the radial velocity (RV) technique. Here we present results from a Spitzer program to observe six of the most favorable RV-detected super-Earth systems, including HD 1461, HD 7924, HD 156668, HIP 57274, and GJ 876. We find no evidence for transits in any of their 4.5 μm flux light curves, and place limits on the allowed transit depths and corresponding planet radii that rule out even the most dense and iron-rich compositions for these objects. We also observed HD 97658, but the observation window was based on a possible ground-based transit detection that was later ruled out; thus the window did not include the predicted time for the transit detection recently made by the Microvariability and Oscillations of Stars space telescope.« less

Electroforming and Switching in Oxides of Transition Metals: The Role of Metal Insulator Transition in the Switching Mechanism

NASA Astrophysics Data System (ADS)

Chudnovskii, F. A.; Odynets, L. L.; Pergament, A. L.; Stefanovich, G. B.

1996-02-01

Electroforming and switching effects in sandwich structures based on anodic films of transition metal oxides (V, Nb, Ti, Fe, Ta, W, Zr, Hf, Mo) have been studied. After being electroformed, some materials exhibited current-controlled negative resistance with S-shapedV-Icharacteristics. For V, Fe, Ti, and Nb oxides, the temperature dependences of the threshold voltage have been measured. As the temperature increased,Vthdecreased to zero at a critical temperatureT0, which depended on the film material. Comparison of theT0values with the temperatures of metal-insulator phase transition for some compounds (Tt= 120 K for Fe3O4, 340 K for VO2, ∼500 K for Ti2O3, and 1070 K for NbO2) showed that switching was related to the transition in the applied electric field. Channels consisting of the above-mentioned lower oxides were formed in the initial anodic films during the electroforming. The possibility of formation of these oxides with a metal-insulator transition was confirmed by thermodynamic calculations.

Semiconducting transition metal oxides.

PubMed

Lany, Stephan

2015-07-22

Open shell transition metal oxides are usually described as Mott or charge transfer insulators, which are often viewed as being disparate from semiconductors. Based on the premise that the presence of a correlated gap and semiconductivity are not mutually exclusive, this work reviews electronic structure calculations on the binary 3d oxides, so to distill trends and design principles for semiconducting transition metal oxides. This class of materials possesses the potential for discovery, design, and development of novel functional semiconducting compounds, e.g. for energy applications. In order to place the 3d orbitals and the sp bands into an integrated picture, band structure calculations should treat both contributions on the same footing and, at the same time, account fully for electron correlation in the 3d shell. Fundamentally, this is a rather daunting task for electronic structure calculations, but quasi-particle energy calculations in GW approximation offer a viable approach for band structure predictions in these materials. Compared to conventional semiconductors, the inherent multivalent nature of transition metal cations is more likely to cause undesirable localization of electron or hole carriers. Therefore, a quantitative prediction of the carrier self-trapping energy is essential for the assessing the semiconducting properties and to determine whether the transport mechanism is a band-like large-polaron conduction or a small-polaron hopping conduction. An overview is given for the binary 3d oxides on how the hybridization between the 3d crystal field symmetries with the O-p orbitals of the ligands affects the effective masses and the likelihood of electron and hole self-trapping, identifying those situations where small masses and band-like conduction are more likely to be expected. The review concludes with an illustration of the implications of the increased electronic complexity of transition metal cations on the defect physics and doping, using

Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts

DOE PAGES

Hunt, Sean T.; Milina, Maria; Alba-Rubio, Ana C.; ...

2016-05-20

Here, we demonstrated the self-assembly of transition metal carbide nanoparticles coated with atomically thin noble metal monolayers by carburizing mixtures of noble metal salts and transition metal oxides encapsulated in removable silica templates. This approach allows for control of the final core-shell architecture, including particle size, monolayer coverage, and heterometallic composition. Carbon-supported Ti 0.1W 0.9C nanoparticles coated with Pt or bimetallic PtRu monolayers exhibited enhanced resistance to sintering and CO poisoning, achieving an order of magnitude increase in specific activity over commercial catalysts for methanol electrooxidation after 10,000 cycles. These core-shell materials provide a new direction to reduce the loading,more » enhance the activity, and increase the stability of noble metal catalysts.« less

Crystallographic phases in heavy rare earth metals under megabar pressures

NASA Astrophysics Data System (ADS)

Samudrala, G. K.; Vohra, Y. K.

2012-07-01

Experiments aimed at understanding the crystallographic phases of heavy rare earth metals were carried out in a diamond anvil cell at the Advanced Photon Source, Argonne National Laboratory. Heavy rare earth metals dysprosium (Dy), holmium (Ho), erbium (Er) and thulium (Tm) were compressed to multi-megabar pressures. The rare earth crystal sequence hcp→Sm-type→dhcp→distorted-fcc (dfcc) is observed in all four elements. Upon further compression, a structural transformation to a monoclinic C2/m phase has been observed. We summarize the results from these experiments and present Rietveld structural refinements on high pressure phases for the specific case of dysprosium.

Pressure induced structural phase transition in IB transition metal nitrides compounds

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

Soni, Shubhangi; Kaurav, Netram, E-mail: netramkaurav@yahoo.co.uk; Jain, A.

2015-06-24

Transition metal mononitrides are known as refractory compounds, and they have, relatively, high hardness, brittleness, melting point, and superconducting transition temperature, and they also have interesting optical, electronic, catalytic, and magnetic properties. Evolution of structural properties would be an important step towards realizing the potential technological scenario of this material of class. In the present study, an effective interionic interaction potential (EIOP) is developed to investigate the pressure induced phase transitions in IB transition metal nitrides TMN [TM = Cu, Ag, and Au] compounds. The long range Coulomb, van der Waals (vdW) interaction and the short-range repulsive interaction upto second-neighbormore » ions within the Hafemeister and Flygare approach with modified ionic charge are properly incorporated in the EIOP. The vdW coefficients are computed following the Slater-Kirkwood variational method, as both the ions are polarizable. The estimated value of the phase transition pressure (Pt) and the magnitude of the discontinuity in volume at the transition pressure are consistent as compared to the reported data.« less

A system of three transiting super-Earths in a cool dwarf star

NASA Astrophysics Data System (ADS)

Díez Alonso, E.; Suárez& Gómez, S. L.; González Hernández, J. I.; Suárez Mascareño, A.; González Gutiérrez, C.; Velasco, S.; Toledo-Padrón, B.; de Cos Juez, F. J.; Rebolo, R.

2018-05-01

We present the detection of three super-Earths transiting the cool star LP415-17, monitored by K2 mission in its 13th campaign. High-resolution spectra obtained with High Accuracy Radial velocity Planet Searcher-North/Telescopio Nazionale Galileo (HARPS-N/TNG) showed that the star is a mid-late K dwarf. Using spectral synthesis models, we infer its effective temperature, surface gravity, and metallicity, and subsequently determined from evolutionary models a stellar radius of 0.58 R⊙. The planets have radii of 1.8, 2.6, and 1.9 R⊕ and orbital periods of 6.34, 13.85, and 40.72 d. High-resolution images discard any significant contamination by an intervening star in the line of sight. The orbit of the furthest planet has radius of 0.18 au, close to the inner edge of the habitable zone. The system is suitable to improve our understanding of formation and dynamical evolution of super-Earth systems in the rocky-gaseous threshold, their atmospheres, internal structure, composition, and interactions with host stars.

Response of the Lattice across the Filling-Controlled Mott Metal-Insulator Transition of a Rare Earth Titanate

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

Kim, Honggyu; Marshall, Patrick B.; Ahadi, Kaveh

The lattice response of a prototype Mott insulator, SmTiO 3, to hole doping is investigated with atomic-scale spatial resolution. SmTiO 3 films are doped with Sr on the Sm site with concentrations that span the insulating and metallic sides of the filling-controlled Mott metal-insulator transition (MIT). The GdFeO 3-type distortions are investigated using an atomic resolution scanning transmission electron microscopy technique that can resolve small lattice distortions with picometer precision. We show that these distortions are gradually and uniformly reduced as the Sr concentration is increased without any phase separation. Significant distortions persist into the metallic state. In conclusion, themore » results present a new picture of the physics of this prototype filling-controlled MIT, which is discussed.« less

Response of the Lattice across the Filling-Controlled Mott Metal-Insulator Transition of a Rare Earth Titanate

DOE PAGES

Kim, Honggyu; Marshall, Patrick B.; Ahadi, Kaveh; ...

2017-11-02

The lattice response of a prototype Mott insulator, SmTiO 3, to hole doping is investigated with atomic-scale spatial resolution. SmTiO 3 films are doped with Sr on the Sm site with concentrations that span the insulating and metallic sides of the filling-controlled Mott metal-insulator transition (MIT). The GdFeO 3-type distortions are investigated using an atomic resolution scanning transmission electron microscopy technique that can resolve small lattice distortions with picometer precision. We show that these distortions are gradually and uniformly reduced as the Sr concentration is increased without any phase separation. Significant distortions persist into the metallic state. In conclusion, themore » results present a new picture of the physics of this prototype filling-controlled MIT, which is discussed.« less

GLANCING VIEWS OF THE EARTH: FROM A LUNAR ECLIPSE TO AN EXOPLANETARY TRANSIT

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

Garcia Munoz, A.; Barrena, R.; Montanes-Rodriguez, P.

2012-08-20

It has been posited that lunar eclipse observations may help predict the in-transit signature of Earth-like extrasolar planets. However, a comparative analysis of the two phenomena addressing in detail the transport of stellar light through the planet's atmosphere has not yet been presented. Here, we proceed with the investigation of both phenomena by making use of a common formulation. Our starting point is a set of previously unpublished near-infrared spectra collected at various phases during the 2008 August lunar eclipse. We then take the formulation to the limit of an infinitely distant observer in order to investigate the in-transit signaturemore » of the Earth-Sun system as being observed from outside our solar system. The refraction bending of sunlight rays that pass through Earth's atmosphere is a critical factor in the illumination of the eclipsed Moon. Likewise, refraction will have an impact on the in-transit transmission spectrum for specific planet-star systems depending on the refractive properties of the planet's atmosphere, the stellar size, and the planet's orbital distance. For the Earth-Sun system, at mid-transit, refraction prevents the remote observer's access to the lower {approx}12-14 km of the atmosphere and, thus, also to the bulk of the spectroscopically active atmospheric gases. We demonstrate that the effective optical radius of the Earth in-transit is modulated by refraction and varies by {approx}12 km from mid-transit to internal contact. The refractive nature of atmospheres, a property which is rarely accounted for in published investigations, will pose additional challenges to the characterization of Earth-like extrasolar planets. Refraction may have a lesser impact for Earth-like extrasolar planets within the habitable zone of some M-type stars.« less

Half-sandwich rare-earth-catalyzed olefin polymerization, carbometalation, and hydroarylation.

PubMed

Nishiura, Masayoshi; Guo, Fang; Hou, Zhaomin

2015-08-18

The search for new catalysts for more efficient, selective chemical transformations and for the synthesis of new functional materials has been a long-standing research subject in both academia and industry. To develop new generations of catalysts that are superior or complementary to the existing ones, exploring the potential of untapped elements is an important strategy. Rare-earth elements, including scandium, yttrium, and the lanthanides (La-Lu), constitute one important frontier in the periodic table. Rare-earth elements possess unique chemical and physical properties that are different from those of main-group and late-transition metals. The development of rare-earth-based catalysts by taking the advantage of these unique properties is of great interest and importance. The most stable oxidation state of rare-earth metals is 3+, which is difficult to change under many reaction conditions. The oxidative addition and reductive elimination processes often observed in catalytic cycles involving late transition metals are generally difficult in the case of rare-earth complexes. The 18-electron rule that is applicable to late-transition-metal complexes does not fit rare-earth complexes, whose structures are mainly governed by the sterics (rather than the electron numbers) of the ligands. In the lanthanide series (La-Lu), the ionic radius gradually decreases with increasing atomic number because of the influence of the 4f electrons, which show poor shielding of nuclear charge. Rare-earth metal ions generally show strong Lewis acidity and oxophilicity. Rare-earth metal alkyl and hydride species are highly reactive, showing both nucleophilicity and basicity. The combination of these features, such as the strong nucleophilicity and moderate basicity of the alkyl and hydride species and the high stability, strong Lewis acidity, and unsaturated C-C bond affinity of the 3+ metal ions, can make rare-earth metals unique candidates for the formation of excellent single

Ferroelectric control of metal-insulator transition

NASA Astrophysics Data System (ADS)

He, Xu; Jin, Kui-juan; Ge, Chen; Ma, Zhong-shui; Yang, Guo-zhen

2016-03-01

We propose a method of controlling the metal-insulator transition of one perovskite material at its interface with another ferroelectric material based on first principle calculations. The operating principle is that the rotation of oxygen octahedra tuned by the ferroelectric polarization can modulate the superexchange interaction in this perovskite. We designed a tri-color superlattice of (BiFeO3)N/LaNiO3/LaTiO3, in which the BiFeO3 layers are ferroelectric, the LaNiO3 layer is the layer of which the electronic structure is to be tuned, and LaTiO3 layer is inserted to enhance the inversion asymmetry. By reversing the ferroelectric polarization in this structure, there is a metal-insulator transition of the LaNiO3 layer because of the changes of crystal field splitting of the Ni eg orbitals and the bandwidth of the Ni in-plane eg orbital. It is highly expected that a metal-transition can be realized by designing the structures at the interfaces for more materials.

Trends in Ionization Energy of Transition-Metal Elements

ERIC Educational Resources Information Center

Matsumoto, Paul S.

2005-01-01

A rationale for the difference in the periodic trends in the ionization energy of the transition-metal elements versus the main-group elements is presented. The difference is that in the transition-metal elements, the electrons enter an inner-shell electron orbital, while in the main-group elements, the electrons enter an outer-shell electron…

Harnessing the metal-insulator transition for tunable metamaterials

NASA Astrophysics Data System (ADS)

Charipar, Nicholas A.; Charipar, Kristin M.; Kim, Heungsoo; Bingham, Nicholas S.; Suess, Ryan J.; Mathews, Scott A.; Auyeung, Raymond C. Y.; Piqué, Alberto

2017-08-01

The control of light-matter interaction through the use of subwavelength structures known as metamaterials has facilitated the ability to control electromagnetic radiation in ways not previously achievable. A plethora of passive metamaterials as well as examples of active or tunable metamaterials have been realized in recent years. However, the development of tunable metamaterials is still met with challenges due to lack of materials choices. To this end, materials that exhibit a metal-insulator transition are being explored as the active element for future metamaterials because of their characteristic abrupt change in electrical conductivity across their phase transition. The fast switching times (▵t < 100 fs) and a change in resistivity of four orders or more make vanadium dioxide (VO2) an ideal candidate for active metamaterials. It is known that the properties associated with thin film metal-insulator transition materials are strongly dependent on the growth conditions. For this work, we have studied how growth conditions (such as gas partial pressure) influence the metalinsulator transition in VO2 thin films made by pulsed laser deposition. In addition, strain engineering during the growth process has been investigated as a method to tune the metal-insulator transition temperature. Examples of both the optical and electrical transient dynamics facilitating the metal-insulator transition will be presented together with specific examples of thin film metamaterial devices.

Maximum-valence radii of transition metals

PubMed Central

Pauling, Linus

1975-01-01

In many of their compounds the transition metals have covalence 9, forming nine bonds with use of nine hybrid spd bond orbitals. A set of maximum-valence single-bond radii is formulated for use in these compounds. These radii are in reasonably good agreement with observed bond lengths. Quadruple bonds between two transition metal atoms are about 50 pm (iron-group atoms) or 55 pm (palladium and platinum-group atoms) shorter than single bonds. This amount of shortening corresponds to four bent single bonds with the best set of bond angles, 79.24° and 128.8°. PMID:16578730

Impurities in Antiferromagnetic Transition-Metal Oxides - Symmetry and Optical Transitions

NASA Astrophysics Data System (ADS)

Petersen, John Emil, III

The study of antiferromagnetic transition-metal oxides is an extremely active area in the physical sciences, where condensed matter physics, inorganic chemistry, and materials science blend together. The sheer number of potential commercial applications is staggering, but much of the fundamental science remains unexplained. This is not due to a lack of effort, however, as theorists have been struggling to understand these materials for decades - particularly the character of the band edges and first optical transitions. The difficulty lies in the strong correlation or Coloumb attraction between the electrons in the anisotropic d orbitals, which conventional band theory cannot describe adequately. The correlation problem is approached here by the well-accepted method of adding a Hubbard potential energy term to the ground state Hamiltonian, calculated within Density Functional Theory. The frequency-dependent complex dielectric function is calculated within the Independent Particle Approximation, and optical transitions are evaluated in multiple different ways. Peaks in the imaginary part of the dielectric function are compared energetically to orbitally decomposed density of states calculations. Optical transitions are typically analyzed in terms of atomic orbitals, which, strictly speaking, gives misleading results. Here, however, from the calculated data, two alternative interpretations are analyzed for each material studied. The first employs rigorous group theoretical analysis to determine allowed electric-dipole transitions, taking into account both orbital hybridization and crystal symmetry. The second interpretation is that of metal cation site hopping. In this interpretation, carriers hop from the x2 - y2 d orbital of one metal cation lattice site to the next metal cation site which is antiferromagnetically aligned. At times, thoughout this work, one interpretation is favorable to the other. Which interpretation is most valid depends on the material

Induction slag reduction process for purifying metals

DOEpatents

Traut, Davis E.; Fisher, II, George T.; Hansen, Dennis A.

1991-01-01

A continuous method is provided for purifying and recovering transition metals such as neodymium and zirconium that become reactive at temperatures above about 500.degree. C. that comprises the steps of contacting the metal ore with an appropriate fluorinating agent such as an alkaline earth metal fluosilicate to form a fluometallic compound, and reducing the fluometallic compound with a suitable alkaline earth or alkali metal compound under molten conditions, such as provided in an induction slag metal furnace. The method of the invention is advantageous in that it is simpler and less expensive than methods used previously to recover pure metals, and it may be employed with a wide range of transition metals that were reactive with enclosures used in the prior art methods and were hard to obtain in uncontaminated form.

Reaction between hydrous wadsleyite and iron: Implication for water distribution in Earth's transition zone

NASA Astrophysics Data System (ADS)

Zhu, F.; Li, J.; Liu, J.; Dong, J.

2017-12-01

The mantle transition zone (TZ) is considered as a potential water reservoir due to large capacities of wadsleyite and ringwoodite to store water in the structures. Whether it is a hydrous layer or an empty reservoir, however, is still under debate. Because the TZ may contain metallic iron1, 2 and water is an oxidizing agent at > 5 GPa, the stability of coexisting iron and TZ hydrous phases needs to be examined. In this study, we conducted multi-anvil experiments on iron with synthetic hydrous wadsleyite or forsterite and water under TZ pressure-temperature conditions. Similar rapid reactions were observed for both types of starting materials, producing ferropericlase, iron-bearing wadsleyite or ringwoodite, and iron hydride. The results imply that a hydrous TZ is incompatible with a reduced state, and that water distribution of TZ is confined to subducting slabs and slab-mantle boundaries, where water or hydrous phases in slab must oxidize the adjacent mantle before they can hydrate the silicates. In contrast, the bulk transition zone may be mostly dry. The iron hydride produced from this slab-mantle interaction may sink to greater depths due to their low melting temperature3, thus providing a pathway for hydrogen to enter the lower mantle and core. References 1. O'Neill HSC, McCammon C, Canil D, Rubie D, Ross C, Seifert F. Mossbauer spectroscopy of mantle transition zone phases and determination of minimum Fe3+ content. American Mineralogist 1993, 78(3-4): 456-460. 2. Rohrbach A, Ballhaus C, Golla-Schindler U, Ulmer P, Kamenetsky VS, Kuzmin DV. Metal saturation in the upper mantle. Nature 2007, 449(7161): 456-458. 3. Sakamaki K, Takahashi E, Nakajima Y, Nishihara Y, Funakoshi K, Suzuki T, et al. Melting phase relation of FeH x up to 20GPa: Implication for the temperature of the Earth's core. Physics of the Earth and Planetary Interiors 2009, 174(1): 192-201.

A super-Earth transiting a nearby low-mass star.

PubMed

Charbonneau, David; Berta, Zachory K; Irwin, Jonathan; Burke, Christopher J; Nutzman, Philip; Buchhave, Lars A; Lovis, Christophe; Bonfils, Xavier; Latham, David W; Udry, Stéphane; Murray-Clay, Ruth A; Holman, Matthew J; Falco, Emilio E; Winn, Joshua N; Queloz, Didier; Pepe, Francesco; Mayor, Michel; Delfosse, Xavier; Forveille, Thierry

2009-12-17

A decade ago, the detection of the first transiting extrasolar planet provided a direct constraint on its composition and opened the door to spectroscopic investigations of extrasolar planetary atmospheres. Because such characterization studies are feasible only for transiting systems that are both nearby and for which the planet-to-star radius ratio is relatively large, nearby small stars have been surveyed intensively. Doppler studies and microlensing have uncovered a population of planets with minimum masses of 1.9-10 times the Earth's mass (M[symbol:see text]), called super-Earths. The first constraint on the bulk composition of this novel class of planets was afforded by CoRoT-7b (refs 8, 9), but the distance and size of its star preclude atmospheric studies in the foreseeable future. Here we report observations of the transiting planet GJ 1214b, which has a mass of 6.55M[symbol:see text]), and a radius 2.68 times Earth's radius (R[symbol:see text]), indicating that it is intermediate in stature between Earth and the ice giants of the Solar System. We find that the planetary mass and radius are consistent with a composition of primarily water enshrouded by a hydrogen-helium envelope that is only 0.05% of the mass of the planet. The atmosphere is probably escaping hydrodynamically, indicating that it has undergone significant evolution during its history. The star is small and only 13 parsecs away, so the planetary atmosphere is amenable to study with current observatories.

Nanodisperse transition metal electrodes (NTME) for electrochemical cells

DOEpatents

Striebel, Kathryn A.; Wen, Shi-Jie

2000-01-01

Disclosed are transition metal electrodes for electrochemical cells using gel-state and solid-state polymers. The electrodes are suitable for use in primary and secondary cells. The electrodes (either negative electrode or positive electrode) are characterized by uniform dispersion of the transition metal at the nanoscale in the polymer. The transition metal moiety is structurally amorphous, so no capacity fade should occur due to lattice expansion/contraction mechanisms. The small grain size, amorphous structure and homogeneous distribution provide improved charge/discharge cycling performance, and a higher initial discharge rate capability. The cells can be cycled at high current densities, limited only by the electrolyte conductivity. A method of making the electrodes (positive and negative), and their usage in electrochemical cells are disclosed.

Cross-linking proteins with bimetallic tetracarboxylate compounds of transition metals

DOEpatents

Kostic, Nenad M.; Chen, Jian

1991-03-05

Stable cross-linked complexes of transition-metal tetracarboxylates and proteins are formed. The preferred transition-metal is rhodium. The protein may be collagen or an enzyme such as a proteolytic enzyme.

Doping of alkali, alkaline-earth, and transition metals in covalent-organic frameworks for enhancing CO2 capture by first-principles calculations and molecular simulations.

PubMed

Lan, Jianhui; Cao, Dapeng; Wang, Wenchuan; Smit, Berend

2010-07-27

We use the multiscale simulation approach, which combines the first-principles calculations and grand canonical Monte Carlo simulations, to comprehensively study the doping of a series of alkali (Li, Na, and K), alkaline-earth (Be, Mg, and Ca), and transition (Sc and Ti) metals in nanoporous covalent organic frameworks (COFs), and the effects of the doped metals on CO2 capture. The results indicate that, among all the metals studied, Li, Sc, and Ti can bind with COFs stably, while Be, Mg, and Ca cannot, because the binding of Be, Mg, and Ca with COFs is very weak. Furthermore, Li, Sc, and Ti can improve the uptakes of CO2 in COFs significantly. However, the binding energy of a CO2 molecule with Sc and Ti exceeds the lower limit of chemisorptions and, thus, suffers from the difficulty of desorption. By the comparative studies above, it is found that Li is the best surface modifier of COFs for CO2 capture among all the metals studied. Therefore, we further investigate the uptakes of CO2 in the Li-doped COFs. Our simulation results show that at 298 K and 1 bar, the excess CO2 uptakes of the Li-doped COF-102 and COF-105 reach 409 and 344 mg/g, which are about eight and four times those in the nondoped ones, respectively. As the pressure increases to 40 bar, the CO2 uptakes of the Li-doped COF-102 and COF-105 reach 1349 and 2266 mg/g at 298 K, respectively, which are among the reported highest scores to date. In summary, doping of metals in porous COFs provides an efficient approach for enhancing CO2 capture.

Recent Transits of the Super-Earth Exoplanet GJ 1214B

NASA Technical Reports Server (NTRS)

Sada, Pedro V.; Deming, Drake; Jackson, Brian; Jennings, Donald E.; Peterson, Steven W.; Haase, Flynn; Bays, Kevin; OGorman, Eamon; Lundsford, Alan

2001-01-01

We report recent ground-based photometry of the transiting super-Earth exoplanet GJ1214b at several wavelengths, including the infrared near 1.25 microns (J-band). We observed a J-band transit with the FLAMINGOS infrared imager and the 2.1-meter telescope on Kitt Peak, and we observed several optical transits using a 0.5-meter telescope on Kitt Peak and the 0.36-meter Universidad de Monterrey Observatory telescope. Our high-precision J-band observations exploit the brightness of the M-dwarf host star at this infrared wavelength as compared to the optical, as well as being significantly less affected by stellar activity and limb darkening. We fit the J-band transit to obtain an independent determination of the planetary and stellar radii. Our radius for the planet (2.61 +0.30 / -0.11 Earth radii) is in excellent agreement with the discovery value reported by Charbonneau et al. based on optical data. We demonstrate that the planetary radius is insensitive to degeneracies in the fitting process. We use all of our observations to improve the transit ephemeris, finding P=1.5804043 +/- 0.0000005 days, and T0=2454964.94390 +/- 0.00006 BJD.

Cross-linking proteins with bimetallic tetracarboxylate compounds of transition metals

DOEpatents

Kostic, N.M.; Chen, J.

1991-03-05

Stable cross-linked complexes of transition-metal tetracarboxylates and proteins are formed. The preferred transition-metal is rhodium. The protein may be collagen or an enzyme such as a proteolytic enzyme. No Drawings

Asymmetric Catalysis with bis(hydroxyphenyl)diamides/rare-earth metal complexes.

PubMed

Kumagai, Naoya; Shibasaki, Masakatsu

2013-01-02

A series of asymmetric catalysts composed of conformationally flexible amide-based chiral ligands and rare-earth metals was developed for proton-transfer catalysis. These ligands derived from amino acids provide an intriguing chiral platform for the formation of asymmetric catalysts upon complexation with rare-earth metals. The scope of this arsenal of catalysts was further broadened by the development of heterobimetallic catalytic systems. The cooperative function of hydrogen bonding and metal coordination resulted in intriguing substrate specificity and stereocontrol, and the dynamic nature of the catalysts led to a switch of their function. Herein, we summarize our recent exploration of this class of catalysts. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activated phosphors having matrices of yttrium-transition metal compound

DOEpatents

De Kalb, E.L.; Fassel, V.A.

1975-07-01

A method is described for preparing a phosphor composition containing a lanthanide activator element with a host matrix having a transition element as a major component. The host matrix is composed of certain rare earth phosphates or vanadates such as YPO$sub 4$ with a portion of the rare earth replaced with one or more of the transition elements. On x-ray or other electromagnetic excitation, trace lanthanide impurities or additives within the phosphor are spectrometrically determined from their characteristic luminescence. (auth)

Metal-Insulator Transition in W-doped VO2 Nanowires

NASA Astrophysics Data System (ADS)

Long, Gen; Parry, James; Whittaker, Luisa; Banerjee, Sarbajit; Zeng, Hao

2010-03-01

We report a systematic study of the metal-insulator transition in W-doped VO2 nanowires. Magnetic susceptibility were measured for a bulk amount of VO2 nanowire powder. The susceptibility shows a sharp drop with decreasing temperature corresponding to the metal-insulator transition. The transition shows large temperature hysteresis for cooling and heating. With increasing doping concentration, the transition temperatures decreases systematically from 320 K to 275K. Charge transport measurements on the same nanowires showed similar behavior. XRD and TEM measurements were taken to further determine the structure of the materials in study.

Luminescent molecular rods - transition-metal alkynyl complexes.

PubMed

Yam, Vivian Wing-Wah; Wong, Keith Man-Chung

2005-01-01

A number of transition-metal complexes have been reported to exhibit rich luminescence, usually originating from phosphorescence. Such luminescence properties of the triplet excited state with a large Stoke's shift, long lifetime, high luminescence quantum yield as well as lower excitation energy, are envisaged to serve as an ideal candidate in the area of potential applications for chemosensors, dye-sensitized solar cells, flat panel displays, optics, new materials and biological sciences. Organic alkynes (poly-ynes), with extended or conjugatedπ-systems and rigid structure with linear geometry, have become a significant research area due to their novel electronic and physical properties and their potential applications in nanotechnology. Owing to the presence of unsaturated sp-hybridized carbon atoms, the alkynyl unit can serve as a versatile building block in the construction of alkynyl transition-metal complexes, not only throughσ-bonding but also viaπ-bonding interactions. By incorporation of linear alkynyl groups into luminescent transition-metal complexes, the alkynyl moiety with goodσ-donor,π-donor andπ-acceptor abilities is envisaged to tune or perturb the emission behaviors, including emission energy (color), intensity and lifetime by its role as an auxiliary ligand as well as to govern the emission origin from its direct involvement. This review summarizes recent efforts on the synthesis of luminescent rod-like alkynyl complexes with different classes of transition metals and details the effects of the introduction of alkynyl groups on the luminescence properties of the complexes.

Transition-Metal Substitution Doping in Synthetic Atomically Thin Semiconductors

DOE PAGES

Gao, Jian; Kim, Young Duck; Liang, Liangbo; ...

2016-09-20

Semiconductor impurity doping has enabled an entire generation of technology. The emergence of alternative semiconductor material systems, such as transition metal dichalcogenides (TMDCs), requires the development of scalable doping strategies. We report an unprecedented one-pot synthesis for transition-metal substitution in large-area, synthetic monolayer TMDCs. Electron microscopy, optical and electronic transport characterization and ab initio calculations indicate that our doping strategy preserves the attractive qualities of TMDC monolayers, including semiconducting transport and strong direct-gap luminescence. These results are expected to encourage exploration of transition-metal substitution in two-dimensional systems, potentially enabling next-generation optoelectronic technology in the atomically-thin regime.

Preparation and magnetic properties of phthalocyanine-based carbon materials containing transition metals

NASA Astrophysics Data System (ADS)

Honda, Z.; Sato, S.; Hagiwara, M.; Kida, T.; Sakai, M.; Fukuda, T.; Kamata, N.

2016-07-01

A simple method for the preparation of bulk quantities of magnetic carbon materials, which contain uniformly dispersed transition metals (M = Fe, Co, Ni, and Cu) as the magnetic components, is presented. By using highly chlorinated metal phthalocyanine as the building block and potassium as the coupling reagent, phthalocyanine-based carbon materials (PBCMs) containing transition metals were obtained. Our experiments demonstrate the structure of these PBCMs consists of transition metals embedded in graphitic carbon that includes a square planar MN4 magnetic core and the Fe and Co-PBCM possess spontaneous magnetization at room temperature. In addition, carbon-coated transition metal particles were obtained by the Wurtz-type reaction with excess amount of potassium coupling agent. The large transition metal surface area and magnetization of these M-PBCMs are useful for spintronic and catalytic applications.

Stable isotopes of transition and post-transition metals as tracers in environmental studies

USGS Publications Warehouse

Bullen, Thomas D.; Baskaran, Mark

2011-01-01

The transition and post-transition metals, which include the elements in Groups 3–12 of the Periodic Table, have a broad range of geological and biological roles as well as industrial applications and thus are widespread in the environment. Interdisciplinary research over the past decade has resulted in a broad understanding of the isotope systematics of this important group of elements and revealed largely unexpected variability in isotope composition for natural materials. Significant kinetic and equilibrium isotope fractionation has been observed for redox sensitive metals such as iron, chromium, copper, molybdenum and mercury, and for metals that are not redox sensitive in nature such as cadmium and zinc. In the environmental sciences, the isotopes are increasingly being used to understand important issues such as tracing of metal contaminant sources and fates, unraveling metal redox cycles, deciphering metal nutrient pathways and cycles, and developing isotope biosignatures that can indicate the role of biological activity in ancient and modern planetary systems.

