Experimental study of the rearrangements of valence protons and neutrons amongst single-particle orbits during double- β decay in Mo 100

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

Freeman, S. J.; Sharp, D. K.; McAllister, S. A.

The rearrangements of protons and neutrons amongst the valence single-particle orbitals during double-beta decay of Mo-100 have been determined by measuring cross sections in (d, p), (p, d), (He-3, a), and (He-3, d) reactions on Mo-98,Mo-100 and Ru-100,Ru-102 targets. The deduced nucleon occupancies reveal significant discrepancies when compared with theoretical calculations; the same calculations have previously been used to determine the nuclear matrix element associated with the decay probability of double-beta decay of the Mo-100 system.

47 CFR 1.1156 - Schedule of regulatory fees and filing locations for international services.

Code of Federal Regulations, 2014 CFR

2014-10-01

... Stations (Geostationary Orbit) $122,400 FCC, International, P.O. Box 979084, St. Louis, MO 63197-9000. Space Stations (Non-Geostationary Orbit) 132,850 FCC, International, P.O. Box 979084, St. Louis, MO...

47 CFR 1.1156 - Schedule of regulatory fees and filing locations for international services.

Code of Federal Regulations, 2013 CFR

2013-10-01

... Stations (Geostationary Orbit) $139,100 FCC, International, P.O. Box 979084, St. Louis, MO 63197-9000. Space Stations (Non-Geostationary Orbit) 149,875 FCC, International, P.O. Box 979084, St. Louis, MO...

47 CFR 1.1156 - Schedule of regulatory fees and filing locations for international services.

Code of Federal Regulations, 2012 CFR

2012-10-01

... Stations (Geostationary Orbit) $132,875 FCC, International, P.O. Box 979084, St. Louis, MO 63197-9000. Space Stations (Non-Geostationary Orbit) 143,150 FCC, International, P.O. Box 979084, St. Louis, MO...

Electronic structure description of the cis-MoOS unit in models for molybdenum hydroxylases.

PubMed

Doonan, Christian J; Rubie, Nick D; Peariso, Katrina; Harris, Hugh H; Knottenbelt, Sushilla Z; George, Graham N; Young, Charles G; Kirk, Martin L

2008-01-09

The molybdenum hydroxylases catalyze the oxidation of numerous aromatic heterocycles and simple organics and, unlike other hydroxylases, utilize water as the source of oxygen incorporated into the product. The electronic structures of the cis-MoOS units in CoCp2[TpiPrMoVOS(OPh)] and TpiPrMoVIOS(OPh) (TpiPr = hydrotris(3-isopropylpyrazol-1-yl)borate), new models for molybdenum hydroxylases, have been studied in detail using S K-edge X-ray absorption spectroscopy, vibrational spectroscopy, and detailed bonding calculations. The results show a highly delocalized Mo=S pi* LUMO redox orbital that is formally Mo(dxy) with approximately 35% sulfido ligand character. Vibrational spectroscopy has been used to quantitate Mo-Ssulfido bond order changes in the cis-MoOS units as a function of redox state. Results support a redox active molecular orbital that has a profound influence on MoOS bonding through changes to the relative electro/nucleophilicity of the terminal sulfido ligand accompanying oxidation state changes. The bonding description for these model cis-MoOS systems supports enzyme mechanisms that are under orbital control and dominantly influenced by the unique electronic structure of the cis-MoOS site. The electronic structure of the oxidized enzyme site is postulated to play a role in polarizing a substrate carbon center for nucleophilic attack by metal activated water and acting as an electron sink in the two-electron oxidation of substrates.

Experimental study of the rearrangements of valence protons and neutrons amongst single-particle orbits during double-β decay in 100Mo

NASA Astrophysics Data System (ADS)

Freeman, S. J.; Sharp, D. K.; McAllister, S. A.; Kay, B. P.; Deibel, C. M.; Faestermann, T.; Hertenberger, R.; Mitchell, A. J.; Schiffer, J. P.; Szwec, S. V.; Thomas, J. S.; Wirth, H.-F.

2017-11-01

The rearrangements of protons and neutrons amongst the valence single-particle orbitals during double-β decay of 100Mo have been determined by measuring cross sections in (d ,p ), (p ,d ), (3He,α ), and (3He,d ) reactions on Mo,10098 and Ru,102100 targets. The deduced nucleon occupancies reveal significant discrepancies when compared with theoretical calculations; the same calculations have previously been used to determine the nuclear matrix element associated with the decay probability of double-β decay of the 100Mo system.

J1-J2 square lattice antiferromagnetism in the orbitally quenched insulator MoOPO4

NASA Astrophysics Data System (ADS)

Yang, L.; Jeong, M.; Babkevich, P.; Katukuri, V. M.; Náfrádi, B.; Shaik, N. E.; Magrez, A.; Berger, H.; Schefer, J.; Ressouche, E.; Kriener, M.; Živković, I.; Yazyev, O. V.; Forró, L.; Rønnow, H. M.

2017-07-01

We report magnetic and thermodynamic properties of a 4 d1 (Mo5 +) magnetic insulator MoOPO4 single crystal, which realizes a J1-J2 Heisenberg spin-1 /2 model on a stacked square lattice. The specific-heat measurements show a magnetic transition at 16 K which is also confirmed by magnetic susceptibility, ESR, and neutron diffraction measurements. Magnetic entropy deduced from the specific heat corresponds to a two-level degree of freedom per Mo5 + ion, and the effective moment from the susceptibility corresponds to the spin-only value. Using ab initio quantum chemistry calculations, we demonstrate that the Mo5 + ion hosts a purely spin-1 /2 magnetic moment, indicating negligible effects of spin-orbit interaction. The quenched orbital moments originate from the large displacement of Mo ions inside the MoO6 octahedra along the apical direction. The ground state is shown by neutron diffraction to support a collinear Néel-type magnetic order, and a spin-flop transition is observed around an applied magnetic field of 3.5 T. The magnetic phase diagram is reproduced by a mean-field calculation assuming a small easy-axis anisotropy in the exchange interactions. Our results suggest 4 d molybdates as an alternative playground to search for model quantum magnets.

Effect of protonation of the N-acetyl neuraminic acid residue of sialyl Lewis(X): a molecular orbital study with insights into its binding properties toward the carbohydrate recognition domain of E-selectin.

PubMed

Pichierri, Fabio; Matsuo, Yo

2002-08-01

Semiempirical molecular orbital (MO) calculations with an implicit treatment of the water environment were employed in order to assess whether the sialyl Lewis(X) (sLe(X)) tetrasaccharide binds to E-selectin in the anionic or neutral (i.e., protonated) state. The analysis of the frontier molecular orbitals, electrostatic potential surfaces, and conformational behavior of the sugar indicates that its neutral form possesses the necessary characteristics for binding. In particular, the LUMO level of the neutral sLe(X) molecule is localized both on the carboxylic group of the N-acetyl neuraminic acid (NeuNAc) residue and on the nearby glycosidic linkage. These two moieties interact with the Arg97 residue of E-selectin, as revealed by a recent crystal structure analysis of the E-selectin/sLe(X) complex. The energetics of this specific interaction was investigated with the aid of ab initio Hartree-Fock MO calculations, which resulted in a BSSE-corrected binding energy of 16.63 kcal/mol. Our observations could open up new perspectives in the design of sLe(X) mimics.

A Simple MO Treatment of Metal Clusters.

ERIC Educational Resources Information Center

Sahyun, M. R. V.

1980-01-01

Illustrates how a qualitative description of the geometry and electronic characteristics of homogeneous metal clusters can be obtained using semiempirical MO (molecular orbital theory) methods. Computer applications of MO methods to inorganic systems are also described. (CS)

Using Solution- and Solid-State S K-edge X-ray Absorption Spectroscopy with Density Functional Theory to Evaluate M–S Bonding for MS42- (M = Cr, Mo, W) Dianions

PubMed Central

Olson, Angela C.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Daly, Scott R.; Kozimor, Stosh A.; MacInnes, Molly M.; Martin, Richard L.; Scott, Brian L.

2014-01-01

Herein, we have evaluated relative changes in M–S electronic structure and orbital mixing in Group 6 MS42- dianions using solid- and solution-phase S K-edge X-ray absorption spectroscopy (XAS; M = Mo, W), as well as density functional theory (DFT; M = Cr, Mo, W) and time-dependent density functional theory (TDDFT) calculations. To facilitate comparison with solution measurements (conducted in acetonitrile), theoretical models included gas-phase calculations as well as those that incorporated an acetonitrile dielectric, the latter of which provided better agreement with experiment. Two pre-edge features arising from S 1s → e* and t2* electron excitations were observed in the S K-edge XAS spectra and were reasonably assigned as 1A1 → 1T2 transitions. For MoS42-, both solution-phase pre-edge peak intensities were consistent with results from the solid-state spectra. For WS42-, solution- and solid-state pre-edge peak intensities for transitions involving e* were equivalent, while transitions involving the t2* orbitals were less intense in solution. Experimental and computational results have been presented in comparison to recent analyses of MO42- dianions, which allowed M–S and M–O orbital mixing to be evaluated as the principle quantum number (n) for the metal valence d orbitals increased (3d, 4d, 5d). Overall, the M–E (E = O, S) analyses revealed distinct trends in orbital mixing. For example, as the Group 6 triad was descended, e* (π*) orbital mixing remained constant in the M–S bonds, but increased appreciably for M–O interactions. For the t2* orbitals (σ* + π*), mixing decreased slightly for M–S bonding and increased only slightly for the M–O interactions. These results suggested that the metal and ligand valence orbital energies and radial extensions delicately influenced the orbital compositions for isoelectronic ME42- (E = O, S) dianions. PMID:25311904

A study on the stability of O{sub 2} on oxometalloporphyrins by the first principles calculations

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

Kubota, Yoshiyuki; Escano, Mary Clare Sison; Dy, Eben Sy

2007-05-21

The authors investigated the interaction of oxometalloporphyrins (MO(por))--specifically, MoO(por), WO(por), TiO(por), VO(por), and CrO(por)--with O{sub 2} by using first principles calculations. MoO(por) and WO(por) undergo reactions with O{sub 2}; on the other hand, TiO(por), VO(por), and CrO(por) do not. Next, they compared the interaction of MoO(por) and WO(por) with O{sub 2}. Activation barriers for the reactions of MoO(por) and WO(por) with a side-on O{sub 2} are small. For MoO(por)(O{sub 2}), the activation barrier for the reverse reaction that liberates O{sub 2} is also small; however, that for WO(por)(O{sub 2}) is large. The experimental results that photoirradiation with visible light ormore » heating of Mo {sup VI}O(tmp)(O{sub 2}) regenerates Mo {sup VI}O(tmp) by liberating O{sub 2} while W {sup VI}O(tmp)(O{sub 2}) does not [J. Tachibana, T. Imamura, and Y. Sasaki, Bull. Chem. Soc. Jpn. 71, 363 (1998)] are explained by the difference in activation barriers of the reverse reactions. This means that bonds formed between the W atom and O{sub 2} are stronger than those between the Mo atom and O{sub 2}. The bond strengths can be explained by differences in the energy levels between the highest occupied molecular orbital of MoO(por) and WO(por), which are mainly formed from the a orbitals of the central metal atom and {pi}{sup *} orbitals of O{sub 2}.« less

Theoretical and experimental studies of the electronic structure of the Mo3(Micro3-0)(Micro3-OR)(Micro-OR)3(OR)6 type of triangulo metal atom cluster compound

NASA Astrophysics Data System (ADS)

Chisholm, M. H.; Cotton, F. A.; Fang, A.; Kober, E. C.

1983-09-01

The electronic structure of a Mo3(Mu sub 3-0) (Mu sub 3-OR) (Mu sub 2-OR)3(OR)6 molecule with R = H, and C3v symmetry, which serves as a model for real molecules in which R = H CH2C(CH)3 or CH(CH3)2 has been calculated by the molecular orbital method of Hall and Fenske. The calculations have been performed not only on the entire molecule, but on the Mo3(12+), Mo3O(OH)(9+) and Mo3O(OH)4(6+) fragments and the metal-metal bonding tracked through these successive stages by the ''clusters in molecules' formalism. In the full molecule, the HOMO is an e orbital that carries most of the e-type M-M bonding, while the a1-type is carried by two MO's, one of which is quite stable. The LUMO is also an e type orbital and the HOMO-LUMO gap is small (ca. 1.5 eV). It is predicted that the Mo3O(OR)10 molecules of this type will have readily accessible redox chemistry in which both oxidation and reduction steps might be slowed or irreversible judging by the character of the HOMO and LUMO of the Mo3O(OR)10 molecule. Experimental observations on Mo3O(ONe)10, Ne = CH2C(CH3)3, are in harmony with this. In addition, the absorption spectrum of Mo3O(ONe)10 has been observed and an assignment based on the calculations in proposed.

Band nesting, massive Dirac fermions, and valley Landé and Zeeman effects in transition metal dichalcogenides: A tight-binding model

NASA Astrophysics Data System (ADS)

Bieniek, Maciej; Korkusiński, Marek; Szulakowska, Ludmiła; Potasz, Paweł; Ozfidan, Isil; Hawrylak, Paweł

2018-02-01

We present here the minimal tight-binding model for a single layer of transition metal dichalcogenides (TMDCs) MX 2(M , metal; X , chalcogen) which illuminates the physics and captures band nesting, massive Dirac fermions, and valley Landé and Zeeman magnetic field effects. TMDCs share the hexagonal lattice with graphene but their electronic bands require much more complex atomic orbitals. Using symmetry arguments, a minimal basis consisting of three metal d orbitals and three chalcogen dimer p orbitals is constructed. The tunneling matrix elements between nearest-neighbor metal and chalcogen orbitals are explicitly derived at K ,-K , and Γ points of the Brillouin zone. The nearest-neighbor tunneling matrix elements connect specific metal and sulfur orbitals yielding an effective 6 ×6 Hamiltonian giving correct composition of metal and chalcogen orbitals but not the direct gap at K points. The direct gap at K , correct masses, and conduction band minima at Q points responsible for band nesting are obtained by inclusion of next-neighbor Mo-Mo tunneling. The parameters of the next-nearest-neighbor model are successfully fitted to MX 2(M =Mo ; X =S ) density functional ab initio calculations of the highest valence and lowest conduction band dispersion along K -Γ line in the Brillouin zone. The effective two-band massive Dirac Hamiltonian for MoS2, Landé g factors, and valley Zeeman splitting are obtained.

Covalency in Metal-Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

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

Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.

Advancing theories of how metal oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal peroxyanions, MO4x-, have formed the basis for new M O bonding theories. Herein, relative changes in M O orbital mixing in MO42- (M = Cr, Mo, W) and MO41- (M = Mn, Tc, Re) are evaluated for the first time by non-resonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and linear-response density functional theory. The results suggest that moving from Groupmore » 6 to Group 7 or down the triads increases M O e () mixing. Meanwhile, t2 mixing ( + ) remains relatively constant within the same Group. These unexpected changes in frontier orbital energy and composition are evaluated in terms of periodic trends in d orbital energy and radial extension.« less

Diverse forms of bonding in two-dimensional Si allotropes: Nematic orbitals in the MoS2 structure

NASA Astrophysics Data System (ADS)

Gimbert, Florian; Lee, Chi-Cheng; Friedlein, Rainer; Fleurence, Antoine; Yamada-Takamura, Yukiko; Ozaki, Taisuke

2014-10-01

The interplay of sp2- and sp3-type bonding defines silicon allotropes in two- and three-dimensional forms. A two-dimensional phase bearing structural resemblance to a single MoS2 layer is found to possess a lower total energy than low-buckled silicene and to be stable in terms of its phonon dispersion relations. A set of cigar-shaped nematic orbitals originating from the Si sp2 orbitals realizes bonding with a sixfold coordination of the inner Si atoms of the layer. The identification of these nematic orbitals advocates diverse Si bonding configurations different from those of C atoms.

Non-enzymatic glucose sensing properties of MoO3 nanorods: experimental and density functional theory investigations

NASA Astrophysics Data System (ADS)

Sharma, Maneesha; Gangan, Abhijeet; Chakraborty, Brahmananda; Sekhar Rout, Chandra

2017-11-01

We report the growth of monoclinic MoO3 nanorods by a simple and highly reproducible hydrothermal method. Structural and morphological studies provide significant insights about the phase and crystalline structure of the synthesized samples. Further, the non-enzymatic glucose sensing properties were investigated and the MoO3 nanorods exhibited a sensitivity of 15.4 µA µM-1 cm-2 in the 5-175 µM linear range. Also, a quick response time of 8 s towards glucose molecules was observed, exhibiting an excellent electrochemical activity. We have also performed density functional theory (DFT) simulations to qualitatively support our experimental observations by investigating the interactions and charge-transfer mechanism of glucose on MoO3. There is a strong interaction between glucose and the MoO3 surface due to charge transfer from a bonded O atom of glucose to a Mo atom of MoO3 resulting in a strong hybridization between the p orbital of O and d orbital of Mo. Thus, the MoO3 nanorod-based electrodes are found to be good glucose sensing materials for practical industrial applications.

Ultra-broadband nonlinear saturable absorption of high-yield MoS2 nanosheets

NASA Astrophysics Data System (ADS)

Wei, Rongfei; Zhang, Hang; Hu, Zhongliang; Qiao, Tian; He, Xin; Guo, Qiangbing; Tian, Xiangling; Chen, Zhi; Qiu, Jianrong

2016-07-01

High-yield MoS2 nanosheets with strong nonlinear optical (NLO) responses in a broad near-infrared range were synthesized by a facile hydrothermal method. The observation of saturable absorption, which was excited by the light with photon energy smaller than the gap energy of MoS2, can be attributed to the enhancement of the hybridization between the Mo d-orbital and S p-orbital by the oxygen incorporation into MoS2. High-yield MoS2 nanosheets with high modulation depth and large saturable intensity generated a stable, passively Q-switched fiber laser pulse at 1.56 μm. The high output power of 1.08 mW can be attained under a very low pump power of 30.87 mW. Compared to recently reported passively Q-switched fiber lasers utilizing exfoliated MoS2 nanosheets, the efficiency of the laser for our passive Q-switching operation is larger and reaches 3.50%. This research may extend the understanding on the NLO properties of MoS2 and indicate the feasibility of the high-yield MoS2 nanosheets to passively Q-switched fiber laser effectively at low pump strengths.

Orbital metastases in Italy

PubMed Central

Magliozzi, Patrizio; Strianese, Diego; Bonavolontà, Paola; Ferrara, Mariantonia; Ruggiero, Pasquale; Carandente, Raffaella; Bonavolontà, Giulio; Tranfa, Fausto

2015-01-01

AIM To describe a series of Italian patients with orbital metastasis focusing on the outcomes in relation to the different primary site of malignancy. METHODS Retrospective chart review of 93 patients with orbital metastasis collected in a tertiary referral centre in a period of 38y and review of literature. RESULTS Out of 93 patients, 52 were females and 41 were males. Median age at diagnosis was 51y (range 1 to 88y). The patients have been divided into four groups on the basis of the year of diagnosis. The frequency of recorded cases had decreased significantly (P<0.05) during the last 9.5y. Primary tumor site was breast in 36 cases (39%), kidney in 10 (11%), lung in 8 (9%), skin in 6 (6%); other sites were less frequent. In 16 case (17%) the primary tumor remained unknown. The most frequent clinical findings were proptosis (73%), limited ocular motility (55%), blepharoptosis (46%) and blurred vision (43%). The diagnosis were established by history, ocular and systemic evaluation, orbital imaging studies and open biopsy or fine needle aspiration biopsy (FNAB). Treatment included surgical excision, irradiation, chemotherapy, hormone therapy, or observation. Ninety-one percent of patients died of metastasis with an overall mean survival time (OMST) after the orbital diagnosis of 13.5mo. CONCLUSION Breast, kidney and lung are the most frequent primary sites of cancer leading to an orbital metastasis. When the primary site is unknown, gastrointestinal tract should be carefully investigated. In the last decade a decrease in the frequency of orbital metastasis has been observed. Surgery provides a local palliation. Prognosis remains poor with a OMST of 13.5mo ranging from the 3mo in the lung cancer to 24mo in the kidney tumor. PMID:26558220

Spin-Orbit Dimers and Noncollinear Phases in d1 Cubic Double Perovskites

NASA Astrophysics Data System (ADS)

Romhányi, Judit; Balents, Leon; Jackeli, George

2017-05-01

We formulate and study a spin-orbital model for a family of cubic double perovskites with d1 ions occupying a frustrated fcc sublattice. A variational approach and a complementary analytical analysis reveal a rich variety of phases emerging from the interplay of Hund's rule and spin-orbit coupling. The phase digram includes noncollinear ordered states, with or without a net moment, and, remarkably, a large window of a nonmagnetic disordered spin-orbit dimer phase. The present theory uncovers the physical origin of the unusual amorphous valence bond state experimentally suggested for Ba2B Mo O6 (B =Y , Lu) and predicts possible ordered patterns in Ba2B Os O6 (B =Na , Li) compounds.

Charge disproportionation in tetragonal La2MoO5, a small band gap semiconductor influenced by direct Mo-Mo bonding.

PubMed

Colabello, Diane M; Camino, Fernando E; Huq, Ashfia; Hybertsen, Mark; Khalifah, Peter G

2015-01-28

The structure of the novel compound La2MoO5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo2O10) and square prismatic (Mo2O8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo2O10 dimers is 2.684(8) Å, while there are two types of Mo2O8 dimers with Mo-Mo bonds lengths of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La2MoO5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo2O10 dimers contain only Mo(5+) (d(1)), while the prismatic Mo2O8 dimers only contain Mo(3+) (d(3)), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo(4+), a phenomenon which has not previously been observed in solid-state compounds. La2MoO5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La2MoO5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. It is shown that the d-orbital splitting associated with the Mo2O8 and Mo2O10 dimeric units can be rationalized using simple molecular orbital bonding concepts.

Covalent functionalization of MoS2 nanosheets synthesized by liquid phase exfoliation to construct electrochemical sensors for Cd (II) detection.

PubMed

Gan, Xiaorong; Zhao, Huimin; Wong, Kwok-Yin; Lei, Dang Yuan; Zhang, Yaobin; Quan, Xie

2018-05-15

Surface functionalization is an effective strategy in the precise control of electronic surface states of two-dimensional materials for promoting their applications. In this study, based on the strong coordination interaction between the transition-metal centers and N atoms, the surface functionalization of few-layer MoS 2 nanosheets was successfully prepared by liquid phase exfoliation method in N, N-dimethylformamide (DMF), 1-methyl-2-pyrrolidinone, and formamide. The cytotoxicity of surface-functionalized MoS 2 nanosheets was for the first time evaluated by the methylthiazolyldiphenyl-tetrazoliumbromide assays. An electrochemical sensor was constructed based on glass carbon electrode (GCE) modified by MoS 2 nanosheets obtained in DMF, which exhibits relatively higher sensitivity to Cd 2+ detection and lower cytotoxicity against MCF-7 cells. The mechanisms of surface functionalization and selectively detecting Cd 2+ were investigated by density functional theory calculations together with various spectroscopic measurements. It was found that surface-functionalized MoS 2 nanosheets could be generated through Mo-N covalent bonds due to the orbital hybridization between the 5 s orbitals of Mo atoms and the 2p orbitals of N atoms of the solvent molecules. The high selectivity of the sensor is attributed to the coordination reaction between Cd 2+ and O donor atoms of DMF adsorbed on MoS 2 nanosheets. The robust anti-interference is ascribed to the strong binding energy of Cd 2+ and O atoms of DMF. Under the optimum conditions, the electrochemical sensor exhibits highly sensitive and selective assaying of Cd 2+ with a measured detection limit of 0.2 nM and a linear range from 2 nM to 20 μM. Copyright © 2018 Elsevier B.V. All rights reserved.

Vibrational and rotational sequences in 101Mo and 103,4Ru studied via multinucleon transfer reactions

DOE PAGES

Regan, P. H.; Wheldon, C.; Yamamoto, A. D.; ...

2005-04-01

The near-yrast states of 42 101Mo 59 and 44 103,4Ru 59,60 have been studied following their population via heavy-ion multinucleon transfer reactions between a 136 Xe beam and a thin, self-supporting 100Mo target. The ground state sequence in 104Ru can be understood as demonstrating a simple evolution from a quasi-vibrational structure at lower spins to statically deformed, quasi-rotational excitation involving the population of a pair of low-Ω h 11/2 neutron orbitals. The effect of the decoupled h 11/2 orbital on this vibration-to-rotational evolution is demonstrated by an extension of the "E-GOS" prescription to include odd-A nuclei. The experimental results aremore » also compared with self-consistent Total Routhian Surface calculations which also highlight the polarising role of the highly aligned neutron h 11/2 orbital in these nuclei.« less

Perpendicular magnetic anisotropy in Mo/Co2FeAl0.5Si0.5/MgO/Mo multilayers with optimal Mo buffer layer thickness

NASA Astrophysics Data System (ADS)

Saravanan, L.; Raja, M. Manivel; Prabhu, D.; Pandiyarasan, V.; Ikeda, H.; Therese, H. A.

2018-05-01

Perpendicular Magnetic Anisotropy (PMA) was realized in as-deposited Mo(10)/Co2FeAl0.5Si0.5(CFAS)(3)/MgO(0.5)/Mo multilayer stacks with large perpendicular magnetic anisotropy energy (Keff). PMA of this multilayer is found to be strongly dependent on the thickness of the individual CFAS (tCFAS), Mo (tMo) and MgO (tMgO) layers and annealing temperatures. The interactions at the Mo/CFAS/MgO interfaces are critical to induce PMA and are tuned by the interfacial oxidation. The major contribution to PMA is due to iron oxide at the CFAS/MgO interface. X-ray diffraction (XRD) and infrared spectroscopic (FT-IR) studies further ascertain this. However, an adequate oxidation of MgO and the formation of (0 2 4) and (0 1 8) planes of α-Fe2O3 at the optimal Mo buffer layer thickness is mainly inducing PMA in Mo/CFAS/MgO/Mo stack. Microstructural changes in the films are observed by atomic force microscopy (AFM). X-ray photoelectron spectroscopy (XPS) demonstrates the oxidation of CFAS/MgO interface and the formation of Fe-O bonds confirming that the real origin of PMA in Mo/CFAS/MgO is due to hybridization of Fe (3dz2) and O (2pz) orbitals and the resulted spin-orbit interaction at their interface. The half-metallic nature CFAS with Mo layer exhibiting PMA can be a potential candidate as p-MTJs electrodes for the new generation spintronic devices.

Charge Disproportionation in Tetragonal La 2MoO 5 , a Small Band Gap Semiconductor Influenced by Direct Mo–Mo Bonding

DOE PAGES

Colabello, Diane M.; Camino, Fernando E.; Huq, Ashfia; ...

2014-12-31

The structure of the novel compound La 2MoO 5 has been solved from powder X-ray and neutron diffraction data and belongs to the tetragonal space group P4/m (no. 83) with a = 12.6847(3) Å and c = 6.0568(2) Å and with Z = 8. It consists of equal proportions of bioctahedral (Mo 2O 10) and square prismatic (Mo 2O 8) dimers, both of which contain direct Mo-Mo bonds and are arranged in 1D chains. The Mo-Mo bond length in the Mo 2O 10dimers is 2.684(8) Å, while there are two types of Mo 2O 8 dimers with Mo-Mo bonds lengthsmore » of 2.22(2) and 2.28(2) Å. Although the average Mo oxidation state in La 2MoO 5 is 4+, the very different Mo-Mo distances reflect the fact that the Mo 2O 10 dimers contain only Mo5+ (d(1)), while the prismatic Mo2O8 dimers only contain Mo 3+ (d 3), a result directly confirmed by density function theory calculations. This is due to the complete disproportionation of Mo 4+, a phenomenon which has not previously been observed in solid-state compounds. La 2MoO 5 is diamagnetic, behavior which is not expected for a nonmetallic transition-metal oxide whose cation sites have an odd number of d-electrons. The resistivity displays the Arrhenius-type activated behavior expected for a semiconductor with a band gap of 0.5 eV, exhibiting an unusually small transport gap relative to other diamagnetic oxides. Diffuse reflectance studies indicate that La 2MoO 5 is a rare example of a stable oxide semiconductor with strong infrared absorbance. Lastly, we show that the d-orbital splitting associated with the Mo 2O 8 and Mo 2O 10 dimeric units can be rationalized using simple molecular orbital bonding concepts.« less

Envelope molecular-orbital theory of extended systems. I. Electronic states of organic quasilinear nanoheterostructures

NASA Astrophysics Data System (ADS)

Arce, J. C.; Perdomo-Ortiz, A.; Zambrano, M. L.; Mujica-Martínez, C.

2011-03-01

A conceptually appealing and computationally economical course-grained molecular-orbital (MO) theory for extended quasilinear molecular heterostructures is presented. The formalism, which is based on a straightforward adaptation, by including explicitly the vacuum, of the envelope-function approximation widely employed in solid-state physics leads to a mapping of the three-dimensional single-particle eigenvalue equations into simple one-dimensional hole and electron Schrödinger-like equations with piecewise-constant effective potentials and masses. The eigenfunctions of these equations are envelope MO's in which the short-wavelength oscillations present in the full MO's, associated with the atomistic details of the molecular potential, are smoothed out automatically. The approach is illustrated by calculating the envelope MO's of high-lying occupied and low-lying virtual π states in prototypical nanometric heterostructures constituted by oligomers of polyacetylene and polydiacetylene. Comparison with atomistic electronic-structure calculations reveals that the envelope-MO energies agree very well with the energies of the π MO's and that the envelope MO's describe precisely the long-wavelength variations of the π MO's. This envelope MO theory, which is generalizable to extended systems of any dimensionality, is seen to provide a useful tool for the qualitative interpretation and quantitative prediction of the single-particle quantum states in mesoscopic molecular structures and the design of nanometric molecular devices with tailored energy levels and wavefunctions.

Driving magnetization dynamics with interfacial spin-orbit torques (Conference Presentation)

NASA Astrophysics Data System (ADS)

Hoffmann, Axel F.; Zhang, Wei; Sklenar, Joseph; Jungfleisch, Matthias Benjamin; Jiang, Wanjun; Hsu, Bo; Xiao, Jiao; Pearson, John E.; Fradin, Frank Y.; Liu, Yaohua; Ketterson, John B.; Yang, Zheng

2016-10-01

Bulk spin Hall effects are well know to provide spin orbit torques, which can be used to drive magnetization dynamics [1]. But one of the reoccurring questions is to what extend spin orbit torques may also originate at the interface between materials with strong spin orbit coupling and the ferromagnets. Using spin torque driven ferromagnetic resonance we show for two systems, where interfacial torques dominate, that they can be large enough to be practically useful. First, we show spin transfer torque driven magnetization dynamics based on Rashba-Edelstein effects at the Bi/Ag interface [2]. Second, we will show that combining permalloy with monolayer MoS2 gives rise to sizable spin-orbit torques. Given the monolayer nature of MoS2 it is clear that bilk spin Hall effects are negligible and therefore the spin transfer torques are completely interfacial in nature. Interestingly the spin orbit torques with MoS2 show a distinct dependence on the orientation of the magnetization in the permalloy, and become strongly enhanced, when the magnetization is pointing perpendicular to the interfacial plane. This work was supported by the U.S. Department of Energy, Office of Science, Materials Science and Engineering Division. [1] A. Hoffmann, IEEE Trans. Mag. 49, 5172 (2013). [2] W. Zhang et al., J. Appl. Phys. 117, 17C727 (2015). [3] M. B. Jungfleisch et al., arXiv:1508.01410.

Methylation of zebularine investigated using density functional theory calculations.

PubMed

Selvam, Lalitha; Chen, Fang Fang; Wang, Feng

2011-07-30

Deoxyribonucleic acid (DNA) methylation is an epigenetic phenomenon, which adds methyl groups into DNA. This study reveals methylation of a nucleoside antibiotic drug 1-(β-D-ribofuranosyl)-2-pyrimidinone (zebularine or zeb) with respect to its methylated analog, 1-(β-D-ribofuranosyl)-5-methyl-2-pyrimidinone (d5) using density functional theory calculations in valence electronic space. Very similar infrared spectra suggest that zeb and d5 do not differ by types of the chemical bonds, but distinctly different Raman spectra of the nucleoside pair reveal that the impact caused by methylation of zeb can be significant. Further valence orbital-based information details on valence electronic structural changes caused by methylation of zebularine. Frontier orbitals in momentum space and position space of the molecules respond differently to methylation. Based on the additional methyl electron density concentration in d5, orbitals affected by the methyl moiety are classified into primary and secondary contributors. Primary methyl contributions include MO8 (57a), MO18 (47a), and MO37 (28a) of d5, which concentrates on methyl and the base moieties, suggest certain connection to their Frontier orbitals. The primary and secondary methyl affected orbitals provide useful information on chemical bonding mechanism of the methylation in zebularine. Copyright © 2011 Wiley Periodicals, Inc.

Quantum chemical studies on hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes

NASA Astrophysics Data System (ADS)

Gövdeli, Nezafet; Karakaş, Duran

2018-07-01

Quantum chemical calculations at B3LYP/LANL2DZ/6-31G(d) level were made on anti-eclipsed, anti-staggered, syn-eclipsed, syn-staggered conformers of hypothetical Fischer type Mo(CO)5[C(OEt)Me] and Mo(CO)5[C(OMe)Et] carbene complexes in the gas phase. The most stable conformer of the complexes was found to be anti-staggered according to the total energy values calculated at given level. Structural parameters, vibration spectra, charge distributions, molecular orbital energy diagrams, contour diagrams of frontier orbitals, molecular electrostatic potential maps and some electronic structure descriptors were obtained for the most stable conformers. NMR spectra of the most stable conformers were calculated at GIAO/B3LYP/LANL2DZ level. The most stable conformer geometry was found to be distorted octahedral. IR and NMR spectra of the complexes are consistent with their geometry. HOMOs of the complexes were found to be center-atomic character and LUMOs were carbene-carbon character. From the calculated charge analysis and molecular electrostatic potential maps, it is found that carbene-carbon acts as electrofil and metal center nucleophile. It is suggested that the catalytic properties of the carbene complexes may be due to the fact that the carbene-carbon behave as electrophile and metal center nucleophile. Some electronic structure descriptors of the complexes were calculated and the molecular properties were estimated.

Freeze-Quench Magnetic Circular Dichroism Spectroscopic Study of the "Very Rapid" Intermediate in Xanthine Oxidase.

PubMed

Jones, Robert M.; Inscore, Frank E.; Hille, Russ; Kirk, Martin L.

1999-11-01

Freeze-quench magnetic circular dichroism spectroscopy (MCD) has been used to trap and study the excited-state electronic structure of the Mo(V) active site in a xanthine oxidase intermediate generated with substoichiometric concentrations of the slow substrate 2-hydroxy-6-methylpurine. EPR spectroscopy has shown that the intermediate observed in the MCD experiment is the "very rapid" intermediate, which lies on the main catalytic pathway. The low-energy (< approximately 30 000 cm(-1)) C-term MCD of this intermediate is remarkably similar to that of the model compound LMoO(bdt) (L = hydrotris(3,5-dimethyl-1-pyrazolyl)borate; bdt = 1,2-benzenedithiolate), and the MCD bands have been assigned as dithiolate S(ip) --> Mo d(xy) and S(op) --> Mo d(xz,yz) LMCT transitions. These transitions result from a coordination geometry of the intermediate where the Mo=O bond is oriented cis to the ene-1,2-dithiolate of the pyranopterin. Since X-ray crystallography has indicated that a terminal sulfido ligand is oriented cis to the ene-1,2-dithiolate in oxidized xanthine oxidase related Desulfovibrio gigas aldehyde oxidoreductase, we have suggested that a conformational change occurs upon substrate binding. The substrate-mediated conformational change is extremely significant with respect to electron-transfer regeneration of the active site, as covalent interactions between the redox-active Mo d(xy) orbital and the S(ip) orbitals of the ene-1,2-dithiolate are maximized when the oxo ligand is oriented cis to the dithiolate plane. This underlies the importance of the ene-1,2-dithiolate portion of the pyranopterin in providing an efficient superexchange pathway for electron transfer. The results of this study indicate that electron-transfer regeneration of the active site may be gated by the orientation of the Mo=O bond relative to the ene-1,2-dithiolate chelate. Poor overlap between the Mo d(xy) orbital and the S(ip) orbitals of the dithiolate in the oxidized enzyme geometry may provide a means of preventing one-electron reduction of the active site, resulting in enzyme inhibition with respect to the two-electron oxidation of native substrates.

Effects of van der Waals interaction and electric field on the electronic structure of bilayer MoS2.

PubMed

Xiao, Jin; Long, Mengqiu; Li, Xinmei; Zhang, Qingtian; Xu, Hui; Chan, K S

2014-10-08

The modification of the electronic structure of bilayer MoS2 by an external electric field can have potential applications in optoelectronics and valleytronics. Nevertheless, the underlying physical mechanism is not clearly understood, especially the effects of the van der Waals interaction. In this study, the spin orbit-coupled electronic structure of bilayer MoS2 has been investigated using the first-principle density functional theory. We find that the van der Waals interaction as well as the interlayer distance has significant effects on the band structure. When the interlayer distance of bilayer MoS2 increases from 0.614 nm to 0.71 nm, the indirect gap between the Γ and Λ points increases from 1.25 eV to 1.70 eV. Meanwhile, the energy gap of bilayer MoS2 transforms from an indirect one to a direct one. An external electric field can shift down (up) the energy bands of the bottom (top) MoS2 layer and also breaks the inversion symmetry of bilayer MoS2. As a result, the electric field can affect the band gaps, the spin-orbit interaction and splits the valance bands into two groups. The present study can help us understand more about the electronic structures of MoS2 materials for potential applications in electronics and optoelectronics.

On the physical interpretation of the nuclear molecular orbital energy.

PubMed

Charry, Jorge; Pedraza-González, Laura; Reyes, Andrés

2017-06-07

Recently, several groups have extended and implemented molecular orbital (MO) schemes to simultaneously obtain wave functions for electrons and selected nuclei. Many of these schemes employ an extended Hartree-Fock approach as a first step to find approximate electron-nuclear wave functions and energies. Numerous studies conducted with these extended MO methodologies have explored various effects of quantum nuclei on physical and chemical properties. However, to the best of our knowledge no physical interpretation has been assigned to the nuclear molecular orbital energy (NMOE) resulting after solving extended Hartree-Fock equations. This study confirms that the NMOE is directly related to the molecular electrostatic potential at the position of the nucleus.

An orbital and electron density analysis of weak interactions in ethanol-water, methanol-water, ethanol and methanol small clusters.

PubMed

Mejía, Sol M; Flórez, Elizabeth; Mondragón, Fanor

2012-04-14

A computational study of (ethanol)(n)-water, n = 1 to 5 heteroclusters was carried out employing the B3LYP∕6-31+G(d) approach. The molecular (MO) and atomic (AO) orbital analysis and the topological study of the electron density provided results that were successfully correlated. Results were compared with those obtained for (ethanol)(n), (methanol)(n), n = 1 to 6 clusters and (methanol)(n)-water, n = 1 to 5 heteroclusters. These systems showed the same trends observed in the (ethanol)(n)-water, n = 1 to 5 heteroclusters such as an O---O distance of 5 Å to which the O-H---O hydrogen bonds (HBs) can have significant influence on the constituent monomers. The HOMO of the hetero(clusters) is less stable than the HOMO of the isolated alcohol monomer as the hetero(cluster) size increases, that destabilization is higher for linear geometries than for cyclic geometries. Changes of the occupancy and energy of the AO are correlated with the strength of O-H---O and C-H---O HBs as well as with the proton donor and/or acceptor character of the involved molecules. In summary, the current MO and AO analysis provides alternative ways to characterize HBs. However, this analysis cannot be applied to the study of H---H interactions observed in the molecular graphs.

Construction of Ligand Group Orbitals for Polyatomics and Transition-Metal Complexes Using an Intuitive Symmetry-Based Approach

ERIC Educational Resources Information Center

Johnson, Adam R.

2013-01-01

A molecular orbital (MO) diagram, especially its frontier orbitals, explains the bonding and reactivity for a chemical compound. It is therefore important for students to learn how to construct one. The traditional methods used to derive these diagrams rely on linear algebra techniques to combine ligand orbitals into symmetry-adapted linear…

The power of exact conditions in electronic structure theory

NASA Astrophysics Data System (ADS)

Bartlett, Rodney J.; Ranasinghe, Duminda S.

2017-02-01

Once electron correlation is included in an effective one-particle operator, one has a correlated orbital theory (COT). One such theory is Kohn-Sham density functional theory (KS-DFT), but there are others. Such methods have the prospect to redefine traditional Molecular Orbital (MO) theory by building a quantitative component upon its conceptual framework. This paper asks the question what conditions should such a theory satisfy and can this be accomplished? One such condition for a COT is that the orbital eigenvalues should satisfy an ionization theorem that generalizes Koopmans' approximation to the exact principal ionization potentials for every electron in a molecule. Guided by this principle, minimal parameterizations of KS-DFT are made that provide a good approximation to a quantitative MO theory.

Carbon Fibers Conductivity Studies

NASA Technical Reports Server (NTRS)

Yang, C. Y.; Butkus, A. M.

1980-01-01

In an attempt to understand the process of electrical conduction in polyacrylonitrile (PAN)-based carbon fibers, calculations were carried out on cluster models of the fiber consisting of carbon, nitrogen, and hydrogen atoms using the modified intermediate neglect of differential overlap (MINDO) molecular orbital (MO) method. The models were developed based on the assumption that PAN carbon fibers obtained with heat treatment temperatures (HTT) below 1000 C retain nitrogen in a graphite-like lattice. For clusters modeling an edge nitrogen site, analysis of the occupied MO's indicated an electron distribution similar to that of graphite. A similar analysis for the somewhat less stable interior nitrogen site revealed a partially localized II electron distribution around the nitrogen atom. The differences in bonding trends and structural stability between edge and interior nitrogen clusters led to a two-step process proposed for nitrogen evolution with increasing HTT.

Effect of molecular intercalation on the local structure of superconducting Nax(NH3)yMoSe2 system

NASA Astrophysics Data System (ADS)

Simonelli, L.; Paris, E.; Wakita, T.; Marini, C.; Terashima, K.; Miao, X.; Olszewski, W.; Ramanan, N.; Heinis, D.; Kubozono, Y.; Yokoya, T.; Saini, N. L.

2017-12-01

We have studied the local structure of layered Nax(NH3)yMoSe2 system by Mo K-edge extended X-ray absorption fine structure (EXAFS) measurements performed as a function of temperature. We find that molecular intercalation in MoSe2 largely affects the Mo-Se network while Mo-Mo seems to sustain small changes. The Einstein temperature (ΘE) of Mo-Mo distance hardly changes (∼264 K) indicating that bond strength of this distance remains unaffected by intercalation. On the other hand, Mo-Se distance suffers a softening, revealed by the decrease of ΘE from ∼364 K to ∼350 K. The results indicate that Na+ ion transported by NH3 molecules may enter between the two MoSe-layers resulting reduced Se-Se coupling. Therefore, increased hybridization between Se 4p and Mo 4d orbitals due to inter-layer disorder is the likely reason of metallicity in intercalated MoSe2 and superconductivity at low temperature.

Impact of MoO3 interlayer on the energy level alignment of pentacene-C60 heterostructure.

PubMed

Zou, Ye; Mao, Hongying; Meng, Qing; Zhu, Daoben

2016-02-28

Using in situ ultraviolet photoelectron spectroscopy, the electronic structure evolutions at the interface between pentacene and fullerene (C60), a classical organic donor-acceptor heterostructure in organic electronic devices, on indium-tin oxide (ITO) and MoO3 modified ITO substrates have been investigated. The insertion of a thin layer MoO3 has a significant impact on the interfacial energy level alignment of pentacene-C60 heterostructure. For the deposition of C60 on pentacene, the energy difference between the highest occupied molecular orbital of donor and the lowest unoccupied molecular orbital of acceptor (HOMO(D)-LUMO(A)) offset of C60/pentacene heterostructure increased from 0.86 eV to 1.54 eV after the insertion of a thin layer MoO3 on ITO. In the inverted heterostructrure where pentacene was deposited on C60, the HOMO(D)-LUMO(A) offset of pentacene/C60 heterostructure increased from 1.32 to 2.20 eV after MoO3 modification on ITO. The significant difference of HOMO(D)-LUMO(A) offset shows the feasibility to optimize organic electronic device performance through interfacial engineering approaches, such as the insertion of a thin layer high work function MoO3 films.

Calculation of photoelectron spectra of molybdenum and tungsten complexes using Green's functions methods.

PubMed

Bayse, Craig A; Ortwine, Kristine N

2007-08-16

Green's functions calculations are presented for several complexes of molybdenum and tungsten, two metals that are similar structurally but display subtle, but significant, differences in electronic structure. Outer valence Green's functions IPs for M(CO)6, M(Me)6, MH6, [MCl4O](-), and [MO4](-) (M = Mo, W) are generally within +/-0.2 eV of available experimental photoelectron spectra. The calculations show that electrons in M-L bonding orbitals are ejected at lower energies for Mo while the detachment energy for electrons in d orbitals varies with metal and complex. For the metal carbonyls, the quasiparticle picture assumed in OVGF breaks down for the inner valence pi CO molecular orbitals due to the coupling of two-hole-one-particle charge transfer states to the one-hole states. Incorporation of the 2h1p states through a Tamm-Dancoff approximation calculation accurately represents the band due to detachment from these molecular orbitals. Though the ordering of IPs for Green's functions methods and DFT Koopmans' theorem IPs is similar for the highest IPs for most compounds considered, the breakdown of the quasiparticle picture for the metal carbonyls suggests that scaling of the latter values may result in a fortuitous or incorrect assignment of experimental VDEs.

Investigation of metal-dithiolate fold angle effects: implications for molybdenum and tungsten enzymes.

PubMed

Joshi, Hemant K; Cooney, J Jon A; Inscore, Frank E; Gruhn, Nadine E; Lichtenberger, Dennis L; Enemark, John H

2003-04-01

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the interactions between the sulfur pi-orbitals of arene dithiolates and high-valent transition metals as minimum molecular models of the active site features of pyranopterin MoW enzymes. The compounds (Tp*)MoO(bdt) (compound 1), Cp(2)Mo(bdt) (compound 2), and Cp(2)Ti(bdt) (compound 3) [where Tp* is hydrotris(3,5-dimethyl-1-pyrazolyl)borate, bdt is 1,2-benzenedithiolate, and Cp is eta(5)- cyclopentadienyl] provide access to three different electronic configurations of the metal, formally d(1), d(2), and d(0), respectively. The gas-phase photoelectron spectra show that ionizations from occupied metal and sulfur based valence orbitals are more clearly observed in compounds 2 and 3 than in compound 1. The observed ionization energies and characters compare very well with those calculated by density functional theory. A "dithiolate-folding-effect" involving an interaction of the metal in-plane and sulfur-pi orbitals is proposed to be a factor in the electron transfer reactions that regenerate the active sites of molybdenum and tungsten enzymes.

A strategy to rotate the Mars Observer orbit node line to advance the mapping schedule

NASA Technical Reports Server (NTRS)

Pernicka, Henry J.; Sweetser, Theodore H.; Roncoli, Ralph B.

1993-01-01

The Mars Observer (MO) spacecraft was successfully launched on September 25, 1992 and will arrive at Mars on August 24, 1993. At Mars, the spacecraft will study the planet's surface, atmosphere, and gravitational and magnetic fields. In order to achieve these scientific objectives, MO will be placed in a 2 PM (descending node) sun-synchronous orbit. Upon arrival at Mars, however, the longitude of the descending node will be approximately 15 deg greater than the desired value. The baseline plan requires a 59 day `waiting' period for the correct solar orientation to occur. During this period, 28 days are required for scientific experimentation but the remaining 30.6 days potentially could be eliminated. The strategy developed in this study examined the possibility of using any `excess' Delta-V available at Mars arrival to rotate the node line to the desired value and thus allow mapping to begin earlier. A preliminary analysis completed prior to launch is described that examined the entire launch period including the required Delta-V to perform the needed nodal rotation. A more detailed study performed after launch is also summarized.

Chevrel-phase solid solution Mo 6Se 8- xTe x. Study of its superconducting, magnetic and NMR properties

NASA Astrophysics Data System (ADS)

Hamard1a, C.; Auffret, V.; Peña, O.; Le Floch, M.; Nowak, B.; Wojakowski, A.

2000-09-01

The Chevrel-phase solid solution Mo 6Se 8-Mo 6Te 8 was studied by X-ray diffraction, AC and DC magnetic susceptibility and 77Se and 125Te NMR spectroscopy. From the smooth evolution of the lattice parameters and superconducting critical temperatures, a progressive substitution of selenium atoms by tellurium is shown, on the whole range of composition 0⩽ x⩽8, in the formulation Mo 6Se 8- xTe x: the unit-cell volume increases linearly because of the larger ionic size of tellurium, while Tc decreases rapidly (from 6.45 down to 0 K) because of the different formal oxidation states of the anions and a probable evolution of the Fermi level in the density of states. Results of magnetic susceptibility support this model and suggest the inhibition of the intrinsic metallic behavior with increasing x. The NMR spectra of the binaries Mo 6Se 8 and Mo 6Te 8 reveal two significant features, attributed to two different chalcogen positions in the R 3¯ symmetry. At low Se contents in Mo 6Se 8- xTe x ( x=7.5, 7 and 6), selenium first fills the two X(2) sites along the three-fold axis (2c positions), and then it becomes statistically distributed over the general 6f positions, leading to broad 77Se NMR lines. On the other hand, substitution of Te atoms in Mo 6Se 8 seems to occur in a random way, creating large perturbations on the 125Te NMR spectra, over the whole range of x. Theoretical analysis based on the presence of two anisotropic lines (of axial and non-axial symmetries, respectively) allowed us to estimate their anisotropy factors and to perfectly simulate the frequency response of both Mo 6Se 8 and Mo 6Te 8 binaries. Analysis of the Knight shift anisotropy leads us to conclude about the importance of the molybdenum z 2 molecular orbital contribution which controls the Mo-X dipolar interactions.

Magnetic and electronic properties of La3 MO7 and possible polaron formation in hole-doped La3 MO7 (M  =  Ru and Os)

NASA Astrophysics Data System (ADS)

Gao, Bin; Weng, Yakui; Zhang, Jun-Jie; Zhang, Huimin; Zhang, Yang; Dong, Shuai

2017-03-01

Oxides with 4d/5d transition metal ions are physically interesting for their particular crystalline structures as well as the spin-orbit coupled electronic structures. Recent experiments revealed a series of 4d/5d transition metal oxides R 3 MO7 (R: rare earth; M: 4d/5d transition metal) with unique quasi-one-dimensional M chains. Here first-principles calculations have been performed to study the electronic structures of La3OsO7 and La3RuO7. Our study confirm both of them to be Mott insulating antiferromagnets with identical magnetic order. The reduced magnetic moments, which are much smaller than the expected value for ideal high-spin state (3 t 2g orbitals occupied), are attributed to the strong p  -  d hybridization with oxygen ions, instead of the spin-orbit coupling. The Ca-doping to La3OsO7 and La3RuO7 can not only modulate the nominal carrier density but also affect the orbital order as well as the local distortions. The Coulombic attraction and particular orbital order would prefer to form polarons, which might explain the puzzling insulating behavior of doped 5d transition metal oxides. In addition, our calculations predict that the Ca-doping can trigger ferromagnetism in La3RuO7 but not in La3OsO7.

Spin-resolved photoemission study of epitaxially grown MoSe 2 and WSe 2 thin films

DOE PAGES

Mo, Sung-Kwan; Hwang, Choongyu; Zhang, Yi; ...

2016-09-12

Few-layer thick MoSe 2 and WSe 2 possess non-trivial spin textures with sizable spin splitting due to the inversion symmetry breaking embedded in the crystal structure and strong spin–orbit coupling. Here, we report a spin-resolved photoemission study of MoSe 2 and WSe 2 thin film samples epitaxially grown on a bilayer graphene substrate. Furthermore, we only found spin polarization in the single- and trilayer samples—not in the bilayer sample—mostly along the out-of-plane direction of the sample surface. The measured spin polarization is found to be strongly dependent on the light polarization as well as the measurement geometry, which reveals intricatemore » coupling between the spin and orbital degrees of freedom in this class of material.« less

Strong electron-hole symmetric Rashba spin-orbit coupling in graphene/monolayer transition metal dichalcogenide heterostructures

NASA Astrophysics Data System (ADS)

Yang, Bowen; Lohmann, Mark; Barroso, David; Liao, Ingrid; Lin, Zhisheng; Liu, Yawen; Bartels, Ludwig; Watanabe, Kenji; Taniguchi, Takashi; Shi, Jing

2017-07-01

Despite its extremely weak intrinsic spin-orbit coupling (SOC), graphene has been shown to acquire considerable SOC by proximity coupling with exfoliated transition metal dichalcogenides (TMDs). Here we demonstrate strong induced Rashba SOC in graphene that is proximity coupled to a monolayer TMD film, Mo S2 or WS e2 , grown by chemical-vapor deposition with drastically different Fermi level positions. Graphene/TMD heterostructures are fabricated with a pickup-transfer technique utilizing hexagonal boron nitride, which serves as a flat template to promote intimate contact and therefore a strong interfacial interaction between TMD and graphene as evidenced by quenching of the TMD photoluminescence. We observe strong induced graphene SOC that manifests itself in a pronounced weak-antilocalization (WAL) effect in the graphene magnetoconductance. The spin-relaxation rate extracted from the WAL analysis varies linearly with the momentum scattering time and is independent of the carrier type. This indicates a dominantly Dyakonov-Perel spin-relaxation mechanism caused by the induced Rashba SOC. Our analysis yields a Rashba SOC energy of ˜1.5 meV in graphene/WS e2 and ˜0.9 meV in graphene/Mo S2 . The nearly electron-hole symmetric nature of the induced Rashba SOC provides a clue to possible underlying SOC mechanisms.