Magnetic and Structural Phase Transitions in Thulium under High Pressures and Low Temperatures

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

Vohra, Yogesh K.; Tsoi, Georgiy M.; Samudrala, Gopi K.

2017-10-01

The nature of 4f electrons in many rare earth metals and compounds may be broadly characterized as being either "localized" or "itinerant", and is held responsible for a wide range of physical and chemical properties. The pressure variable has a very dramatic effect on the electronic structure of rare earth metals which in turn drives a sequence of structural and magnetic transitions. We have carried out four-probe electrical resistance measurements on rare earth metal Thulium (Tm) under high pressures to 33 GPa and low temperatures to 10 K to monitor the magnetic ordering transition. These studies are complemented by anglemore » dispersive x-ray diffraction studies to monitor crystallographic phase transitions at high pressures and low temperatures. We observe an abrupt increase in magnetic ordering temperature in Tm at a pressure of 17 GPa on phase transition from ambient pressure hcp-phase to α-Sm phase transition. In addition, measured equation of state (EOS) at low temperatures show anomalously low thermal expansion coefficients likely linked to magnetic transitions.« less

Cascade morphology transition in bcc metals

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

Setyawan, Wahyu; Selby, A.; Juslin, Niklas

2015-06-10

Energetic atom collisions in solids induce shockwaves with complex morphologies. In this paper, we establish the existence of a morphological transition in such cascades. The order parameter of the morphology is defined as the exponent,more » $b$, in the defect production curve as a function of cascade energy ($$N_F$$$ \\sim$$$E_{MD}^b$$). Response of different bcc metals can be compared in a consistent energy domain when the energy is normalized by the transition energy, $$\\mu$$, between the high- and the low-energy regime. Using Cr, Fe, Mo and W data, an empirical formula of $$\\mu$$ as a function of displacement threshold energy, $$E_d$$, is presented for bcc metals.« less

Cascade morphology transition in bcc metals

DOE PAGES

Setyawan, Wahyu; Selby, Aaron P.; Juslin, Niklas; ...

2015-05-18

Energetic atom collisions in solids induce shockwaves with complex morphologies. In this paper, we establish the existence of a morphological transition in such cascades. The order parameter of the morphology is defined as the exponent, b, in the defect production curve as a function of cascade energy (N-F similar to E-MD(b)). Response of different bcc metals can be compared in a consistent energy domain when the energy is normalized by the transition energy, mu, between the high-and the low-energy regime. Using Cr, Fe, Mo and W data, an empirical formula of mu as a function of displacement threshold energy, E-d,more » is presented for bcc metals.« less

Trion formation dynamics in monolayer transition metal dichalcogenides

DOE PAGES

Singh, Akashay; Moody, Galan; Schaibley, John R.; ...

2016-01-05

Here, we report charged exciton (trion) formation dynamics in doped monolayer transition metal dichalcogenides, specifically molybdenum diselenide (MoSe 2), using resonant two-color pump-probe spectroscopy. When resonantly pumping the exciton transition, trions are generated on a picosecond time scale through exciton-electron interaction. As the pump energy is tuned from the high energy to low energy side of the inhomogeneously broadened exciton resonance, the trion formation time increases by ~50%. This feature can be explained by the existence of both localized and delocalized excitons in a disordered potential and suggests the existence of an exciton mobility edge in transition metal dichalcogenides.

Novel photoinduced phase transitions in transition metal oxides and diluted magnetic semiconductors.

PubMed

Mizokawa, Takashi

2012-10-23

Some transition metal oxides have frustrated electronic states under multiphase competition due to strongly correlated d electrons with spin, charge, and orbital degrees of freedom and exhibit drastic responses to external stimuli such as optical excitation. Here, we present photoemission studies on Pr0.55(Ca1 - ySry)0.45MnO3 (y = 0.25), SrTiO3, and Ti1 - xCoxO2 (x = 0.05, 0.10) under laser illumination and discuss electronic structural changes induced by optical excitation in these strongly correlated oxides. We discuss the novel photoinduced phase transitions in these transition metal oxides and diluted magnetic semiconductors on the basis of polaronic pictures such as orbital, ferromagnetic, and ferroelectric polarons.

Preparation of nanoporous metal foam from high nitrogen transition metal complexes

DOEpatents

Tappan, Bryce C.; Huynh, My Hang V.; Hiskey, Michael A.; Son, Steven F.; Oschwald, David M.; Chavez, David E.; Naud, Darren L.

2006-11-28

Nanoporous metal foams are prepared by ignition of high nitrogen transition metal complexes. The ammonium salts of iron(III) tris[bi(tetrazolato)-amine], cobalt(III) tris(bi(tetrazolato)amine), and high nitrogen compounds of copper and silver were prepared as loose powders, pressed into pellets and wafers, and ignited under an inert atmosphere to form nanoporous metal foam monoliths having very high surface area and very low density.

Transition-metal-ion-mediated polymerization of dopamine: mussel-inspired approach for the facile synthesis of robust transition-metal nanoparticle-graphene hybrids.

PubMed

Yang, Liping; Kong, Junhua; Zhou, Dan; Ang, Jia Ming; Phua, Si Lei; Yee, Wu Aik; Liu, Hai; Huang, Yizhong; Lu, Xuehong

2014-06-16

Inspired by the high transition-metal-ion content in mussel glues, and the cross-linking and mechanical reinforcement effects of some transition-metal ions in mussel threads, high concentrations of nickel(II), cobalt(II), and manganese(II) ions have been purposely introduced into the reaction system for dopamine polymerization. Kinetics studies were conducted for the Ni(2+)-dopamine system to investigate the polymerization mechanism. The results show that the Ni(2+) ions could accelerate the assembly of dopamine oligomers in the polymerization process. Spectroscopic and electron microscopic studies reveal that the Ni(2+) ions are chelated with polydopamine (PDA) units, forming homogeneous Ni(2+)-PDA complexes. This facile one-pot approach is utilized to construct transition-metal-ion-PDA complex thin coatings on graphene oxide, which can be carbonized to produce robust hybrid nanosheets with well-dispersed metallic nickel/metallic cobalt/manganese(II) oxide nanoparticles embedded in PDA-derived thin graphitic carbon layers. The nickel-graphene hybrid prepared by using this approach shows good catalytic properties and recyclability for the reduction of p-nitrophenol. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activation of methane by transition metal-substituted aluminophosphate molecular sieves

DOEpatents

Iton, Lennox E.; Maroni, Victor A.

1991-01-01

Aluminophosphate molecular sieves substituted with cobalt, manganese or iron and having the AlPO.sub.4 -34 or AlPO.sub.4 -5, or related AlPO.sub.4 structure activate methane starting at approximately 350.degree. C. Between 400.degree. and 500.degree. C. and at methane pressures .ltoreq.1 atmosphere the rate of methane conversion increases steadily with typical conversion efficiencies at 500.degree. C. approaching 50% and selectivity to the production of C.sub.2+ hydrocarbons approaching 100%. The activation mechanism is based on reduction of the transition metal(III) form of the molecular sieve to the transition metal(II) form with accompanying oxidative dehydrogenation of the methane. Reoxidation of the - transition metal(II) form to the transition metal(III) form can be done either chemically (e.g., using O.sub.2) or electrochemically.

Quantum spin liquids and the metal-insulator transition in doped semiconductors.

PubMed

Potter, Andrew C; Barkeshli, Maissam; McGreevy, John; Senthil, T

2012-08-17

We describe a new possible route to the metal-insulator transition in doped semiconductors such as Si:P or Si:B. We explore the possibility that the loss of metallic transport occurs through Mott localization of electrons into a quantum spin liquid state with diffusive charge neutral "spinon" excitations. Such a quantum spin liquid state can appear as an intermediate phase between the metal and the Anderson-Mott insulator. An immediate testable consequence is the presence of metallic thermal conductivity at low temperature in the electrical insulator near the metal-insulator transition. Further, we show that though the transition is second order, the zero temperature residual electrical conductivity will jump as the transition is approached from the metallic side. However, the electrical conductivity will have a nonmonotonic temperature dependence that may complicate the extrapolation to zero temperature. Signatures in other experiments and some comparisons with existing data are made.

Tunable magnetic and magnetocaloric properties in heavy rare-earth based metallic glasses through the substitution of similar elements

NASA Astrophysics Data System (ADS)

Zhang, Huiyan; Li, Ran; Zhang, Leilei; Zhang, Tao

2014-04-01

The influence of interchangeable substitution of similar heavy rare-earth-elements (HRE), i.e., Gd-Ho, Gd-Er, and Ho-Er, on the magnetic and magnetocaloric properties of HRE55Al27.5Co17.5 metallic glasses was evaluated. The magnetic transition temperature (TC) can be tuned in a wide temperature range from 8 K to 93 K by adjusting the substitutional concentration in the resulting metallic glasses. A roughly linear correlation between peak value of magnetic entropy change (|ΔSMpk|) and TC-2/3 was obtained in the three systems. This kind of substitutional adjustment provides a useful method for designing desirable candidates in metallic glasses with high magnetic entropy change, large magnetic cooling efficiency, and tunable TC for magnetic refrigerant in nitrogen and hydrogen liquefaction temperature ranges.

Density functional theory based screening of ternary alkali-transition metal borohydrides: A computational material design project

NASA Astrophysics Data System (ADS)

Hummelshøj, J. S.; Landis, D. D.; Voss, J.; Jiang, T.; Tekin, A.; Bork, N.; Dułak, M.; Mortensen, J. J.; Adamska, L.; Andersin, J.; Baran, J. D.; Barmparis, G. D.; Bell, F.; Bezanilla, A. L.; Bjork, J.; Björketun, M. E.; Bleken, F.; Buchter, F.; Bürkle, M.; Burton, P. D.; Buus, B. B.; Calborean, A.; Calle-Vallejo, F.; Casolo, S.; Chandler, B. D.; Chi, D. H.; Czekaj, I.; Datta, S.; Datye, A.; DeLaRiva, A.; Despoja, V.; Dobrin, S.; Engelund, M.; Ferrighi, L.; Frondelius, P.; Fu, Q.; Fuentes, A.; Fürst, J.; García-Fuente, A.; Gavnholt, J.; Goeke, R.; Gudmundsdottir, S.; Hammond, K. D.; Hansen, H. A.; Hibbitts, D.; Hobi, E.; Howalt, J. G.; Hruby, S. L.; Huth, A.; Isaeva, L.; Jelic, J.; Jensen, I. J. T.; Kacprzak, K. A.; Kelkkanen, A.; Kelsey, D.; Kesanakurthi, D. S.; Kleis, J.; Klüpfel, P. J.; Konstantinov, I.; Korytar, R.; Koskinen, P.; Krishna, C.; Kunkes, E.; Larsen, A. H.; Lastra, J. M. G.; Lin, H.; Lopez-Acevedo, O.; Mantega, M.; Martínez, J. I.; Mesa, I. N.; Mowbray, D. J.; Mýrdal, J. S. G.; Natanzon, Y.; Nistor, A.; Olsen, T.; Park, H.; Pedroza, L. S.; Petzold, V.; Plaisance, C.; Rasmussen, J. A.; Ren, H.; Rizzi, M.; Ronco, A. S.; Rostgaard, C.; Saadi, S.; Salguero, L. A.; Santos, E. J. G.; Schoenhalz, A. L.; Shen, J.; Smedemand, M.; Stausholm-Møller, O. J.; Stibius, M.; Strange, M.; Su, H. B.; Temel, B.; Toftelund, A.; Tripkovic, V.; Vanin, M.; Viswanathan, V.; Vojvodic, A.; Wang, S.; Wellendorff, J.; Thygesen, K. S.; Rossmeisl, J.; Bligaard, T.; Jacobsen, K. W.; Nørskov, J. K.; Vegge, T.

2009-07-01

We present a computational screening study of ternary metal borohydrides for reversible hydrogen storage based on density functional theory. We investigate the stability and decomposition of alloys containing 1 alkali metal atom, Li, Na, or K (M1); and 1 alkali, alkaline earth or 3d/4d transition metal atom (M2) plus two to five (BH4)- groups, i.e., M1M2(BH4)2-5, using a number of model structures with trigonal, tetrahedral, octahedral, and free coordination of the metal borohydride complexes. Of the over 700 investigated structures, about 20 were predicted to form potentially stable alloys with promising decomposition energies. The M1(Al/Mn/Fe)(BH4)4, (Li/Na)Zn(BH4)3, and (Na/K)(Ni/Co)(BH4)3 alloys are found to be the most promising, followed by selected M1(Nb/Rh)(BH4)4 alloys.

A Liquid Chromatography Detector for Transition and Rare-Earth Metal Ions Based on a Cupric Ion-Selective Electrode

DTIC Science & Technology

1981-05-01

RARE-EARTH METAL IONS BASED ON A CUPRIC ION-SELECTIVE ELECTRODE By - 4 R. CAMERON DOREY TECHNICAL REPORT FJSRL-TR-81-0005 MAY 1981 Approved for public...FORM . REPORT NUMBER 12. GOVT ACCESSION NO. 3. RECIPIENT’S CATALOG NUMBER FJSRL-TR-81-0005BO CO ENGO 4 . TITLE (and Subtitle) 5. TYPE OF REPORT & PERIOD...common anions, including halide ions, is shown, and the advantages and limitations of the system are discussed. II ’ 4 UNCLASSIFIED SECURITY

Thermodynamic Hydricity of Transition Metal Hydrides

DOE PAGES

Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.; ...

2016-08-02

Transition metal hydrides play a critical role in stoichiometric and catalytic transformations. Knowledge of free energies for cleaving metal hydride bonds enables the prediction of chemical reactivity, such as for the bond-forming and bondbreaking events that occur in a catalytic reaction. Thermodynamic hydricity is the free energy required to cleave an M-H bond to generate a hydride ion (H -). Three primary methods have been developed for hydricity determination: the hydride transfer method establishes hydride transfer equilibrium with a hydride donor/acceptor pair of known hydricity, the H 2 heterolysis method involves measuring the equilibrium of heterolytic cleavage of H 2more » in the presence of a base, and the potential-pK a method considers stepwise transfer of a proton and two electrons to give a net hydride transfer. Using these methods, over 100 thermodynamic hydricity values for transition metal hydrides have been determined in acetonitrile or water. In acetonitrile, the hydricity of metal hydrides spans a range of more than 50 kcal/mol. Finally, methods for using hydricity values to predict chemical reactivity are also discussed, including organic transformations, the reduction of CO 2, and the production and oxidation of hydrogen.« less

The effects of refraction on transit transmission spectroscopy: application to Earth-like exoplanets

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

Misra, Amit; Meadows, Victoria; Crisp, Dave, E-mail: amit0@astro.washington.edu

2014-09-01

We quantify the effects of refraction in transit transmission spectroscopy on spectral absorption features and on temporal variations that could be used to obtain altitude-dependent spectra for planets orbiting stars of different stellar types. We validate our model against altitude-dependent transmission spectra of the Earth from ATMOS and against lunar eclipse spectra from Pallé et al. We perform detectability studies to show the potential effects of refraction on hypothetical observations of Earth analogs with the James Webb Space Telescope NIRSPEC. Due to refraction, there will be a maximum tangent pressure level that can be probed during transit for each givenmore » planet-star system. We show that because of refraction, for an Earth-analog planet orbiting in the habitable zone of a Sun-like star only the top 0.3 bars of the atmosphere can be probed, leading to a decrease in the signal-to-noise ratio (S/N) of absorption features by 60%, while for an Earth-analog planet orbiting in the habitable zone of an M5V star it is possible to probe almost the entire atmosphere with minimal decreases in S/N. We also show that refraction can result in temporal variations in the transit transmission spectrum which may provide a way to obtain altitude-dependent spectra of exoplanet atmospheres. Additionally, the variations prior to ingress and subsequent to egress provide a way to probe pressures greater than the maximum tangent pressure that can be probed during transit. Therefore, probing the maximum range of atmospheric altitudes, and in particular the near-surface environment of an Earth-analog exoplanet, will require looking at out-of-transit refracted light in addition to the in-transit spectrum.« less

Nanostructured transition metal oxides useful for water oxidation catalysis

DOEpatents

Frei, Heinz M; Jiao, Feng

2013-12-24

The present invention provides for a composition comprising a nanostructured transition metal oxide capable of oxidizing two H.sub.2O molecules to obtain four protons. In some embodiments of the invention, the composition further comprises a porous matrix wherein the nanocluster of the transition metal oxide is embedded on and/or in the porous matrix.

Process for preparing higher oxides of the alkali and alkaline earth metals

NASA Technical Reports Server (NTRS)

Sadhukhan, P.; Bell, A. (Inventor)

1978-01-01

High purity inorganic higher oxides of the alkali and alkaline earth metals are prepared by subjecting the hydroxide of the alkali and alkaline earth metal to a radio frequency discharge sustained in oxygen. The process is particulary adaptable to the production of high purity potassium superoxide by subjecting potassium hydroxide to glow discharge sustained in oxygen under the pressure of about 0.75 to 1.00 torr.

Theory of quantum metal to superconductor transitions in highly conducting systems

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

Spivak, B.

2010-04-06

We derive the theory of the quantum (zero temperature) superconductor to metal transition in disordered materials when the resistance of the normal metal near criticality is small compared to the quantum of resistivity. This can occur most readily in situations in which 'Anderson's theorem' does not apply. We explicitly study the transition in superconductor-metal composites, in an swave superconducting film in the presence of a magnetic field, and in a low temperature disordered d-wave superconductor. Near the point of the transition, the distribution of the superconducting order parameter is highly inhomogeneous. To describe this situation we employ a procedure whichmore » is similar to that introduced by Mott for description of the temperature dependence of the variable range hopping conduction. As the system approaches the point of the transition from the metal to the superconductor, the conductivity of the system diverges, and the Wiedemann-Franz law is violated. In the case of d-wave (or other exotic) superconductors we predict the existence of (at least) two sequential transitions as a function of increasing disorder: a d-wave to s-wave, and then an s-wave to metal transition.« less

On the thermodynamics of phase transitions in metal hydrides

NASA Astrophysics Data System (ADS)

di Vita, Andrea

2012-02-01

Metal hydrides are solutions of hydrogen in a metal, where phase transitions may occur depending on temperature, pressure etc. We apply Le Chatelier's principle of thermodynamics to a particular phase transition in TiH x , which can approximately be described as a second-order phase transition. We show that the fluctuations of the order parameter correspond to fluctuations both of the density of H+ ions and of the distance between adjacent H+ ions. Moreover, as the system approaches the transition and the correlation radius increases, we show -with the help of statistical mechanics-that the statistical weight of modes involving a large number of H+ ions (`collective modes') increases sharply, in spite of the fact that the Boltzmann factor of each collective mode is exponentially small. As a result, the interaction of the H+ ions with collective modes makes a tiny suprathermal fraction of the H+ population appear. Our results hold for similar transitions in metal deuterides, too. A violation of an -insofar undisputed-upper bound on hydrogen loading follows.

A SUPER-EARTH TRANSITING A NAKED-EYE STAR

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

Winn, Joshua N.; Matthews, Jaymie M.; Kallinger, Thomas

We have detected transits of the innermost planet 'e' orbiting 55 Cnc (V = 6.0), based on two weeks of nearly continuous photometric monitoring with the MOST space telescope. The transits occur with the period (0.74 days) and phase that had been predicted by Dawson and Fabrycky, and with the expected duration and depth for the crossing of a Sun-like star by a hot super-Earth. Assuming the star's mass and radius to be 0.963{sup +0.051}{sub -0.029} M{sub sun} and 0.943 {+-} 0.010 R{sub sun}, the planet's mass, radius, and mean density are 8.63 {+-} 0.35 M{sub +}, 2.00 {+-} 0.14more » R{sub +}, and 5.9{sup +1.5}{sub -1.1} g cm{sup -3}, respectively. The mean density is comparable to that of Earth, despite the greater mass and consequently greater compression of the interior of 55 Cnc e. This suggests a rock-iron composition supplemented by a significant mass of water, gas, or other light elements. Outside of transits, we detected a sinusoidal signal resembling the expected signal due to the changing illuminated phase of the planet, but with a full range (168 {+-} 70 ppm) too large to be reflected light or thermal emission. This signal has no straightforward interpretation and should be checked with further observations. The host star of 55 Cnc e is brighter than that of any other known transiting planet, which will facilitate future investigations.« less

A Simple, General Synthetic Route toward Nanoscale Transition Metal Borides.

PubMed

Jothi, Palani R; Yubuta, Kunio; Fokwa, Boniface P T

2018-04-01

Most nanomaterials, such as transition metal carbides, phosphides, nitrides, chalcogenides, etc., have been extensively studied for their various properties in recent years. The similarly attractive transition metal borides, on the contrary, have seen little interest from the materials science community, mainly because nanomaterials are notoriously difficult to synthesize. Herein, a simple, general synthetic method toward crystalline transition metal boride nanomaterials is proposed. This new method takes advantage of the redox chemistry of Sn/SnCl 2 , the volatility and recrystallization of SnCl 2 at the synthesis conditions, as well as the immiscibility of tin with boron, to produce crystalline phases of 3d, 4d, and 5d transition metal nanoborides with different morphologies (nanorods, nanosheets, nanoprisms, nanoplates, nanoparticles, etc.). Importantly, this method allows flexibility in the choice of the transition metal, as well as the ability to target several compositions within the same binary phase diagram (e.g., Mo 2 B, α-MoB, MoB 2 , Mo 2 B 4 ). The simplicity and wide applicability of the method should enable the fulfillment of the great potential of this understudied class of materials, which show a variety of excellent chemical, electrochemical, and physical properties at the microscale. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydroxyapatite substituted by transition metals: experiment and theory.

PubMed

Zilm, M E; Chen, L; Sharma, V; McDannald, A; Jain, M; Ramprasad, R; Wei, M

2016-06-28

Bioceramics are versatile materials for hard tissue engineering. Hydroxyapatite (HA) is a widely studied biomaterial for bone grafting and tissue engineering applications. The crystal structure of HA allows for a wide range of substitutions, which allows for tailoring materials properties. Transition metals and lanthanides are of interest since substitution in HA can result in magnetic properties. In this study, experimental results were compared to theoretical calculations of HA substituted with a transition metal. Calculation of a 10 atomic percent substitution of a transition metal ion Mn(2+), Fe(2+), and Co(2+) substituted HA samples lead to magnetic moments of 5, 4, and 3 Bohr magnetons, respectively. Hydroxyapatite substituted by transition metals (MHA) was fabricated through an ion exchange procedure and characterized with X-ray diffraction, Fourier transform infra-red spectroscopy (FTIR), X-ray photoelectron spectroscopy, and vibrating sample magnetometer, and results were compared to theoretical calculations. All the substitutions resulted in phase-pure M(2+)HA with lattice parameters and FTIR spectra in good agreement with calculations. Magnetic measurements revealed that the substitution of Mn(2+) has the greatest effect on the magnetic properties of HA followed by the substitution of Fe(2+) and then Co(2+). The present work underlines the power of synergistic theoretical-experimental work in guiding the rational design of materials.

Hot carrier dynamics in plasmonic transition metal nitrides

NASA Astrophysics Data System (ADS)

Habib, Adela; Florio, Fred; Sundararaman, Ravishankar

2018-06-01

Extraction of non-equilibrium hot carriers generated by plasmon decay in metallic nano-structures is an increasingly exciting prospect for utilizing plasmonic losses, but the search for optimum plasmonic materials with long-lived carriers is ongoing. Transition metal nitrides are an exciting class of new plasmonic materials with superior thermal and mechanical properties compared to conventional noble metals, but their suitability for plasmonic hot carrier applications remains unknown. Here, we present fully first principles calculations of the plasmonic response, hot carrier generation and subsequent thermalization of all group IV, V and VI transition metal nitrides, fully accounting for direct and phonon-assisted transitions as well as electron–electron and electron–phonon scattering. We find the largest frequency ranges for plasmonic response in ZrN, HfN and WN, between those of gold and silver, while we predict strongest absorption in the visible spectrum for the VN, NbN and TaN. Hot carrier generation is dominated by direct transitions for most of the relevant energy range in all these nitrides, while phonon-assisted processes dominate only below 1 eV plasmon energies primarily for the group IV nitrides. Finally, we predict the maximum hot carrier lifetimes to be around 10 fs for group IV and VI nitrides, a factor of 3–4 smaller than noble metals, due to strong electron–phonon scattering. However, we find longer carrier lifetimes for group V nitrides, comparable to silver for NbN and TaN, while exceeding 100 fs (twice that of silver) for VN, making them promising candidates for efficient hot carrier extraction.

Proposal for Laser Cooling of Alkaline Earth Monoalkoxide Free Radicals

NASA Astrophysics Data System (ADS)

Baum, Louis; Kozyryev, Ivan; Matsuda, Kyle; Doyle, John M.

2016-05-01

Cold samples of polyatomic molecules will open new avenues in physics, chemistry, and quantum science. Non-diagonal Franck-Condon factors, technically challenging wavelengths, and the lack of strong electronic transitions inhibit direct laser cooling of nonlinear molecules. We identify a scheme for optical cycling in certain molecules with six or more atoms. Replacing hydrogen in alcohols with an alkaline earth metal (M) leads to alkaline earth monoalkoxide free radicals (MOR), which have favorable properties for laser cooling. M-O bond is very ionic, so the metal orbitals are slightly affected by the nature of R on the ligand. Diagonal Franck-Condon factors, laser accessible transitions, and a small hyperfine structure make MOR molecules suitable for laser cooling. We explore a scheme for optical cycling on the A - X transition of SrOCH3 . Molecules lost to dark vibrational states will be repumped on the B - X transition. Extension to larger species is possible through expansion of the R group since transitions involve the promotion of the metal-centered nonbonding valence electron. We will detail our estimations of the Franck-Condon factors, simulations of the cooling process and describe progress towards the Doppler cooling of MOR polyatomics.

Metal-metal bond lengths in complexes of transition metals.

PubMed

Pauling, L

1976-12-01

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

Synthesis of Oxides Containing Transition Metals

DTIC Science & Technology

1990-07-09

metal oxide single crystals by the electrolysis of molten salts containing mixtures of the appropriate oxides. Andreiux and Bozon (33-34) were able to...examples of unusual transition metal oxides which can be prepared (usually as single crystals) by electrolysis of fused salts . Summary The methods of...ferrites with the composition MFe 204 involved the thermal decomposition of oxalate (3) or pyridinate salts (1). The synthesis of ferrites from mixed

New chemistry of transition metal oxyhydrides

PubMed Central

Kobayashi, Yoji; Hernandez, Olivier; Tassel, Cédric; Kageyama, Hiroshi

2017-01-01

Abstract In this review we describe recent advances in transition metal oxyhydride chemistry obtained by topochemical routes, such as low temperature reduction with metal hydrides, or high-pressure solid-state reactions. Besides the crystal chemistry, magnetic and transport properties of the bulk powder and epitaxial thin film samples, the remarkable lability of the hydride anion is particularly highlighted as a new strategy to discover unprecedented mixed anion materials. PMID:29383042

Transition metal doped (X = V, Cr) CdS monolayer: A DFT study

NASA Astrophysics Data System (ADS)

Deb, Jyotirmoy; Paul, Debolina; Sarkar, Utpal

2018-05-01

In this work based on density functional theory approach with generalized gradient approximation we have investigated the effect doping and co-doping of transition metal atoms in CdS monolayer sheet. On the basis cohesive energy, we have determined the stability of all the transition metal doped systems. CdS monolayer is of nonmagnetic character but the insertion of transition metal atoms introduces the spontaneous spin polarization which results in a significant value of magnetic moment. The band structure analysis reveals that three different types of conducting nature such as spin-select-half-semiconductor, half metallic and metallic nature with total spin polarization has also been observed. The versatile conducting nature of the transition metal doped CdS monolayer predicts the possibility of using these systems in spintronics mainly as a spin filter and also to form metal-semiconductor interface etc. at nanoscale level.

Transition metal catalysis in the generation of petroleum and natural gas. Final report, September 1, 1992--October 31, 1995

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

Mango, F.D.

1997-01-21

This project originated on the premise that natural gas could be formed catalytically in the earth rather than thermally as commonly believed. The intention was to test this hypothetical view and to explore generally the role of sedimentary metals in the generation of light hydrocarbons (C1 - C9). We showed the metalliferous source rocks are indeed catalytic in the generation of natural gas. Various metal compounds in the pure state show the same levels of catalytic activity as sedimentary rocks and the products are identical. Nickel is particularly active among the early transition metals and is projected to remain catalyticallymore » robust at all stages of catagenesis. Nickel oxide promotes the formation of n-alkanes in addition to natural gas (NG), demonstrating the full scope of the hypothetical catalytic process. The composition of catalytic gas duplicates the entire range of natural gas, from so-called wet gas to dry gas (60 to 95+ wt % methane), while gas generated thermally is consistently depleted in methane (10 to 60 wt % methane). These results support the view that metal catalysis is a major pathway through which natural gas is formed in the earth.« less

Covalence of atoms in the heavier transition metals*

PubMed Central

Pauling, Linus

1977-01-01

The observed magnetic properties of the heavier transition metals permit them to have larger metallic valences than their iron-group congeners. With 0.72 metallic orbital, as found for the iron-group metals, the maximum metallic valence and minimum interatomic distance would occur for 8.28 transargononic electrons. The curves of observed interatomic distances for the close-packed metals of the second and third long periods have minima at this point, supporting the assignment of high valences to these metals. Values of the single-bond radii corresponding to these valences are calculated. PMID:16592407

Hydrogen and dihydrogen bonding of transition metal hydrides

NASA Astrophysics Data System (ADS)

Jacobsen, Heiko

2008-04-01

Intermolecular interactions between a prototypical transition metal hydride WH(CO) 2NO(PH 3) 2 and a small proton donor H 2O have been studied using DFT methodology. The hydride, nitrosyl and carbonyl ligand have been considered as site of protonation. Further, DFT-D calculations in which empirical corrections for the dispersion energy are included, have been carried out. A variety of pure and hybrid density functionals (BP86, PW91, PBE, BLYP, OLYP, B3LYP, B1PW91, PBE0, X3LYP) have been considered, and our calculations indicate the PBE functional and its hybrid variation are well suited for the calculation of transition metal hydride hydrogen and dihydrogen bonding. Dispersive interactions make up for a sizeable portion of the intermolecular interaction, and amount to 20-30% of the bond energy and to 30-40% of the bond enthalpy. An energy decomposition analysis reveals that the H⋯H bond of transition metal hydrides contains both covalent and electrostatic contributions.

Role of phonons in the metal-insulator phase transition.

NASA Technical Reports Server (NTRS)

Langer, W. D.

1972-01-01

Review, for the transition series oxides, of the Mattis and Lander model, which is one of electrons interacting with lattice vibrations (electron and phonon interaction). The model displays superconducting, insulating, and metallic phases. Its basic properties evolve from a finite crystallographic distortion associated with a dominant phonon mode and the splitting of the Brillouin zone into two subzones, a property of simple cubic and body centered cubic lattices. The order of the metal-insulator phase transition is examined. The basic model has a second-order phase transition and the effects of additional mechanisms on the model are calculated. The way in which these mechanisms affect the magnetically ordered transition series oxides as described by the Hubbard model is discussed.

The Electronic Structure of Transition Metal Coated Fullerenes

NASA Astrophysics Data System (ADS)

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

1998-03-01

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

Rare-earth transition-metal gallium chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se)

NASA Astrophysics Data System (ADS)

Rudyk, Brent W.; Stoyko, Stanislav S.; Oliynyk, Anton O.; Mar, Arthur

2014-02-01

Six series of quaternary rare-earth transition-metal chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se), comprising 33 compounds in total, have been prepared by reactions of the elements at 1050 °C (for the sulphides) or 900 °C (for the selenides). They adopt noncentrosymmetric hexagonal structures (ordered Ce3Al1.67S7-type, space group P63, Z=2) with cell parameters in the ranges of a=9.5-10.2 Å and c=6.0-6.1 Å for the sulphides and a=10.0-10.5 Å and c=6.3-6.4 Å for the selenides as refined from powder X-ray diffraction data. Single-crystal structures were determined for five members of the sulphide series RE3FeGaS7 (RE=La, Pr, Tb) and RE3CoGaS7 (RE=La, Tb). The highly anisotropic crystal structures consist of one-dimensional chains of M-centred face-sharing octahedra and stacks of Ga-centred tetrahedra all pointing in the same direction. Magnetic measurements on the sulphides reveal paramagnetic behaviour in some cases and long-range antiferromagnetic behaviour with low Néel temperatures (15 K or lower) in others. Ga L-edge XANES spectra support the presence of highly cationic Ga tetrahedral centres with a tendency towards more covalent Ga-Ch character on proceeding from the sulphides to the selenides. Band structure calculations on La3FeGaS7 indicate that the electronic structure is dominated by Fe 3d-based states near the Fermi level.