Atomic oxygen interaction with spacecraft materials: Relationship between orbital and ground-based testing for materials certification

NASA Technical Reports Server (NTRS)

Cross, Jon B.; Koontz, Steven L.; Lan, Esther H.

1993-01-01

The effects of atomic oxygen on boron nitride (BN), silicon nitride (Si3N4), Intelsat 6 solar cell interconnects, organic polymers, and MoS2 and WS2 dry lubricant, were studied in Low Earth Orbit (LEO) flight experiments and in a ground based simulation facility. Both the inflight and ground based experiments employed in situ electrical resistance measurements to detect penetration of atomic oxygen through materials and Electron Spectroscopy for Chemical Analysis (ESCA) analysis to measure chemical composition changes. Results are given. The ground based results on the materials studied to date show good qualitative correlation with the LEO flight results, thus validating the simulation fidelity of the ground based facility in terms of reproducing LEO flight results. In addition it was demonstrated that ground based simulation is capable of performing more detailed experiments than orbital exposures can presently perform. This allows the development of a fundamental understanding of the mechanisms involved in the LEO environment degradation of materials.

First-principles studies of chromium line-ordered alloys in a molybdenum disulfide monolayer

NASA Astrophysics Data System (ADS)

Andriambelaza, N. F.; Mapasha, R. E.; Chetty, N.

2017-08-01

Density functional theory calculations have been performed to study the thermodynamic stability, structural and electronic properties of various chromium (Cr) line-ordered alloy configurations in a molybdenum disulfide (MoS2) hexagonal monolayer for band gap engineering. Only the molybdenum (Mo) sites were substituted at each concentration in this study. For comparison purposes, different Cr line-ordered alloy and random alloy configurations were studied and the most thermodynamically stable ones at each concentration were identified. The configurations formed by the nearest neighbor pair of Cr atoms are energetically most favorable. The line-ordered alloys are constantly lower in formation energy than the random alloys at each concentration. An increase in Cr concentration reduces the lattice constant of the MoS2 system following the Vegard’s law. From density of states analysis, we found that the MoS2 band gap is tunable by both the Cr line-ordered alloys and random alloys with the same magnitudes. The reduction of the band gap is mainly due to the hybridization of the Cr 3d and Mo 4d orbitals at the vicinity of the band edges. The band gap engineering and magnitudes (1.65 eV to 0.86 eV) suggest that the Cr alloys in a MoS2 monolayer are good candidates for nanotechnology devices.

The effects of local bond relaxations on the electronic and photocatalysis performances of nonmetal doped 3R-MoS2 based photocatalyst: density functional theory

NASA Astrophysics Data System (ADS)

Chen, Dajin; Lu, Song; Li, Huanhuan; Li, Can; Li, Lei; Gong, Yinyan; Niu, Lengyuan; Liu, Xinjuan; Wang, Tao

2017-03-01

To investigate the effects of local bond relaxations on the electronic and photocatalysis performances of MoS2 photocatalyst, the thermodynamic, electronic and optical performances of nonmetal doped 3R-MoS2 have been calculated using density functional theory. Results shown that the positive or negative charges of impurity ions are decided by the Pauling electronegativity differences between Mo (or S) and nonmetal atoms, the H, B, Si, Cl, Br and I ions priority to occupy the interstitial site and the other ones tend to occupy the substitutional site. The localized electrons around NM ions are caused by the relaxed Mo-NM and S1-NM bonds, which can effectively affect the electronic and photocatalytic performances of specimens. The optical performances have been altered by the slightest changes of band gap and the newly formed impurity levels; the active sites have been also changed based on the different distributions of the highest occupied molecular orbital and the lowest unoccupied molecular orbital. In brief, the B, N, F, Si, P, Cl, As, Se, Te and Br ions contribute to the separation of photogenerated e-/h+ pairs and enhance the photocatalysis efficiency, but the H, C, O, and I ions will become the recombination centers of photogenerated e-/h+ pairs and should be avoided adding into 3R-MoS2.

Core molecule dependence of energy migration in phenylacetylene nanostar dendrimers: Ab initio molecular orbital-configuration interaction based quantum master equation study

NASA Astrophysics Data System (ADS)

Kishi, Ryohei; Minami, Takuya; Fukui, Hitoshi; Takahashi, Hideaki; Nakano, Masayoshi

2008-06-01

The core molecule dependence of energy (exciton) migration in phenylacetylene nanostar dendrimers is investigated using the ab initio molecular orbital (MO)-configuration interaction based quantum master equation approach. We examine three kinds of core molecular species, i.e., benzene, anthracene, and pentacene, with different highest occupied MO-lowest unoccupied MO (HOMO-LUMO) gaps, which lead to different orbital interactions between the dendron parts and the core molecule. The nanostars bearing anthracene and pentacene cores are characterized by multistep exciton states with spatially well-segmented distributions: The exciton distributions of high-lying exciton states are spatially localized well in the periphery region, whereas those of low-lying exciton states are done in the core region. On the other hand, for the nanostar bearing benzene core, which also has multistep exciton states, the spatial exciton distributions of low-lying exciton states are delocalized over the dendron and the core regions. It is found that the former nanostars exhibit nearly complete exciton migration from the periphery to the core molecule in contrast to the latter one, in which significant exciton distribution remains in the dendron parts attached to the core after the exciton relaxation, although all these dendrimers exhibit fast exciton relaxation from the initially populated states. It is predicted from the analysis based on the MO correlation diagrams and the relative relaxation factor that the complete exciton migration to the core occurs not only when the HOMO-LUMO gap of the core molecule is nearly equal to that of the dendron parts attached to the core (anthracene case) but also when fairly smaller than that (pentacene case), whereas the complete migration is not achieved when the HOMO-LUMO gap of the core is larger than that of the dendron parts (benzene case). These results suggest that the fast and complete exciton migration of real dendrimers could be realized by adjusting the HOMO-LUMO gap of the core molecule to be smaller than that of dendron parts, although there exist more complicated relaxation processes as compared to simple dendritic aggregate models studied so far.

Vibrational modes in thymine molecule from an ab initio MO calculation

NASA Astrophysics Data System (ADS)

Aida, Misako; Kaneko, Motohisa; Dupuis, Michel; Ueda, Toyotoshi; Ushizawa, Koichi; Ito, Gen; Kumakura, Akiko; Tsuboi, Masamichi

1997-03-01

Ab initio self-consistent field molecular orbital (SCF MO) calculations have been made of the thymine molecule for the equilibrium geometry, harmonic force constants, vibrational frequencies, vibrational modes, infrared intensities, and Raman intensities. The results have been correlated with the observed Raman and infrared spectra of thymine crystalline powder.

Computational predictions of stereochemistry in asymmetric thiazolium- and triazolium-catalyzed benzoin condensations.

PubMed

Dudding, Travis; Houk, Kendall N

2004-04-20

The catalytic asymmetric thiazolium- and triazolium-catalyzed benzoin condensations of aldehydes and ketones were studied with computational methods. Transition-state geometries were optimized by using Morokuma's IMOMO [integrated MO (molecular orbital) + MO method] variation of ONIOM (n-layered integrated molecular orbital method) with a combination of B3LYP/6-31G(d) and AM1 levels of theory, and final transition-state energies were computed with single-point B3LYP/6-31G(d) calculations. Correlations between experiment and theory were found, and the origins of stereoselection were identified. Thiazolium catalysts were predicted to be less selective then triazolium catalysts, a trend also found experimentally.

Investigation of metal–dithiolate fold angle effects: Implications for molybdenum and tungsten enzymes

PubMed Central

Joshi, Hemant K.; Cooney, J. Jon A.; Inscore, Frank E.; Gruhn, Nadine E.; Lichtenberger, Dennis L.; Enemark, John H.

2003-01-01

Gas-phase photoelectron spectroscopy and density functional theory have been used to investigate the interactions between the sulfur π-orbitals of arene dithiolates and high-valent transition metals as minimum molecular models of the active site features of pyranopterin Mo/W enzymes. The compounds (Tp*)MoO(bdt) (compound 1), Cp2Mo(bdt) (compound 2), and Cp2Ti(bdt) (compound 3) [where Tp* is hydrotris(3,5-dimethyl-1-pyrazolyl)borate, bdt is 1,2-benzenedithiolate, and Cp is η5- cyclopentadienyl] provide access to three different electronic configurations of the metal, formally d1, d2, and d0, respectively. The gas-phase photoelectron spectra show that ionizations from occupied metal and sulfur based valence orbitals are more clearly observed in compounds 2 and 3 than in compound 1. The observed ionization energies and characters compare very well with those calculated by density functional theory. A “dithiolate-folding-effect” involving an interaction of the metal in-plane and sulfur-π orbitals is proposed to be a factor in the electron transfer reactions that regenerate the active sites of molybdenum and tungsten enzymes. PMID:12655066

Monte Carlo simulations on atropisomerism of thienotriazolodiazepines applicable to slow transition phenomena using potential energy surfaces by ab initio molecular orbital calculations.

PubMed

Morikami, Kenji; Itezono, Yoshiko; Nishimoto, Masahiro; Ohta, Masateru

2014-01-01

Compounds with a medium-sized flexible ring often show atropisomerism that is caused by the high-energy barriers between long-lived conformers that can be isolated and often have different biological properties to each other. In this study, the frequency of the transition between the two stable conformers, aS and aR, of thienotriazolodiazepine compounds with flexible 7-membered rings was estimated computationally by Monte Carlo (MC) simulations and validated experimentally by NMR experiments. To estimate the energy barriers for transitions as precisely as possible, the potential energy (PE) surfaces used in the MC simulations were calculated by molecular orbital (MO) methods. To accomplish the MC simulations with the MO-based PE surfaces in a practical central processing unit (CPU) time, the MO-based PE of each conformer was pre-calculated and stored before the MC simulations, and then only referred to during the MC simulations. The activation energies for transitions calculated by the MC simulations agreed well with the experimental ΔG determined by the NMR experiments. The analysis of the transition trajectories of the MC simulations revealed that the transition occurred not only through the transition states, but also through many different transition paths. Our computational methods gave us quantitative estimates of atropisomerism of the thienotriazolodiazepine compounds in a practical period of time, and the method could be applicable for other slow-dynamics phenomena that cannot be investigated by other atomistic simulations.

A first-principles study of impurity effects on monolayer MoS2: bandgap dominated by donor impurities

NASA Astrophysics Data System (ADS)

Zhang, Hua; Zhou, Wenzhe; Yang, Zhixiong; Wu, Shoujian; Ouyang, Fangping; Xu, Hui

2017-12-01

Based on the first principles calculation, the electrical properties and optical properties of monolayer molybdenum disulfide (MoS2) substitutionally doped by the VB and VIIB transition metal atoms (V, Nb, Ta, Mn, Tc, Re) were investigated. It is found that n-type doping or p-type doping tunes the Fermi level into the conduction band or the valence band respectively, leading to the degenerate semiconductor, while the compensatorily doped systems where the number of valence electrons is not alerted remain direct band gap ranging from 0.958 eV to 1.414 eV. According to the analysis on densities of states, the LUMO orbitals of donor impurities play the crucial role in band gap tuning. Hence, the band gap and optical properties of doped MoS2 are dominated by the species of the donor. Due to the reduction of the band gap, doped MoS2 have a lower threshold energy of photon absorption and an enhanced absorption in near infrared region. These results provide a significant guidance for the design of new 2D optoelectronic materials based on transition metal disulfide.

Poincaré chaos and unpredictable functions

NASA Astrophysics Data System (ADS)

Akhmet, Marat; Fen, Mehmet Onur

2017-07-01

The results of this study are continuation of the research of Poincaré chaos initiated in the papers (M. Akhmet and M.O. Fen, Commun Nonlinear Sci Numer Simulat 40 (2016) 1-5; M. Akhmet and M.O. Fen, Turk J Math, doi:10.3906/mat-1603-51, in press). We focus on the construction of an unpredictable function, continuous on the real axis. As auxiliary results, unpredictable orbits for the symbolic dynamics and the logistic map are obtained. By shaping the unpredictable function as well as Poisson function we have performed the first step in the development of the theory of unpredictable solutions for differential and discrete equations. The results are preliminary ones for deep analysis of chaos existence in differential and hybrid systems. Illustrative examples concerning unpredictable solutions of differential equations are provided.

Relative Stabilities and Reactivities of Isolated Versus Conjugated Alkenes: Reconciliation Via a Molecular Orbital Approach

NASA Astrophysics Data System (ADS)

Sotiriou-Leventis, Chariklia; Hanna, Samir B.; Leventis, Nicholas

1996-04-01

The well-accepted practice of generating a pair of molecular orbitals, one of lower energy and another of higher energy than the original pair of overlapping atomic orbitals, and the concept of a particle in a one-dimensional box are implemented in a simplified, nonmathematical method that explains the relative stabilities and reactivities of alkenes with conjugated versus isolated double bonds. In this method, Huckel-type MO's of higher polyenes are constructed by energy rules of linear combination of atomic orbitals. One additional rule is obeyed: bonding molecular orbitals overlap only with bonding molecular orbitals, and antibonding molecular orbitals overlap only with antibonding molecular orbitals.

Computational predictions of stereochemistry in asymmetric thiazolium- and triazolium-catalyzed benzoin condensations

PubMed Central

Dudding, Travis; Houk, Kendall N.

2004-01-01

The catalytic asymmetric thiazolium- and triazolium-catalyzed benzoin condensations of aldehydes and ketones were studied with computational methods. Transition-state geometries were optimized by using Morokuma's IMOMO [integrated MO (molecular orbital) + MO method] variation of ONIOM (n-layered integrated molecular orbital method) with a combination of B3LYP/6–31G(d) and AM1 levels of theory, and final transition-state energies were computed with single-point B3LYP/6–31G(d) calculations. Correlations between experiment and theory were found, and the origins of stereoselection were identified. Thiazolium catalysts were predicted to be less selective then triazolium catalysts, a trend also found experimentally. PMID:15079058

Electronic transitions and band offsets in C60:SubPc and C60:MgPc on MoO3 studied by modulated surface photovoltage spectroscopy

NASA Astrophysics Data System (ADS)

Fengler, S.; Dittrich, Th.; Rusu, M.

2015-07-01

Electronic transitions at interfaces between MoO3 layers and organic layers of C60, SubPc, MgPc, and nano-composite layers of SubPc:C60 and MgPc:C60 have been studied by modulated surface photovoltage (SPV) spectroscopy. For all systems, time dependent and modulated SPV signals pointed to dissociation of excitons at the MoO3/organic layer interfaces with a separation of holes towards MoO3. The highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps (EHL) of C60, SubPc, and MgPc and the effective EHL of SubPc:C60 and MgPc:C60 were measured. The offsets between the LUMO (ΔEL) or HOMO (ΔEH) bands were obtained with high precision and amounted to 0.33 or 0.73 eV for SubPc:C60, respectively, and to -0.33 or 0.67 eV for MgPc:C60, respectively. Exponential tails below EHL and most pronounced sub-bandgap transitions were characterized and ascribed to disorder and transitions from HOMO bands to unoccupied defect states.

Embryonal rhabdomyosarcoma in the maxillary sinus with orbital involvement in a pediatric patient: Case report

PubMed Central

de Melo, Ana Carolina Rodrigues; Lyra, Tácio Candeia; Ribeiro, Isabella Lima Arrais; da Paz, Alexandre Rolim; Bonan, Paulo Rogério Ferreti; de Castro, Ricardo Dias; Valença, Ana Maria Gondim

2017-01-01

This report presents a case of embryonal rhabdomyosarcoma (eRMS) located in the left maxillary sinus and invading the orbital cavity in a ten-year-old male patient who was treated at a referral hospital. The images provided from the computed tomography showed a heterogeneous mass with soft-tissue density, occupying part of the left half of the face inside the maxillary sinus, and infiltrating and destroying the bone structure of the maxillary sinus, left orbit, ethmoidal cells, nasal cavity, and sphenoid sinus. An analysis of the histological sections revealed an undifferentiated malignant neoplasm infiltrating the skeletal muscle tissue. The immunohistochemical analysis was positive for the antigens: MyoD1, myogenin, desmin, and Ki67 (100% positivity in neoplastic cells), allowing the identification of the tumour as an eRMS. The treatment protocol included initial chemotherapy followed by radiotherapy and finally surgery. The total time of the treatment was nine months, and in 18-mo of follow-up period did not show no local recurrences and a lack of visual impairment. PMID:29291204

Trends in MODIS Geolocation Error Analysis

NASA Technical Reports Server (NTRS)

Wolfe, R. E.; Nishihama, Masahiro

2009-01-01

Data from the two MODIS instruments have been accurately geolocated (Earth located) to enable retrieval of global geophysical parameters. The authors describe the approach used to geolocate with sub-pixel accuracy over nine years of data from M0DIS on NASA's E0S Terra spacecraft and seven years of data from MODIS on the Aqua spacecraft. The approach uses a geometric model of the MODIS instruments, accurate navigation (orbit and attitude) data and an accurate Earth terrain model to compute the location of each MODIS pixel. The error analysis approach automatically matches MODIS imagery with a global set of over 1,000 ground control points from the finer-resolution Landsat satellite to measure static biases and trends in the MO0lS geometric model parameters. Both within orbit and yearly thermally induced cyclic variations in the pointing have been found as well as a general long-term trend.

In-plane current-driven spin-orbit torque switching in perpendicularly magnetized films with enhanced thermal tolerance

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

Wu, Di; Department of Optical Science and Engineering, Key Laboratory of Micro and Nano Photonic Structures; Yu, Guoqiang, E-mail: guoqiangyu@ucla.edu

2016-05-23

We study spin-orbit-torque (SOT)-driven magnetization switching in perpendicularly magnetized Ta/Mo/Co{sub 40}Fe{sub 40}B{sub 20} (CoFeB)/MgO films. The thermal tolerance of the perpendicular magnetic anisotropy (PMA) is enhanced, and the films sustain the PMA at annealing temperatures of up to 430 °C, due to the ultra-thin Mo layer inserted between the Ta and CoFeB layers. More importantly, the Mo insertion layer also allows for the transmission of the spin current generated in the Ta layer due to spin Hall effect, which generates a damping-like SOT and is able to switch the perpendicular magnetization. When the Ta layer is replaced by a Pt layer,more » i.e., in a Pt/Mo/CoFeB/MgO multilayer, the direction of the SOT-induced damping-like effective field becomes opposite because of the opposite sign of spin Hall angle in Pt, which indicates that the SOT-driven switching is dominated by the spin current generated in the Ta or Pt layer rather than the Mo layer. Quantitative characterization through harmonic measurements reveals that the large SOT effective field is preserved for high annealing temperatures. This work provides a route to applying SOT in devices requiring high temperature processing steps during the back-end-of-line processes.« less

Sulfur K-edge XAS of WV=O vs. MoV=O Bis(dithiolene) Complexes: Contributions of Relativistic Effects to Electronic Structure and Reactivity of Tungsten Enzymes†

PubMed Central

Tenderholt, Adam L.; Szilagyi, Robert K.; Holm, Richard H.; Hodgson, Keith O.; Hedman, Britt; Solomon, Edward I.

2009-01-01

Molybdenum- or tungsten-containing enzymes catalyze oxygen atom transfer reactions involved in carbon, sulfur, or nitrogen metabolism. It has been observed that reduction potentials and oxygen atom transfer rates are different for W relative to Mo enzymes and the isostructural Mo/W complexes. Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations on [MoVO(bdt)2]− and [WVO(bdt)2]−, where bdt = benzene-1,2-dithiolate(2−), have been used to determine that the energies of the half-filled redox-active orbital, and thus the reduction potentials and M=O bond strengths, are different for these complexes due to relativistic effects in the W sites. PMID:17720249

Magic Clusters of MoS2 by Edge S2 Interdimer Spacing Modulation.

PubMed

Ryou, Junga; Kim, Yong-Sung

2018-05-17

Edge atomic and electronic structures of S-saturated Mo-edge triangular MoS 2 nanoclusters are investigated using density functional theory calculations. The edge electrons described by the S 2 -p x p x π* (S 2 -Π x ) and Mo-d xy orbitals are found to interplay to pin the S 2 -Π x Fermi wavenumber at k F = 2/5 as the nanocluster size increases, and correspondingly, the ×5 Peierls edge S 2 interdimer spacing modulation is induced. For the particular sizes of N = 5 n - 2 and 5 n, where N is the number of Mo atoms at one edge representing the nanocluster size and n is a positive integer, the effective ×5 interdimer spacing modulation stabilizes the nanoclusters, which are identified here to be the magic S-saturated Mo-edge triangular MoS 2 nanoclusters. With the S 2 -Π x Peierls gap, the MoS 2 nanoclusters become far-edge S 2 -Π x semiconducting and subedge Mo-d xy metallic as N → ∞.

The Synergistic Effects of MoS2 and Liquid Lubrication

NASA Astrophysics Data System (ADS)

Buttery, M.; Roberts, E.; Stanley, S.; Murer, J.

2015-09-01

We present an overview of a three-stage program on the potential for hybrid lubrication of MoS2 and PFPE fluids (Fomblin Z25 & Braycote 601EF) performed at the European Space Tribology Laboratory (ESTL).Tests were performed using a spiral orbit tribometer (SOT) and a pin-on-disc tribometer (POD), demonstrating encouraging results. Hybrid lubrication allows for extended periods of in-air running of MoS2 with no detrimental effect to the subsequent in-vacuum lifetime. In addition, hybrid lubrication was shown to be synergistic, with the lifetime of the hybrid fluid/MoS2 lubrication extended in comparison to the individual constituents, with no detriment to the friction.

Research Update: Spin transfer torques in permalloy on monolayer MoS 2

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

Zhang, Wei; Sklenar, Joseph; Hsu, Bo

2016-03-01

We observe current induced spin transfer torque resonance in permalloy (Py) grown on monolayer MoS2. By passing rf current through the Py/MoS2 bilayer, field-like and damping-like torques are induced which excite the ferromagnetic resonance of Py. The signals are detected via a homodyne voltage from anisotropic magnetoresistance of Py. In comparison to other bilayer systems with strong spin-orbit torques, the monolayer MoS2 cannot provide bulk spin Hall effects and thus indicates the purely interfacial nature of the spin transfer torques. Therefore our results indicate the potential of two-dimensional transition-metal dichalcogenide for the use of interfacial spin-orbitronics applications.

Research update: Spin transfer torques in permalloy on monolayer MoS 2

DOE PAGES

Zhang, Wei; Sklenar, Joseph; Hsu, Bo; ...

2016-03-03

We observe current induced spin transfertorque resonance in permalloy (Py) grown on monolayer MoS 2. By passing rf current through the Py/MoS 2 bilayer, field-like and damping-like torques are induced which excite the ferromagnetic resonance of Py. The signals are detected via a homodyne voltage from anisotropic magnetoresistance of Py. In comparison to other bilayer systems with strong spin-orbit torques, the monolayer MoS 2 cannot provide bulk spin Hall effects and thus indicates the purely interfacial nature of the spin transfer torques. Furthermore, our results indicate the potential of two-dimensional transition-metal dichalcogenide for the use of interfacial spin-orbitronics applications.

Behaviour of DFT-based approaches to the spin-orbit term of zero-field splitting tensors: a case study of metallocomplexes, MIII(acac)3 (M = V, Cr, Mn, Fe and Mo).

PubMed

Sugisaki, Kenji; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Takui, Takeji

2017-11-15

Spin-orbit contributions to the zero-field splitting (ZFS) tensor (D SO tensor) of M III (acac) 3 complexes (M = V, Cr, Mn, Fe and Mo; acac = acetylacetonate anion) are evaluated by means of ab initio (a hybrid CASSCF/MRMP2) and DFT (Pederson-Khanna (PK) and natural orbital-based Pederson-Khanna (NOB-PK)) methods, focusing on the behaviour of DFT-based approaches to the D SO tensors against the valence d-electron configurations of the transition metal ions in octahedral coordination. Both the DFT-based approaches reproduce trends in the D tensors. Significantly, the differences between the theoretical and experimental D (D = D ZZ - (D XX + D YY )/2) values are smaller in NOB-PK than in PK, emphasising the usefulness of the natural orbital-based approach to the D tensor calculations of transition metal ion complexes. In the case of d 2 and d 4 electronic configurations, the D SO (NOB-PK) values are considerably underestimated in the absolute magnitude, compared with the experimental ones. The D SO tensor analysis based on the orbital region partitioning technique (ORPT) revealed that the D SO contributions attributed to excitations from the singly occupied region (SOR) to the unoccupied region (UOR) are significantly underestimated in the DFT-based approaches to all the complexes under study. In the case of d 3 and d 5 configurations, the (SOR → UOR) excitations contribute in a nearly isotropic manner, which causes fortuitous error cancellations in the DFT-based D SO values. These results indicate that more efforts to develop DFT frameworks should be directed towards the reproduction of quantitative D SO tensors of transition metal complexes with various electronic configurations and local symmetries around metal ions.

Isolation, characterization, and computational studies of the novel [Mo3(mu3-Br)2(mu-Br)3Br6]2- cluster anion.

PubMed

Paraskevopoulou, Patrina; Makedonas, Christodoulos; Psaroudakis, Nikolaos; Mitsopoulou, Christiana A; Floros, Georgios; Seressioti, Andriana; Ioannou, Marinos; Sanakis, Yiannis; Rath, Nigam; Gómez García, Carlos J; Stavropoulos, Pericles; Mertis, Konstantinos

2010-03-01

The novel trimolybdenum cluster [Mo(3)(mu(3)-Br)(2)(mu-Br)(3)Br(6)](2-) (1, {Mo(3)}(9+), 9 d-electrons) has been isolated from the reaction of [Mo(CO)(6)] with 1,2-C(2)H(4)Br(2) in refluxing PhCl. The compound has been characterized in solution by electrospray ionization mass spectrometry (ESI-MS), UV-vis spectroscopy, cyclic voltammetry, and in the solid state by X-ray analysis (counter-cations: (n-Bu)(4)N(+) (1), Et(4)N(+), Et(3)BzN(+)), electron paramagnetic resonance (EPR), magnetic susceptibility measurements, and infrared spectroscopy. The least disordered (n-Bu)(4)N(+) salt crystallizes in the monoclinic space group C2/c, a = 20.077(2) A, b = 11.8638(11) A, c = 22.521(2) A, alpha = 90 deg, beta = 109.348(4) deg, gamma = 90 deg, V = 5061.3(9) A(3), Z = 4 and contains an isosceles triangular metal arrangement, which is capped by two bromine ligands. Each edge of the triangle is bridged by bromine ions. The structure is completed by six terminal bromine ligands. According to the magnetic measurements and the EPR spectrum the trimetallic core possesses one unpaired electron. Electrochemical data show that oxidation by one electron of 1 is reversible, thus proceeding with retention of the trimetallic core, while the reduction is irreversible. The effective magnetic moment of 1 (mu(eff), 1.55 mu(B), r.t.) is lower than the spin-only value (1.73 mu(B)) for S = 1/2 systems, most likely because of high spin-orbit coupling of Mo(III) and/or magnetic coupling throughout the lattice. The ground electronic state of 1 was studied using density functional theory techniques under the broken symmetry formalism. The ground state is predicted to exhibit strong antiferromagnetic coupling between the three molybdenum atoms of the core. Moreover, our calculated data predict two broken symmetry states that differ only by 0.4 kcal/mol (121 cm(-1)). The antiferromagnetic character is delocalized over three magnetic orbitals populated by three electrons. The assignment of the infrared spectra is also provided.

Identifying the Unique Properties of α-Bi 2Mo 3O 12 for the Activation of Propene

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

Licht, Rachel B.; Getsoian, Andrew; Bell, Alexis T.

In order to understand the remarkable activity of α-Bi 2Mo 3O 12 for selective oxidation and ammoxidation of propene, the propene activation ability of four molybdenum-based mixed metal oxides - Bi 2Mo 3O 12, PbMoO 4, Bi 2Pb 5Mo 8O 32, and MoO 3 - was investigated using density functional theory. Propene activation is considered to occur via abstraction of a hydrogen atom from the methyl group of physisorbed propene by lattice oxygen. For each material, the apparent activation energy was estimated by summing the heat of adsorption of propene, the C-H bond dissociation energy, and the hydrogen attachment energymore » (HAE) for hydrogen addition to lattice oxygen; this sum provides a lower bound for the apparent activation energy. It was found that two structural features of oxide surfaces are essential to achieve low activation barriers: under-coordinated surface cation sites enable strong propene adsorption, and suitable 5- or 6-coordinate geometries at molybdenum result in favorable HAEs. The impact of molybdenum coordination on HAE was elucidated by carrying out a molecular orbital analysis using a cluster model of the molybdate unit. This effort revealed that, in 5- and 6-coordinate molybdates, oxygen donor atoms trans to molybdenyl oxo atoms destabilize the molybdate prior to H addition but stabilize the molybdate after H addition, thereby providing an HAE ~15 kcal/mol more favorable than that on 4-coordinate molybdate oxo atoms. Bi 3+ cations in Bi 2Mo 3O 12 thus promote catalytic activity by providing both strong adsorption sites for propene and forcing molybdate into 5-coordinate geometries that lead to particularly favorable values of the HAE. (Graph Presented).« less

Identifying the Unique Properties of α-Bi 2Mo 3O 12 for the Activation of Propene

DOE PAGES

Licht, Rachel B.; Getsoian, Andrew; Bell, Alexis T.

2016-12-30

In order to understand the remarkable activity of α-Bi 2Mo 3O 12 for selective oxidation and ammoxidation of propene, the propene activation ability of four molybdenum-based mixed metal oxides - Bi 2Mo 3O 12, PbMoO 4, Bi 2Pb 5Mo 8O 32, and MoO 3 - was investigated using density functional theory. Propene activation is considered to occur via abstraction of a hydrogen atom from the methyl group of physisorbed propene by lattice oxygen. For each material, the apparent activation energy was estimated by summing the heat of adsorption of propene, the C-H bond dissociation energy, and the hydrogen attachment energymore » (HAE) for hydrogen addition to lattice oxygen; this sum provides a lower bound for the apparent activation energy. It was found that two structural features of oxide surfaces are essential to achieve low activation barriers: under-coordinated surface cation sites enable strong propene adsorption, and suitable 5- or 6-coordinate geometries at molybdenum result in favorable HAEs. The impact of molybdenum coordination on HAE was elucidated by carrying out a molecular orbital analysis using a cluster model of the molybdate unit. This effort revealed that, in 5- and 6-coordinate molybdates, oxygen donor atoms trans to molybdenyl oxo atoms destabilize the molybdate prior to H addition but stabilize the molybdate after H addition, thereby providing an HAE ~15 kcal/mol more favorable than that on 4-coordinate molybdate oxo atoms. Bi 3+ cations in Bi 2Mo 3O 12 thus promote catalytic activity by providing both strong adsorption sites for propene and forcing molybdate into 5-coordinate geometries that lead to particularly favorable values of the HAE. (Graph Presented).« less

Photoreflectance study of the near-band-edge transitions of chemical vapor deposition-grown mono- and few-layer MoS{sub 2} films

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

Lin, Kuang-I, E-mail: kilin@mail.ncku.edu.tw; Chen, Yen-Jen; Wang, Bo-Yan

2016-03-21

Room-temperature photoreflectance (PR) and reflectance (R) spectroscopy are utilized to investigate the near-band-edge transitions of molybdenum disulfide (MoS{sub 2}) thin films grown on sapphire substrates by a hot-wall chemical vapor deposition system. The layer thickness and optical properties of the MoS{sub 2} thin films are confirmed by Raman spectroscopy, atomic force microscope, and photoluminescence (PL) analysis. The B exciton shows relatively weak PL intensity in comparing with the A exciton even for monolayer MoS{sub 2} films. In the R spectrum of few‐layer MoS{sub 2}, it is not possible to clearly observe exciton related features. The PR spectra have two sharp,more » derivative-like features on a featureless background. Throughout the PR lineshape fitting, the transition energies are designated as the A and B excitons at the K-point of the Brillouin zone, but at room temperature there seems to be no distinguishable feature corresponding to an H‐point transition for the mono- and few-layer MoS{sub 2} films unlike in bulk. These transition energies are slightly larger than those obtained by PL, which is attributed to the Stokes shifts related to doping level. The obtained values of valence-band spin-orbit splitting are in good agreement with those from other experimental methods. By comparing the PR lineshapes, the dominant modulation mechanism is attributed to variations of the exciton transition energies due to change in the built-in electric field. On the strength of this study, PR spectroscopy is demonstrated as a powerful technique for characterizing the near-band-edge transitions of MoS{sub 2} from monolayer to bulk.« less

Magnetic anisotropy of [Mo(CN)7]4- anions and fragments of cyano-bridged magnetic networks.

PubMed

Chibotaru, Liviu F; Hendrickx, Marc F A; Clima, Sergiu; Larionova, Joulia; Ceulemans, Arnout

2005-08-18

Quantum chemistry calculations of CASSCF/CASPT2 level together with ligand field analysis are used for the investigation of magnetic anisotropy of [Mo(CN)7]4- complexes. We have considered three types of heptacyano environments: two ideal geometries, a pentagonal bipyramid and a capped trigonal prism, and the heptacyanomolybdate fragment of the cyano-bridged magnetic network K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O. At all geometries the first excited Kramers doublet is found remarkably close to the ground one due to a small orbital energy gap in the ligand field spectrum, which ranges between a maximal value in the capped trigonal prism (800 cm(-1)) and zero in the pentagonal bipyramid. The small value of this gap explains (i) the axial form of the g tensor and (ii) the strong magnetic anisotropy even in strongly distorted complexes. Comparison with available experimental data for the g tensor of the mononuclear precursors reveals good agreement with the present calculations for the capped trigonal prismatic complex and a significant discrepancy for the pentagonal bipyramidal one. The calculations for the heptacyanomolybdate fragment of K2[Mn(H2O)2]3[Mo(CN)7]2.6H2O give g(perpendicular)/g(parallel) approximately 0.5 and the orientation of the local anisotropy axis close to the symmetry axis of an idealized pentagonal bipyramid. These findings are expected to be important for the understanding of the magnetism of anisotropic Mo(III)-Mn(II) cyano-bridged networks based on the [Mo(CN)7]4- building block.

Rashba effect and enriched spin-valley coupling in Ga X /M X2 (M = Mo, W; X = S, Se, Te) heterostructures

NASA Astrophysics Data System (ADS)

Zhang, Qingyun; Schwingenschlögl, Udo

2018-04-01

Using first-principles calculations, we investigate the electronic properties of the two-dimensional Ga X /MX 2 (M = Mo, W; X = S, Se, Te) heterostructures. Orbital hybridization between Ga X and MX 2 is found to result in Rashba splitting at the valence-band edge around the Γ point, which grows for increasing strength of the spin-orbit coupling in the p orbitals of the chalcogenide atoms. The location of the valence-band maximum in the Brillouin zone can be tuned by strain and application of an out-of-plane electric field. The coexistence of Rashba splitting (in-plane spin direction) and band splitting at the K and K' valleys (out-of-plane spin direction) makes Ga X /MX 2 heterostructures interesting for spintronics and valleytronics. They are promising candidates for two-dimensional spin-field-effect transistors and spin-valley Hall effect devices. Our findings shed light on the spin-valley coupling in van der Waals heterostructures.

Size Dependence of S-bonding on (111) Facets of Cu Nanoclusters

DOE PAGES

Boschen, Jeffery S.; Lee, Jiyoung; Windus, Theresa L.; ...

2016-04-21

We demonstrate a strong damped oscillatory size dependence of the adsorption energy for sulfur on the (111) facets of tetrahedral Cu nanoclusters up to sizes of ~300 atoms. This behavior reflects quantum size effects. Consistent results are obtained from density functional theory analyses utilizing either atomic orbital or plane-wave bases and using the same Perdew–Burke–Ernzerhof functional. Behavior is interpreted via molecular orbitals (MO), density of states (DOS), and crystal orbital Hamilton population (COHP) analyses.

Exploring the Nature of the H[subscript 2] Bond. 1. Using Spreadsheet Calculations to Examine the Valence Bond and Molecular Orbital Methods

ERIC Educational Resources Information Center

Halpern, Arthur M.; Glendening, Eric D.

2013-01-01

A three-part project for students in physical chemistry, computational chemistry, or independent study is described in which they explore applications of valence bond (VB) and molecular orbital-configuration interaction (MO-CI) treatments of H[subscript 2]. Using a scientific spreadsheet, students construct potential-energy (PE) curves for several…

Photoelectron spectroscopy of the doubly-charged anions [MIVO(mnt)2]2- (M = Mo, W; mnt = S2C2(CN)2(2-): access to the ground and excited states of the [MVO(mnt)2]- anion.

PubMed

Waters, Tom; Wang, Xue-Bin; Yang, Xin; Zhang, Lianyi; O'Hair, Richard A J; Wang, Lai-Sheng; Wedd, Anthony G

2004-04-28

Photodetachment photoelectron spectroscopy was used to investigate the electronic structure of the doubly charged complexes [MIVO(mnt)2]2- (M = Mo, W; mnt = 1,2-dicyanoethenedithiolato). These dianions are stable in the gas phase and are minimal models for the active sites of the dimethyl sulfoxide reductase family of molybdenum enzymes and of related tungsten enzymes. Adiabatic and vertical electron binding energies for both species were measured, providing detailed information about molecular orbital energy levels of the parent dianions as well as the ground and excited states of the product anions [MVO(mnt)2]-. Density functional theory calculations were used to assist assignment of the detachment features. Differences in energy between these features provided the energies of ligand-to-metal charge-transfer transitions from S(pi) and S(sigma) molecular orbitals to the singly occupied metal-based orbital of the products [MVO(mnt)2]-. These unique data for the M(V) species were obtained at the C(2)(v)() geometry of the parent M(IV) dianions. However, theoretical calculations and available condensed phase data suggested that a geometry featuring differentially folded dithiolene ligands (Cs point symmetry) was slightly lower in energy. The driving force for ligand folding is a favorable covalent interaction between the singly occupied metal-based molecular orbital (a1 in C2v) point symmetry; highest occupied molecular orbital (HOMO)) and the least stable of the occupied sulfur-based molecular orbitals (b1 in C2v point symmetry, HOMO-1) that is only possible upon reduction to the lower symmetry. This ligand folding induces a large increase in the intensity predicted for the a' S(pi) --> a' dx2 - y2 charge-transfer transition originating from the HOMO-2 of [MVO(mnt)2](-) under Cs point symmetry. Electronic absorption spectra are available for the related species [MoVO(bdt)2]- (bdt = 1,2-benzenedithiolato) and for the oxidized form of dimethyl sulfoxide reductase. The intense absorptions at approximately 1.7 eV have been assigned previously to S(sigma) --> Mo transitions, assuming C2v geometry. The present work indicates that the alternative a' S(pi) --> a' dx2 - y2 of Cs geometry must be considered. Overall, this study confirms that the electronic structure of the M-dithiolene units are exquisitely sensitive to dithiolene ligand folding, reinforcing the proposal that these units are tunable conduits for electron transfer in enzyme systems.

Energetics using the single point IMOMO (integrated molecular orbital+molecular orbital) calculations: Choices of computational levels and model system

NASA Astrophysics Data System (ADS)

Svensson, Mats; Humbel, Stéphane; Morokuma, Keiji

1996-09-01

The integrated MO+MO (IMOMO) method, recently proposed for geometry optimization, is tested for accurate single point calculations. The principle idea of the IMOMO method is to reproduce results of a high level MO calculation for a large ``real'' system by dividing it into a small ``model'' system and the rest and applying different levels of MO theory for the two parts. Test examples are the activation barrier of the SN2 reaction of Cl-+alkyl chlorides, the C=C double bond dissociation of olefins and the energy of reaction for epoxidation of benzene. The effects of basis set and method in the lower level calculation as well as the effects of the choice of model system are investigated in detail. The IMOMO method gives an approximation to the high level MO energetics on the real system, in most cases with very small errors, with a small additional cost over the low level calculation. For instance, when the MP2 (Møller-Plesset second-order perturbation) method is used as the lower level method, the IMOMO method reproduces the results of very high level MO method within 2 kcal/mol, with less than 50% of additional computer time, for the first two test examples. When the HF (Hartree-Fock) method is used as the lower level method, it is less accurate and depends more on the choice of model system, though the improvement over the HF energy is still very significant. Thus the IMOMO single point calculation provides a method for obtaining reliable local energetics such as bond energies and activation barriers for a large molecular system.

Extraordinary attributes of 2-dimensional MoS2 nanosheets

NASA Astrophysics Data System (ADS)

Rao, C. N. R.; Maitra, Urmimala; Waghmare, Umesh V.

2014-08-01

The discovery of the amazing properties of graphene has stimulated exploration of single- and few-layer structures of layered inorganic materials. Of all the inorganic 2D nanosheet structures, those of MoS2 have attracted great attention because of their novel properties such as the presence of a direct bandgap, good field-effect transistor characteristics, large spin-orbit splitting, intense photoluminescence, catalytic properties, magnetism, superconductivity, ferroelectricity and several other properties with potential applications in electronics, optoelectronics, energy devices and spintronics. MoS2 nanosheets have been used in lithium batteries, supercapacitors and to generate hydrogen. Highlights of the impressive properties of MoS2 nanosheets, along with their structural and spectroscopic features are presented in this Letter. MoS2 typifies the family of metal dichalcogenides such as MoSe2 and WS2 and there is much to be done on nanosheets of these materials. Linus Pauling would have been pleased to see how molybdenite whose structure he studied in 1923 has become so important today.

Networks consolidation program: Maintenance and Operations (M&O) staffing estimates

NASA Technical Reports Server (NTRS)

Goodwin, J. P.

1981-01-01

The Mark IV-A consolidate deep space and high elliptical Earth orbiter (HEEO) missions tracking and implements centralized control and monitoring at the deep space communications complexes (DSCC). One of the objectives of the network design is to reduce maintenance and operations (M&O) costs. To determine if the system design meets this objective an M&O staffing model for Goldstone was developed which was used to estimate the staffing levels required to support the Mark IV-A configuration. The study was performed for the Goldstone complex and the program office translated these estimates for the overseas complexes to derive the network estimates.

Electronic structure evolution and energy level alignment at C60/4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl) benzenamine]/MoOx/indium tin oxide interfaces

NASA Astrophysics Data System (ADS)

Liu, Xiaoliang; Yi, Shijuan; Wang, Chenggong; Wang, Congcong; Gao, Yongli

2014-04-01

The electronic structure evolution and energy level alignment have been investigated at interfaces comprising fullerene (C60)/4,4'-cyclohexylidenebis[N,N-bis(4-methylphenyl) benzenamine] (TAPC)/ molybdenum oxide (MoOx)/ indium tin oxide with ultraviolet photoemission spectroscopy and inverse photoemission spectroscopy. With deposition of TAPC upon MoOx, a dipole of 1.58 eV was formed at the TAPC/MoOx interface due to electron transfer from TAPC to MoOx. The highest occupied molecular orbital (HOMO) onset of TAPC was pinned closed to the Fermi level, leading to a p-doped region and thus increasing the carrier concentration at the very interface. The downward band bending and the resulting built-in field in TAPC were favorable for the hole transfer toward the TAPC/MoOx interface. The rigid downward shift of energy levels of TAPC indicated no significant interface chemistry at the interface. With subsequent deposition of C60 on TAPC, a dipole of 0.27 eV was observed at the C60/TAPC heterojunction due to the electron transfer from TAPC to C60. This led to a drop of the HOMO of TAPC near the C60/TAPC interface, and hence further enhanced the band bending in TAPC. The band bending behavior was also observed in C60, similarly creating a built-in field in C60 film and improving the electron transfer away from the C60/TAPC interface. It can be deduced from the interface analysis that a promising maximum open circuit voltage of 1.5 eV is achievable in C60/TAPC-based organic photovoltaic cells.

The Mars mapper science and mission planning tool

NASA Technical Reports Server (NTRS)

Lo, Martin W.

1993-01-01

The Mars Mapper Program (MOm) is an interactive tool for science and mission design developed for the Mars Observer Mission (MO). MOm is a function of the Planning and Sequencing Element of the MO Ground Data System. The primary users of MOm are members of the science and mission planning teams. Using MOm, the user can display digital maps of Mars in various projections and resolutions ranging from 1 to 256 pixels per degree squared. The user can overlay the maps with ground tracks of the MO spacecraft (S/C) and footprints and swaths of the various instruments on-board the S/C. Orbital and instrument geometric parameters can be computed on demand and displayed on the digital map or plotted in XY-plots. The parameter data can also be saved into files for other uses. MOm is divided into 3 major processes: Generator, Mapper, Plotter. The Generator Process is the main control which spawns all other processes. The processes communicate via sockets. At any one time, only 1 copy of MOm may operate on the system. However, up to 5 copies of each of the major processes may be invoked from the Generator. MOm is developed on the Sun SPARCStation 2GX with menu driven graphical user interface (GUI). The map window and its overlays are mouse-sensitized to permit on-demand calculations of various parameters along an orbit. The program is currently under testing and will be delivered to the MO Mission System Configuration Management for distribution to the MO community in 3/93.

Noble metal (Pt or Au)-doped monolayer MoS2 as a promising adsorbent and gas-sensing material to SO2, SOF2 and SO2F2: a DFT study

NASA Astrophysics Data System (ADS)

Chen, Dachang; Zhang, Xiaoxing; Tang, Ju; Cui, Hao; Li, Yi

2018-02-01

We explored the adsorption of SO2, SOF2, and SO2F2 on Pt- or Au-doped MoS2 monolayer based on density functional theory. The adsorption energy, adsorption distance, charge transfer as well as density of states were discussed. SO2 and SOF2 exhibit strong chemical interactions with Pt-doped MoS2 based on large adsorption energy, charge transfer, and changes of electron orbitals in gas molecule. SO2 also shows obvious chemisorption on Au-doped MoS2 with apparent magnetism transfer from Au to gas molecules. The adsorption of SO2F2 on Pt-MoS2 and SOF2 on Au-MoS2 exhibits weaker chemical interactions and SO2F2 losses electrons when adsorbed on Pt-MoS2 which is different from other gas adsorption. The adsorption of SO2F2 on Au-MoS2 represents no obvious chemical interaction but physisorption. The gas-sensing properties are also evaluated based on DFT results. This work could provide prospects and application value for typical noble metal-doped MoS2 as gas-sensing materials.

Electronic structure calculations on multiply charged anions containing M bond S bonds (M = Cr, Mo, W) and their heterobimetallic cluster complexes

NASA Astrophysics Data System (ADS)

Gili, Pedro; Tsipis, Athanassios C.

Molecular and electronic structures of multiply charged mononuclear [CrS4]2-/3-, [MoOxS4-x]2-/3- (x = 0-4) and [WS4]2-/3- anionic species, and their heterobimetallic dinuclear and trinuclear clusters formulated as [MoOS3(CuCl)]2-, [WOS3(CuCl)]2-, [MoS4{Cu(CN)}]2-, [(CN)Cu(?-CrS4)Cu(CN)]2-, [(CN)Cu(?-MoS4)Cu(CN)]2-, [ClCu(?-MoS4)CuCl]2-, [Cl2Fe(?-MoS4)CuCl2]2-, and [(CN)Cu(?-WS4)Cu(CN)]2- have been investigated using electronic structure calculation (HF, MP4SDQ and DFT) methods. For the discrete mononuclear anions HF/lanl2dz(M)?6-31+G*(S,O) method provided the best description of their molecular structures, while for the heterobimetallic dinuclear and trinuclear clusters the B3LYP/lanl2dz(M)?6-31+G* method gave equilibrium geometries closely resembling the experimental ones. Electronic and spectroscopic (IR, UV-Vis) properties of the thiometalates are discussed in relation to their structures, while the bonding mechanism was analyzed in the framework of the natural bond orbital (NBO) approach. The nature of the highest occupied molecular orbitals (HOMOs) of all thiometalates indicated their ability to act as ligands coordinated with metal centers and forming clusters of higher nuclearity. The lowest-lying vertical one-electron detachment processes from the ground state of the [CrS4]2/3-, [MoOxS4-x]2/3- (x = 0-4) and [WS4]2/3- anions have been calculated using the outer valence Green's function (OVGF) method. Interestingly, in the heterobimetallic dinuclear and trinuclear clusters intemetallic M?M? interactions exist corresponding to d10 ? d0 dative bonding. Finally, the complete energetic and geometric profile of the successive acid-catalyzed formation reactions:and the reverse hydrolysis reactions have been delineated and details of the mechanism have been furnished.

Lesson learned from FORMOSAT-2 mission operations

NASA Astrophysics Data System (ADS)

Chern, Jeng-Shing; Wu, An-Ming; Lin, Shin-Fa

2006-07-01

The mission operations (MO) of FORMOSAT-2 (formerly called ROCSAT-2) started from 17:47:03 UTC on 20 May 2004 after the satellite had been launch from Vandenberg, California. It took 3 days to check the performance and function of all subsystems of satellite bus, and 11 days to raise the satellite from 723 km parking orbit to 888 km mission orbit. Then the primary payload, a remote sensing instrument (RSI), was turned on and the first image was taken on 4 June 2004. In June and July of 2004, the acceptance criteria verification for bus and RSI was performed using the pre-programmed maneuver and images taken. Started from late June 2004, the secondary payload was turned on. It is an imager for sprites and upper atmospheric lightning (ISUAL). A red sprite was captured on 4 July 2004. This is the first time to observe the upward lightning phenomena between thundercloud and ionoshpere from space. The verification and validation of FORMOSAT-2 satellite including bus and payloads were completed in early August 2004. It follows the normal MO phase. During the 1 year 4 months MO from May 2004 to September 2005, a couple hundreds of anomalies (in both satellite and ground systems) and several automatic reconfiguration orders (AROs) (in satellite system) occurred. Shortly after satellite launch, the number of anomalies increases drastically. Also, the planning and scheduling system (PSS) for the RSI operation is not very efficient, and is not compatible with the very unique and advantageous capability of daily revisit of FORMOSAT-2. Some of the AROs were caused by the improper MO timeline design and results in violating satellite constraint. Almost all problems have been solved or avoided by the MO team of the National Space Organization (NSPO). In June 2005, NSPO organized a working group to review the status of health (SOH). It has been concluded that FORMOSAT-2 is in good condition except there is some shift in its orbit. We have learned many lessons from this practice. It is the purpose of this paper to share our experiences.

The global SMOS Level 3 daily soil moisture and brightness temperature maps

NASA Astrophysics Data System (ADS)

Bitar, Ahmad Al; Mialon, Arnaud; Kerr, Yann H.; Cabot, François; Richaume, Philippe; Jacquette, Elsa; Quesney, Arnaud; Mahmoodi, Ali; Tarot, Stéphane; Parrens, Marie; Al-Yaari, Amen; Pellarin, Thierry; Rodriguez-Fernandez, Nemesio; Wigneron, Jean-Pierre

2017-06-01

The objective of this paper is to present the multi-orbit (MO) surface soil moisture (SM) and angle-binned brightness temperature (TB) products for the SMOS (Soil Moisture and Ocean Salinity) mission based on a new multi-orbit algorithm. The Level 3 algorithm at CATDS (Centre Aval de Traitement des Données SMOS) makes use of MO retrieval to enhance the robustness and quality of SM retrievals. The motivation of the approach is to make use of the longer temporal autocorrelation length of the vegetation optical depth (VOD) compared to the corresponding SM autocorrelation in order to enhance the retrievals when an acquisition occurs at the border of the swath. The retrieval algorithm is implemented in a unique operational processor delivering multiple parameters (e.g. SM and VOD) using multi-angular dual-polarisation TB from MO. A subsidiary angle-binned TB product is provided. In this study the Level 3 TB V310 product is showcased and compared to SMAP (Soil Moisture Active Passive) TB. The Level 3 SM V300 product is compared to the single-orbit (SO) retrievals from the Level 2 SM processor from ESA with aligned configuration. The advantages and drawbacks of the Level 3 SM product (L3SM) are discussed. The comparison is done on a global scale between the two datasets and on the local scale with respect to in situ data from AMMA-CATCH and USDA ARS Watershed networks. The results obtained from the global analysis show that the MO implementation enhances the number of retrievals: up to 9 % over certain areas. The comparison with the in situ data shows that the increase in the number of retrievals does not come with a decrease in quality, but rather at the expense of an increased time lag in product availability from 6 h to 3.5 days, which can be a limiting factor for applications like flood forecast but reasonable for drought monitoring and climate change studies. The SMOS L3 soil moisture and L3 brightness temperature products are delivered using an open licence and free of charge using a web application (https://www.catds.fr/sipad/). The RE04 products, versions 300 and 310, used in this paper are also available at ftp://ext-catds-cpdc:catds2010@ftp.ifremer.fr/Land_products/GRIDDED/L3SM/RE04/.

Destructive quantum interference in electron transport: A reconciliation of the molecular orbital and the atomic orbital perspective

NASA Astrophysics Data System (ADS)

Zhao, Xin; Geskin, Victor; Stadler, Robert

2017-03-01

Destructive quantum interference (DQI) in single molecule electronics is a purely quantum mechanical effect and is entirely defined by the inherent properties of the molecule in the junction such as its structure and symmetry. This definition of DQI by molecular properties alone suggests its relation to other more general concepts in chemistry as well as the possibility of deriving simple models for its understanding and molecular device design. Recently, two such models have gained a wide spread attention, where one was a graphical scheme based on visually inspecting the connectivity of the carbon sites in conjugated π systems in an atomic orbital (AO) basis and the other one puts the emphasis on the amplitudes and signs of the frontier molecular orbitals (MOs). There have been discussions on the range of applicability for these schemes, but ultimately conclusions from topological molecular Hamiltonians should not depend on whether they are drawn from an AO or a MO representation, as long as all the orbitals are taken into account. In this article, we clarify the relation between both models in terms of the zeroth order Green's function and compare their predictions for a variety of systems. From this comparison, we conclude that for a correct description of DQI from a MO perspective, it is necessary to include the contributions from all MOs rather than just those from the frontier orbitals. The cases where DQI effects can be successfully predicted within a frontier orbital approximation we show them to be limited to alternant even-membered hydrocarbons, as a direct consequence of the Coulson-Rushbrooke pairing theorem in quantum chemistry.