An Alternative Approach to the Teaching of Systematic Transition Metal Chemistry.

ERIC Educational Resources Information Center

Hathaway, Brian

1979-01-01

Presents an alternative approach to teaching Systematic Transition Metal Chemistry with the transition metal chemistry skeleton features of interest. The "skeleton" is intended as a guide to predicting the chemistry of a selected compound. (Author/SA)

Phase diagram of the ultrafast photoinduced insulator-metal transition in vanadium dioxide

NASA Astrophysics Data System (ADS)

Cocker, T. L.; Titova, L. V.; Fourmaux, S.; Holloway, G.; Bandulet, H.-C.; Brassard, D.; Kieffer, J.-C.; El Khakani, M. A.; Hegmann, F. A.

2012-04-01

We use time-resolved terahertz spectroscopy to probe the ultrafast dynamics of the insulator-metal phase transition induced by femtosecond laser pulses in a nanogranular vanadium dioxide (VO2) film. Based on the observed thresholds for characteristic transient terahertz dynamics, a phase diagram of critical pump fluence versus temperature for the insulator-metal phase transition in VO2 is established for the first time over a broad range of temperatures down to 17 K. We find that both Mott and Peierls mechanisms are present in the insulating state and that the photoinduced transition is nonthermal. We propose a critical-threshold model for the ultrafast photoinduced transition based on a critical density of electrons and a critical density of coherently excited phonons necessary for the structural transition to the metallic state. As a result, evidence is found at low temperatures for an intermediate metallic state wherein the Mott state is melted but the Peierls distortion remains intact, consistent with recent theoretical predictions. Finally, the observed terahertz conductivity dynamics above the photoinduced transition threshold reveal nucleation and growth of metallic nanodomains over picosecond time scales.

Evaluating transition-metal catalysis in gas generation from the Permian Kupferschiefer by hydrous pyrolysis

USGS Publications Warehouse

Lewan, M.D.; Kotarba, M.J.; Wieclaw, D.; Piestrzynski, A.

2008-01-01

Transition metals in source rocks have been advocated as catalysts in determining extent, composition, and timing of natural gas generation (Mango, F. D. (1996) Transition metal catalysis in the generation of natural gas. Org. Geochem.24, 977–984). This controversial hypothesis may have important implications concerning gas generation in unconventional shale-gas accumulations. Although experiments have been conducted to test the metal-catalysis hypothesis, their approach and results remain equivocal in evaluating natural assemblages of transition metals and organic matter in shale. The Permian Kupferschiefer of Poland offers an excellent opportunity to test the hypothesis with immature to marginally mature shale rich in both transition metals and organic matter. Twelve subsurface samples containing similar Type-II kerogen with different amounts and types of transition metals were subjected to hydrous pyrolysis at 330° and 355 °C for 72 h. The gases generated in these experiments were quantitatively collected and analyzed for molecular composition and stable isotopes. Expelled immiscible oils, reacted waters, and spent rock were also quantitatively collected. The results show that transition metals have no effect on methane yields or enrichment. δ13C values of generated methane, ethane, propane and butanes show no systematic changes with increasing transition metals. The potential for transition metals to enhance gas generation and oil cracking was examined by looking at the ratio of the generated hydrocarbon gases to generated expelled immiscible oil (i.e., GOR), which showed no systematic change with increasing transition metals. Assuming maximum yields at 355 °C for 72 h and first-order reaction rates, pseudo-rate constants for methane generation at 330 °C were calculated. These rate constants showed no increase with increasing transition metals. The lack of a significant catalytic effect of transition metals on the extent, composition, and timing of

Metal-metal bond lengths in complexes of transition metals*

PubMed Central

Pauling, Linus

1976-01-01

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

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, Victor A.; Iton, Lennox E.; Pasterczyk, James W.; Winterer, Markus; Krause, Theodore R.

1994-01-01

A zeolite based catalyst for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C.sub.2 + hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Transition metal-substituted cobalt ferrite nanoparticles for biomedical applications.

PubMed

Sanpo, Noppakun; Berndt, Christopher C; Wen, Cuie; Wang, James

2013-03-01

Transition metals of copper, zinc, chromium and nickel were substituted into cobalt ferrite nanoparticles via a sol-gel route using citric acid as a chelating agent. The microstructure and elemental composition were characterized using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy. Phase analysis of transition metal-substituted cobalt ferrite nanoparticles was performed via X-ray diffraction. Surface wettability was measured using the water contact angle technique. The surface roughness of all nanoparticles was measured using profilometry. Moreover, thermogravimetric analysis and differential scanning calorimetry were performed to determine the temperature at which the decomposition and oxidation of the chelating agents took place. Results indicated that the substitution of transition metals influences strongly the microstructure, crystal structure and antibacterial property of the cobalt ferrite nanoparticles. Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Transition metal sulfide loaded catalyst

DOEpatents

Maroni, V.A.; Iton, L.E.; Pasterczyk, J.W.; Winterer, M.; Krause, T.R.

1994-04-26

A zeolite-based catalyst is described for activation and conversion of methane. A zeolite support includes a transition metal (Mo, Cr or W) sulfide disposed within the micropores of the zeolite. The catalyst allows activation and conversion of methane to C[sub 2]+ hydrocarbons in a reducing atmosphere, thereby avoiding formation of oxides of carbon.

Fabrication of carbon nanotube films from alkyne-transition metal complexes

DOEpatents

Iyer, Vivekanantan S [Delft, NL; Vollhardt, K Peter C. [Oakland, CA

2007-08-28

A simple method for the production or synthesis of carbon nanotubes as free-standing films or nanotube mats by the thermal decomposition of transition metal complexed alkynes with aryl, alkyl, alkenyl, or alkynyl substituents. In particular, transition metal (e.g. Co, Ni, Fe, Mo) complexes of diarylacetylenes, e.g. diphenylacetylene, and solid mixtures of these complexes with suitable, additional carbon sources are heated in a vessel. More specifically, the heating of the transition metal complex is completed at a temperature between 400-800.degree. C. and more particularly 550-700.degree. C. for between 0.1 to 24 hours and more particularly 0.5-3 hours in a sealed vessel under a partial pressure of argon or helium.

THEORETICAL TRANSIT SPECTRA FOR GJ 1214b AND OTHER 'SUPER-EARTHS'

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

Howe, Alex R.; Burrows, Adam S., E-mail: arhowe@astro.princeton.edu, E-mail: burrows@astro.princeton.edu

2012-09-10

We present new calculations of transit spectra of super-Earths that allow for atmospheres with arbitrary proportions of common molecular species and haze. We test this method with generic spectra, reproducing the expected systematics and absorption features, then apply it to the nearby super-Earth GJ 1214b, which has produced conflicting observational data, leaving the questions of a hydrogen-rich versus hydrogen-poor atmosphere and the water content of the atmosphere ambiguous. We present representative transit spectra for a range of classes of atmosphere models for GJ 1214b. Our analysis supports a hydrogen-rich atmosphere with a cloud or haze layer, although a hydrogen-poor modelmore » with {approx}<10% water is not ruled out. Several classes of models are ruled out, however, including hydrogen-rich atmospheres with no haze, hydrogen-rich atmospheres with a haze of {approx}0.01 {mu}m tholin particles, and hydrogen-poor atmospheres with major sources of absorption other than water. We propose an observational test to distinguish hydrogen-rich from hydrogen-poor atmospheres. Finally, we provide a library of theoretical transit spectra for super-Earths with a broad range of parameters to facilitate future comparison with anticipated data.« less

Porous nanoarchitectures of spinel-type transition metal oxides for electrochemical energy storage systems.

PubMed

Park, Min-Sik; Kim, Jeonghun; Kim, Ki Jae; Lee, Jong-Won; Kim, Jung Ho; Yamauchi, Yusuke

2015-12-14

Transition metal oxides possessing two kinds of metals (denoted as AxB3-xO4, which is generally defined as a spinel structure; A, B = Co, Ni, Zn, Mn, Fe, etc.), with stoichiometric or even non-stoichiometric compositions, have recently attracted great interest in electrochemical energy storage systems (ESSs). The spinel-type transition metal oxides exhibit outstanding electrochemical activity and stability, and thus, they can play a key role in realising cost-effective and environmentally friendly ESSs. Moreover, porous nanoarchitectures can offer a large number of electrochemically active sites and, at the same time, facilitate transport of charge carriers (electrons and ions) during energy storage reactions. In the design of spinel-type transition metal oxides for energy storage applications, therefore, nanostructural engineering is one of the most essential approaches to achieving high electrochemical performance in ESSs. In this perspective, we introduce spinel-type transition metal oxides with various transition metals and present recent research advances in material design of spinel-type transition metal oxides with tunable architectures (shape, porosity, and size) and compositions on the micro- and nano-scale. Furthermore, their technological applications as electrode materials for next-generation ESSs, including metal-air batteries, lithium-ion batteries, and supercapacitors, are discussed.

When VSEPR Fails: Experimental and Theoretical Investigations of the Behavior of Alkaline-Earth-Metal Acetylides

PubMed Central

Guino-o, Marites A.; Alexander, Jacob S.; McKee, Michael L.; Hope, Håkon; Englich, Ulrich B.

2014-01-01

The synthesis, structural, and spectral characterization as well as a theoretical study of a family of alkaline-earth-metal acetylides provides insights into synthetic access and the structural and bonding characteristics of this group of highly reactive compounds. Based on our earlier communication that reported unusual geometry for a family of triphenylsilyl-substituted alkaline-earth-metal acetylides, we herein present our studies on an expanded family of target derivatives, providing experimental and theoretical data to offer new insights into the intensively debated theme of structural chemistry in heavy alkaline-earth-metal chemistry. PMID:19844925

Ultrafast photo-induced dynamics across the metal-insulator transition of VO2

NASA Astrophysics Data System (ADS)

Wang, Siming; Ramírez, Juan Gabriel; Jeffet, Jonathan; Bar-Ad, Shimshon; Huppert, Dan; Schuller, Ivan K.

2017-04-01

The transient reflectivity of VO2 films across the metal-insulator transition clearly shows that with low-fluence excitation, when insulating domains are dominant, energy transfer from the optically excited electrons to the lattice is not instantaneous, but precedes the superheating-driven expansion of the metallic domains. This implies that the phase transition in the coexistence regime is lattice-, not electronically-driven, at weak laser excitation. The superheated phonons provide the latent heat required for the propagation of the optically-induced phase transition. For VO2 this transition path is significantly different from what has been reported in the strong-excitation regime. We also observe a slow-down of the superheating-driven expansion of the metallic domains around the metal-insulator transition, which is possibly due to the competition among several co-existing phases, or an emergent critical-like behavior.

The Importance of Transition Metals in the Expanding Network of Microbial Metabolism in the Archean Eon

NASA Astrophysics Data System (ADS)

Moore, E. K.; Jelen, B. I.; Giovannelli, D.; Prabhu, A.; Raanan, H.; Falkowski, P. G.

2017-12-01

Deep time changes in Earth surface redox conditions, particularly due to global oxygenation, has impacted the availability of different metals and substrates that are central in biology. Oxidoreductase proteins are molecular nanomachines responsible for all biological electron transfer processes across the tree of life. These enzymes largely contain transition metals in their active sites. Microbial metabolic pathways form a global network of electron transfer, which expanded throughout the Archean eon. Older metabolisms (sulfur reduction, methanogenesis, anoxygenic photosynthesis) accessed negative redox potentials, while later evolving metabolisms (oxygenic photosynthesis, nitrification/denitrification, aerobic respiration) accessed positive redox potentials. The incorporation of different transition metals facilitated biological innovation and the expansion of the network of microbial metabolism. Network analysis was used to examine the connections between microbial taxa, metabolic pathways, crucial metallocofactors, and substrates in deep time by incorporating biosignatures preserved in the geologic record. Nitrogen fixation and aerobic respiration have the highest level of betweenness among metabolisms in the network, indicating that the oldest metabolisms are not the most central. Fe has by far the highest betweenness among metals. Clustering analysis largely separates High Metal Bacteria (HMB), Low Metal Bacteria (LMB), and Archaea showing that simple un-weighted links between taxa, metabolism, and metals have phylogenetic relevance. On average HMB have the highest betweenness among taxa, followed by Archaea and LMB. There is a correlation between the number of metallocofactors and metabolic pathways in representative bacterial taxa, but Archaea do not follow this trend. In many cases older and more recently evolved metabolisms were clustered together supporting previous findings that proliferation of metabolic pathways is not necessarily chronological.

Spin-exchange interaction between transition metals and metalloids in soft-ferromagnetic metallic glasses

NASA Astrophysics Data System (ADS)

Das, Santanu; Choudhary, Kamal; Chernatynskiy, Aleksandr; Choi Yim, Haein; Bandyopadhyay, Asis K.; Mukherjee, Sundeep

2016-06-01

High-performance magnetic materials have immense industrial and scientific importance in wide-ranging electronic, electromechanical, and medical device technologies. Metallic glasses with a fully amorphous structure are particularly suited for advanced soft-magnetic applications. However, fundamental scientific understanding is lacking for the spin-exchange interaction between metal and metalloid atoms, which typically constitute a metallic glass. Using an integrated experimental and molecular dynamics approach, we demonstrate the mechanism of electron interaction between transition metals and metalloids. Spin-exchange interactions were investigated for a Fe-Co metallic glass system of composition [(Co1-x Fe x )0.75B0.2Si0.05]96Cr4. The saturation magnetization increased with higher Fe concentration, but the trend significantly deviated from simple rule of mixtures. Ab initio molecular dynamics simulation was used to identify the ferromagnetic/anti-ferromagnetic interaction between the transition metals and metalloids. The overlapping band-structure and density of states represent ‘Stoner type’ magnetization for the amorphous alloys in contrast to ‘Heisenberg type’ in crystalline iron. The enhancement of magnetization by increasing iron was attributed to the interaction between Fe 3d and B 2p bands, which was further validated by valence-band study.

Application of Freeze-Dried Powders of Genetically Engineered Microbial Strains as Adsorbents for Rare Earth Metal Ions.

PubMed

Moriwaki, Hiroshi; Masuda, Reiko; Yamazaki, Yuki; Horiuchi, Kaoru; Miyashita, Mari; Kasahara, Jun; Tanaka, Tatsuhito; Yamamoto, Hiroki

2016-10-12

The adsorption behaviors of the rare earth metal ions onto freeze-dried powders of genetically engineered microbial strains were compared. Cell powders obtained from four kinds of strains, Bacillus subtilis 168 wild type (WT), lipoteichoic acid-defective (ΔLTA), wall teichoic acid-defective (ΔWTA), and cell wall hydrolases-defective (EFKYOJLp) strains, were used as an adsorbent of the rare earth metal ions at pH 3. The adsorption ability of the rare earth metal ions was in the order of EFKYOJLp > WT > ΔLTA > ΔWTA. The order was the same as the order of the phosphorus quantity of the strains. This result indicates that the main adsorption sites for the ions are the phosphate groups and the teichoic acids, LTA and WTA, that contribute to the adsorption of the rare earth metal ions onto the cell walls. The contribution of WTA was clearly greater than that of LTA. Each microbial powder was added to a solution containing 16 kinds of rare earth metal ions, and the removals (%) of each rare earth metal ion were obtained. The scandium ion showed the highest removal (%), while that of the lanthanum ion was the lowest for all the microbial powders. Differences in the distribution coefficients between the kinds of lanthanide ions by the EFKYOJLp and ΔWTA powders were greater than those of the other strains. Therefore, the EFKYOJLp and ΔWTA powders could be applicable for the selective extraction of the lanthanide ions. The ΔLTA powder coagulated by mixing with a rare earth metal ion, although no sedimentation of the WT or ΔWTA powder with a rare earth metal ion was observed under the same conditions. The EFKYOJLp powder was also coagulated, but its flocculating activity was lower than that of ΔLTA. The ΔLTA and EFKYOJLp powders have a long shape compared to those of the WT or ΔWTA strain. The shapes of the cells will play an important role in the sedimentation of the microbial powders with rare earth metal ions. As the results, three kinds of the genetically

Pure electronic metal-insulator transition at the interface of complex oxides

DOE PAGES

Meyers, D.; Liu, Jian; Freeland, J. W.; ...

2016-06-21

We observed complex materials in electronic phases and transitions between them often involve coupling between many degrees of freedom whose entanglement convolutes understanding of the instigating mechanism. Metal-insulator transitions are one such problem where coupling to the structural, orbital, charge, and magnetic order parameters frequently obscures the underlying physics. We demonstrate a way to unravel this conundrum by heterostructuring a prototypical multi-ordered complex oxide NdNiO3 in ultra thin geometry, which preserves the metal-to-insulator transition and bulk-like magnetic order parameter, but entirely suppresses the symmetry lowering and long-range charge order parameter. Furthermore, these findings illustrate the utility of heterointerfaces as amore » powerful method for removing competing order parameters to gain greater insight into the nature of the transition, here revealing that the magnetic order generates the transition independently, leading to an exceptionally rare purely electronic metal-insulator transition with no symmetry change.« less

Hund's rule in superatoms with transition metal impurities.

PubMed

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

2011-06-21

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

Environmental Defects And Economic Impact On Global Market Of Rare Earth Metals

NASA Astrophysics Data System (ADS)

Charalampides, G.; Vatalis, K.; Karayannis, V.; Baklavaridis, A.

2016-11-01

Rare earth elements include the 14 lanthanides as well as lanthanium and often yttrium. Actually, most of them are not very rare and occur widely dispersed in a variety of rocks. Rare earth metals are vital to some of the world's faster growing industries: catalysts, Nd-magnets, ceramics, glass, metallurgy, battery alloys, electronics and phosphors. Worldwide, the main countries for distribution of rare earths deposits include China, USA, Russia, Brasil, India, Australia, Greenland and Malaysia. The mining and processing of rare earth metals usually result in significant environmental defects. Many deposits are associated with high concentrations of radioactive elements such as uranium and thorium, which requires separate treatment and disposal. The accumulation of rare earth elements in soils has occurred due to pollution caused by the exploitation of rare earth resources and the wide use of rare earths as fertilizers in agriculture. This accumulation has a toxic effect on the soil microfauna community. However, there are large differences in market prices due to the degree of purity determined by the specifications in the applications. The main focus of this article is to overview Rare Earth Metals’ overall impact on global economy and their environmental defects on soils during processing techniques and as they are used as fertilizers.

Critical behavior at a dynamic vortex insulator-to-metal transition

DOE PAGES

Poccia, Nicola; Baturina, Tatyana I.; Coneri, Francesco; ...

2015-09-10

An array of superconducting islands placed on a normal metal film offers a tunable realization of nanopatterned superconductivity. This system enables elucidating open questions concerning the nature of competing vortex states and phase transitions between them. A square array creates the egg crate potential in which magnetic field-induced vortices are frozen into a vortex insulator. We observe a vortex insulator-to-vortex metal transition driven by the applied electric current and determine critical exponents strikingly coinciding with those for thermodynamic liquid-gas transition. Lastly, our findings offer a comprehensive description of dynamic critical behavior and establish a deep connection between equilibrium and nonequilibriummore » phase transitions.« less

Critical behavior at a dynamic vortex insulator-to-metal transition.

PubMed

Poccia, Nicola; Baturina, Tatyana I; Coneri, Francesco; Molenaar, Cor G; Wang, X Renshaw; Bianconi, Ginestra; Brinkman, Alexander; Hilgenkamp, Hans; Golubov, Alexander A; Vinokur, Valerii M

2015-09-11

An array of superconducting islands placed on a normal metal film offers a tunable realization of nanopatterned superconductivity. This system enables investigation of the nature of competing vortex states and phase transitions between them. A square array creates the eggcrate potential in which magnetic field-induced vortices are frozen into a vortex insulator. We observed a vortex insulator-vortex metal transition driven by the applied electric current and determined critical exponents that coincided with those for thermodynamic liquid-gas transition. Our findings offer a comprehensive description of dynamic critical behavior and establish a deep connection between equilibrium and nonequilibrium phase transitions. Copyright © 2015, American Association for the Advancement of Science.

Hall effect at a tunable metal-insulator transition

NASA Astrophysics Data System (ADS)

Teizer, W.; Hellman, F.; Dynes, R. C.

2003-03-01

Using a rotating magnetic field, the Hall effect in three-dimensional amorphous GdxSi1-x has been measured in the critical regime of the metal-insulator transition for a constant total magnetic field. The Hall coefficient R0 is negative, indicating electronlike conductivity, with a magnitude that increases with decreasing conductivity. R0 diverges at the metal-insulator transition, and displays critical behavior with exponent -1 [R0˜(H-HC)-1]. This dependence is interpreted as a linear decrease in the density of mobile carriers n˜R-10˜H-HC, indicative of the dominant influence of interaction effects.

Characterizing K2 Planet Discoveries: A Super-Earth Transiting the Bright K Dwarf HIP 116454

NASA Astrophysics Data System (ADS)

Vanderburg, Andrew; Montet, Benjamin T.; Johnson, John Asher; Buchhave, Lars A.; Zeng, Li; Pepe, Francesco; Collier Cameron, Andrew; Latham, David W.; Molinari, Emilio; Udry, Stéphane; Lovis, Christophe; Matthews, Jaymie M.; Cameron, Chris; Law, Nicholas; Bowler, Brendan P.; Angus, Ruth; Baranec, Christoph; Bieryla, Allyson; Boschin, Walter; Charbonneau, David; Cosentino, Rosario; Dumusque, Xavier; Figueira, Pedro; Guenther, David B.; Harutyunyan, Avet; Hellier, Coel; Kuschnig, Rainer; Lopez-Morales, Mercedes; Mayor, Michel; Micela, Giusi; Moffat, Anthony F. J.; Pedani, Marco; Phillips, David F.; Piotto, Giampaolo; Pollacco, Don; Queloz, Didier; Rice, Ken; Riddle, Reed; Rowe, Jason F.; Rucinski, Slavek M.; Sasselov, Dimitar; Ségransan, Damien; Sozzetti, Alessandro; Szentgyorgyi, Andrew; Watson, Chris; Weiss, Werner W.

2015-02-01

We report the first planet discovery from the two-wheeled Kepler (K2) mission: HIP 116454 b. The host star HIP 116454 is a bright (V = 10.1, K = 8.0) K1 dwarf with high proper motion and a parallax-based distance of 55.2 ± 5.4 pc. Based on high-resolution optical spectroscopy, we find that the host star is metal-poor with [Fe/H] =-0.16 ± 0.08 and has a radius R sstarf = 0.716 ± 0.024 R ⊙ and mass M sstarf = 0.775 ± 0.027 M ⊙. The star was observed by the Kepler spacecraft during its Two-Wheeled Concept Engineering Test in 2014 February. During the 9 days of observations, K2 observed a single transit event. Using a new K2 photometric analysis technique, we are able to correct small telescope drifts and recover the observed transit at high confidence, corresponding to a planetary radius of Rp = 2.53 ± 0.18 R ⊕. Radial velocity observations with the HARPS-N spectrograph reveal a 11.82 ± 1.33 M ⊕ planet in a 9.1 day orbit, consistent with the transit depth, duration, and ephemeris. Follow-up photometric measurements from the MOST satellite confirm the transit observed in the K2 photometry and provide a refined ephemeris, making HIP 116454 b amenable for future follow-up observations of this latest addition to the growing population of transiting super-Earths around nearby, bright stars.

Fluorescent probes and bioimaging: alkali metals, alkaline earth metals and pH.

PubMed

Yin, Jun; Hu, Ying; Yoon, Juyoung

2015-07-21

All living species and life forms have an absolute requirement for bio-functional metals and acid-base equilibrium chemistry owing to the critical roles they play in biological processes. Hence, a great need exists for efficient methods to detect and monitor biometals and acids. In the last few years, great attention has been paid to the development of organic molecule based fluorescent chemosensors. The availability of new synthetic fluorescent probes has made fluorescence microscopy an indispensable tool for tracing biologically important molecules and in the area of clinical diagnostics. This review highlights the recent advances that have been made in the design and bioimaging applications of fluorescent probes for alkali metals and alkaline earth metal cations, including lithium, sodium and potassium, magnesium and calcium, and for pH determination within biological systems.

Transition Metal Oxides as Electrocatalysts for the Oxygen Evolution Reaction in Alkaline Solutions: An Application-Inspired Renaissance.

PubMed

Song, Fang; Bai, Lichen; Moysiadou, Aliki; Lee, Seunghwa; Hu, Chao; Liardet, Laurent; Hu, Xile

2018-06-27

Water splitting is the essential chemical reaction to enable the storage of intermittent energies such as solar and wind in the form of hydrogen fuel. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting. Though metal oxides had been reported as OER electrocatalysts more than half a century ago, the recent interest in renewable energy storage has spurred a renaissance of the studies of transition metal oxides as Earth-abundant and nonprecious OER catalysts. This Perspective presents major progress in several key areas of the field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials. A personal overview of the past achievements and future challenges is also provided.

Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

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

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.

Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed ( hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. Thismore » is followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.« less

Magnetic ordering temperatures in rare earth metal dysprosium under ultrahigh pressures

DOE PAGES

Samudrala, Gopi K.; Tsoi, Georgiy M.; Weir, Samuel T.; ...

2014-04-03

Magnetic ordering temperatures in heavy rare earth metal Dysprosium (Dy) have been studied using an ultrasensitive electrical transport measurement technique in a designer diamond anvil cell to extreme conditions of pressure to 69 GPa and temperature to 10 K. Previous studies using magnetic susceptibility measurements at high pressures were only able to track magnetic ordering temperature till 7 GPa in the hexagonal close packed ( hcp) phase of Dy. Our studies indicate that the magnetic ordering temperature shows an abrupt drop of 80 K at the hcp-Sm phase transition followed by a gradual decrease that continues till 17 GPa. Thismore » is followed by a rapid increase in the magnetic ordering temperatures in the double hexagonal close packed phase and finally leveling off in the distorted face centered cubic phase of Dy. Lastly, our studies reaffirm that 4f-shell remain localized in Dy and there is no loss of magnetic moment or 4f-shell delocalization for pressures up to 69 GPa.« less

Dynamical Generation of the Transition Zone in the Earth's Mantle

NASA Astrophysics Data System (ADS)

Hansen, U.; Stemmer, K.

2005-12-01

The internal structure of the Earth is made up by a series of layers, though it is unclear how many layers exist and if there are layers invisible to remote sensing techniques. The transition zone is likely to be a boundary layer separating the convective systems in the lower and upper mantle. It seems likely that currently there is some mass exchange across this boundary, rather than the two systems beeing strictly separated.a Double-diffusive convection(d.d.c) is a vital mechanism which can generate layered structure and may thus be an important mmical machinery behind the formation of the transition zone. Double-diffusive convection determines the dynamics of systems whose density is influenced by at least two components with different molecular diffusivities.In the mantle, composition and temperature play the role of those two components. By means of numerical experiments we demonstrate that under mantle relevant conditions d.d.c typically leads to the formation of a transition zone. The calculations encompass two- and three dimensional Cartesian geometries as well as fully 3D spherical domains. We have further included strongly temperature dependent viscosity and find that this leads to even more pronounced layering. In most cases a layered flow pattern emerges, where two layers with a transition zone in between resembles a quasistationary state. Thus, the transition zone can be the result of a self organization process of the convective flow in the mantle. The presence of a phase transition further helps to stabilize the boundary against overturning, even on a time scale on the order of the age of the Earth.

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

PubMed Central

Manna, Kuntal; Ji, Pengfei; Lin, Zekai; Greene, Francis X.; Urban, Ania; Thacker, Nathan C.; Lin, Wenbin

2016-01-01

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturated metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals. PMID:27574182

Chemoselective single-site Earth-abundant metal catalysts at metal–organic framework nodes

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

Manna, Kuntal; Ji, Pengfei; Lin, Zekai

2016-08-30

Earth-abundant metal catalysts are critically needed for sustainable chemical synthesis. Here we report a simple, cheap and effective strategy of producing novel earth-abundant metal catalysts at metal–organic framework (MOF) nodes for broad-scope organic transformations. The straightforward metalation of MOF secondary building units (SBUs) with cobalt and iron salts affords highly active and reusable single-site solid catalysts for a range of organic reactions, including chemoselective borylation, silylation and amination of benzylic C–H bonds, as well as hydrogenation and hydroboration of alkenes and ketones. Our structural, spectroscopic and kinetic studies suggest that chemoselective organic transformations occur on site-isolated, electron-deficient and coordinatively unsaturatedmore » metal centres at the SBUs via σ-bond metathesis pathways and as a result of the steric environment around the catalytic site. MOFs thus provide a novel platform for the development of highly active and affordable base metal catalysts for the sustainable synthesis of fine chemicals.« less

Covalent bonds against magnetism in transition metal compounds

PubMed Central

Streltsov, Sergey V.; Khomskii, Daniel I.

2016-01-01

Magnetism in transition metal compounds is usually considered starting from a description of isolated ions, as exact as possible, and treating their (exchange) interaction at a later stage. We show that this standard approach may break down in many cases, especially in 4d and 5d compounds. We argue that there is an important intersite effect—an orbital-selective formation of covalent metal–metal bonds that leads to an “exclusion” of corresponding electrons from the magnetic subsystem, and thus strongly affects magnetic properties of the system. This effect is especially prominent for noninteger electron number, when it results in suppression of the famous double exchange, the main mechanism of ferromagnetism in transition metal compounds. We study this mechanism analytically and numerically and show that it explains magnetic properties of not only several 4d–5d materials, including Nb2O2F3 and Ba5AlIr2O11, but can also be operative in 3d transition metal oxides, e.g., in CrO2 under pressure. We also discuss the role of spin–orbit coupling on the competition between covalency and magnetism. Our results demonstrate that strong intersite coupling may invalidate the standard single-site starting point for considering magnetism, and can lead to a qualitatively new behavior. PMID:27601669

Electrocatalysis using transition metal carbide and oxide nanocrystals

NASA Astrophysics Data System (ADS)

Regmi, Yagya N.

Carbides are one of the several families of transition metal compounds that are considered economic alternatives to catalysts based on noble metals and their compounds. Phase pure transition metal carbides of group 4-6 metals, in the first three periods, were synthesized using a common eutectic salt flux synthesis method, and their electrocatalytic activities compared under uniform electrochemical conditions. Mo2C showed highest hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) activities among the nine metal carbides investigated, but all other metal carbides also showed substantial activities. All the metal carbides showed remarkable enhancement in catalytic activities as supports, when compared to traditional graphitic carbon as platinum support. Mo2C, the most active transition metal carbide electrocatalyst, was prepared using four different synthesis routes, and the synthesis route dependent activities compared. Bifunctional Mo 2C that is HER as well as oxygen evolution reaction (OER) active, was achieved when the carbide was templated on a multiwalled carbon nanotube using carbothermic reduction method. Bimetallic carbides of Fe, Co, and Ni with Mo or W were prepared using a common carbothermic reduction method. Two different stoichiometries of bimetallic carbides were obtained for each system within a 60 °C temperature window. While the bimetallic carbides showed relatively lower electrocatalytic activities towards HER and ORR in comparison to Mo2C and WC, they revealed remarkably higher OER activities than IrO2 and RuO2, the state-of-the-art OER catalysts. Bimetallic oxides of Fe, Co, and Ni with Mo and W were also prepared using a hydrothermal synthesis method and they also revealed OER activities that are much higher than RuO2 and IrO2. Additionally, the OER activities were dependent on the degree and nature of hydration in the bimetallic oxide crystal lattice, with the completely hydrated, as synthesized, cobalt molybdate and nickel

Ultrafast photophysics of transition metal complexes.

PubMed

Chergui, Majed

2015-03-17

The properties of transition metal complexes are interesting not only for their potential applications in solar energy conversion, OLEDs, molecular electronics, biology, photochemistry, etc. but also for their fascinating photophysical properties that call for a rethinking of fundamental concepts. With the advent of ultrafast spectroscopy over 25 years ago and, more particularly, with improvements in the past 10-15 years, a new area of study was opened that has led to insightful observations of the intramolecular relaxation processes such as internal conversion (IC), intersystem crossing (ISC), and intramolecular vibrational redistribution (IVR). Indeed, ultrafast optical spectroscopic tools, such as fluorescence up-conversion, show that in many cases, intramolecular relaxation processes can be extremely fast and even shorter than time scales of vibrations. In addition, more and more examples are appearing showing that ultrafast ISC rates do not scale with the magnitude of the metal spin-orbit coupling constant, that is, that there is no heavy-atom effect on ultrafast time scales. It appears that the structural dynamics of the system and the density of states play a crucial role therein. While optical spectroscopy delivers an insightful picture of electronic relaxation processes involving valence orbitals, the photophysics of metal complexes involves excitations that may be centered on the metal (called metal-centered or MC) or the ligand (called ligand-centered or LC) or involve a transition from one to the other or vice versa (called MLCT or LMCT). These excitations call for an element-specific probe of the photophysics, which is achieved by X-ray absorption spectroscopy. In this case, transitions from core orbitals to valence orbitals or higher allow probing the electronic structure changes induced by the optical excitation of the valence orbitals, while also delivering information about the geometrical rearrangement of the neighbor atoms around the atom of

Transition-metal impurities in semiconductors and heterojunction band lineups

NASA Astrophysics Data System (ADS)

Langer, Jerzy M.; Delerue, C.; Lannoo, M.; Heinrich, Helmut

1988-10-01

The validity of a recent proposal that transition-metal impurity levels in semiconductors may serve as a reference in band alignment in semiconductor heterojunctions is positively verified by using the most recent data on band offsets in the following lattice-matched heterojunctions: Ga1-xAlxAs/GaAs, In1-xGaxAsyP1-y/InP, In1-xGaxP/GaAs, and Cd1-xHgxTe/CdTe. The alignment procedure is justified theoretically by showing that transition-metal energy levels are effectively pinned to the average dangling-bond energy level, which serves as the reference level for the heterojunction band alignment. Experimental and theoretical arguments showing that an increasingly popular notion on transition-metal energy-level pinning to the vacuum level is unjustified and must be abandoned in favor of the internal-reference rule proposed recently [J. M. Langer and H. Heinrich, Phys. Rev. Lett. 55, 1414 (1985)] are presented.

Complete phase diagram of rare-earth nickelates from first-principles

NASA Astrophysics Data System (ADS)

Varignon, Julien; Grisolia, Mathieu N.; Íñiguez, Jorge; Barthélémy, Agnès; Bibes, Manuel

2017-12-01

The structural, electronic and magnetic properties of AMO3 perovskite oxides, where M is a 3d transition metal, are highly sensitive to the geometry of the bonds between the metal-d and oxygen-p ions (through octahedra rotations and distortions) and to their level of covalence. This is particularly true in rare-earth nickelates RNiO3 that display a metal-insulator transition with complex spin orders tunable by the rare-earth size, and are on the border line between dominantly ionic (lighter elements) and covalent characters (heavier elements). Accordingly, computing their ground state is challenging and a complete theoretical description of their rich phase diagram is still missing. Here, using first-principles simulations, we successfully describe the electronic and magnetic experimental ground state of nickelates. We show that the insulating phase is characterized by a split of the electronic states of the two Ni sites (i.e., resembling low-spin 4+ and high-spin 2+) with a concomitant shift of the oxygen-2p orbitals toward the depleted Ni cations. Therefore, from the point of view of the charge, the two Ni sites appear nearly identical whereas they are in fact distinct. Performing such calculations for several nickelates, we built a theoretical phase diagram that reproduces all their key features, namely a systematic dependence of the metal-insulator transition with the rare-earth size and the crossover between a second to first order transition for R = Pr and Nd. Finally, our results hint at strategies to control the electronic and magnetic phases of perovskite oxides by fine tuning of the level of covalence.

Rare earth elements and permanent magnets (invited)

NASA Astrophysics Data System (ADS)

Dent, Peter C.

2012-04-01

Rare earth (RE) magnets have become virtually indispensible in a wide variety of industries such as aerospace, automotive, electronics, medical, and military. RE elements are essential ingredients in these high performance magnets based on intermetallic compounds RECo5, RE2TM17 (TM: transition metal), and RE2TM14B. Rare earth magnets are known for their superior magnetic properties—high induction, and coercive force. These properties arise due to the extremely high magnetocrystalline anisotropy made possible by unique 3d-4f interactions between transition metals and rare earths. For more than 40 years, these magnets remain the number one choice in applications that require high magnetic fields in extreme operating conditions—high demagnetization forces and high temperature. EEC produces and specializes in RECo5 and RE2TM17 type sintered magnets. Samarium and gadolinium are key RE ingredients in the powder metallurgical magnet production processes which include melting, crushing, jet milling, pressing, sintering, and heat treating. The magnetic properties and applications of these magnets will be discussed. We will also briefly discuss the past, current, and future of the permanent magnet business. Currently, over 95% of all pure rare earth oxides are sourced from China, which currently controls the market. We will provide insights regarding current and potential new magnet technologies and designer choices, which may mitigate rare earth supply chain issues now and into the future.

Transition Metal d-Orbital Splitting Diagrams: An Updated Educational Resource for Square Planar Transition Metal Complexes

ERIC Educational Resources Information Center

Bo¨rgel, Jonas; Campbell, Michael G.; Ritter, Tobias

2016-01-01

The presentation of d-orbital splitting diagrams for square planar transition metal complexes in textbooks and educational materials is often inconsistent and therefore confusing for students. Here we provide a concise summary of the key features of orbital splitting diagrams for square planar complexes, which we propose may be used as an updated…

2D transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Manzeli, Sajedeh; Ovchinnikov, Dmitry; Pasquier, Diego; Yazyev, Oleg V.; Kis, Andras

2017-08-01

Graphene is very popular because of its many fascinating properties, but its lack of an electronic bandgap has stimulated the search for 2D materials with semiconducting character. Transition metal dichalcogenides (TMDCs), which are semiconductors of the type MX2, where M is a transition metal atom (such as Mo or W) and X is a chalcogen atom (such as S, Se or Te), provide a promising alternative. Because of its robustness, MoS2 is the most studied material in this family. TMDCs exhibit a unique combination of atomic-scale thickness, direct bandgap, strong spin-orbit coupling and favourable electronic and mechanical properties, which make them interesting for fundamental studies and for applications in high-end electronics, spintronics, optoelectronics, energy harvesting, flexible electronics, DNA sequencing and personalized medicine. In this Review, the methods used to synthesize TMDCs are examined and their properties are discussed, with particular attention to their charge density wave, superconductive and topological phases. The use of TMCDs in nanoelectronic devices is also explored, along with strategies to improve charge carrier mobility, high frequency operation and the use of strain engineering to tailor their properties.

Metal sulfide and rare-earth phosphate nanostructures and methods of making same

DOEpatents

Wong, Stanislaus; Zhang, Fen

2014-05-13

The present invention provides a method of producing a crystalline metal sulfide nanostructure. The metal is a transitional metal or a Group IV metal. In the method, a porous membrane is placed between a metal precursor solution and a sulfur precursor solution. The metal cations of the metal precursor solution and sulfur ions of the sulfur precursor solution react, thereby producing a crystalline metal sulfide nanostructure.

Electronic structure of negative charge transfer CaFeO3 across the metal-insulator transition

NASA Astrophysics Data System (ADS)

Rogge, Paul C.; Chandrasena, Ravini U.; Cammarata, Antonio; Green, Robert J.; Shafer, Padraic; Lefler, Benjamin M.; Huon, Amanda; Arab, Arian; Arenholz, Elke; Lee, Ho Nyung; Lee, Tien-Lin; Nemšák, Slavomír; Rondinelli, James M.; Gray, Alexander X.; May, Steven J.

2018-01-01

We investigated the metal-insulator transition for epitaxial thin films of the perovskite CaFeO3, a material with a significant oxygen ligand hole contribution to its electronic structure. We find that biaxial tensile and compressive strain suppress the metal-insulator transition temperature. By combining hard x-ray photoelectron spectroscopy, soft x-ray absorption spectroscopy, and density functional calculations, we resolve the element-specific changes to the electronic structure across the metal-insulator transition. We demonstrate that the Fe sites undergo no observable spectroscopic change between the metallic and insulating states, whereas the O electronic configuration undergoes significant changes. This strongly supports the bond-disproportionation model of the metal-insulator transition for CaFeO3 and highlights the importance of ligand holes in its electronic structure. By sensitively measuring the ligand hole density, however, we find that it increases by ˜5 -10 % in the insulating state, which we ascribe to a further localization of electron charge on the Fe sites. These results provide detailed insight into the metal-insulator transition of negative charge transfer compounds and should prove instructive for understanding metal-insulator transitions in other late transition metal compounds such as the nickelates.

Correlation between oxygen adsorption energy and electronic structure of transition metal macrocyclic complexes.

PubMed

Liu, Kexi; Lei, Yinkai; Wang, Guofeng

2013-11-28

Oxygen adsorption energy is directly relevant to the catalytic activity of electrocatalysts for oxygen reduction reaction (ORR). In this study, we established the correlation between the O2 adsorption energy and the electronic structure of transition metal macrocyclic complexes which exhibit activity for ORR. To this end, we have predicted the molecular and electronic structures of a series of transition metal macrocyclic complexes with planar N4 chelation, as well as the molecular and electronic structures for the O2 adsorption on these macrocyclic molecules, using the density functional theory calculation method. We found that the calculated adsorption energy of O2 on the transition metal macrocyclic complexes was linearly related to the average position (relative to the lowest unoccupied molecular orbital of the macrocyclic complexes) of the non-bonding d orbitals (d(z(2)), d(xy), d(xz), and d(yz)) which belong to the central transition metal atom. Importantly, our results suggest that varying the energy level of the non-bonding d orbitals through changing the central transition metal atom and/or peripheral ligand groups could be an effective way to tuning their O2 adsorption energy for enhancing the ORR activity of transition metal macrocyclic complex catalysts.

Selective extraction and recovery of rare earth metals from phosphor powders in waste fluorescent lamps using an ionic liquid system.

PubMed

Yang, Fan; Kubota, Fukiko; Baba, Yuzo; Kamiya, Noriho; Goto, Masahiro

2013-06-15

The recycling of rare earth metals from phosphor powders in waste fluorescent lamps by solvent extraction using ionic liquids was studied. Acid leaching of rare earth metals from the waste phosphor powder was examined first. Yttrium (Y) and europium (Eu) dissolved readily in the acid solution; however, the leaching of other rare earth metals required substantial energy input. Ionization of target rare earth metals from the waste phosphor powders into the leach solution was critical for their successful recovery. As a high temperature was required for the complete leaching of all rare earth metals, ionic liquids, for which vapor pressure is negligible, were used as an alternative extracting phase to the conventional organic diluent. An extractant, N, N-dioctyldiglycol amic acid (DODGAA), which was recently developed, showed a high affinity for rare earth metal ions in liquid-liquid extraction although a conventional commercial phosphonic extractant did not. An effective recovery of the rare earth metals, Y, Eu, La and Ce, from the metal impurities, Fe, Al and Zn, was achieved from the acidic leach solution of phosphor powders using an ionic liquid containing DODGAA as novel extractant system. Copyright © 2013 Elsevier B.V. All rights reserved.

Improving the Transition of Earth Satellite Observations from Research to Operations

NASA Technical Reports Server (NTRS)

Goodman, Steven J.; Lapenta, William M.; Jedlovec, Gary J.

2004-01-01

There are significant gaps between the observations, models, and decision support tools that make use of new data. These challenges include: 1) Decreasing the time to incorporate new satellite data into operational forecast assimilation systems, 2) Blending in-situ and satellite observing systems to produce the most accurate and comprehensive data products and assessments, 3) Accelerating the transition from research to applications through national test beds, field campaigns, and pilot demonstrations, and 4) Developing the partnerships and organizational structures to effectively transition new technology into operations. At the Short-term Prediction Research and Transition (SPORT) Center in Huntsville, Alabama, a NASA-NOAA-University collaboration has been developed to accelerate the infusion of NASA Earth science observations, data assimilation and modeling research into NWS forecast operations and decision-making. The SPoRT Center research focus is to improve forecasts through new observation capability and the regional prediction objectives of the US Weather Research Program dealing with 0-1 day forecast issues such as convective initiation and 24-hr quantitative precipitation forecasting. The near real-time availability of high-resolution experimental products of the atmosphere, land, and ocean from the Moderate Resolution Imaging Spectroradiometer (MODIS), the Advanced Infrared Spectroradiometer (AIRS), and lightning mapping systems provide an opportunity for science and algorithm risk reduction, and for application assessment prior to planned observations from the next generation of operational low Earth orbiting and geostationary Earth orbiting satellites. This paper describes the process for the transition of experimental products into forecast operations, current products undergoing assessment by forecasters, and plans for the future. The SPoRT Web page is at (http://www.ghcc.msfc.nasa.gov/sport).

First-principles study on interlayer state in alkali and alkaline earth metal atoms intercalated bilayer graphene

NASA Astrophysics Data System (ADS)

Kaneko, Tomoaki; Saito, Riichiro

2017-11-01

Energetics and electronic structures of alkali metal (Li, Na, K, Rb, and Cs) and alkaline earth metal (Be, Mg, Ca, Sr, and Ba) atoms intercalated bilayer graphene are systematically investigated using first-principles calculations based on density functional theory. Formation of alkali and alkaline earth metal atoms intercalated bilayer graphene is exothermic except for Be and Mg. The interlayer state between two graphene layers is occupied for K, Rb, Cs, Ca, Sr, and Ba. We find that the energetic position of the interlayer states between bilayer graphene monotonically shifts downward with increasing of interlayer distance. The interlayer distances of more than 4.5 Å and 4.0 Å, respectively, are necessary for the occupation of the interlayer state in bilayer graphene for alkali and alkaline earth metal atoms, which is almost independent of the intercalant metal species. We discuss the relevance to occurrence of superconductivity for the metal intercalated bilayer graphene in terms of the occupation of the interlayer state and the phonon frequency of metal ions.

Molten metal containment vessel with rare earth oxysulfide protective coating thereon and method of making same

DOEpatents

Krikorian, Oscar H.; Curtis, Paul G.

1992-01-01

An improved molten metal containment vessel is disclosed in which wetting of the vessel's inner wall surfaces by molten metal is inhibited by coating at least the inner surfaces of the containment vessel with one or more rare earth oxysulfide or rare earth sulfide compounds to inhibit wetting and or adherence by the molten metal to the surfaces of the containment vessel.

Shear Viscosity Coefficient of 5d Liquid Transition Metals

NASA Astrophysics Data System (ADS)

Thakor, P. B.; Sonvane, Y. A.; Gajjar, P. N.; Jani, A. R.

2011-07-01

In the present paper we have calculated shear viscosity coefficient (η) of 5 d liquid transition metals. To calculate effective pair potential ν(r) and pair distribution function g(r) we have used our own newly constructed model potential and Percus- Yevick hard sphere (PYHS) structure factor S(q) respectively. We have also investigated the effect of different correction function like Hartree (H), Taylor (T) and Sarkar et al. (S) on shear viscosity coefficient (η). Our newly constructed model potential successfully explains the shear viscosity coefficient (η) of 5 d liquid transition metals.

Thermal conductivity switch: Optimal semiconductor/metal melting transition

NASA Astrophysics Data System (ADS)

Kim, Kwangnam; Kaviany, Massoud

2016-10-01

Scrutinizing distinct solid/liquid (s /l ) and solid/solid (s /s ) phase transitions (passive transitions) for large change in bulk (and homogenous) thermal conductivity, we find the s /l semiconductor/metal (S/M) transition produces the largest dimensionless thermal conductivity switch (TCS) figure of merit ZTCS (change in thermal conductivity divided by smaller conductivity). At melting temperature, the solid phonon and liquid molecular thermal conductivities are comparable and generally small, so the TCS requires localized electron solid and delocalized electron liquid states. For cyclic phase reversibility, the congruent phase transition (no change in composition) is as important as the thermal transport. We identify X Sb and X As (X =Al , Cd, Ga, In, Zn) and describe atomic-structural metrics for large ZTCS, then show the superiority of S/M phonon- to electron-dominated transport melting transition. We use existing experimental results and theoretical and ab initio calculations of the related properties for both phases (including the Kubo-Greenwood and Bridgman formulations of liquid conductivities). The 5 p orbital of Sb contributes to the semiconductor behavior in the solid-phase band gap and upon disorder and bond-length changes in the liquid phase this changes to metallic, creating the large contrast in thermal conductivity. The charge density distribution, electronic localization function, and electron density of states are used to mark this S/M transition. For optimal TCS, we examine the elemental selection from the transition, basic, and semimetals and semiconductor groups. For CdSb, addition of residual Ag suppresses the bipolar conductivity and its ZTCS is over 7, and for Zn3Sb2 it is expected to be over 14, based on the structure and transport properties of the better-known β -Zn4Sb3 . This is the highest ZTCS identified. In addition to the metallic melting, the high ZTCS is due to the electron-poor nature of II-V semiconductors, leading to the

Weyl Semimetal to Metal Phase Transitions Driven by Quasiperiodic Potentials

NASA Astrophysics Data System (ADS)

Pixley, J. H.; Wilson, Justin H.; Huse, David A.; Gopalakrishnan, Sarang

2018-05-01

We explore the stability of three-dimensional Weyl and Dirac semimetals subject to quasiperiodic potentials. We present numerical evidence that the semimetal is stable for weak quasiperiodic potentials, despite being unstable for weak random potentials. As the quasiperiodic potential strength increases, the semimetal transitions to a metal, then to an "inverted" semimetal, and then finally to a metal again. The semimetal and metal are distinguished by the density of states at the Weyl point, as well as by level statistics, transport, and the momentum-space structure of eigenstates near the Weyl point. The critical properties of the transitions in quasiperiodic systems differ from those in random systems: we do not find a clear critical scaling regime in energy; instead, at the quasiperiodic transitions, the density of states appears to jump abruptly (and discontinuously to within our resolution).

Energetic Ionic Liquids Based on Anionic Rare Earth Nitrate Complexes (Preprint)

DTIC Science & Technology

2008-07-10

a glass transition temperature (Tg) at -46 oC. However, it is only stable in dry air, and thus must be protected from water. At 75 oC, clear weight...involved highly toxic and corrosive chemicals, N2O4 and NOCl. Ligands which coordinate via oxygen atoms to a rare earth metal ion give rise to stable...complexes. Thus higher air and thermal stabilities may be obtained by introducing rare earth metal nitrates as main components of ionic liquids. We

Ultrathin and Atomically Flat Transition-Metal Oxide: Promising Building Blocks for Metal-Insulator Electronics.

PubMed

Cui, Qingsong; Sakhdari, Maryam; Chamlagain, Bhim; Chuang, Hsun-Jen; Liu, Yi; Cheng, Mark Ming-Cheng; Zhou, Zhixian; Chen, Pai-Yen

2016-12-21

We present a new and viable template-assisted thermal synthesis method for preparing amorphous ultrathin transition-metal oxides (TMOs) such as TiO 2 and Ta 2 O 5 , which are converted from crystalline two-dimensional (2D) transition-metal dichalcogenides (TMDs) down to a few atomic layers. X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning transmission electron microscopy (STEM) were used to characterize the chemical composition and bonding, surface morphology, and atomic structure of these ultrathin amorphous materials to validate the effectiveness of our synthesis approach. Furthermore, we have fabricated metal-insulator-metal (MIM) diodes using the TiO 2 and Ta 2 O 5 as ultrathin insulating layers with low potential barrier heights. Our MIM diodes show a clear transition from direct tunneling to Fowler-Nordheim tunneling, which was not observed in previously reported MIM diodes with TiO 2 or Ta 2 O 5 as the insulating layer. We attribute the improved performance of our MIM diodes to the excellent flatness and low pinhole/defect densities in our TMO insulting layers converted from 2D TMDs, which enable the low-threshold and controllable electron tunneling transport. We envision that it is possible to use the ultrathin TMOs converted from 2D TMDs as the insulating layer of a wide variety of metal-insulator and field-effect electronic devices for various applications ranging from microwave mixing, parametric conversion, infrared photodetection, emissive energy harvesting, to ultrafast electronic switching.

Ammonia and hydrazine. Transition-metal-catalyzed hydroamination and metal-free catalyzed functionalization

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

Bertrand, Guy

2012-06-29

The efficient and selective preparation of organic molecules is critical for mankind. For the future, it is of paramount importance to find catalysts able to transform abundant and cheap feedstocks into useful compounds. Acyclic and heterocyclic nitrogen-containing derivatives are common components of naturally occurring compounds, agrochemicals, cosmetics, and pharmaceuticals; they are also useful intermediates in a number of industrial processes. One of the most widely used synthetic strategies, allowing the formation of an N-C bond, is the addition of an N-H bond across a carbon-carbon multiple bond, the so-called hydroamination reaction. This chemical transformation fulfills the principle of “green chemistry”more » since it ideally occurs with 100% atom economy. Various catalysts have been found to promote this reaction, although many limitations remain; one of the most prominent is the lack of methods that permit the use of NH 3 and NH 2NH 2 as the amine partners. In fact, ammonia and hydrazine have rarely succumbed to homogeneous catalytic transformations. Considering the low cost and abundance of ammonia (136 million metric tons produced in 2011) and hydrazine, catalysts able to improve the reactivity and selectivity of the NH 3- and NH 2NH 2-hydroamination reaction, and more broadly speaking the functionalization of these chemicals, are highly desirable. In the last funded period, we discovered the first homogeneous catalysts able to promote the hydroamination of alkynes and allenes with ammonia and the parent hydrazine. The key feature of our catalytic systems is that the formation of catalytically inactive Werner complexes is reversible, in marked contrast to most of the known ammonia and hydrazine transition metal complexes. This is due to the peculiar electronic properties of our neutral ancillary ligands, especially their strong donating capabilities. However, our catalysts currently require high temperatures and long reaction times. To address

Synthetic Fabrication of Nanoscale MoS2-Based Transition Metal Sulfides

PubMed Central

Wang, Shutao; An, Changhua; Yuan, Jikang

2010-01-01

Transition metal sulfides are scientifically and technologically important materials. This review summarizes recent progress on the synthetic fabrication of transition metal sulfides nanocrystals with controlled shape, size, and surface functionality. Special attention is paid to the case of MoS2 nanoparticles, where organic (surfactant, polymer), inorganic (support, promoter, doping) compounds and intercalation chemistry are applied.

Low frequency vibrational spectra and the nature of metal-oxygen bond of alkaline earth metal acetylacetonates

NASA Astrophysics Data System (ADS)

Fakheri, Hamideh; Tayyari, Sayyed Faramarz; Heravi, Mohammad Momen; Morsali, Ali

2017-12-01

Theoretical quantum chemistry calculations were used to assign the observed vibrational band frequencies of Be, Mg, Ca, Sr, and Ba acetylacetonates complexes. Density functional theory (DFT) calculations have been carried out at the B3LYP level, using LanL2DZ, def2SVP, and mixed, GenECP, (def2SVP for metal ions and 6-311++G** for all other atoms) basis sets. The B3LYP level, with mixed basis sets, was utilized for calculations of vibrational frequencies, IR intensity, and Raman activity. Analysis of the vibrational spectra indicates that there are several bands which could almost be assigned mainly to the metal-oxygen vibrations. The strongest Raman band in this region could be used as a measure of the stability of the complex. The effects of central metal on the bond orders and charge distributions in alkaline earth metal acetylacetonates were studied by the Natural Bond Orbital (NBO) method for fully optimized compounds. Optimization were performed at the B3LYP/6-311++G** level for the lighter alkaline earth metal complexes (Be, Mg, and Ca acetylacetonates) while the B3LYP level, using LanL2DZ (extrabasis, d and f on oxygen and metal atoms), def2SVP and mixed (def2SVP on metal ions and 6-311++G** for all other atoms) basis sets for all understudy complexes. Calculations indicate that the covalence nature of metal-oxygen bonds considerably decreases from Be to Ba complexes. The nature of metal-oxygen bond was further studied by using Atoms In Molecules (AIM) analysis. The topological parameters, Wiberg bond orders, natural charges of O and metal ions, and also some vibrational band frequencies were correlated with the stability constants of understudy complexes.

High Pressure Phase Transformations in Heavy Rare Earth Metals and Connections to Actinide Crystal Structures

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

Vohra, Yogesh K.; Sangala, Bagvanth Reddy; Stemshorn, Andrew K.

2008-07-01

High-pressure studies have been performed on heavy rare earth metals Terbium (Tb) to 155 GPa and Holmium (Ho) to 134 GPa in a diamond anvil cell at room temperature. The following crystal structure sequence was observed in both metals hcp {yields} Sm-type {yields} dhcp {yields} distorted fcc (hR-24) {yields} monoclinic (C2/m) with increasing pressure. The last transformation to a low symmetry monoclinic phase is accompanied by a volume collapse of 5 % for Tb at 51 GPa and a volume collapse of 3 % for Ho at 103 GPa. This volume collapse under high pressure is reminiscent of f-shell delocalizationmore » in light rare earth metal Cerium (Ce), Praseodymium (Pr), and heavy actinide metals Americium (Am) and Curium (Cm). The orthorhombic Pnma phase that has been reported in Am and Cm after f-shell delocalization is not observed in heavy rare earth metals under high pressures. (authors)« less

Transition metals in the transition zone: Crystal chemistry of minor element substitution in wadsleyite

DOE PAGES

Zhang, Li; Smyth, Joseph R.; Allaz, Julien; ...

2016-10-01

As the most abundant solid phase at depths of 410 to 525 km, wadsleyite constitutes a large geochemical reservoir in the Earth. In order to better understand the implications of minor element substitution and cation ordering in wadsleyite, we have synthesized wadsleyites coexisting with pyroxenes with about 3 wt% of either TiO 2, Cr 2O 3, V 2O 3, CoO, NiO, or ZnO under hydrous conditions in separate experiments at 1300 °C and 15 GPa. We have refined the crystal structures of these wadsleyites by single-crystal X-ray diffraction, analyzed the compositions by electron microprobe, and estimated M3 vacancy concentration frommore » b/a cell-parameter ratios. According to the crystal structure refinements, trivalent cations Fe 3+, Cr 3+ and V 3+, show a strong preference for M3 over M1 and M2 and significant substitution up to 2.7 % (atomic percent) at the tetrahedral site (T site). Divalent cations, Ni 2+, Co 2+, and Zn 2+ show site preferences similar to those of Fe2+ with M1≈ M3 > M2 > T. Transition metal site preferences appear to correlate with crystal field stabilization energies (CFSE) and are inconsistent with cation radius effects. The avoidance of Ni 2+, Co 2+ and Fe 2+ for the M2 site in both wadsleyite and olivine can be influenced by CFSE, which has a positive correlation with site preferences at octahedral sites, indicating that avoidance of the lower-symmetry M2 site is stronger for cations having lower (greater absolute value) CFSE. Ti 4+ substitutes primarily into the M3 octahedron, rather than M1, M2, or T sites. Electron microprobe analysis reveals that Ti 4+, Cr 3+, and V 3+ have greater solubility in wadsleyite than in olivine. Furthermore these transition metal cations may be enriched in a melt or an accessory phase if hydrous melting occurs on upward convection across the wadsleyite-olivine boundary and may be useful as indicators of high pressure origin.« less

Adjustable metal-semiconductor transition of FeS thin films by thermal annealing

NASA Astrophysics Data System (ADS)

Fu, Ganhua; Polity, Angelika; Volbers, Niklas; Meyer, Bruno K.; Mogwitz, Boris; Janek, Jürgen

2006-12-01

FeS polycrystalline thin films were prepared on float glass at 500°C by radio-frequency reactive sputtering. The influence of vacuum annealing on the metal-semiconductor transition of FeS films was investigated. It has been found that with the increase of the annealing temperature from 360to600°C, the metal-semiconductor transition temperature of FeS films first decreases and then increases, associated with first a reduction and then an enhancement of hysteresis width. The thermal stress is considered to give rise to the abnormal change of the metal-semiconductor transition of the FeS film during annealing.

Earth Science Markup Language: Transitioning From Design to Application

NASA Technical Reports Server (NTRS)

Moe, Karen; Graves, Sara; Ramachandran, Rahul

2002-01-01

The primary objective of the proposed Earth Science Markup Language (ESML) research is to transition from design to application. The resulting schema and prototype software will foster community acceptance for the "define once, use anywhere" concept central to ESML. Supporting goals include: 1. Refinement of the ESML schema and software libraries in cooperation with the user community. 2. Application of the ESML schema and software libraries to a variety of Earth science data sets and analysis tools. 3. Development of supporting prototype software for enhanced ease of use. 4. Cooperation with standards bodies in order to assure ESML is aligned with related metadata standards as appropriate. 5. Widespread publication of the ESML approach, schema, and software.

REVIEWS OF TOPICAL PROBLEMS: Universal viscosity growth in metallic melts at megabar pressures: the vitreous state of the Earth's inner core

NASA Astrophysics Data System (ADS)

Brazhkin, Vadim V.; Lyapin, A. G.

2000-05-01

Experimental data on and theoretical models for the viscosity of various types of liquids and melts under pressure are reviewed. Experimentally, the least studied melts are those of metals, whose viscosity is considered to be virtually constant along the melting curve. The authors' new approach to the viscosity of melts involves the measurement of the grain size in solidified samples. Measurements on liquid metals at pressures up to 10 GPa using this method show, contrary to the empirical approach, that the melt viscosity grows considerably along the melting curves. Based on the experimental data and on the critical analysis of current theories, a hypothesis of a universal viscosity behavior is introduced for liquids under pressure. Extrapolating the liquid iron results to the pressures and temperatures at the Earth's core reveals that the Earth's outer core is a very viscous melt with viscosity values ranging from 102 Pa s to 1011 Pa s depending on the depth. The Earth's inner core is presumably an ultraviscous (>1011 Pa s) glass-like liquid — in disagreement with the current idea of a crystalline inner core. The notion of the highly viscous interior of celestial bodies sheds light on many mysteries of planetary geophysics and astronomy. From the analysis of the pressure variation of the melting and glass-transition temperatures, an entirely new concept of a stable metallic vitreous state arises, calling for further experimental and theoretical study.

Metallic hydrogen

NASA Astrophysics Data System (ADS)

Silvera, Isaac F.; Dias, Ranga

2018-06-01

Hydrogen is the simplest and most abundant element in the Universe. There are two pathways for creating metallic hydrogen under high pressures. Over 80 years ago Wigner and Huntington predicted that if solid molecular hydrogen was sufficiently compressed in the T  =  0 K limit, molecules would dissociate to form atomic metallic hydrogen (MH). We have observed this transition at a pressure of 4.95 megabars. MH in this form has probably never existed on Earth or in the Universe; it may be a room temperature superconductor and is predicted to be metastable. If metastable it will have an important technological impact. Liquid metallic hydrogen can also be produced at intermediate pressures and high temperatures and is believed to make up ~90% of the planet Jupiter. We have observed this liquid–liquid transition, also known as the plasma phase transition, at pressures of ~1–2 megabar and temperatures ~1000–2000 K. However, in this paper we shall focus on the Wigner–Huntington transition. We shall discuss the methods used to observe metallic hydrogen at extreme conditions of static pressure in the laboratory, extending our understanding of the phase diagram of the simplest atom in the periodic table.

Hund’s rule in superatoms with transition metal impurities

PubMed Central

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

2011-01-01

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

Metal Insulator transition in Vanadium Dioxide

NASA Astrophysics Data System (ADS)

Jovaini, Azita; Fujita, Shigeji; Suzuki, Akira; Godoy, Salvador

2012-02-01

MAR12-2011-000262 Abstract Submitted for the MAR12 Meeting of The American Physical Society Sorting Category: 03.9 (T) On the metal-insulator-transition in vanadium dioxide AZITA JOVAINI, SHIGEJI FUJITA, University at Buffalo, SALVADOR GODOY, UNAM, AKIRA SUZUKI, Tokyo University of Science --- Vanadium dioxide (VO2) undergoes a metal-insulator transition (MIT) at 340 K with the structural change from tetragonal to monoclinic crystal. The conductivity _/ drops at MIT by four orders of magnitude. The low temperature monoclinic phase is known to have a lower ground-state energy. The existence of the k-vector k is prerequisite for the conduction since the k appears in the semiclassical equation of motion for the conduction electron (wave packet). The tetragonal (VO2)3 unit is periodic along the crystal's x-, y-, and z-axes, and hence there is a three-dimensional k-vector. There is a one-dimensional k for a monoclinic crystal. We believe this difference in the dimensionality of the k-vector is the cause of the conductivity drop. Prefer Oral Session X Prefer .