Magnetic field dependence of electronic properties of MoS2 quantum dots with different edges

NASA Astrophysics Data System (ADS)

Chen, Qiao; Li, L. L.; Peeters, F. M.

2018-02-01

Using the tight-binding approach, we investigate the energy spectrum of square, triangular, and hexagonal MoS2 quantum dots (QDs) in the presence of a perpendicular magnetic field. Novel edge states emerge in MoS2 QDs, which are distributed over the whole edge which we call ring states. The ring states are robust in the presence of spin-orbit coupling (SOC). The corresponding energy levels of the ring states oscillate as a function of the perpendicular magnetic field which are related to Aharonov-Bohm oscillations. Oscillations in the magnetic field dependence of the energy levels and the peaks in the magneto-optical spectrum emerge (disappear) as the ring states are formed (collapsed). The period and the amplitude of the oscillation decrease with the size of the MoS2 QDs.

Reaction of the Mo3S4 cluster with dimethylacetylenedicarboxylate: an ESR-active cluster and an organometallic cluster formed by alpha,beta-conjugate addition.

PubMed

Ide, Yasuhiro; Shibahara, Takashi

2007-01-22

A seven-electron cluster [Mo3(mu3-S){mu3-SC(CO(2)CH(3))=C(CO(2)CH(3))S}{mu-SC(CO(2)CH(3))=CH(CO(2)CH(3))}(dtp)3(mu-OAc)] [2, S2P(OC(2)H(5))2-; dtp = diethyldithiophosphate] and an organometallic cluster [Mo3(mu3-S){mu3-SC(CO(2)CH(3))=C(CO(2)CH(3))S}{mu-SC(CO(2)CH(3))CH(OCH(3))(CO2)}(dtp)2(CH(3)OH)(mu-OAc)](Mo-C) (3) were obtained by reaction in methanol of the sulfur-bridged trinuclear complex [Mo3(mu3-S)(mu-S)3(dtp)3(CH(3)CN)(mu-OAc)] (1) with dimethylacetylenedicarboxylate (DMAD). The X-ray structures of 2 and 3 revealed the adduct formation of two DMAD molecules to the respective Mo(3)S(4) cores. 2 is paramagnetic and obeys the Curie-Weiss law: the mu(eff) value at 300 K is 1.90 muB. The electron spin resonance signal was observed at 173 K. The density functional theory calculation of 2 demonstrated that the main components of the singly occupied molecular orbitals of alpha and beta spins are Mo d electrons and the main components of lowest unoccupied molecular orbitals are of Mo and the olefin moiety with one C-S bond. A one-electron reversible oxidation process of 2 was observed at E1/2 = -0.11 V vs Fc/Fc+. The electronic spectrum of 2 has a peak at 468 nm (epsilon = 2170 M(-1) cm(-1)) and shoulders at 640 (918) and 797 (605) nm, and 3 has shoulders at 441 (1740) and 578 (625) nm and a distinct peak at 840 (467) nm. An intermediate [Mo3(mu3-S){mu3-SC(CO(2)CH(3))=C(CO(2)CH(3))S}{mu-SC(CO(2)CH(3))=CH(CO(2)CH(3))}(dtp)3(mu-OAc)]+ (4) is tentatively suggested: a one-electron reduction of 4 gives 2, and a nucleophilic conjugate addition of CH(3)O- to the alpha,beta-unsaturated carbonyl group of 4 gives 3.

Dual role of monolayer MoS{sub 2} in enhanced photocatalytic performance of hybrid MoS{sub 2}/SnO{sub 2} nanocomposite

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

Ding, Shuang-Shuang; Huang, Wei-Qing, E-mail: wqhuang@hnu.edu.cn, E-mail: gfhuang@hnu.edu.cn; Yang, Yin-Cai

2016-05-28

The enhanced photocatalytic performance of various MoS{sub 2}-based nanomaterials has recently been observed, but the role of monolayer MoS{sub 2} is still not well elucidated at the electronic level. Herein, focusing on a model system, hybrid MoS{sub 2}/SnO{sub 2} nanocomposite, we first present a theoretical elucidation of the dual role of monolayer MoS{sub 2} as a sensitizer and a co-catalyst by performing density functional theory calculations. It is demonstrated that a type-II, staggered, band alignment of ∼0.49 eV exists between monolayer MoS{sub 2} and SnO{sub 2} with the latter possessing the higher electron affinity, or work function, leading to the robustmore » separation of photoexcited charge carriers between the two constituents. Under irradiation, the electrons are excited from Mo 4d orbitals to SnO{sub 2}, thus enhancing the reduction activity of latter, indicating that the monolayer MoS{sub 2} is an effective sensitizer. Moreover, the Mo atoms, which are catalytically inert in isolated monolayer MoS{sub 2}, turn into catalytic active sites, making the monolayer MoS{sub 2} to be a highly active co-catalyst in the composite. The dual role of monolayer MoS{sub 2} is expected to arise in other MoS{sub 2}-semiconductor nanocomposites. The calculated absorption spectra can be rationalized by available experimental results. These findings provide theoretical evidence supporting the experimental reports and pave the way for developing highly efficient MoS{sub 2}-based photocatalysts.« less

Scanning tunneling spectroscopy of MoS2 monolayer in presence of ethanol gas

NASA Astrophysics Data System (ADS)

Hosseini, Seyed Ali; Iraji zad, Azam; Berahman, Masoud; Aghakhani Mahyari, Farzaneh; Shokouh, Seyed Hossein Hosseini

2018-04-01

Due to high surface to volume ratio and tunable band gap, two dimensional (2D) layered materials such as MoS2, is good candidate for gas sensing applications. This research mainly focuses on variation of Density of States (DOS) of MoS2 monolayes caused by ethanol adsorption. The nanosheets are synthesized by liquid exfoliation, and then using Scanning Tunneling Spectroscopy (STS) and Density Functional Theory (DFT), local electronic characteristic such as DOS and band gap in non-vacuum condition are analyzed. The results show that ethanol adsorption enhances DOS and deform orbitals near the valence and conduction bands that increase transport of carriers on the sheet.

Charged particles radiation measurements with Liulin-MO dosimeter of FREND instrument aboard ExoMars Trace Gas Orbiter during the transit and in high elliptic Mars orbit

NASA Astrophysics Data System (ADS)

Semkova, Jordanka; Koleva, Rositza; Benghin, Victor; Dachev, Tsvetan; Matviichuk, Yuri; Tomov, Borislav; Krastev, Krasimir; Maltchev, Stephan; Dimitrov, Plamen; Mitrofanov, Igor; Malahov, Alexey; Golovin, Dmitry; Mokrousov, Maxim; Sanin, Anton; Litvak, Maxim; Kozyrev, Andrey; Tretyakov, Vladislav; Nikiforov, Sergey; Vostrukhin, Andrey; Fedosov, Fedor; Grebennikova, Natalia; Zelenyi, Lev; Shurshakov, Vyacheslav; Drobishev, Sergey

2018-03-01

ExoMars is a joint ESA-Rosscosmos program for investigating Mars. Two missions are foreseen within this program: one consisting of the Trace Gas Orbiter (TGO), that carries scientific instruments for the detection of trace gases in the Martian atmosphere and for the location of their source regions, plus an Entry, Descent and landing demonstrator Module (EDM), launched on March 14, 2016; and the other, featuring a rover and a surface platform, with a launch date of 2020. On October 19, 2016 TGO was inserted into high elliptic Mars' orbit. The dosimetric telescope Liulin-MO for measuring the radiation environment onboard the ExoMars 2016 TGO is a module of the Fine Resolution Epithermal Neutron Detector (FREND). Here we present first results from measurements of the charged particle fluxes, dose rates, Linear Energy Transfer (LET) spectra and estimation of dose equivalent rates in the interplanetary space during the cruise of TGO to Mars and first results from dosimetric measurements in high elliptic Mars' orbit. A comparison is made with the dose rates obtained by RAD instrument onboard Mars Science Laboratory during the cruise to Mars in 2011-2012 and with the Galactic Cosmic Rays (GCR) count rates provided by other particle detectors currently in space. The average measured dose rate in Si from GCR during the transit to Mars for the period April 22-September 15, 2016 is 372 ± 37 μGy d-1 and 390 ± 39 μGy d-1 in two perpendicular directions. The dose equivalent rate from GCR for the same time period is about 2 ± 0.3 mSv d-1. This is in good agreement with RAD results for radiation dose rate in Si from GCR in the interplanetary space, taking into account the different solar activity during the measurements of both instruments. About 10% increase of the dose rate, and 15% increase of the dose equivalent rate for 10.5 months flight is observed. It is due to the increase of Liulin-MO particle fluxes for that period and corresponds to the overall GCR intensity increase during the declining phase of the solar activity. Data show that during the cruise to Mars and back (6 months in each direction), taken during the declining of solar activity, the crewmembers of future manned flights to Mars will accumulate at least 60% of the total dose limit for the cosmonaut's/astronaut's career in case their shielding conditions are close to the average shielding of Liulin-MO detectors-about 10 g cm-2. The dosimetric measurements in high elliptic Mars' orbit demonstrate strong dependence of the GCR fluxes near the TGO pericenter on satellite's field of view shadowed by Mars.

Mobility spectrum analytical approach for the type-II Weyl semimetal Td-MoTe2

NASA Astrophysics Data System (ADS)

Pei, Q. L.; Luo, X.; Chen, F. C.; Lv, H. Y.; Sun, Y.; Lu, W. J.; Tong, P.; Sheng, Z. G.; Han, Y. Y.; Song, W. H.; Zhu, X. B.; Sun, Y. P.

2018-02-01

The extreme magnetoresistance (XMR) in orthorhombic W/MoTe2 arises from the combination of the perfect electron-hole (e-h) compensation effect and the unique orbital texture topology, which have comprised an intriguing research field in materials physics. Herein, we apply a special analytical approach as a function of mobility (μ-spectrum) without any hypothesis. Based on the interpretations of longitudinal and transverse electric transport of Td-MoTe2, the types and the numbers of carriers can be obtained. There are three observations: the large residual resistivity ratio can be observed in the MoTe2 single crystal sample, which indicates that the studied crystal is of high quality; we observed three electron-pockets and three hole-ones from the μ-spectrum and that the ratio of h/e is much less than 1, which shows that MoTe2 is more e-like; different from the separated peaks obtained from the hole-like μ-spectrum, those of the electron-like one are continuous, which may indicate the topological feature of electron-pockets in Td-MoTe2. The present results may provide an important clue to understanding the mechanism of the XMR effect in Td-MoTe2.

Tunable magnetic coupling in Mn-doped monolayer MoS2 under lattice strain

NASA Astrophysics Data System (ADS)

Miao, Yaping; Huang, Yuhong; Bao, Hongwei; Xu, Kewei; Ma, Fei; Chu, Paul K.

2018-05-01

First-principles calculations are conducted to study the electronic and magnetic states of Mn-doped monolayer MoS2 under lattice strain. Mn-doped MoS2 exhibits half-metallic and ferromagnetic (FM) characteristics in which the majority spin channel exhibits metallic features but there is a bandgap in the minority spin channel. The FM state and the total magnetic moment of 1 µ B are always maintained for the larger supercells of monolayer MoS2 with only one doped Mn, no matter under tensile or compressive strain. Furthermore, the FM state will be enhanced by the tensile strain if two Mo atoms are substituted by Mn atoms in the monolayer MoS2. The magnetic moment increases up to 0.50 µ B per unit cell at a tensile strain of 7%. However, the Mn-doped MoS2 changes to metallic and antiferromagnetic under compressive strain. The spin polarization of Mn 3d orbitals disappears gradually with increasing compressive strain, and the superexchange interaction between Mn atoms increases gradually. The results suggest that the electronic and magnetic properties of Mn-doped monolayer MoS2 can be effectively modulated by strain engineering providing insight into application to electronic and spintronic devices.

Block-localized wavefunction (BLW) method at the density functional theory (DFT) level.

PubMed

Mo, Yirong; Song, Lingchun; Lin, Yuchun

2007-08-30

The block-localized wavefunction (BLW) approach is an ab initio valence bond (VB) method incorporating the efficiency of molecular orbital (MO) theory. It can generate the wavefunction for a resonance structure or diabatic state self-consistently by partitioning the overall electrons and primitive orbitals into several subgroups and expanding each block-localized molecular orbital in only one subspace. Although block-localized molecular orbitals in the same subspace are constrained to be orthogonal (a feature of MO theory), orbitals between different subspaces are generally nonorthogonal (a feature of VB theory). The BLW method is particularly useful in the quantification of the electron delocalization (resonance) effect within a molecule and the charge-transfer effect between molecules. In this paper, we extend the BLW method to the density functional theory (DFT) level and implement the BLW-DFT method to the quantum mechanical software GAMESS. Test applications to the pi conjugation in the planar allyl radical and ions with the basis sets of 6-31G(d), 6-31+G(d), 6-311+G(d,p), and cc-pVTZ show that the basis set dependency is insignificant. In addition, the BLW-DFT method can also be used to elucidate the nature of intermolecular interactions. Examples of pi-cation interactions and solute-solvent interactions will be presented and discussed. By expressing each diabatic state with one BLW, the BLW method can be further used to study chemical reactions and electron-transfer processes whose potential energy surfaces are typically described by two or more diabatic states.

Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments

NASA Astrophysics Data System (ADS)

Schaugaard, Richard N.; Topolski, Josey E.; Ray, Manisha; Raghavachari, Krishnan; Jarrold, Caroline Chick

2018-02-01

Recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y ≥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with η2-acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. The results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the π orbitals in ethylene.

The effects of surface polarity and dangling bonds on the electronic properties of MoS2 on SiO2

NASA Astrophysics Data System (ADS)

Sung, Ha-Jun; Choe, Duk-Hyun; Chang, Kee Joo

2015-03-01

MoS2 has recently attracted much attention due to its intriguing physical phenomena and possible applications for the next generation electronic devices. In pristine monolayer MoS2, strong spin-orbit coupling and inversion symmetry breaking allow for an effective coupling between the spin and valley degrees of freedom, inducing valley polarization at the K valleys. However, the spin-valley coupling disappears in bilayer MoS2 because the inversion symmetry is restored. In this work, we investigate the effects of surface polarity and dangling bonds on the electronic properties of MoS2 on α-quartz SiO2 through first-principles calculations. In monolayer MoS2, a transition can take place from the direct-gap to indirect-gap semiconductor in the presence of O dangling bonds. In bilayer MoS2, O dangling bonds induce dipole fields across the interface and thus break the inversion symmetry, resulting in the valley polarization, similar to that of pristine monolayer MoS2. Based on the results, we discuss the origin of the valley polarization observed in MoS2 deposited on SiO2 This work was supported by National Research Foundation of Korea (NRF) under Grant No. NRF-2005-0093845 and by Samsung Science and Technology Foundation under Grant No. SSTFBA1401-08.

Electron Spectroscopic Methods in Teaching.

ERIC Educational Resources Information Center

Allan, Michael

1987-01-01

Discusses electron-loss spectroscopy and the experimentally observed excitation energies in terms of qualitative MO theory. Reviews information on photoelectron spectroscopy and electron transmission spectroscopy and their relation to the occupied and unoccupied orbital levels. Focuses on teaching applications. (ML)

47 CFR 1.1156 - Schedule of regulatory fees and filing locations for international services.

Code of Federal Regulations, 2011 CFR

2011-10-01

... applies for the listed services: Fee category Fee amount Address Space Stations (Geostationary Orbit) $131,375 FCC, International, P.O. Box 979084,St. Louis, MO 63197-9000. Space Stations (Non-Geostationary...

47 CFR 1.1156 - Schedule of regulatory fees and filing locations for international services.

Code of Federal Regulations, 2010 CFR

2010-10-01

... applies for the listed services: Fee category Fee amount Address Space Stations (Geostationary Orbit) $127,925 FCC, International, P.O. Box 979084, St. Louis, MO 63197-9000 Space Stations (Non-Geostationary...

A comparison of the bonding in organoiron clusters

NASA Astrophysics Data System (ADS)

Buhl, Margaret L.; Long, Gary J.

1994-12-01

The Mössbauer effect hyperfine parameters and the results of the Fenske-Hall molecular orbit (mo) calculations have been used to study the electronic properties of trinuclear iron, tetranuclear iron butterfly, Fe-Co, and Fe-Cu carbonyl clusters. The more negative Fe charge and the larger Fe 4s population in an Fe(CO)4 fragment as compared with that in an Fe(CO)3 or an Fe(CO)2 fragment is a result of the CO ligands rather than the near-neighbor metals. The clusters which contain heterometals have more negative isomer shifts. The isomer shift correlated well with the sum of the Fe 4s orbital population and the Zeff these electrons experience. The mo wave functions and the atomic charges generally give a larger calculated Δ E Q than is observed, indicating the need to include Sternheimer factors in the calculation. The valence contribution dominates the EFG.

Charge transfer induced by MoO3 at boron subphthalocyanine chloride/α-sexithiophene heterojunction interface

NASA Astrophysics Data System (ADS)

Foggiatto, Alexandre L.; Sakurai, Takeaki

2018-03-01

The energy-level alignment of boron subphthalocyanine chloride (SubPc)/α-sexithiophene (6T) grown on MoO3 was investigated using ultraviolet and X-ray photoelectron spectroscopy (UPS and XPS). We demonstrated that the p-doping effect generated by the MoO3 layer can induce charge transfer at the organic-organic heterojunction interface. After the deposition of 6T on MoO3, the fermi level becomes pinned close to the 6T highest occupied molecular orbital (HOMO) level and when SubPc is deposited, owing to its tail states, charge transfer occurs in order to achieve thermodynamic equilibrium. We also demonstrated that the charge transfer can be reduced by annealing the film. We suggested that the reduction of the misalignment on the film induces a reduction in the density of gap states, which controls the charge transfer.

The Role of Interfacial Electronic Properties on Phonon Transport in Two-Dimensional MoS 2 on Metal Substrates

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

Yan, Zhequan; Chen, Liang; Yoon, Mina

2016-11-08

In this paper, we investigate the role of interfacial electronic properties on the phonon transport in two-dimensional MoS 2 adsorbed on metal substrates (Au and Sc) using first-principles density functional theory and the atomistic Green’s function method. Our study reveals that the different degree of orbital hybridization and electronic charge distribution between MoS 2 and metal substrates play a significant role in determining the overall phonon–phonon coupling and phonon transmission. The charge transfer caused by the adsorption of MoS 2 on Sc substrate can significantly weaken the Mo–S bond strength and change the phonon properties of MoS 2, which resultmore » in a significant change in thermal boundary conductance (TBC) from one lattice-stacking configuration to another for same metallic substrate. In a lattice-stacking configuration of MoS 2/Sc, weakening of the Mo–S bond strength due to charge redistribution results in decrease in the force constant between Mo and S atoms and substantial redistribution of phonon density of states to low-frequency region which affects overall phonon transmission leading to 60% decrease in TBC compared to another configuration of MoS 2/Sc. Strong chemical coupling between MoS 2 and the Sc substrate leads to a significantly (~19 times) higher TBC than that of the weakly bound MoS 2/Au system. Our findings demonstrate the inherent connection among the interfacial electronic structure, the phonon distribution, and TBC, which helps us understand the mechanism of phonon transport at the MoS 2/metal interfaces. Finally, the results provide insights for the future design of MoS 2-based electronics and a way of enhancing heat dissipation at the interfaces of MoS 2-based nanoelectronic devices.« less

EPR/ENDOR and Theoretical Study of the Jahn-Teller-Active [HIPTN3N]MoVL Complexes (L = N-, NH).

PubMed

Sharma, Ajay; Roemelt, Michael; Reithofer, Michael; Schrock, Richard R; Hoffman, Brian M; Neese, Frank

2017-06-19

The molybdenum trisamidoamine (TAA) complex [Mo] {[3,5-(2,4,6-i-Pr 3 C 6 H 2 ) 2 C 6 H 3 NCH 2 CH 2 N]Mo} carries out catalytic reduction of N 2 to ammonia (NH 3 ) by protons and electrons at room temperature. A key intermediate in the proposed [Mo] nitrogen reduction cycle is nitridomolybdenum(VI), [Mo(VI)]N. The addition of [e - /H + ] to [Mo(VI)]N to generate [Mo(V)]NH might, in principle, follow one of three possible pathways: direct proton-coupled electron transfer; H + first and then e - ; e - and then H + . In this study, the paramagnetic Mo(V) intermediate {[Mo]N} - and the [Mo]NH transfer product were generated by irradiating the diamagnetic [Mo]N and {[Mo]NH} + Mo(VI) complexes, respectively, with γ-rays at 77 K, and their electronic and geometric structures were characterized by electron paramagnetic resonance and electron nuclear double resonance spectroscopies, combined with quantum-chemical computations. In combination with previous X-ray studies, this creates the rare situation in which each one of the four possible states of [e - /H + ] delivery has been characterized. Because of the degeneracy of the electronic ground states of both {[Mo(V)]N} - and [Mo(V)]NH, only multireference-based methods such as the complete active-space self-consistent field (CASSCF) and related methods provide a qualitatively correct description of the electronic ground state and vibronic coupling. The molecular g values of {[Mo]N} - and [Mo]NH exhibit large deviations from the free-electron value g e . Their actual values reflect the relative strengths of vibronic and spin-orbit coupling. In the course of the computational treatment, the utility and limitations of a formal two-state model that describes this competition between couplings are illustrated, and the implications of our results for the chemical reactivity of these states are discussed.

Photoelectron Spectroscopy of Free Multiply Charged Keggin Anions α-[PM12O40]3- (M = Mo, W) in the Gas Phase

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

Waters, Tom; Huang, Xin; Wang, Xue B.

2006-09-21

Two polyoxometalate Keggin-type anions, a-PM12O403- (M = Mo, W), were transferred to the gas phase by electrospray; their electronic structure and stability were probed by photoelectron spectroscopy. These triply charged anions were found to be highly stable in the gas phase with large adiabatic electron detachment energies of 1.7 and 2.1 eV for M = Mo and W, respectively. The magnitude of the repulsive Coulomb barrier was measured as ~3.4 eV for both anions, providing an experimental estimate for the intramolecular Coulomb repulsion present in these highly charged anions. Density functional theory calculations were carried out and compared with themore » experimental data, providing insight into the electronic structure and valence molecular orbitals of the two Keggin anions. The calculations indicated that the highest occupied molecular orbital and other frontier orbitals for PM12O403- are localized primarily on the u2-oxo bridging ligands of the polyoxometalate framework, consistent with the reactivity on the u2-oxo sites observed in solution. It was shown that the HOMO of PW12O403- is stabilized relative to that of PMo12O403- by ~0.35 eV. The experimental adiabatic electron detachment energies of PM12O403- (i.e., the electron affinities of PM12O402-) are combined with recent calculations on the proton affinity of PM12O403- to yield O-H bond dissociation energies in PM12O39(OH)2- as ~5.1 eV« less

Adsorption of phenol and hydrazine upon pristine and X-decorated (X = Sc, Ti, Cr and Mn) MoS2 monolayer

NASA Astrophysics Data System (ADS)

Wang, Meiyan; Wang, Wei; Ji, Min; Cheng, Xinlu

2018-05-01

Using density functional theory (DFT), we present a theoretical investigation of phenol (C6H5OH) and hydrazine (N2H4) on pristine and decorated MoS2 monolayer. In our work, we first focus on the interactions between several metal atoms and MoS2 monolayer and then choose the MoS2 nanosheet decorated by Sc, Ti, Cr and Mn to be the substrate. Furthermore, the properties of phenol and N2H4 on pure and X-doped (X = Sc, Ti, Cr and Mn) MoS2 base materials are discussed in terms of adsorption energy, adsorption distance, charge transfer, charge density difference, HOMO and LUMO molecular orbitals and density of states (DOS). The results predict that the adsorption of phenol and hydrazine upon X-decorated MoS2 monolayers are more favorable than the adsorption on isolated ones, which demonstrating that Sc, Ti, Cr and Mn doping help to improve the adsorption abilities. Calculations also show shorter adsorption distance and more charge transfer for Sc-, Ti-, Cr- and Mn-doped systems than the pristine one. The results confirm that X-doped MoS2 monolayer can be used as effective and potential adsorbents for toxic phenol and hydrazine.

Development of spontaneous magnetism and half-metallicity in monolayer MoS2

NASA Astrophysics Data System (ADS)

Rahman, Altaf Ur; Rahman, Gul; García-Suárez, Víctor M.

2017-12-01

Half-metallic behavior and ferromagnetism are predicted in strained MoS2 with different light elements adsorbed using density functional theory. We find that strain increases the density of states at the Fermi energy for Y doping (Y = H, Li, and F) at the S sites and strain-driven magnetism develops in agreement with the Stoner mean field model. Strain-driven magnetism requires less strain (∼3%) for H doping as compared with F and Li doping. No saturation of the spin-magnetic moment is observed in Li-doped MoS2 due to less charge transfer from the Mo d electrons and the added atoms do not significantly increase the Spin-orbit coupling. Half-metallic ferromagnetism is predicted in H and F-doped MoS2. Fixed magnetic moments calculations are also performed, and the DFT computed data is fitted with the Landau mean field theory to investigate the emergence of spontaneous magnetism in Y-doped MoS2. We predict spontaneous magnetism in systems with large (small) mag netic moments for H/F (Li) atoms. The large (small) magnetic moments are atttributed to the electronegativity difference between S and Y atoms. These results suggest that H and F adsorbed monolayer MoS2 is a good candidate for spin-based electronic devices.

Room-temperature superparamagnetism due to giant magnetic anisotropy in Mo S defected single-layer MoS2.

PubMed

Khan, M A; Leuenberger, Michael N

2018-04-18

Room-temperature superparamagnetism due to a large magnetic anisotropy energy (MAE) of a single atom magnet has always been a prerequisite for nanoscale magnetic devices. Realization of two dimensional (2D) materials such as single-layer (SL) MoS 2 , has provided new platforms for exploring magnetic effects, which is important for both fundamental research and for industrial applications. Here, we use density functional theory (DFT) to show that the antisite defect (Mo S ) in SL MoS 2 is magnetic in nature with a magnetic moment μ of  ∼2 [Formula: see text] and, remarkably, exhibits an exceptionally large atomic scale MAE [Formula: see text] of  ∼500 meV. Our calculations reveal that this giant anisotropy is the joint effect of strong crystal field and significant spin-orbit coupling (SOC). In addition, the magnetic moment μ can be tuned between 1 [Formula: see text] and 3 [Formula: see text] by varying the Fermi energy [Formula: see text], which can be achieved either by changing the gate voltage or by chemical doping. We also show that MAE can be raised to  ∼1 eV with n-type doping of the MoS 2 :Mo S sample. Our systematic investigations deepen our understanding of spin-related phenomena in SL MoS 2 and could provide a route to nanoscale spintronic devices.

Room-temperature superparamagnetism due to giant magnetic anisotropy in Mo S defected single-layer MoS2

NASA Astrophysics Data System (ADS)

Khan, M. A.; Leuenberger, Michael N.

2018-04-01

Room-temperature superparamagnetism due to a large magnetic anisotropy energy (MAE) of a single atom magnet has always been a prerequisite for nanoscale magnetic devices. Realization of two dimensional (2D) materials such as single-layer (SL) MoS2, has provided new platforms for exploring magnetic effects, which is important for both fundamental research and for industrial applications. Here, we use density functional theory (DFT) to show that the antisite defect (Mo S ) in SL MoS2 is magnetic in nature with a magnetic moment μ of  ∼2 μB and, remarkably, exhibits an exceptionally large atomic scale MAE =\\varepsilon\\parallel-\\varepsilon\\perp of  ∼500 meV. Our calculations reveal that this giant anisotropy is the joint effect of strong crystal field and significant spin–orbit coupling (SOC). In addition, the magnetic moment μ can be tuned between 1 μB and 3 μB by varying the Fermi energy \\varepsilonF , which can be achieved either by changing the gate voltage or by chemical doping. We also show that MAE can be raised to  ∼1 eV with n-type doping of the MoS2:Mo S sample. Our systematic investigations deepen our understanding of spin-related phenomena in SL MoS2 and could provide a route to nanoscale spintronic devices.

Strict Correlation of HOMO Topology and Magnetic Aromaticity Indices in d-Block Metalloaromatics.

PubMed

Mauksch, Michael; Tsogoeva, Svetlana B

2018-05-16

Magnetic aromaticity and antiaromaticity of closed shell metalloaromatics with 4d transition metals (Nb, Tc, Rh) is strictly correlated with orbital topology (Möbius or Hückel) of their π-HOMO, investigated computationally with DFT methods. A surprisingly simple rule emerged: the metallacycle is aromatic (antiaromatic) when the number of π MO's is even and the π-HOMO is of Möbius (Hückel) topology - and vice versa when the number of π MO's is odd. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Seniority Number in Valence Bond Theory.

PubMed

Chen, Zhenhua; Zhou, Chen; Wu, Wei

2015-09-08

In this work, a hierarchy of valence bond (VB) methods based on the concept of seniority number, defined as the number of singly occupied orbitals in a determinant or an orbital configuration, is proposed and applied to the studies of the potential energy curves (PECs) of H8, N2, and C2 molecules. It is found that the seniority-based VB expansion converges more rapidly toward the full configuration interaction (FCI) or complete active space self-consistent field (CASSCF) limit and produces more accurate PECs with smaller nonparallelity errors than its molecular orbital (MO) theory-based analogue. Test results reveal that the nonorthogonal orbital-based VB theory provides a reverse but more efficient way to truncate the complete active Hilbert space by seniority numbers.

Photoelectron imaging spectroscopy of MoC{sup −} and NbN{sup −} diatomic anions: A comparative study

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

Liu, Qing-Yu; Li, Zi-Yu; He, Sheng-Gui, E-mail: shengguihe@iccas.ac.cn, E-mail: chenh@iccas.ac.cn

2015-04-28

The isoeletronic diatomic MoC{sup −} and NbN{sup −} anions have been prepared by laser ablation and studied by photoelectron imaging spectroscopy combined with quantum chemistry calculations. The photoelectron spectra of NbN{sup −} can be very well assigned on the basis of literature reported optical spectroscopy of NbN. In contrast, the photoelectron spectra of MoC{sup −} are rather complex and the assignments suffered from the presence of many electronically hot bands and limited information from the reported optical spectroscopy of MoC. The electron affinities of NbN and MoC have been determined to be 1.450 ± 0.003 eV and 1.360  ±  0.003more » eV, respectively. The good resolution of the imaging spectroscopy provided a chance to resolve the Ω splittings of the X{sup 3}Σ{sup −} (Ω = 0 and 1) state of MoC and the X{sup 4}Σ{sup −} (Ω = 1/2 and 3/2) state of MoC{sup −} for the first time. The spin-orbit splittings of the X{sup 2}Δ state of NbN{sup −} and the a{sup 2}Δ state of MoC{sup −} were also determined. The similarities and differences between the electronic structures of the NbN and MoC systems were discussed.« less

Influence of MoOx interlayer on the maximum achievable open-circuit voltage in organic photovoltaic cells

NASA Astrophysics Data System (ADS)

Zou, Yunlong; Holmes, Russell

2013-03-01

Transition metal oxides including molybdenum oxide (MoOx) are characterized by large work functions and deep energy levels relative to the organic semiconductors used in photovoltaic cells (OPVs). These materials have been used in OPVs as interlayers between the indium-tin-oxide anode and the active layers to increase the open-circuit voltage (VOC) and power conversion efficiency. We examine the role of MoOx in determining the maximum achievable VOC in planar heterojunction OPVs based on the donor-acceptor pairing of boron subphthalocyanine chloride (SubPc) and C60. While causing minor changes in VOC at room temperature, the inclusion of MoOx significantly changes the temperature dependence of VOC. Devices containing no interlayer show a maximum VOC\\ of 1.2 V, while devices containing MoOx show no saturation in VOC, reaching a value of >1.4 V at 110 K. We propose that the MoOx-SubPc interface forms a dissociating Schottky junction that provides an additional contribution to VOC at low temperature. Separate measurements of photoluminescence confirm that excitons in SubPc can be quenched by MoOx. Charge transfer at this interface is by hole extraction from SubPc to MoOx, and this mechanism favors donors with a deep highest occupied molecular orbital (HOMO) energy level. Consistent with this expectation, the temperature dependence of VOC for devices constructed using a donor with a shallower HOMO level, e.g. copper phthalocyanine, is independent of the presence of MoOx.

Equine orbital neoplasia: a review of 10 cases (1983-1998).

PubMed Central

Baptiste, K E; Grahn, B H

2000-01-01

The clinical manifestations, laboratory findings, and survival times of 10 horses with orbital neoplasms are reported. In all cases, orbital neoplasms were malignant and locally invasive with no defined surgical circumscribed edges. It was often difficult to identify the primary cell type of the neoplasia in histologic specimens due to the poorly differentiated, anaplastic nature of the majority of cases. All except one horse were eventually euthanized 2 mo to 5 y after diagnosis due to poor response to treatment, metastasis, or unrelenting orbital neoplasia. Mean survival time increased with surgical treatment, but no significant difference was found among no treatment, chemotherapy, surgical mass removal, or exenteration/enucleation. Equine practitioners should be aware of the marked difference in prognosis of orbital neoplasms compared with ocular or localized eyelid neoplasia. Images Figure 1. Figure 2. Figure 3. PMID:10769765

A two-dimensional spin field-effect switch

NASA Astrophysics Data System (ADS)

Yan, Wenjing; Txoperena, Oihana; Llopis, Roger; Dery, Hanan; Hueso, Luis E.; Casanova, Fèlix

2016-11-01

Future development in spintronic devices will require an advanced control of spin currents, for example by an electric field. Here we demonstrate an approach that differs from previous proposals such as the Datta and Das modulator, and that is based on a van de Waals heterostructure of atomically thin graphene and semiconducting MoS2. Our device combines the superior spin transport properties of graphene with the strong spin-orbit coupling of MoS2 and allows switching of the spin current in the graphene channel between ON and OFF states by tuning the spin absorption into the MoS2 with a gate electrode. Our proposal holds potential for technologically relevant applications such as search engines or pattern recognition circuits, and opens possibilities towards electrical injection of spins into transition metal dichalcogenides and alike materials.

Rashba-type spin splitting and the electronic structure of ultrathin Pb/MoTe2 heterostructure

NASA Astrophysics Data System (ADS)

Du, X.; Wang, Z. Y.; Huang, G. Q.

2016-11-01

The spin-polarized band structures of the Pb(111)/MoTe2 heterostructure are studied by the first-principles calculations. Due to strong spin-orbit coupling and space inversion asymmetry, large Rashba spin splitting of electronic bands appears in this hybrid system. The spin splitting is completely out-of-plane and opposite at \\bar{K} and {\\bar{K}}\\prime points. Rashba spin splitting also appears along the in-plane momentum direction around the \\bar{{{Γ }}} point due to the existence of surface potential gradient induced by charge transfer at interface. Furthermore, our calculations show that the spin-polarized bands closely approach the Fermi level in Pb/MoTe2 heterostructure, showing that this heterostructure may be a good candidate in valleytronics or spintronics.

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.

Electronic and magnetic properties of RMnO3/AMnO3 heterostructures

NASA Astrophysics Data System (ADS)

Yu, Rong; Yunoki, Seiji; Dong, Shuai; Dagotto, Elbio

2009-09-01

The ground-state properties of RMnO3/AMnO3 (RMO/AMO) heterostructures (with R=La,Pr,… , a trivalent rare-earth cation and A=Sr,Ca,… , a divalent alkaline cation) are studied using a two-orbital double-exchange model including the superexchange coupling and Jahn-Teller lattice distortions. To describe the charge transfer across the interface, the long-range Coulomb interaction is taken into account at the mean-field level, by self-consistently solving the Poisson’s equation. The calculations are carried out numerically on finite clusters. We find that the state stabilized near the interface of the heterostructure is similar to the state of the bulk compound (R,A)MO at electronic density close to 0.5. For instance, a charge and orbitally ordered CE state is found at the interface if the corresponding bulk (R,A)MO material is a narrow-to-intermediate bandwidth manganite. But instead the interface regime accommodates an A-type antiferromagnetic state with a uniform x2-y2 orbital order, if the bulk (R,A)MO corresponds to a wide bandwidth manganite. We argue that these results explain some of the properties of long-period (RMO)m/(AMO)n superlattices, such as (PrMnO3)m/(CaMnO3)n and (LaMnO3)m/(SrMnO3)n . We also remark that the intermediate states in between the actual interface and the bulklike regimes of the heterostructure are dependent on the bandwidth and the screening of the Coulomb interaction. In these regions of the heterostructures, states are found that do not have an analog in experimentally known bulk phase diagrams. These new states of the heterostructures provide a natural interpolation between magnetically ordered states that are stable in the bulk at different electronic densities.

The Computer Bulletin Board.

ERIC Educational Resources Information Center

Batt, Russell H., Ed.

1988-01-01

Notes two uses of computer spreadsheets in the chemistry classroom. Discusses the general use of the spreadsheet to easily provide changing parameters of equations and then replotting the results on the screen. Presents a molecular orbital spreadsheet calculation of the LCAO-MO approach. Supplies representative printouts and graphs. (MVL)

Magnetotransport properties of MoP 2

DOE PAGES

Wang, Aifeng; Graf, D.; Stein, Aaron; ...

2017-11-02

We report magnetotransport and de Haas–van Alphen (dHvA) effect studies on MoP 2 single crystals, predicted to be a type- II Weyl semimetal with four pairs of robust Weyl points located below the Fermi level and long Fermi arcs. The temperature dependence of resistivity shows a peak before saturation, which does not move with magnetic field. Large nonsaturating magnetoresistance (MR) was observed, and the field dependence of MR exhibits a crossover from semiclassical weak-field B 2 dependence to the high-field linear-field dependence, indicating the presence of Dirac linear energy dispersion. In addition, a systematic violation of Kohler's rule was observed,more » consistent with multiband electronic transport. Strong spin-orbit coupling splitting has an effect on dHvA measurements whereas the angular-dependent dHvA orbit frequencies agree well with the calculated Fermi surface. The cyclotron effective mass ~1.6m e indicates the bands might be trivial, possibly since the Weyl points are located below the Fermi level.« less

The continuous and discrete molecular orbital x-ray bands from Xe(q+) (12≤q≤29) +Zn collisions.

PubMed

Guo, Yipan; Yang, Zhihu; Hu, Bitao; Wang, Xiangli; Song, Zhangyong; Xu, Qiumei; Zhang, Boli; Chen, Jing; Yang, Bian; Yang, Jie

2016-07-29

In this paper, the x-ray emissions are measured by the interaction of 1500-3500 keV Xe(q+) (q = 12, 15, 17, 19, 21, 23, 26 and 29) ions with Zn target. When q < 29, we observe Ll, Lα, Lβ1, Lβ2 and Lγ characteristic x-rays from Xe(q+) ions and a broad M-shell molecular orbital (MO) x-ray band from the transient quasi-molecular levels. It is found that their yields quickly increase with different rates as the incident energy increases. Besides, the widths of the broad MO x-ray bands are about 0.9-1.32 keV over the energy range studied and are proportional to v(1/2) (v = projectile velocity). Most remarkably, when the projectile charge state is 29, the broad x-ray band separates into several narrow discrete spectra, which was never observed before in this field.

Study on Silver-plated Molybdenum Interconnected Materials for LEO Solar Cell Array

NASA Astrophysics Data System (ADS)

Zhu, Jia-jun; Hu, Yu-hao; Xu, Meng; Yang, Wu-lin; Fu, Li-cai; Li, De-yi; Zhou, Ling-ping

2017-09-01

Atomic oxygen (AO) is one of the most important environmental factors that affected the performance of low earth orbit spacecraft in orbit. In which, silver was the most common materials as the interconnected materials. However, with the poor AO resistance of silver, the interconnectors could be failure easier, and the lifetime of the spacecraft was also reduced. In this paper, the silver-plated molybdenum interconnected materials made by Ag thin films deposited on the Mo foils by vacuum deposition methods was studied. And the effects of the preparation process on the micro-structure of the Ag thin films, the interfacial adhesive strength and the electrical conductivity of the composites were investigated. It was found that the Ag thin films deposited on the Mo substrates coated the Ag thin films by ion beam assisted deposition(IBAD) methods exhibited a perfectly (200) preferred orientation. The interfacial adhesive strength had been increased to 18.58MPa. And the composites also have excellent electrical performance.

Laboratory investigations: Low Earth orbit environment chemistry with spacecraft surfaces

NASA Technical Reports Server (NTRS)

Cross, Jon B.

1990-01-01

Long-term space operations that require exposure of material to the low earth orbit (LEO) environment must take into account the effects of this highly oxidative atmosphere on material properties and the possible contamination of the spacecraft surroundings. Ground-based laboratory experiments at Los Alamos using a newly developed hyperthermal atomic oxygen (AO) source have shown that not only are hydrocarbon based materials effected but that inorganic materials such as MoS2 are also oxidized and that thin protective coatings such as Al2O3 can be breached, producing oxidation of the underlying substrate material. Gas-phase reaction products, such as SO2 from oxidation of MoS2 and CO and CO2 from hydrocarbon materials, have been detected and have consequences in terms of spacecraft contamination. Energy loss through gas-surface collisions causing spacecraft drag has been measured for a few select surfaces and has been found to be highly dependent on the surface reactivity.

On the Highest Oxidation States of Metal Elements in MO4 Molecules (M = Fe, Ru, Os, Hs, Sm, and Pu).

PubMed

Huang, Wei; Xu, Wen-Hua; Schwarz, W H E; Li, Jun

2016-05-02

Metal tetraoxygen molecules (MO4, M = Fe, Ru, Os, Hs, Sm, Pu) of all metal atoms M with eight valence electrons are theoretically studied using density functional and correlated wave function approaches. The heavier d-block elements Ru, Os, Hs are confirmed to form stable tetraoxides of Td symmetry in (1)A1 electronic states with empty metal d(0) valence shell and closed-shell O(2-) ligands, while the 3d-, 4f-, and 5f-elements Fe, Sm, and Pu prefer partial occupation of their valence shells and peroxide or superoxide ligands at lower symmetry structures with various spin couplings. The different geometric and electronic structures and chemical bonding types of the six iso-stoichiometric species are explained in terms of atomic orbital energies and orbital radii. The variations found here contribute to our general understanding of the periodic trends of oxidation states across the periodic table.

On Valence-Band Splitting in Layered MoS2.

PubMed

Zhang, Youwei; Li, Hui; Wang, Haomin; Liu, Ran; Zhang, Shi-Li; Qiu, Zhi-Jun

2015-08-25

As a representative two-dimensional semiconducting transition-metal dichalcogenide (TMD), the electronic structure in layered MoS2 is a collective result of quantum confinement, interlayer interaction, and crystal symmetry. A prominent energy splitting in the valence band gives rise to many intriguing electronic, optical, and magnetic phenomena. Despite numerous studies, an experimental determination of valence-band splitting in few-layer MoS2 is still lacking. Here, we show how the valence-band maximum (VBM) splits for one to five layers of MoS2. Interlayer coupling is found to contribute significantly to phonon energy but weakly to VBM splitting in bilayers, due to a small interlayer hopping energy for holes. Hence, spin-orbit coupling is still predominant in the splitting. A temperature-independent VBM splitting, known for single-layer MoS2, is, thus, observed for bilayers. However, a Bose-Einstein type of temperature dependence of VBM splitting prevails in three to five layers of MoS2. In such few-layer MoS2, interlayer coupling is enhanced with a reduced interlayer distance, but thermal expansion upon temperature increase tends to decouple adjacent layers and therefore decreases the splitting energy. Our findings that shed light on the distinctive behaviors about VBM splitting in layered MoS2 may apply to other hexagonal TMDs as well. They will also be helpful in extending our understanding of the TMD electronic structure for potential applications in electronics and optoelectronics.

Interlayer excitons in MoSe2/WSe2 heterostructures from first principles

NASA Astrophysics Data System (ADS)

Gillen, Roland; Maultzsch, Janina

2018-04-01

Based on ab initio theoretical calculations of the optical spectra of vertical heterostructures of MoSe2 (or MoS2) and WSe2 sheets, we reveal two spin-orbit-split Rydberg series of excitonic states below the A excitons of MoSe2 and WSe2 with a significant binding energy on the order of 250 meV for the first excitons in the series. At the same time, we predict from accurate many-body G0W0 calculations that crystallographically aligned MoSe2/WSe2 heterostructures exhibit an indirect fundamental band gap. Due to the type-II nature of the MoSe2/WSe2 heterostructure, the indirect transition and the exciton Rydberg series corresponding to a direct transition exhibit a distinct interlayer nature with spatial charge separation of the coupled electrons and holes. Our calculations confirm the recent experimental observation of a doublet nature of the long-lived states in photoluminescence spectra of Mo X2/W Y2 heterostructures, and we attribute these two contributions to momentum-direct interlayer excitons at the K point of the hexagonal Brillouin zone and to momentum-indirect excitons at the indirect fundamental band gap. Our calculations further suggest a noticeable effect of stacking order on the electronic band gaps and on the peak energies of the interlayer excitons and their oscillation strengths.

Electronic properties of thiolate compounds of oxomolybdenum(V) and their tungsten and selenium analogues. Effects of /sup 17/O, /sup 98/Mo, and /sup 95/Mo isotope substitution upon ESR spectra

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

Hanson, G.R.; Brunette, A.A.; McDonell, A.C.

1981-04-22

The series of crystalline, mononuclear B/sup +/(MO(XR)/sub 4/)/sup -/ and triply bridged binuclear B/sup +/(M/sub 2/O/sub 2/(XR)/sub 6/(OMe))/sup -/(M = Mo, W; X = S, Se; R = aryl; B = quaternary cation) salts have been isolated and the anions (MoO(SR)/sub 4/)/sup -/ (R = Et, CH/sub 2/Ph) stabilized in solution at -60/sup 0/C. The mononuclear anions are intensely colored due to a ligand-to-metal charge-transfer transition which is absent in the binuclear species. The magnetic susceptibilities of (Et/sub 4/N)(MO(SPh)/sub 4/) show a Curie dependence in the range 300 to 4.2 K with minor deviations in the tungsten compound. The behaviormore » is essentially that of magnetically dilute 4d/sup 1/ and 5d/sup 1/ systems exhibiting a tetragonal ligand field and greatly reduced spin-orbit coupling on the metal. The presence of strong spin-spin coupling in the binuclear compounds leads to magnetic moments close to 0. ESR spectra (at X- and Q-band frequencies) of the mononuclear anions exhibit axial symmetry, and /sup 98/Mo and /sup 95/Mo isotope substitution and computer simulation permit accurate extraction of the g and hyperfine tensor anisotropies. Exceptionally arrow line widths permit observation of /sup 17/O-superhyperfine coupling in /sup 17/O-enriched (/sup 98/MoO(SPh)/sub 4/)/sup -/(a = 2.2 x 10/sup -4/cm/sup -1/).« less

STS-57 crewmembers train in JSC's FB Shuttle Mission Simulator (SMS)

NASA Technical Reports Server (NTRS)

1993-01-01

STS-57 Endeavour, Orbiter Vehicle (OV) 105, Mission Specialist 2 (MS2) Nancy J. Sherlock, holding computer diskettes and procedural checklist, discusses equipment operation with Commander Ronald J. Grabe on the middeck of JSC's fixed based (FB) shuttle mission simulator (SMS). Payload Commander (PLC) G. David Low points to a forward locker location as MS3 Peter J.K. Wisoff switches controls on overhead panels MO42F and MO58F, and MS4 Janice E. Voss looks on. The FB-SMS is located in the Mission Simulation and Training Facility Bldg 5.

Bonding between graphene and MoS 2 monolayers without and with Li intercalation

DOE PAGES

Ahmed, Towfiq; Modine, N. A.; Zhu, Jian-Xin

2015-07-27

We performed density functional theory (DFT) calculations for a bi-layered heterostructure combining a graphene layer with a MoS 2 layer with and without intercalated Li atoms. Our calculations demonstrate the importance of the van der Waals (vdW) interaction, which is crucial for forming stable bonding between the layers. Our DFT calculation correctly reproduces the linear dispersion, or Dirac cone, feature at the Fermi energy for the isolated graphene monolayer and the band gap for the MoS 2 monolayer. For the combined graphene/MoS 2 bi-layer, we observe interesting electronic structure and density of states (DOS) characteristics near the Fermi energy, showingmore » both the gap like features of the MoS 2 layer and in-gap states with linear dispersion contributed mostly by the graphene layer. Our calculated total DOS in this vdW heterostructure reveals that the graphene layer significantly contributes to pinning the Fermi energy at the center of the band gap of MoS 2. We also find that intercalating Li ions in between the layers of the graphene/MoS2 heterostructure enhances the binding energy through orbital hybridizations between cations (Li adatoms) and anions (graphene and MoS 2 monolayers). Moreover, we calculate the dielectric function of the Li intercalated graphene/MoS 2 heterostructure, the imaginary component of which can be directly compared with experimental measurements of optical conductivity in order to validate our theoretical prediction. We observe sharp features in the imaginary component of the dielectric function, which shows the presence of a Drude peak in the optical conductivity, and therefore metallicity in the lithiated graphene/MoS 2 heterostructure.« less

Alkali Metal Cation versus Proton and Methyl Cation Affinities: Structure and Bonding Mechanism

PubMed Central

Boughlala, Zakaria; Fonseca Guerra, Célia

2016-01-01

Abstract We have analyzed the structure and bonding of gas‐phase Cl−X and [HCl−X]+ complexes for X+= H+, CH3 +, Li+, and Na+, using relativistic density functional theory (DFT). We wish to establish a quantitative trend in affinities of the anionic and neutral Lewis bases Cl− and HCl for the various cations. The Cl−X bond becomes longer and weaker along X+ = H+, CH3 +, Li+, and Na+. Our main purpose is to understand the heterolytic bonding mechanism behind the intrinsic (i.e., in the absence of solvent) alkali metal cation affinities (AMCA) and how this compares with and differs from those of the proton affinity (PA) and methyl cation affinity (MCA). Our analyses are based on Kohn–Sham molecular orbital (KS‐MO) theory in combination with a quantitative energy decomposition analysis (EDA) that pinpoints the importance of the different features in the bonding mechanism. Orbital overlap appears to play an important role in determining the trend in cation affinities. PMID:27551660

A two-dimensional spin field-effect switch

DOE PAGES

Yan, Wenjing; Txoperena, Oihana; Llopis, Roger; ...

2016-11-11

Future development in spintronic devices will require an advanced control of spin currents, for example by an electric field. Here we demonstrate an approach that differs from previous proposals such as the Datta and Das modulator, and that is based on a van de Waals heterostructure of atomically thin graphene and semiconducting MoS 2. Our device combines the superior spin transport properties of graphene with the strong spin–orbit coupling of MoS 2 and allows switching of the spin current in the graphene channel between ON and OFF states by tuning the spin absorption into the MoS 2 with a gatemore » electrode. Lastly, our proposal holds potential for technologically relevant applications such as search engines or pattern recognition circuits, and opens possibilities towards electrical injection of spins into transition metal dichalcogenides and alike materials.« less

Density functional theory calculations of 95Mo NMR parameters in solid-state compounds.

PubMed

Cuny, Jérôme; Furet, Eric; Gautier, Régis; Le Pollès, Laurent; Pickard, Chris J; d'Espinose de Lacaillerie, Jean-Baptiste

2009-12-21

The application of periodic density functional theory-based methods to the calculation of (95)Mo electric field gradient (EFG) and chemical shift (CS) tensors in solid-state molybdenum compounds is presented. Calculations of EFG tensors are performed using the projector augmented-wave (PAW) method. Comparison of the results with those obtained using the augmented plane wave + local orbitals (APW+lo) method and with available experimental values shows the reliability of the approach for (95)Mo EFG tensor calculation. CS tensors are calculated using the recently developed gauge-including projector augmented-wave (GIPAW) method. This work is the first application of the GIPAW method to a 4d transition-metal nucleus. The effects of ultra-soft pseudo-potential parameters, exchange-correlation functionals and structural parameters are precisely examined. Comparison with experimental results allows the validation of this computational formalism.

Optoelectronics of supported and suspended 2D semiconductors

NASA Astrophysics Data System (ADS)

Bolotin, Kirill

2014-03-01

Two-dimensional semiconductors, materials such monolayer molybdenum disulfide (MoS2) are characterized by strong spin-orbit and electron-electron interactions. However, both electronic and optoelectronic properties of these materials are dominated by disorder-related scattering. In this talk, we investigate approaches to reduce scattering and explore physical phenomena arising in intrinsic 2D semiconductors. First, we discuss fabrication of pristine suspended monolayer MoS2 and use photocurrent spectroscopy measurements to study excitons in this material. We observe band-edge and van Hove singularity excitons and estimate their binding energies. Furthermore, we study dissociation of these excitons and uncover the mechanism of their contribution to photoresponse of MoS2. Second, we study strain-induced modification of bandstructures of 2D semiconductors. With increasing strain, we find large and controllable band gap reduction of both single- and bi-layer MoS2. We also detect experimental signatures consistent with strain-induced transition from direct to indirect band gap in monolayer MoS2. Finally, we fabricate heterostructures of dissimilar 2D semiconductors and study their photoresponse. For closely spaced 2D semiconductors we detect charge transfer, while for separation larger than 10nm we observe Forster-like energy transfer between excitations in different layers.

Superconductivity in Potassium-Doped Metallic Polymorphs of MoS2.