Pressure-driven insulator-metal transition in cubic phase UO2

NASA Astrophysics Data System (ADS)

Huang, Li; Wang, Yilin; Werner, Philipp

2017-09-01

Understanding the electronic properties of actinide oxides under pressure poses a great challenge for experimental and theoretical studies. Here, we investigate the electronic structure of cubic phase uranium dioxide at different volumes using a combination of density functional theory and dynamical mean-field theory. The ab initio calculations predict an orbital-selective insulator-metal transition at a moderate pressure of ∼45 GPa. At this pressure the uranium's 5f 5/2 state becomes metallic, while the 5f 7/2 state remains insulating up to about 60 GPa. In the metallic state, we observe a rapid decrease of the 5f occupation and total angular momentum with pressure. Simultaneously, the so-called “Zhang-Rice state”, which is of predominantly 5f 5/2 character, quickly disappears after the transition into the metallic phase.

Visualization of a stable intermediate phase in photoinduced metal-to-insulator transition in manganites

NASA Astrophysics Data System (ADS)

Lin, Hanxuan; Liu, Hao; Bai, Yu; Miao, Tian; Yu, Yang; Zhu, Yinyan; Chen, Hongyan; Kou, Yunfang; Niu, Jiebin; Wang, Wenbin; Yin, Lifeng; Shen, Jian

First order metal-insulator transition, accounting for various intriguing phenomena, is one of the most important phase transitions in condensed matter systems. Aside from the initial and final states, i.e. the metallic and insulating phases, no stable intermediate phase has been experimentally identified in such first order phase transition, though some transient phases do exist at the ultrafast time scale. Here, using our unique low-temperature, high-field magnetic force microscopy with photoexcitation, we directly observed a stable intermediate phase emerging and mediating the photoinduced first order metal-insulator transition in manganites. This phase is characteristic of low net magnetization and high resistivity. Our observations unveil the microscopic details of the photoinduced metal-insulator transition in manganites, which may be insightful to study first order metal-insulator transition in other condensed matter systems. This work was supported by National Key Research Program of China (2016YFA0300702), National Basic Research Program of China (973 Program) under the Grant No. 2013CB932901 and 2014CB921104; National Natural Science Foundation of China (11274071, 11504053).

Two planetary systems with transiting Earth-size and super-Earth planets orbiting late-type dwarf stars

NASA Astrophysics Data System (ADS)

Alonso, E. Díez; Hernández, J. I. González; Suárez Gómez, S. L.; Aguado, D. S.; González Gutiérrez, C.; Suárez Mascareño, A.; Cabrera-Lavers, A.; González-Nuevo, J.; Toledo-Padrón, B.; Gracia, J.; de Cos Juez, F. J.; Rebolo, R.

2018-06-01

We present two new planetary systems found around cool dwarf stars with data from the K2 mission. The first system was found in K2-XX1 (EPIC 248545986), characterized in this work as M3.0V and observed in the 14th campaign of K2. It consists of three Earth-size transiting planets with radii of 1.1, 1.0 and 1.1 R⊕, showing a compact configuration with orbital periods of 5.24, 7.78 and 10.1 days, close to 2:3:4 resonance. The second was found in K2-XX2 (EPIC 249801827), characterized in this work as M0.5V and observed in the 15th campaign. It consists of two transiting super-Earths with radii 2.0 and 1.8 R⊕ and orbital periods of 6.03 and 20.5 days. The equilibrium temperatures of the atmospheres of these planets are estimated to be in the range of 380-600 K and the amplitudes of signals in transmission spectroscopy are estimated at ˜ 10 ppm.

Metal-insulator transition in NiS2-xSex

NASA Astrophysics Data System (ADS)

Kuneš, J.; Baldassarre, L.; Schächner, B.; Rabia, K.; Kuntscher, C. A.; Korotin, Dm. M.; Anisimov, V. I.; McLeod, J. A.; Kurmaev, E. Z.; Moewes, A.

2010-01-01

The origin of the gap in NiS2 as well as the pressure- and doping-induced metal-insulator transition in the NiS2-xSex solid solutions are investigated both theoretically using the first-principles band structures combined with the dynamical mean-field approximation for the electronic correlations and experimentally by means of infrared and x-ray absorption spectroscopies. The bonding-antibonding splitting in the S-S (Se-Se) dimer is identified as the main parameter controlling the size of the charge gap. The implications for the metal-insulator transition driven by pressure and Se doping are discussed.

Phase transitions in MgSiO3 post-perovskite in super-Earth mantles

NASA Astrophysics Data System (ADS)

Umemoto, Koichiro; Wentzcovitch, Renata M.; Wu, Shunqing; Ji, Min; Wang, Cai-Zhuang; Ho, Kai-Ming

2017-11-01

The highest pressure form of the major Earth-forming mantle silicate is MgSiO3 post-perovskite (PPv). Understanding the fate of PPv at TPa pressures is the first step for understanding the mineralogy of super-Earths-type exoplanets, arguably the most interesting for their similarities with Earth. Modeling their internal structure requires knowledge of stable mineral phases, their properties under compression, and major element abundances. Several studies of PPv under extreme pressures support the notion that a sequence of pressure induced dissociation transitions produce the elementary oxides SiO2 and MgO as the ultimate aggregation form at ∼3 TPa. However, none of these studies have addressed the problem of mantle composition, particularly major element abundances usually expressed in terms of three main variables, the Mg/Si and Fe/Si ratios and the Mg#, as in the Earth. Here we show that the critical compositional parameter, the Mg/Si ratio, whose value in the Earth's mantle is still debated, is a vital ingredient for modeling phase transitions and internal structure of super-Earth mantles. Specifically, we have identified new sequences of phase transformations, including new recombination reactions that depend decisively on this ratio. This is a new level of complexity that has not been previously addressed, but proves essential for modeling the nature and number of internal layers in these rocky mantles.

Metal Transport across Biomembranes: Emerging Models for a Distinct Chemistry*

PubMed Central

Argüello, José M.; Raimunda, Daniel; González-Guerrero, Manuel

2012-01-01

Transition metals are essential components of important biomolecules, and their homeostasis is central to many life processes. Transmembrane transporters are key elements controlling the distribution of metals in various compartments. However, due to their chemical properties, transition elements require transporters with different structural-functional characteristics from those of alkali and alkali earth ions. Emerging structural information and functional studies have revealed distinctive features of metal transport. Among these are the relevance of multifaceted events involving metal transfer among participating proteins, the importance of coordination geometry at transmembrane transport sites, and the presence of the largely irreversible steps associated with vectorial transport. Here, we discuss how these characteristics shape novel transition metal ion transport models. PMID:22389499

Metal transport across biomembranes: emerging models for a distinct chemistry.

PubMed

Argüello, José M; Raimunda, Daniel; González-Guerrero, Manuel

2012-04-20

Transition metals are essential components of important biomolecules, and their homeostasis is central to many life processes. Transmembrane transporters are key elements controlling the distribution of metals in various compartments. However, due to their chemical properties, transition elements require transporters with different structural-functional characteristics from those of alkali and alkali earth ions. Emerging structural information and functional studies have revealed distinctive features of metal transport. Among these are the relevance of multifaceted events involving metal transfer among participating proteins, the importance of coordination geometry at transmembrane transport sites, and the presence of the largely irreversible steps associated with vectorial transport. Here, we discuss how these characteristics shape novel transition metal ion transport models.

Transition-Metal-Free Alkynylation of Aryl Chlorides

PubMed Central

Truong, Thanh; Daugulis, Olafs

2011-01-01

Two sets of conditions have been developed for a base-mediated, transition-metal-free alkynylation of aryl chlorides that proceeds via benzyne intermediates. The first set of conditions involves the use of TMPLi base in a pentane/THF mixture at 25 °C. The second set involves use of a metal alkoxide base in dioxane at elevated temperature. Reasonable functional group tolerance has been observed. Fluoro, trifluoromethyl, silyl, cyano, and alcohol functionalities are compatible with the reaction conditions. PMID:21786825

Microalloying of transition metal silicides by mechanical activation and field-activated reaction

DOEpatents

Munir, Zuhair A [Davis, CA; Woolman, Joseph N [Davis, CA; Petrovic, John J [Los Alamos, NM

2003-09-02

Alloys of transition metal suicides that contain one or more alloying elements are fabricated by a two-stage process involving mechanical activation as the first stage and densification and field-activated reaction as the second stage. Mechanical activation, preferably performed by high-energy planetary milling, results in the incorporation of atoms of the alloying element(s) into the crystal lattice of the transition metal, while the densification and field-activated reaction, preferably performed by spark plasma sintering, result in the formation of the alloyed transition metal silicide. Among the many advantages of the process are its ability to accommodate materials that are incompatible in other alloying methods.

High Pressure Synthesis of Transition Metal Carbonyls.

ERIC Educational Resources Information Center

Hagen, A. P.; And Others

1979-01-01

Presents an experiment which uses readily available starting materials and inexpensive equipment for synthesis of transition metal carbonyls at 1000 atm and which is intended to give students experience in techniques used in research and industry. Safety precautions are emphasized. (Author/SA)

GROUND-BASED TRANSIT OBSERVATIONS OF THE SUPER-EARTH 55 Cnc e

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

De Mooij, E. J. W.; López-Morales, M.; Karjalainen, R.

2014-12-20

We report the first ground-based detections of the shallow transit of the super-Earth exoplanet 55 Cnc e using a 2 m class telescope. Using differential spectrophotometry, we observed one transit in 2013 and another in 2014, with average spectral resolutions of ∼700 and ∼250, spanning the Johnson BVR photometric bands. We find a white light planet-to-star radius ratio of 0.0190{sub −0.0027}{sup +0.0023} from the 2013 observations and 0.0200{sub −0.0018}{sup +0.0017} from the 2014 observations. The two data sets combined result in a radius ratio of 0.0198{sub −0.0014}{sup +0.0013}. These values are all in agreement with previous space-based results. Scintillation noise in themore » data prevents us from placing strong constraints on the presence of an extended hydrogen-rich atmosphere. Nevertheless, our detections of 55 Cnc e in transit demonstrate that moderate-sized telescopes on the ground will be capable of routine follow-up observations of super-Earth candidates discovered by the Transiting Exoplanet Survey Satellite around bright stars. We expect it also will be possible to place constraints on the atmospheric characteristics of those planets by devising observational strategies to minimize scintillation noise.« less

Three Transits for the Price of One: Super-Earth Transits of the Nearest Planetary System Discovered By Kepler/K2

NASA Astrophysics Data System (ADS)

Redfield, Seth; Niraula, Prajwal; Hedges, Christina; Crossfield, Ian; Kreidberg, Laura; Greene, Tom; Rodriguez, Joey; Vanderburg, Andrew; Laughlin, Gregory; Millholland, Sarah; Wang, Songhu; Cochran, William; Livingston, John; Gandolfi, Davide; Guenther, Eike; Fridlund, Malcolm; Korth, Judith

2018-05-01

We propose primary transit observations of three Super-Earth planets in the newly discovered planetary system around a bright, nearby star, GJ 9827. We recently announced the detection of three super-Earth planets in 1:3:5 commensurability, the inner planet, GJ 9827 b having a period of 1.2 days. This is the nearest planetary system that Kepler or K2 has found, at 30 pc, and given its brightness is one of the top systems for follow-up characterization. This system presents a unique opportunity to acquire three planetary transits for the price of one. There are several opportunities in the Spitzer visibility windows to obtain all three transits in a short period of time. We propose 3.6 micron observations of all three Super-Earth transits in a single 18-hour observation window. The proximity to a 1:3:5 resonance is intriguing from a dynamical standpoint as well. Indeed, anomalous transit timing offsets have been measured for planet d in Hubble observations that suffer from partial phase coverage. The short cadence and extended coverage of Spitzer is essential to provide a firm determination of the ephemerides and characterize any transit timing variations. Constraining these orbital parameters is critical for follow-up observations from space and ground-based telescopes. Due to the brightness of the host star, this planetary system is likely to be extensively observed in the years to come. Indeed, our team has acquired observations of the planets orbiting GJ9827 with Hubble in the ultraviolet and infrared. The proposed observations will provide infrared atmospheric measurements and firm orbital characterization which is critical for planning and designing future observations, in particular atmospheric characterization with JWST.

Metallic Hydrogen

NASA Astrophysics Data System (ADS)

Silvera, Isaac; Zaghoo, Mohamed; Salamat, Ashkan

2015-03-01

Hydrogen is the simplest and most abundant element in the Universe. At high pressure it is predicted to transform to a metal with remarkable properties: room temperature superconductivity, a metastable metal at ambient conditions, and a revolutionary rocket propellant. Both theory and experiment have been challenged for almost 80 years to determine its condensed matter phase diagram, in particular the insulator-metal transition. Hydrogen is predicted to dissociate to a liquid atomic metal at multi-megabar pressures and T =0 K, or at megabar pressures and very high temperatures. Thus, its predicted phase diagram has a broad field of liquid metallic hydrogen at high pressure, with temperatures ranging from thousands of degrees to zero Kelvin. In a bench top experiment using static compression in a diamond anvil cell and pulsed laser heating, we have conducted measurements on dense hydrogen in the region of 1.1-1.7 Mbar and up to 2200 K. We observe a first-order phase transition in the liquid phase, as well as sharp changes in optical transmission and reflectivity when this phase is entered. The optical signature is that of a metal. The mapping of the phase line of this transition is in excellent agreement with recent theoretical predictions for the long-sought plasma phase transition to metallic hydrogen. Research supported by the NSF, Grant DMR-1308641, the DOE Stockpile Stewardship Academic Alliance Program, Grant DE-FG52-10NA29656, and NASA Earth and Space Science Fellowship Program, Award NNX14AP17H.

Properties of Transition Metal Doped Alumina

NASA Astrophysics Data System (ADS)

Nykwest, Erik; Limmer, Krista; Brennan, Ray; Blair, Victoria; Ramprasad, Rampi

Crystallographic texture can have profound effects on the properties of a material. One method of texturing is through the application of an external magnetic field during processing. While this method works with highly magnetic systems, doping is required to couple non-magnetic systems with the external field. Experiments have shown that low concentrations of rare earth (RE) dopants in alumina powders have enabled this kind of texturing. The magnetic properties of RE elements are directly related to their f orbital, which can have as many as 7 unpaired electrons. Since d-block elements can have as many as 5 unpaired electrons the effects of substitutional doping of 3d transition metals (TM) for Al in alpha (stable) and theta (metastable) alumina on the local structure and magnetic properties, in addition to the energetic cost, have been calculated by performing first-principles calculations based on density functional theory. This study has led to the development of general guidelines for the magnetic moment distribution at and around the dopant atom, and the dependence of this distribution on the dopant atom type and its coordination environment. It is anticipated that these findings can aid in the selection of suitable dopants help to guide parallel experimental efforts. This project was supported in part by an internship at the Army Research Laboratory, administered by the Oak Ridge Institute for Science and Education, along with a grant of computer time from the DoD High Performance Computing Modernization Program.

A Review on the Synthesis and Applications of Mesostructured Transition Metal Phosphates

PubMed Central

Lin, Ronghe; Ding, Yunjie

2013-01-01

Considerable efforts have been devoted to extending the range of the elemental composition of mesoporous materials since the pioneering work of the M41S family of ordered mesoporous silica by Mobil researchers. The synthesis of transition metal-containing mesostructured materials with large surface area and high porosity has drawn great attention for its potential applications in acid and redox catalysis, photocatalysis, proton conducting devices, environmental restoration and so on. Thus, various transition metals-containing mesoporous materials, including transition metal-substituted mesoporous silicates, mesostructured transition metal oxides and transition metal phosphates (TMP), have been documented in the literature. Among these, mesostructured TMP materials are less studied, but possess some unique features, partly because of the easy and facile functionalization of PO4 and/or P–OH groups, rendering them interesting functional materials. This review first introduced the general synthesis strategies for manufacturing mesostructured TMP materials, as well as advantages and disadvantages of the respective method; then, we surveyed the ongoing developments of fabrication and application of the TMP materials in three groups on the basis of their components and application fields. Future perspectives on existing problems related to the present synthesis routes and further modifying of the functional groups for the purpose of tailoring special physical-chemical properties to meet wide application requirements were also provided in the last part. PMID:28809304

Predicting a new phase (T'') of two-dimensional transition metal di-chalcogenides and strain-controlled topological phase transition

NASA Astrophysics Data System (ADS)

Ma, Fengxian; Gao, Guoping; Jiao, Yalong; Gu, Yuantong; Bilic, Ante; Zhang, Haijun; Chen, Zhongfang; Du, Aijun

2016-02-01

Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T''), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T'' MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T'' phase unambiguously display similar band topologies and strain controlled topological phase transitions. Our findings greatly enrich the 2D families of transition metal dichalcogenides and offer a feasible way to control the electronic states of 2D topological insulators for the fabrication of high-speed spintronics devices.Single layered transition metal dichalcogenides have attracted tremendous research interest due to their structural phase diversities. By using a global optimization approach, we have discovered a new phase of transition metal dichalcogenides (labelled as T''), which is confirmed to be energetically, dynamically and kinetically stable by our first-principles calculations. The new T'' MoS2 phase exhibits an intrinsic quantum spin Hall (QSH) effect with a nontrivial gap as large as 0.42 eV, suggesting that a two-dimensional (2D) topological insulator can be achieved at room temperature. Most interestingly, there is a topological phase transition simply driven by a small tensile strain of up to 2%. Furthermore, all the known MX2 (M = Mo or W; X = S, Se or Te) monolayers in the new T'' phase unambiguously display similar band topologies and strain controlled topological

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

Discovery of Temperate Earth-Sized Planets Transiting a Nearby Ultracool Dwarf Star

NASA Technical Reports Server (NTRS)

Jehin, Emmanuel; Gillon, Michael; Lederer, Susan M.; Delrez, Laetitia; De Wit, Julien; Burdanov, Artem; Van Grootel, Valerie; Burgasser, Adam; Triaud, Amaury; Demory, Brice-Olivier;

Adsorption Behavior of Rare Earth Metal Cations in the Interlayer Space of γ-ZrP.

PubMed

Takei, Takahiro; Iidzuka, Kiyoaki; Miura, Akira; Yanagida, Sayaka; Kumada, Nobuhiro; Magome, Eisuke; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

2016-10-04

Adsorption competencies of rare earth metal cations in γ-zirconium phosphate were examined by ICP, synchrotron X-ray diffraction (SXRD), and ab initio simulation. The adsorption amounts are around 0.06-0.10 per zirconium phosphate. From the SXRD patterns of the adsorbed samples, the basal spacing estimated by c sin β increased linearly with an increasing ionic radius of rare earth metal cation, though a and b lattice constants show no change. These SXRD patterns can be classified into four groups that have different super lattices. The four superlattices have multiplicities of x131, x241, and x221 for the xabc axis, and the location of the rare earth metal cation in the original unit cell changes depending on the superlattice cell. In the x131 superlattice, Yb and Er occupied the site near the zirconium phosphate layer, though La and Ce in the x221 superlattice remained in the center position between the phosphate sheet. For the ab initio simulation of γ-ZrP with the typical rare earth metal cations (Tb, Eu, Dy, and La), the results of simulation show a similar tendency of the position estimated by SXRD refinements.

Pressure-induced metal-insulator transitions in chalcogenide NiS2-xSex

NASA Astrophysics Data System (ADS)

Hussain, Tayyaba; Oh, Myeong-jun; Nauman, Muhammad; Jo, Younjung; Han, Garam; Kim, Changyoung; Kang, Woun

2018-05-01

We report the temperature-dependent resistivity ρ(T) of chalcogenide NiS2-xSex (x = 0.1) using hydrostatic pressure as a control parameter in the temperature range of 4-300 K. The insulating behavior of ρ(T) survives at low temperatures in the pressure regime below 7.5 kbar, whereas a clear insulator-to-metallic transition is observed above 7.5 kbar. Two types of magnetic transitions, from the paramagnetic (PM) to the antiferromagnetic (AFM) state and from the AFM state to the weak ferromagnetic (WF) state, were evaluated and confirmed by magnetization measurement. According to the temperature-pressure phase diagram, the WF phase survives up to 7.5 kbar, and the transition temperature of the WF transition decreases as the pressure increases, whereas the metal-insulator transition temperature increases up to 9.4 kbar. We analyzed the metallic behavior and proposed Fermi-liquid behavior of NiS1.9Se0.1.

Pseudopotentials for quantum Monte Carlo studies of transition metal oxides

DOE PAGES

Krogel, Jaron T.; Santana Palacio, Juan A.; Reboredo, Fernando A.

2016-02-22

Quantum Monte Carlo (QMC) calculations of transition metal oxides are partially limited by the availability of high-quality pseudopotentials that are both accurate in QMC and compatible with major plane-wave electronic structure codes. We have generated a set of neon-core pseudopotentials with small cutoff radii for the early transition metal elements Sc to Zn within the local density approximation of density functional theory. The pseudopotentials have been directly tested for accuracy within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (M) atoms and the binding curve of each M-O dimer. We find the ionization potentialsmore » to be accurate to 0.16(1) eV, on average, relative to experiment. The equilibrium bond lengths of the dimers are within 0.5(1)% of experimental values, on average, and the binding energies are also typically accurate to 0.18(3) eV. The level of accuracy we find for atoms and dimers is comparable to what has recently been observed for bulk metals and oxides using the same pseudopotentials. Our QMC pseudopotential results compare well with the findings of previous QMC studies and benchmark quantum chemical calculations.« less

Theoretical research program to study transition metal trimers and embedded clusters

NASA Technical Reports Server (NTRS)

Walch, S. P.

1984-01-01

Small transition metal clusters were studied at a high level of approximation, including all the valence electrons in the calculation and extensive electron correlation, in order to understand the electronic structure of these small metal clusters. By comparison of dimers, trimers, and possibly higher clusters, the information obtained was used to provide insights into the electronic structure of bulk transition metals. Small metal clusters are currently of considerable experimental interest and some information is becomming available both from matrix electron spin resonance studies and from gas phase spectroscopy. Collaboration between theorists and experimentalists is thus expected to be especially profitable at this time since there is some experimental information which can serve to guide the theoretical work.

Potentiometric and spectroscopic study of the interaction of 3d transition metal ions with inositol hexakisphosphate

NASA Astrophysics Data System (ADS)

Veiga, Nicolás; Macho, Israel; Gómez, Kerman; González, Gabriel; Kremer, Carlos; Torres, Julia

2015-10-01

Among myo-inositol phosphates, the most abundant in nature is the myo-inositol hexakisphosphate, InsP6. Although it is known to be vital to cell functioning, the biochemical research into its metabolism needs chemical and structural analysis of all the protonation, complexation and precipitation processes that it undergoes in the biological media. In view of its high negative charge at physiological level, our group has been leading a thorough research into the InsP6 chemical and structural behavior in the presence of the alkali and alkaline earth metal ions essential for life. The aim of this article is to extend these studies, dealing with the chemical and structural features of the InsP6 interaction with biologically relevant 3d transition metal ions (Fe(II), Fe(III), Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)), in a non-interacting medium and under simulated physiological conditions. The metal-complex stability constants were determined by potentiometry, showing under ligand-excess conditions the formation of mononuclear species in different protonation states. Under metal ion excess, polymetallic species were detected for Fe(II), Fe(III), Zn(II) and Cu(II). Additionally, the 31P NMR and UV-vis spectroscopic studies provided interesting structural aspects of the strong metal ion-InsP6 interaction.

Pressure-driven insulator-metal transition in cubic phase UO 2

DOE PAGES

Huang, Li; Wang, Yilin; Werner, Philipp

2017-09-21

Understanding the electronic properties of actinide oxides under pressure poses a great challenge for experimental and theoretical studies. Here, we investigate the electronic structure of cubic phase uranium dioxide at different volumes using a combination of density functional theory and dynamical mean-field theory. The ab initio calculations predict an orbital-selective insulator-metal transition at a moderate pressure of ~45 GPa. At this pressure the uranium's 5f 5/2 state becomes metallic, while the 5f 7/2 state remains insulating up to about 60 GPa. In the metallic state, we observe a rapid decrease of the 5f occupation and total angular momentum with pressure.more » Simultaneously, the so-called "Zhang-Rice state", which is of predominantly 5f 5/2 character, quickly disappears after the transition into the metallic phase.« less

Two-order parameters theory of the metal-insulator phase transition kinetics in the magnetic field

NASA Astrophysics Data System (ADS)

Dubovskii, L. B.

2018-05-01

The metal-insulator phase transition is considered within the framework of the Ginzburg-Landau approach for the phase transition described with two coupled order parameters. One of the order parameters is the mass density which variation is responsible for the origin of nonzero overlapping of the two different electron bands and the appearance of free electron carriers. This transition is assumed to be a first-order phase one. The free electron carriers are described with the vector-function representing the second-order parameter responsible for the continuous phase transition. This order parameter determines mostly the physical properties of the metal-insulator transition and leads to a singularity of the surface tension at the metal-insulator interface. The magnetic field is involved into the consideration of the system. The magnetic field leads to new singularities of the surface tension at the metal-insulator interface and results in a drastic variation of the phase transition kinetics. A strong singularity in the surface tension results from the Landau diamagnetism and determines anomalous features of the metal-insulator transition kinetics.

Topotactic Metal-Insulator Transition in Epitaxial SrFeO x Thin Films

DOE PAGES

Khare, Amit; Shin, Dongwon; Yoo, Tae Sup; ...

2017-07-31

Multivalent transition metal oxides provide fascinating and rich physics related to oxygen stoichiometry. In particular, the adoptability of various valence states of transition metals enables perovskite oxides to display mixed (oxygen) ionic and electronic conduction and catalytic activity useful in many practical applications, including solid-oxide fuel cells (SOFCs), rechargeable batteries, gas sensors, and memristive devices. For proper realization of the ionic conduction and catalytic activity, it is essential to understand the reversible oxidation and reduction process, which is governed by oxygen storage/release steps in oxides. Topotactic phase transformation facilitates the redox process in perovskites with specific oxygen vacancy ordering bymore » largely varying the oxygen concentration of a material without losing the lattice framework. The concentration and diffusion of oxide ions (O 2–), the valence state of the transition metal cations, and the thermodynamic structural integrity together provide fundamental understanding and ways to explicitly control the redox reaction.[6] In addition, it offers an attractive route for tuning the emergent physical properties of transition metal oxides, via strong coupling between the crystal lattice and electronic structure.« less

Pore-Environment Engineering with Multiple Metal Sites in Rare-Earth Porphyrinic Metal-Organic Frameworks.

PubMed

Zhang, Liangliang; Yuan, Shuai; Feng, Liang; Guo, Bingbing; Qin, Jun-Sheng; Xu, Ben; Lollar, Christina; Sun, Daofeng; Zhou, Hong-Cai

2018-04-23

Multi-component metal-organic frameworks (MOFs) with precisely controlled pore environments are highly desired owing to their potential applications in gas adsorption, separation, cooperative catalysis, and biomimetics. A series of multi-component MOFs, namely PCN-900(RE), were constructed from a combination of tetratopic porphyrinic linkers, linear linkers, and rare-earth hexanuclear clusters (RE 6 ) under the guidance of thermodynamics. These MOFs exhibit high surface areas (up to 2523 cm 2  g -1 ) and unlimited tunability by modification of metal nodes and/or linker components. Post-synthetic exchange of linear linkers and metalation of two organic linkers were realized, allowing the incorporation of a wide range of functional moieties. Two different metal sites were sequentially placed on the linear linker and the tetratopic porphyrinic linker, respectively, giving rise to an ideal platform for heterogeneous catalysis. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Altered transition metal homeostasis in Niemann-Pick disease, Type C1

PubMed Central

Hung, Ya Hui; Faux, Noel G.; Killilea, David W.; Yanjanin, Nicole; Firnkes, Sally; Volitakis, Irene; Ganio, George; Walterfang, Mark; Hastings, Caroline; Porter, Forbes D.; Ory, Daniel S.; Bush, Ashley I.

2014-01-01

The loss of NPC1 protein function is the predominant cause of Niemann-Pick type C1 disease (NP-C1), a systemic and neurodegenerative disorder characterized by late-endosomal/lysosomal accumulation of cholesterol and other lipids. Limited evidence from post-mortem human tissues, an Npc1−/− mouse model, and cell culture studies also suggest failure of metal homeostasis in NP-C1. To investigate these findings, we performed a comprehensive transition metal analysis of cerebrospinal fluid (CSF), plasma and tissue samples from human NP-C1 patients and an Npc1−/− mouse model. NPC1 deficiency in the Npc1−/− mouse model resulted in a perturbation of transition metal homeostasis in the plasma and key organs (brain, liver, spleen, heart, lungs, and kidneys). Analysis of human patient CSF, plasma and post-mortem brain tissues also indicated disrupted metal homeostasis. There was a disparity in the direction of metal changes between the human and the Npc1−/− mouse samples, which may reflect species-specific metal metabolism. Nevertheless, common to both species is brain zinc accumulation. Furthermore, treatment with the glucosylceramide synthase inhibitor miglustat, the only drug shown in a controlled clinical trial to have some efficacy for NP-C1, did not correct the alterations in CSF and plasma transition metal and ceruloplasmin (CP) metabolism in NP-C1 patients. These findings highlight the importance of NPC1 function in metal homeostasis, and indicate that metal-targeting therapy may be of value as a treatment for NP-C. PMID:24343124

Vibrational energy transfer dynamics in ruthenium polypyridine transition metal complexes.

PubMed

Fedoseeva, Marina; Delor, Milan; Parker, Simon C; Sazanovich, Igor V; Towrie, Michael; Parker, Anthony W; Weinstein, Julia A

2015-01-21

Understanding the dynamics of the initial stages of vibrational energy transfer in transition metal complexes is a challenging fundamental question which is also of crucial importance for many applications, such as improving the performance of solar devices or photocatalysis. The present study investigates vibrational energy transport in the ground and the electronic excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2, a close relative of the efficient "N3" dye used in dye-sensitized solar cells. Using the emerging technique of ultrafast two-dimensional infrared spectroscopy, we show that, similarly to other transition-metal complexes, the central Ru heavy atom acts as a "bottleneck" making the energy transfer from small ligands with high energy vibrational stretching frequencies less favorable and thereby affecting the efficiency of vibrational energy flow in the complex. Comparison of the vibrational relaxation times in the electronic ground and excited state of Ru(4,4'-(COOEt)2-2,2-bpy)2(NCS)2 shows that it is dramatically faster in the latter. We propose to explain this observation by the intramolecular electrostatic interactions between the thiocyanate group and partially oxidised Ru metal center, which increase the degree of vibrational coupling between CN and Ru-N modes in the excited state thus reducing structural and thermodynamic barriers that slow down vibrational relaxation and energy transport in the electronic ground state. As a very similar behavior was earlier observed in another transition-metal complex, Re(4,4'-(COOEt)2-2,2'-bpy)(CO)3Cl, we suggest that this effect in vibrational energy dynamics might be common for transition-metal complexes with heavy central atoms.

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

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

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

2016-01-28

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

CHARACTERIZING K2 PLANET DISCOVERIES: A SUPER-EARTH TRANSITING THE BRIGHT K DWARF HIP 116454

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

Vanderburg, Andrew; Montet, Benjamin T.; Johnson, John Asher

We report the first planet discovery from the two-wheeled Kepler (K2) mission: HIP 116454 b. The host star HIP 116454 is a bright (V = 10.1, K = 8.0) K1 dwarf with high proper motion and a parallax-based distance of 55.2 ± 5.4 pc. Based on high-resolution optical spectroscopy, we find that the host star is metal-poor with [Fe/H] =–0.16 ± 0.08 and has a radius R {sub *} = 0.716 ± 0.024 R {sub ☉} and mass M {sub *} = 0.775 ± 0.027 M {sub ☉}. The star was observed by the Kepler spacecraft during its Two-Wheeled Concept Engineering Test in 2014more » February. During the 9 days of observations, K2 observed a single transit event. Using a new K2 photometric analysis technique, we are able to correct small telescope drifts and recover the observed transit at high confidence, corresponding to a planetary radius of R{sub p} = 2.53 ± 0.18 R {sub ⊕}. Radial velocity observations with the HARPS-N spectrograph reveal a 11.82 ± 1.33 M {sub ⊕} planet in a 9.1 day orbit, consistent with the transit depth, duration, and ephemeris. Follow-up photometric measurements from the MOST satellite confirm the transit observed in the K2 photometry and provide a refined ephemeris, making HIP 116454 b amenable for future follow-up observations of this latest addition to the growing population of transiting super-Earths around nearby, bright stars.« less

Positive magnetoresistance effect in rare earth cobaltites

NASA Astrophysics Data System (ADS)

Troyanchuk, I. O.; Bushinskii, M. V.; Karpinsky, D. V.; Dobryanskii, V. M.; Sikolenko, V. V.; Balagurov, A. M.