PubMed

Zhang, Renyan; Tsai, I-Ling; Chapman, James; Khestanova, Ekaterina; Waters, John; Grigorieva, Irina V

2016-01-13

Superconducting layered transition metal dichalcogenides (TMDs) stand out among other superconductors due to the tunable nature of the superconducting transition, coexistence with other collective electronic excitations (charge density waves), and strong intrinsic spin-orbit coupling. Molybdenum disulfide (MoS2) is the most studied representative of this family of materials, especially since the recent demonstration of the possibility to tune its critical temperature, Tc, by electric-field doping. However, just one of its polymorphs, band-insulator 2H-MoS2, has so far been explored for its potential to host superconductivity. We have investigated the possibility to induce superconductivity in metallic polytypes, 1T- and 1T'-MoS2, by potassium (K) intercalation. We demonstrate that at doping levels significantly higher than that required to induce superconductivity in 2H-MoS2, both 1T and 1T' phases become superconducting with Tc = 2.8 and 4.6 K, respectively. Unusually, K intercalation in this case is responsible both for the structural and superconducting phase transitions. By adding new members to the family of superconducting TMDs, our findings open the way to further manipulate and enhance the electronic properties of these technologically important materials.

A new approach to the method of source-sink potentials for molecular conduction

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

Pickup, Barry T., E-mail: B.T.Pickup@sheffield.ac.uk, E-mail: P.W.Fowler@sheffield.ac.uk; Fowler, Patrick W., E-mail: B.T.Pickup@sheffield.ac.uk, E-mail: P.W.Fowler@sheffield.ac.uk; Borg, Martha

2015-11-21

We re-derive the tight-binding source-sink potential (SSP) equations for ballistic conduction through conjugated molecular structures in a form that avoids singularities. This enables derivation of new results for families of molecular devices in terms of eigenvectors and eigenvalues of the adjacency matrix of the molecular graph. In particular, we define the transmission of electrons through individual molecular orbitals (MO) and through MO shells. We make explicit the behaviour of the total current and individual MO and shell currents at molecular eigenvalues. A rich variety of behaviour is found. A SSP device has specific insulation or conduction at an eigenvalue ofmore » the molecular graph (a root of the characteristic polynomial) according to the multiplicities of that value in the spectra of four defined device polynomials. Conduction near eigenvalues is dominated by the transmission curves of nearby shells. A shell may be inert or active. An inert shell does not conduct at any energy, not even at its own eigenvalue. Conduction may occur at the eigenvalue of an inert shell, but is then carried entirely by other shells. If a shell is active, it carries all conduction at its own eigenvalue. For bipartite molecular graphs (alternant molecules), orbital conduction properties are governed by a pairing theorem. Inertness of shells for families such as chains and rings is predicted by selection rules based on node counting and degeneracy.« less

Theoretical study of inverted sandwich type complexes of 4d transition metal elements: interesting similarities to and differences from 3d transition metal complexes.

PubMed

Kurokawa, Yusaku I; Nakao, Yoshihide; Sakaki, Shigeyoshi

2012-03-08

Inverted sandwich type complexes (ISTCs) of 4d metals, (μ-η(6):η(6)-C(6)H(6))[M(DDP)](2) (DDPH = 2-{(2,6-diisopropylphenyl)amino}-4-{(2,6-diisopropylphenyl)imino}pent-2-ene; M = Y, Zr, Nb, Mo, and Tc), were investigated with density functional theory (DFT) and MRMP2 methods, where a model ligand AIP (AIPH = (Z)-1-amino-3-imino-prop-1-ene) was mainly employed. When going to Nb (group V) from Y (group III) in the periodic table, the spin multiplicity of the ground state increases in the order singlet, triplet, and quintet for M = Y, Zr, and Nb, respectively, like 3d ISTCs reported recently. This is interpreted with orbital diagram and number of d electrons. However, the spin multiplicity decreases to either singlet or triplet in ISTC of Mo (group VI) and to triplet in ISTC of Tc (group VII), where MRMP2 method is employed because the DFT method is not useful here. These spin multiplicities are much lower than the septet of ISTC of Cr and the nonet of that of Mn. When going from 3d to 4d, the position providing the maximum spin multiplicity shifts to group V from group VII. These differences arise from the size of the 4d orbital. Because of the larger size of the 4d orbital, the energy splitting between two d(δ) orbitals of M(AIP) and that between the d(δ) and d(π) orbitals are larger in the 4d complex than in the 3d complex. Thus, when occupation on the d(δ) orbital starts, the low spin state becomes ground state, which occurs at group VI. Hence, the ISTC of Nb (group V) exhibits the maximum spin multiplicity.

COMPARATIVE ASSESSMENT OF THE COMPOSITION AND CHARGE STATE OF NITROGENASE FeMo-COFACTOR

PubMed Central

Harris, Travis V.; Szilagyi, Robert K.

2011-01-01

A significant limitation in our understanding of the molecular mechanism of biological nitrogen fixation is the uncertain composition of the FeMo-cofactor (FeMo-co) of nitrogenase. In this study we present a systematic, density functional theory-based evaluation of spin coupling schemes, iron oxidation states, ligand protonation states, and interstitial ligand composition using a wide range of experimental criteria. The employed functionals and basis sets were validated with molecular orbital information from X-ray absorption spectroscopic data of relevant iron-sulfur clusters. Independently from the employed level of theory, the electronic structure with the greatest number of antiferromagnetic interactions corresponds to the lowest energy state for a given charge and oxidation state distribution of the iron ions. The relative spin state energies of resting and oxidized FeMo-co already allowed the exclusion of certain iron oxidation state distributions and interstitial ligand compositions. Geometry optimized FeMo-co structures of several models further eliminated additional states and compositions, while reduction potentials indicated a strong preference for the most likely charge state of FeMo-co. Mössbauer and ENDOR parameter calculations were found to be remarkably dependent on the employed training set, density functional and basis set. Overall, we found that a more oxidized [MoIV-2FeII-5FeIII-9S2−-C4−] composition with a hydroxyl-protonated homocitrate ligand satisfies all of the available experimental criteria, and is thus favored over the currently preferred composition of [MoIV-4FeII-3FeIII-9S2−-N3−] from the literature. PMID:21545160

Exploration of a Variety of Copper Molybdate Coordination Hybrids Based on a Flexible Bis(1,2,4-triazole) Ligand: A Look through the Composition-Space Diagram.

PubMed

Senchyk, Ganna A; Lysenko, Andrey B; Domasevitch, Konstantin V; Erhart, Oliver; Henfling, Stefan; Krautscheid, Harald; Rusanov, Eduard B; Krämer, Karl W; Decurtins, Silvio; Liu, Shi-Xia

2017-11-06

We investigated the coordination ability of the bis(1,2,4-triazolyl) module, tr 2 pr = 1,3-bis(1,2,4-triazol-4-yl)propane, toward the engineering of solid-state structures of copper polyoxomolybdates utilizing a composition space diagram approach. Different binding modes of the ligand including [N-N]-bridging and N-terminal coordination and the existence of favorable conformation forms (anti/anti, gauche/anti, and gauche/gauche) resulted in varieties of mixed metal Cu I /Mo VI and Cu II /Mo VI coordination polymers prepared under hydrothermal conditions. The composition space analysis employed was aimed at both the development of new coordination solids and their crystallization fields through systematic changes of the reagent ratios [copper(II) and molybdenum(VI) oxide precursors and the tr 2 pr ligand]. Nine coordination compounds were synthesized and structurally characterized. The diverse coordination architectures of the compounds are composed of cationic fragments such as [Cu II 3 (μ 2 -OH) 2 (μ 2 -tr) 2 ] 4+ , [Cu II 3 (μ 2 -tr) 6 ] 6+ , [Cu II 2 (μ 2 -tr) 3 ] 4+ , etc., connected to polymeric arrays by anionic species (molybdate MoO 4 2- , isomeric α-, δ-, and β-octamolybdates {Mo 8 O 26 } 4- or {Mo 8 O 28 H 2 } 6- ). The inorganic copper(I,II)/molybdenum(VI) oxide matrix itself forms discrete or low-dimensional subtopological motifs (0D, 1D, or 2D), while the organic spacers interconnect them into higher-dimensional networks. The 3D coordination hybrids show moderate thermal stability up to 230-250 °C, while for the 2D compounds, the stability of the framework is distinctly lower (∼190 °C). The magnetic properties of the most representative samples were investigated. The magnetic interactions were rationalized in terms of analyzing the planes of the magnetic orbitals.

Linear Discriminant Analysis for the in Silico Discovery of Mechanism-Based Reversible Covalent Inhibitors of a Serine Protease: Application of Hydration Thermodynamics Analysis and Semi-empirical Molecular Orbital Calculation.

PubMed

Masuda, Yosuke; Yoshida, Tomoki; Yamaotsu, Noriyuki; Hirono, Shuichi

2018-01-01

We recently reported that the Gibbs free energy of hydrolytic water molecules (ΔG wat ) in acyl-trypsin intermediates calculated by hydration thermodynamics analysis could be a useful metric for estimating the catalytic rate constants (k cat ) of mechanism-based reversible covalent inhibitors. For thorough evaluation, the proposed method was tested with an increased number of covalent ligands that have no corresponding crystal structures. After modeling acyl-trypsin intermediate structures using flexible molecular superposition, ΔG wat values were calculated according to the proposed method. The orbital energies of antibonding π* molecular orbitals (MOs) of carbonyl C=O in covalently modified catalytic serine (E orb ) were also calculated by semi-empirical MO calculations. Then, linear discriminant analysis (LDA) was performed to build a model that can discriminate covalent inhibitor candidates from substrate-like ligands using ΔG wat and E orb . The model was built using a training set (10 compounds) and then validated by a test set (4 compounds). As a result, the training set and test set ligands were perfectly discriminated by the model. Hydrolysis was slower when (1) the hydrolytic water molecule has lower ΔG wat ; (2) the covalent ligand presents higher E orb (higher reaction barrier). Results also showed that the entropic term of hydrolytic water molecule (-TΔS wat ) could be used for estimating k cat and for covalent inhibitor optimization; when the rotational freedom of the hydrolytic water molecule is limited, the chance for favorable interaction with the electrophilic acyl group would also be limited. The method proposed in this study would be useful for screening and optimizing the mechanism-based reversible covalent inhibitors.

Infrared spectroscopy of undoped and Cu-doped (80-x)Sb{sub 2}O{sub 3}-20Li{sub 2}O-xMoO{sub 3} glasses

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

Petkova, P., E-mail: Petya232@abv.bg; Vasilev, P.; Mustafa, M.

2016-04-21

In this work, the absorption spectra of the undoped and doped with 0.1% and 0.2% CuO{sub 2} glasses with the composition (80-x)Sb{sub 2}O{sub 3}-20Li{sub 2}O-xMoO{sub 3} are measured in the spectral region 1300-1800 nm. The optical structure of Cu{sup 2+} is investigated and the energies of the electron transitions in this metal cation are determined. The spin-orbit interaction, Lattice Compatibility Theory (LCT) analyses and the influence of molybdenum are also discussed.

Electronic structure evolution in doping of fullerene (C{sub 60}) by ultra-thin layer molybdenum trioxide

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

Wang, Chenggong; Wang, Congcong; Kauppi, John

2015-08-28

Ultra-thin layer molybdenum oxide doping of fullerene has been investigated using ultraviolet photoemission spectroscopy (UPS) and X-ray photoemission spectroscopy (XPS). The highest occupied molecular orbital (HOMO) can be observed directly with UPS. It is observed that the Fermi level position in fullerene is modified by ultra-thin-layer molybdenum oxide doping, and the HOMO onset is shifted to less than 1.3 eV below the Fermi level. The XPS results indicate that charge transfer was observed from the C{sub 60} to MoO{sub x} and Mo{sup 6+} oxides is the basis as hole dopants.

An ab initio MO study of heavy atom effects on the zero-field splitting tensors of high-spin nitrenes: how the spin-orbit contributions are affected.

PubMed

Sugisaki, Kenji; Toyota, Kazuo; Sato, Kazunobu; Shiomi, Daisuke; Kitagawa, Masahiro; Takui, Takeji

2014-05-21

The CASSCF and the hybrid CASSCF-MRMP2 methods are applied to the calculations of spin-spin and spin-orbit contributions to the zero-field splitting tensors (D tensors) of the halogen-substituted spin-septet 2,4,6-trinitrenopyridines, focusing on the heavy atom effects on the spin-orbit term of the D tensors (D(SO) tensors). The calculations reproduced experimentally determined |D| values within an error of 15%. Halogen substitutions at the 3,5-positions are less influential in the spin-spin dipolar (D(SS)) term of 2,4,6-trinitrenopyridines, although the D(SO) terms are strongly affected by the introduction of heavier halogens. The absolute sign of the D(SO) value (D = D(ZZ) - (D(XX) + D(YY))/2) of 3,5-dibromo derivative 3 is predicted to be negative, which contradicts the Pederson-Khanna (PK) DFT result previously reported. The large negative contributions to the D(SO) value of 3 arise from the excited spin-septet states ascribed mainly to the excitations of in-plane lone pair of bromine atoms → SOMO of π nature. The importance of the excited states involving electron transitions from the lone pair orbital of the halogen atom is also confirmed in the D(SO) tensors of halogen-substituted para-phenylnitrenes. A new scheme based on the orbital region partitioning is proposed for the analysis of the D(SO) tensors as calculated by means of the PK-DFT approach.

Valley- and spin-polarized oscillatory magneto-optical absorption in monolayer MoS2 quantum rings

NASA Astrophysics Data System (ADS)

Oliveira, D.; Villegas-Lelovsky, L.; Soler, M. A. G.; Qu, Fanyao

2018-03-01

Besides optical valley selectivity, strong spin-orbit interaction along with Berry curvature effects also leads to unconventional valley- and spin-polarized Landau levels in monolayer transition metal dichalcogenides (TMDCs) under a perpendicular magnetic field. We find that these unique properties are inherited to the magneto-optical absorption spectrum of the TMDC quantum rings (QRs). In addition, it is robust against variation of the magnetic flux and of the QR geometry. In stark contrast to the monolayer bulk material, the MoS2 QRs manifest themselves in both the optical valley selectivity and unprecedented size tunability of the frequency of the light absorbed. We also find that when the magnetic field setup is changed, the phase transition from Aharonov-Bohm (AB) quantum interference to aperiodic oscillation of magneto-optical absorption spectrum takes place. The exciton spectrum in a realistic finite thickness MoS2 QR is also discussed.

Astronaut Charles Conrad as test subject for Lower Body Negative Pressure

NASA Image and Video Library

1973-06-09

S73-27707 (9 June 1973) --- Astronaut Charles Conrad Jr., Skylab 2 commander, serves as test subject for the Lower Body Negative Pressure (MO92) Experiment, as seen in this reproduction taken from a color television transmission made by a TV camera aboard the Skylab 1/2 space station cluster in Earth orbit. Scientist-astronaut Joseph P. Kerwin, Skylab 2 science pilot, assists Conrad into the LBNP device. Kerwin served as monitor for the experiment. The purpose of the MO92 experiment is to provide information concerning the time course of cardiovascular adaptation during flight, and to provide inflight data for predicting the degree of orthostatic intolerance and impairment of physical capacity to be expected upon return to Earth environment. The data collected in support of MO92 blood pressure, heart rate, body temperature, vectorcardiogram, LBNPD pressure, leg volume changes, and body weight. Photo credit: NASA

Linear and nonlinear magneto-optical properties of monolayer MoS2

NASA Astrophysics Data System (ADS)

Nguyen, Chuong V.; Hieu, Nguyen N.; Muoi, Do; Duque, Carlos A.; Feddi, Elmustapha; Nguyen, Hieu V.; Phuong, Le T. T.; Hoi, Bui D.; Phuc, Huynh V.

2018-01-01

In this work, using the compact density matrix approach, we study the linear and nonlinear magneto-optical properties of monolayer molybdenum disulfide (MoS2) via an investigation of the absorption coefficients (MOACs) and refractive index changes (RICs). The results are presented as functions of photon energy and external magnetic field. Our results show that the MOACs and the RICs appear as a series of peaks in the inter-band transitions between Landau levels, while the intra-band transitions result in only one peak. Because of the strong spin-orbit coupling, the peaks caused by the spin-up and -down states are different. With the increase in the magnetic field, both MOACs and RICs give a blue-shift and reduce in their amplitudes. These results suggest a potential application of monolayer MoS2 in the optoelectronic technology, magneto-optical, valleytronic, and spintronic devices.

Interplay between Organic-Organometallic Electrophores within Bis(cyclopentadienyl)Molybdenum Dithiolene Tetrathiafulvalene Complexes.

PubMed

Bellec, Nathalie; Vacher, Antoine; Barrière, Frédéric; Xu, Zijun; Roisnel, Thierry; Lorcy, Dominique

2015-05-18

Tetrathiafulvalenes (TTF) and bis(cyclopentadienyl) molybdenum dithiolene complexes, Cp2Mo(dithiolene) complexes, are known separately to act as good electron donor molecules. For an investigation of the interaction between both electrophores, two types of complexes were synthesized and characterized. The first type has one Cp2Mo fragment coordinated to one TTF dithiolate ligand, and the second type has one TTF bis(dithiolate) bridging two Cp2Mo fragments. Comparisons of the electrochemical properties of these complexes with those of models of each separate electrophore provide evidence for their mutual influence. All of these complexes act as very good electron donors with a first oxidation potential 430 mV lower than the tetrakis(methylthio)TTF. DFT calculations suggest that the HOMO of the neutral complex and the SOMO of the cation are delocalized across the whole TTF dithiolate ligand. The X-ray crystal structure analyses of the neutral and the mono-oxidized Cp2Mo(dithiolene)(bismethylthio)TTF complexes are consistent with the delocalized assignment of the highest occupied frontier molecular orbitals. UV-vis-NIR spectroelectrochemical investigations confirm this electronic delocalization within the TTF dithiolate ligand.

Transition metal atoms absorbed on MoS2/h-BN heterostructure: stable geometries, band structures and magnetic properties.

PubMed

Wu, Yanbing; Huang, Zongyu; Liu, Huating; He, Chaoyu; Xue, Lin; Qi, Xiang; Zhong, Jianxin

2018-06-15

We have studied the stable geometries, band structures and magnetic properties of transition-metal (V, Cr, Mn, Fe, Co and Ni) atoms absorbed on MoS2/h-BN heterostructure systems by first-principles calculations. By comparing the adsorption energies, we find that the adsorbed transition metal (TM) atoms prefer to stay on the top of Mo atoms. The results of the band structure without spin-orbit coupling (SOC) interaction indicate that the Cr-absorbed systems behave in a similar manner to metals, and the Co-absorbed system exhibits a half-metallic state. We also deduce that the V-, Mn-, Fe-absorbed systems are semiconductors with 100% spin polarization at the HOMO level. The Ni-absorbed system is a nonmagnetic semiconductor. In contrast, the Co-absorbed system exhibits metallic state, and the bandgap of V-absorbed system decreases slightly according to the SOC calculations. In addition, the magnetic moments of all the six TM atoms absorbed on the MoS2/h-BN heterostructure systems decrease when compared with those of their free-standing states.

Towards a multiconfigurational method of increments

NASA Astrophysics Data System (ADS)

Fertitta, E.; Koch, D.; Paulus, B.; Barcza, G.; Legeza, Ö.

2018-06-01

The method of increments (MoI) allows one to successfully calculate cohesive energies of bulk materials with high accuracy, but it encounters difficulties when calculating dissociation curves. The reason is that its standard formalism is based on a single Hartree-Fock (HF) configuration whose orbitals are localised and used for the many-body expansion. In situations where HF does not allow a size-consistent description of the dissociation, the MoI cannot be guaranteed to yield proper results either. Herein, we address the problem by employing a size-consistent multiconfigurational reference for the MoI formalism. This leads to a matrix equation where a coupling derived by the reference itself is employed. In principle, such an approach allows one to evaluate approximate values for the ground as well as excited states energies. While the latter are accurate close to the avoided crossing only, the ground state results are very promising for the whole dissociation curve, as shown by the comparison with density matrix renormalisation group benchmarks. We tested this two-state constant-coupling MoI on beryllium rings of different sizes and studied the error introduced by the constant coupling.

Robust spin-valley polarization in commensurate Mo S2 /graphene heterostructures

NASA Astrophysics Data System (ADS)

Du, Luojun; Zhang, Qian; Gong, Benchao; Liao, Mengzhou; Zhu, Jianqi; Yu, Hua; He, Rui; Liu, Kai; Yang, Rong; Shi, Dongxia; Gu, Lin; Yan, Feng; Zhang, Guangyu; Zhang, Qingming

2018-03-01

The investigation and control of quantum degrees of freedom (DoFs) of carriers lie at the heart of condensed-matter physics and next-generation electronics/optoelectronics. van der Waals heterostructures stacked from distinct two-dimensional (2D) crystals offer an unprecedented platform for combining the superior properties of individual 2D materials and manipulating spin, layer, and valley DoFs. Mo S2 /graphene heterostructures, harboring prominent spin-transport properties of graphene, giant spin-orbit coupling, and spin-valley polarization of Mo S2 , are predicted as a perfect venue for optospintronics. Here, we report the epitaxial growth of commensurate Mo S2 on graphene with high quality by chemical vapor deposition, and demonstrate robust temperature-independent spin-valley polarization at off-resonant excitation. We further show that the helicity of B exciton is larger than that of A exciton, allowing the manipulation of spin bits in the commensurate heterostructures by both optical helicity and wavelength. Our results open a window for controlling spin DoF by light and pave a way for taking spin qubits as information carriers in the next-generation valley-controlled optospintronics.

Magnetic and Geochemical Records of Glacial Terminations, Weathering and Carbon Burial in the Southeastern South China Sea for the Last 800 kyr

NASA Astrophysics Data System (ADS)

Kandasamy, S.; Kao, S.; Hsu, S.; Lee, T.; Velasco, V. M.; Soon, W.; Chen, M.

2013-12-01

Rebuilding of past climate and oceanographic records from monsoon dominated Asia is of vital importance for understanding the causes and mechanisms of global and regional climate changes at orbital-millennial timescales. South China Sea (SCS) provides the best marine platform to investigate a number of paleoclimate and paleoceanographic problems on different timescales mainly because of high sedimentation rates, good preservation of microfossils and the location of SCS as a connector between the Western Pacific Warm Pool and the SE Asian monsoon. Here we investigate magnetic, geochemical and isotopic records from a piston core MD97-2142 rose from the southeastern SCS to understand the past glacial terminations, chemical weathering and carbon burial on orbital to millennial timescales for the last 800 kyr. Terrigenous content and Al/Ti ratio reveal higher terrigenous input during glacial periods and vice versa during interglacials. Proxies of chemical weathering reveal larger fluctuations between 150 and 500 kyr than that of the last 150 kyr. Records of C/N ratio and carbon isotope of total organic carbon (δ13CTOC) mimic each other with higher marine productivity during marine isotope stages (MIS) 8, 10 and 12. Enrichment factors of Mn and Mo (EF Mn and EF Mo) show roughly an opposite pattern with <1 EF Mo almost throughout the last 500 kyr may suggest that the southeastern part of SCS has never been attained anoxic condition both glacial and interglacial intervals from MIS 1 through MIS 13. EF Mn shows >1 in most odd MIS, whereas <~1 EF Mn was evident in even MIS, suggesting that the former condition was likely attributed to bottom water ventilation associated with high sea levels during interglacials. We found through two endmember mixing model of δ13CTOC that lower burial of terrigenous fraction of TOC (OCTERR) during glacial intervals (MIS 6, 8, 10 and 12), but vice versa during interglacial (MIS 7, 9 and 11) periods. Our bulk magnetic susceptibility (MS) time series documents the last seven glacial terminations (T1-T7) with distinctive behaviors of T4 and T6. Wavelet analysis of MS record exhibits statistically significant periodicity at 239 kyr, 142 kyr, 85 kyr, 45 kyr, 24 kyr and 13 kyr of eccentricity, obliquity and precession cycles. With the help of diverse proxy records, the role of insolation, monsoon forcing and sea level on the variation of productivity, terrigenous input and carbon burial will be discussed on orbital and millennial timescales.

Electron-positron momentum density in Tl 2Ba 2CuO 6

NASA Astrophysics Data System (ADS)

Barbiellini, B.; Gauthier, M.; Hoffmann, L.; Jarlborg, T.; Manuel, A. A.; Massidda, S.; Peter, M.; Triscone, G.

1994-08-01

We present calculations of the electron-positron momentum density for the high- Tc superconductor Tl 2Ba 2CuO 6, together with some preliminary two-dimensional angular correlation of the annihilation radiation (2D-ACAR) measurements. The calculations are based on the first-principles electronic structure obtained using the full-potential linearized augmented plane wave (FLAPW) and the linear muffin-tin orbital (LMTO) methods. We also use a linear combination of the atomic orbitals-molecular orbital method (LCAO-MO) to discuss orbital contributions to the anisotropies. Some agreement between calculated and measured 2D-ACAR anisotropies encourage sample improvement for further Fermi surface investigations. Indeed, our results indicate a non-negligle overlap of the positron wave function with the CuOo 2 plane electrons. Therefore, this compound may be well suited for investigating the relevant CuO 2 Fermi surface by 2D-ACAR.

Nonlinear d10-ML2 Transition-Metal Complexes

PubMed Central

Wolters, Lando P; Bickelhaupt, F Matthias

2013-01-01

We have investigated the molecular geometries of a series of dicoordinated d10-transition-metal complexes ML2 (M=Co−, Rh−, Ir−, Ni, Pd, Pt, Cu+, Ag+, Au+; L=NH3, PH3, CO) using relativistic density functional theory (DFT) at ZORA-BLYP/TZ2P. Not all complexes have the expected linear ligand–metal–ligand (L–M–L) angle: this angle varies from 180° to 128.6° as a function of the metal as well as the ligands. Our main objective is to present a detailed explanation why ML2 complexes can become bent. To this end, we have analyzed the bonding mechanism in ML2 as a function of the L–M–L angle using quantitative Kohn–Sham molecular orbital (MO) theory in combination with an energy decomposition analysis (EDA) scheme. The origin of bent L–M–L structures is π backdonation. In situations of strong π backdonation, smaller angles increase the overlap of the ligand’s acceptor orbital with a higher-energy donor orbital on the metal-ligand fragment, and therefore favor π backdonation, resulting in additional stabilization. The angle of the complexes thus depends on the balance between this additional stabilization and increased steric repulsion that occurs as the complexes are bent. PMID:24551547

The role of spin-orbit coupling in topologically protected interface states in Dirac materials

NASA Astrophysics Data System (ADS)

Abergel, D. S. L.; Edge, Jonathan M.; Balatsky, Alexander V.

2014-06-01

We highlight the fact that two-dimensional (2D) materials with Dirac-like low energy band structures and spin-orbit coupling (SOC) will produce linearly dispersing topologically protected Jackiw-Rebbi modes at interfaces where the Dirac mass changes sign. These modes may support persistent spin or valley currents parallel to the interface, and the exact arrangement of such topologically protected currents depends crucially on the details of the SOC in the material. As examples, we discuss buckled 2D hexagonal lattices such as silicene or germanene, and transition metal dichalcogenides such as Mo{{S}_{2}}.

Interaction Mode and Regioselectivity in Vitamin B12-Dependent Dehalogenation of Aryl Halides by Dehalococcoides mccartyi Strain CBDB1.

PubMed

Zhang, Shangwei; Adrian, Lorenz; Schüürmann, Gerrit

2018-02-20

The bacterium Dehalococcoides, strain CBDB1, transforms aromatic halides through reductive dehalogenation. So far, however, the structures of its vitamin B 12 -containing dehalogenases are unknown, hampering clarification of the catalytic mechanism and substrate specificity as basis for targeted remediation strategies. This study employs a quantum chemical donor-acceptor approach for the Co(I)-substrate electron transfer. Computational characterization of the substrate electron affinity at carbon-halogen bonds enables discriminating aromatic halides ready for dehalogenation by strain CBDB1 (active substrates) from nondehalogenated (inactive) counterparts with 92% accuracy, covering 86 of 93 bromobenzenes, chlorobenzenes, chlorophenols, chloroanilines, polychlorinated biphenyls, and dibenzo-p-dioxins. Moreover, experimental regioselectivity is predicted with 78% accuracy by a site-specific parameter encoding the overlap potential between the Co(I) HOMO (highest occupied molecular orbital) and the lowest-energy unoccupied sigma-symmetry substrate MO (σ*), and the observed dehalogenation pathways are rationalized with a success rate of 81%. Molecular orbital analysis reveals that the most reactive unoccupied sigma-symmetry orbital of carbon-attached halogen X (σ C-X * ) mediates its reductive cleavage. The discussion includes predictions for untested substrates, thus providing opportunities for targeted experimental investigations. Overall, the presently introduced orbital interaction model supports the view that with bacterial strain CBDB1, an inner-sphere electron transfer from the supernucleophile B 12 Co(I) to the halogen substituent of the aromatic halide is likely to represent the rate-determining step of the reductive dehalogenation.

New rhenium(I) compounds containing the donor-acceptor diphosphine ligands 2-(ferrocenylidene)-4,5-bis(diphenylphosphino)4-cyclopenten-1,3-dione (fbpcd) and 2-(3-ferrocenylprop-2-ynylidene)-4,5-bis(diphenylphosphino)4-cyclopenten-1,3-dione (fpbpcd): Electrochemical behavior, MO properties, and X-ray diffraction structure of fac-BrRe(CO)(3)(fpbpcd)

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

Poola, Bhaskar; Richmond, Michael G.

2009-01-01

Displacement of the labile THF molecules in BrRe(CO){sub 3}(THF){sub 2} (1) by the diphosphine ligands 2-(ferrocenylidene)-4,5-bis(diphenylphosphino)4-cyclopenten-1,3-dione (fbpcd) and 2-(3-ferrocenylprop-2-ynylidene)-4,5-bis(diphenylphosphino)4-cyclopenten- 1,3-dione (fpbpcd) yields the mononuclear compounds fac-BrRe(CO){sub 3}(fbpcd) (2) and fac-BrRe(CO){sub 3}(fpbpcd) (3), respectively. The new ligand fpbpcd ligand has been synthesized from 3-ferrocenylpropynal and the parent diphosphine ligand 4,5-bis(diphenylphosphino)-4-cyclopenten-1,3-dione (bpcd) through a Knoevenagel condensation. 2 and 3 have been isolated and fully characterized by IR and NMR spectroscopies ({sup 1}H and {sup 31}P), ESI mass spectrometry, and X-ray diffraction analysis in the case of 3. The electrochemical properties of compounds 2 and 3 have been examined by cyclic voltammetry, andmore » the nature of the HOMO and LUMO levels in these systems has been confirmed by MO calculations at the extended Hueckel level. The redox and MO data are discussed relative to the redox and orbital properties of related functionalized diphosphines based on the bpcd platform.« less

MnMoO4 nanolayers : Synthesis characterizations and electrochemical detection of QA

NASA Astrophysics Data System (ADS)

Muthamizh, S.; Kumar, S. Praveen; Munusamy, S.; Narayanan, V.

2018-04-01

MnMoO4 nanolayers were prepared by precipitation method. The MnMoO4 nanolayers were synthesized by using commercially available (CH3COO)2Mn.4H2O and Na2WO4.2H2O. The XRD pattern reveals that the synthesized MnMoO4 has monoclinic structure. In addition, lattice parameter values were also calculated using XRD data. The Raman analysis confirm the presence of Mo-O in MnMoO4 nanolayers. DRS-UV analysis shows that MnMoO4 has a band gap of 2.59 eV. FE-SEM and HR-TEM analysis along with EDAX confirms the material morphology in stacked layers like structure in nano scale. Synthesized nanolayers were utilized for the detection of biomolecule quercetin (QA).

Selectivity in Ketenimine Cycloadditions. Photoelectron Hel Spectra of Ketenimines

NASA Astrophysics Data System (ADS)

Bernardi, Fernando; Bottoni, Andrea; Ballaglia, Arturo; Distefano, Giuseppe; Dondoni, Alessandro

1980-05-01

The first few bands in the photoelectron (Hel) spectra of ketenimines R1R2C-C=NR3(R1,R2=H, CH3, C5H6, CH2=CH; R3=alkyl or aryl group) are assigned to the corresponding molecular orbitals. The assignment is based on SCF-MO calculations made at three different levels (CNDO/2, ab-initio STO-3C and 4-31G) coupled with perturbational molecular orbital analyses. The π-orbitals of the unsaturated substituents are found to interact with one of the two perpendicular π-electron systems of the>C=C=N- residue, the critical factor being the position of attack of the substituent. The relevance of these results on the site selectivity observed in cycloaddition reactions of these species is discussed.

The In-Orbit Battery Reconditioning Experience On Board the Orion 1 Spacecraft

NASA Technical Reports Server (NTRS)

Hoover, S. A.; Daughtridge, S.; Johnson, P. J.; King, S. T.

1997-01-01

The Orion 1 spacecraft is a three-axis stabilized geostationary earth orbiting commercial communications satellite which was launched on November 29, 1994 aboard an Atlas II launch vehicle. The power subsystem is a dual bus, dual battery semi-regulated system with one 78 Ampere-hour nickel-hydrogen battery per bus. The batteries were built and tested by Eagle Picher Industries, Inc., of Joplin, MO and were integrated into the spacecraft by its manufacturer, Matra Marconi Space UK Ltd. This paper presents the results obtained during the first four in-orbit reconditioning cycles and compares the battery performance to ground test data. In addition, the on-station battery management strategy and implementation constraints are described. Battery performance has been nominal throughout each reconditioning cycle and subsequent eclipse season.

Ab initio quantum chemical calculations of the interaction between radioactive elements and imidazolium based ionic liquids

NASA Astrophysics Data System (ADS)

Saravanan, A. V. Sai; Abishek, B.; Anantharaj, R.

2018-04-01

The fundamental natures of the molecular level interaction and charge transfer between specific radioactive elements and ionic liquids of 1-butyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide ([BMIM]+[NTf2]-), 1-Butyl-3-methylimidazolium ethylsulfate ([BMIM]+[ES]-) and 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]+[BF4]-) were investigated utilising HF theory and B3LYP hybrid DFT. The ambiguity in reaction mechanism of the interacting species dictates to employ Effective Core Potential (ECP) basis sets such as UGBS, SDD, and SDDAll to account for the relativistic effects of deep core electrons in the system involving potential, heavy and hazardous radioactive elements present in nuclear waste. The SCF energy convergence of each system validates the characterisation of the molecular orbitals as a linear combination of atomic orbitals utilising fixed MO coefficients and the optimized geometry of each system is visualised based on which Mulliken partial charge analysis is carried out to account for the polarising behaviour of the radioactive element and charge transfer between the IL phase by comparison with the bare IL species.

Structure-property relationships: Synthesis and characterization of Perovskite-related transition metal oxides

NASA Astrophysics Data System (ADS)

Whaley, Louis

The fundamental structural component of perovskite-related phases is the octahedrally coordinated transition metal ion, symbolized as BO6 . Corner-sharing networks of BO6 octahedra are present in perovskites and related Ruddlesden-Popper Phases, ABO3 and AO(ABO 3)n, respectively. Face-sharing octahedra arranged into columns are characteristic of hexagonal, perovskite-related phases, and the relationship will be described in detail in Chapter 1. Edge sharing octahedra are characteristic of Keggin- and Lindquist-type polyoxometallates, which at first glance, seem unconnected from perovskites. However, Chapter 1 will show the deep connections among all of the phases mentioned above, by starting with perovskite phases. Temperature- and field-dependent, magnetic and electronic transitions are linked to the structure by overlap of metal d-orbitals with oxygen 2p orbitals, and (in special cases) direct d-d overlap. A mixed-transition metal oxide with two or more type of B ions provides an environment in which dissimilar B-ion orbitals can interact via exchange of charge carriers (hole or electron transport). The general goal in choosing two B ions is to provide an opportunity for the large combined magnetic moment and a low barrier to hopping of charge carriers, achieved by pairing a 3d-ion having 3 to 5 unpaired d-electrons, with a 4d or 5d transition metal ion, having 1 or 2 unpaired electrons, such as Fe(III) and Mo(V), which have compatible reduction potentials (i.e., they can co-exist in the same oxide, and exchange takes place with a low barrier). This research includes the following systems: an n = 2 Ruddlesden-Popper (RP) phase, Sr3Fe5/4Mo3/4O6.9, containing 3-7% Sr2FeMoO6, as intergrowths (not separate crystal grains, by high-resolution transmission electron microscopy), and G-type antiferromagnetism below 150°K and a "partial spin-reorientation transition" by powder neutron diffraction (PND), not previously reported for n = 2 RP phases in the Sr-Fe-Mo-O system; A B-site ordered double perovskite with an unusual a+b+c+ Glazer octahedral tilt system was synthesized, SrFe1/4Re3/4O 3; single crystals of two anhydrous 1-ethyl-3-methylimidazolium (EMI) salts, EMI octamolybdate, (C6H11N2) 4Mo8O26; and EMI decatungstate, (C6H 11N2)4W10O32; and single crystals of an incommensurate modulated phase, "Sr3CoRh2O 9-delta", with a structure comprising two interpenetrating modulated lattices. Properties of the phases are also reported.

The formation of Colloidal 2D/3D MoS2 Nanostructures in Organic Liquid Environment

NASA Astrophysics Data System (ADS)

Durgun, Engin; Sen, H. Sener; Oztas, Tugba; Ortac, Bulend

2015-03-01

2D MoS2 nanosheets (2D MoS2 NS) and fullerene-like MoS2 nanostructures (3D MoS2 NS) with varying sizes are synthesized by nanosecond laser ablation of hexagonal crystalline 2H-MoS2 powder in methanol. Structural, chemical, and optical properties of MoS2 NS are characterized by optical microscopy, SEM, TEM, XRD, Raman and UV/VIS/NIR absorption spectroscopy techniques. Results of structural analysis show that the obtained MoS2 NS mainly present layered morphology from micron to nanometer surface area. Detailed analysis of the product also proves the existence of inorganic polyhedral fullerene-like 3D MoS2 NS generated by pulsed laser ablation in methanol. The possible factors which may lead to formation of both 2D and 3D MoS2 NS in methanol are examined by ab initio calculations and shown that it is correlated with vacancy formation. The hexagonal crystalline structure of MoS2 NS was determined by XRD analysis. The colloidal MoS2 NS solution presents broadband absorption edge tailoring from UV region to NIR region. Investigations of MoS2 NS show that the one step physical process of pulsed laser ablation-bulk MoS2 powder interaction in organic solution opens doors to the formation of ``two scales'' micron- and nanometer-sized layered and fullerene-like morphology MoS2 structures. This work was partially supported by TUBITAK under the Project No. 113T050 and Bilim Akademisi - The Science Academy, Turkey under the BAGEP program.

Vibrational and optical properties of MoS2: From monolayer to bulk

NASA Astrophysics Data System (ADS)

Molina-Sánchez, Alejandro; Hummer, Kerstin; Wirtz, Ludger

2015-12-01

Molybdenum disulfide, MoS2, has recently gained considerable attention as a layered material where neighboring layers are only weakly interacting and can easily slide against each other. Therefore, mechanical exfoliation allows the fabrication of single and multi-layers and opens the possibility to generate atomically thin crystals with outstanding properties. In contrast to graphene, it has an optical gap of ~1.9 eV. This makes it a prominent candidate for transistor and opto-electronic applications. Single-layer MoS2 exhibits remarkably different physical properties compared to bulk MoS2 due to the absence of interlayer hybridization. For instance, while the band gap of bulk and multi-layer MoS2 is indirect, it becomes direct with decreasing number of layers. In this review, we analyze from a theoretical point of view the electronic, optical, and vibrational properties of single-layer, few-layer and bulk MoS2. In particular, we focus on the effects of spin-orbit interaction, number of layers, and applied tensile strain on the vibrational and optical properties. We examine the results obtained by different methodologies, mainly ab initio approaches. We also discuss which approximations are suitable for MoS2 and layered materials. The effect of external strain on the band gap of single-layer MoS2 and the crossover from indirect to direct band gap is investigated. We analyze the excitonic effects on the absorption spectra. The main features, such as the double peak at the absorption threshold and the high-energy exciton are presented. Furthermore, we report on the the phonon dispersion relations of single-layer, few-layer and bulk MoS2. Based on the latter, we explain the behavior of the Raman-active A1g and E2g1 modes as a function of the number of layers. Finally, we compare theoretical and experimental results of Raman, photoluminescence, and optical-absorption spectroscopy.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

NASA Astrophysics Data System (ADS)

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-Ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-04-01

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g-1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g-1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

Probing the Fermi surface and magnetotransport properties of MoAs2

NASA Astrophysics Data System (ADS)

Singha, Ratnadwip; Pariari, Arnab; Gupta, Gaurav Kumar; Das, Tanmoy; Mandal, Prabhat

2018-04-01

Transition-metal dipnictides (TMDs) have recently been identified as possible candidates to host a topology-protected electronic band structure. These materials belong to an isostructural family and show several exotic transport properties. Especially, the large values of magnetoresistance (MR) and carrier mobility have drawn significant attention from the perspective of technological applications. In this paper, we investigate the magnetotransport and Fermi surface properties of single-crystalline MoAs2, another member of this group of compounds. A field-induced resistivity plateau and a large MR have been observed, which are comparable to those in several topological systems. Interestingly, in contrast to other isostructural materials, the carrier density in MoAs2 is quite high and shows single-band-dominated transport. The Fermi pockets, which have been identified from the quantum oscillation, are the largest among the members of this group and have significant anisotropy with crystallographic direction. Our first-principles calculations reveal a substantial difference between the band structures of MoAs2 and that of other TMDs. The calculated Fermi surface consists of one electron pocket and another "open-orbit" hole pocket, which has not been observed in TMDs so far.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode.

PubMed

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-04-18

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na(1/3)Ru(2/3)]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

All-Electrical Spin Field Effect Transistor in van der Waals Heterostructures at Room Temperature

NASA Astrophysics Data System (ADS)

Dankert, André; Dash, Saroj

Spintronics aims to exploit the spin degree of freedom in solid state devices for data storage and information processing. Its fundamental concepts (creation, manipulation and detection of spin polarization) have been demonstrated in semiconductors and spin transistor structures using electrical and optical methods. However, an unsolved challenge is the realization of all-electrical methods to control the spin polarization in a transistor manner at ambient temperatures. Here we combine graphene and molybdenum disulfide (MoS2) in a van der Waals heterostructure to realize a spin field-effect transistor (spin-FET) at room temperature. These two-dimensional crystals offer a unique platform due to their contrasting properties, such as weak spin-orbit coupling (SOC) in graphene and strong SOC in MoS2. The gate-tuning of the Schottky barrier at the MoS2/graphene interface and MoS2 channel yields spins to interact with high SOC material and allows us to control the spin polarization and lifetime. This all-electrical spin-FET at room temperature is a substantial step in the field of spintronics and opens a new platform for testing a plethora of exotic physical phenomena, which can be key building blocks in future device architectures.

Mars Lower Thermosphere Variability from Odyssey and MRO Aerobraking Measurements

NASA Astrophysics Data System (ADS)

Forbes, J. M.; Zhang, X.

2017-12-01

During the aerobraking phases of the Mars Odyssey (MO) and Mars Reconnaissance Orbiter (MRO) missions, accelerometer measurements of total mass density at periapsis altitudes near 105 km were made in Mars' polar regions (> 75o latitude) during Northern Hemisphere winter (MO, Ls = 288-297) and Southern Hemisphere winter (MRO, Ls = 69-87). These measurements cover overlapping local times spanning nearly 8 hours. Prior to the local time transition, the MO and MRO accelerometers sample the high-latitude regions at nearly the same latitudes (70-85o) and same local times (1800-1900), and after the transition periapsis precesses relatively quickly (over roughly 20-30 sols) from 80o to 20o latitude in each hemisphere while keeping the local time constant near 0200-0300 LT. These observations offer the unprecedented opportunity to compare and contrast the behaviors of Mars' polar and middle latitude regions under similar geographic, altitude and local time conditions in the two hemispheres (albeit during different years), which is the focus of this paper. Particularly noteworthy are the slow (mostly eastward) migrations of longitudinal features in both MO and MRO data, which suggest modulations of non-migrating tides by planetary waves with periods of order 15-20 days.

Bond angles in transition metal tetracarbonyl compounds: A further test of the theory of hybrid bond orbitals*

PubMed Central

Pauling, Linus

1978-01-01

An equation for the bond angles OC—M—CO for tetracarbonyl groups in which the transition metal atom M is enneacovalent, derived from the simple theory of hybrid sp3d5 bond orbitals, is tested by comparison of the calculated values of the angles with the experimental values reported for many compounds containing M(CO)4 groups, especially those with M = Fe, Mn, Re, Cr, or Mo. The importance of the energy of resonance of single bonds and double bonds in stabilizing octahedral complexes of chromium and manganese with carbonyl, phosphine, arsine, and thio groups is also discussed. PMID:16592490

Tunable, Highly Stable Lasers for Coherent Lidar

NASA Technical Reports Server (NTRS)

Henderson, Sammy W.; Hale, Charley P.; EEpagnier, David M.

2006-01-01

Practical space-based coherent laser radar systems envisioned for global winds measurement must be very efficient and must contend with unique problems associated with the large platform velocities that the instruments experience in orbit. To compensate for these large platform-induced Doppler shifts in space-based applications, agile-frequency offset-locking of two single-frequency Doppler reference lasers was thoroughly investigated. Such techniques involve actively locking a frequency-agile master oscillator (MO) source to a comparatively static local oscillator (LO) laser, and effectively producing an offset between MO (the lidar slave oscillator seed source, typically) and heterodyne signal receiver LO that lowers the bandwidth of the receiver data-collection system and permits use of very high-quantum-efficiency, reasonably- low-bandwidth heterodyne photoreceiver detectors and circuits. Recent work on MO/LO offset locking has focused on increasing the offset locking range, improving the graded-InGaAs photoreceiver performance, and advancing the maturity of the offset locking electronics. A figure provides a schematic diagram of the offset-locking system.

Chromatic Mechanical Response in 2-D Layered Transition Metal Dichalcogenide (TMDs) based Nanocomposites

PubMed Central

Rahneshin, Vahid; Khosravi, Farhad; Ziolkowska, Dominika A.; Jasinski, Jacek B.; Panchapakesan, Balaji

2016-01-01

The ability to convert photons of different wavelengths directly into mechanical motion is of significant interest in many energy conversion and reconfigurable technologies. Here, using few layer 2H-MoS2 nanosheets, layer by layer process of nanocomposite fabrication, and strain engineering, we demonstrate a reversible and chromatic mechanical response in MoS2-nanocomposites between 405 nm to 808 nm with large stress release. The chromatic mechanical response originates from the d orbitals and is related to the strength of the direct exciton resonance A and B of the few layer 2H-MoS2 affecting optical absorption and subsequent mechanical response of the nanocomposite. Applying uniaxial tensile strains to the semiconducting few-layer 2H-MoS2 crystals in the nanocomposite resulted in spatially varying energy levels inside the nanocomposite that enhanced the broadband optical absorption up to 2.3 eV and subsequent mechanical response. The unique photomechanical response in 2H-MoS2 based nanocomposites is a result of the rich d electron physics not available to nanocomposites based on sp bonded graphene and carbon nanotubes, as well as nanocomposite based on metallic nanoparticles. The reversible strain dependent optical absorption suggest applications in broad range of energy conversion technologies that is not achievable using conventional thin film semiconductors. PMID:27713550

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.

Many-body expansion of the Fock matrix in the fragment molecular orbital method

NASA Astrophysics Data System (ADS)

Fedorov, Dmitri G.; Kitaura, Kazuo

2017-09-01

A many-body expansion of the Fock matrix in the fragment molecular orbital method is derived up to three-body terms for restricted Hartree-Fock and density functional theory in the atomic orbital basis and compared to the expansion in the basis of fragment molecular orbitals (MOs). The physical nature of many-body corrections is revealed in terms of charge transfer terms. An improvement of the fragment MO expansion is proposed by adding exchange to the embedding. The accuracy of all developed methods is demonstrated in comparison to unfragmented results for polyalanines, a water cluster, Trp-cage (PDB: 1L2Y) and crambin (PDB: 1CRN) proteins, a zeolite cluster, a Si nano-wire, and a boron nitride ribbon. The physical nature of metallicity is discussed, and it is shown what kinds of metallic systems can be treated by fragment-based methods. The density of states is calculated for a fully closed and a partially open nano-ring of boron nitride with a diameter of 105 nm.

A Mo-95 and C-13 Solid-state NMR and Relativistic DFT Investigation of Mesitylenetricarbonylmolybdenum(0) -a Typical Transition Metal Piano-stool Complex

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

Bryce, David L.; Wasylishen, Roderick E.

2002-06-21

The chemical shift (CS) and electric field gradient (EFG) tensors in the piano-stool compound mesitylenetricarbonylmolybdenum(0), 1, have been investigated via {sup 95}Mo and {sup 13}C solid-state magic-angle spinning (MAS) NMR as well as relativistic zeroth-order regular approximation density functional theory (ZORA-DFT) calculations. Molybdenum-95 (I = 5/2) MAS NMR spectra acquired at 18.8 T are dominated by the anisotropic chemical shift interaction ({Omega} = 775 {+-} 30 ppm) rather than the 2nd-order quadrupolar interaction (C{sub Q} = -0.96 {+-} 0.15 MHz), an unusual situation for a quadrupolar nucleus. ZORA-DFT calculations of the {sup 95}Mo EFG and CS tensors are in agreementmore » with the experimental data. Mixing of appropriate occupied and virtual d-orbital dominated MOs in the region of the HOMO-LUMO gap are shown to be responsible for the large chemical shift anisotropy. The small, but non-negligible, {sup 95}Mo quadrupolar interaction is discussed in terms of the geometry about Mo. Carbon-13 CPMAS spectra acquired at 4.7 T demonstrate the crystallographic and magnetic nonequivalence of the twelve {sup 13}C nuclei in 1, despite the chemical equivalence of some of these nuclei in isotropic solutions. The principal components of the carbon CS tensors are determined via a Herzfeld-Berger analysis, and indicate that motion of the mesitylene ring is slow compared to a rate which would influence the carbon CS tensors (i.e. tens of {micro}s). ZORA-DFT calculations reproduce the experimental carbon CS tensors accurately. Oxygen-17 EFG and CS tensors for 1 are also calculated and discussed in terms of existing experimental data for related molybdenum carbonyl compounds. This work provides an example of the information available from combined multi-field solid-state multinuclear magnetic resonance and computational investigations of transition metal compounds, in particular the direct study of quadrupolar transition metal nuclei with relatively small magnetic moments.« less

Effect of MoO3 on electron paramagnetic resonance spectra, optical spectra and dc conductivity of vanadyl ion doped alkali molybdo-borate glasses

NASA Astrophysics Data System (ADS)

Agarwal, A.; Khasa, S.; Seth, V. P.; Sanghi, S.; Arora, M.

2014-02-01

Alkali molybdo-borate glasses having composition xMoO3·(30 - x)M2O·70B2O3 and xMoO3·(70 - x)B2O3·30M2O (M = Li, Na, K) with 0 ⩽ x ⩽ 15 (mol%) doped with 2.0 mol% of V2O5 have been prepared in order to study the influence of MoO3 on electrical conductivity, electron paramagnetic resonance (EPR) and optical spectra. From EPR studies it is observed that V4+ ions in these samples exist as VO2+ ions in octahedral coordination with a tetragonal compression and belong to C4V symmetry. The tetragonal nature and octahedral symmetry of V4+O6 complex increase as well as decrease depending upon the composition of glasses with increase in MoO3 but 3dxy orbit of unpaired electron in the VO2+ ion expands in all the glasses. The decrease in optical band gap suggests that there is an increase in the concentration of non-bridging oxygen's. From the study of optical transmission spectra it is observed that for all the glasses the degree of covalency of the σ-bonding decreases with increase in MoO3 content and the degree of covalency of the π-bonding also varies. These results based on optical spectroscopy are in agreement with EPR findings. It is found that dc conductivity decreases and activation energy increases with increase in MoO3:M2O (M = Li, Na, K) ratio in MoO3·M2O·B2O3 glasses, whereas the conductivity increases and activation energy decreases with increase in MoO3:B2O3 ratio in xMoO3·B2O3·M2O glasses, which is governed by the increase in nonbridging oxygen's. The variation in theoretical optical basicity, Λth is also studied.

Friction and Environmental Sensitivity of Molybdenum Disulfide: Effects of Microstructure

NASA Astrophysics Data System (ADS)

Curry, John F.

For nearly a century, molybdenum disulfide has been employed as a solid lubricant to reduce the friction and wear between surfaces. MoS2 is in a class of unique materials, transition metal dichalcogens (TMDC), that have a single crystal structure forming lamellae that interact via weak van der Waals forces. This dissertation focuses on the link between the microstructure of MoS2 and the energetics of running film formation to reduce friction, and effects of environmental sensitivities on performance. Nitrogen impinged MoS2 films are utilized as a comparator to amorphous PVD deposited MoS2 in many of the studies due to the highly ordered surface parallel basal texture of sprayed films. Comparisons showed that films with a highly ordered structure can reduce high friction behavior during run-in. It is thought that shear induced reorientation of amorphous films contributes to typically high initial friction during run-in. In addition to a reduction in initial friction, highly ordered MoS2 films are shown to be more resistant to penetration from oxidative aging processes. High sensitivity, low-energy ion scattering (HS-LEIS) enabled depth profiles that showed oxidation limited to the first monolayer for ordered films and throughout the depth (4-5 nm) for amorphous films. X-ray photoelectron spectroscopy supported these findings, showing far more oxidation in amorphous films than ordered films. Many of these results show the benefits of a well run-in coating, yet transient increases in initial friction can still be noticed after only 5 - 10 minutes. It was found that the transient return to high initial friction after dwell times past 5 - 10 minutes was not due to adsorbed species such as water, but possibly an effect of basal plane relaxation to a commensurate state. Additional techniques and methods were developed to study the effect of adsorbed water and load on running film formation via spiral orbit XRD studies. Spiral orbit experiments enabled large enough worn areas for study in the XRD. Diffraction patterns for sputtered coatings at high loads (1N) showed more intense signals for surface parallel basal plane representation than lower loads (100mN). Tests run in dry and humid nitrogen (20% RH), however, showed no differences in reorientation of basal planes. Microstructure was found to be an important factor in determining the tribological performance of MoS2 films in a variety of testing conditions and environments. These findings will be useful in developing a mechanistic framework that better understands the energetics of running film formation and how different environments play a role.

Efficient charge injection in p-type polymer field-effect transistors with low-cost molybdenum electrodes through V2O5 interlayer.

PubMed

Baeg, Kang-Jun; Bae, Gwang-Tae; Noh, Yong-Young

2013-06-26

Here we report high-performance polymer OFETs with a low-cost Mo source/drain electrode by efficient charge injection through the formation of a thermally deposited V2O5 thin film interlayer. A thermally deposited V2O5 interlayer is formed between a regioregular poly(3-hexylthiophene) (rr-P3HT) or a p-type polymer semiconductor containing dodecyl-substituted thienylenevinylene (TV) and dodecylthiophene (PC12TV12T) and the Mo source/drain electrode. The P3HT or PC12TV12T OFETs with the bare Mo electrode exhibited lower charge carrier mobility than those with Au owing to a large barrier height for hole injection (0.5-1.0 eV). By forming the V2O5 layer, the P3HT or PC12TV12T OFETs with V2O5 on the Mo electrode exhibited charge carrier mobility comparable to that of a pristine Au electrode. Best P3HT or PC12TV12T OFETs with 5 nm thick V2O5 on Mo electrode show the charge carrier mobility of 0.12 and 0.38 cm(2)/(V s), respectively. Ultraviolet photoelectron spectroscopy results exhibited the work-function of the Mo electrode progressively changed from 4.3 to 4.9 eV with an increase in V2O5 thickness from 0 to 5 nm, respectively. Interestingly, the V2O5-deposited Mo exhibits comparable Rc to Au, which mainly results from the decreased barrier height for hole carrier injection from the low-cost metal electrode to the frontier molecular orbital of the p-type polymer semiconductor after the incorporation of the transition metal oxide hole injection layer, such as V2O5. This enables the development of large-area, low-cost electronics with the Mo electrodes and V2O5 interlayer.

Vibrational spectroscopy investigation and density functional theory calculations on (E)-N‧-(4-methoxybenzylidene) benzohydrazide

NASA Astrophysics Data System (ADS)

Saleem, H.; Subashchandrabose, S.; Ramesh Babu, N.; Syed Ali Padusha, M.

2015-05-01

The FT-IR, FT-Raman and UV-Vis spectra of the Schiff base compound (E)-N‧-(4-methoxybenzylidene) benzohydrazide (MBBH) have been recorded and analyzed. The optimized geometrical parameters were calculated. The complete vibrational assignments were performed on the basis of TED of the vibrational modes, calculated with the help of SQM method. NBO analysis has been carried out to explore the hyperconjugative interactions and their second order stabilization energy within the molecule. The molecular orbitals (MO's) and its energy gap were studied. The first order hyperpolarizability (β0) and related properties (β, α0, Δα) of MBBH are also calculated. All theoretical calculations were performed on the basis of B3LYP/6-311++G(d,p) level of theory.

Strain and structure heterogeneity in MoS 2 atomic layers grown by chemical vapour deposition

DOE PAGES

Liu, Zheng; Amani, Matin; Najmaei, Sina; ...

2014-11-18

Monolayer molybdenum disulfide (MoS 2) has attracted tremendous attention due to its promising applications in high-performance field-effect transistors, phototransistors, spintronic devices, and nonlinear optics. The enhanced photoluminescence effect in monolayer MoS 2 was discovered and, as a strong tool, was employed for strain and defect analysis in MoS 2. Recently, large-size monolayer MoS 2 has been produced by chemical vapor deposition but has not yet been fully explored. Here we systematically characterize chemical vapor deposition grown MoS 2 by PL spectroscopy and mapping, and demonstrate non-uniform strain in single-crystalline monolayer MoS 2 and strain-induced band gap engineering. We also evaluatemore » the effective strain transferred from polymer substrates to MoS 2 by three-dimensional finite element analysis. In addition, our work demonstrates that PL mapping can be used as a non-contact approach for quick identification of grain boundaries in MoS 2.« less

Two-dimensional hybrid materials: MoS2-RGO nanocomposites enhanced the barrier properties of epoxy coating

NASA Astrophysics Data System (ADS)

Chen, Chunlin; He, Yi; Xiao, Guoqing; Xia, Yunqin; Li, Hongjie; He, Ze

2018-06-01

By the way of hydrothermal reaction, the MoS2 nanoparticles were loaded on the surface of GO sheets uniformly. Then, the MoS2-RGO composites were modified with γ-(2,3-epoxypropoxy)propytrimethoxysilane (KH560), and followed by preparing the MoS2-RGO/epoxy composite coatings. The morphology and structure of MoS2-RGO were characterized though SEM, TEM, FT-IR and XPS. Besides, the corrosion resistance properties of the as-prepared MoS2-RGO/epoxy composite coatings were characterized by means of electrochemical impedance spectroscopy (EIS) and polarization curves analysis, and then the thermal stability and water permeability resistance of coatings were characterized. The results showed that the MoS2 could be loaded on the surface of GO uniformly when the ratio between MoS2 and GO is 1:1. The anti-corrosion property and permeability resistance of the MoS2-RGO/epoxy composites coating was enhanced significantly due to its excellent barrier property. Besides, the thermal property analysis exhibits that the lamellar structure of MoS2, GO and MoS2-RGO can effectively block the escape of the pyrolysis products, resulting in the maximum thermal weightlessness reduced.

Double perovskites with strong spin-orbit coupling

NASA Astrophysics Data System (ADS)

Cook, Ashley M.

We first present theoretical analysis of powder inelastic neutron scattering experiments in Ba2FeReO6 performed by our experimental collaborators. Ba2FeReO6, a member of the double perovskite family of materials, exhibits half-metallic behavior and high Curie temperatures Tc, making it of interest for spintronics applications. To interpret the experimental data, we develop a local moment model, which incorporates the interaction of Fe spins with spin-orbital locked magnetic moments on Re, and show that it captures the experimental observations. We then develop a tight-binding model of the double perovskite Ba 2FeReO6, a room temperature ferrimagnet with correlated and spin-orbit coupled Re t2g electrons moving in the background of Fe moments stabilized by Hund's coupling. We show that for such 3d/5d double perovskites, strong correlations on the 5d-element (Re) are essential in driving a half-metallic ground state. Incorporating both strong spin-orbit coupling and the Hubbard repulsion on Re leads to a band structure consistent with ab initio calculations. The uncovered interplay of strong correlations and spin-orbit coupling lends partial support to our previous work, which used a local moment description to capture the spin wave dispersion found in neutron scattering measurements. We then adapt this tight-binding model to study {111}-grown bilayers of half-metallic double perovskites such as Sr2FeMoO6. The combination of spin-orbit coupling, inter-orbital hybridization and symmetry-allowed trigonal distortion leads to a rich phase diagram with tunable ferromagnetic order, topological C= +/-1, +/-2 Chern bands, and a C = +/-2 quantum anomalous Hall insulator regime. We have also performed theoretical analysis of inelastic neutron scattering (INS) experiments to investigate the magnetic excitations in the weakly distorted face-centered-cubic (fcc) iridate double perovskites La2ZnIrO 6 and La2MgIrO6. Models with dominant Kitaev exchange seem to most naturally account for the neutron data as well as the measured frustration parameters of these materials, while the uniaxial Ising anisotropy does not. Our findings highlight how even seemingly conventional magnetic orders in oxide materials containing heavy transition metal ions may be driven by highly-directional exchange interactions rooted in strong spin-orbit coupling. Motivated by experiments on the double perovskites La2ZnIrO 6 and La2MgIrO6, we lastly study the magnetism of spin-orbit coupled jeff =1/2 iridium moments on the three-dimensional, geometrically frustrated, facecentered cubic lattice. The symmetry-allowed nearest-neighbor interaction includes Heisenberg, Kitaev, and symmetric off-diagonal exchange. A Luttinger-Tisza analysis shows a rich variety of orders, including collinear AII type antiferromagnetism, stripe order with moments along the {111}-direction, and incommensurate non-coplanar spirals, and we use Monte Carlo simulations to determine their magnetic ordering temperatures.

Astronaut Owen Garriott lies in Lower Body Negative Pressure Device

NASA Image and Video Library

1973-08-06

SL3-108-1278 (July-September 1973) --- Scientist-astronaut Owen K. Garriott, science pilot of the Skylab 3 mission, lies in the Lower Body Negative Pressure Device in the work and experiments area of the Orbital Workshop (OWS) crew quarters of the Skylab space station cluster in Earth orbit. This picture was taken with a hand-held 35mm Nikon camera. Astronauts Garriott, Alan L. Bean and Jack R. Lousma remained with the Skylab space station in orbit for 59 days conducting numerous medical, scientific and technological experiments. The LBNPD (MO92) Experiment is to provide information concerning the time course of cardiovascular adaptation during flight, and to provide in-flight data for predicting the degree of orthostatic intolerance and impairment of physical capacity to be expected upon return to Earth environment. The bicycle ergometer is in the right foreground. Photo credit: NASA

RDM lifetime measurements in 107Cd

NASA Astrophysics Data System (ADS)

Andgren, K.; Ashley, S. F.; Regan, P. H.; McCutchan, E. A.; Zamfir, N. V.; Amon, L.; Cakirli, R. B.; Casten, R. F.; Clark, R. M.; Gürdal, G.; Keyes, K. L.; Meyer, D. A.; Erduran, M. N.; Papenberg, A.; Pietralla, N.; Plettner, C.; Rainovski, G.; Ribas, R. V.; Thomas, N. J.; Vinson, J.; Warner, D. D.; Werner, V.; Williams, E.

2005-10-01

Lifetimes for decays linking near-yrast states in 107Cd have been measured using the recoil distance method (RDM). The nucleus of interest was populated via the 98Mo(12C,3n)107Cd fusion-evaporation reaction at an incident beam energy of 60 MeV. From the measured lifetimes, transition probabilities have been deduced and compared with the theoretical B(E2) values for limiting cases of harmonic vibrational and axially deformed rotational systems. Our initial results suggest a rotor-like behaviour for the structure based on the unnatural-parity, h11/2 orbital in 107Cd, providing further evidence for the role of this 'shape-polarizing' orbital in stabilizing the nuclear deformation in the A ~ 100 transitional region.

Magnetic MoS2 on multiwalled carbon nanotubes for sulfide sensing.

PubMed

Li, Chunxiang; Zhang, Dan; Wang, Jiankang; Hu, Pingan; Jiang, Zhaohua

2017-07-04

A novel hybrid metallic cobalt insided in multiwalled carbon nanotubles/molybdenum disulfide (Co@CNT/MoS 2 ) modified glass carbon electrode (GCE) was fabricated with a adhesive of Nafion suspension and used as chemical sensors for sulfide detection. Single-layered MoS 2 was coated on CNTs through magnetic traction force between paramagnetic monolayer MoS 2 and Co particles in CNTs. Co particles faciliated the collection of paramagnetic monolayer MoS 2 exfoliated from bulk MoS 2 in solution. Amperometric analysis, cycle voltammetry, cathodic stripping analysis and linear sweep voltammetry results showed the Co@CNT/MoS 2 modified GCE exhibited excellent electrochemical activity to sulfide in buffer solutions, but amperometric analysis was found to be more sensitive than the other methods. The amperometric response result indicated the Co@CNT/MoS 2 -modified GCE electrode was an excellent electrochemical sensor for detecting S 2- with a detection limit of 7.6 nM and sensitivity of 0.23 mA/μM. The proposed electrode was used for the determination of sulfide levels in hydrogen sulfide-pretreated fruits, and the method was also verified with recovery studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Micro-structural study and Rietveld analysis of fast reactor fuels: U-Mo fuels

NASA Astrophysics Data System (ADS)

Chakraborty, S.; Choudhuri, G.; Banerjee, J.; Agarwal, Renu; Khan, K. B.; Kumar, Arun

2015-12-01

U-Mo alloys are the candidate fuels for both research reactors and fast breeder reactors. In-reactor performance of the fuel depends on the microstructural stability and thermal properties of the fuel. To improve the fuel performance, alloying elements viz. Zr, Mo, Nb, Ti and fissium are added in the fuel. The first reactor fuels are normally prepared by injection casting. The objective of this work is to compare microstructure, phase-fields and hardness of as-cast four different U-Mo alloy (2, 5, 10 and 33 at.% Mo) fuels with the equilibrium microstructure of the alloys. Scanning electron microscope with energy dispersive spectrometer and optical microscope have been used to characterize the morphology of the as-cast and annealed alloys. The monoclinic α'' phase in as-cast U-10 at.% Mo alloy has been characterized through Rietveld analysis. A comparison of metallographic and Rietveld analysis of as-cast (dendritic microstructure) and annealed U-33 at.% Mo alloy, corresponding to intermetallic compound, has been reported here for the first time. This study will provide in depth understanding of microstructural and phase evolution of U-Mo alloys as fast reactor fuel.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode

PubMed Central

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-01-01

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na1/3Ru2/3]O2 slabs delivers a capacity of 180 mAh g−1 (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g−1 (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes. PMID:27088834

Transport properties and device-design of Z-shaped MoS2 nanoribbon planar junctions

NASA Astrophysics Data System (ADS)

Zhang, Hua; Zhou, Wenzhe; Liu, Qi; Yang, Zhixiong; Pan, Jiangling; Ouyang, Fangping; Xu, Hui

2017-09-01

Based on MoS2 nanoribbons, metal-semiconductor-metal planar junction devices were constructed. The electronic and transport properties of the devices were studied by using density function theory (DFT) and nonequilibrium Green's functions (NEGF). It is found that a band gap about 0.4 eV occurs in the planar junction. The electron and hole transmissions of the devices are mainly contributed by the Mo atomic orbitals. The electron transport channel is located at the edge of armchair MoS2 nanoribbon, while the hole transport channel is delocalized in the channel region. The I-V curve of the two-probe device shows typical transport behavior of Schottky barrier, and the threshold voltage is of about 0.2 V. The field effect transistors (FET) based on the planar junction turn out to be good bipolar transistors, the maximum current on/off ratio can reach up to 1 × 104, and the subthreshold swing is 243 mV/dec. It is found that the off-state current is dependent on the length and width of the channel, while the on-state current is almost unaffected. The switching performance of the FET is improved with increasing the length of the channel, and shows oscillation behavior with the change of the channel width.

Electronic structures of WAlO(y) and WAlO(y)(-) (y = 2-4) determined by anion photoelectron spectroscopy and density functional theory calculations.

PubMed

Mann, Jennifer E; Waller, Sarah E; Jarrold, Caroline Chick

2012-07-28

The anion photoelectron spectra of WAlO(y)(-) (y = 2-4) are presented and assigned based on results of density functional theory calculations. The WAlO(2)(-) and WAlO(3)(-) spectra are both broad, with partially resolved vibrational structure. In contrast, the WAlO(4)(-) spectrum features well-resolved vibrational structure with contributions from three modes. There is reasonable agreement between experiment and theory for all oxides, and calculations are in particular validated by the near perfect agreement between the WAlO(4)(-) photoelectron spectrum and a Franck-Condon simulation based on computationally determined spectroscopic parameters. The structures determined from this study suggest strong preferential W-O bond formation, and ionic bonding between Al(+) and WO(y)(-2) for all anions. Neutral species are similarly ionic, with WAlO(2) and WAlO(3) having electronic structure that suggests Al(+) ionically bound to WO(y)(-) and WAlO(4) being described as Al(+2) ionically bound to WO(4)(-2). The doubly-occupied 3sp hybrid orbital localized on the Al center is energetically situated between the bonding O-local molecular orbitals and the anti- or non-bonding W-local molecular orbitals. The structures determined in this study are very similar to structures recently determined for the analogous MoAlO(y)(-)/MoAlO(y) cluster series, with subtle differences found in the electronic structures [S. E. Waller, J. E. Mann, E. Hossain, M. Troyer, and C. C. Jarrold, J. Chem. Phys. 137, 024302 (2012)].

Tuning the electrical transport of type II Weyl semimetal WTe2 nanodevices by Mo doping

NASA Astrophysics Data System (ADS)

Fu, Dongzhi; Pan, Xingchen; Bai, Zhanbin; Fei, Fucong; Umana-Membreno, Gilberto A.; Song, Honglian; Wang, Xuelin; Wang, Baigeng; Song, Fengqi

2018-04-01

We fabricated nanodevices from MoxW1-xTe2 (x = 0, 0.07, 0.35), and conducted a systematic comparative study of their electrical transport. Magnetoresistance measurements show that Mo doping can significantly suppress mobility and magnetoresistance. The results for the analysis of the two band model show that doping with Mo does not break the carrier balance. Through analysis of Shubnikov-de Haas oscillations, we found that Mo doping also has a strong suppressive effect on the quantum oscillation of the sample, and the higher the ratio of Mo, the fewer pockets were observed in our experiments. Furthermore, the effective mass of electron and hole increases gradually with increasing Mo ratio, while the corresponding quantum mobility decreases rapidly.

Design and performance of an arcjet nuclear electric propulsion system for a mid-1990's reference mission

NASA Technical Reports Server (NTRS)

Deininger, William D.; Vondra, Robert J.

1987-01-01

The design and performance of an arcjet nuclear-electric-propulsion spacecraft, suitable for use in the Space Nuclear Power System (SNPS) reference mission, are outlined. The vehicle design was based on a 30-kW ammonia arcjet system operating at an Isp of 1050 s and an efficiency of 45 percent. The arcjet/gimbal system, power-processing unit, and propellant-feed system are described. A 100-kWe SNPS was assumed, and the spacecraft mass was baselined at 5250 kg (excluding the propellant-feed system). A radiation/arcjet efflux diagnostics package was included in the performance analysis. This spacecraft, assuming a Shuttle launch from KSC, can perform a 50-deg inclination change and reach a final orbit of 35,860 km with a 120-d trip time providing a 4-mo active load for the SNPS. Alternatively, a Titan IV launch would provide a mass margin of 120 kg to a 10,000-km, 58-deg final orbit in 74 d. This spacecraft meets the reference-mission constraint of low developmental risk, and is scalable to power levels projected for future space platforms.

Redox properties of biscyclopentadienyl uranium(V) imido-halide complexes: a relativistic DFT study.

PubMed

Elkechai, Aziz; Kias, Farida; Talbi, Fazia; Boucekkine, Abdou

2014-06-01

Calculations of ionization energies (IE) and electron affinities (EA) of a series of biscyclopentadienyl imido-halide uranium(V) complexes Cp*2U(=N-2,6-(i)Pr2-C6H3)(X) with X =  F, Cl, Br, and I, related to the U(IV)/U(V) and U(V)/U(VI) redox systems, were carried out, for the first time, using density functional theory (DFT) in the framework of the relativistic zeroth order regular approximation (ZORA) coupled with the conductor-like screening model (COSMO) solvation approach. A very good linear correlation (R(2) =  0.993) was obtained, between calculated ionization energies at the ZORA/BP86/TZP level, and the experimental half-wave oxidation potentials E1/2. A similar linear correlation between the computed electron affinities and the electrochemical reduction U(IV)/U(III) potentials (R(2) =  0.996) is obtained. The importance of solvent effects and of spin-orbit coupling is definitively confirmed. The molecular orbital analysis underlines the crucial role played by the 5f orbitals of the central metal whereas the Nalewajski-Mrozek (N-M) bond indices explain well the bond distances variations following the redox processes. The IE variation of the complexes, i.e., IE(F) < IE(Cl) < IE(Br) < IE(I) is also well rationalized considering the frontier MO diagrams of these species. Finally, this work confirms the relevance of the Hirshfeld charges analysis which bring to light an excellent linear correlation (R(2) =  0.999) between the variations of the uranium charges and E1/2 in the reduction process of the U(V) species.

Variable system: An alternative approach for the analysis of mediated moderation.

PubMed

Kwan, Joyce Lok Yin; Chan, Wai

2018-06-01

Mediated moderation (meMO) occurs when the moderation effect of the moderator (W) on the relationship between the independent variable (X) and the dependent variable (Y) is transmitted through a mediator (M). To examine this process empirically, 2 different model specifications (Type I meMO and Type II meMO) have been proposed in the literature. However, both specifications are found to be problematic, either conceptually or statistically. For example, it can be shown that each type of meMO model is statistically equivalent to a particular form of moderated mediation (moME), another process that examines the condition when the indirect effect from X to Y through M varies as a function of W. Consequently, it is difficult for one to differentiate these 2 processes mathematically. This study therefore has 2 objectives. First, we attempt to differentiate moME and meMO by proposing an alternative specification for meMO. Conceptually, this alternative specification is intuitively meaningful and interpretable, and, statistically, it offers meMO a unique representation that is no longer identical to its moME counterpart. Second, using structural equation modeling, we propose an integrated approach for the analysis of meMO as well as for other general types of conditional path models. VS, a computer software program that implements the proposed approach, has been developed to facilitate the analysis of conditional path models for applied researchers. Real examples are considered to illustrate how the proposed approach works in practice and to compare its performance against the traditional methods. (PsycINFO Database Record (c) 2018 APA, all rights reserved).

An Evaluation of Liquid, Solid, and Grease Lubricants for Space Mechanisms Using a Spiral Orbit Tribometer

NASA Technical Reports Server (NTRS)

Buttery, Michael

2010-01-01

We present the findings of the test program performed by The European Space Tribology Laboratory (ESTL) to evaluate the performance (friction and lifetime) of a number of space lubricants under vacuum using a Spiral Orbit Tribometer (SOT). Focus was given to a comparison of various popular space oils, a comparison study between the old and new MAPLUB grease formulations, and the performance of commonly used solid lubricants under various conditions. Tests demonstrated that the lifetimes of hydrocarbon NYE oils 2001 & 2001A outperformed those of the perfluroropolyalkylether (PFPE) oils Fomblin Z25 & Z60, though these pairs displayed similar behavior. This relationship was also generally seen for greases; with the lifetimes of the multiple alkylated cyclopentane (MAC)-based greases being extended in comparison to the PFPE-based greases. Testing on greases also demonstrated similar performance between the old (-a) and new (-b) formulations when considering PFPE-based MAPLUB greases, and indeed for all tested PFPE-based non-MAPLUB greases, but significantly shorter lifetimes for the new formulations when considering MAC-based MAPLUB greases. MAPLUB MAC greases containing molybdenum disulphide (MoS2) thickener were also found to display reduced lifetimes. For solid lubricants, lead displayed significantly extended lifetimes over MoS2, speculated to be caused by redistribution of lead from the ball onto all contact surfaces during the test. Friction coefficients were seen to be some 2.5x higher for lead than for MoS2 under similar conditions, a result that corresponds well with conventional bearing tests. The work described was performed under contract for the European Space Agency as part of the Tribology Applications Program, with all funding for testing and apparatus provided by European Space Agency (ESA).

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

Fang, Zongtang; Both, Johan; Li, Shenggang

The heats of formation and the normalized clustering energies (NCEs) for the group 4 and group 6 transition metal oxide (TMO) trimers and tetramers have been calculated by the Feller-Peterson-Dixon (FPD) method. The heats of formation predicted by the FPD method do not differ much from those previously derived from the NCEs at the CCSD(T)/aT level except for the CrO3 nanoclusters. New and improved heats of formation for Cr3O9 and Cr4O12 were obtained using PW91 orbitals instead of Hartree-Fock (HF) orbitals. Diffuse functions are necessary to predict accurate heats of formation. The fluoride affinities (FAs) are calculated with the CCSD(T)more » method. The relative energies (REs) of different isomers, NCEs, electron affinities (EAs), and FAs of (MO2)n ( M = Ti, Zr, Hf, n = 1 – 4 ) and (MO3)n ( M = Cr, Mo, W, n = 1 – 3) clusters have been benchmarked with 55 exchange-correlation DFT functionals including both pure and hybrid types. The absolute errors of the DFT results are mostly less than ±10 kcal/mol for the NCEs and the EAs, and less than ±15 kcal/mol for the FAs. Hybrid functionals usually perform better than the pure functionals for the REs and NCEs. The performance of the two types of functionals in predicting EAs and FAs is comparable. The B1B95 and PBE1PBE functionals provide reliable energetic properties for most isomers. Long range corrected pure functionals usually give poor FAs. The standard deviation of the absolute error is always close to the mean errors and the probability distributions of the DFT errors are often not Gaussian (normal). The breadth of the distribution of errors and the maximum probability are dependent on the energy property and the isomer.« less

Is there any difference in survivorship of total hip arthroplasty with different bearing surfaces? A systematic review and network meta-analysis.

PubMed

Yin, Si; Zhang, Dangfeng; Du, Hui; Du, Heng; Yin, Zhanhai; Qiu, Yusheng

2015-01-01

Although many total hip bearing implants are widely used all over the world, simultaneous comparisons across the numerous available bearing surfaces are rare. The purpose of this study was to compare the survivorship of total hip arthroplasty (THA) with six available bearing implants. We conducted a systematic review of randomized controlled trials (RCTs) reporting survivorship or revision of ceramic-on-ceramic (CoC), ceramic-on-conventional polyethylene (CoPc), ceramic-on-highly-crosslinked polyethylene (CoPxl), metal-on-conventional polyethylene (MoPc), metal-on-highly-crosslinked polyethylene (MoPxl), or metal-on-metal (MoM) bearing implants. The synthesis of present evidence was performed by both the traditional direct-comparison meta-analysis and network meta-analysis. In total, 40 RCTs involving a total of 5321 THAs were identified. The pooled data of network meta-analysis showed no difference in relative risk (RR) of revision across CoC, CoPc, CoPxl and MoPxl bearings. However, the MoM bearing was demonstrated with a significant higher risk of revision compared with CoC (RR 5.10; 95% CI=1.62 to 16.81), CoPc (RR 4.80; 95% CI=1.29 to 17.09), or MoPxl (RR 3.85; 95% CI=1.16 to 14.29), and the MoPc bearing was indicated with a higher risk of revision compared with CoC (RR 2.83; 95% CI=1.20 to 6.63). The ranking probabilities of the effective interventions also revealed the inferiority of the MoM and MoPc implants in survivorship (both 0%, 95% CI=0% to 0%) compared with CoC (39%, 95% CI=0% to 100%), CoPc (33%, 95% CI=0% to 100%), CoPxl (7%, 95% CI=0% to 100%) or MoPxl (21%, 95% CI=0% to 100%). The present evidence indicated the similar performance in survivorship among CoC, CoPc, CoPxl and MoPxl bearing implants, and that all likely have superiority compared with the MoM and MoPc bearing implants in THA procedures. Long-term RCT data are required to confirm these conclusions and better inform clinical decisions.

Photoelectron Spectroscopy of the Doubly-Charged Anions [MIVO(mnt)2]2- (M=Mo, W; mnt=S2C2(CN)22-): Access to the Ground and Excited States of the [MvO(mnt)2]-Anion

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

Waters, Tom; Wang, Xue B.; Yang, Xin

2004-04-21

Photodetachment photoelectron spectroscopy was used to investigate the electronic structure of the doubly charged complexes [MIVO(mnt)2]2- (M=Mo, W;mnt=1,2 dicyanoethenedithiolato). These dianions are stable in the gas phase and are minimal models for the active sites of the dimethyl sulfoxide reductase family of molybdenum enzymes and of related tungsten enzymes. Adiabatic and vertical electron binding energies for both species were measured, providing detailed information about molecular orbital energy levels of the parent dianions as well as the ground and excited states of the product anions [MvO(mnt)2]. Density functional theory calculations were used to assist assignment of the detachment features.

Mo-CBP3, an Antifungal Chitin-Binding Protein from Moringa oleifera Seeds, Is a Member of the 2S Albumin Family

PubMed Central

Freire, José E. C.; Vasconcelos, Ilka M.; Moreno, Frederico B. M. B.; Batista, Adelina B.; Lobo, Marina D. P.; Pereira, Mirella L.; Lima, João P. M. S.; Almeida, Ricardo V. M.; Sousa, Antônio J. S.; Monteiro-Moreira, Ana C. O.; Oliveira, José T. A.; Grangeiro, Thalles B.

2015-01-01

Mo-CBP3 is a chitin-binding protein from M. oleifera seeds that inhibits the germination and mycelial growth of phytopathogenic fungi. This protein is highly thermostable and resistant to pH changes, and therefore may be useful in the development of new antifungal drugs. However, the relationship of MoCBP3 with the known families of carbohydrate-binding domains has not been established. In the present study, full-length cDNAs encoding 4 isoforms of Mo-CBP3 (Mo-CBP3-1, Mo-CBP3-2, Mo-CBP3-3 and Mo-CBP3-4) were cloned from developing seeds. The polypeptides encoded by the Mo-CBP3 cDNAs were predicted to contain 160 (Mo-CBP3-3) and 163 amino acid residues (Mo-CBP3-1, Mo-CBP3-2 and Mo-CBP3-4) with a signal peptide of 20-residues at the N-terminal region. A comparative analysis of the deduced amino acid sequences revealed that Mo-CBP3 is a typical member of the 2S albumin family, as shown by the presence of an eight-cysteine motif, which is a characteristic feature of the prolamin superfamily. Furthermore, mass spectrometry analysis demonstrated that Mo-CBP3 is a mixture of isoforms that correspond to different mRNA products. The identification of Mo-CBP3 as a genuine member of the 2S albumin family reinforces the hypothesis that these seed storage proteins are involved in plant defense. Moreover, the chitin-binding ability of Mo-CBP3 reveals a novel functionality for a typical 2S albumin. PMID:25789746

In silico simulations of tunneling barrier measurements for molecular orbital-mediated junctions: A molecular orbital theory approach to scanning tunneling microscopy

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

Terryn, Raymond J.; Sriraman, Krishnan; Olson, Joel A., E-mail: jolson@fit.edu

A new simulator for scanning tunneling microscopy (STM) is presented based on the linear combination of atomic orbitals molecular orbital (LCAO-MO) approximation for the effective tunneling Hamiltonian, which leads to the convolution integral when applied to the tip interaction with the sample. This approach intrinsically includes the structure of the STM tip. Through this mechanical emulation and the tip-inclusive convolution model, dI/dz images for molecular orbitals (which are closely associated with apparent barrier height, ϕ{sub ap}) are reported for the first time. For molecular adsorbates whose experimental topographic images correspond well to isolated-molecule quantum chemistry calculations, the simulator makes accuratemore » predictions, as illustrated by various cases. Distortions in these images due to the tip are shown to be in accord with those observed experimentally and predicted by other ab initio considerations of tip structure. Simulations of the tunneling current dI/dz images are in strong agreement with experiment. The theoretical framework provides a solid foundation which may be applied to LCAO cluster models of adsorbate–substrate systems, and is extendable to emulate several aspects of functional STM operation.« less

Quantitative analysis of trap states through the behavior of the sulfur ions in MoS2 FETs following high vacuum annealing

NASA Astrophysics Data System (ADS)

Bae, Hagyoul; Jun, Sungwoo; Kim, Choong-Ki; Ju, Byeong-Kwon; Choi, Yang-Kyu

2018-03-01

Few-layer molybdenum disulfide (MoS2) has attracted a great deal of attention as a semiconductor material for electronic and optoelectronic devices. However, the presence of localized states inside the bandgap is a critical issue that must be addressed to improve the applicability of MoS2 technology. In this work, we investigated the density of states (DOS: g(E)) inside the bandgap of MoS2 FET by using a current-voltage (I-V) analysis technique with the aid of high vacuum annealing (HVA). The g(E) can be obtained by combining the trap density and surface potential (ψ S) extracted from a consistent subthreshold current (I D-sub). The electrical performance of MoS2 FETs is strongly dependent on the inherent defects, which are closely related to the g(E) in the MoS2 active layer. By applying the proposed technique to the MoS2 FETs, we were able to successfully characterize the g(E) after stabilization of the traps by the HVA, which reduces the hysteresis distorting the intrinsic g(E). Also, the change of sulfur ions in MoS2 film before and after the HVA treatment is investigated directly by Auger electron spectroscopy analysis. The proposed technique provides a new methodology for active channel engineering of 2D channel based FETs such as MoS2, MoTe2, WSe2, and WS2.

A NICMOS direct imaging search for giant planets around the seven single white dwarfs in the Hyades

NASA Astrophysics Data System (ADS)

Zinnecker, Hans

2003-07-01

We propose to use the NIC1 camera on HST to search for massive giant planets around the known seven single white dwarfs in the nearby Hyades cluster at sub-arcsec separations. At an age of 625 Myr, the white dwarfs had protogenitor masses of about 3 solar masses, and massive gaseous giant planets should have formed in the massive circumstellar disks around these ex Herbig A0 stars, probably at orbital separations similar or slightly larger than that of Jupiter {5 AU} in our own solar system. Such planets would have survived the post-Main Sequence mass loss of the parent star, and would have migrated outward adiabatically by a factor 4.5, equal to the ratio of initial to final stellar mass {3Mo/0.66Mo}, due to conservation of orbital angular momentum during the mass loss {AGB and PN} phase. Thus the orbital separation NOW would be 4.5 x 5 AU = 22.5 AU, which at the distance of the Hyades {45 pc} corresponds to 0.50 arcsec. Simulations with TinyTim then show that giant planets at this separation with masses in the range 6-12 Jupiter masses and apparent J and H magnitudes in the range 20.5-23.3 mag {from Baraffe or Burrows models} can be spatially resolved around the Hyades white dwarfs. Their J and H brightnesses are known to be 15 +/- 0.5 mag, implying a median star-planet brightness ratio of 1000:1 {7.5 mag}. This combination of dynamic range and orbital separation is observable with NICMOS, by subtracting images taken at two roll angles. Therefore, the proposed near-IR diffraction-limited observations in the F110W and F160W filters promise to resolve giant planets around low-mass stars for the first time. If successful, the observations would also prove that giant planets do form around early-type stars more massive than the Sun.

Spin heat capacity of monolayer and AB-stacked bilayer MoS2 in the presence of exchange magnetic field

NASA Astrophysics Data System (ADS)

Hoi, Bui Dinh; Yarmohammadi, Mohsen; Mirabbaszadeh, Kavoos

2017-04-01

Dirac theory and Green's function technique are carried out to compute the spin dependent band structures and corresponding electronic heat capacity (EHC) of monolayer (ML) and AB-stacked bilayer (BL) molybdenum disulfide (MoS2) two-dimensional (2D) crystals. We report the influence of induced exchange magnetic field (EMF) by magnetic insulator substrates on these quantities for both structures. The spin-up (down) subband gaps are shifted with EMF from conduction (valence) band to valence (conduction) band at both Dirac points in the ML because of the spin-orbit coupling (SOC) which leads to a critical EMF in the K point and EHC returns to its initial states for both spins. In the BL case, EMF results split states and the decrease (increase) behavior of spin-up (down) subband gaps has been observed at both K and K‧ valleys which is due to the combined effect of SOC and interlayer coupling. For low and high EMFs, EHC of BL MoS2 does not change for spin-up subbands while increases for spin-down subbands.

Electronic structure of monolayer 1T'-MoTe2 grown by molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Tang, Shujie; Zhang, Chaofan; Jia, Chunjing; Ryu, Hyejin; Hwang, Choongyu; Hashimoto, Makoto; Lu, Donghui; Liu, Zhi; Devereaux, Thomas P.; Shen, Zhi-Xun; Mo, Sung-Kwan

2018-02-01

Monolayer transition metal dichalcogenides (TMDCs) in the 1T' structural phase have drawn a great deal of attention due to the prediction of quantum spin Hall insulator states. The band inversion and the concomitant changes in the band topology induced by the structural distortion from 1T to 1T' phases are well established. However, the bandgap opening due to the strong spin-orbit coupling (SOC) is only verified for 1T'-WTe2 recently and still debated for other TMDCs. Here we report a successful growth of high-quality monolayer 1T'-MoTe2 on a bilayer graphene substrate through molecular beam epitaxy. Using in situ angle-resolved photoemission spectroscopy (ARPES), we have investigated the low-energy electronic structure and Fermi surface topology. The SOC-induced breaking of the band degeneracy points between the valence and conduction bands is clearly observed by ARPES. However, the strength of SOC is found to be insufficient to open a bandgap, which makes monolayer 1T'-MoTe2 on bilayer graphene a semimetal.

Electronic structure of monolayer 1T'-MoTe 2 grown by molecular beam epitaxy

DOE PAGES

Tang, Shujie; Zhang, Chaofan; Jia, Chunjing; ...

2017-11-14

Monolayer transition metal dichalcogenides (TMDCs) in the 1T' structural phase have drawn a great deal of attention due to the prediction of quantum spin Hall insulator states. The band inversion and the concomitant changes in the band topology induced by the structural distortion from 1T to 1T' phases are well established. However, the bandgap opening due to the strong spin-orbit coupling (SOC) is only verified for 1T'-WTe 2 recently and still debated for other TMDCs. Here we report a successful growth of high-quality monolayer 1T'-MoTe 2 on a bilayer graphene substrate through molecular beam epitaxy. Using in situ angle-resolved photoemissionmore » spectroscopy (ARPES), we have investigated the low-energy electronic structure and Fermi surface topology. The SOC-induced breaking of the band degeneracy points between the valence and conduction bands is clearly observed by ARPES. However, the strength of SOC is found to be insufficient to open a bandgap, which makes monolayer 1T'-MoTe 2 on bilayer graphene a semimetal.« less

Pressure dependence of electron density distribution and d-p-π hybridization in titanate perovskite ferroelectrics

NASA Astrophysics Data System (ADS)

Yamanaka, Takamitsu; Nakamoto, Yuki; Ahart, Muhtar; Mao, Ho-kwang

2018-04-01

Electron density distributions of PbTi O3 , BaTi O3 , and SrTi O3 were determined by synchrotron x-ray powder diffraction up to 55 GPa at 300 K and ab initio quantum chemical molecular orbital (MO) calculations, together with a combination of maximum entropy method calculations. The intensity profiles of Bragg peaks reveal split atoms in both ferroelectric PbTi O3 and BaTi O3 , reflecting the two possible positions occupied by the Ti atom. The experimentally obtained atomic structure factor was used for the determination of the deformation in electron density and the d-p-π hybridization between dx z (and dy z) of Ti and px (and py) of O in the Ti-O bond. Ab initio MO calculations proved the change of the molecular orbital coupling and of Mulliken charges with a structure transformation. The Mulliken charge of Ti in the Ti O6 octahedron increased in the ionicity with increasing pressure in the cubic phase. The bonding nature is changed with a decrease in the hybridization of the Ti-O bond and the localization of the electron density with increasing pressure. The hybridization decreases with pressure and disappears in the cubic paraelectric phase, which has a much more localized electron density distribution.

{Mo96La8} eggshell ring and self-assembly to {Mo132} Keplerate through Mo-blue intermediate, involved in UV-photolysis of [Mo7O24](6-)/carboxylic acid system at pH 4.

PubMed

Yamase, Toshihiro; Kumagai, Shun; Prokop, Petra V; Ishikawa, Eri; Tomsa, Adrian-Raul

2010-10-18

The prolonged UV-photolysis of aqueous solutions containing [Mo(7)O(24)](6-) and C(2)H(5)CO(2)H (as electron donor) at pH 3.9-4.1 generates the carboxylate-coordinated {Mo(132)} Keplerate (1a) isolated as a formamidinium/ammonium-mixed salt, [HC(NH(2))(2)](26)(NH(4))(28)[Mo(V)(60)Mo(VI)(72)O(372)(H(2)O)(48)(C(2)H(5)CO(2))(36)((i)C(3)H(7)CO(2))(6)]·16H(2)O (1), through the Mo-blue intermediate (2). The coordination of 2 to La(3+) gives rise to the formation of the chain structure of the C(2)-symmetric {Mo(96)La(8)} eggshell rings, formulated by H(22)[Mo(V)(20)Mo(VI)(76)O(301)(H(2)O)(29){La(H(2)O)(6)}(2)]{La(H(2)O)(5)}(6)]·54.5H(2)O (3). The eggshell-ring geometry results from the insertion of [Mo(VI)(2)O(7)(H(2)O)](2-) (spacer) into the equator outer ring of the wheel-shaped Mo-blue, and 10 {(Mo(VI))(Mo(VI)(5))} pentagonal subunits alternately above and below the equator outer ring are connected by eight La(3+) and two {Mo(VI)(2)} linkers within two inner rings. The neighboring eggshell rings are linked through two Mo-O-Mo bonds formed by dehydrative condensation between the {Mo(VI)(2)} linkers to result in the chain structure. Together with the results of the elemental analysis and IR, electronic absorption, (13)C NMR, and ESI-MS spectra for 2, the ring profile analysis of 3 let us identify 2 with a carbolylate-coordinated Mo-blue ring of high nuclearity. The Mo(VI)→Mo(V) photoreductive change of 2 to the 60-electron reduced Keplerate in the presence of C(2)H(5)CO(2)H involves both degradation of the outer ring and splitting of the binuclear linkers, which leads to the formation of [(Mo(VI))Mo(VI)(5)O(21)(H(2)O)(4)(carboxylate)](7-) pentagonal subunits and [Mo(V)(2)O(4)(carboxylate)](+)/[Mo(V)O(2)(carboxylate)(1/2)](0.5+)-mixed linkers for 1.

Implications of Motivating Operations for the Functional Analysis of Consumer Choice

ERIC Educational Resources Information Center

Fagerstrom, Asle; Foxall, Gordon R.; Arntzen, Erik

2010-01-01

The present article introduces the concept of Motivating Operation (MO) to the context of consumer choice and discusses the function of the concept of MO in the context of the Behavioral Perspective Model (BPM). Including MO as part of the consumer behavior setting leads to a more comprehensive analysis and, as a result, improves our understanding…

Application of Time-Dependent Density Functional and Natural Bond Orbital Theories to the UV-vis Absorption Spectra of Some Phenolic Compounds.

PubMed

Marković, Svetlana; Tošović, Jelena

2015-09-03

The UV-vis properties of 22 natural phenolic compounds, comprising anthraquinones, neoflavonoids, and flavonoids were systematically examined. The time-dependent density functional theory (TDDFT) approach in combination with the B3LYP, B3LYP-D2, B3P86, and M06-2X functionals was used to simulate the UV-vis spectra of the investigated compounds. It was shown that all methods exhibit very good (B3LYP slightly better) performance in reproducing the examined UV-vis spectra. However, the shapes of the Kohn-Sham molecular orbitals (MOs) involved in electronic transitions were misleading in constructing the MO correlation diagrams. To provide better understanding of redistribution of electron density upon excitation, the natural bond orbital (NBO) analysis was applied. Bearing in mind the spatial and energetic separations, as well as the character of the π bonding, lone pair, and π* antibonding natural localized molecular orbitals (NLMOs), the "NLMO clusters" were constructed. NLMO cluster should be understood as a part of a molecule characterized with distinguished electron density. It was shown that all absorption bands including all electronic transitions need to be inspected to fully understand the UV-vis spectrum of a certain compound, and, thus, to learn more about its UV-vis light absorption. Our investigation showed that the TDDFT and NBO theories are complementary, as the results from the two approaches can be combined to interpret the UV-vis spectra. Agreement between the predictions of the TDDFT approach and those based on the NLMO clusters is excellent in the case of major electronic transitions and long wavelengths. It should be emphasized that the approach for investigation of UV-vis light absorption based on the NLMO clusters is applied for the first time.

Catalytic hydrodeoxygenation of methyl-substituted phenols: correlations of kinetic parameters with molecular properties.

PubMed

Massoth, F E; Politzer, P; Concha, M C; Murray, J S; Jakowski, J; Simons, Jack

2006-07-27

The hydrodeoxygenation of methyl-substituted phenols was carried out in a flow microreactor at 300 degrees C and 2.85 MPa hydrogen pressure over a sulfided CoMo/Al(2)O(3) catalyst. The primary reaction products were methyl-substituted benzene, cyclohexene, cyclohexane, and H(2)O. Analysis of the results suggests that two independent reaction paths are operative, one leading to aromatics and the other to partially or completely hydrogenated cyclohexanes. The reaction data were analyzed using Langmuir-Hinshelwood kinetics to extract the values of the reactant-to-catalyst adsorption constant and of the rate constants characterizing the two reaction paths. The adsorption constant was found to be the same for both reactions, suggesting that a single catalytic site center is operative in both reactions. Ab initio electronic structure calculations were used to evaluate the electrostatic potentials and valence orbital ionization potentials for all of the substituted phenol reactants. Correlations were observed between (a) the adsorption constant and the two reaction rate constants measured for various methyl-substitutions and (b) certain moments of the electrostatic potentials and certain orbitals' ionization potentials of the isolated phenol molecules. On the basis of these correlations to intrinsic reactant-molecule properties, a reaction mechanism is proposed for each pathway, and it is suggested that the dependencies of adsorption and reaction rates upon methyl-group substitution are a result of the substituents' effects on the electrostatic potential and orbitals rather than geometric (steric) effects.

Accounting for the differences in the structures and relative energies of the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I4 2+, the Se-I pi-bonded Se2I4 2+, and their higher-energy isomers by AIM, MO, NBO, and VB methodologies.

PubMed

Brownridge, Scott; Crawford, Margaret-Jane; Du, Hongbin; Harcourt, Richard D; Knapp, Carsten; Laitinen, Risto S; Passmore, Jack; Rautiainen, J Mikko; Suontamo, Reijo J; Valkonen, Jussi

2007-02-05

The bonding in the highly homoatomic np pi-np pi (n > or = 3)-bonded S2I42+ (three sigma + two pi bonds), the Se-I pi-bonded Se2I42+ (four sigma + one pi bonds), and their higher-energy isomers have been studied using modern DFT and ab initio calculations and theoretical analysis methods: atoms in molecules (AIM), molecular orbital (MO), natural bond orbital (NBO), and valence bond (VB) analyses, giving their relative energies, theoretical bond orders, and atomic charges. The aim of this work was to seek theory-based answers to four main questions: (1) Are the previously proposed simple pi*-pi* bonding models valid for S2I42+ and Se2I42+? (2) What accounts for the difference in the structures of S2I42+ and Se2I42+? (3) Why are the classically bonded isolobal P2I4 and As2I4 structures not adopted? (4) Is the high experimentally observed S-S bond order supported by theoretical bond orders, and how does it relate to high bond orders between other heavier main group elements? The AIM analysis confirmed the high bond orders and established that the weak bonds observed in S2I42+ and Se2I42+ are real and the bonding in these cations is covalent in nature. The full MO analysis confirmed that S2I42+ contains three sigma and two pi bonds, that the positive charge is essentially equally distributed over all atoms, that the bonding between S2 and two I2+ units in S2I42+ is best described by two mutually perpendicular 4c2e pi*-pi* bonds, and that in Se2I42+, two SeI2+ moieties are joined by a 6c2e pi*-pi* bond, both in agreement with previously suggested models. The VB treatment provided a complementary approach to MO analysis and provided insight how the formation of the weak bonds affects the other bonds. The NBO analysis and the calculated AIM charges showed that the minimization of the electrostatic repulsion between EI2+ units (E = S, Se) and the delocalization of the positive charge are the main factors that explain why the nonclassical structures are favored for S2I42+ and Se2I42+. The difference in the structures of S2I42+ and Se2I42+ is related to the high strength of the S-S pi bond compared to the weak S-I sigma bond and the additional stabilization from increased delocalization of positive charge in the structure of S2I42+ compared to the structure of Se2I42+. The investigation of the E2X42+ series (E = S, Se, Te; X = Cl, Br, I) revealed that only S2I42+ adopts the highly np pi-np pi (n > or = 3)-bonded structure, while all other dications favor the pi-bonded Se2I42+ structure. Theoretical bond order calculations for S2I42+ confirm the previously presented experimentally based bond orders for S-S (2.1-2.3) and I-I (1.3-1.5) bonds. The S-S bond is determined to have the highest reported S-S bond order in an isolated compound and has a bond order that is either similar to or slightly less than the Si-Si bond order in the proposed triply bonded [(Me3Si)2CH]2(iPr)SiSi triple bond SiSi(iPr)[CH(SiMe3)2]2 depending on the definition of bond orders used.

Spectroscopic and density functional theory studies of trans-3-(trans-4-imidazolyl)acrylic acid.

PubMed

Arjunan, V; Remya, P; Sathish, U; Rani, T; Mohan, S

2014-08-14

The structural parameters, thermodynamic properties and vibrational frequencies of the optimised geometry of trans-3-(trans-4-imidazolyl)acrylic acid have been determined from B3LYP methods with 6-311++G(**) and cc-pVTZ basis sets. The effects of substituents (acrylyl group) on the imidazole vibrational frequencies are analysed. The vibrational frequencies of the fundamental modes of trans-3-(trans-4-imidazolyl)acrylic acid have been precisely assigned and analysed and the theoretical results are compared with the experimental vibrations. (1)H and (13)C NMR isotropic chemical shifts are calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound are also determined from DFT method. The total electron density and electrostatic potential of the compound are determined by natural bond orbital analysis. Various reactivity and selectivity descriptors such as chemical hardness, chemical potential, softness, electrophilicity, nucleophilicity and the appropriate local quantities employing natural population analysis (NPA) are calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

Dynamic motif occupancy (DynaMO) analysis identifies transcription factors and their binding sites driving dynamic biological processes

PubMed Central

Kuang, Zheng; Ji, Zhicheng

2018-01-01

Abstract Biological processes are usually associated with genome-wide remodeling of transcription driven by transcription factors (TFs). Identifying key TFs and their spatiotemporal binding patterns are indispensable to understanding how dynamic processes are programmed. However, most methods are designed to predict TF binding sites only. We present a computational method, dynamic motif occupancy analysis (DynaMO), to infer important TFs and their spatiotemporal binding activities in dynamic biological processes using chromatin profiling data from multiple biological conditions such as time-course histone modification ChIP-seq data. In the first step, DynaMO predicts TF binding sites with a random forests approach. Next and uniquely, DynaMO infers dynamic TF binding activities at predicted binding sites using their local chromatin profiles from multiple biological conditions. Another landmark of DynaMO is to identify key TFs in a dynamic process using a clustering and enrichment analysis of dynamic TF binding patterns. Application of DynaMO to the yeast ultradian cycle, mouse circadian clock and human neural differentiation exhibits its accuracy and versatility. We anticipate DynaMO will be generally useful for elucidating transcriptional programs in dynamic processes. PMID:29325176

Complications Are Not Increased With Acetabular Revision of Metal-on-metal Total Hip Arthroplasty.

PubMed

Penrose, Colin T; Seyler, Thorsten M; Wellman, Samuel S; Bolognesi, Michael P; Lachiewicz, Paul F

2016-10-01

Isolated revision of the acetabular component in the setting of total hip arthroplasty has an increased risk of dislocation. With local soft tissue destruction frequently associated with failed metal-on-metal (MoM) bearings, it is presumed that acetabular revision of these hips will have even greater risk of complications. However, no study directly compares the complications of MoM with metal-on-polyethylene (MoP) acetabular revisions. In the context of a large database analysis, we asked the following questions: (1) Are there differences in early medical or wound complications after isolated acetabular revision of MoM and MoP bearing surfaces? (2) Are there differences in the frequency of dislocation, deep infection, and rerevision based on the bearing surface of the original implant? A review of the 100% Medicare database from 2005 to 2012 was performed using International Classification of Diseases, 9th Revision and Current Procedural Terminology codes. We identified 451 patients with a MoM bearing and 628 patients with a MoP bearing who had an isolated acetabular revision and a minimum followup of 2 years. The incidence, odds ratios, and 95% confidence intervals for early medical or wound complications were calculated using a univariate analysis at 30 days with patient sex and age group-adjusted analysis for blood transfusion. The incidence, odds ratio, and 95% confidence intervals for dislocation, deep infection, and rerevision were calculated using a univariate analysis at 30 day, 90 days, 1 year, and 2 years using a subgroup analysis with the Cochran-Mantel-Haenszel test to adjust for patient gender and age groups. There were no differences between the MoM and MoP isolated acetabular revisions in the incidence of 30-day local complications. There was a greater risk of transfusion in the MoP group than the MoM group (134 of 451 [30%] versus 230 of 628 [37%]; odds ratio [OR], 0.731; 95% confidence interval [CI], 0.565-0.948; p = 0.018). There were no differences at 2 years between the MoM and MoP acetabular revisions in the incidence of dislocation, infection, or rerevision. When analyzed by patient sex and age group, there were more infections in the age 70 to 79 years MoP group compared with MoM (10 of 451 [5%] versus 29 of 628 [10%]; OR, 4.47; CI, 1.699-11.761; p = 0.001). There were high rates of dislocation, infection, and rerevision in both revision cohorts. The rate of dislocation was not greater after acetabular revision of MoM bearings at 2 years. Based on these findings, clinicians should counsel these patients preoperatively about the risks of these complications. Dual-mobility and constrained components have specific advantages and disadvantages in these settings and should be further studied. Level III, therapeutic study.

Remarkably high mobility ultra-thin-film metal-oxide transistor with strongly overlapped orbitals

NASA Astrophysics Data System (ADS)

Wei Shih, Chen; Chin, Albert; Fu Lu, Chun; Fang Su, Wei

2016-01-01

High mobility channel thin-film-transistor (TFT) is crucial for both display and future generation integrated circuit. We report a new metal-oxide TFT that has an ultra-thin 4.5 nm SnO2 thickness for both active channel and source-drain regions, very high 147 cm2/Vs field-effect mobility, high ION/IOFF of 2.3 × 107, small 110 mV/dec sub-threshold slope, and a low VD of 2.5 V for low power operation. This mobility is already better than chemical-vapor-deposition grown multi-layers MoS2 TFT. From first principle quantum-mechanical calculation, the high mobility TFT is due to strongly overlapped orbitals.

Remarkably high mobility ultra-thin-film metal-oxide transistor with strongly overlapped orbitals

PubMed Central

Wei Shih, Chen; Chin, Albert; Fu Lu, Chun; Fang Su, Wei

2016-01-01

High mobility channel thin-film-transistor (TFT) is crucial for both display and future generation integrated circuit. We report a new metal-oxide TFT that has an ultra-thin 4.5 nm SnO2 thickness for both active channel and source-drain regions, very high 147 cm2/Vs field-effect mobility, high ION/IOFF of 2.3 × 107, small 110 mV/dec sub-threshold slope, and a low VD of 2.5 V for low power operation. This mobility is already better than chemical-vapor-deposition grown multi-layers MoS2 TFT. From first principle quantum-mechanical calculation, the high mobility TFT is due to strongly overlapped orbitals. PMID:26744240

Lessons learned - MO&DA at JPL. [Mission Operations and Data Analysis cost reduction of planetary exploration

NASA Technical Reports Server (NTRS)

Handley, Thomas H., Jr.