2009-06-01

The structure, magnetic, and magnetotransport properties of the Pr0.5Sr0.5Co1 - x Fe x O3 system have been studied. The ferromagnet-spin glass ( x = 0.5)- G-type antiferromagnet ( x = 0.7) transitions and the metal—insulator transitions ( x = 0.25) have been revealed. It has been established that the magnetoresistance of the metallic ferromagnetic cobaltites changes sign from positive to negative as the external magnetic field increases. The positive component increases and the negative component decreases with decreasing temperature. The negative magnetoresistance increases sharply in the insulating spinglass phase. Possible causes of the low-magnetic-field positive magnetoresistance in the rare earth metallic cobaltites are discussed.

Edge Delamination of Monolayer Transition Metal Dichalcogenides.

PubMed

Ly, Thuc Hue; Yun, Seok Joon; Thi, Quoc Huy; Zhao, Jiong

2017-07-25

Delamination of thin films from the supportive substrates is a critical issue within the thin film industry. The emergent two-dimensional, atomic layered materials, including transition metal dichalcogenides, are highly flexible; thus buckles and wrinkles can be easily generated and play vital roles in the corresponding physical properties. Here we introduce one kind of patterned buckling behavior caused by the delamination from a substrate initiated at the edges of the chemical vapor deposition synthesized monolayer transition metal dichalcogenides, led by thermal expansion mismatch. The atomic force microscopy and optical characterizations clearly showed the puckered structures associated with the strain, whereas the transmission electron microscopy revealed the special sawtooth-shaped edges, which break the geometrical symmetry for the buckling behavior of hexagonal samples. The condition of the edge delamination is in accordance with the fracture behavior of thin film interfaces. This edge delamination and buckling process is universal for most ultrathin two-dimensional materials, which requires more attention in various future applications.

Transition-metal phosphors with cyclometalating ligands: fundamentals and applications.

PubMed

Chi, Yun; Chou, Pi-Tai

2010-02-01

One goal of this critical review is to provide advanced methodologies for systematic preparation of transition-metal based phosphors that show latent applications in the field of organic light emitting diodes (OLEDs). We are therefore reviewing various types of cyclometalating chelates for which the favorable metal-chelate bonding interaction, on the one hand, makes the resulting phosphorescent complexes highly emissive in both fluid and solid states at room temperature. On the other hand, fine adjustment of ligand-centered pi-pi* electronic transitions allows tuning of emission wavelength across the whole visible spectrum. The cyclometalating chelates are then classified according to types of cyclometalating groups, i.e. either aromatic C-H or azolic N-H fragment, and the adjacent donor fragment involved in the formation of metallacycles; the latter is an N-containing heterocycle, N-heterocyclic (NHC) carbene fragment or even diphenylphosphino group. These cyclometalating ligands are capable to react with heavy transition-metal elements, namely: Ru(II), Os(II), Ir(III) and Pt(II), to afford a variety of highly emissive phosphors, for which the photophysical properties as a function of chelate or metal characteristics are systematically discussed. Using Ir(III) complexes as examples, the C--N chelates possessing both C-H site and N-heterocyclic donor group are essential for obtaining phosphors with emission ranging from sky-blue to saturated red, while the N--N chelates such as 2-pyridyl-C-linked azolates are found useful for serving as true-blue chromophores due to their increased ligand-centered pi-pi* energy gap. Lastly, the remaining NHC carbene and benzyl phosphine chelates are highly desirable to serve as ancillary chelates in localizing the electronic transition between the metal and remaining lower energy chromophoric chelates. As for the potential opto-electronic applications, many of them exhibit remarkable performance data, which are convincing to pave a

Structural Flexibility and Alloying in Ultrathin Transition-Metal Chalcogenide Nanowires

DOE PAGES

Lin, Junhao; Zhang, Yuyang; Zhou, Wu; ...

2016-01-18

Metallic transition-metal chalcogenide (TMC) nanowires are an important building block for 2D electronics that may be fabricated within semiconducting transition-metal dichalcogenide (TMDC) monolayers. Tuning the geometric structure and electronic properties of such nanowires is a promising way to pattern diverse functional channels for wiring multiple units inside a 2D electronic circuit. Nevertheless, few experimental investigations have been reported exploring the structural and compositional tunability of these nanowires, due to difficulties in manipulating the structure and chemical composition of an individual nanowire. Here, using a combination of scanning transmission electron microscopy (STEM) and density functional theory (DFT), we report that TMCmore » nanowires have substantial intrinsic structural flexibility and their chemical composition can be manipulated.« less

Photoinduced metal-to-insulator transition in a manganite thin film.

PubMed

Takubo, N; Onishi, I; Takubo, K; Mizokawa, T; Miyano, K

2008-10-24

A persistent photoinduced metal-to-insulator transition has been confirmed in a manganite thin film, Pr_(0.55)(Ca_(0.75)Sr_(0.25))_(0.45)MnO3, near a multicritical point by monitoring with transport measurements and x-ray photoemission spectroscopy. Together with the previously reported reverse effect, the photoinduced insulator-to-metal transition, it is found that the relative stability of the metallic and insulating phases interchanges around 80 K in the middle of a very wide hysteresis loop, which is a manifestation of the large potential barrier due to the long-range elastic energy. It is shown that photons are much more effective in overcoming the barrier via the electronically excited intermediate states than via the heat mode.

Pentadienyl chemistry of the heavy alkaline-earth metals revisited.

PubMed

Reiners, Matthias; Fecker, Ann Christin; Freytag, Matthias; Jones, Peter G; Walter, Marc D

2014-05-14

Open-metallocenes of the heavy alkaline-earth metals [(η(5)-Pdl')2M(thf)n] (M = Ca (1), Sr (2), n = 1; M = Ba (3), n = 2; Pdl' = 2,4-tBu2C5H5) are readily prepared by salt-metathesis between MI2 and KPdl' and characterized by NMR spectroscopy and X-ray diffraction studies.

Numerical simulations of the optical gain of crystalline fiber doped by rare earth and transition ion

NASA Astrophysics Data System (ADS)

Daoui, A. K.; Boubir, B.; Adouane, A.; Demagh, N.; Ghoumazi, M.

2015-02-01

A fiber laser is a laser whose gain medium is a doped fiber, although lasers whose cavity is made wholly of fibers have also been called fiber lasers. The gain media in a fiber laser is usually fiber doped with rare-earth ions, such as erbium (Er), neodymium (Nd), ytterbium (Yb), thulium (Tm), or praseodymium (Pr), which is doped into the core of the optical fiber, similar to those used to transmit telecommunications signals. Fiber lasers find many applications in materials processing, including cutting, welding, drilling, and marking metal. To maximize their market penetration, it is necessary to increase their output power. In this work, we present a detailed study based on the numerical simulation using MATLAB, of one of the principal characteristics of a fiber laser doped with rare earth ions and transition ion. The gain depends on several parameters such as the length of the doped fiber, the density, the pump power, noise, etc.). The used program resolves the state equations in this context together with those governing the light propagation phenomena. The developed code can also be used to study the dynamic operating modes of a doped fiber laser.

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Spin decoherence of InAs surface electrons by transition metal ions

NASA Astrophysics Data System (ADS)

Zhang, Yao; Soghomonian, V.; Heremans, J. J.

2018-04-01

Spin interactions between a two-dimensional electron system at the InAs surface and transition metal ions, Fe3 +, Co2 +, and Ni2 +, deposited on the InAs surface, are probed by antilocalization measurements. The spin-dependent quantum interference phenomena underlying the quantum transport phenomenon of antilocalization render the technique sensitive to the spin states of the transition metal ions on the surface. The experiments yield data on the magnitude and temperature dependence of the electrons' inelastic scattering rates, spin-orbit scattering rates, and magnetic spin-flip rates as influenced by Fe3 +, Co2 +, and Ni2 +. A high magnetic spin-flip rate is shown to mask the effects of spin-orbit interaction, while the spin-flip rate is shown to scale with the effective magnetic moment of the surface species. The spin-flip rates and their dependence on temperature yield information about the spin states of the transition metal ions at the surface, and in the case of Co2 + suggest either a spin transition or formation of a spin-glass system.

Janus monolayers of transition metal dichalcogenides.

PubMed

Lu, Ang-Yu; Zhu, Hanyu; Xiao, Jun; Chuu, Chih-Piao; Han, Yimo; Chiu, Ming-Hui; Cheng, Chia-Chin; Yang, Chih-Wen; Wei, Kung-Hwa; Yang, Yiming; Wang, Yuan; Sokaras, Dimosthenis; Nordlund, Dennis; Yang, Peidong; Muller, David A; Chou, Mei-Yin; Zhang, Xiang; Li, Lain-Jong

2017-08-01

Structural symmetry-breaking plays a crucial role in determining the electronic band structures of two-dimensional materials. Tremendous efforts have been devoted to breaking the in-plane symmetry of graphene with electric fields on AB-stacked bilayers or stacked van der Waals heterostructures. In contrast, transition metal dichalcogenide monolayers are semiconductors with intrinsic in-plane asymmetry, leading to direct electronic bandgaps, distinctive optical properties and great potential in optoelectronics. Apart from their in-plane inversion asymmetry, an additional degree of freedom allowing spin manipulation can be induced by breaking the out-of-plane mirror symmetry with external electric fields or, as theoretically proposed, with an asymmetric out-of-plane structural configuration. Here, we report a synthetic strategy to grow Janus monolayers of transition metal dichalcogenides breaking the out-of-plane structural symmetry. In particular, based on a MoS 2 monolayer, we fully replace the top-layer S with Se atoms. We confirm the Janus structure of MoSSe directly by means of scanning transmission electron microscopy and energy-dependent X-ray photoelectron spectroscopy, and prove the existence of vertical dipoles by second harmonic generation and piezoresponse force microscopy measurements.

Hydrogenation-controlled phase transition on two-dimensional transition metal dichalcogenides and their unique physical and catalytic properties.

PubMed

Qu, Yuanju; Pan, Hui; Kwok, Chi Tat

2016-09-30

Two-dimensional (2D) transition metal dichalcogenides (TMDs) have been widely used from nanodevices to energy harvesting/storage because of their tunable physical and chemical properties. In this work, we systematically investigate the effects of hydrogenation on the structural, electronic, magnetic, and catalytic properties of 33 TMDs based on first-principles calculations. We find that the stable phases of TMD monolayers can transit from 1T to 2H phase or vice versa upon the hydrogenation. We show that the hydrogenation can switch their magnetic and electronic states accompanying with the phase transition. The hydrogenation can tune the magnetic states of TMDs among non-, ferro, para-, and antiferro-magnetism and their electronic states among semiconductor, metal, and half-metal. We further show that, out of 33 TMD monolayers, 2H-TiS 2 has impressive catalytic ability comparable to Pt in hydrogen evolution reaction in a wide range of hydrogen coverages. Our findings would shed the light on the multi-functional applications of TMDs.

Studies of high temperature ternary phases in mixed-metal-rich early transition metal sulfide and phosphide systems

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

Marking, Gregory Allen

1994-01-04

Investigations of ternary mixed early transition metal-rich sulfide and phosphide systems resulted in the discovery of new structures and new phases. A new series of Zr and Hf - group V transition metal - sulfur K-phases was synthesized and crystallographically characterized. When the group V transition metal was Nb or Ta, the unit cell volume was larger than any previously reported K-phase. The presence of adventitious oxygen was determined in two K-phases through a combination of neutron scattering and X-ray diffraction experiments. A compound Hf 10Ta 3S 3 was found to crystallize in a new-structure type similar to the knownmore » gamma brasses. This structure is unique in that it is the only reported "stuffed" gamma-brass type structure. The metal components, Hf and Ta, are larger in size and more electropositive than the metals found in normal gamma brasses (e.g. Cu and Zn) and because of the larger metallic radii, sulfur can be incorporated into the structure where it plays an integral role in stabilizing this phase relative to others. X-ray single-crystal, X-ray powder and neutron powder refinements were performed on this structure. A new structure was found in the ternary Nb-Zr-P system which has characteristics in common with many known early transition metal-rich sulfides, selenides, and phosphides. This structure has the simplest known interconnection of the basic building blocks known for this structural class. Anomalous scattering was a powerful tool for differentiating between Zr and Nb when using Mo Kα X-radiation. The compounds ZrNbP and HfNbP formed in the space group Prima with the simple Co 2Si structure which is among the most common structures found for crystalline solid materials. Solid solution compounds in the Ta-Nb-P, Ta-Zr-P, Nb-Zr-P, Hf-Nb-P, and Hf-Zr-S systems were crystallographically characterized. The structural information corroborated ideas about bonding in metal-rich compounds.« less

Phase-field model of insulator-to-metal transition in VO2 under an electric field

NASA Astrophysics Data System (ADS)

Shi, Yin; Chen, Long-Qing

2018-05-01

The roles of an electric field and electronic doping in insulator-to-metal transitions are still not well understood. Here we formulated a phase-field model of insulator-to-metal transitions by taking into account both structural and electronic instabilities as well as free electrons and holes in VO2, a strongly correlated transition-metal oxide. Our phase-field simulations demonstrate that in a VO2 slab under a uniform electric field, an abrupt universal resistive transition occurs inside the supercooling region, in sharp contrast to the conventional Landau-Zener smooth electric breakdown. We also show that hole doping may decouple the structural and electronic phase transitions in VO2, leading to a metastable metallic monoclinic phase which could be stabilized through a geometrical confinement and the size effect. This work provides a general mesoscale thermodynamic framework for understanding the influences of electric field, electronic doping, and stress and strain on insulator-to-metal transitions and the corresponding mesoscale domain structure evolution in VO2 and related strongly correlated systems.

Effect of rare earth metal on the spin-orbit torque in magnetic heterostructures

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

Ueda, Kohei; Pai, Chi-Feng; Tan, Aik Jun

2016-06-06

We report the effect of the rare earth metal Gd on current-induced spin-orbit torques (SOTs) in perpendicularly magnetized Pt/Co/Gd heterostructures, characterized using harmonic measurements and spin-torque ferromagnetic resonance (ST-FMR). By varying the Gd metal layer thickness from 0 nm to 8 nm, harmonic measurements reveal a significant enhancement of the effective fields generated from the Slonczewski-like and field-like torques. ST-FMR measurements confirm an enhanced effective spin Hall angle and show a corresponding increase in the magnetic damping constant with increasing Gd thickness. These results suggest that Gd plays an active role in generating SOTs in these heterostructures. Our finding may lead tomore » spin-orbitronics device application such as non-volatile magnetic random access memory, based on rare earth metals.« less

A correlation between the heavy element content of transiting extrasolar planets and the metallicity of their parent stars

NASA Astrophysics Data System (ADS)

Guillot, T.; Santos, N. C.; Pont, F.; Iro, N.; Melo, C.; Ribas, I.

2006-07-01

Context.Nine extrasolar planets with masses between 110 and 430 M_⊕ are known to transit their star. The knowledge of their masses and radii allows an estimate of their composition, but uncertainties on equations of state, opacities and possible missing energy sources imply that only inaccurate constraints can be derived when considering each planet separately.Aims.We seek to better understand the composition of transiting extrasolar planets by considering them as an ensemble, and by comparing the obtained planetary properties to that of the parent stars.Methods.We use evolution models and constraints on the stellar ages to derive the mass of heavy elements present in the planets. Possible additional energy sources like tidal dissipation due to an inclined orbit or to downward kinetic energy transport are considered.Results.We show that the nine transiting planets discovered so far belong to a quite homogeneous ensemble that is characterized by a mass of heavy elements that is a relatively steep function of the stellar metallicity, from less than 20 earth masses of heavy elements around solar composition stars, to up to ~100 M_⊕ for three times the solar metallicity (the precise values being model-dependant). The correlation is still to be ascertained however. Statistical tests imply a worst-case 1/3 probability of a false positive.Conclusions.Together with the observed lack of giant planets in close orbits around metal-poor stars, these results appear to imply that heavy elements play a key role in the formation of close-in giant planets. The large masses of heavy elements inferred for planets orbiting metal rich stars was not anticipated by planet formation models and shows the need for alternative theories including migration and subsequent collection of planetesimals.

Theoretical Study of pKa Values for Trivalent Rare-Earth Metal Cations in Aqueous Solution.

PubMed

Yu, Donghai; Du, Ruobing; Xiao, Ji-Chang; Xu, Shengming; Rong, Chunying; Liu, Shubin

2018-01-18

Molecular acidity of trivalent rare-earth metal cations in aqueous solution is an important factor dedicated to the efficiency of their extraction and separation processes. In this work, the aqueous acidity of these metal ions has been quantitatively investigated using a few theoretical approaches. Our computational results expressed in terms of pK a values agree well with the tetrad effect of trivalent rare-earth ions extensively reported in the extraction and separation of these elements. Strong linear relationships have been observed between the acidity and quantum electronic descriptors such as the molecular electrostatic potential on the acidic nucleus and the sum of the valence natural atomic orbitals energies of the dissociating proton. Making use of the predicted pK a values, we have also predicted the major ionic forms of these species in the aqueous environment with different pH values, which can be employed to rationalize the behavior difference of different rare-earth metal cations during the extraction process. Our present results should provide needed insights not only for the qualitatively understanding about the extraction and separation between yttrium and lanthanide elements but also for the prediction of novel and more efficient rare-earth metal extractants in the future.

Theoretical study of the alkaline-earth metal superoxides BeO2 through SrO2

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Sodupe, Mariona; Langhoff, Stephen R.

1992-01-01

Three competing bonding mechanisms have been identified for the alkaline-earth metal superoxides: these result in a change in the optimal structure and ground state as the alkaline-earth metal becomes heavier. For example, BeO2 has a linear 3Sigma(-)g ground-state structure, whereas both CaO2 and SrO2 have C(2v)1A1 structures. For MgO2, the theoretical calculations are less definitive, as the 3A2 C(2v) structure is computed to lie only about 3 kcal/mol above the 3Sigma(-)g linear structure. The bond dissociation energies for the alkaline-earth metal superoxides have been computed using extensive Gaussian basis sets and treating electron correlation at the modified coupled-pair functional or coupled-cluster singles and doubles level with a perturbational estimate of the triple excitations.

Alkaline earth metal doped tin oxide as a novel oxygen storage material

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

Dong, Qiang, E-mail: dong@tagen.tohoku.ac.jp; Yin, Shu; Yoshida, Mizuki

2015-09-15

Alkaline earth metal doped tin oxide (SnO{sub 2}) hollow nanospheres with a diameter of 50 nm have been synthesized successfully via a facial solvothermal route in a very simple system composed of only ethanol, acetic acid, SnCl{sub 4}·5H{sub 2}O and A(NO{sub 3}){sub 2}·xH{sub 2}O (A = Mg, Ca, Sr, Ba). The synthesized undoped SnO{sub 2} and A-doped SnO{sub 2} hollow nanospheres were characterized by the oxygen storage capacity (OSC), X-ray diffraction, transmission electron microscopy and the Brunauer–Emmet–Teller (BET) technique. The OSC values of all samples were measured using thermogravimetric-differential thermal analysis. The incorporation of alkaline earth metal ion into tinmore » oxide greatly enhanced the thermal stability and OSC. Especially, Ba-doped SnO{sub 2} hollow nanospheres calcined at 1000 °C for 20 h with a BET surface area of 61 m{sup 2} g{sup −1} exhibited the considerably high OSC of 457 μmol-O g{sup −1} and good thermal stability. Alkaline earth metal doped tin oxide has the potential to be a novel oxygen storage material.« less

Flexible metallic seal for transition duct in turbine system

DOEpatents

Flanagan, James Scott; LeBegue, Jeffrey Scott; McMahan, Kevin Weston; Dillard, Daniel Jackson; Pentecost, Ronnie Ray

2014-04-22

A turbine system is disclosed. In one embodiment, the turbine system includes a transition duct. The transition duct includes an inlet, an outlet, and a passage extending between the inlet and the outlet and defining a longitudinal axis, a radial axis, and a tangential axis. The outlet of the transition duct is offset from the inlet along the longitudinal axis and the tangential axis. The transition duct further includes an interface member for interfacing with a turbine section. The turbine system further includes a flexible metallic seal contacting the interface member to provide a seal between the interface member and the turbine section.

Planar heterostructures of single-layer transition metal dichalcogenides: Composite structures, Schottky junctions, tunneling barriers, and half metals

NASA Astrophysics Data System (ADS)

Aras, Mehmet; Kılıç, ćetin; Ciraci, S.

2017-02-01

Planar composite structures formed from the stripes of transition metal dichalcogenides joined commensurately along their zigzag or armchair edges can attain different states in a two-dimensional (2D), single-layer, such as a half metal, 2D or one-dimensional (1D) nonmagnetic metal and semiconductor. Widening of stripes induces metal-insulator transition through the confinements of electronic states to adjacent stripes, that results in the metal-semiconductor junction with a well-defined band lineup. Linear bending of the band edges of the semiconductor to form a Schottky barrier at the boundary between the metal and semiconductor is revealed. Unexpectedly, strictly 1D metallic states develop in a 2D system along the boundaries between stripes, which pins the Fermi level. Through the δ doping of a narrow metallic stripe one attains a nanowire in the 2D semiconducting sheet or narrow band semiconductor. A diverse combination of constituent stripes in either periodically repeating or finite-size heterostructures can acquire critical fundamental features and offer device capacities, such as Schottky junctions, nanocapacitors, resonant tunneling double barriers, and spin valves. These predictions are obtained from first-principles calculations performed in the framework of density functional theory.

First-order metal-insulator transitions in vanadates from first principles

NASA Astrophysics Data System (ADS)

Kumar, Anil; Rabe, Karin

2013-03-01

Materials that exhibit first-order metal-insulator transitions, with the accompanying abrupt change in the conductivity, have potential applications as switches in future electronic devices. Identification of materials and exploration of the atomic-scale mechanisms for switching between the two electronic states is a focus of current research. In this work, we search for first-order metal-insulator transitions in transition metal compounds, with a particular focus on d1 and d2 systems, by using first principles calculations to screen for an alternative low-energy state having not only a electronic character opposite to that of the ground state, but a distinct structure and/or magnetic ordering which would permit switching by an applied field or stress. We will present the results of our investigation of the perovskite compounds SrVO3, LaVO3, CaVO3, YVO3, LaTiO3 and related layered phase, including superlattices and Ruddlesden-Popper phases. While the pure compounds do not satisfy the search criteria, the layered phases show promising results.

Stabilization of Lithium Transition Metal Silicates in the Olivine Structure

DOE PAGES

Sun, Xiaoqi; Tripathi, Rajesh; Popov, Guerman; ...

2017-07-28

While olivine LiFePO 4 shows amongst the best electrochemical properties of Li-ion positive electrodes with respect to rate behavior owing to facile Li + migration pathways in the framework, replacing the [PO 4] 3- polyanion with a silicate [SO 4] 4- moitie in olivine is desirable. This would allow additional balancing alkali content and hence electron transfer, and increase the capacity. We demonstrate the first stabilization of a lithium transition-metal silicate (as a pure silicate) in the olivine structure type. Using LiInSiO 4 and LiScSiO 4 as the parent materials, transition metal (Mn, Fe, Co) substitutions on the In/Sc sitemore » were investigated by computational modelling via atomic scale simulation. Transition metal substitution was found to be only favourable for Co, a finding confirmed by the successful solid state synthesis of olivine LixInyCo 2-x-ySiO 4. Finally, the stabilization of the structure was achieved by entropy provided by cation disorder.« less

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, Michael A.; Hallen, Richard T.

1990-01-01

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the produce gas from coal gasification processes.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, Michael A.; Hallen, Richard T.

1991-01-01

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately .pi.-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancilliary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H.sub.2 from mixed gas streams such as the product gas from coal gasification processes.

Ferroelasticity and domain physics in two-dimensional transition metal dichalcogenide monolayers.

PubMed

Li, Wenbin; Li, Ju

2016-02-24

Monolayers of transition metal dichalcogenides can exist in several structural polymorphs, including 2H, 1T and 1T'. The low-symmetry 1T' phase has three orientation variants, resulting from the three equivalent directions of Peierls distortion in the parental 1T phase. Using first-principles calculations, we predict that mechanical strain can switch the relative thermodynamic stability between the orientation variants of the 1T' phase. We find that such strain-induced variant switching only requires a few percent elastic strain, which is eminently achievable experimentally with transition metal dichalcogenide monolayers. Calculations indicate that the transformation barrier associated with such variant switching is small (<0.2 eV per chemical formula unit), suggesting that strain-induced variant switching can happen under laboratory conditions. Monolayers of transition metal dichalcogenides with 1T' structure therefore have the potential to be ferroelastic and shape memory materials with interesting domain physics.

Strain-induced metal-insulator transitions in d1 perovskites within DFT+DMFT

NASA Astrophysics Data System (ADS)

Dymkowski, Krzysztof; Ederer, Claude

2014-03-01

We present results of combined density functional theory plus dynamical mean-field theory (DFT+DMFT) calculations, assessing the effect of epitaxial strain on the electronic properties of the Mott insulator LaTiO3 and the correlated metal SrVO3. In particular, we take into account the effect of strain on the collective tilts and rotations of the oxygen octahedra in the orthorhombically distorted Pbnm perovskite structure of LaTiO3. We find that LaTiO3 undergoes an insulator-to-metal transition under a compressive strain of about - 2 %, consistent with recent experimental observations. We show that this transition is driven mainly by strain-induced changes in the crystal-field splitting between the Ti t2 g orbitals, which in turn are related to changes in the octahedral tilt distortion. We compare this with the case of SrVO3, without octahedral tilts, where we find a metal-to-insulator transition under tensile epitaxial strain. Similar to LaTiO3, this metal-insulator transition is linked to the strain-induced change in the crystal-field splitting within the t2 g orbitals.

Recent advances in transition metal-catalyzed N -atom transfer reactions of azides

PubMed Central

Driver, Tom G.

2011-01-01

Transition metal-catalyzed N-atom transfer reactions of azides provide efficient ways to construct new carbon–nitrogen and sulfur–nitrogen bonds. These reactions are inherently green: no additive besides catalyst is needed to form the nitrenoid reactive intermediate, and the by-product of the reaction is environmentally benign N2 gas. As such, azides can be useful precursors for transition metal-catalyzed N-atom transfer to sulfides, olefins and C–H bonds. These methods offer competitive selectivities and comparable substrate scope as alternative processes to generate metal nitrenoids. PMID:20617243

Covalent functionalization of monolayered transition metal dichalcogenides by phase engineering.

PubMed

Voiry, Damien; Goswami, Anandarup; Kappera, Rajesh; e Silva, Cecilia de Carvalho Castro; Kaplan, Daniel; Fujita, Takeshi; Chen, Mingwei; Asefa, Tewodros; Chhowalla, Manish

2015-01-01

Chemical functionalization of low-dimensional materials such as nanotubes, nanowires and graphene leads to profound changes in their properties and is essential for solubilizing them in common solvents. Covalent attachment of functional groups is generally achieved at defect sites, which facilitate electron transfer. Here, we describe a simple and general method for covalent functionalization of two-dimensional transition metal dichalcogenide nanosheets (MoS₂, WS₂ and MoSe₂), which does not rely on defect engineering. The functionalization reaction is instead facilitated by electron transfer between the electron-rich metallic 1T phase and an organohalide reactant, resulting in functional groups that are covalently attached to the chalcogen atoms of the transition metal dichalcogenide. The attachment of functional groups leads to dramatic changes in the optoelectronic properties of the material. For example, we show that it renders the metallic 1T phase semiconducting, and gives it strong and tunable photoluminescence and gate modulation in field-effect transistors.

Structure, bonding, and catalytic activity of monodisperse, transition-metal-substituted CeO2 nanoparticles.

PubMed

Elias, Joseph S; Risch, Marcel; Giordano, Livia; Mansour, Azzam N; Shao-Horn, Yang

2014-12-10

We present a simple and generalizable synthetic route toward phase-pure, monodisperse transition-metal-substituted ceria nanoparticles (M0.1Ce0.9O2-x, M = Mn, Fe, Co, Ni, Cu). The solution-based pyrolysis of a series of heterobimetallic Schiff base complexes ensures a rigorous control of the size, morphology and composition of 3 nm M0.1Ce0.9O2-x crystallites for CO oxidation catalysis and other applications. X-ray absorption spectroscopy confirms the dispersion of aliovalent (M(3+) and M(2+)) transition metal ions into the ceria matrix without the formation of any bulk transition metal oxide phases, while steady-state CO oxidation catalysis reveals an order of magnitude increase in catalytic activity with copper substitution. Density functional calculations of model slabs of these compounds confirm the stabilization of M(3+) and M(2+) in the lattice of CeO2. These results highlight the role of the host CeO2 lattice in stabilizing high oxidation states of aliovalent transition metal dopants that ordinarily would be intractable, such as Cu(3+), as well as demonstrating a rational approach to catalyst design. The current work demonstrates, for the first time, a generalizable approach for the preparation of transition-metal-substituted CeO2 for a broad range of transition metals with unparalleled synthetic control and illustrates that Cu(3+) is implicated in the mechanism for CO oxidation on CuO-CeO2 catalysts.

Key role of lattice symmetry in the metal-insulator transition of NdNiO 3 films

DOE PAGES

Zhang, Jack Y.; Kim, Honggyu; Mikheev, Evgeny; ...

2016-04-01

Here, bulk NdNiO 3 exhibits a metal-to-insulator transition (MIT) as the temperature is lowered that is also seen in tensile strained films. In contrast, films that are under a large compressive strain typically remain metallic at all temperatures. To clarify the microscopic origins of this behavior, we use position averaged convergent beam electron diffraction in scanning transmission electron microscopy to characterize strained NdNiO 3 films both above and below the MIT temperature. We show that a symmetry lowering structural change takes place in case of the tensile strained film, which undergoes an MIT, but is absent in the compressively strainedmore » film. Using space group symmetry arguments, we show that these results support the bond length disproportionation model of the MIT in the rare-earth nickelates. Furthermore, the results provide insights into the non-Fermi liquid phase that is observed in films for which the MIT is absent.« less

High-pressure metallization of FeO and implications for the earth's core

NASA Technical Reports Server (NTRS)

Knittle, Elise; Jeanloz, Raymond

1986-01-01

The phase diagram of FeO has been experimentally determined to pressures of 155 GPa and temperatures of 4000 K using shock-wave and diamond-cell techniques. A metallic phase of FeO is observed at pressures greater than 70 GPa and temperatures exceeding 1000 K. The metallization of FeO at high pressures implies that oxygen can be present as the light alloying element of the earth's outer core, in accord with the geochemical predictions of Ringwood (1977 and 1979). The high pressures necessary for this metallization suggest that the core has acquired its composition well after the initial stages of the earth's accretion. Direct experimental observations at elevated pressures and temperatures indicate that core-forming alloy can react chemically with oxides such as those forming the mantle. The core and mantle may never have reached complete chemical equilibrium, however. If this is the case, the core-mantle boundary is likely to be a zone of active chemical reactions.

Terrestrial magma ocean and core segregation in the earth

NASA Technical Reports Server (NTRS)

Ohtani, Eiji; Yurimoto, Naoyoshi

1992-01-01

According to the recent theories of formation of the earth, the outer layer of the proto-earth was molten and the terrestrial magma ocean was formed when its radius exceeded 3000 km. Core formation should have started in this magma ocean stage, since segregation of metallic iron occurs effectively by melting of the proto-earth. Therefore, interactions between magma, mantle minerals, and metallic iron in the magma ocean stage controlled the geochemistry of the mantle and core. We have studied the partitioning behaviors of elements into the silicate melt, high pressure minerals, and metallic iron under the deep upper mantle and lower mantle conditions. We employed the multi-anvil apparatus for preparing the equilibrating samples in the ranges from 16 to 27 GPa and 1700-2400 C. Both the electron probe microanalyzer (EPMA) and the Secondary Ion Mass spectrometer (SIMS) were used for analyzing the run products. We obtained the partition coefficients of various trace elements between majorite, Mg-perovskite, and liquid, and magnesiowustite, Mg-perovskite, and metallic iron. The examples of the partition coefficients of some key elements are summarized in figures, together with the previous data. We may be able to assess the origin of the mantle abundances of the elements such as transition metals by using the partitioning data obtained above. The mantle abundances of some transition metals expected by the core-mantle equilibrium under the lower mantle conditions cannot explain the observed abundance of some elements such as Mn and Ge in the mantle. Estimations of the densities of the ultrabasic magma Mg-perovskite at high pressure suggest existence of a density crossover in the deep lower mantle; flotation of Mg-perovskite occurs in the deep magma ocean under the lower mantle conditions. The observed depletion of some transition metals such as V, Cr, Mn, Fe, Co, and Ni in the mantle may be explained by the two stage process, the core-mantle equilibrium under the lower

Studies of Metal-Metal Bonded Compounds in Catalysis

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

Berry, John F.

The overall goals of this research are (1) to define the fundamental coordination chemistry underlying successful catalytic transformations promoted by metal-metal bonded compounds, and (2) to explore new chemical transformations that occur at metal-metal bonded sites that could lead to the discovery of new catalytic processes. Transformations of interest include metal-promoted reactions of carbene, nitrene, or nitrido species to yield products with new C–C and C–N bonds, respectively. The most promising suite of transition metal catalysts for these transformations is the set of metal-metal bonded coordination compounds of Ru and Rh of the general formula M 2(ligand) 4, where Mmore » = Ru or Rh and ligand = a monoanionic, bridging ligand such as acetate. Development of new catalysts and improvement of catalytic conditions have been stymied by a general lack of knowledge about the nature of highly reactive intermediates in these reactions, the knowledge that is to be supplied by this work. Our three specific objectives for this year have been (A) to trap, isolate, and characterize new reactive intermediates of general relevance to catalysis, (B) to explore the electronic structure and reactivity of these unusual species, and how these two properties are interrelated, and (C) to use our obtained mechanistic knowledge to design new catalysts with a focus on Earth-abundant first-row transition metal compounds.« less

The Electrochemical Synthesis of Transition-Metal Acetylacetonates

ERIC Educational Resources Information Center

Long, S. R.; Browning, S. R.; Lagowski, J. J.

2008-01-01

The electrochemical synthesis of transition-metal acetylacetonates described here can form the basis of assisting in the transformation of an entry-level laboratory course into a research-like environment where all members of a class are working on the same problem, but where each member has a personal responsibility for the synthesis and…

Designing Superhard Materials by Incorporating Boron Into Heavy Transition Metals

NASA Astrophysics Data System (ADS)

Liang, Yongcheng; Li, Anhu; Zhao, Jianzhi; Zhang, Wenqing

First-principles calculations on the incompressibility, elasticity and hardness of the Os, OsB2, Re, and ReB2 materials have systematically been performed by the plane-wave basis pseudopotential method. Transition metals Os and Re, which have high bulk modulus but low hardness, can be converted into hard materials by combining them with small B atoms. Moreover, electronic and structural mechanisms of ReB2 and OsB2 are analyzed in detail and compared. It is shown that incorporating small B atoms into heavy transition metals should be a valid pathway to obtain new superhard materials.

Electric field-triggered metal-insulator transition resistive switching of bilayered multiphasic VOx

NASA Astrophysics Data System (ADS)

Won, Seokjae; Lee, Sang Yeon; Hwang, Jungyeon; Park, Jucheol; Seo, Hyungtak

2018-01-01

Electric field-triggered Mott transition of VO2 for next-generation memory devices with sharp and fast resistance-switching response is considered to be ideal but the formation of single-phase VO2 by common deposition techniques is very challenging. Here, VOx films with a VO2-dominant phase for a Mott transition-based metal-insulator transition (MIT) switching device were successfully fabricated by the combined process of RF magnetron sputtering of V metal and subsequent O2 annealing to form. By performing various material characterizations, including scanning transmission electron microscopy-electron energy loss spectroscopy, the film is determined to have a bilayer structure consisting of a VO2-rich bottom layer acting as the Mott transition switching layer and a V2O5/V2O3 mixed top layer acting as a control layer that suppresses any stray leakage current and improves cyclic performance. This bilayer structure enables excellent electric field-triggered Mott transition-based resistive switching of Pt-VOx-Pt metal-insulator-metal devices with a set/reset current ratio reaching 200, set/reset voltage of less than 2.5 V, and very stable DC cyclic switching upto 120 cycles with a great set/reset current and voltage distribution less than 5% of standard deviation at room temperature, which are specifications applicable for neuromorphic or memory device applications. [Figure not available: see fulltext.

Stabilization of fullerene-like boron cages by transition metal encapsulation

NASA Astrophysics Data System (ADS)

Lv, Jian; Wang, Yanchao; Zhang, Lijun; Lin, Haiqing; Zhao, Jijun; Ma, Yanming

2015-06-01

The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ~38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials.The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters

Preparation of transition metal nanoparticles and surfaces modified with (CO)polymers synthesized by RAFT

DOEpatents

McCormick, III., Charles L.; Lowe, Andrew B.; Sumerlin, Brent S.

2006-11-21

A new, facile, general one-phase method of generating thio-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the stops of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Preparation of transition metal nanoparticles and surfaces modified with (co)polymers synthesized by RAFT

DOEpatents

McCormick, III, Charles L.; Lowe, Andrew B [Hattiesburg, MS; Sumerlin, Brent S [Pittsburgh, PA

2011-12-27

A new, facile, general one-phase method of generating thiol-functionalized transition metal nanoparticles and surfaces modified by (co)polymers synthesized by the RAFT method is described. The method includes the steps of forming a (co)polymer in aqueous solution using the RAFT methodology, forming a colloidal transition metal precursor solution from an appropriate transition metal; adding the metal precursor solution or surface to the (co)polymer solution, adding a reducing agent into the solution to reduce the metal colloid in situ to produce the stabilized nanoparticles or surface, and isolating the stabilized nanoparticles or surface in a manner such that aggregation is minimized. The functionalized surfaces generated using these methods can further undergo planar surface modifications, such as functionalization with a variety of different chemical groups, expanding their utility and application.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, M.A.; Hallen, R.T.

1991-10-15

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the product gas from coal gasification processes. 3 figures.

Bridged transition-metal complexes and uses thereof for hydrogen separation, storage and hydrogenation

DOEpatents

Lilga, M.A.; Hallen, R.T.

1990-08-28

The present invention constitutes a class of organometallic complexes which reversibly react with hydrogen to form dihydrides and processes by which these compounds can be utilized. The class includes bimetallic complexes in which two cyclopentadienyl rings are bridged together and also separately [pi]-bonded to two transition metal atoms. The transition metals are believed to bond with the hydrogen in forming the dihydride. Transition metals such as Fe, Mn or Co may be employed in the complexes although Cr constitutes the preferred metal. A multiple number of ancillary ligands such as CO are bonded to the metal atoms in the complexes. Alkyl groups and the like may be substituted on the cyclopentadienyl rings. These organometallic compounds may be used in absorption/desorption systems and in facilitated transport membrane systems for storing and separating out H[sub 2] from mixed gas streams such as the producer gas from coal gasification processes. 3 figs.

Electronic band structure of 4d and 5d transition metal trichalcogenides

NASA Astrophysics Data System (ADS)

Sugita, Yusuke; Miyake, Takashi; Motome, Yukitoshi

2018-05-01

Transition metal trichalcogenides (TMTs), a family of van der Waals materials, have gained increasing interests from the discovery of magnetism in few-layer forms. Although TMTs with 3d transition metal elements have been studied extensively, much less is explored for the 4d and 5d cases, where the interesting interplay between electron correlations and the relativistic spin-orbit coupling is expected. Using ab initio calculations, we here investigate the electronic property of TMTs with 4d and 5d transition metal elements. We show that the band structures exhibit multiple node-like features near the Fermi level. These are the remnant of multiple Dirac cones that were recently discovered in the monolayer cases. Our results indicate that the peculiar two-dimensional multiple Dirac cones are concealed even in the layered bulk systems.

Recent Transits of the Super-Earth Exoplanet GJ 1214b

NASA Astrophysics Data System (ADS)

Sada, Pedro V.; Deming, Drake; Jackson, Brian; Jennings, Donald E.; Peterson, Steven W.; Haase, Flynn; Bays, Kevin; O'Gorman, Eamon; Lundsford, Alan

2010-09-01

We report recent ground-based photometry of the transiting super-Earth exoplanet GJ 1214b at several wavelengths, including the infrared near 1.25 μm (J band). We observed a J-band transit with the FLAMINGOS infrared imager and the 2.1 m telescope on Kitt Peak, and we observed several optical transits using a 0.5 m telescope on Kitt Peak and the 0.36 m Universidad de Monterrey Observatory telescope. Our high-precision J-band observations exploit the brightness of the M dwarf host star at this infrared wavelength as compared with the optical and are significantly less affected by stellar activity and limb darkening. We fit the J-band transit to obtain an independent determination of the planetary and stellar radii. Our radius for the planet (2.61+0.30 -0.11 R ⊕) is in excellent agreement with the discovery value reported by Charbonneau et al. based on optical data. We demonstrate that the planetary radius is insensitive to degeneracies in the fitting process. We use all of our observations to improve the transit ephemeris, finding P = 1.5804043 ± 0.0000005 days and T 0 = 2454964.94390 ± 0.00006 BJD.

Ferroelasticity and domain physics in two-dimensional transition metal dichalcogenide monolayers

DOE PAGES

Li, Wenbin; Li, Ju

2016-02-24

Monolayers of transition metal dichalcogenides can exist in several structural polymorphs, including 2H, 1T and 1T'. The low-symmetry 1T' phase has three orientation variants, resulting from the three equivalent directions of Peierls distortion in the parental 1T phase. Using first-principles calculations, we predict that mechanical strain can switch the relative thermodynamic stability between the orientation variants of the 1T' phase. We find that such strain-induced variant switching only requires a few percent elastic strain, which is eminently achievable experimentally with transition metal dichalcogenide monolayers. Calculations indicate that the transformation barrier associated with such variant switching is small (<0.2 eV permore » chemical formula unit), suggesting that strain-induced variant switching can happen under laboratory conditions. Furthermore, monolayers of transition metal dichalcogenides with 1T' structure therefore have the potential to be ferroelastic and shape memory materials with interesting domain physics.« less

Transition-metal doped sulfide, selenide, and telluride laser crystal and lasers

DOEpatents

Krupke, W.F.; Page, R.H.; DeLoach, L.D.; Payne, S.A.

1996-07-30

A new class of solid state laser crystals and lasers are formed of transition metal doped sulfide, selenide, and telluride host crystals which have four fold coordinated substitutional sites. The host crystals include II-VI compounds. The host crystal is doped with a transition metal laser ion, e.g., chromium, cobalt or iron. In particular, Cr{sup 2+}-doped ZnS and ZnSe generate laser action near 2.3 {micro}m. Oxide, chloride, fluoride, bromide and iodide crystals with similar structures can also be used. Important aspects of these laser materials are the tetrahedral site symmetry of the host crystal, low excited state absorption losses and high luminescence efficiency, and the d{sup 4} and d{sup 6} electronic configurations of the transition metal ions. The same materials are also useful as saturable absorbers for passive Q-switching applications. The laser materials can be used as gain media in amplifiers and oscillators; these gain media can be incorporated into waveguides and semiconductor lasers. 18 figs.

Transition-metal doped sulfide, selenide, and telluride laser crystal and lasers

DOEpatents

Krupke, William F.; Page, Ralph H.; DeLoach, Laura D.; Payne, Stephen A.

1996-01-01

A new class of solid state laser crystals and lasers are formed of transition metal doped sulfide, selenide, and telluride host crystals which have four fold coordinated substitutional sites. The host crystals include II-VI compounds. The host crystal is doped with a transition metal laser ion, e.g., chromium, cobalt or iron. In particular, Cr.sup.2+ -doped ZnS and ZnSe generate laser action near 2.3 .mu.m. Oxide, chloride, fluoride, bromide and iodide crystals with similar structures can also be used. Important aspects of these laser materials are the tetrahedral site symmetry of the host crystal, low excited state absorption losses and high luminescence efficiency, and the d.sup.4 and d.sup.6 electronic configurations of the transition metal ions. The same materials are also useful as saturable absorbers for passive Q-switching applications. The laser materials can be used as gain media in amplifiers and oscillators; these gain media can be incorporated into waveguides and semiconductor lasers.

Engineering of Transition Metal Catalysts Confined in Zeolites

PubMed Central

2018-01-01

Transition metal–zeolite composites are versatile catalytic materials for a wide range of industrial and lab-scale processes. Significant advances in fabrication and characterization of well-defined metal centers confined in zeolite matrixes have greatly expanded the library of available materials and, accordingly, their catalytic utility. In this review, we summarize recent developments in the field from the perspective of materials chemistry, focusing on synthesis, postsynthesis modification, (operando) spectroscopy characterization, and computational modeling of transition metal–zeolite catalysts. PMID:29861546

Controls on the Transition Metal Isotopic Composition of Seawater: Diatom Culture Experiments

NASA Astrophysics Data System (ADS)

Vance, D.; Archer, C.; Kennaway, G.; Cox, E.; Statham, P. J.

2004-12-01

Many transition metals are essential micronutrients for marine phytoplankton. As a result the expectation is that biological processes play an important, perhaps a dominant, role in their marine isotope geochemistry. These observations raise the prospect of using isotope records to trace transition metal micronutrient usage in the past oceans, an issue that is of importance to the efficiency of the biological pump and atmospheric carbon dioxide. As such, the characterisation of trace metal isotopic fractionations associated with marine primary productivity are an important scientific goal. Here we report fractionations associated with Fe, Cu and Zn sequestration by diatoms, one of the main primary producers in the oceans. Axenic unialgal cultures of Thalassiosira weissflogii and Thalassiosira pseudonana were established in artificial seawater + F/2 medium at 18° C on a 16:8 light:dark cycle. The cultures were filtered to separate diatom material from residual media and analysed for Zn, Cu and Fe concentrations and isotope composition using techniques described elsewhere1,2. Aliquots of the starting medium were also measured for each batch of cultures. The diatom organic material shows small, but consistent and resolvable, positive fractionations (0.1-0.3 per mil) for Fe, Cu and Zn relative to the starting medium. In the case of all three metals, but particularly for Zn (70-95% depending on experiment size), the diatoms had sequestered a large proportion of the available metal, suggesting that the fractionation factor for metal usage by the diatoms is much greater than 1.0001 to 1.0003. Time-series experiments are under way to determine the exact magnitude of the fractionation factor. The mass-balance is supported by the fact that the residual medium is around -0.4 per mil for Zn. The fact that diatoms incorporate trace metals that are isotopically heavier than the nutrient pool is a surprising result, the expectation having been that, as with carbon, the

Spin doping using transition metal phthalocyanine molecules

PubMed Central

Atxabal, A.; Ribeiro, M.; Parui, S.; Urreta, L.; Sagasta, E.; Sun, X.; Llopis, R.; Casanova, F.; Hueso, L. E.

2016-01-01

Molecular spins have become key enablers for exploring magnetic interactions, quantum information processes and many-body effects in metals. Metal-organic molecules, in particular, let the spin state of the core metal ion to be modified according to its organic environment, allowing localized magnetic moments to emerge as functional entities with radically different properties from its simple atomic counterparts. Here, using and preserving the integrity of transition metal phthalocyanine high-spin complexes, we demonstrate the magnetic doping of gold thin films, effectively creating a new ground state. We demonstrate it by electrical transport measurements that are sensitive to the scattering of itinerant electrons with magnetic impurities, such as Kondo effect and weak antilocalization. Our work expands in a simple and powerful way the classes of materials that can be used as magnetic dopants, opening a new channel to couple the wide range of molecular properties with spin phenomena at a functional scale. PMID:27941810

Transition metal-catalyzed oxidation of sulfur(IV) oxides. Atmospheric-relevant processes and mechanisms

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

Brandt, C.; Eldik, R. van

1995-01-01

The transition metal-catalyzed oxidation of sulfur(IV) oxides has been known for more than 100 years. There is a significant lack of information on the actual role of the transition metal-catalyzed reactions, and much of the earlier work was performed without a detailed knowledge of the chemical system. For this reason attention is focused on the role of transition metal ions in the oxidation of sulfur(IV) oxides in terms of the coordination chemistry involved, as well as the stability and chemical behavior of the various participating species. The oxidation process of sulfur(IV) oxides plays an important role in atmospheric chemistry (e.g.more » acid rain formation) as well as industrial processes (e.g. desulfurization of plume gases and ore). The present report deals with the mechanism of the transition metal-catalyzed oxidation of sulfur(IV) oxides with the aim to discuss this in terms of atmospheric and chemical processes. In addition, the authors would like to emphasize the key role of oxygen in these processes. 1,076 refs.« less

Mechanical and electronic properties of Janus monolayer transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Shi, Wenwu; Wang, Zhiguo

2018-05-01

The mechanical and electronic properties of Janus monolayer transition metal dichalcogenides MXY (M  =  Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W; X/Y  =  S, Se, Te) were investigated using density functional theory. Results show that breaking the out-of-plane structural symmetry can be used to tune the electronic and mechanical behavior of monolayer transition metal dichalcogenides. The band gaps of monolayer WXY and MoXY are in the ranges of 0.16–1.91 and 0.94–1.69 eV, respectively. A semiconductor to metallic phase transition occurred in Janus monolayer MXY (M  =  Ti, Zr and Hf). The monolayers MXY (M  =  V, Nb, Ta and Cr) show metallic characteristics, which show no dependence on the structural symmetry breaking. The mechanical properties of MXY depended on the composition. Monolayer MXY (M  =  Mo, Ti, Zr, Hf and W) showed brittle characteristic, whereas monolayer CrXY and VXY are with ductile characteristic. The in-plane stiffness of pristine and Janus monolayer MXY are in the range between 22 and 158 N m‑1. The tunable electronic and mechanical properties of these 2D materials would advance the development of ultra-sensitive detectors, nanogenerators, low-power electronics, and energy harvesting and electromechanical systems.

Ground-based Search of Earth-mass Exoplanets using Transit-Timing Variations

NASA Astrophysics Data System (ADS)

Fernandez, J. M.

2010-10-01

This work presents recent results from a ground-based transit follow-up program of the extrasolar planet XO-2b in order to find Earth-mass companions. It also introduces the future use of the MONET 1m-class robotic telescopes as part of the effort to overcome the difficulties of this kind of project.

Metal-semiconductor barrier modulation for high photoresponse in transition metal dichalcogenide field effect transistors.

PubMed

Li, Hua-Min; Lee, Dae-Yeong; Choi, Min Sup; Qu, Deshun; Liu, Xiaochi; Ra, Chang-Ho; Yoo, Won Jong

2014-02-10

A gate-controlled metal-semiconductor barrier modulation and its effect on carrier transport were investigated in two-dimensional (2D) transition metal dichalcogenide (TMDC) field effect transistors (FETs). A strong photoresponse was observed in both unipolar MoS2 and ambipolar WSe2 FETs (i) at the high drain voltage due to a high electric field along the channel for separating photo-excited charge carriers and (ii) at the certain gate voltage due to the optimized barriers for the collection of photo-excited charge carriers at metal contacts. The effective barrier height between Ti/Au and TMDCs was estimated by a low temperature measurement. An ohmic contact behavior and drain-induced barrier lowering (DIBL) were clearly observed in MoS2 FET. In contrast, a Schottky-to-ohmic contact transition was observed in WSe2 FET as the gate voltage increases, due to the change of majority carrier transport from holes to electrons. The gate-dependent barrier modulation effectively controls the carrier transport, demonstrating its great potential in 2D TMDCs for electronic and optoelectronic applications.

Single-layer transition metal sulfide catalysts

DOEpatents

Thoma, Steven G [Albuquerque, NM

2011-05-31

Transition Metal Sulfides (TMS), such as molybdenum disulfide (MoS.sub.2), are the petroleum industry's "workhorse" catalysts for upgrading heavy petroleum feedstocks and removing sulfur, nitrogen and other pollutants from fuels. We have developed an improved synthesis technique to produce SLTMS catalysts, such as molybdenum disulfide, with potentially greater activity and specificity than those currently available. Applications for this technology include heavy feed upgrading, in-situ catalysis, bio-fuel conversion and coal liquefaction.

MOST Detects Transits of HD 97658b, a Warm, Likely Volatile-rich Super-Earth

NASA Astrophysics Data System (ADS)

Dragomir, Diana; Matthews, Jaymie M.; Eastman, Jason D.; Cameron, Chris; Howard, Andrew W.; Guenther, David B.; Kuschnig, Rainer; Moffat, Anthony F. J.; Rowe, Jason F.; Rucinski, Slavek M.; Sasselov, Dimitar; Weiss, Werner W.

2013-07-01

Through photometric monitoring of the extended transit window of HD 97658b with the MOST space telescope, we have found that this exoplanet transits with an ephemeris consistent with that predicted from radial velocity measurements. The mid-transit times are 5.6σ earlier than those of the unverified transit-like signals reported in 2011, and we find no connection between the two sets of events. The transit depth together with our determined stellar radius (R_\\star = 0.703^{+0.039}_{-0.034}\\ R_\\odot) indicates a 2.34^{+0.18}_{-0.15} R ⊕ super-Earth. When combined with the radial velocity determined mass of 7.86 ± 0.73 M ⊕, our radius measure allows us to derive a planet density of 3.44^{+0.91}_{-0.82} g cm-3. Models suggest that a planet with our measured density has a rocky core that is enveloped in an atmosphere composed of lighter elements. The star of the HD 97658 system is the second brightest known to host a transiting super-Earth, facilitating follow-up studies of this not easily daunted, warm and likely volatile-rich exoplanet. Based on data from the MOST satellite, a Canadian Space Agency mission operated by Microsatellite Systems Canada Inc. (MSCI; former Dynacon Inc.) and the Universities of Toronto and British Columbia, with the assistance of the University of Vienna.

Orientation-adjusted anomalous insulator-metal transition in NdNiO3/LaMnO3 bilayers

NASA Astrophysics Data System (ADS)

Pan, S. Y.; Shi, L.; Zhao, J. Y.; Zhou, S. M.; Xu, X. M.

2018-04-01

NdNiO3/LaMnO3 (NNO/LMO) bilayers were epitaxially grown on SrTiO3 (STO) substrates with different orientations by the polymer-assisted deposition technique. A well crystallization quality of the bilayers is confirmed by X-ray diffraction. Two consecutive transitions, an anomalous insulator-metal transition at ˜100 K followed by the typical metal-insulator transition at ˜171 K, are observed in the (001)-oriented NNO/LMO/STO bilayer. The anomalous insulator-metal transition temperature increases to 142 K for the (111)-oriented NNO/LMO/STO bilayer. Meanwhile, the magnetic properties of the NNO/LMO bilayers show an obvious difference with [100] and [111] orientations. Considering the different strain directions and the related oxygen octahedral distortion/rotation, it is suggested that the magnetic changes and the low-temperature anomalous insulator-metal transition in the NNO/LMO bilayers are attributed to the strong interlayer exchange coupling and charge transfer adjusted by the substrate orientation, which can be an effective technique to tune the properties of transition-metal oxide films.

Semiconductor-to-metal transition in rutile TiO 2 induced by tensile strain

DOE PAGES

Benson, Eric E.; Miller, Elisa M.; Nanayakkara, Sanjini U.; ...

2017-02-10

Here, we report the first observation of a reversible, degenerate doping of titanium dioxide with strain, which is referred to as a semiconductor-to-metal transition. Application of tensile strain to a ~50 nm film of rutile TiO 2 thermally grown on a superelastic nitinol (NiTi intermetallic) substrate causes reversible degenerate doping as evidenced by electrochemistry, X-ray photoelectron spectroscopy (XPS), and conducting atomic force microscopy (CAFM). Cyclic voltammetry and impedance measurements show behavior characteristic of a highly doped n-type semiconductor for unstrained TiO 2 transitioning to metallic behavior under tensile strain. The transition reverses when strain is removed. Valence band XPS spectramore » show that samples strained to 5% exhibit metallic-like intensity near the Fermi level. Strain also induces a distinct transition in CAFM current-voltage curves from rectifying (typical of an n-type semiconductor) to ohmic (metal-like) behavior. We propose that strain raises the energy distribution of oxygen vacancies ( n-type dopants) near the conduction band and causes an increase in carrier concentration. As the carrier concentration is increased, the width of the depletion region is reduced, which then permits electron tunneling through the space charge barrier resulting in the observed metallic behavior.« less

Transition Metal Transport in Plants and Associated Endosymbionts: Arbuscular Mycorrhizal Fungi and Rhizobia

PubMed Central

González-Guerrero, Manuel; Escudero, Viviana; Saéz, Ángela; Tejada-Jiménez, Manuel

2016-01-01

Transition metals such as iron, copper, zinc, or molybdenum are essential nutrients for plants. These elements are involved in almost every biological process, including photosynthesis, tolerance to biotic and abiotic stress, or symbiotic nitrogen fixation. However, plants often grow in soils with limiting metallic oligonutrient bioavailability. Consequently, to ensure the proper metal levels, plants have developed a complex metal uptake and distribution system, that not only involves the plant itself, but also its associated microorganisms. These microorganisms can simply increase metal solubility in soils and making them more accessible to the host plant, as well as induce the plant metal deficiency response, or directly deliver transition elements to cortical cells. Other, instead of providing metals, can act as metal sinks, such as endosymbiotic rhizobia in legume nodules that requires relatively large amounts to carry out nitrogen fixation. In this review, we propose to do an overview of metal transport mechanisms in the plant–microbe system, emphasizing the role of arbuscular mycorrhizal fungi and endosymbiotic rhizobia. PMID:27524990

Negative refraction using Raman transitions and chirality

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

Sikes, D. E.; Yavuz, D. D.

2011-11-15

We present a scheme that achieves negative refraction with low absorption in far-off resonant atomic systems. The scheme utilizes Raman resonances and does not require the simultaneous presence of an electric-dipole transition and a magnetic-dipole transition near the same wavelength. We show that two interfering Raman tran-sitions coupled to a magnetic-dipole transition can achieve a negative index of refraction with low absorption through magnetoelectric cross-coupling. We confirm the validity of the analytical results with exact numerical simulations of the density matrix. We also discuss possible experimental implementations of the scheme in rare-earth metal atomic systems.

New insight into enhanced superconductivity in metals near the metal-insulator transition.

PubMed

Osofsky, M S; Soulen, R J; Claassen, J H; Trotter, G; Kim, H; Horwitz, J S

2001-11-05

We have studied the transport properties of disordered WSi films near the metal/insulator transition (MIT) and we have also reviewed the data for several other disordered materials near their MIT. In all cases, we found the presence of enhanced superconductivity. We constructed a superconductivity "phase diagram" (i.e., T(c) versus sigma) for each system, which reveals a striking correlation: In all cases, T(c) values are significantly enhanced only for samples whose conductivities lie within a narrow range on the metallic side of, and moderately near, the MIT. We present a heuristic model to explain this phenomenon.

Voltage-induced Metal-Insulator Transitions in Perovskite Oxide Thin Films Doped with Strongly Correlelated Electrons

NASA Astrophysics Data System (ADS)

Wang, Yudi; Gil Kim, Soo; Chen, I.-Wei

2007-03-01

We have observed a reversible metal-insulator transition in perovskite oxide thin films that can be controlled by charge trapping pumped by a bipolar voltage bias. In the as-fabricated state, the thin film is metallic with a very low resistance comparable to that of the metallic bottom electrode, showing decreasing resistance with decreasing temperature. This metallic state switches to a high-resistance state after applying a voltage bias: such state is non-ohmic showing a negative temperature dependence of resistance. Switching at essentially the same voltage bias was observed down to 2K. The metal-insulator transition is attributed to charge trapping that disorders the energy of correlated electron states in the conduction band. By increasing the amount of charge trapped, which increases the disorder relative to the band width, increasingly more insulating states with a stronger temperature dependence of resistivity are accessed. This metal-insulator transition provides a platform to engineer new nonvolatile memory that does not require heat (as in phase transition) or dielectric breakdown (as in most other oxide resistance devices).

Thermal properties of zirconium diboride -- transition metal boride solid solutions

NASA Astrophysics Data System (ADS)

McClane, Devon Lee

This research focuses on the thermal properties of zirconium diboride (ZrB2) based ceramics. The overall goal was to improve the understanding of how different transition metal (TM) additives influence thermal transport in ZrB2. To achieve this, ZrB2 with 0.5 wt% carbon, and 3 mol% of individual transition metal borides, was densified by hot-press sintering. The transition metals that were investigated were: Y, Ti, Hf, V, Nb, Ta, Cr, Mo, W, and Re. The room temperature thermal diffusivities of the compositions ranged from 0.331 cm2/s for nominally pure ZrB2 to 0.105 cm2/s for (Zr,Cr)B2 and converged around 0.155cm2/s at higher temperatures for all compositions. Thermal conductivities were calculated from the diffusivities, using temperature-dependent values for density and heat capacity. The electron contribution to thermal conductivity was calculated from measured electrical resistivity according to the Wiedemann-Franz law. The phonon contribution to thermal conductivity was calculated by subtracting the electron contribution from the total thermal conductivity. Rietveld refinement of x-ray diffraction data was used to determine the lattice parameters of the compositions. The decrease in thermal conductivity for individual additives correlated directly to the metallic radius of the additive. Additional strain appeared to exist for additives when the stable TM boride for that metal had different crystal symmetries than ZrB2. This research provided insight into how additives and impurities affect thermal transport in ZrB2. The research potentially offers a basis for future modeling of thermal conductivity in ultra-high temperature ceramics based on the correlation between metallic radius and the decrease in thermal conductivity.

Experimentally determined Si isotope fractionation between silicate and Fe metal and implications for Earth's core formation

NASA Astrophysics Data System (ADS)

Shahar, Anat; Ziegler, Karen; Young, Edward D.; Ricolleau, Angele; Schauble, Edwin A.; Fei, Yingwei

2009-10-01

Stable isotope fractionation amongst phases comprising terrestrial planets and asteroids can be used to elucidate planet-forming processes. To date, the composition of the Earth's core remains largely unknown though cosmochemical and geophysical evidence indicates that elements lighter than iron and nickel must reside there. Silicon is often cited as a light element that could explain the seismic properties of the core. The amount of silicon in the core, if any, can be deduced from the difference in 30Si/ 28Si between meteorites and terrestrial rocks if the Si isotope fractionation between silicate and Fe-rich metal is known. Recent studies (e.g., [Georg R.B., Halliday A.N., Schauble E.A., Reynolds B.C., 2007. Silicon in the Earth's core. Nature 447 (31), 1102-1106.]; [Fitoussi, C., Bourdon, B., Kleine, T., Oberli, F., Reynolds, B. C., 2009. Si isotope systematics of meteorites and terrestrial peridotites: implications for Mg/Si fractionation in the solar nebula and for Si in the Earth's core. Earth Planet. Sci. Lett. 287, 77-85.]) showing (sometimes subtle) differences between 30Si/ 28Si in meteorites and terrestrial rocks suggest that Si missing from terrestrial rocks might be in the core. However, any conclusion based on Earth-meteorite comparisons depends on the veracity of the 30Si/ 28Si fractionation factor between silicates and metals at appropriate conditions. Here we present the first direct experimental evidence that silicon isotopes are not distributed uniformly between iron metal and rock when equilibrated at high temperatures. High-precision measurements of the silicon isotope ratios in iron-silicon alloy and silicate equilibrated at 1 GPa and 1800 °C show that Si in silicate has higher 30Si/ 28Si than Si in metal, by at least 2.0‰. These findings provide an experimental foundation for using isotope ratios of silicon as indicators of terrestrial planet formation processes. They imply that if Si isotope equilibrium existed during segregation of Earth

Water-induced convection in the Earth's mantle transition zone

NASA Astrophysics Data System (ADS)

Richard, Guillaume C.; Bercovici, David

2009-01-01

Water enters the Earth's mantle by subduction of oceanic lithosphere. Most of this water immediately returns to the atmosphere through arc volcanism, but a part of it is expected as deep as the mantle transition zone (410-660 km depth). There, slabs can be deflected and linger before sinking into the lower mantle. Because it lowers the density and viscosity of the transition zone minerals (i.e., wadsleyite and ringwoodite), water is likely to affect the dynamics of the transition zone mantle overlying stagnant slabs. The consequences of water exchange between a floating slab and the transition zone are investigated. In particular, we focus on the possible onset of small-scale convection despite the adverse thermal gradient (i.e., mantle is cooled from below by the slab). The competition between thermal and hydrous effects on the density and thus on the convective stability of the top layer of the slab is examined numerically, including water-dependent density and viscosity and temperature-dependent water solubility. For plausible initial water content in a slab (≥0.5 wt %), an episode of convection is likely to occur after a relatively short time delay (5-20 Ma) after the slab enters the transition zone. However, water induced rheological weakening is seen to be a controlling parameter for the onset time of convection. Moreover, small-scale convection above a stagnant slab greatly enhances the rate of slab dehydration. Small-scale convection also facilitates heating of the slab, which in itself may prolong the residence time of the slab in the transition zone.