1993-01-01

The issues of how to avoid future surprise growth in Mission Operations and Data Analysis (MO&DA) costs and how to minimize total MO&DA costs for planetary missions are discussed within the context of JPL mission operations support. It is argued that there is no simple, single solution: the entire Project life-cycle must be addressed. It is concluded that cost models that can predict both MO&DA cost as well as Ground System development costs are needed. The first year MO&DA budget plotted against the total of ground and flight systems developments is shown. In order to better recognize changes and control costs in general, a modified funding line item breakdown is recommended to distinguish between development costs (prelaunch and postlaunch) and MO&DA costs.

In-situ synthesis of MoSi{sub 2}-Al{sub 2}O{sub 3} composite by a thermite reaction

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

Deevi, S.C.; Deevi, S.

1995-08-01

In this paper, the authors discuss the reaction mechanism involved in the thermite reaction leading to the synthesis of a composite since in an actual combustion synthesis, the reaction propagates at a velocity of 10 to 20 mm/sec. Reaction mechanism was determined by using a differential thermal analysis (DTA) and X-ray diffraction (XRD). During the combustion synthesis of MoSi{sub 2}-{alpha}Al{sub 2}O{sub 3}, reaction of MoO{sub 3}, Al and Si occurs rapidly and the reactants and products are expected to be in the liquid state at the combustion temperature. MoO{sub 3} is first reduced to MoO{sub 2}, and the reaction betweenmore » MoO{sub 2}, Al and Si leads to a composite of MoSi{sub 2}-{alpha}Al{sub 2}O{sub 3}. Differential thermal analysis reveals that the onset of exothermic reactions is preceded by melting indicating the necessity of molten Al for the synthesis of the composite. The reaction between MoO{sub 2} + 2Al +2Si can be moderated with Mo-Si mixtures such that the ratio of MoSi{sub 2} to Al{sub 2}O{sub 3} can be increased in the composite of MoSi{sub 2}-{alpha}Al{sub 2}O{sub 3}.« less

Auger Spectroscopy Analysis of Spalled LEU-10Mo Foils

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

Lawrence, Samantha Kay; Schulze, Roland K.

2017-08-03

Presentation includes slides on Surface Science used to probe LEU-10Mo Spall; Auger highlights graphitic-like inclusions and Mo-deficient oxide on base metal; Higher C concentration detected within spall area Images Courtesy; Depth profiling reveals thick oxide; Mo concentration nears nominal only at depths ~400 nm; and lastly Key Findings.

Surface structure of bulk 2H-MoS2(0001) and exfoliated suspended monolayer MoS2: A selected area low energy electron diffraction study

NASA Astrophysics Data System (ADS)

Dai, Zhongwei; Jin, Wencan; Grady, Maxwell; Sadowski, Jerzy T.; Dadap, Jerry I.; Osgood, Richard M.; Pohl, Karsten

2017-06-01

We have used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS2) and mechanically exfoliated and suspended monolayer MoS2. Our results show that the surface structure of bulk 2H-MoS2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320 K than previously reported at 95 K. We concluded that suspended monolayer MoS2 shows a large interlayer relaxation compared to the MoS2 sandwich layer terminating the bulk surface. The Debye temperature of MoS2 was concluded to be about 600 K, which agrees with a previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.

Surface structure of bulk 2H-MoS 2 (0001) and exfoliated suspended monolayer MoS 2 : A selected area low energy electron diffraction study

DOE PAGES

Dai, Zhongwei; Jin, Wencan; Grady, Maxwell; ...

2017-02-10

Here, we used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS 2) and mechanically exfoliated and suspended monolayer MoS 2. Our results show that the surface structure of bulk 2H-MoS 2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320 K than previously reported at 95 K. We concluded that suspended monolayer MoS 2 shows a large interlayer relaxation compared to the MoS 2 sandwich layer terminating the bulk surface. The Debye temperature of MoS 2 was concluded to be aboutmore » 600 K, which agrees with a previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.« less

Observation of Vacancies, Faults, and Superstructures in Ln5Mo2O12 (Ln = La, Y, and Lu) Compounds with Direct Mo-Mo Bonding.

PubMed

Colabello, Diane M; Sobalvarro, Elizabeth M; Sheckelton, John P; Neuefeind, Joerg C; McQueen, Tyrel M; Khalifah, Peter G

2017-11-06

Among oxide compounds with direct metal-metal bonding, the Y 5 Mo 2 O 12 (A 5 B 2 O 12 ) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2 O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal-metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal-metal bonding have integer oxidation states resulting from the lifting of orbital degeneracy typically induced by the metal-metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5 Mo 2 O 12 (Ln = La-Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2 O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1-2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5 Mo 2 O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. This represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic interactions within the one-dimensional octahedral chains of this system.

In pursuit of barrierless transition metal dichalcogenides lateral heterojunctions

NASA Astrophysics Data System (ADS)

Aierken, Yierpan; Sevik, Cem; Gülseren, Oğuz; Peeters, François M.; Çakır, Deniz

2018-07-01

There is an increasing need to understand interfaces between two-dimensional materials to realize an energy efficient boundary with low contact resistance and small heat dissipation. In this respect, we investigated the impact of charge and substitutional atom doping on the electronic transport properties of the hybrid metallic-semiconducting lateral junctions, formed between metallic (1T and 1T d ) and semiconducting (1H) phases of MoS2 by means of first-principles and non-equilibrium Green function formalism based calculations. Our results clearly revealed the strong influence of the type of interface and crystallographic orientation of the metallic phase on the transport properties of these systems. The Schottky barrier height, which is the dominant mechanism for contact resistance, was found to be as large as 0.63 eV and 1.19 eV for holes and electrons, respectively. We found that armchair interfaces are more conductive as compared to zigzag termination due to the presence of the metallic Mo zigzag chains that are directed along the transport direction. In order to manipulate these barrier heights we investigated the influence of electron doping of the metallic part (i.e. 1T d -MoS2). We observed that the Fermi level of the hybrid system moves towards the conduction band of semiconducting 1H-MoS2 due to filling of 4d-orbital of metallic MoS2, and thus the Schottky barrier for electrons decreases considerably. Besides electron doping, we also investigated the effect of substitutional doping of metallic MoS2 by replacing Mo atoms with either Re or Ta. Due to its valency, Re (Ta) behaves as a donor (acceptor) and reduces the Schottky barrier for electrons (holes). Since Re and Ta based transition metal dichalcogenides crystallize in either the 1T d or 1T phase, substitutional doping with these atom favors the stabilization of the 1T d phase of MoS2. Co-doping of hybrid structure results in an electronic structure, which facilities easy dissociation of excitons created in the 1H part.

In pursuit of barrierless transition metal dichalcogenides lateral heterojunctions.

PubMed

Aierken, Yierpan; Sevik, Cem; Gülseren, Oğuz; Peeters, François M; Çakır, Deniz

2018-07-20

There is an increasing need to understand interfaces between two-dimensional materials to realize an energy efficient boundary with low contact resistance and small heat dissipation. In this respect, we investigated the impact of charge and substitutional atom doping on the electronic transport properties of the hybrid metallic-semiconducting lateral junctions, formed between metallic (1T and 1T d ) and semiconducting (1H) phases of MoS 2 by means of first-principles and non-equilibrium Green function formalism based calculations. Our results clearly revealed the strong influence of the type of interface and crystallographic orientation of the metallic phase on the transport properties of these systems. The Schottky barrier height, which is the dominant mechanism for contact resistance, was found to be as large as 0.63 eV and 1.19 eV for holes and electrons, respectively. We found that armchair interfaces are more conductive as compared to zigzag termination due to the presence of the metallic Mo zigzag chains that are directed along the transport direction. In order to manipulate these barrier heights we investigated the influence of electron doping of the metallic part (i.e. 1T d -MoS 2 ). We observed that the Fermi level of the hybrid system moves towards the conduction band of semiconducting 1H-MoS 2 due to filling of 4d-orbital of metallic MoS 2 , and thus the Schottky barrier for electrons decreases considerably. Besides electron doping, we also investigated the effect of substitutional doping of metallic MoS 2 by replacing Mo atoms with either Re or Ta. Due to its valency, Re (Ta) behaves as a donor (acceptor) and reduces the Schottky barrier for electrons (holes). Since Re and Ta based transition metal dichalcogenides crystallize in either the 1T d or 1T phase, substitutional doping with these atom favors the stabilization of the 1T d phase of MoS 2 . Co-doping of hybrid structure results in an electronic structure, which facilities easy dissociation of excitons created in the 1H part.

NO-sensing performance of vacancy defective monolayer MoS2 predicted by density function theory

NASA Astrophysics Data System (ADS)

Li, Feifei; Shi, Changmin

2018-03-01

Using density functional theory (DFT), we predict the NO-sensing performance of monolayer MoS2 (MoS2-MLs) with and without MoS3-vacancy/S-vacancy defects. Our theoretical results demonstrate that MoS3- and S-vacancy defective MoS2-MLs show stronger chemisorption and greater electron transfer effects than pure MoS2-MLs. The charge transfer analysis showed pure and defective MoS2-MLs all act as donors. Both MoS3-vacancy and S-vacancy defects induce dramatic changes of electronic properties of MoS2-MLs, which have direct relationship with gas sensing performance. In addition, S-vacancy defect leads to more electrons transfer to NO molecule than MoS3-vacancy defect. The H2O molecule urges more electrons transfer from MoS3- or S-vacancy defective MoS2-MLs to NO molecule. We believe that this calculation results will provide some information for future experiment.

Theoretical ultra-fast spectroscopy in transition metal dichalcogenides

NASA Astrophysics Data System (ADS)

Molina-Sanchez, Alejandro; Sangalli, Davide; Marini, Andrea; Wirtz, Ludger

Semiconducting 2D-materials like the transition metal dichalcogenides (TMDs) MoS2, MoSe2, WS2, WSe2 are promising alternatives to graphene for designing novel opto-electronic devices. The strong spin-orbit interaction along with the breaking of inversion symmetry in single-layer TMDs allow using the valley-index as a new quantum number. The practical use of valley physics depends on the lifetimes of valley-polarized excitons which are affected by scattering at phonons, impurities and by carrier-carrier interactions. The carrier dynamics can be monitored using ultra-fast spectroscopies such as pump-probe experiments. The carrier dynamics is simulated using non-equilibrium Green's function theory in an ab-initio framework. We include carrier relaxation through electron-phonon interaction. We obtain the transient absorption spectra of single-layer TMD and compare our simulations with recent pump-probe experiments

Experimental and Calculational Studies of the Interactions of BF3 with Fluoroethers

NASA Technical Reports Server (NTRS)

Zehe, Michael J.; Morales, Wilfredo; Ball, David W.

1998-01-01

BF3 was co-condensed with (C2H5)2O, (CF3CH2)2O and (C2F5)2O in excess argon at 15 K. Infrared spectra of the matrices showed a definite Lewis acid-base interaction between BF3 and diethyl ether; a weak but definite interaction with bis(2,2,2,-trifluorodiethyl)ether, and no observable interaction with perfluorodiethyl ether. Molecular orbital (MO) calculations complemented the experimental observations by revealing that fluorine atoms on the ethers decreased electron localization about the oxygen atom. Thus, the experimental data and MO calculations indicated a clear trend between strength of interaction with BF3 and the degree of ether F substitution. The implications of the results for commercial perfluoro ether lubricant/metal oxide surface interactions are discussed.

Reduced-cost linear-response CC2 method based on natural orbitals and natural auxiliary functions

PubMed Central

Mester, Dávid

2017-01-01

A reduced-cost density fitting (DF) linear-response second-order coupled-cluster (CC2) method has been developed for the evaluation of excitation energies. The method is based on the simultaneous truncation of the molecular orbital (MO) basis and the auxiliary basis set used for the DF approximation. For the reduction of the size of the MO basis, state-specific natural orbitals (NOs) are constructed for each excited state using the average of the second-order Møller–Plesset (MP2) and the corresponding configuration interaction singles with perturbative doubles [CIS(D)] density matrices. After removing the NOs of low occupation number, natural auxiliary functions (NAFs) are constructed [M. Kállay, J. Chem. Phys. 141, 244113 (2014)], and the NAF basis is also truncated. Our results show that, for a triple-zeta basis set, about 60% of the virtual MOs can be dropped, while the size of the fitting basis can be reduced by a factor of five. This results in a dramatic reduction of the computational costs of the solution of the CC2 equations, which are in our approach about as expensive as the evaluation of the MP2 and CIS(D) density matrices. All in all, an average speedup of more than an order of magnitude can be achieved at the expense of a mean absolute error of 0.02 eV in the calculated excitation energies compared to the canonical CC2 results. Our benchmark calculations demonstrate that the new approach enables the efficient computation of CC2 excitation energies for excited states of all types of medium-sized molecules composed of up to 100 atoms with triple-zeta quality basis sets. PMID:28527453

Synthesis and Characterization of Molybdenum (Mo) Thin Films Using DC-Magnetron Sputtering

NASA Astrophysics Data System (ADS)

Pandharkar, Subhash M.; Rondiya, Sachin R.; Rokade, Avinash V.; Gabhale, Bharat B.; Pathan, Habib M.; Jadkar, Sandesh R.

2018-03-01

In present work, we report synthesis of Mo thin films by DC-magnetron sputtering method. The structural, optical, morphological and electrical properties were investigated as a function of target-to-substrate distance. From the results, it is evident that with increase in target-to-substrate distance the thickness of films decreases while its sheet resistance and electrical resistivity increases, which is confirmed by van der Pauw method. Low angle XRD analysis revealed that with increase in target-to-substrate distance preferred orientation of Mo crystallites changes from (211) to (110) and its size decreases. The FE-SEM analysis revealed a significant change in surface morphology with increase in target-to-substrate distance. UV-Visible spectroscopy analysis showed that Mo films deposited at high target-to-substrate distance have more reflection than those deposited at lower target-to-substrate. Finally, adhesion test was performed using scotch hatch tape adhesion test which show all Mo films have excellent adhesion over the entire range of target-to-substrate distance studied. The employment of such Mo films as back contact can be useful to improve efficiency of CZTS solar cells.

Isothermal and cyclic oxidation resistance of pack siliconized Mo-Si-B alloy

NASA Astrophysics Data System (ADS)

Majumdar, Sanjib

2017-08-01

Oxidation behaviour of MoSi2 coated Mo-9Si-8B-0.75Y (at.%) alloy has been investigated at three critical temperatures including 750, 900 and 1400 °C in static air. Thermogravimetric analysis (TGA) data indicates a remarkable improvement in the oxidation resistance of the silicide coated alloy in both isothermal and cyclic oxidation tests. The cross-sectional scanning electron microscopy and energy dispersive spectroscopic analysis reveal the occurrence of internal oxidation particularly at the crack fronts formed in the outer MoSi2 layer during thermal cycling. The dominant oxidation mechanisms at 750-900 °C and 1400 °C are identified. Development of MoB inner layer further improves the oxidation resistance of the silicide coated alloy.

Analysis of MoDOT communication and outreach effectiveness

DOT National Transportation Integrated Search

2008-07-01

Personal interviews were held with MoDOT personnel to assess MoDOTs current communication practices and existing customer segmentation practices. Focus groups were then held to help gauge the effectiveness of existing communication practices and t...

Phase relations in the system CuMoS

USGS Publications Warehouse

Dawei, H.; Chang, L.L.Y.; Knowles, C.R.

1990-01-01

Phase relations in the system CuMoS were studied in the temperature range 500-1000 ??C by using the conventional sealed, evacuated glass capsule technique. Reflected-light microscopy, X-ray powder diffraction and electron microprobe analysis were used for phase characterization. The chevrel-type phase, CuxMo3S4, is stable above 600??C, and forms equilibrium assemblages with the cubic Cu2S solid solution, copper, molybdenum, Mo2S3 and MoS2. Its solid solution ranges from Cu1.50-2.00Mo3S4 at 700??C to Cu1.22-2.00Mo3S4 at 1000 ??C. ?? 1990.

Enzalutamide in Men with Chemotherapy-naïve Metastatic Castration-resistant Prostate Cancer: Extended Analysis of the Phase 3 PREVAIL Study

PubMed Central

Beer, Tomasz M.; Armstrong, Andrew J.; Rathkopf, Dana; Loriot, Yohann; Sternberg, Cora N.; Higano, Celestia S.; Iversen, Peter; Evans, Christopher P.; Kim, Choung-Soo; Kimura, Go; Miller, Kurt; Saad, Fred; Bjartell, Anders S.; Borre, Michael; Mulders, Peter; Tammela, Teuvo L.; Parli, Teresa; Sari, Suha; van Os, Steve; Theeuwes, Ad; Tombal, Bertrand

2017-01-01

Enzalutamide significantly improved radiographic progression-free survival (rPFS) and overall survival (OS) among men with chemotherapy-naïve metastatic castration-resistant prostate cancer at the prespecified interim analysis of PREVAIL, a phase 3, double-blind, randomized study. We evaluated the longer-term efficacy and safety of enzalutamide up to the prespecified number of deaths in the final analysis, which included an additional 20 mo of follow-up for investigator-assessed rPFS, 9 mo of follow-up for OS, and 4 mo of follow-up for safety. Enzalutamide reduced the risk of radiographic progression or death by 68% (hazard ratio [HR] 0.32, 95% confidence interval [CI] 0.28–0.37; p < 0.0001) and the risk of death by 23% (HR 0.77, 95% CI 0.67–0.88; p = 0.0002). Median investigator-assessed rPFS was 20.0 mo (95% CI 18.9–22.1) in the enzalutamide arm and 5.4 mo (95% CI 4.1–5.6) in the placebo arm. Median OS was 35.3 mo (95% CI 32.2–not yet reached) in the enzalutamide arm and 31.3 mo (95% CI 28.8–34.2) in the placebo arm. At the time of the OS analysis, 167 patients in the placebo arm had crossed over to receive enzalutamide. The most common adverse events in the enzalutamide arm were fatigue, back pain, constipation, and arthralgia. This final analysis of PREVAIL provides more complete assessment of the clinical benefit of enzalutamide. PMID:27477525

Information origins of the chemical bond: Bond descriptors from molecular communication channels in orbital resolution

NASA Astrophysics Data System (ADS)

Nalewajski, Roman F.

The flow of information in the molecular communication networks in the (condensed) atomic orbital (AO) resolution is investigated and the plane-wave (momentum-space) interpretation of the average Fisher information in the molecular information system is given. It is argued using the quantum-mechanical superposition principle that, in the LCAO MO theory the squares of corresponding elements of the Charge and Bond-Order (CBO) matrix determine the conditional probabilities between AO, which generate the molecular communication system of the Orbital Communication Theory (OCT) of the chemical bond. The conditional-entropy ("noise," information-theoretic "covalency") and the mutual-information (information flow, information-theoretic "ionicity") descriptors of these molecular channels are related to Wiberg's covalency indices of chemical bonds. The illustrative application of OCT to the three-orbital model of the chemical bond X-Y, which is capable of describing the forward- and back-donations as well as the atom promotion accompanying the bond formation, is reported. It is demonstrated that the entropy/information characteristics of these separate bond-effects can be extracted by an appropriate reduction of the output of the molecular information channel, carried out by combining several exits into a single (condensed) one. The molecular channels in both the AO and hybrid orbital representations are examined for both the molecular and representative promolecular input probabilities.

Structure and stability of molybdenum sulfide fullerenes.

PubMed

Bar-Sadan, M; Enyashin, A N; Gemming, S; Popovitz-Biro, R; Hong, S Y; Prior, Yehiam; Tenne, R; Seifert, G

2006-12-21

MoS2 nanooctahedra are believed to be the smallest stable closed-cage structures of MoS2, i.e., the genuine inorganic fullerenes. Here a combination of experiments and density functional tight binding calculations with molecular dynamics annealing are used to elucidate the structures and electronic properties of octahedral MoS2 fullerenes. Through the use of these calculations MoS2 octahedra were found to be stable beyond nMo > 100 but with the loss of 12 sulfur atoms in the six corners. In contrast to bulk and nanotubular MoS2, which are semiconductors, the Fermi level of the nanooctahedra is situated within the band, thus making them metallic-like. A model is used for extending the calculations to much larger sizes. These model calculations show that, in agreement with experiment, the multiwall nanooctahedra are stable over a limited size range of 104-105 atoms, whereupon they are converted into multiwall MoS2 nanoparticles with a quasi-spherical shape. On the experimental side, targets of MoS2 and MoSe2 were laser-ablated and analyzed mostly through transmission electron microscopy. This analysis shows that, in qualitative agreement with the theoretical analysis, multilayer nanooctahedra of MoS2 with 1000-25 000 atoms (Mo + S) are stable. Furthermore, this and previous work show that beyond approximately 105 atoms fullerene-like structures with quasi-spherical forms and 30-100 layers become stable. Laser-ablated WS2 samples yielded much less faceted and sometimes spherically symmetric nanocages.

Dynamic motif occupancy (DynaMO) analysis identifies transcription factors and their binding sites driving dynamic biological processes.

PubMed

Kuang, Zheng; Ji, Zhicheng; Boeke, Jef D; Ji, Hongkai

2018-01-09

Biological processes are usually associated with genome-wide remodeling of transcription driven by transcription factors (TFs). Identifying key TFs and their spatiotemporal binding patterns are indispensable to understanding how dynamic processes are programmed. However, most methods are designed to predict TF binding sites only. We present a computational method, dynamic motif occupancy analysis (DynaMO), to infer important TFs and their spatiotemporal binding activities in dynamic biological processes using chromatin profiling data from multiple biological conditions such as time-course histone modification ChIP-seq data. In the first step, DynaMO predicts TF binding sites with a random forests approach. Next and uniquely, DynaMO infers dynamic TF binding activities at predicted binding sites using their local chromatin profiles from multiple biological conditions. Another landmark of DynaMO is to identify key TFs in a dynamic process using a clustering and enrichment analysis of dynamic TF binding patterns. Application of DynaMO to the yeast ultradian cycle, mouse circadian clock and human neural differentiation exhibits its accuracy and versatility. We anticipate DynaMO will be generally useful for elucidating transcriptional programs in dynamic processes. © The Author(s) 2017. Published by Oxford University Press on behalf of Nucleic Acids Research.

Thermoelectric Properties of Electron-Doped SrMnO3 Single Crystals with Perovskite Structure

NASA Astrophysics Data System (ADS)

Suzuki, T.; Sakai, H.; Taguchi, Y.; Tokura, Y.

2012-06-01

Thermoelectric properties have been investigated for single crystals of Sr(Mn1- x Mo x )O3 with the perovskite structure. Similar to (Sr1- x Ce x )MnO3, the Seebeck coefficient for lightly electron-doped compounds ( x ≤ 0.01) is enhanced upon G-type antiferromagnetic ordering, while maintaining metallic conduction. This results in enhancement of the figure of merit ( ZT). On the other hand, the Seebeck coefficient for the more electron-doped compound ( x = 0.025) changes sign from negative to positive within a spin and orbital ordered phase (with C-type antiferromagnetic configuration and Mn 3 z 2 - r 2 type orbital order) as the temperature is lowered, whereas the Hall coefficient remains negative in the whole temperature range. The enhancement of the ZT value in the G-type antiferromagnetic phase implies the possibility for improvement of the thermoelectric efficiency by using the coupling between charge, spin, orbital, and lattice degrees of freedom in strongly correlated electron systems.

Magneto-optical Kerr spectroscopy of noble metals

NASA Astrophysics Data System (ADS)

Uba, L.; Uba, S.; Antonov, V. N.

2017-12-01

Magneto-optical (MO) response of the noble metals Cu, Ag, and Au in the joint experimental and ab initio theoretical study is reported. The magneto-optical polar Kerr effect (MOKE) spectra of the noble-metal films were measured with the high sensitivity in the applied magnetic field of 1.5 T over the photon energy range 0.74-5.8 eV. Complete set of the optical conductivity tensor elements was determined precisely from the MOKE and the optical spectra measured at the same energy points. The importance of the off-diagonal intraband Drude-type transitions is demonstrated explicitly for each noble metal and found to be a substantial contribution to the observed spectra. It is shown that the first-principles calculations using the spin-polarized fully relativistic Dirac linear-muffin-tin-orbital method with the inclusion of correlation effects by GGA+U approach reproduce well the experimental spectra and allow to explain the microscopic origin of the noble metals' magneto-optical response in terms of interband transitions. Although the energy band structures of Cu, Ag, and Au are very similar, there are some distinctive differences in bandwidths and the energy positions of the bands (especially in X and L symmetry points), mainly due to different spin-orbit splitting and differences in the spatial extent of 3 d , 4 d , and 5 d valence wave functions of noble metals. It was found that the small differences in the band positions lead to significant differences in the MO properties of three noble metals. Although the spin-orbit interaction in Au is about six times larger than in Cu, and approximately two times larger than in Ag, the absolute value of Kerr rotation in Au is of the same magnitude as in Cu and one order of magnitude smaller as compared to Ag. The sharp Kerr effect spectral peak in Ag is not due to the electronic interband transitions, but rather to the plasma-edge splitting. The band-by-band decomposition of the Cu, Ag, and Au MO spectra is presented and the interband transitions responsible for the prominent structures in the spectra are identified. It has been found that main magneto-optical activity of noble metals in external magnetic field originates from interband transitions at well-defined small-volume regions of Brillouin zone located near the "neck" and "belly" of the Fermi surface.

Standard Gibbs energy of formation of Mo 3Te 4 by emf measurements

NASA Astrophysics Data System (ADS)

Mallika, C.; Sreedharan, O. M.

1990-03-01

The emf of the galvanic cells Pt, Mo, MoO 2¦8 YSZ¦'FeO', Fe, Pt (I) and Pt, Fe,'FeO' ¦8 YSZ¦MoO 2, Mo 3Te 4, MoTe 2(α), C, Pt (II) were measured over the temperature ranges 837 to 1151 K and 775 to 1196 K, respectively, using 8 mass% yttria-stabilized zirconia (8 YSZ) as the solid electrolyte. From the emf values, the partial molar Gibbs energy of solution of molybdenum in Mo 3Te 4/MoTe 2(α), Δ ḠMo was found to be Δ ḠMo ± 1.19 ( kJ/mol) = -025.08 + 0.00420T(K) . Using the literature data for the Gibbs energy of formation of MoTe 2(α). the expression ΔG° f( Mo3Te4, s) ± 5.97 (kj/mol) = -253.58 + 0.09214 T( K) was derived for the range 775 to 1196 K. A third-law analysis yielded a value of -209 ± 10 kJ/mol for ΔH° f.298o of Mo 3Te 4(s).

A Simple Process for Synthesis of Transparent Thin Films of Molybdenum Trioxide in the Orthorhombic Phase ( α-MoO3)

NASA Astrophysics Data System (ADS)

Chibane, Loundja; Belkaid, Mohamed Said; Zirmi, Rachid; Moussi, Abderrahmane

2017-04-01

Transparent orthorhombic molybdenum trioxide (α-MoO3) thin films were prepared on glass substrates by sol-gel dip coating technique of a quality comparable to those prepared by more sophisticated techniques regarded as very costly and difficult to carry out. The prepared films were annealed in air at different temperatures in the range of 150-350°C. X-ray diffraction analysis of the films prepared at 250°C and 350°C confirmed the formation of a single-phase of MoO3 in an orthorhombic crystal system (α-MoO3). Scanning electron microscopy of the films annealed at 350°C indicated a stack of nano-layers with thickness of approximately 30 nm-40 nm. Fourier transform infrared transmittance analysis revealed the Mo=O stretching vibration, which is an indicator of the layered orthorhombic MoO3 phase. Energy dispersive x-ray analysis confirmed the existence of Mo and O in the deposited films. A maximum optical transmittance of 82% in the visible range was obtained from the films annealed at 350°C. The band gap value of the films was evaluated and it was in the range of 3.28 eV-3.40 eV. The obtained results showed that the α-MoO3 thin films prepared at 350°C exhibit good structural, chemical, and optical properties, which might be of interest to the photovoltaic and optoelectronic devices.

Stacking-dependent interlayer coupling in trilayer MoS 2 with broken inversion symmetry

DOE PAGES

Yan, Jiaxu; Wang, Xingli; Tay, Beng Kang; ...

2015-11-13

The stacking configuration in few-layer two-dimensional (2D) materials results in different structural symmetries and layer-to-layer interactions, and hence it provides a very useful parameter for tuning their electronic properties. For example, ABA-stacking trilayer graphene remains semimetallic similar to that of monolayer, while ABC-stacking is predicted to be a tunable band gap semiconductor under an external electric field. Such stacking dependence resulting from many-body interactions has recently been the focus of intense research activities. Here we demonstrate that few-layer MoS 2 samples grown by chemical vapor deposition with different stacking configurations (AA, AB for bilayer; AAB, ABB, ABA, AAA for trilayer)more » exhibit distinct coupling phenomena in both photoluminescence and Raman spectra. By means of ultralow-frequency (ULF) Raman spectroscopy, we demonstrate that the evolution of interlayer interaction with various stacking configurations correlates strongly with layer-breathing mode (LBM) vibrations. Our ab initio calculations reveal that the layer-dependent properties arise from both the spin–orbit coupling (SOC) and interlayer coupling in different structural symmetries. Lastly, such detailed understanding provides useful guidance for future spintronics fabrication using various stacked few-layer MoS 2 blocks.« less

Radiation shielding materials characterization in the MoMa-Count program and further evolutions

NASA Astrophysics Data System (ADS)

Lobascio, Cesare

In the frame of the space research programme MoMa (From Molecules to Man) -Count (Coun-termeasures), funded by the Italian Space Agency, multi-functional protections for human space exploration have been investigated, paying particular attention to flexible materials, selected also for their excellent structural, thermal and ballistic performances. Flexible materials such as Kevlar R are qualified for space application, but have poorly known space radiation prop-erties, with consequent uncertainties about their shielding efficiency against the radiation en-vironment. The necessary evaluation of their shielding efficiency has been chiefly based on dedicated ground experiments in accelerators, supplemented by Monte Carlo simulations of the particle transport in the materials or multi-layers. In addition, flight experiments have been performed in Low Earth Orbit (LEO), onboard the International Space Station (ISS) and the re-entry capsule Foton, to measure the shielding behaviour in the actual operating environment of space, via dedicated detectors and dosimeters. This paper aims at presenting the results and lessons learned accrued within the MoMa-Count program, as well as the future actions planned for improving radiation shielding in long duration human exploration missions.

Stacking-dependent interlayer coupling in trilayer MoS 2 with broken inversion symmetry

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

Yan, Jiaxu; Wang, Xingli; Tay, Beng Kang

The stacking configuration in few-layer two-dimensional (2D) materials results in different structural symmetries and layer-to-layer interactions, and hence it provides a very useful parameter for tuning their electronic properties. For example, ABA-stacking trilayer graphene remains semimetallic similar to that of monolayer, while ABC-stacking is predicted to be a tunable band gap semiconductor under an external electric field. Such stacking dependence resulting from many-body interactions has recently been the focus of intense research activities. Here we demonstrate that few-layer MoS 2 samples grown by chemical vapor deposition with different stacking configurations (AA, AB for bilayer; AAB, ABB, ABA, AAA for trilayer)more » exhibit distinct coupling phenomena in both photoluminescence and Raman spectra. By means of ultralow-frequency (ULF) Raman spectroscopy, we demonstrate that the evolution of interlayer interaction with various stacking configurations correlates strongly with layer-breathing mode (LBM) vibrations. Our ab initio calculations reveal that the layer-dependent properties arise from both the spin–orbit coupling (SOC) and interlayer coupling in different structural symmetries. Lastly, such detailed understanding provides useful guidance for future spintronics fabrication using various stacked few-layer MoS 2 blocks.« less

Multifunctional Beta Ti Alloy with Improved Specific Strength

NASA Astrophysics Data System (ADS)

Park, Chan Hee; Hong, Jae-Keun; Lee, Sang Won; Yeom, Jong-Taek

2017-12-01

Gum metals feature properties such as ultrahigh strength, ultralow elastic modulus, superelasticity, and superplasticity. They are composed of elements from Groups 4 and 5 of the periodic table and exist when the valance electron concentration (\\overline{e/a}) is 4.24; the bond order (\\overline{Bo}) is 2.87; and the "d" electron-orbital energy level (\\overline{Md}) is 2.45 eV. Typical compositions include Ti-23Nb-2Zr-0.7Ta-O and Ti-12Ta-9Nb-6Zr-3 V-O, which contain large amounts of heavy Group-5 elements such as Nb and Ta. In the present study, to improve the specific strength of a multifunctional beta Ti alloy, three alloys (Ti-20Nb-5Zr-1Fe-O, Ti-12Zr-10Mo-4Nb-O, and Ti-24Zr-9Cr-3Mo-O) were designed by satisfying the above three requirements while adding Fe, Mo, and Cr, which are not only lightweight but also have strong hardening effects. Microstructural and mechanical property analyses revealed that Ti-20Nb-5Zr-1Fe-O has a 25% higher specific strength than gum metal while maintaining an ultralow elastic modulus.

Hyperspherical close-coupling calculations for charge-transfer cross sections in He2++H(1s) collisions at low energies

NASA Astrophysics Data System (ADS)

Liu, Chien-Nan; Le, Anh-Thu; Morishita, Toru; Esry, B. D.; Lin, C. D.

2003-05-01

A theory for ion-atom collisions at low energies based on the hyperspherical close-coupling (HSCC) method is presented. In hyperspherical coordinates the wave function is expanded in analogy to the Born-Oppenheimer approximation where the adiabatic channel functions are calculated with B-spline basis functions while the coupled hyperradial equations are solved by a combination of R-matrix propagation and the slow/smooth variable discretization method. The HSCC method is applied to calculate charge-transfer cross sections for He2++H(1s)→He+(n=2)+H+ reactions at center-of-mass energies from 10 eV to 4 keV. The results are shown to be in general good agreement with calculations based on the molecular orbital (MO) expansion method where electron translation factors (ETF’s) or switching functions have been incorporated in each MO. However, discrepancies were found at very low energies. It is shown that the HSCC method can be used to study low-energy ion-atom collisions without the need to introduce the ad hoc ETF’s, and the results are free from ambiguities associated with the traditional MO expansion approach.

Relativistically corrected nuclear magnetic resonance chemical shifts calculated with the normalized elimination of the small component using an effective potential-NMR chemical shifts of molybdenum and tungsten

NASA Astrophysics Data System (ADS)

Filatov, Michael; Cremer, Dieter

2003-07-01

A new method for relativistically corrected nuclear magnetic resonance (NMR) chemical shifts is developed by combining the individual gauge for the localized orbital approach for density functional theory with the normalized elimination of a small component using an effective potential. The new method is used for the calculation of the NMR chemical shifts of 95Mo and 183W in various molybdenum and tungsten compounds. It is shown that quasirelativistic corrections lead to an average improvement of calculated NMR chemical shift values by 300 and 120 ppm in the case of 95Mo and 183W, respectively, which is mainly due to improvements in the paramagnetic contributions. The relationship between electronic structure of a molecule and the relativistic paramagnetic corrections is discussed. Relativistic effects for the diamagnetic part of the magnetic shielding caused by a relativistic contraction of the s,p orbitals in the core region concern only the shielding values, however, have little consequence for the shift values because of the large independence from electronic structure and a cancellation of these effects in the shift values. It is shown that the relativistic corrections can be improved by level shift operators and a B3LYP hybrid functional, for which Hartree-Fock exchange is reduced to 15%.

A reaction mechanism-based prediction of mutagenicity: α-halo carbonyl compounds adduct with DNA by SN2 reaction.

PubMed

Haranosono, Yu; Ueoka, Hiroki; Kito, Gakushi; Nemoto, Shingo; Kurata, Masaaki; Sakaki, Hideyuki

2018-01-01

Most of the α-halo carbonyl (AHC) compounds tend to be predicted as mutagenic by structure-activity relationship based on structural category only, because they have an alkyl halide structure as a structural alert of mutagenicity. However, some AHC compounds are not mutagenic. We hypothesized that AHC reacts with DNA by S N 2 reaction, and the reactivity relates to mutagenicity. As an index of S N 2 reactivity, we focused on molecular orbitals (MOs), as the direction and position of two molecules in collision are important in the S N 2 reaction. The MOs suitable for S N 2 reaction (SN2MOs) were selected by chemical-visual inspection based on the shape of the MO. We used the level gap and the energy gap between SN2MO and the lowest unoccupied molecular orbital as the descriptors of S N 2 reactivity. As the results, S N 2 reactivity related to mutagenicity and we were able to predict mutagenicity of 20 AHC compounds with 95.0% concordance. It was suggested that S N 2 reaction is a reaction mechanism of AHC compounds and DNA in the mutagenic process. The method allows for discrimination among structurally similar compounds by combination with quantitative structure-activity relationships. The combination approach is expected to be useful for the mutagenic assessment of pharmaceutical impurities.

UV-vis, IR and 1H NMR spectroscopic studies of some mono- and bis-azo-compounds based on 2,7-dihydroxynaphthalene and aniline derivatives

NASA Astrophysics Data System (ADS)

Issa, Raafat M.; Fayed, Tarek A.; Awad, Mohammed K.; El-Kony, Sanaa M.

2005-12-01

The absorption spectra of mono- and bis-azo-derivatives obtained by coupling the diazonium salts of aromatic amines and 2,7-dihydroxynaphthalene have been studied in six organic solvents. The different absorption bands have been assigned and the effect of solvents on the charge transfer band is also discussed. The diagnostic IR spectral bands and 1H NMR signals are assigned and discussed in relation to molecular structure. Also, semi-empirical molecular orbital calculations using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory have been performed to investigate the molecular and electronic structures of these compounds. According to these calculations, an intramolecular hydrogen bonding is essential for stabilization of such molecules.

Single and double beta decays in the A=100, A=116 and A=128 triplets of isobars

NASA Astrophysics Data System (ADS)

Suhonen, J.; Civitarese, O.

2014-04-01

In this paper we analyze the ground-state-to-ground-state two-neutrino double beta (2νββ) decays and single EC and β- decays for the A=100 (100Mo-100Tc-100Ru), A=116 (116Cd-116In-116Sn) and A=128 (128Te-128I-128Xe) triplets of isobars. We use the proton-neutron quasiparticle random-phase approximation (pnQRPA) with realistic G-matrix-derived effective interactions in very large single-particle bases. The purpose is to access the effective value of the axial-vector coupling constant gA in the pnQRPA calculations. We show that the three triplets of isobars represent systems with different characteristics of orbital occupancies and cumulative 2νββ nuclear matrix elements. Our analysis points to a considerably quenched averaged effective value of ≈0.6±0.2 in the pnQRPA calculations.

Microwave effects on NiMoS and CoMoS single-sheet catalysts.

PubMed

Borges, I; Silva, Alexander M; Modesto-Costa, Lucas

2018-05-04

Single-sheet nanoclusters of MoS 2 , NiMoS or CoMoS are widely used in hydrodesulfurization (HDS) catalysis in the petroleum industry. In HDS reactions under microwave irradiation, experiments indirectly pointed out that for pristine MoS 2 reaction rates are accelerated because hot spots are generated on the catalyst bed. In this work, we investigated NiMoS and CoMoS isolated single-sheet substituted catalysts before and after thiophene adsorption focusing on quantifying the effect of microwave irradiation. For that purpose, density functional theory (DFT) molecular charge densities of each system were decomposed according to the distributed multipole analysis (DMA) of Stone. Site dipole values of each system were directly associated with a larger or smaller interaction with the microwave field according to a proposed general approach. We showed that microwave enhancement of HDS reaction rates can occur more efficiently in the CoMoS and NiMoS promoted clusters compared to pristine MoS 2 in the following order: CoMoS > NiMoS > MoS 2 . The atomic origin of the catalyst hot spots induced by microwaves was clearly established in the promoted clusters.

Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

PubMed

Okubo, Masashi; Yamada, Atsuo

2017-10-25

Lithium-ion batteries are key energy-storage devices for a sustainable society. The most widely used positive electrode materials are LiMO 2 (M: transition metal), in which a redox reaction of M occurs in association with Li + (de)intercalation. Recent developments of Li-excess transition-metal oxides, which deliver a large capacity of more than 200 mAh/g using an extra redox reaction of oxygen, introduce new possibilities for designing higher energy density lithium-ion batteries. For better engineering using this fascinating new chemistry, it is necessary to achieve a full understanding of the reaction mechanism by gaining knowledge on the chemical state of oxygen. In this review, a summary of the recent advances in oxygen-redox battery electrodes is provided, followed by a systematic demonstration of the overall electronic structures based on molecular orbitals with a focus on the local coordination environment around oxygen. We show that a π-type molecular orbital plays an important role in stabilizing the oxidized oxygen that emerges upon the charging process. Molecular orbital principles are convenient for an atomic-level understanding of how reversible oxygen-redox reactions occur in bulk, providing a solid foundation toward improved oxygen-redox positive electrode materials for high energy-density batteries.

Self-standing paper based anodes prepared from siliconcarbonitride-MoS2 composite for Li-ion battery applications

NASA Astrophysics Data System (ADS)

David, Lamuel; Singh, Gurpreet

2013-03-01

We study synthesis of free-standing polymer derived SiCN/ MoS2 composite paper anode for Li-ion battery application. This was achieved following a two-step approach: First, polysilazane was interfaced with exfoliated MoS2 nanosheets which upon pyrolysis resulted in SiCN/MoS2 composite. Second, dispersion of SiCN/MoS2 in isopropanol was vacuum filtered resulting in formation of a self-standing composite paper. Physical and chemical characterization of the composite was carried out by use of electron microscopy, Fourier transform infrared spectroscopy (FT-IR) and Thermo-gravimetric analysis (TGA). FT-IR data indicated complete conversion of polysilazane precursor to SiCN ceramic, while electron microscopy confirmed layered structure of the paper. Thermo-gravimetric analysis showed enhanced thermodynamic stability of the composite paper up to 800 °C. Electrochemical analysis of SiCN/MoS2 composite paper anodes showed that Li-ion can reversible intercalate in the voltage range of 0-2.5 V with a first cycle discharge capacity of 770 mAh/g at a current density of 100 mA/g.

Non-Specific Root Transport of Nutrient Gives Access to an Early Nutritional Indicator: The Case of Sulfate and Molybdate

PubMed Central

Etienne, Philippe; Diquélou, Sylvain; Koprivova, Anna; Kopriva, Stanislav; Arkoun, Mustapha; Gallardo, Karine; Turner, Marie; Cruz, Florence; Yvin, Jean-Claude

2016-01-01

Under sulfur (S) deficiency, crosstalk between nutrients induced accumulation of other nutrients, particularly molybdenum (Mo). This disturbed balanced between S and Mo could provide a way to detect S deficiency and therefore avoid losses in yield and seed quality in cultivated species. Under hydroponic conditions, S deprivation was applied to Brassica napus to determine the precise kinetics of S and Mo uptake and whether sulfate transporters were involved in Mo uptake. Leaf contents of S and Mo were also quantified in a field-grown S deficient oilseed rape crop with different S and N fertilization applications to evaluate the [Mo]:[S] ratio, as an indicator of S nutrition. To test genericity of this indicator, the [Mo]:[S] ratio was also assessed with other cultivated species under different controlled conditions. During S deprivation, Mo uptake was strongly increased in B. napus. This accumulation was not a result of the induction of the molybdate transporters, Mot1 and Asy, but could be a direct consequence of Sultr1.1 and Sultr1.2 inductions. However, analysis of single mutants of these transporters in Arabidopsis thaliana suggested that other sulfate deficiency responsive transporters may be involved. Under field conditions, Mo content was also increased in leaves by a reduction in S fertilization. The [Mo]:[S] ratio significantly discriminated between the plots with different rates of S fertilization. Threshold values were estimated for the hierarchical clustering of commercial crops according to S status. The use of the [Mo]:[S] ratio was also reliable to detect S deficiency for other cultivated species under controlled conditions. The analysis of the leaf [Mo]:[S] ratio seems to be a practical indicator to detect early S deficiency under field conditions and thus improve S fertilization management. PMID:27870884

Role of Si on the Diffusional Interactions Between U-Mo and Al-Si Alloys at 823 K (550 °C)

NASA Astrophysics Data System (ADS)

Perez, Emmanuel; Sohn, Yong-Ho; Keiser, Dennis D.

2013-01-01

U-Mo dispersions in Al-alloy matrix and monolithic fuels encased in Al-alloy are under development to fulfill the requirements for research and test reactors to use low-enriched molybdenum stabilized uranium alloy fuels. Significant interaction takes place between the U-Mo fuel and Al during manufacturing and in-reactor irradiation. The interaction products are Al-rich phases with physical and thermal characteristics that adversely affect fuel performance and result in premature failure. Detailed analysis of the interdiffusion and microstructural development of this system was carried through diffusion couples consisting of U-7 wt pct Mo, U-10 wt pct Mo and U-12 wt pct Mo in contact with pure Al, Al-2 wt pct Si, and Al-5 wt pct Si, annealed at 823 K (550 °C) for 1, 5 and 20 hours. Scanning electron microscopy and transmission electron microscopy were employed for the analysis. Diffusion couples consisting of U-Mo in contact with pure Al contained UAl3, UAl4, U6Mo4Al43, and UMo2Al20 phases. Additions of Si to the Al significantly reduced the thickness of the interdiffusion zone. The interdiffusion zones developed Al- and Si-enriched regions, whose locations and size depended on the Si and Mo concentrations in the terminal alloys. In these couples, the (U,Mo)(Al,Si)3 phase was observed throughout the interdiffusion zone, and the U6Mo4Al43 and UMo2Al20 phases were observed only where the Si concentrations were low.

Spin-triplet superconductivity in a weak-coupling Hubbard model for the quasi-one-dimensional compound Li0.9Mo6O17

NASA Astrophysics Data System (ADS)

Cho, Weejee; Platt, Christian; McKenzie, Ross H.; Raghu, Srinivas

2015-10-01

The purple bronze Li0.9Mo6O17 is of interest due to its quasi-one-dimensional electronic structure and the possible Luttinger liquid behavior resulting from it. For sufficiently low temperatures, it is a superconductor with a pairing symmetry that is still to be determined. To shed light on this issue, we analyze a minimal Hubbard model for this material involving four molybdenum orbitals per unit cell near quarter filling, using asymptotically exact perturbative renormalization group methods. We find that spin-triplet odd-parity superconductivity is the dominant instability. Approximate nesting properties of the two quasi-one-dimensional Fermi surfaces enhance certain second-order processes, which play crucial roles in determining the structure of the pairing gap. Notably, we find that the gap has more sign changes than required by the point-group symmetry.

Spin triplet superconductivity in a weak-coupling Hubbard model for the quasi-one-dimensional compound Li0.9 Mo6 O17

NASA Astrophysics Data System (ADS)

Platt, Christian; Cho, Weejee; McKenzie, Ross H.; Raghu, Sri

The purple bronze Li0.9Mo6O17 is of interest due to its quasi-one-dimensional electronic structure and the possible Luttinger liquid behavior resulting from it. For sufficiently low temperatures, it is a superconductor with a pairing symmetry that is still to be determined. To shed light on this issue, we analyze a minimal Hubbard model for this material involving four Molybdenum orbitals per unit cell near quarter filling, using asymptotically exact perturbative renormalization group methods. We find that spin triplet odd-parity superconductivity is the dominant instability. Approximate nesting properties of the two quasi-one-dimensional Fermi surfaces enhance certain second-order processes, which play crucial roles in determining the structure of the pairing gap. Notably, we find that the gap has accidental nodes, i.e. it has more sign changes than required by the point-group symmetry.

Photoelectron Spectroscopy of Free Polyoxoanions Mo6O19 2- and W6O19 2- in the Gas Phase

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

Infante, Ivan A.; Visscher, Lucas; Wang, Xue B.

2004-09-22

Two doubly charged polyoxoanions, Mo6O19 2- and W6O19 2-, were observed in the gas phase using electrospray ionization. Their electronic structures were investigated using photoelectron spectroscopy and quasi-relativistic density functional calculations. Each dianion was found to be highly stable despite the presence of strong intramolecular coulomb repulsion, estimated to be about 2 eV for each system. The valence detachment features were all shown to originate from electronic excitations involving oxygen lone-pair type orbitals. Their observed energies were in excellent agreement with the theoretical vertical detachment energies calculated using time-dependent density functional theory. Despite being multiply charged, polyoxometalate oxide clusters canmore » be studied in the gas phase, providing the opportunity for detailed benchmark theoretical studies on the electronic structures of these important transition-metal oxide systems.« less

Evolution of the Valley Position in Bulk Transition-Metal Chalcogenides and Their Monolayer Limit.

PubMed

Yuan, Hongtao; Liu, Zhongkai; Xu, Gang; Zhou, Bo; Wu, Sanfeng; Dumcenco, Dumitru; Yan, Kai; Zhang, Yi; Mo, Sung-Kwan; Dudin, Pavel; Kandyba, Victor; Yablonskikh, Mikhail; Barinov, Alexei; Shen, Zhixun; Zhang, Shoucheng; Huang, Yingsheng; Xu, Xiaodong; Hussain, Zahid; Hwang, Harold Y; Cui, Yi; Chen, Yulin

2016-08-10

Layered transition metal chalcogenides with large spin orbit coupling have recently sparked much interest due to their potential applications for electronic, optoelectronic, spintronics, and valleytronics. However, most current understanding of the electronic structure near band valleys in momentum space is based on either theoretical investigations or optical measurements, leaving the detailed band structure elusive. For example, the exact position of the conduction band valley of bulk MoS2 remains controversial. Here, using angle-resolved photoemission spectroscopy with submicron spatial resolution (micro-ARPES), we systematically imaged the conduction/valence band structure evolution across representative chalcogenides MoS2, WS2, and WSe2, as well as the thickness dependent electronic structure from bulk to the monolayer limit. These results establish a solid basis to understand the underlying valley physics of these materials, and also provide a link between chalcogenide electronic band structure and their physical properties for potential valleytronics applications.

Chapter 5 Multiple, Localized, and Delocalized/Conjugated Bonds in the Orbital Communication Theory of Molecular Systems

NASA Astrophysics Data System (ADS)

Nalewajski, Roman F.

Information theory (IT) probe of the molecular electronic structure, within the communication theory of chemical bonds (CTCB), uses the standard entropy/information descriptors of the Shannon theory of communication to characterize a scattering of the electronic probabilities and their information content throughout the system chemical bonds generated by the occupied molecular orbitals (MO). These "communications" between the basis-set orbitals are determined by the two-orbital conditional probabilities: one- and two-electron in character. They define the molecular information system, in which the electron-allocation "signals" are transmitted between various orbital "inputs" and "outputs". It is argued, using the quantum mechanical superposition principle, that the one-electron conditional probabilities are proportional to the squares of corresponding elements of the charge and bond-order (CBO) matrix of the standard LCAO MO theory. Therefore, the probability of the interorbital connections in the molecular communication system is directly related to Wiberg's quadratic covalency indices of chemical bonds. The conditional-entropy (communication "noise") and mutual-information (information capacity) descriptors of these molecular channels generate the IT-covalent and IT-ionic bond components, respectively. The former reflects the electron delocalization (indeterminacy) due to the orbital mixing, throughout all chemical bonds in the system under consideration. The latter characterizes the localization (determinacy) in the probability scattering in the molecule. These two IT indices, respectively, indicate a fraction of the input information lost in the channel output, due to the communication noise, and its surviving part, due to deterministic elements in probability scattering in the molecular network. Together, these two components generate the system overall bond index. By a straightforward output reduction (condensation) of the molecular channel, the IT indices of molecular fragments, for example, localized bonds, functional groups, and forward and back donations accompanying the bond formation, and so on, can be extracted. The flow of information in such molecular communication networks is investigated in several prototype molecules. These illustrative (model) applications of the orbital communication theory of chemical bonds (CTCB) deal with several classical issues in the electronic structure theory: atom hybridization/promotion, single and multiple chemical bonds, bond conjugation, and so on. The localized bonds in hydrides and delocalized [pi]-bonds in simple hydrocarbons, as well as the multiple bonds in CO and CO2, are diagnosed using the entropy/information descriptors of CTCB. The atom promotion in hydrides and bond conjugation in [pi]-electron systems are investigated in more detail. A major drawback of the previous two-electron approach to molecular channels, namely, two weak bond differentiation in aromatic systems, has been shown to be remedied in the one-electron approach.

Systematic analysis of hot Yb* isotopes using the energy density formalism

NASA Astrophysics Data System (ADS)

Jain, Deepika; Sharma, Manoj K.; Rajni; Kumar, Raj; Gupta, Raj K.

2014-10-01

A systematic study of the spin-orbit density interaction potential is carried out, with spherical as well as deformed choices of nuclei, for a variety of near-symmetric and asymmetric colliding nuclei leading to various isotopes of the compound nucleus Yb*, using the semiclassical extended Thomas-Fermi formulation (ETF) of the Skyrme energy density formalism (SEDF). We observe that the spin-orbit density interaction barrier height ( and barrier position ( increase systematically with the increase in number of neutrons in both the projectile and target, for spherical systems. On allowing deformation effects with optimum orientations, the barrier-height increases by a large order of magnitude, as compared to the spherical case, in going from 156Yb* to 172Yb* nuclear systems formed via near-symmetric Ni+Mo or asymmetric O+Sm colliding nuclei, except that for the oblate-shaped nuclei, the is the highest and shifts towards a smaller (compact) interaction radius. The temperature does not change the behavior of spin-orbit density dependent ( and independent ( interaction potentials, except for some minor changes in the magnitude. The orientation degree of freedom also plays an important role in modifying the barrier characteristics and hence produces a large effect on the fusion cross section. The fusion excitation function of the compound nuclei 160, 164Yb* formed in different incoming channels, show clearly that the new forces GSkI and KDE0v1 respond better than the old SIII force. Among the first two, KDE0v1 seems to perform better. The fusion cross-sections are also predicted for a few other isotopes of Yb*.

Magnetic exchange in {Gd(III)-radical} complexes: method assessment, mechanism of coupling and magneto-structural correlations.

PubMed

Gupta, Tulika; Rajeshkumar, Thayalan; Rajaraman, Gopalan

2014-07-28

Density functional studies have been performed on ten different {Gd(III)-radical} complexes exhibiting both ferro and antiferromagnetic exchange interaction with an aim to assess a suitable exchange-correlation functional within DFT formalism. This study has also been extended to probe the mechanism of magnetic coupling and to develop suitable magneto-structural correlations for this pair. Our method assessments reveal the following order of increasing accuracy for the evaluation of J values compared to experimental coupling constants: B(40HF)LYP < BHandHLYP < TPSSH < PW91 < PBE < BP86 < OLYP < BLYP < PBE0 < X3LYP < B3LYP < B2PLYP. Grimme's double-hybrid functional is found to be superior compared to other functionals tested and this is followed very closely by the conventional hybrid B3LYP functional. At the basis set front, our calculations reveal that the incorporation of relativistic effect is important in these calculations and the relativistically corrected effective core potential (ECP) basis set is found to yield better Js compared to other methods. The supposedly empty 5d/6s/6p orbitals of Gd(III) are found to play an important role in the mechanism of magnetic coupling and different contributions to the exchange terms are probed using Molecular Orbital (MO) and Natural Bond Orbital (NBO) analysis. Magneto-structural correlations for Gd-O distances, Gd-O-N angles and Gd-O-N-C dihedral angles are developed where the bond angles as well as dihedral angle parameters are found to dictate the sign and strength of the magnetic coupling in this series.

Forces and electronic transport in a contact formed by a graphene tip and a defective MoS2 monolayer: a theoretical study.

PubMed

di Felice, D; Dappe, Y J; González, C

2018-06-01

A theoretical study of a graphene-like tip used in atomic force microscopy (AFM) is presented. Based on first principles simulations, we proved the low reactivity of this kind of tip, using a MoS 2 monolayer as the testing sample. Our simulations show that the tip-MoS 2 interaction is mediated through weak van der Waals forces. Even on the defective monolayer, the interaction is reduced by one order of magnitude with respect to the values obtained using a highly reactive metallic tip. On the pristine monolayer, the S atoms were imaged for large distances together with the substitutional defects which should be observed as brighter spots in non-contact AFM measurements. This result is in contradiction with previous simulations performed with Cu or Si tips where the metallic defects were imaged for much larger distances than the S atoms. For shorter distances, the Mo sites will be brighter even though a vacancy is formed. On the other hand, the largest conductance value is obtained over the defect formed by two Mo atoms occupying a S divacancy when the half-occupied p y -states of the graphene-like tip find a better coupling with d-orbitals of the highest substitutional atom. Due to the weak interaction, no conductance plateau is formed in any of the sites. A great advantage of this tip lies in the absence of atomic transfer between the tip and the sample leading to a more stable AFM measurement. Finally, and as previously shown, we confirm the atomic resolution in a scanning tunneling microscopy simulation using this graphene-based tip.

Forces and electronic transport in a contact formed by a graphene tip and a defective MoS2 monolayer: a theoretical study

NASA Astrophysics Data System (ADS)

di Felice, D.; Dappe, Y. J.; González, C.

2018-06-01

A theoretical study of a graphene-like tip used in atomic force microscopy (AFM) is presented. Based on first principles simulations, we proved the low reactivity of this kind of tip, using a MoS2 monolayer as the testing sample. Our simulations show that the tip–MoS2 interaction is mediated through weak van der Waals forces. Even on the defective monolayer, the interaction is reduced by one order of magnitude with respect to the values obtained using a highly reactive metallic tip. On the pristine monolayer, the S atoms were imaged for large distances together with the substitutional defects which should be observed as brighter spots in non-contact AFM measurements. This result is in contradiction with previous simulations performed with Cu or Si tips where the metallic defects were imaged for much larger distances than the S atoms. For shorter distances, the Mo sites will be brighter even though a vacancy is formed. On the other hand, the largest conductance value is obtained over the defect formed by two Mo atoms occupying a S divacancy when the half-occupied p y -states of the graphene-like tip find a better coupling with d-orbitals of the highest substitutional atom. Due to the weak interaction, no conductance plateau is formed in any of the sites. A great advantage of this tip lies in the absence of atomic transfer between the tip and the sample leading to a more stable AFM measurement. Finally, and as previously shown, we confirm the atomic resolution in a scanning tunneling microscopy simulation using this graphene-based tip.

The molecular mechanism of Mo isotope fractionation during adsorption to birnessite

USGS Publications Warehouse

Wasylenki, L.E.; Weeks, C.L.; Bargar, J.R.; Spiro, T.G.; Hein, J.R.; Anbar, A.D.

2011-01-01

Fractionation of Mo isotopes during adsorption to manganese oxides is a primary control on the global ocean Mo isotope budget. Previous attempts to explain what drives the surprisingly large isotope effect ??97/95Modissolved-??97/95Moadsorbed=1.8??? have not successfully resolved the fractionation mechanism. New evidence from extended X-ray absorption fine structure analysis and density functional theory suggests that Mo forms a polymolybdate complex on the surfaces of experimental and natural samples. Mo in this polynuclear structure is in distorted octahedral coordination, while Mo remaining in solution is predominantly in tetrahedral coordination as MoO42- Our results indicate that the difference in coordination environment between dissolved Mo and adsorbed Mo is the cause of isotope fractionation. The molecular mechanism of metal isotope fractionation in this system should enable us to explain and possibly predict metal isotope effects in other systems where transition metals adsorb to mineral surfaces. ?? 2011 Elsevier Ltd.

Differentiation and activation of equine monocyte-derived dendritic cells are not correlated with CD206 or CD83 expression

PubMed Central

Moyo, Nathifa A; Marchi, Emanuele; Steinbach, Falko

2013-01-01

Dendritic cells (DC) are the main immune mediators inducing primary immune responses. DC generated from monocytes (MoDC) are a model system to study the biology of DC in vitro, as they represent inflammatory DC in vivo. Previous studies on the generation of MoDC in horses indicated that there was no distinct difference between immature and mature DC and that the expression profile was distinctly different from humans, where CD206 is expressed on immature MoDC whereas CD83 is expressed on mature MoDC. Here we describe the kinetics of equine MoDC differentiation and activation, analysing both phenotypic and functional characteristics. Blood monocytes were first differentiated with equine granulocyte–macrophage colony-stimulating factor and interleukin-4 generating immature DC (iMoDC). These cells were further activated with a cocktail of cytokines including interferon-γ) but not CD40 ligand to obtain mature DC (mMoDC). To determine the expression of a broad range of markers for which no monoclonal antibodies were available to analyse the protein expression, microarray and quantitative PCR analysis were performed to carry out gene expression analysis. This study demonstrates that equine iMoDC and mMoDC can be distinguished both phenotypically and functionally but the expression pattern of some markers including CD206 and CD83 is dissimilar to the human system. PMID:23461413

Development of a multi-variate calibration approach for quantitative analysis of oxidation resistant Mo-Si-B coatings using laser ablation inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Cakara, Anja; Bonta, Maximilian; Riedl, Helmut; Mayrhofer, Paul H.; Limbeck, Andreas

2016-06-01

Nowadays, for the production of oxidation protection coatings in ultrahigh temperature environments, alloys of Mo-Si-B are employed. The properties of the material, mainly the oxidation resistance, are strongly influenced by the Si to B ratio; thus reliable analytical methods are needed to assure exact determination of the material composition for the respective applications. For analysis of such coatings, laser ablation inductively coupled mass spectrometry (LA-ICP-MS) has been reported as a versatile method with no specific requirements on the nature of the sample. However, matrix effects represent the main limitation of laser-based solid sampling techniques and usually the use of matrix-matched standards for quantitative analysis is required. In this work, LA-ICP-MS analysis of samples with known composition and varying Mo, Si and B content was carried out. Between known analyte concentrations and derived LA-ICP-MS signal intensities no linear correlation could be found. In order to allow quantitative analysis independent of matrix effects, a multiple linear regression model was developed. Besides the three target analytes also the signals of possible argides (40Ar36Ar and 98Mo40Ar) as well as detected impurities of the Mo-Si-B coatings (108Pd) were considered. Applicability of the model to unknown samples was confirmed using external validation. Relative deviations from the values determined using conventional liquid analysis after sample digestion between 5 and 10% for the main components Mo and Si were observed.

The irradiation behavior of atomized U-Mo alloy fuels at high temperature

NASA Astrophysics Data System (ADS)

Park, Jong-Man; Kim, Ki-Hwan; Kim, Chang-Kyu; Meyer, M. K.; Hofman, G. L.; Strain, R. V.

2001-04-01

Post-irradiation examinations of atomized U-10Mo, U-6Mo, and U-6Mo-1.7Os dispersion fuels from the RERTR-3 experiment irradiated in the Advanced Test Reactor (ATR) were carried out in order to investigate the fuel behavior of high uranium loading (8 gU/cc) at a high temperature (higher than 200°C). It was observed after about 40 at% BU that the U-Mo alloy fuels at a high temperature showed similar irradiation bubble morphologies compared to those at a lower temperature found in the RERTR-1 irradiation result, but there was a thick reaction layer with the aluminum matrix which was found to be greatly affected by the irradiation temperature and to a lesser degree by the fuel composition. In addition, the chemical analysis for the irradiated U-Mo fuels using the Electron Probe Micro Analysis (EPMA) method were conducted to investigate the compositional changes during the formation of the reaction product.

Speciation of Energy Critical Elements in Marine Ferromanganese Crusts and Nodules by Principal Component Analysis and Least-squares fits to XAFS Spectra

NASA Astrophysics Data System (ADS)

Foster, A. L.; Klofas, J. M.; Hein, J. R.; Koschinsky, A.; Bargar, J.; Dunham, R. E.; Conrad, T. A.

2011-12-01

Marine ferromanganese crusts and nodules ("Fe-Mn crusts") are considered a potential mineral resource due to their accumulation of several economically-important elements at concentrations above mean crustal abundances. They are typically composed of intergrown Fe oxyhydroxide and Mn oxide; thicker (older) crusts can also contain carbonate fluorapatite. We used X-ray absorption fine-structure (XAFS) spectroscopy, a molecular-scale structure probe, to determine the speciation of several elements (Te, Bi, Mo, Zr, Pt) in Fe-Mn crusts. As a first step in analysis of this dataset, we have conducted principal component analysis (PCA) of Te K-edge and Mo K-edge, k3-weighted XAFS spectra. The sample set consisted of 12 homogenized, ground Fe-Mn crust samples from 8 locations in the global ocean. One sample was subjected to a chemical leach to selectively remove Mn oxides and the elements associated with it. The samples in the study set contain 50-205 mg/kg Te (average = 88) and 97-802 mg/kg Mo (average = 567). PCAs of background-subtracted, normalized Te K-edge and Mo K-edge XAFS spectra were performed on a data matrix of 12 rows x 122 columns (rows = samples; columns = Te or Mo fluorescence value at each energy step) and results were visualized without rotation. The number of significant components was assessed by the Malinowski indicator function and ability of the components to reconstruct the features (minus noise) of all sample spectra. Two components were significant by these criteria for both Te and Mo PCAs and described a total of 74 and 75% of the total variance, respectively. Reconstruction of potential model compounds by the principal components derived from PCAs on the sample set ("target transformation") provides a means of ranking models in terms of their utility for subsequent linear-combination, least-squares (LCLS) fits (the next step of data analysis). Synthetic end-member models of Te4+, Te6+, and Mo adsorbed to Fe(III) oxyhydroxide and Mn oxide were tested. Te6+ sorbed to Fe oxyhydroxide and Mo sorbed to Fe oxyhydroxide were identified as the best models for Te and Mo PCAs, respectively. However, in the case of Mo, least-squares fits contradicted these results, indicating that about 80% of Mo in crust samples was associated with Mn oxides. Ultimately it was discovered that the sample from which Mn oxide had been leached was skewing the results in the Mo PCA but not in the Te PCA. When the leached sample was removed and the Mo PCA repeated (n = 11), target transformation indicated that Mo sorbed to Mn oxide was indeed the best model for the set. Our results indicate that Te and Mo are strongly partitioned into different phases in these Fe-Mn crusts, and emphasize the importance of evaluating outliers and their effects on PCA.

Observation of Vacancies, Faults, and Superstructures in Ln 5Mo 2O 12 (Ln = La, Y, and Lu) Compounds with Direct Mo–Mo Bonding

DOE PAGES

Colabello, Diane M.; Sobalvarro, Elizabeth M.; Sheckelton, John P.; ...

2017-10-26

Among oxide compounds with direct metal–metal bonding, the Y 5Mo 2O 12 (A 5B 2O 12) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal–metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal–metal bonding have integer oxidation states resulting from the lifting of orbital degeneracymore » typically induced by the metal–metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5Mo 2O 12 (Ln = La–Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown in this paper that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1–2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5Mo 2O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. Finally, this represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic interactions within the one-dimensional octahedral chains of this system.« less

Observation of Vacancies, Faults, and Superstructures in Ln 5Mo 2O 12 (Ln = La, Y, and Lu) Compounds with Direct Mo–Mo Bonding

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

Colabello, Diane M.; Sobalvarro, Elizabeth M.; Sheckelton, John P.

Among oxide compounds with direct metal–metal bonding, the Y 5Mo 2O 12 (A 5B 2O 12) structural family of compounds has a particularly intriguing low-dimensional structure due to the presence of bioctahedral B 2O 10 dimers arranged in one-dimensional edge-sharing chains along the direction of the metal–metal bonds. Furthermore, these compounds can have a local magnetic moment due to the noninteger oxidation state (+4.5) of the transition metal, in contrast to the conspicuous lack of a local moment that is commonly observed when oxide compounds with direct metal–metal bonding have integer oxidation states resulting from the lifting of orbital degeneracymore » typically induced by the metal–metal bonding. Although a monoclinic C2/m structure has been previously proposed for Ln 5Mo 2O 12 (Ln = La–Lu and Y) members of this family based on prior single crystal diffraction data, it is found that this structural model misses many important structural features. On the basis of synchrotron powder diffraction data, it is shown in this paper that the C2/m monoclinic unit cell represents a superstructure relative to a previously unrecognized orthorhombic Immm subcell and that the superstructure derives from the ordering of interchangeable Mo 2O 10 and LaO 6 building blocks. The superstructure for this reason is typically highly faulted, as evidenced by the increased breadth of superstructure diffraction peaks associated with a coherence length of 1–2 nm in the c* direction. Finally, it is shown that oxygen vacancies can occur when Ln = La, producing an oxygen deficient stoichiometry of La 5Mo 2O 11.55 and an approximately 10-fold reduction in the number of unpaired electrons due to the reduction of the average Mo valence from +4.5 to +4.05, a result confirmed by magnetic susceptibility measurements. Finally, this represents the first observation of oxygen vacancies in this family of compounds and provides an important means of continuously tuning the magnetic interactions within the one-dimensional octahedral chains of this system.« less

Cobalt internal standard for Ni to assist the simultaneous determination of Mo and Ni in plant materials by high-resolution continuum source graphite furnace atomic absorption spectrometry employing direct solid sample analysis.

PubMed

de Babos, Diego Victor; Bechlin, Marcos André; Barros, Ariane Isis; Ferreira, Edilene Cristina; Gomes Neto, José Anchieta; de Oliveira, Silvana Ruella

2016-05-15

A new method is proposed for the simultaneous determination of Mo and Ni in plant materials by high-resolution continuum source graphite furnace atomic absorption spectrometry (HR-CS GFAAS), employing direct solid sample analysis (DSS) and internal standardization (IS). Cobalt was used as internal standard to minimize matrix effects during Ni determinations, enabling the use of aqueous standards for calibration. Correlation coefficients for the calibration curves were typically better than 0.9937. The performance of the method was checked by analysis of six plant certified reference materials, and the results for Mo and Ni were in agreement with the certified values (95% confidence level, t-test). Analysis was made of different types of plant materials used as renewable sources of energy, including sugarcane leaves, banana tree fiber, soybean straw, coffee pods, orange bagasse, peanut hulls, and sugarcane bagasse. The concentrations found for Mo and Ni ranged from 0.08 to 0.63 ng mg(-1) and from 0.41 to 6.92 ng mg(-1), respectively. Precision (RSD) varied from 2.1% to 11% for Mo and from 3.7% to 10% for Ni. Limits of quantification of 0.055 and 0.074 ng were obtained for Mo and Ni, respectively. Copyright © 2016 Elsevier B.V. All rights reserved.

The Montreal Cognitive Assessment and the mini-mental state examination as screening instruments for cognitive impairment: item analyses and threshold scores.

PubMed

Damian, Anne M; Jacobson, Sandra A; Hentz, Joseph G; Belden, Christine M; Shill, Holly A; Sabbagh, Marwan N; Caviness, John N; Adler, Charles H

2011-01-01

To perform an item analysis of the Montreal Cognitive Assessment (MoCA) versus the Mini-Mental State Examination (MMSE) in the prediction of cognitive impairment, and to examine the characteristics of different MoCA threshold scores. 135 subjects enrolled in a longitudinal clinicopathologic study were administered the MoCA by a single physician and the MMSE by a trained research assistant. Subjects were classified as cognitively impaired or cognitively normal based on independent neuropsychological testing. 89 subjects were found to be cognitively normal, and 46 cognitively impaired (20 with dementia, 26 with mild cognitive impairment). The MoCA was superior in both sensitivity and specificity to the MMSE, although not all MoCA tasks were of equal predictive value. A MoCA threshold score of 26 had a sensitivity of 98% and a specificity of 52% in this population. In a population with a 20% prevalence of cognitive impairment, a threshold of 24 was optimal (negative predictive value 96%, positive predictive value 47%). This analysis suggests the potential for creating an abbreviated MoCA. For screening in primary care, the MoCA threshold of 26 appears optimal. For testing in a memory disorders clinic, a lower threshold has better predictive value. Copyright © 2011 S. Karger AG, Basel.

Crystal Structure Analysis and the Identification of Distinctive Functional Regions of the Protein Elicitor Mohrip2.

PubMed

Liu, Mengjie; Duan, Liangwei; Wang, Meifang; Zeng, Hongmei; Liu, Xinqi; Qiu, Dewen

2016-01-01

The protein elicitor MoHrip2, which was extracted from Magnaporthe oryzae as an exocrine protein, triggers the tobacco immune system and enhances blast resistance in rice. However, the detailed mechanisms by which MoHrip2 acts as an elicitor remain unclear. Here, we investigated the structure of MoHrip2 to elucidate its functions based on molecular structure. The three-dimensional structure of MoHrip2 was obtained. Overall, the crystal structure formed a β-barrel structure and showed high similarity to the pathogenesis-related (PR) thaumatin superfamily protein thaumatin-like xylanase inhibitor (TL-XI). To investigate the functional regions responsible for MoHrip2 elicitor activities, the full length and eight truncated proteins were expressed in Escherichia coli and were evaluated for elicitor activity in tobacco. Biological function analysis showed that MoHrip2 triggered the defense system against Botrytis cinerea in tobacco. Moreover, only MoHrip2M14 and other fragments containing the 14 amino acids residues in the middle region of the protein showed the elicitor activity of inducing a hypersensitive response and resistance related pathways, which were similar to that of full-length MoHrip2. These results revealed that the central 14 amino acid residues were essential for anti-pathogenic activity.

EPR and ESE of CuS4 complex in Cu(dmit)2: g-Factor and hyperfine splitting correlation in tetrahedral Cu-sulfur complexes

NASA Astrophysics Data System (ADS)

Hoffmann, Stanisław K.; Goslar, Janina; Lijewski, Stefan; Zalewska, Alina

2013-11-01

Pseudotetrahedral CuS4 complexes of Cu(dmit)2 compound in DMF solution were studied by EPR, UV-Vis and electron spin echo methods. After rapid freezing at 77 K a good glassy state is formed and the CuS4 complex has a D2d symmetry of a compressed tetrahedron with xy ground state and spin-Hamiltonian parameters g|| = 2.089, g⊥ = 2.026, A|| = 146 × 10-4 cm-1 and A⊥ = 30 × 10-4 cm-1. The complex is not deformed in the glassy state and is very rigid as indicated by the echo detected spectrum and by electron spin relaxation which is governed by reorientations of methyl groups of surrounding DMF molecules as shown by electron spin echo envelope modulation (ESEEM) spectrum. The g|| and A|| of Cu(dmit)2 and other CuS4 complexes collected in Peisach-Blumberg correlation diagram were analyzed using extended Molecular Orbital theory. We explain why the correlation line for copper-sulfur complexes has larger slope compared to the CuO4 and CuN4 tetrahedra. Along the correlation line the delocalization of unpaired electron density onto ligand is constant and varies from β = 0.78-0.83 for g|| in the range 2.06-2.10 of correlation diagram. The slope of the line is determined by the product of MO-coefficients αc1, where α is a parameter characterizing delocalization of unpaired electron in x2-y2 and c1 < 1 is a mixing parameter decreasing when 4p contribution grows. We found, unexpectedly, that αc1≈0.7 for all CuS4 complexes suggesting a correlation between degree of tetrahedral deformation and MO-parameters. MO-coefficients for Cu(dmit)2 are α = 0.753, β = 0.752 and c1 = 0.930 confirming a strong delocalization of unpaired electron in xy and x2-y2 orbitals.

The Synthesis and Characterization of Aromatic Hybrid Anderson–Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions

PubMed Central

Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

2015-01-01

Four aromatic hybrid Anderson polyoxomolybdates with Fe3+ or Mn3+ as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, 1H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3[FeMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-FeMo6-bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRIS–R=(HOCH2)3C–R)), (TBA)3[FeMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-FeMo6-cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3[MnMo6O18{(OCH2)3CNHCOC6H5}2]⋅3.5 ACN (TBA-MnMo6-bzn), and (TBA)3[MnMo6O18{(OCH2)3CNHCOC8H7}2]⋅2.5 ACN (TBA-MnMo6-cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mm) sodium salts Na3[FeMo6O18{(OCH2)3CNHCOC6H5}2] (Na-FeMo6-bzn), Na3[FeMo6O18{(OCH2)3CNHCOC8H7}2] (Na-FeMo6-cin), Na3[MnMo6O18{(OCH2)3CNHCOC6H5}2] (Na-MnMo6-bzn), and Na3[MnMo6O18{(OCH2)3CNHCOC8H7}2] (Na-MnMo6-cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate–polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern–Volmer analysis, which suggested the formation of a 1:1 POM–protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. PMID:26527418

Phase stability and electronic structure of UMo2Al20: A first-principles study

NASA Astrophysics Data System (ADS)

Liu, Peng-Chuang; Xian, Ya-Jiang; Wang, Xin; Zhang, Yu-Ting; Zhang, Peng-Cheng

2017-09-01

In this paper, the phase stability of UMo2Al20 was explored using cluster formula in combination with first-principles calculations. Cluster formula analysis uncovered that the compound was composed of two principal clusters, i.e. [Mo-Al12] and [U-Al16]. The electronic interactions between U, Mo and Al atoms in this compound were discussed using elastic property, Bader charges and energy-resolved local bonding analysis, as well as the electronic interactions between Mo and Al atoms in [Mo-Al12] cluster and between U and Al atoms in [U-Al16] cluster. It revealed that UMo2Al20 satisfied the mechanical stability criterion for cubic system, and exhibited near ionic bonding character with weak bonding directionality. The calculations within both standard DFT and HSE frameworks demonstrated that U and Al atoms acted as an electron donor while Mo atoms acted as electron acceptor. The intrinsic stability of UMo2Al20 mainly stemmed from the bonding states of Mo-Al bonds and Al-Al bonds in [Mo-Al12] cluster. These calculations provide a further insight on the CeCr2Al20-type ternary compounds.

Antisite-disorder, magnetic and thermoelectric properties of Mo-rich Sr2Fe1-yMo1+yO6 (0 ≤y≤ 0.2) double perovskites.

PubMed

Popuri, Srinivasa R; Redpath, Debbie; Chan, Gavin; Smith, Ronald I; Cespedes, Oscar; Bos, Jan-Willem G

2015-06-21

Structure analysis using X-ray and neutron powder diffraction and elemental mapping has been used to demonstrate that nominal A-site deficient Sr(2-x)FeMoO(6-δ) (0 ≤x≤ 0.5) compositions form as Mo-rich Sr(2)Fe(1-y)Mo(1+y)O(6) (0 ≤y≤ 0.2) perovskites at high temperatures and under reducing atmospheres. These materials show a gradual transition from the Fe and Mo rock salt ordered double perovskite structure to a B-site disordered arrangement. Analysis of the fractions of B-O-B' linkages revealed a gradual increase in the number of Mo-O-Mo linkages at the expense of the ferrimagnetic (FIM) Fe-O-Mo linkages that dominate the y = 0 material. All samples contain about 10-15% antiferromagnetic (AF) Fe-O-Fe linkages, independent of the degree of B-site ordering. The magnetic susceptibility of the y = 0.2 sample is characteristic of a small domain ferrimagnet (T(c)∼ 250 K), while room temperature neutron powder diffraction demonstrated the presence of G-type AF ordering linked to the Fe-O-Fe linkages (m(Fe) = 1.25(7)μ(B)). The high temperature thermoelectric properties are characteristic of a metal with a linear temperature dependence of the Seebeck coefficient, S (for all y) and electrical resistivity ρ (y≥ 0.1). The largest thermoelectric power factor S(2)/ρ = 0.12 mW m(-1) K(-1) is observed for Sr(2)FeMoO(6) at 1000 K.

Keplerate cluster (Mo-132) mediated electrostatic assembly of nanoparticles.

PubMed

Gooch, Jonathan; Jalan, Abhishek A; Jones, Stephanie; Hine, Corey R; Alam, Rabeka; Garai, Somenath; Maye, Mathew M; Müller, Achim; Zubieta, Jon

2014-10-15

The electrostatic assembly between a series of differently charged Mo-132-type Keplerates present in the compounds (NH4)42[{(Mo(VI))Mo(VI)5O21(H2O)6}12 {Mo(V)2O4(CH3COO)}30].ca. {300 H2O+10 CH3COONH4} (Mo-132a), (NH4)72-n[{(H2O)81-n+(NH4)n} {(Mo(VI))Mo(VI)5O21(H2O)6}12 {Mo(V)2O4(SO4)}30].ca. 200 H2O (Mo-132b), and Na10(NH4)62[{(Mo(VI))Mo(VI)5O21(H2O)6}12 {Mo(V)2O4(HPO4)}30]. ca. {300H2O+2Na(+)+2NH4(+)+4H2PO4(-)} (Mo-132c) with cationic gold nanoparticles (AuNPs) was investigated for the first time. The rapid electrostatic assembly from nanoscopic entities to micron scale aggregates was observed upon precipitation, which closely matched the point of aggregate electroneutrality. Successful assembly was demonstrated using UV-vis, DLS, TEM, and zeta-potential analysis. Results indicate that the point at which precipitation occurs is related to charge balance or electroneutrality, and that counterions at both the Mo-132 and AuNP play a significant role in assembly. Copyright © 2014 Elsevier Inc. All rights reserved.

Synthesis and optical properties of Tb-doped pentazinc dimolybdate pentahydrate

NASA Astrophysics Data System (ADS)

Zhai, Bao-gai; Ma, Qing-lan; Yang, Long; Huang, Yuan Ming

Tb3+ doped pentazinc bimolybdate pentahydrate (Zn5Mo2O11·5H2O) was synthesized via the precipitation method. Thermal gravimetric analysis and differential scanning calorimetric analysis indicate that Zn5Mo2O11·5H2O is decomposed into ZnMoO4 at the phase transition temperature 267 °C. The photoluminescence characterization shows that the characteristic emissions of Tb3+ at 488, 544, 586 and 613 nm are superimposed over a broad emission band of Zn5Mo2O11·5H2O. The characteristic emissions of Tb3+ ions get weakened in intensity as the calcination temperature increases from 150 to 267 °C. Our results have demonstrated that Tb3+ can be used as an effective and direct probe in the spectroscopic studies on the phase transition of Zn5Mo2O11·5H2O.

Strongly luminescent monolayered MoS2 prepared by effective ultrasound exfoliation.

PubMed

Štengl, Václav; Henych, Jiří

2013-04-21

Intense ultrasound in a pressurized batch reactor was used for preparation of monolayered MoS2 nanosheets from natural mineral molybdenite. Exfoliation of bulk MoS2 using ultrasound is an attractive route to large-scale preparation of monolayered crystals. To evaluate the quality of delamination, methods like X-ray diffraction, Raman spectroscopy and microscopic techniques (TEM and AFM) were employed. From single- or few-layered products obtained from intense sonication, MoS2 quantum dots (MoSQDs) were prepared by a one-pot reaction by refluxing exfoliated nanosheets of MoS2 in ethylene glycol under atmospheric pressure. The synthesised MoSQDs were characterised by photoluminescence spectroscopy and laser-scattering particle size analysis. Our easy preparation leads to very strongly green luminescing quantum dots.

RoMo: An efficient strategy for functional mosaic analysis via stochastic Cre recombination and gene targeting in the ROSA26 locus.

PubMed

Movahedi, Kiavash; Wiegmann, Robert; De Vlaminck, Karen; Van Ginderachter, Jo A; Nikolaev, Viacheslav O

2018-07-01

Functional mosaic analysis allows for the direct comparison of mutant cells with differentially marked control cells in the same organism. While this offers a powerful approach for elucidating the role of specific genes or signalling pathways in cell populations of interest, genetic strategies for generating functional mosaicism remain challenging. We describe a novel and streamlined approach for functional mosaic analysis, which combines stochastic Cre/lox recombination with gene targeting in the ROSA26 locus. With the RoMo strategy a cell population of interest is randomly split into a cyan fluorescent and red fluorescent subset, of which the latter overexpresses a chosen transgene. To integrate this approach into high-throughput gene targeting initiatives, we developed a procedure that utilizes Gateway cloning for the generation of new targeting vectors. RoMo can be used for gain-of-function experiments or for altering signaling pathways in a mosaic fashion. To demonstrate this, we developed RoMo-dnGs mice, in which Cre-recombined red fluorescent cells co-express a dominant-negative Gs protein. RoMo-dnGs mice allowed us to inhibit G protein-coupled receptor activation in a fraction of cells, which could then be directly compared to differentially marked control cells in the same animal. We demonstrate how RoMo-dnGs mice can be used to obtain mosaicism in the brain and in peripheral organs for various cell types. RoMo offers an efficient new approach for functional mosaic analysis that extends the current toolbox and may reveal important new insights into in vivo gene function. © 2018 Wiley Periodicals, Inc.

Molybdenum L-Edge XAS Spectra of MoFe Nitrogenase

PubMed Central

Bjornsson, Ragnar; Delgado-Jaime, Mario U; Lima, Frederico A; Sippel, Daniel; Schlesier, Julia; Weyhermüller, Thomas; Einsle, Oliver; Neese, Frank; DeBeer, Serena

2015-01-01

A molybdenum L-edge X-ray absorption spectroscopy (XAS) study is presented for native and oxidized MoFe protein of nitrogenase as well as Mo-Fe model compounds. Recently collected data on MoFe protein (in oxidized and reduced forms) is compared to previously published Mo XAS data on the isolated FeMo cofactor in NMF solution and put in context of the recent Mo K-edge XAS study, which showed a MoIII assignment for the molybdenum atom in FeMoco. The L3-edge data are interpreted within a simple ligand-field model, from which a time-dependent density functional theory (TDDFT) approach is proposed as a way to provide further insights into the analysis of the molybdenum L3-edges. The calculated results reproduce well the relative spectral trends that are observed experimentally. Ultimately, these results give further support for the MoIII assignment in protein-bound FeMoco, as well as isolated FeMoco. PMID:26213424

Experimental detection of active defects in few layers MoS2 through random telegraphic signals analysis observed in its FET characteristics

NASA Astrophysics Data System (ADS)

Fang, Nan; Nagashio, Kosuke; Toriumi, Akira

2017-03-01

Transition-metal dichalcogenides (TMDs), such as molybdenum disulfide (MoS2), are expected to be promising for next generation device applications. The existence of sulfur vacancies formed in MoS2, however, will potentially make devices unstable and problematic. Random telegraphic signals (RTSs) have often been studied in small area Si metal-oxide-semiconductor field-effect transistors (MOSFETs) to identify the carrier capture and emission processes at defects. In this paper, we have systemically analyzed RTSs observed in atomically thin layer MoS2 FETs. Several types of RTSs have been analyzed. One is the simple on/off type of telegraphic signals, the second is multilevel telegraphic signals with a superposition of the simple signals, and the third is multilevel telegraphic signals that are correlated with each other. The last one is discussed from the viewpoint of the defect-defect interaction in MoS2 FETs with a weak screening in atomically confined two-dimensional electron-gas systems. Furthermore, the position of defects causing RTSs has also been investigated by preparing MoS2 FETs with multi-probes. The electron beam was locally irradiated to intentionally generate defects in the MoS2 channel. It is clearly demonstrated that the MoS2 channel is one of the RTS origins. RTS analysis enables us to analyze the defect dynamics of TMD devices.

Structures and Evolutions of Explosive Cyclones over the Northwestern and Northeastern Pacific

NASA Astrophysics Data System (ADS)

Zhang, Shuqin; Fu, Gang

2018-06-01

In this study, the structures and evolutions of moderate (MO) explosive cyclones (ECs) over the Northwestern Pacific (NWP) and Northeastern Pacific (NEP) are investigated and compared using composite analysis with cyclone-relative coordinates. Final Operational Global Analysis data gathered during the cold seasons (October-April) of the 15 years from 2000 to 2015 are used. The results indicate that MO NWP ECs have strong baroclinicity and abundant latent heat release at low levels and strong upper-level forcing, which favors explosive cyclogenesis. The rapid development of MO NEP ECs results from their interaction with a northern cyclone and a large middle-level advection of cyclonic vorticity. The structural differences between MO NWP ECs and MO NEP ECs are significant. This results from their specific large-scale atmospheric and oceanic environments. MO NWP ECs usually develop rapidly in the east and southeast of the Japan Islands; the intrusion of cold dry air from the East Asian continent leads to strong baroclinicity, and the Kuroshio/Kuroshio Extension provides abundant latent heat release at low levels. The East Asian subtropical westerly jet stream supplies strong upper-level forcing. While MO NEP ECs mainly occur over the NEP, the low-level baroclinicity, upper-level jet stream, and warm ocean currents are relatively weaker. The merged cyclone associated with a strong middle-level trough transports large cyclonic vorticity to MO NEP ECs, which favors their rapid development.

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

Kumar, Prabhat, E-mail: prabhat89k@gmail.com; Singh, Megha; Sharma, Rabindar K.

In this report, the effect of plasma voltage on plasma assisted sulfurization (PAS) of vertically aligned molybdenum trioxide (α- MoO{sub 3}) nanoflakes (NFs) on glass substrates has been studied systematically. MoO{sub 3} NFs were deposited using plasma assisted sublimation process. These nanoflakes were subjected to H{sub 2}S/Ar plasma at two different plasma voltages 600 and 1000 volts; to study the effect of plasma ionization on degree of sulfurization of MoO{sub 3} into MoS{sub 2}. XRD and Raman analysis show that film sulfurized at 1000 volts have relatively higher degree of conversion into MoS{sub 2}, as more intense peaks of MoS{submore » 2} and MoO{sub 2} are obtained than that sulfurized at 600 volts. HRTEM of sulfurized film shows that outer surface of nanoflake has been converted into MoS{sub 2} (4-5 monolayers). Meanwhile, MoO{sub 3} was reduced into MoO{sub 2} as confirmed by XRD and Raman results. All the observed results are well in consonance with each other.« less

Comparison of Alternate and Original Items on the Montreal Cognitive Assessment.

PubMed

Lebedeva, Elena; Huang, Mei; Koski, Lisa

2016-03-01

The Montreal Cognitive Assessment (MoCA) is a screening tool for mild cognitive impairment (MCI) in elderly individuals. We hypothesized that measurement error when using the new alternate MoCA versions to monitor change over time could be related to the use of items that are not of comparable difficulty to their corresponding originals of similar content. The objective of this study was to compare the difficulty of the alternate MoCA items to the original ones. Five selected items from alternate versions of the MoCA were included with items from the original MoCA administered adaptively to geriatric outpatients (N = 78). Rasch analysis was used to estimate the difficulty level of the items. None of the five items from the alternate versions matched the difficulty level of their corresponding original items. This study demonstrates the potential benefits of a Rasch analysis-based approach for selecting items during the process of development of parallel forms. The results suggest that better match of the items from different MoCA forms by their difficulty would result in higher sensitivity to changes in cognitive function over time.

Synthesis and Characterization of Molybdenum Based Colloidal Particles.

PubMed

Moreno; Vidoni; Ovalles; Chaudret; Urbina; Krentzein

1998-11-15

The synthesis and characterization of molybdenum colloidal particles were evaluated using thermal and sonochemical methods and starting from different metal precursors, Mo(CO)6 and (NH4)2MoS4. The products were characterized by elemental analysis, spectroscopic (UV, FTIR), and surface analysis (XPS) techniques, as well as by transmission electron microscopy (TEM) for determining the particle sizes. Using Mo(CO)6 as metal source, particle sizes with an average diameter of 1.5 nm can be obtained using tert-amyl alcohol as solvent and tetrahydrothiophene as sulfurating ligand. The characterization of these particles showed that they are composed of molybdenum oxide MoO3. Using (NH4)2MoS4 as metal precursor, particles with average diameters of 4.7 and 2.5 nm were synthesized using thermal and sonochemical methods, respectively. The characterization of these particles showed them to be composed of molybdenum sulfide, MoS2. The sonochemical method proved to be the fastest and most convenient synthetic pathway of obtaining small colloidal particles at low temperatures and with control of the average size. Copyright 1998 Academic Press.

Failure Behavior Characterization of Mo-Modified Ti Surface by Impact Test and Finite Element Analysis

NASA Astrophysics Data System (ADS)

Ma, Yong; Qin, Jianfeng; Zhang, Xiangyu; Lin, Naiming; Huang, Xiaobo; Tang, Bin

2015-07-01

Using the impact test and finite element simulation, the failure behavior of the Mo-modified layer on pure Ti was investigated. In the impact test, four loads of 100, 300, 500, and 700 N and 104 impacts were adopted. The three-dimensional residual impact dents were examined using an optical microscope (Olympus-DSX500i), indicating that the impact resistance of the Ti surface was improved. Two failure modes cohesive and wearing were elucidated by electron backscatter diffraction and energy-dispersive spectrometer performed in a field-emission scanning electron microscope. Through finite element forward analysis performed at a typical impact load of 300 N, stress-strain distributions in the Mo-modified Ti were quantitatively determined. In addition, the failure behavior of the Mo-modified layer was determined and an ideal failure model was proposed for high-load impact, based on the experimental and finite element forward analysis results.

Technology requirements for large flexible space structures

NASA Technical Reports Server (NTRS)

Wada, B. K.; Freeland, R. E.; Garcia, N. F.

1983-01-01

Research, test, and demonstration experiments necessary for establishing a data base that will permit construction of large, lightweight flexible space structures meeting on-orbit pointing and surface precesion criteria are discussed. Attention is focused on the wrap-rib proof-of-concept antenna structures developed from technology used on the ATS-6 satellite. The target structure will be up to 150 m in diameter or smaller, operate at RF levels, be amenable to packaging for carriage in the Shuttle bay, be capable of being ground-tested, and permit on-orbit deployment and retraction. Graphite/epoxy has been chosen as the antenna ribs material, and the antenna mesh will be gold-plated Mo wire. A 55-m diam reflector was built as proof-of-concept with ground-test capability. Tests will proceed on components, a model, the entire structure, and in-flight. An analytical model has been formulated to characterize the antenna's thermal behavior. The flight test of the 55-m prototype in-orbit offers the chance to validate the analytical model and characterize the control, mechanical, and thermal characteristics of the antenna configuration.

The stabilization mechanism of titanium cluster

NASA Astrophysics Data System (ADS)

Sun, Houqian; Ren, Yun; Hao, Yuhua; Wu, Zhaofeng; Xu, Ning

2015-05-01

A systematic and comparative theoretical study on the stabilization mechanism of titanium cluster has been performed by selecting the clusters Tin (n=3, 4, 5, 7, 13, 15 and 19) as representatives in the framework of density-functional theory. For small clusters Tin (n=3, 4 and 5), the binding energy gain due to spin polarization is substantially larger than that due to structural distortion. For medium clusters Ti13 and Ti15, both have about the same contribution. For Tin (n=4, 5, 13 and 15), when the undistorted high symmetric structure with spin-polarization is changed into the lowest energy structure, the energy level spelling due to distortion fails to reverse the level order of occupied and unoccupied molecular orbital (MO) of two type spin states, the spin configuration remains unchanged. In spin restricted and undistorted high symmetric structure, d orbitals participate in the hybridization in MOs, usually by way of a less distorted manner, and weak bonds are formed. In contrast, d orbitals take part in the formation of MOs in the ground state structure, usually in a distorted manner, and strong covalent metallic bonds are formed.

Halogen Bonding versus Hydrogen Bonding: A Molecular Orbital Perspective

PubMed Central

Wolters, Lando P; Bickelhaupt, F Matthias

2012-01-01

We have carried out extensive computational analyses of the structure and bonding mechanism in trihalides DX⋅⋅⋅A− and the analogous hydrogen-bonded complexes DH⋅⋅⋅A− (D, X, A=F, Cl, Br, I) using relativistic density functional theory (DFT) at zeroth-order regular approximation ZORA-BP86/TZ2P. One purpose was to obtain a set of consistent data from which reliable trends in structure and stability can be inferred over a large range of systems. The main objective was to achieve a detailed understanding of the nature of halogen bonds, how they resemble, and also how they differ from, the better understood hydrogen bonds. Thus, we present an accurate physical model of the halogen bond based on quantitative Kohn–Sham molecular orbital (MO) theory, energy decomposition analyses (EDA) and Voronoi deformation density (VDD) analyses of the charge distribution. It appears that the halogen bond in DX⋅⋅⋅A− arises not only from classical electrostatic attraction but also receives substantial stabilization from HOMO–LUMO interactions between the lone pair of A− and the σ* orbital of D–X. PMID:24551497

Sulfur Adsorption on the Goethite (110) Surface

NASA Astrophysics Data System (ADS)

Simonetti, S.; Damiani, D.; Brizuela, G.; Juan, A.

The electronic structure of S adsorption on goethite (110) surface has been studied by ASED-MO cluster calculations. For S location, the most exposed surface atoms of goethite surface were selected. The calculations show that the surface offers several places for S adsorption. The most energetically stable system corresponds to S location above H atom. We studied in detail the configurations that correspond to the higher OP values. For these configurations, the H-S and Fe-S computed distances are 2.1 and 3.7 Å, respectively. The H-S and Fe-S are mainly bonding interaction with OP values of 0.156 and 0.034, respectively. The Fe-S interaction mainly involves Fe 3dx2-y2 atomic orbitals with lesser participation of Fe 4py and Fe 3dyz atomic orbitals. The O-S interaction shows the same bonding and antibonding contributions giving a small OP value. The O-S interaction involves O 2p orbitals. There is an electron transfer to the Fe atom from the S atom. On the other hand, there is an electron transfer to S atom from the H and O atoms, respectively.

Semiempirical UNO-CAS and UNO-CI: method and applications in nanoelectronics.

PubMed

Dral, Pavlo O; Clark, Timothy

2011-10-20

Unrestricted Natural Orbital-Complete Active Space Configuration Interaction, abbreviated as UNO-CAS, has been implemented for NDDO-based semiempirical molecular-orbital (MO) theory. A computationally more economic technique, UNO-CIS, in which we use a configuration interaction (CI) calculation with only single excitations (CIS) to calculate excited states, has also been implemented and tested. The class of techniques in which unrestricted natural orbitals (UNOs) are used as the reference for CI calculations is denoted UNO-CI. Semiempirical UNO-CI gives good results for the optical band gaps of organic semiconductors such as polyynes and polyacenes, which are promising materials for nanoelectronics. The results of these semiempirical UNO-CI techniques are generally in better agreement with experiment than those obtained with the corresponding conventional semiempirical CI methods and comparable to or better than those obtained with far more computationally expensive methods such as time-dependent density-functional theory. We also show that symmetry breaking in semiempirical UHF calculations is very useful for predicting the diradical character of organic compounds in the singlet spin state.

Investigating the Geochemical Model for Molybdenum Mineralization in the JEB Tailings Management Facility at McClean Lake, Saskatchewan: An X-ray Absorption Spectroscopy Study.

PubMed

Blanchard, Peter E R; Hayes, John R; Grosvenor, Andrew P; Rowson, John; Hughes, Kebbi; Brown, Caitlin

2015-06-02

The geochemical model for Mo mineralization in the JEB Tailings Management Facility (JEB TMF), operated by AREVA Resources Canada at McClean Lake, Saskatchewan, was investigated using X-ray Absorption Near-Edge Spectroscopy (XANES), an elemental-specific technique that is sensitive to low elemental concentrations. Twenty five samples collected during the 2013 sampling campaign from various locations and depths in the TMF were analyzed by XANES. Mo K-edge XANES analysis indicated that the tailings consisted primarily of Mo(6+) species: powellite (CaMoO4), ferrimolybdite (Fe2(MoO4)3·8H2O), and molybdate adsorbed on ferrihydrite (Fe(OH)3 - MoO4). A minor concentration of a Mo(4+) species in the form of molybdenite (MoS2) was also present. Changes in the Mo mineralization over time were inferred by comparing the relative amounts of the Mo species in the tailings to the independently measured aqueous Mo pore water concentration. It was found that ferrimolybdite and molybdate adsorbed on ferrihydrite initially dissolves in the TMF and precipitates as powellite.

Enzalutamide in Men with Chemotherapy-naïve Metastatic Castration-resistant Prostate Cancer: Extended Analysis of the Phase 3 PREVAIL Study.

PubMed

Beer, Tomasz M; Armstrong, Andrew J; Rathkopf, Dana; Loriot, Yohann; Sternberg, Cora N; Higano, Celestia S; Iversen, Peter; Evans, Christopher P; Kim, Choung-Soo; Kimura, Go; Miller, Kurt; Saad, Fred; Bjartell, Anders S; Borre, Michael; Mulders, Peter; Tammela, Teuvo L; Parli, Teresa; Sari, Suha; van Os, Steve; Theeuwes, Ad; Tombal, Bertrand

2017-02-01

Enzalutamide significantly improved radiographic progression-free survival (rPFS) and overall survival (OS) among men with chemotherapy-naïve metastatic castration-resistant prostate cancer at the prespecified interim analysis of PREVAIL, a phase 3, double-blind, randomized study. We evaluated the longer-term efficacy and safety of enzalutamide up to the prespecified number of deaths in the final analysis, which included an additional 20 mo of follow-up for investigator-assessed rPFS, 9 mo of follow-up for OS, and 4 mo of follow-up for safety. Enzalutamide reduced the risk of radiographic progression or death by 68% (hazard ratio [HR] 0.32, 95% confidence interval [CI] 0.28-0.37; p<0.0001) and the risk of death by 23% (HR 0.77, 95% CI 0.67-0.88; p=0.0002). Median investigator-assessed rPFS was 20.0 mo (95% CI 18.9-22.1) in the enzalutamide arm and 5.4 mo (95% CI 4.1-5.6) in the placebo arm. Median OS was 35.3 mo (95% CI 32.2-not yet reached) in the enzalutamide arm and 31.3 mo (95% CI 28.8-34.2) in the placebo arm. At the time of the OS analysis, 167 patients in the placebo arm had crossed over to receive enzalutamide. The most common adverse events in the enzalutamide arm were fatigue, back pain, constipation, and arthralgia. This final analysis of PREVAIL provides more complete assessment of the clinical benefit of enzalutamide. PREVAIL is registered on ClinicalTrials.gov as NCT01212991. According to data from longer follow-up, enzalutamide continued to provide benefit over placebo in patients with metastatic castration-resistant prostate cancer. Copyright © 2016 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Molten salt corrosion behavior of structural materials in LiCl-KCl-UCl3 by thermogravimetric study

NASA Astrophysics Data System (ADS)

Rao, Ch Jagadeeswara; Ningshen, S.; Mallika, C.; Mudali, U. Kamachi

2018-04-01

The corrosion resistance of structural materials has been recognized as a key issue in the various unit operations such as salt purification, electrorefining, cathode processing and injection casting in the pyrochemical reprocessing of spent metallic nuclear fuels. In the present work, the corrosion behavior of the candidate materials of stainless steel (SS) 410, 2.25Cr-1Mo and 9Cr-1Mo steels was investigated in molten LiCl-KCl-UCl3 salt by thermogravimetric analysis under inert and reactive atmospheres at 500 and 600 °C, for 6 h duration. Insignificant weight gain (less than 1 mg/cm2) in the inert atmosphere and marginal weight gain (maximum 5 mg/cm2) in the reactive atmosphere were observed at both the temperatures. Chromium depletion rates and formation of Cr-rich corrosion products increased with increasing temperature of exposure in both inert and reactive atmospheres as evidenced by SEM and EDS analysis. The corrosion attack by LiCl-KCl-UCl3 molten salt, under reactive atmosphere for 6 h duration was more in the case of SS410 than 9Cr-1Mo steel followed by 2.25Cr-1Mo steel at 500 °C and the corrosion attack at 600 °C followed the order: 9Cr-1Mo steel >2.25Cr-1Mo steel > SS410. Outward diffusion of the minor alloying element, Mo was observed in 9Cr-1Mo and 2.25Cr-1Mo steels at both temperatures under reactive atmosphere. Laser Raman spectral analysis of the molten salt corrosion tested alloys under a reactive atmosphere at 500 and 600 °C for 6 h revealed the formation of unprotected Fe3O4 and α-as well as γ-Fe2O3. The results of the present study facilitate the selection of structural materials for applications in the corrosive molten salt environment at high temperatures.

The Synthesis and Characterization of Aromatic Hybrid Anderson-Evans POMs and their Serum Albumin Interactions: The Shift from Polar to Hydrophobic Interactions.

PubMed

Al-Sayed, Emir; Blazevic, Amir; Roller, Alexander; Rompel, Annette

2015-12-01

Four aromatic hybrid Anderson polyoxomolybdates with Fe(3+) or Mn(3+) as the central heteroatom have been synthesized by using a pre-functionalization protocol and characterized by using single-crystal X-ray diffraction, FTIR, ESI-MS, (1) H NMR spectroscopy, and elemental analysis. Structural analysis revealed the formation of (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-FeMo6 -bzn; TBA=tetrabutylammonium, ACN=acetonitrile, bzn=TRIS-benzoic acid alkanolamide, TRISR=(HOCH2 )3 CR)), (TBA)3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-FeMo6 -cin; cin=TRIS-cinnamic acid alkanolamide), (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ]⋅3.5 ACN (TBA-MnMo6 -bzn), and (TBA)3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ]⋅2.5 ACN (TBA-MnMo6 -cin). To make these four compounds applicable in biological systems, an ion exchange was performed that gave the water-soluble (up to 80 mM) sodium salts Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-FeMo6 -bzn), Na3 [FeMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-FeMo6 -cin), Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC6 H5 }2 ] (Na-MnMo6 -bzn), and Na3 [MnMo6 O18 {(OCH2 )3 CNHCOC8 H7 }2 ] (Na-MnMo6 -cin). The hydrolytic stability of the sodium salts was examined by applying ESI-MS in the pH range of 4 to 9. Sodium dodecylsulfate-polyacrylamide gel electrophoresis (SDS-PAGE) showed that human and bovine serum albumin (HSA and BSA) remain intact in solutions that contain up to 100 equivalents of the sodium salts over more than 4 d at 20 °C. Tryptophan (Trp) fluorescence quenching was applied to study the interactions between the sodium salts and HSA and BSA at pH 5.5 and 7.4. The quenching constants were extracted by using Stern-Volmer analysis, which suggested the formation of a 1:1 POM-protein complex in all samples. It is suggested that the aromatic hybrid POM approaches subdomain IIA of HSA and exhibits hydrophobic interactions with its hydrophobic tails, whereas the Anderson core is stabilized through electrostatic interactions with polar amino acid side chains from, for example, subdomain IB. © 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.

A two-dimensional spin field-effect switch

NASA Astrophysics Data System (ADS)

Casanova, Felix

The integration of the spin degree of freedom in charge-based electronic devices has revolutionised both sensing and memory capability in microelectronics. Further development in spintronic devices requires electrical manipulation of spin current for logic operations. The mainstream approach followed so far, inspired by the seminal proposal of the Datta and Das spin modulator, has relied on the spin-orbit field as a medium for electrical control of the spin state. However, the still standing challenge is to find a material whose spin-orbit coupling (SOC) is weak enough to transport spins over long distances, while also being strong enough to allow their electrical manipulation. In our recent work, we demonstrate a radically different approach by engineering a van der Waals heterostructure from atomically thin crystals, and which combines the superior spin transport properties of graphene with the strong SOC of MoS2, a transition metal dichalcogenide with semiconducting properties. The spin transport in the graphene channel is modulated between ON and OFF states by tuning the spin absorption into the MoS2 layer with a gate electrode. Our demonstration of a spin field-effect switch using two-dimensional (2D) materials identifies a new route towards spin logic operations for beyond CMOS technology. Furthermore, the van der Waals heterostructure at the core of our experiments opens the path for fundamental research of exotic transport properties predicted for transition metal dichalcogenides, in which electrical spin injection has so far been elusive.