Correlation-driven insulator-metal transition in near-ideal vanadium dioxide films

DOE PAGES

Gray, A. X.; Jeong, J.; Aetukuri, N. P.; ...

2016-03-18

We use polarization- and temperature-dependent x-ray absorption spectroscopy, in combination with photoelectron microscopy, x-ray diffraction, and electronic transport measurements, to study the driving force behind the insulator-metal transition in VO 2. We show that both the collapse of the insulating gap and the concomitant change in crystal symmetry in homogeneously strained single-crystalline VO 2 films are preceded by the purely electronic softening of Coulomb correlations within V-V singlet dimers. Furthermore, this process starts 7 K (±0.3 K) below the transition temperature, as conventionally defined by electronic transport and x-ray diffraction measurements, and sets the energy scale for driving the near-room-temperaturemore » insulator-metal transition in this technologically promising material.« less

Magnetic fluctuations driven insulator-to-metal transition in Ca(Ir(1-x)Rux)O3.

PubMed

Gunasekera, J; Harriger, L; Dahal, A; Heitmann, T; Vignale, G; Singh, D K

2015-12-09

Magnetic fluctuations in transition metal oxides are a subject of intensive research because of the key role they are expected to play in the transition from the Mott insulator to the unconventional metallic phase of these materials, and also as drivers of superconductivity. Despite much effort, a clear link between magnetic fluctuations and the insulator-to-metal transition has not yet been established. Here we report the discovery of a compelling link between magnetic fluctuations and the insulator-to-metal transition in Ca(Ir1-xRux)O3 perovskites as a function of the substitution coefficient x. We show that when the material turns from insulator to metal, at a critical value of x ~ 0.3, magnetic fluctuations tend to change their character from antiferromagnetic, a Mott insulator phase, to ferromagnetic, an itinerant electron state with Hund's orbital coupling. These results are expected to have wide-ranging implications for our understanding of the unconventional properties of strongly correlated electrons systems.

Thermophysical Property Measurements of Silicon-Transition Metal Alloys

NASA Technical Reports Server (NTRS)

Banish, R. Michael; Erwin, William R.; Sansoucie, Michael P.; Lee, Jonghyun; Gave, Matthew A.

2014-01-01

Metals and metallic alloys often have high melting temperatures and highly reactive liquids. Processing reactive liquids in containers can result in significant contamination and limited undercooling. This is particularly true for molten silicon and it alloys. Silicon is commonly termed "the universal solvent". The viscosity, surface tension, and density of several silicon-transition metal alloys were determined using the Electrostatic Levitator system at the Marshall Space Flight Center. The temperature dependence of the viscosity followed an Arrhenius dependence, and the surface tension followed a linear temperature dependence. The density of the melts, including the undercooled region, showed a linear behavior as well. Viscosity and surface tension values were obtain for several of the alloys in the undercooled region.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces.

PubMed

Crawford, Paul; Hu, P

2006-12-14

The dissociative adsorption of N2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Delayed Ionization in Transition Metal Carbon Clusters

NASA Astrophysics Data System (ADS)

Kooi, S. E.; Castleman, A. W., Jr.

1997-03-01

Mass spectrometric studies of several single and binary transition metal carbon cluster systems, produced in a laser vaporization source, reveal several species that undergo delayed ionization. Pulsed extraction and blocking electric fields, in a time-of-flight mass spectrometer, allow the study of delayed ionization over a time window after excitation with a pulsed laser. In systems where metallocarbohedrenes (Met-Cars) are produced, the Met-Cars are the dominate delayed species. Delayed ionization of binary metal Met-Cars Ti_xM_yC_12 (M=Zr,Nb,Y; x+y=8) is dependent on the ratio of the two metals. Delayed behavior is investigated over a range of photoionization wavelengths and fluences. In order to determine the degree to which the delayed ionization is thermionic in character, the experimental data have been compared to Klots's model for thermionic emission from small particles.

Method of synthesizing bulk transition metal carbide, nitride and phosphide catalysts

DOEpatents

Choi, Jae Soon; Armstrong, Beth L; Schwartz, Viviane

2015-04-21

A method for synthesizing catalyst beads of bulk transmission metal carbides, nitrides and phosphides is provided. The method includes providing an aqueous suspension of transition metal oxide particles in a gel forming base, dropping the suspension into an aqueous solution to form a gel bead matrix, heating the bead to remove the binder, and carburizing, nitriding or phosphiding the bead to form a transition metal carbide, nitride, or phosphide catalyst bead. The method can be tuned for control of porosity, mechanical strength, and dopant content of the beads. The produced catalyst beads are catalytically active, mechanically robust, and suitable for packed-bed reactor applications. The produced catalyst beads are suitable for biomass conversion, petrochemistry, petroleum refining, electrocatalysis, and other applications.

Composite nanoparticles containing rare earth metal and methods of preparation thereof

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

Kandapallil, Binil Itty Ipe; Krishnan, Lakshmi; Johnson, Francis

The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.

Conductivity Dynamics of the Metal to Insulator Transition in EuNiO3/LANiO3 Superlattices

DTIC Science & Technology

2016-02-07

lead to emergent phenomena with the insulator -to- insulator transition (IMT) being one of the most enigmatic from fundamental and applied perspectives...2015 Approved for Public Release; Distribution Unlimited Final Report: Conductivity Dynamics of the Metal to Insulator Transition in EuNiO3/LANiO3...Conductivity Dynamics of the Metal to Insulator Transition in EuNiO3/LANiO3 Superlattices Report Title In numerous transition metal oxides (TMO

Trends in hydrogen chemisorption on transition metals

NASA Astrophysics Data System (ADS)

Muscat, J. P.

1981-10-01

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

[Spectroscopic studies on transition metal ions in colored diamonds].

PubMed

Meng, Yu-Fei; Peng, Ming-Sheng

2004-07-01

Transition metals like nickel, cobalt and iron have been often used as solvent catalysts in high pressure high temperature (HPHT) synthesis of diamond, and nickel and cobalt ions have been found in diamond lattice. Available studies indicated that nickel and cobalt ions could enter the lattice as interstitial or substitutional impurities and form complexes with nitrogen. Polarized microscopy, SEM-EDS, EPR, PL and FTIR have been used in this study to investigate six fancy color natural and synthetic diamonds in order to determine the spectroscopic characteristics and the existing forms of transition metal ions in colored diamond lattice. Cobalt-related optical centers were first found in natural chameleon diamonds, and some new nickel and cobalt-related optical and EPR centers have also been detected in these diamond samples.

Polaronic Transport in Phosphate Glasses Containing Transition Metal Ions

NASA Astrophysics Data System (ADS)

Henderson, Mark

The goal of this dissertation is to characterize the basic transport properties of phosphate glasses containing various amounts of TIs and to identify and explain any electronic phase transitions which may occur. The P2 O5-V2O5-WO3 (PVW) glass system will be analyzed to find the effect of TI concentration on conduction. In addition, the effect of the relative concentrations of network forming ions (SiO2 and P2O5) on transport will be studied in the P2O5-SiO2-Fe2O 3 (PSF) system. Also presented is a numerical study on a tight-binding model adapted for the purposes of modelling Gaussian traps, mimicking TI's, which are arranged in an extended network. The results of this project will contribute to the development of fundamental theories on the electronic transport in glasses containing mixtures of transition oxides as well as those containing multiple network formers without discernible phase separation. The present study on the PVW follows up on previous investigation into the effect on mixed transition ions in oxide glasses. Past research has focused on glasses containing transition metal ions from the 3d row. The inclusion of tungsten, a 5d transition metal, adds a layer of complexity through the mismatch of the energies of the orbitals contributing to localized states. The data have indicated that a transition reminiscent of a metal-insulator transition (MIT) occurs in this system as the concentration of tungsten increases. As opposed to some other MIT-like transitions found in phosphate glass systems, there seems to be no polaron to bipolaron conversion. Instead, the individual localization parameter for tungsten noticeably decreases dramatically at the transition point as well as the adiabaticity. Another distinctive feature of this project is the study of the PSF system, which contains two true network formers, phosphorous pentoxide (P2O 5) and silicon dioxide (SiO2). It is not usually possible to do a reliable investigation of the conduction properties of

Suppression of Structural Phase Transition in VO2 by Epitaxial Strain in Vicinity of Metal-insulator Transition

PubMed Central

Yang, Mengmeng; Yang, Yuanjun; Bin Hong; Wang, Liangxin; Hu, Kai; Dong, Yongqi; Xu, Han; Huang, Haoliang; Zhao, Jiangtao; Chen, Haiping; Song, Li; Ju, Huanxin; Zhu, Junfa; Bao, Jun; Li, Xiaoguang; Gu, Yueliang; Yang, Tieying; Gao, Xingyu; Luo, Zhenlin; Gao, Chen

2016-01-01

Mechanism of metal-insulator transition (MIT) in strained VO2 thin films is very complicated and incompletely understood despite three scenarios with potential explanations including electronic correlation (Mott mechanism), structural transformation (Peierls theory) and collaborative Mott-Peierls transition. Herein, we have decoupled coactions of structural and electronic phase transitions across the MIT by implementing epitaxial strain on 13-nm-thick (001)-VO2 films in comparison to thicker films. The structural evolution during MIT characterized by temperature-dependent synchrotron radiation high-resolution X-ray diffraction reciprocal space mapping and Raman spectroscopy suggested that the structural phase transition in the temperature range of vicinity of the MIT is suppressed by epitaxial strain. Furthermore, temperature-dependent Ultraviolet Photoelectron Spectroscopy (UPS) revealed the changes in electron occupancy near the Fermi energy EF of V 3d orbital, implying that the electronic transition triggers the MIT in the strained films. Thus the MIT in the bi-axially strained VO2 thin films should be only driven by electronic transition without assistance of structural phase transition. Density functional theoretical calculations further confirmed that the tetragonal phase across the MIT can be both in insulating and metallic states in the strained (001)-VO2/TiO2 thin films. This work offers a better understanding of the mechanism of MIT in the strained VO2 films. PMID:26975328

Metallic rare-earth silicide nanowires on silicon surfaces.

PubMed

Dähne, Mario; Wanke, Martina

2013-01-09

The formation, atomic structure, and electronic properties of self-assembled rare-earth silicide nanowires on silicon surfaces were studied by scanning tunneling microscopy and angle-resolved photoelectron spectroscopy. Metallic dysprosium and erbium silicide nanowires were observed on both the Si(001) and Si(557) surfaces. It was found that they consist of hexagonal rare-earth disilicides for both surface orientations. On Si(001), the nanowires are characterized by a one-dimensional band structure, while the electronic dispersion is two-dimensional for the nanowires formed on Si(557). This behavior is explained by the different orientations of the hexagonal c axis of the silicide leading to different conditions for the carrier confinement. By considering this carrier confinement it is demonstrated how the one-dimensional band structure of the nanowires on Si(001) can be derived from the two-dimensional one of the silicide monolayer on Si(111).

RECENT TRANSITS OF THE SUPER-EARTH EXOPLANET GJ 1214b

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

Sada, Pedro V.; Deming, Drake; Jackson, Brian

We report recent ground-based photometry of the transiting super-Earth exoplanet GJ 1214b at several wavelengths, including the infrared near 1.25 {mu}m (J band). We observed a J-band transit with the FLAMINGOS infrared imager and the 2.1 m telescope on Kitt Peak, and we observed several optical transits using a 0.5 m telescope on Kitt Peak and the 0.36 m Universidad de Monterrey Observatory telescope. Our high-precision J-band observations exploit the brightness of the M dwarf host star at this infrared wavelength as compared with the optical and are significantly less affected by stellar activity and limb darkening. We fit themore » J-band transit to obtain an independent determination of the planetary and stellar radii. Our radius for the planet (2.61{sup +0.30} {sub -0.11} R {sub +}) is in excellent agreement with the discovery value reported by Charbonneau et al. based on optical data. We demonstrate that the planetary radius is insensitive to degeneracies in the fitting process. We use all of our observations to improve the transit ephemeris, finding P = 1.5804043 {+-} 0.0000005 days and T {sub 0} = 2454964.94390 {+-} 0.00006 BJD.« less

Kinetics of self-interstitial migration in bcc and fcc transition metals

NASA Astrophysics Data System (ADS)

Bukkuru, S.; Bhardwaj, U.; Srinivasa Rao, K.; Rao, A. D. P.; Warrier, M.; Valsakumar, M. C.

2018-03-01

Radiation damage is a multi-scale phenomenon. A thorough understanding of diffusivities and the migration energies of defects is a pre-requisite to quantify the after-effects of irradiation. We investigate the thermally activated mobility of self-interstitial atom (SIA) in bcc transition metals Fe, Mo, Nb and fcc transition metals Ag, Cu, Ni, Pt using molecular dynamics (MD) simulations. The self-interstitial diffusion involves various mechanisms such as interstitialcy, dumbbell or crowdion mechanisms. Max-Space Clustering (MSC) method has been employed to identify the interstitial and its configuration over a wide range of temperature. The self-interstitial diffusion is Arrhenius like, however, there is a slight deviation at high temperatures. The migration energies, pre-exponential factors of diffusion and jump-correlation factors, obtained from these simulations can be used as inputs to Monte Carlo simulations of defect transport. The jump-correlation factor shows the degree of preference of rectilinear or rotational jumps. We obtain the average jump-correlation factor of 1.4 for bcc metals and 0.44 for fcc metals. It indicates that rectilinear jumps are preferred in bcc metals and rotational jumps are preferred in fcc metals.

Stabilization of fullerene-like boron cages by transition metal encapsulation.

PubMed

Lv, Jian; Wang, Yanchao; Zhang, Lijun; Lin, Haiqing; Zhao, Jijun; Ma, Yanming

2015-06-21

The stabilization of fullerene-like boron (B) cages in the free-standing form has been long sought after and a challenging problem. Studies that have been carried out for more than a decade have confirmed that the planar or quasi-planar polymorphs are energetically favored ground states over a wide range of small and medium-sized B clusters. Recently, the breakthroughs represented by Nat. Chem., 2014, 6, 727 established that the transition from planar/quasi-planar to cage-like Bn clusters occurs around n = ∼38-40, paving the way for understanding the intriguing chemistry of B-fullerene. We herein demonstrate that the transition demarcation, n, can be significantly reduced with the help of transition metal encapsulation. We explore via extensive first-principles swarm-intelligence based structure searches the free energy landscapes of B24 clusters doped by a series of transition metals and find that the low-lying energy regime is generally dominated by cage-like isomers. This is in sharp contrast to that of bare B24 clusters, where the quasi-planar and rather irregular polyhedrons are prevalent. Most strikingly, a highly symmetric B cage with D3h symmetry is discovered in the case of Mo or W encapsulation. The endohedral D3h cages exhibit robust thermodynamic, dynamic and chemical stabilities, which can be rationalized in terms of their unique electronic structure of an 18-electron closed-shell configuration. Our results indicate that transition metal encapsulation is a feasible route for stabilizing medium-sized B cages, offering a useful roadmap for the discovery of more B fullerene analogues as building blocks of nanomaterials.

Control of the metal-insulator transition in vanadium dioxide by modifying orbital occupancy

NASA Astrophysics Data System (ADS)

Aetukuri, Nagaphani B.; Gray, Alexander X.; Drouard, Marc; Cossale, Matteo; Gao, Li; Reid, Alexander H.; Kukreja, Roopali; Ohldag, Hendrik; Jenkins, Catherine A.; Arenholz, Elke; Roche, Kevin P.; Dürr, Hermann A.; Samant, Mahesh G.; Parkin, Stuart S. P.

2013-10-01

External control of the conductivity of correlated oxides is one of the most promising schemes for realizing energy-efficient electronic devices. Vanadium dioxide (VO2), an archetypal correlated oxide compound, undergoes a temperature-driven metal-insulator transition near room temperature with a concomitant change in crystal symmetry. Here, we show that the metal-insulator transition temperature of thin VO2(001) films can be changed continuously from ~285 to ~345K by varying the thickness of the RuO2 buffer layer (resulting in different epitaxial strains). Using strain-, polarization- and temperature-dependent X-ray absorption spectroscopy, in combination with X-ray diffraction and electronic transport measurements, we demonstrate that the transition temperature and the structural distortion across the transition depend on the orbital occupancy in the metallic state. Our findings open up the possibility of controlling the conductivity in atomically thin VO2 layers by manipulating the orbital occupancy by, for example, heterostructural engineering.

Evaluating DFT for Transition Metals and Binaries: Developing the V/DM-17 Test Set

NASA Astrophysics Data System (ADS)

Decolvenaere, Elizabeth; Mattsson, Ann

We have developed the V-DM/17 test set to evaluate the experimental accuracy of DFT calculations of transition metals. When simulation and experiment disagree, the disconnect in length-scales and temperatures makes determining ``who is right'' difficult. However, methods to evaluate the experimental accuracy of functionals in the context of solid-state materials science, especially for transition metals, is lacking. As DFT undergoes a shift from a descriptive to a predictive tool, these issues of verification are becoming increasingly important. With undertakings like the Materials Project leading the way in high-throughput predictions and discoveries, the development of a one-size-fits-most approach to verification is critical. Our test set evaluates 26 transition metal elements and 80 transition metal alloys across three physical observables: lattice constants, elastic coefficients, and formation energy of alloys. Whether or not the formation energy can be reproduced measures whether the relevant physics are captured in a calculation. This is especially important question in transition metals, where active d-electrons can thwart commonly used techniques. In testing the V/DM-17 test set, we offer new views into the performance of existing functionals. Sandia National Labs is a multi-mission laboratory managed and operated by Sandia Corp., a wholly owned subsidiary of Lockheed Martin Corp., for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

Status in calculating electronic excited states in transition metal oxides from first principles.

PubMed

Bendavid, Leah Isseroff; Carter, Emily Ann

2014-01-01

Characterization of excitations in transition metal oxides is a crucial step in the development of these materials for photonic and optoelectronic applications. However, many transition metal oxides are considered to be strongly correlated materials, and their complex electronic structure is challenging to model with many established quantum mechanical techniques. We review state-of-the-art first-principles methods to calculate charged and neutral excited states in extended materials, and discuss their application to transition metal oxides. We briefly discuss developments in density functional theory (DFT) to calculate fundamental band gaps, and introduce time-dependent DFT, which can model neutral excitations. Charged excitations can be described within the framework of many-body perturbation theory based on Green's functions techniques, which predominantly employs the GW approximation to the self-energy to facilitate a feasible solution to the quasiparticle equations. We review the various implementations of the GW approximation and evaluate each approach in its calculation of fundamental band gaps of many transition metal oxides. We also briefly review the related Bethe-Salpeter equation (BSE), which introduces an electron-hole interaction between GW-derived quasiparticles to describe accurately neutral excitations. Embedded correlated wavefunction theory is another framework used to model localized neutral or charged excitations in extended materials. Here, the electronic structure of a small cluster is modeled within correlated wavefunction theory, while its coupling to its environment is represented by an embedding potential. We review a number of techniques to represent this background potential, including electrostatic representations and electron density-based methods, and evaluate their application to transition metal oxides.

First-principles studies on 3d transition metal atom adsorbed twin graphene

NASA Astrophysics Data System (ADS)

Li, Lele; Zhang, Hong; Cheng, Xinlu; Miyamoto, Yoshiyuki

2018-05-01

Twin graphene is a new two-dimensional semiconducting carbon allotrope which is proposed recently. The structural, magnetic and electronic properties are investigated for 3d transition metal (TM) atom adsorbed twin graphene by means of GGA+U calculations. The results show most of single 3d transition metal atom except Zn can make twin graphene magnetization. The adsorption of single TM atom can also make the twin graphene systems turn to half metal (V adsorption), half-semiconductor (Fe adsorption) or metal (Sc, Cr, Mn, Co and Cu adsorption). The semiconducting nature still exists for Ti, Ni and Zn adsorption. All the 3d TM adatoms belong to n-type doping for transferring charge to the neighboring C atoms and have strong covalent bond with these C atoms. The influence of Hubbard U value on half-metallic V adsorbed system is also considered. As the U increases, the system can gradually transform from metal to half metal and metal. The effect of the coverage is investigated for two TM atoms (Sc-Fe) adsorption, too. We can know TM atoms adsorbed twin graphene have potentials to be spintronic device and nanomagnets from the results.

Covalency and the metal-insulator transition in titanate and vanadate perovskites

NASA Astrophysics Data System (ADS)

Dang, Hung T.; Millis, Andrew J.; Marianetti, Chris A.

2014-04-01

A combination of density functional and dynamical mean-field theory is applied to the perovskites SrVO3, LaTiO3, and LaVO3. We show that DFT + DMFT in conjunction with the standard fully localized-limit (FLL) double-counting predicts that LaTiO3 and LaVO3 are metals even though experimentally they are correlation-driven ("Mott") insulators. In addition, the FLL double counting implies a splitting between oxygen p and transition metal d levels, which differs from experiment. Introducing into the theory an ad hoc double counting correction, which reproduces the experimentally measured insulating gap leads also to a p-d splitting consistent with experiment if the on-site interaction U is chosen in a relatively narrow range (˜6±1 eV). The results indicate that these early transition metal oxides will serve as critical test for the formulation of a general ab initio theory of correlated electron metals.

Metal insulator transitions in perovskite SrIrO{sub 3} thin films

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

Biswas, Abhijit; Jeong, Yoon Hee, E-mail: yhj@postech.ac.kr; Kim, Ki-Seok

Understanding of metal insulator transitions in a strongly correlated system, driven by Anderson localization (disorder) and/or Mott localization (correlation), is a long standing problem in condensed matter physics. The prevailing fundamental question would be how these two mechanisms contrive to accomplish emergent anomalous behaviors. Here, we have grown high quality perovskite SrIrO{sub 3} thin films, containing a strong spin orbit coupled 5d element Ir, on various substrates such as GdScO{sub 3} (110), DyScO{sub 3} (110), SrTiO{sub 3} (001), and NdGaO{sub 3} (110) with increasing lattice mismatch, in order to carry out a systematic study on the transport properties. We foundmore » that metal insulator transitions can be induced in this system; by either reducing thickness (on best lattice matched substrate) or changing degree of lattice strain (by lattice mismatch between film and substrates) of films. Surprisingly these two pathways seek two distinct types of metal insulator transitions; the former falls into disorder driven Anderson type whereas the latter turns out to be of unconventional Mott-Anderson type with the interplay of disorder and correlation. More interestingly, in the metallic phases of SrIrO{sub 3}, unusual non-Fermi liquid characteristics emerge in resistivity as Δρ ∝ T{sup ε} with ε evolving from 4/5 to 1 to 3/2 with increasing lattice strain. We discuss theoretical implications of these phenomena to shed light on the metal insulator transitions.« less

Quantum Griffiths singularity of superconductor-metal transition in Ga thin films.

PubMed

Xing, Ying; Zhang, Hui-Min; Fu, Hai-Long; Liu, Haiwen; Sun, Yi; Peng, Jun-Ping; Wang, Fa; Lin, Xi; Ma, Xu-Cun; Xue, Qi-Kun; Wang, Jian; Xie, X C

2015-10-30

The Griffiths singularity in a phase transition, caused by disorder effects, was predicted more than 40 years ago. Its signature, the divergence of the dynamical critical exponent, is challenging to observe experimentally. We report the experimental observation of the quantum Griffiths singularity in a two-dimensional superconducting system. We measured the transport properties of atomically thin gallium films and found that the films undergo superconductor-metal transitions with increasing magnetic field. Approaching the zero-temperature quantum critical point, we observed divergence of the dynamical critical exponent, which is consistent with the Griffiths singularity behavior. We interpret the observed superconductor-metal quantum phase transition as the infinite-randomness critical point, where the properties of the system are controlled by rare large superconducting regions. Copyright © 2015, American Association for the Advancement of Science.

Rare earth element recycling from waste nickel-metal hydride batteries.

PubMed

Yang, Xiuli; Zhang, Junwei; Fang, Xihui

2014-08-30

With an increase in number of waste nickel-metal hydride batteries, and because of the importance of rare earth elements, the recycling of rare earth elements is becoming increasingly important. In this paper, we investigate the effects of temperature, hydrochloric acid concentration, and leaching time to optimize leaching conditions and determine leach kinetics. The results indicate that an increase in temperature, hydrochloric acid concentration, and leaching time enhance the leaching rate of rare earth elements. A maximum rare earth elements recovery of 95.16% was achieved at optimal leaching conditions of 70°C, solid/liquid ratio of 1:10, 20% hydrochloric acid concentration, -74μm particle size, and 100min leaching time. The experimental data were best fitted by a chemical reaction-controlled model. The activation energy was 43.98kJ/mol and the reaction order for hydrochloric acid concentration was 0.64. The kinetic equation for the leaching process was found to be: 1-(1-x)(1/3)=A/ρr0[HCl](0.64)exp-439,8008.314Tt. After leaching and filtration, by adding saturated oxalic solution to the filtrate, rare earth element oxalates were obtained. After removing impurities by adding ammonia, filtering, washing with dilute hydrochloric acid, and calcining at 810°C, a final product of 99% pure rare earth oxides was obtained. Copyright © 2014 Elsevier B.V. All rights reserved.

Two-State Reactivity in Low-Valent Iron-Mediated C-H Activation and the Implications for Other First-Row Transition Metals.

PubMed

Sun, Yihua; Tang, Hao; Chen, Kejuan; Hu, Lianrui; Yao, Jiannian; Shaik, Sason; Chen, Hui

2016-03-23

C-H bond activation/functionalization promoted by low-valent iron complexes has recently emerged as a promising approach for the utilization of earth-abundant first-row transition metals to carry out this difficult transformation. Herein we use extensive density functional theory and high-level ab initio coupled cluster calculations to shed light on the mechanism of these intriguing reactions. Our key mechanistic discovery for C-H arylation reactions reveals a two-state reactivity (TSR) scenario in which the low-spin Fe(II) singlet state, which is initially an excited state, crosses over the high-spin ground state and promotes C-H bond cleavage. Subsequently, aryl transmetalation occurs, followed by oxidation of Fe(II) to Fe(III) in a single-electron transfer (SET) step in which dichloroalkane serves as an oxidant, thus promoting the final C-C coupling and finalizing the C-H functionalization. Regeneration of the Fe(II) catalyst for the next round of C-H activation involves SET oxidation of the Fe(I) species generated after the C-C bond coupling. The ligand sphere of iron is found to play a crucial role in the TSR mechanism by stabilization of the reactive low-spin state that mediates the C-H activation. This is the first time that the successful TSR concept conceived for high-valent iron chemistry is shown to successfully rationalize the reactivity for a reaction promoted by low-valent iron complexes. A comparative study involving other divalent middle and late first-row transition metals implicates iron as the optimum metal in this TSR mechanism for C-H activation. It is predicted that stabilization of low-spin Mn(II) using an appropriate ligand sphere should produce another promising candidate for efficient C-H bond activation. This new TSR scenario therefore emerges as a new strategy for using low-valent first-row transition metals for C-H activation reactions.

Alkaline earth metallocenes coordinated with ester pendants: synthesis, structural characterization, and application in metathesis reactions.

PubMed

Li, Heng; Zhang, Wen-Xiong; Xi, Zhenfeng

2013-09-16

A variety of ester-substituted cyclopentadiene derivatives have been synthesized by one-pot reactions of 1,4-dilithio-1,3-butadienes, CO, and acid chlorides. Direct deprotonation of the ester-substituted cyclopentadienes with Ae[N(SiMe3 )2 ]2 (Ae=Ca, Sr, Ba) efficiently generated members of a new class of heavier alkaline earth (Ca, Sr, Ba) metallocenes in good to excellent yields. Single-crystal X-ray structural analysis demonstrated that these heavier alkaline earth metallocenes incorporated two intramolecularly coordinated ester pendants and multiply-substituted cyclopentadienyl ligands. The corresponding transition metal metallocenes, such as ferrocene derivatives and half-sandwich cyclopentadienyl tricarbonylrhenium complexes, could be generated highly efficiently by metathesis reactions. The multiply-substituted cyclopentadiene ligands bearing an ester pendant, and the corresponding heavier alkaline earth and transition-metal metallocenes, may have further applications in coordination chemistry, organometallic chemistry, and organic synthesis. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impurity effects in transition metal silicides

NASA Technical Reports Server (NTRS)

Lien, C.-D.; Nicolet, M.-A.

1984-01-01

Impurities can affect the properties of silicides directly by virtue of their presence. Impurities can also influence the processes by which silicides are formed. The effect of impurities on the reaction of transition metal films with a silicon substrate induced by thermal annealing are well documented. The interpretation of these results is discussed. It is shown that impurity redistribution is a major factor in determining how significant the effect of an impurity is. Redistribution observed for dopant impurities is also discussed.

Transition Metal Nitrides for Electrocatalytic Energy Conversion: Opportunities and Challenges.

PubMed

Xie, Junfeng; Xie, Yi

2016-03-07

Electrocatalytic energy conversion has been considered as one of the most efficient and promising pathways for realizing energy storage and energy utilization in modern society. To improve electrocatalytic reactions, specific catalysts are needed to lower the overpotential. In the search for efficient alternatives to noble metal catalysts, transition metal nitrides have attracted considerable interest due to their high catalytic activity and unique electronic structure. Over the past few decades, numerous nitride-based catalysts have been explored with respect to their ability to drive various electrocatalytic reactions, such as the hydrogen evolution reaction and the oxygen evolution reaction to achieve water splitting and the oxygen reduction reaction coupled with the methanol oxidation reaction to construct fuel cells or rechargeable Li-O2 batteries. This Minireview provides a brief overview of recent progress on electrocatalysts based on transition metal nitrides, and outlines the current challenges and future opportunities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

PubMed Central

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; Wang, Shibing; Lin, Yu; Zeng, Qiaoshi; Xu, Gang; Liu, Zhenxian; Solanki, G. K.; Patel, K. D.; Cui, Yi; Hwang, Harold Y.; Mao, Wendy L.

2015-01-01

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe2 up to ∼60 GPa using multiple experimental techniques and ab-initio calculations. MoSe2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSe2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides. PMID:26088416

Pressure induced metallization with absence of structural transition in layered molybdenum diselenide

DOE PAGES

Zhao, Zhao; Zhang, Haijun; Yuan, Hongtao; ...

2015-06-19

Layered transition-metal dichalcogenides have emerged as exciting material systems with atomically thin geometries and unique electronic properties. Pressure is a powerful tool for continuously tuning their crystal and electronic structures away from the pristine states. Here, we systematically investigated the pressurized behavior of MoSe 2 up to ~60 GPa using multiple experimental techniques and ab-initio calculations. MoSe 2 evolves from an anisotropic two-dimensional layered network to a three-dimensional structure without a structural transition, which is a complete contrast to MoS 2. The role of the chalcogenide anions in stabilizing different layered patterns is underscored by our layer sliding calculations. MoSemore » 2 possesses highly tunable transport properties under pressure, determined by the gradual narrowing of its band-gap followed by metallization. The continuous tuning of its electronic structure and band-gap in the range of visible light to infrared suggest possible energy-variable optoelectronics applications in pressurized transition-metal dichalcogenides.« less

Dynamical Correlation In Some Liquid Alkaline Earth Metals Near Melting

NASA Astrophysics Data System (ADS)

Thakore, B. Y.; Suthar, P. H.; Khambholja, S. G.; Gajjar, P. N.; Jani, A. R.

2010-12-01

The study of dynamical variables: velocity autocorrelation function (VACF) and power spectrum of liquid alkaline earth metals (Ca, Sr, and Ba) have been presented based on the static harmonic well approximation. The effective interatomic potential for liquid metals is computed using our well recognized model potential with the exchange correlation functions due to Hartree, Taylor, Ichimaru and Utsumi, Farid et al. and Sarkar et al. It is observed that the VACF computed using Sarkar et al. gives the good agreement with available molecular dynamics simulation (MD) results [Phys Rev. B 62, 14818 (2000)]. The shoulder of the power spectrum depends upon the type of local field correlation function used.

Local structural aspects of metal-metal transition in IrTe2 from x-ray PDF