Individual and collective modes of surface magnetoplasmon in thiolate-protected silver nanoparticles studied by MCD spectroscopy

NASA Astrophysics Data System (ADS)

Yao, Hiroshi; Shiratsu, Taisuke

2016-05-01

Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiol (DT)-, azobenzenethiol (ABT)-, and ABT/DT mixed-monolayer-protected Ag nanoparticles. ABT-protected Ag nanoparticles are somewhat aggregated and thus exhibit a broad, collective mode of plasmonic absorption, whereas other samples with highly-dispersed nanoparticles show an individual mode of LSPR absorption. In all Ag nanoparticles, a derivative-like MCD signal is observed under an applied magnetic field of 1.6 T, which can be explained in terms of two circular modes of magnetoplasmon caused by the increase (or decrease) in the Lorentz force imparted on the free electrons that oscillate in the left (or right) circular orbits in the nanosphere. For the Ag nanoparticles exhibiting an individual LSPR mode, in particular, simultaneous deconvolution analysis of UV-vis absorption and MCD spectra reveal that (i) the amplitude of the magnetoplasmonic component with lower frequency (ω-), resulting from the reduction in the confinement strength of collective electrons by the Lorentz force, is stronger than that with a higher frequency (ω+) (ii) the accurate shift or cyclotron frequency between two magnetoplasmonic modes (ωc = ω+ - ω-) is size-dependent, and presents a very large value with implications for the apparent enhancement of the local magnetic-field in the Ag nanoparticles. These results strongly suggest that the Ag-thiolate layer or Ag-S bonding on the nanoparticle surface plays a significant role in the MO enhancement.Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiol (DT)-, azobenzenethiol (ABT)-, and ABT/DT mixed-monolayer-protected Ag nanoparticles. ABT-protected Ag nanoparticles are somewhat aggregated and thus exhibit a broad, collective mode of plasmonic absorption, whereas other samples with highly-dispersed nanoparticles show an individual mode of LSPR absorption. In all Ag nanoparticles, a derivative-like MCD signal is observed under an applied magnetic field of 1.6 T, which can be explained in terms of two circular modes of magnetoplasmon caused by the increase (or decrease) in the Lorentz force imparted on the free electrons that oscillate in the left (or right) circular orbits in the nanosphere. For the Ag nanoparticles exhibiting an individual LSPR mode, in particular, simultaneous deconvolution analysis of UV-vis absorption and MCD spectra reveal that (i) the amplitude of the magnetoplasmonic component with lower frequency (ω-), resulting from the reduction in the confinement strength of collective electrons by the Lorentz force, is stronger than that with a higher frequency (ω+) (ii) the accurate shift or cyclotron frequency between two magnetoplasmonic modes (ωc = ω+ - ω-) is size-dependent, and presents a very large value with implications for the apparent enhancement of the local magnetic-field in the Ag nanoparticles. These results strongly suggest that the Ag-thiolate layer or Ag-S bonding on the nanoparticle surface plays a significant role in the MO enhancement. Electronic supplementary information (ESI) available: EDX spectroscopic analysis of various Ag nanoparticle samples; MCD signals normalized to absorbance for the Ag(DT)L and Ag(DT)S samples; deconvolution of UV-vis absorption and MCD spectra using three Lorentzian components; IR spectral changes upon photoisomerization; thermal cis-to-trans relaxation of azobenzene in the Ag(ABT) sample; UV-vis absorption spectra of Ag nanoparticle samples in the presence/absence of a magnetic field of 1.6 T. See DOI: 10.1039/c6nr00631k

Creep Rupture Analysis and Life Estimation of 1.25Cr-0.5Mo, 2.25Cr-1Mo and Modified 9Cr-1Mo Steel: A Comparative Study

NASA Astrophysics Data System (ADS)

Roy, Prabir Kumar

2018-04-01

This paper highlights a comparative assessment of creep life of 1.25Cr-0.5Mo, 2.25Cr-1Mo and modified 9Cr-1Mo steels based on accelerated creep rupture tests. Creep rupture test data have been analysed and creep life of the above mentioned materials have been assessed using Larson Miller parameter at the stress levels of 60 and 42 MPa for different temperatures. Limiting steam temperatures for minimum design life of 105 h at 42 and 60 MPa for the above mentioned steels have also been calculated. Microstructural studies for the three above mentioned steels are also done.

Exposure to a mildly aversive early life experience leads to prefrontal cortex deficits in the rat.

PubMed

Stamatakis, Antonios; Manatos, Vasileios; Kalpachidou, Theodora; Stylianopoulou, Fotini

2016-11-01

Aversive early life experiences in humans have been shown to result in deficits in the function of the prefrontal cortex (PFC). In an effort to elucidate possible neurobiological mechanisms involved, we investigated in rats, the effects of a mildly aversive early experience on PFC structure and function. The early experience involved exposure of rat pups during postnatal days (PND) 10-13 to a T-maze in which they search for their mother, but upon finding her are prohibited contact with her, thus being denied the expected reward (DER). We found that the DER experience resulted in adulthood in impaired PFC function, as assessed by two PFC-dependent behavioral tests [attention set-shifting task (ASST) and fear extinction]. In the ASST, DER animals showed deficits specifically in the intra-dimensional reversal shifts and a lower activation-as determined by c-Fos immunohistochemistry-of the medial orbital cortex (MO), a PFC subregion involved in this aspect of the task. Furthermore, the DER experience resulted in decreased glutamatergic neuron and dendritic spine density in the MO and infralimbic cortex (IL) in the adult brain. The decreased neuronal density was detected as early as PND12 and was accompanied by increased micro- and astroglia-density in the MO/IL.

Surface Characterization of New Biomaterials

NASA Astrophysics Data System (ADS)

Minciuna, M. G.; Vizureanu, P.; Abdullah, M. M. B.; Achitei, D. C.; Istrate, B.; Cimpoesu, R.; Focsaneanu, S. C.

2017-06-01

This paper presents the characterization of new alloys CoCrMoSi6, CoCrMoSi7, CoCrMoSi10, in terms of hardness determinations, fractographic analysis and surface analysis. The original version of the alloy was obtained by casting process in a vacuum arc furnace. Experimental results obtained from this study confirms that by increasing content of silicon, the mechanical properties are superior and the positive results obtained at surface studies favoring the formation of compounds, that lead to the reduction of alloying grade for α solid solution and the plasticity of the alloys.

Synergistic effects of Mo and F doping on the quality factor of ZnO thin films prepared by a fully automated home-made nebulizer spray technique

NASA Astrophysics Data System (ADS)

Ravichandran, K.; Dineshbabu, N.; Arun, T.; Manivasaham, A.; Sindhuja, E.

2017-01-01

Transparent conducting oxide films of undoped, Mo doped, Mo + F co-doped ZnO were deposited using a facile homemade nebulizer spray pyrolysis technique. The effects of Mo and F doping on the structural, optical, electrical and surface morphological properties were investigated using XRD, UV-vis-NIR spectroscopy, I-V and Hall probe techniques, FESEM and AFM, and XPS, respectively. The XRD analysis confirms that all the films are well crystallized with hexagonal wurtzite structure. All the synthesized samples exhibit high transmittance (above 85%) in the visible region. The current-voltage (I-V) characteristics show the ohmic conduction nature of the films. The Hall probe measurements show that the synergistic effects of Mo and F doping cause desirable improvements in the quality factor of the ZnO films. A minimum resistivity of 5.12 × 10-3 Ω cm with remarkably higher values of mobility and carrier concentration is achieved for Mo (2 at.%) + F (15 at.%) co-doped ZnO films. A considerable variation in the intensity of deep level emission caused by Mo and F doping is observed in the photoluminescence (PL) studies. The presence of the constituent elements in the samples is confirmed by XPS analysis.

Phthalocyanine Doped Metal Oxide Nanoparticles on Multiwalled Carbon Nanotubes Platform for the detection of Dopamine

NASA Astrophysics Data System (ADS)

Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Fayemi, Omolola E.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

2017-03-01

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ.

Phthalocyanine Doped Metal Oxide Nanoparticles on Multiwalled Carbon Nanotubes Platform for the detection of Dopamine

PubMed Central

Mphuthi, Ntsoaki G.; Adekunle, Abolanle S.; Fayemi, Omolola E.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

2017-01-01

The electrocatalytic properties of metal oxides (MO = Fe3O4, ZnO) nanoparticles doped phthalocyanine (Pc) and functionalized MWCNTs, decorated on glassy carbon electrode (GCE) was investigated. Successful synthesis of the metal oxide nanoparticles and the MO/Pc/MWCNT composite were confirmed using UV-Vis, EDX, XRD and TEM techniques. Successful modification of GCE with the MO and their composite was also confirmed using cyclic voltammetry (CV) technique. GCE-MWCNT/ZnO/29H,31H-Pc was the best electrode towards DA detection with very low detection limit (0.75 μM) which compared favourably with literature, good sensitivity (1.45 μA/μM), resistance to electrode fouling, and excellent ability to detect DA without interference from AA signal. Electrocatalytic oxidation of DA on GCE-MWCNT/ZnO/29H,31H-Pc electrode was diffusion controlled but characterized with some adsorption of electro-oxidation reaction intermediates products. The fabricated sensors are easy to prepare, cost effective and can be applied for real sample analysis of dopamine in drug composition. The good electrocatalytic properties of 29H,31H-Pc and 2,3-Nc were related to their (quantum chemically derived) frontier molecular orbital energies and global electronegativities. The better performance of 29H,31H-Pc than 2,3-Nc in aiding electrochemical oxidation of DA might be due to its better electron accepting ability, which is inferred from its lower ELUMO and higher χ. PMID:28256521

Chemical Bonding: The Orthogonal Valence-Bond View

PubMed Central

Sax, Alexander F.

2015-01-01

Chemical bonding is the stabilization of a molecular system by charge- and spin-reorganization processes in chemical reactions. These processes are said to be local, because the number of atoms involved is very small. With multi-configurational self-consistent field (MCSCF) wave functions, these processes can be calculated, but the local information is hidden by the delocalized molecular orbitals (MO) used to construct the wave functions. The transformation of such wave functions into valence bond (VB) wave functions, which are based on localized orbitals, reveals the hidden information; this transformation is called a VB reading of MCSCF wave functions. The two-electron VB wave functions describing the Lewis electron pair that connects two atoms are frequently called covalent or neutral, suggesting that these wave functions describe an electronic situation where two electrons are never located at the same atom; such electronic situations and the wave functions describing them are called ionic. When the distance between two atoms decreases, however, every covalent VB wave function composed of non-orthogonal atomic orbitals changes its character from neutral to ionic. However, this change in the character of conventional VB wave functions is hidden by its mathematical form. Orthogonal VB wave functions composed of orthonormalized orbitals never change their character. When localized fragment orbitals are used instead of atomic orbitals, one can decide which local information is revealed and which remains hidden. In this paper, we analyze four chemical reactions by transforming the MCSCF wave functions into orthogonal VB wave functions; we show how the reactions are influenced by changing the atoms involved or by changing their local symmetry. Using orthogonal instead of non-orthogonal orbitals is not just a technical issue; it also changes the interpretation, revealing the properties of wave functions that remain otherwise undetected. PMID:25906476

In-situ Raman and X-ray photoelectron spectroscopic studies on the pitting corrosion of modified 9Cr-1Mo steel in neutral chloride solution

NASA Astrophysics Data System (ADS)

Ramya, S.; Nanda Gopala Krishna, D.; Mudali, U. Kamachi

2018-01-01

In-situ Raman and X-ray photoelectron spectroscopic studies were performed for the identification of native and corroded surface oxide layers of modified 9Cr-1Mo steel. The Raman data obtained for native oxide layer of modified 9Cr-1Mo steel revealed that it was mainly composed of oxides of Fe and Cr. The presence of alloying element Mo was found to be less significant in the native oxide film. The oxides of Cr were dominant at the surface and were found to be decreasing closer to metal/oxide layer interface. The changes in the chemical composition of the native films upon in-situ pitting during potentiostatic polarization experiment were characterized by in-situ Raman analysis. The corrosion products of potentiostatically polarized modified 9Cr-1Mo steel was composed of dominant Fe (III) phases viz., γ- Fe2O3, α and γ - FeOOH along with the oxides of chromium. The results from Raman analysis were corroborated with the XPS experiments on as received and pitted samples of modified 9Cr-1Mo steel specimens. It was observed that the oxides of Cr and Mo contributed for the stability of the surface layer by forming Cr2O3 and MoO3. Also, the study attempted to find out the intermediate corrosion products inside the metastable pits to account for the pseudo passive behavior of modified 9Cr-1Mo steel in 0.1 M NaCl solution.

Inclusion of orbital relaxation and correlation through the unitary group adapted open shell coupled cluster theory using non-relativistic and scalar relativistic Hamiltonians to study the core ionization potential of molecules containing light to medium-heavy elements

NASA Astrophysics Data System (ADS)

Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

2018-02-01

The orbital relaxation attendant on ionization is particularly important for the core electron ionization potential (core IP) of molecules. The Unitary Group Adapted State Universal Coupled Cluster (UGA-SUMRCC) theory, recently formulated and implemented by Sen et al. [J. Chem. Phys. 137, 074104 (2012)], is very effective in capturing orbital relaxation accompanying ionization or excitation of both the core and the valence electrons [S. Sen et al., Mol. Phys. 111, 2625 (2013); A. Shee et al., J. Chem. Theory Comput. 9, 2573 (2013)] while preserving the spin-symmetry of the target states and using the neutral closed-shell spatial orbitals of the ground state. Our Ansatz invokes a normal-ordered exponential representation of spin-free cluster-operators. The orbital relaxation induced by a specific set of cluster operators in our Ansatz is good enough to eliminate the need for different sets of orbitals for the ground and the core-ionized states. We call the single configuration state function (CSF) limit of this theory the Unitary Group Adapted Open-Shell Coupled Cluster (UGA-OSCC) theory. The aim of this paper is to comprehensively explore the efficacy of our Ansatz to describe orbital relaxation, using both theoretical analysis and numerical performance. Whenever warranted, we also make appropriate comparisons with other coupled-cluster theories. A physically motivated truncation of the chains of spin-free T-operators is also made possible by the normal-ordering, and the operational resemblance to single reference coupled-cluster theory allows easy implementation. Our test case is the prediction of the 1s core IP of molecules containing a single light- to medium-heavy nucleus and thus, in addition to demonstrating the orbital relaxation, we have addressed the scalar relativistic effects on the accuracy of the IPs by using a hierarchy of spin-free Hamiltonians in conjunction with our theory. Additionally, the contribution of the spin-free component of the two-electron Gaunt term, not usually taken into consideration, has been estimated at the Self-Consistent Field (ΔSCF) level and is found to become increasingly important and eventually quite prominent for molecules with third period atoms and below. The accuracies of the IPs computed using UGA-OSCC are found to be of the same order as the Coupled Cluster Singles Doubles (ΔCCSD) values while being free from spin contamination. Since the UGA-OSCC uses a common set of orbitals for the ground state and the ion, it obviates the need of two N5 AO to MO transformation in contrast to the ΔCCSD method.

Inclusion of orbital relaxation and correlation through the unitary group adapted open shell coupled cluster theory using non-relativistic and scalar relativistic Hamiltonians to study the core ionization potential of molecules containing light to medium-heavy elements.

PubMed

Sen, Sangita; Shee, Avijit; Mukherjee, Debashis

2018-02-07

The orbital relaxation attendant on ionization is particularly important for the core electron ionization potential (core IP) of molecules. The Unitary Group Adapted State Universal Coupled Cluster (UGA-SUMRCC) theory, recently formulated and implemented by Sen et al. [J. Chem. Phys. 137, 074104 (2012)], is very effective in capturing orbital relaxation accompanying ionization or excitation of both the core and the valence electrons [S. Sen et al., Mol. Phys. 111, 2625 (2013); A. Shee et al., J. Chem. Theory Comput. 9, 2573 (2013)] while preserving the spin-symmetry of the target states and using the neutral closed-shell spatial orbitals of the ground state. Our Ansatz invokes a normal-ordered exponential representation of spin-free cluster-operators. The orbital relaxation induced by a specific set of cluster operators in our Ansatz is good enough to eliminate the need for different sets of orbitals for the ground and the core-ionized states. We call the single configuration state function (CSF) limit of this theory the Unitary Group Adapted Open-Shell Coupled Cluster (UGA-OSCC) theory. The aim of this paper is to comprehensively explore the efficacy of our Ansatz to describe orbital relaxation, using both theoretical analysis and numerical performance. Whenever warranted, we also make appropriate comparisons with other coupled-cluster theories. A physically motivated truncation of the chains of spin-free T-operators is also made possible by the normal-ordering, and the operational resemblance to single reference coupled-cluster theory allows easy implementation. Our test case is the prediction of the 1s core IP of molecules containing a single light- to medium-heavy nucleus and thus, in addition to demonstrating the orbital relaxation, we have addressed the scalar relativistic effects on the accuracy of the IPs by using a hierarchy of spin-free Hamiltonians in conjunction with our theory. Additionally, the contribution of the spin-free component of the two-electron Gaunt term, not usually taken into consideration, has been estimated at the Self-Consistent Field (ΔSCF) level and is found to become increasingly important and eventually quite prominent for molecules with third period atoms and below. The accuracies of the IPs computed using UGA-OSCC are found to be of the same order as the Coupled Cluster Singles Doubles (ΔCCSD) values while being free from spin contamination. Since the UGA-OSCC uses a common set of orbitals for the ground state and the ion, it obviates the need of two N 5 AO to MO transformation in contrast to the ΔCCSD method.

Comparison of metal ion concentrations and implant survival after total hip arthroplasty with metal-on-metal versus metal-on-polyethylene articulations

PubMed Central

Dahlstrand, Henrik; Stark, André; Wick, Marius C; Anissian, Lucas; Hailer, Nils P; Weiss, Rüdiger J

2017-01-01

Background and purpose Large metal-on-metal (MoM) articulations are associated with metal wear and corrosion, leading to increased metal ion concentrations and unacceptable revision rates. There are few comparative studies of 28-mm MoM articulations with conventional metal-on-polyethylene (MoP) couplings. We present a long-term follow-up of a randomized controlled trial comparing MoM versus MoP 28-mm articulations, focused on metal ions and implant survival. Patients and methods 85 patients with a mean age of 65 years at surgery were randomized to a MoM (Metasul) or a MoP (Protasul) bearing. After 16 years, 38 patients had died and 4 had undergone revision surgery. 13 patients were unavailable for clinical follow-up, leaving 30 patients (n = 14 MoM and n = 16 MoP) for analysis of metal ion concentrations and clinical outcome. Results 15-year implant survival was similar in both groups (MoM 96% [95% CI 88–100] versus MoP 97% [95% CI 91–100]). The mean serum cobalt concentration was 4-fold higher in the MoM (1.5 μg/L) compared with the MoP cohort (0.4 μg/L, p < 0.001) and the mean chromium concentration was double in the MoM (2.2 μg/L) compared with the MoP cohort (1.0 μg/L, p = 0.05). Mean creatinine levels were similar in both groups (MoM 93 μmol/L versus MoP 92 μmol/L). Harris hip scores differed only marginally between the MoM and MoP cohorts. Interpretation This is the longest follow-up of a randomized trial on 28-mm MoM articulations, and although implant survival in the 2 groups was similar, metal ion concentrations remained elevated in the MoM cohort even in the long term. PMID:28699417

Orbit Maneuver for Responsive Coverage Using Electric Propulsion

DTIC Science & Technology

2010-03-01

24 4. Results and Analysis ...Orbit Analysis ............................................................................28 Figure 3.6 Circular Orbit Analysis ...29 Figure 3.7 Elliptical Orbit Analysis

Congenital Microphthalmia, Anophthalmia and Coloboma among Live Births in Denmark.

PubMed

Roos, Laura; Jensen, Hanne; Grønskov, Karen; Holst, René; Tümer, Zeynep

2016-10-01

This study aims to quantify the occurrence of the congenital eye malformations anophthalmia (AO), microphthalmia (MO) and coloboma among liveborn infants in Denmark, and to estimate the rate of chromosomal abnormalities in this group of patients. A cohort of patients born in 1995-2012 with diagnoses of MO/AO or coloboma was identified from the Danish National Patient Registry (DNPR), and their ocular and extra-ocular diagnoses were reviewed. In order to assess the occurrence of chromosomal abnormalities in the cohort, the data were cross-referenced with the Danish Cytogenetic Central Registry (DCCR). We identified 415 patients with MO/AO/coloboma in the DNPR. The total number of live births from 1995-2012 was 1,174,299, and the average birth prevalence of MO/AO/coloboma was 3.6/10,000 live births and of MO/AO was 1.2/10,000 live births. Extra-ocular abnormalities were observed in 32.1% of MO/AO cases and 21.7% of coloboma cases. Chromosome analysis was performed in 36.1% of the cohort, and 14.7% of cases had an abnormal karyotype. In 8.7% of the cohort, a chromosome microarray analysis was performed, and in 44.4% of cases, a possibly pathogenic copy number variation was observed. The birth prevalence of MO/AO/coloboma in Denmark has been steady at 3.6/10,000 live births during the last 17 years. The rate of syndromic cases was lower compared to other studies. A relatively high rate of pathogenic chromosomal aberrations was observed, suggesting an important role for cytogenetic analysis in this group of patients.

Sulfur K-edge X-ray absorption spectroscopy and density functional theory calculations on monooxo Mo(IV) and bisoxo Mo(VI) bis-dithiolenes: insights into the mechanism of oxo transfer in sulfite oxidase and its relation to the mechanism of DMSO reductase.

PubMed

Ha, Yang; Tenderholt, Adam L; Holm, Richard H; Hedman, Britt; Hodgson, Keith O; Solomon, Edward I

2014-06-25

Sulfur K-edge X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations have been used to determine the electronic structures of two complexes [Mo(IV)O(bdt)2](2-) and [Mo(VI)O2(bdt)2](2-) (bdt = benzene-1,2-dithiolate(2-)) that relate to the reduced and oxidized forms of sulfite oxidase (SO). These are compared with those of previously studied dimethyl sulfoxide reductase (DMSOr) models. DFT calculations supported by the data are extended to evaluate the reaction coordinate for oxo transfer to a phosphite ester substrate. Three possible transition states are found with the one at lowest energy, stabilized by a P-S interaction, in good agreement with experimental kinetics data. Comparison of both oxo transfer reactions shows that in DMSOr, where the oxo is transferred from the substrate to the metal ion, the oxo transfer induces electron transfer, while in SO, where the oxo transfer is from the metal site to the substrate, the electron transfer initiates oxo transfer. This difference in reactivity is related to the difference in frontier molecular orbitals (FMO) of the metal-oxo and substrate-oxo bonds. Finally, these experimentally related calculations are extended to oxo transfer by sulfite oxidase. The presence of only one dithiolene at the enzyme active site selectively activates the equatorial oxo for transfer, and allows facile structural reorganization during turnover.

Modification of the optoelectronic properties of two-dimensional MoS2 crystals by ultraviolet-ozone treatment

NASA Astrophysics Data System (ADS)

Yang, Hae In; Park, Seonyoung; Choi, Woong

2018-06-01

We report the modification of the optoelectronic properties of mechanically-exfoliated single layer MoS2 by ultraviolet-ozone exposure. Photoluminescence emission of pristine MoS2 monotonically decreased and eventually quenched as ultraviolet-ozone exposure time increased from 0 to 10 min. The reduction of photoluminescence emission accompanied reduction of Raman modes, suggesting structural degradation in ultraviolet-ozone exposed MoS2. Analysis with X-ray photoelectron spectroscopy revealed that the formation of Ssbnd O and Mosbnd O bonding increases with ultraviolet-ozone exposure time. Measurement of electrical transport properties of MoS2 in a bottom-gate thin-film transistor configuration suggested the presence of insulating MoO3 after ultraviolet-ozone exposure. These results demonstrate that ultraviolet-ozone exposure can significantly influence the optoelectronic properties of single layer MoS2, providing important implications on the application of MoS2 and other two-dimensional materials into optoelectronic devices.

HYDROTHERMAL SYNTHESIS OF α-MoO3 NANORODS FOR NO2 DETECTION

NASA Astrophysics Data System (ADS)

Bai, Shouli; Chen, Song; Tian, Yuan; Luo, Ruixian; Li, Dianqing; Chen, Aifan

2012-12-01

Thermodynamically stable molybdenum trioxide nanorods have been successfully synthesized by a simple hydrothermal process. The product exhibits high-quality, single-crystalline layered orthorhombic structure (α-MoO3), and aspect ratio over 20 by characterizations of X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and Fourier transform infrared (FT-IR). The growth mechanism of α-MoO3 nanorods can be understood by electroneutral and dehydration reaction, which is highly dependent on solution acidity and hydrothermal temperature. The sensing tests show that the sensor based on MoO3 nanorods exhibits high sensitivity to NO2 and is not interferred by CO and CH4, which makes this kind sensor a competitive candidate for NO2 detection. The intrinsic sensing performance of MoO3 maybe arise from its nonstoichiometry of MoO3 owing to the presence of Mo5+ and oxygen vacancy in MoO3 lattice, which has been confirmed by X-ray photoelectron spectroscopy (XPS) analysis. The sensing mechanism of MoO3 for NO2 is also discussed.

Double perovskite Sr2FeMoO6-xNx (x=0.3, 1.0) oxynitrides with anionic ordering

NASA Astrophysics Data System (ADS)

Retuerto, M.; de la Calle, C.; Martínez-Lope, M. J.; Porcher, F.; Krezhov, K.; Menéndez, N.; Alonso, J. A.

2012-01-01

Two new oxynitride double perovskites of composition Sr2FeMoO6-xNx (x=0.3, 1.0) have been synthesized by annealing precursor powders obtained by citrate techniques in flowing ammonia at 750 °C and 650 °C, respectively. The polycrystalline samples have been characterized by chemical analysis, x-ray and neutron diffraction (NPD), Mössbauer spectroscopy and magnetic measurements. They exhibit a tetragonal structure with a=5.5959(1) Å, c=7.9024(2) Å, V=247.46(2) Å3 for Sr2FeMoO5.7N0.3; and a=5.6202(2) Å, c=7.9102(4) Å, V=249.85(2) Å3 for Sr2FeMoO5N; space group I4/m, Z=2. The nitridation process seems to extraordinarily improve the long-range Fe/Mo ordering, achieving 95% at moderate temperatures of 750 °C. The analysis of high resolution NPD data, based on the contrast existing between the scattering lengths of O and N, shows that both atoms are located at (O,N)2 anion substructure corresponding to the basal ab plane of the perovskite structure, whereas the O1 site is fully occupied by oxygen atoms. The evolution of the and distances suggests a shift towards a configuration close to Fe4+(3d4, S=2):Mo5+(4d1, S=1/2). The magnetic susceptibility shows a ferrimagnetic transition with a reduced saturation magnetization compared to Sr2FeMoO6, due to the different nature of the magnetic double exchange interactions through Fe-N-Mo-N-Fe paths in contrast to the stronger Fe-O-Mo-O-Fe interactions. Also, the effect observed by low-temperature NPD seems to reduce the ordered Fe moments and enhance the Mo moments, in agreement with the evolution of the oxidation states, thus decreasing the saturation magnetization.

Construction of MoS2/Si nanowire array heterojunction for ultrahigh-sensitivity gas sensor

NASA Astrophysics Data System (ADS)

Wu, Di; Lou, Zhenhua; Wang, Yuange; Xu, Tingting; Shi, Zhifeng; Xu, Junmin; Tian, Yongtao; Li, Xinjian

2017-10-01

Few-layer MoS2 thin films were synthesized by a two-step thermal decomposition process. In addition, MoS2/Si nanowire array (SiNWA) heterojunctions exhibiting excellent gas sensing properties were constructed and investigated. Further analysis reveals that such MoS2/SiNWA heterojunction devices are highly sensitive to nitric oxide (NO) gas under reverse voltages at room temperature (RT). The gas sensor demonstrated a minimum detection limit of 10 ppb, which represents the lowest value obtained for MoS2-based sensors, as well as an ultrahigh response of 3518% (50 ppm NO, ˜50% RH), with good repeatability and selectivity of the MoS2/SiNWA heterojunction. The sensing mechanisms were also discussed. The performance of the MoS2/SiNWA heterojunction gas sensors is superior to previous results, revealing that they have great potential in applications relating to highly sensitive gas sensors.

Construction of MoS2/Si nanowire array heterojunction for ultrahigh-sensitivity gas sensor.

PubMed

Wu, Di; Lou, Zhenhua; Wang, Yuange; Xu, Tingting; Shi, Zhifeng; Xu, Junmin; Tian, Yongtao; Li, Xinjian

2017-10-27

Few-layer MoS 2 thin films were synthesized by a two-step thermal decomposition process. In addition, MoS 2 /Si nanowire array (SiNWA) heterojunctions exhibiting excellent gas sensing properties were constructed and investigated. Further analysis reveals that such MoS 2 /SiNWA heterojunction devices are highly sensitive to nitric oxide (NO) gas under reverse voltages at room temperature (RT). The gas sensor demonstrated a minimum detection limit of 10 ppb, which represents the lowest value obtained for MoS 2 -based sensors, as well as an ultrahigh response of 3518% (50 ppm NO, ∼50% RH), with good repeatability and selectivity of the MoS 2 /SiNWA heterojunction. The sensing mechanisms were also discussed. The performance of the MoS 2 /SiNWA heterojunction gas sensors is superior to previous results, revealing that they have great potential in applications relating to highly sensitive gas sensors.

Measurement of the 97Mo(n ,γ ) reaction with the DANCE γ calorimeter array

NASA Astrophysics Data System (ADS)

Walker, C. L.; Krtička, M.; Baramsai, B.; Bečvář, F.; Bredeweg, T. A.; Chyzh, A.; Haight, R. C.; Jandel, M.; Kroll, J.; Mitchell, G. E.; O'Donnell, J. M.; Rundberg, R. S.; Ullmann, J. L.; Valenta, S.; Wilhelmy, J. B.

2015-07-01

Spectra of γ rays following the 97Mo(n ,γ ) reaction were measured as a function of incident neutron energy with the DANCE (Detector for Advanced Neutron Capture Experiments) array of 160 BaF2 scintillation detectors at the Los Alamos Neutron Science Center using an enriched 97Mo target. These spectra were used for the assignment of spins of the 97Mo resonances up to neutron energy En=1.7 keV, as well as in the study of photon strength functions (PSFs) in 98Mo. Analysis of the spectra with the nuclear statistical model showed that they can be well reproduced with the same PSF models which well described the γ decay following slow neutron capture in 95Mo. On the other hand, the spectra are inconsistent with PSFs describing some other experimental data in 98Mo.

Two-dimensional molybdenum disulphide nanoflakes synthesized by liquid-solid phase reaction method: regenerative photocatalytic performance under UV-visible light irradiation by advance oxidation process

NASA Astrophysics Data System (ADS)

Afsar, M. F.; Rafiq, M. A.; Siddique, Fizza; Saira, F.; Chaudhary, M. M.; Hasan, M. M.; Tok, A. I. Y.

2018-05-01

Molybdenum disulphide (MoS2) nanoflakes were prepared through liquid-solid phase reaction technique. X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM) analysis revealed the formation of pure, polycrystalline, hexagonal phase of MoS2 nanoflakes. The texture coefficient (T{c}hkl) analysis showed that (100) plane was preferentially oriented. The specific surface area of the nanoflakes was 21 m2 g‑1 as determined using Brunaure-Emmett-Teller (BET) technique. A band gap of ∼2.05 eV for MoS2 nanoflakes was estimated from UV-visible spectrum. Regenerative photocatalytic activity of MoS2 nanoflakes was assessed by degrading methylene blue (MB) and safranin-o (SO) dyes under UV-visible light irradiation. Under light irradiation, degradation efficiency for MB was ∼99.58% in 100 min while for SO it was ∼99.89% in 70 min. The MoS2 nanoflakes exhibited excellent photocatalytic performance and good stability in a wide pH range (3–11). MoS2 nanoflakes showed a high reaction rate constant (k app ) for SO ∼ 0.104 49 min‑1 and MB ∼ 0.092 18 min‑1 as compared to other MoS2 nanostructures. The obtained exceptional photocatalytic performance of MoS2 nanoflakes offers potential applications for the treatment of polluted water as well as in other correlated fields.

Synthesis of strongly fluorescent molybdenum disulfide nanosheets for cell-targeted labeling.

PubMed

Wang, Nan; Wei, Fang; Qi, Yuhang; Li, Hongxiang; Lu, Xin; Zhao, Guoqiang; Xu, Qun

2014-11-26

MoS2 nanosheets with polydispersity of the lateral dimensions from natural mineral molybdenite have been prepared in the emulsions microenvironment built by the water/surfactant/CO2 system. The size, thickness, and atomic structure are characterized by transmission electron microscopy (TEM), atomic force microscopy (AFM), and laser-scattering particle size analysis. Meanwhile, by the analysis of photoluminescence spectroscopy and microscope, the MoS2 nanosheets with smaller lateral dimensions exhibit extraordinary photoluminescence properties different from those with relatively larger lateral dimensions. The discovery of the excitation dependent photoluminescence for MoS2 nanosheets makes them potentially of interests for the applications in optoelectronics and biology. Moreover, we demonstrate that the fabricated MoS2 nanosheets can be a nontoxic fluorescent label for cell-targeted labeling application.

Some features of the oxidative conversion of Mo(CO)/sub 6/ in a medium of hydroperoxide or tert-butyl hydroperoxide and an aromatic hydrocarbon

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

Fomin, V.M.; Lunin, A.V.; Aleksandrov, Yu.A.

1988-03-10

Occurrence of the reaction under study was followed from the decrease in hydroperoxide or of Mo(CO)/sub 6/. The Mo(CO)/sub 6/ content of the reaction was found by determining either the concentration of this compound directly or by determining the concentration of the gaseous products from its transformations (CO + CO/sub 2/). Hydroperoxides (I) and (II) were determined iodometrically. Metal-containing products of the oxidation of Mo(CO)/sub 6/, molybdenum oxides and peroxides, were analyzed by IR and ESR spectroscopy, elemental analysis, and iodometry. Analysis of transformation products of the hydroperoxides (phenol, acetone, dimethylphenylcarbinol, acetophenone, tert-butyl alcohol, water, and oxygen) was performed usingmore » gas chromatography. Results are presented.« less

The modulation of Schottky barriers of metal-MoS2 contacts via BN-MoS2 heterostructures.

PubMed

Su, Jie; Feng, Liping; Zhang, Yan; Liu, Zhengtang

2016-06-22

Using first-principles calculations within density functional theory, we systematically studied the effect of BN-MoS2 heterostructure on the Schottky barriers of metal-MoS2 contacts. Two types of FETs are designed according to the area of the BN-MoS2 heterostructure. Results show that the vertical and lateral Schottky barriers in all the studied contacts, irrespective of the work function of the metal, are significantly reduced or even vanish when the BN-MoS2 heterostructure substitutes the monolayer MoS2. Only the n-type lateral Schottky barrier of Au/BN-MoS2 contact relates to the area of the BN-MoS2 heterostructure. Notably, the Pt-MoS2 contact with n-type character is transformed into a p-type contact upon substituting the monolayer MoS2 by a BN-MoS2 heterostructure. These changes of the contact natures are ascribed to the variation of Fermi level pinning, work function and charge distribution. Analysis demonstrates that the Fermi level pinning effects are significantly weakened for metal/BN-MoS2 contacts because no gap states dominated by MoS2 are formed, in contrast to those of metal-MoS2 contacts. Although additional BN layers reduce the interlayer interaction and the work function of the metal, the Schottky barriers of metal/BN-MoS2 contacts still do not obey the Schottky-Mott rule. Moreover, different from metal-MoS2 contacts, the charges transfer from electrodes to the monolayer MoS2, resulting in an increment of the work function of these metals in metal/BN-MoS2 contacts. These findings may prove to be instrumental in the future design of new MoS2-based FETs with ohmic contact or p-type character.

MoCAP proteins regulated by MoArk1-mediated phosphorylation coordinate endocytosis and actin dynamics to govern development and virulence of Magnaporthe oryzae

PubMed Central

Yang, Jun; Chen, Deng; Liu, Muxing; Zhang, Haifeng; Zheng, Xiaobo; Wang, Ping; Peng, Youliang; Zhang, Zhengguang

2017-01-01

Actin organization is a conserved cellular process that regulates the growth and development of eukaryotic cells. It also governs the virulence process of pathogenic fungi, such as the rice blast fungus Magnaporthe oryzae, with mechanisms not yet fully understood. In a previous study, we found that actin-regulating kinase MoArk1 displays conserved functions important in endocytosis and actin organization, and MoArk1 is required for maintaining the growth and full virulence of M. oryzae. To understand how MoArk1 might function, we identified capping protein homologs from M. oryzae (MoCAP) that interact with MoArk1 in vivo. MoCAP is heterodimer consisting of α and β subunits MoCapA and MoCapB. Single and double deletions of MoCAP subunits resulted in abnormal mycelial growth and conidia formation. The ΔMocap mutants also exhibited reduced appressorium penetration and invasive hyphal growth within host cells. Furthermore, the ΔMocap mutants exhibited delayed endocytosis and abnormal cytoskeleton assembly. Consistent with above findings, MoCAP proteins interacted with MoAct1, co-localized with actin during mycelial development, and participated in appressorial actin ring formation. Further analysis revealed that the S85 residue of MoCapA and the S285 residue of MoCapB were subject to phosphorylation by MoArk1 that negatively regulates MoCAP functions. Finally, the addition of exogenous phosphatidylinositol 4,5-bisphosphate (PIP2) failed to modulate actin ring formation in ΔMocap mutants, in contrast to the wild-type strain, suggesting that MoCAP may also mediate phospholipid signaling in the regulation of the actin organization. These results together demonstrate that MoCAP proteins whose functions are regulated by MoArk1 and PIP2 are important for endocytosis and actin dynamics that are directly linked to growth, conidiation and pathogenicity of M. oryzae. PMID:28542408

Atomic layer deposition of molybdenum disulfide films using MoF 6 and H 2 S

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

Mane, Anil U.; Letourneau, Steven; Mandia, David J.

2018-01-01

Molybdenum sulfide films were grown by atomic layer deposition on silicon and fused silica substrates using molybdenum hexafluoride (MoF6) and hydrogen sulfide at 200 degrees C. In situ quartz crystal microbalance (QCM) measurements confirmed linear growth at 0.46 angstrom/cycle and self-limiting chemistry for both precursors. Analysis of the QCM step shapes indicated that MoS2 is the reaction product, and this finding is supported by x-ray photoelectron spectroscopy measurements showing that Mo is predominantly in the Mo(IV) state. However, Raman spectroscopy and x-ray diffraction measurements failed to identify crystalline MoS2 in the as-deposited films, and this might result from unreacted MoFxmore » residues in the films. Annealing the films at 350 degrees C in a hydrogen rich environment yielded crystalline MoS2 and reduced the F concentration in the films. Optical transmission measurements yielded a bandgap of 1.3 eV. Finally, the authors observed that the MoS2 growth per cycle was accelerated when a fraction of the MoF6 pulses were substituted with diethyl zinc. Published by the AVS« less

Three-dimensional nanoporous MoS2 framework decorated with Au nanoparticles for surface-enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Sheng, Yingqiang; Jiang, Shouzhen; Yang, Cheng; Liu, Mei; Liu, Aihua; Zhang, Chao; Li, Zhen; Huo, Yanyan; Wang, Minghong; Man, Baoyuan

2017-08-01

The three-dimensional (3D) MoS2 decorated with Au nanoparticles (Au NPs) hybrids (3D MoS2-Au NPs) for surface-enhanced Raman scattering (SERS) sensing was demonstrated in this paper. SEM, Raman spectroscopy, TEM, SAED, EDX and XRD were performed to characterize 3D MoS2-Au NPs hybrids. Rhodamine 6G (R6G), fluorescein and gallic acid molecules were used as the probe for the SERS detection of the 3D MoS2-Au NPs hybrids. In addition, we modeled the enhancement of the electric field of MoS2-Au NPs hybrids using Finite-difference time-domain (FDTD) analysis, which can further give assistance to the mechanism understanding of the SERS activity.

Determination of band alignment at two-dimensional MoS2/Si van der Waals heterojunction

NASA Astrophysics Data System (ADS)

Goel, Neeraj; Kumar, Rahul; Mishra, Monu; Gupta, Govind; Kumar, Mahesh

2018-06-01

To understand the different mechanism occurring at the MoS2-silicon interface, we have fabricated a MoS2/Si heterojunction by exfoliating MoS2 on top of the silicon substrate. Raman spectroscopy and atomic force microscopy (AFM) measurement expose the signature of few-layers in the deposited MoS2 flake. Herein, the temperature dependence of the energy barrier and carrier density at the MoS2/Si heterojunction has been extensively investigated. Furthermore, to study band alignment at the MoS2/Si interface, we have calculated a valence band offset of 0.66 ± 0.17 eV and a conduction band offset of 0.42 ± 0.17 eV using X-ray and Ultraviolet photoelectron spectroscopy. We determined a type-II band alignment at the interface which is very conducive for the transport of photoexcited carriers. As a proof-of-concept application, we extend our analysis of the photovoltaic behavior of the MoS2/Si heterojunction. This work provides not only a comparative study between MoS2/p-Si and MoS2/n-Si heterojunctions but also paves the way to engineer the properties of the interface for the future integration of MoS2 with silicon.

Comparison of Alternate and Original Items on the Montreal Cognitive Assessment

PubMed Central

Lebedeva, Elena; Huang, Mei; Koski, Lisa

2016-01-01

Background The Montreal Cognitive Assessment (MoCA) is a screening tool for mild cognitive impairment (MCI) in elderly individuals. We hypothesized that measurement error when using the new alternate MoCA versions to monitor change over time could be related to the use of items that are not of comparable difficulty to their corresponding originals of similar content. The objective of this study was to compare the difficulty of the alternate MoCA items to the original ones. Methods Five selected items from alternate versions of the MoCA were included with items from the original MoCA administered adaptively to geriatric outpatients (N = 78). Rasch analysis was used to estimate the difficulty level of the items. Results None of the five items from the alternate versions matched the difficulty level of their corresponding original items. Conclusions This study demonstrates the potential benefits of a Rasch analysis-based approach for selecting items during the process of development of parallel forms. The results suggest that better match of the items from different MoCA forms by their difficulty would result in higher sensitivity to changes in cognitive function over time. PMID:27076861

Accurate force field for molybdenum by machine learning large materials data

NASA Astrophysics Data System (ADS)

Chen, Chi; Deng, Zhi; Tran, Richard; Tang, Hanmei; Chu, Iek-Heng; Ong, Shyue Ping

2017-09-01

In this work, we present a highly accurate spectral neighbor analysis potential (SNAP) model for molybdenum (Mo) developed through the rigorous application of machine learning techniques on large materials data sets. Despite Mo's importance as a structural metal, existing force fields for Mo based on the embedded atom and modified embedded atom methods do not provide satisfactory accuracy on many properties. We will show that by fitting to the energies, forces, and stress tensors of a large density functional theory (DFT)-computed dataset on a diverse set of Mo structures, a Mo SNAP model can be developed that achieves close to DFT accuracy in the prediction of a broad range of properties, including elastic constants, melting point, phonon spectra, surface energies, grain boundary energies, etc. We will outline a systematic model development process, which includes a rigorous approach to structural selection based on principal component analysis, as well as a differential evolution algorithm for optimizing the hyperparameters in the model fitting so that both the model error and the property prediction error can be simultaneously lowered. We expect that this newly developed Mo SNAP model will find broad applications in large and long-time scale simulations.

Ab initio molecular orbital calculations on the associated complexes of lithium cyanide with ammonia

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

Mohandas, P.; Shivaglal, M.C.; Chandrasekhar, J.

Ab initio molecular orbital (MO) calculations with the 3-21G and 6-31G basis sets are carried out on a series of complexes of NH{sub 3} with Li{sup +}, C{triple_bond}N{sup -}, LiCN, and its isomer LiNC. The BSSE-corrected interaction energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies are evaluated for 15 species. Complexes with trifurcated (C{sub 3v}) structures are calculated to be saddle points on the potential energy surfaces and have one imaginary frequency each. Calculated energies, geometrical parameters, internal force constants, and harmonic vibrational frequencies of the various species considered are discussed in terms of the nature of associationmore » of LiCN with ammonia. The vibrational frequencies of the relevant complexed species are compared with the experimental frequencies reported earlier for solutions of lithium cyanide in liquid ammonia. 40 refs., 1 fig., 4 tabs.« less

Oxygen evolution on a SrFeO3 anode - Mechanistic considerations from molecular orbital theory

NASA Technical Reports Server (NTRS)

Mehandru, S. P.; Anderson, Alfred B.

1989-01-01

Various pathways proposed in the literature for the evolution of O2 in electrochemical oxidations are explored using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory and the cluster models of the SrFeO3 surface as a prototype material. Calculations indicate that oxygen atoms can be easily formed on the (100) surface as well as on the edge cation sites of a SrFeO3 anode by the discharge of OH(-), followed by its deprotonation and electron transfer to the electrode. The O atoms can form O2 on the edge and corner sites, where the Fe(4+) is coordinated to four and three bulk oxygen anions, respectively. The calculations strongly disfavor mechanisms involving coupling of oxygen atoms adsorbed on different cations as well as a mechanism featuring an ozone intermediate.

Synthesis, structure and DFT study of cymantrenyl Fischer carbene complexes of group VI and VII transition metals

NASA Astrophysics Data System (ADS)

Fraser, Roan; van Rooyen, Petrus H.; Landman, Marilé

2016-02-01

Bi- and trimetallic carbene complexes of group VI and VII transition metals (Cr, Mo, W, Mn and Re), with CpMn(CO)3 as the initial synthon, have been synthesised according to the classical Fischer methodology. Crystal structures of the novel carbene complexes with general formula [Mx(CO)y-1{C(OEt)(MnCp(CO)3)}], where x = 1 then y = 3 or 6; x = 2 then y = 10, of the complexes are reported. A density functional theory (DFT) study was undertaken to determine natural bonding orbitals (NBOs) and conformational as well as isomeric aspects of the polymetallic complexes. Application of the second-order perturbation theory (SOPT) of the natural bond orbital (NBO) method revealed stabilizing interactions between the methylene C-H bonds and the carbonyl ligands of the carbene metal moiety. These stabilization interactions show a linear decrease for the group VI metal carbene complexes down the group.

A HeI photoelectron spectrum of the [Al(CH 3) 3] 2 dimer

NASA Astrophysics Data System (ADS)

Wang, Dianxun; Qian, Ximei; Zheng, Shijun; Shi, Yizhong

1997-10-01

The HeI photoelectron spectrum (PES) of the [Al(CH 3) 3] 2 dimer is recorded for the first time. To assign the PES bands, an ab initio SCF MO calculation for the dimer has also been performed. The four splitting peaks of the first PE band are respectively designated to electron ionization of the four frontier 8b u, 13a g, 7b g, and 7b u orbitals of the dimer. They originate from the recombination of the two HOMO (5e') of the two monomers in the forming of the dimer. That is to say, during the formation of the dimer from the two monomers, the reduction of molecular symmetry (from the C 3h symmetry of the monomer to the C 2h symmetry of the dimer) leads to the undegeneration of the degenerate orbitals.

Enhanced magnetic anisotropies of single transition-metal adatoms on a defective MoS2 monolayer.

PubMed

Cong, W T; Tang, Z; Zhao, X G; Chu, J H

2015-03-23

Single magnetic atoms absorbed on an atomically thin layer represent the ultimate limit of bit miniaturization for data storage. To approach the limit, a critical step is to find an appropriate material system with high chemical stability and large magnetic anisotropic energy. Here, on the basis of first-principles calculations and the spin-orbit coupling theory, it is elucidated that the transition-metal Mn and Fe atoms absorbed on disulfur vacancies of MoS2 monolayers are very promising candidates. It is analysed that these absorption systems are of not only high chemical stabilities but also much enhanced magnetic anisotropies and particularly the easy magnetization axis is changed from the in-plane one for Mn to the out-of-plane one for Fe by a symmetry-lowering Jahn-Teller distortion. The results point out a promising direction to achieve the ultimate goal of single adatomic magnets with utilizing the defective atomically thin layers.

Electronic transport in disordered MoS2 nanoribbons

NASA Astrophysics Data System (ADS)

Ridolfi, Emilia; Lima, Leandro R. F.; Mucciolo, Eduardo R.; Lewenkopf, Caio H.

2017-01-01

We study the electronic structure and transport properties of zigzag and armchair monolayer molybdenum disulfide nanoribbons using an 11-band tight-binding model that accurately reproduces the material's bulk band structure near the band gap. We study the electronic properties of pristine zigzag and armchair nanoribbons, paying particular attention to the edges states that appear within the MoS2 bulk gap. By analyzing both their orbital composition and their local density of states, we find that in zigzag-terminated nanoribbons these states can be localized at a single edge for certain energies independent of the nanoribbon width. We also study the effects of disorder in these systems using the recursive Green's function technique. We show that for the zigzag nanoribbons, the conductance due to the edge states is strongly suppressed by short-range disorder such as vacancies. In contrast, the local density of states still shows edge localization. We also show that long-range disorder has a small effect on the transport properties of nanoribbons within the bulk gap energy window.

Molecular Design of High Performance Molecular Devices Based on Direct Ab-initio Molecular Dynamics Method: Diffusion of Lithium Ion on Fluorinated Amorphous Carbon

NASA Astrophysics Data System (ADS)

Kawabata, Hiroshi; Iyama, Tetsuji; Tachikawa, Hiroto

2008-01-01

Hybrid density functional theory (DFT) calculations have been carried out for the lithium adsorbed on a fluorinated graphene surface (F-graphene, C96F24) to elucidate the effect of fluorination of amorphous carbon on the diffusion mechanism of lithium ion. Also, direct molecular orbital-molecular dynamics (MO-MD) calculation [H. Tachikawa and A. Shimizu: J. Phys. Chem. B 109 (2005) 13255] was applied to diffusion processes of the Li+ ion on F-graphene. The B3LYP/LANL2MB calculation showed that the Li+ ion is most stabilized around central position of F-graphene, and the energy was gradually instabilized for the edge region. The direct MO-MD calculations showed that the Li+ ion diffuses on the bulk surface region of F-graphite at 300 K. The nature of the interaction between Li+ and F-graphene was discussed on the basis of theoretical results.

Earth Observations taken by the Expedition 27 Crew

NASA Image and Video Library

2011-05-12

ISS027-E-027026 (12 May 2011) --- An Expedition 27 crew member recorded this image aboard the International Space Station as the orbital outpost was passing over the Mississippi River flood waters from 220 miles above. North is toward the bottom of the image, which was captured using a 400-mm lens. This highly impacted area, centered near 36.6 degrees north latitude and 89.5 degrees west longitude, is just east of New Madrid, Mo. (visible in upper right). Levees appear to be intact here, but there is extensive lowland crop flooding.

A 20k Payload Launch Vehicle Fast Track Development Concept Using an RD-180 Engine and a Centaur Upper Stage

NASA Technical Reports Server (NTRS)

Toelle, Ronald (Compiler)

1995-01-01

A launch vehicle concept to deliver 20,000 lb of payload to a 100-nmi orbit has been defined. A new liquid oxygen/kerosene booster powered by an RD-180 engine was designed while using a slightly modified Centaur upper stage. The design, development, and test program met the imposed 40-mo schedule by elimination of major structural testing by increased factors of safety and concurrent engineering concepts. A growth path to attain 65,000 lb of payload is developed.

Exploring the molecular mechanisms of Traditional Chinese Medicine components using gene expression signatures and connectivity map.

PubMed

Yoo, Minjae; Shin, Jimin; Kim, Hyunmin; Kim, Jihye; Kang, Jaewoo; Tan, Aik Choon

2018-04-04

Traditional Chinese Medicine (TCM) has been practiced over thousands of years in China and other Asian countries for treating various symptoms and diseases. However, the underlying molecular mechanisms of TCM are poorly understood, partly due to the "multi-component, multi-target" nature of TCM. To uncover the molecular mechanisms of TCM, we perform comprehensive gene expression analysis using connectivity map. We interrogated gene expression signatures obtained 102 TCM components using the next generation Connectivity Map (CMap) resource. We performed systematic data mining and analysis on the mechanism of action (MoA) of these TCM components based on the CMap results. We clustered the 102 TCM components into four groups based on their MoAs using next generation CMap resource. We performed gene set enrichment analysis on these components to provide additional supports for explaining these molecular mechanisms. We also provided literature evidence to validate the MoAs identified through this bioinformatics analysis. Finally, we developed the Traditional Chinese Medicine Drug Repurposing Hub (TCM Hub) - a connectivity map resource to facilitate the elucidation of TCM MoA for drug repurposing research. TCMHub is freely available in http://tanlab.ucdenver.edu/TCMHub. Molecular mechanisms of TCM could be uncovered by using gene expression signatures and connectivity map. Through this analysis, we identified many of the TCM components possess diverse MoAs, this may explain the applications of TCM in treating various symptoms and diseases. Copyright © 2018 The Authors. Published by Elsevier B.V. All rights reserved.

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 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. Electronic supplementary information (ESI) available: Detailed computational method; structural data of T'' MoS2; DOS of the T'' MoS2 phase under different strains; orbital energy of T'' MoS2 under different strains; electronic structures for all other five MX2 in the T'' phase; edge states of T'' MoS2. See DOI: 10.1039/c5nr07715j

Validation of a novel Montreal Cognitive Assessment scoring algorithm in non-demented Parkinson's disease patients.

PubMed

Sulzer, Patricia; Becker, Sara; Maetzler, Walter; Kalbe, Elke; van Nueten, Luc; Timmers, Maarten; Machetanz, Gerrit; Streffer, Johannes; Salvadore, Giacomo; Scholz, Erich; Tkaczynska, Zuzanna; Brockmann, Kathrin; Berg, Daniela; Liepelt-Scarfone, Inga

2018-06-23

The early diagnosis of mild cognitive impairment (PD-MCI) in Parkinson's disease (PD) is essential as it increases the future risk for PD dementia (PDD). Recently, a novel weighting algorithm for the Montreal Cognitive Assessment (MoCA) subtests has been reported, to best discriminate between those with and without cognitive impairment in PD. The aim of our study was to validate this scoring algorithm in a large sample of non-demented PD patients, hypothesizing that the weighted MoCA would have a higher diagnostic accuracy for PD-MCI than the original MoCA. In 202 non-demented PD patients, we evaluated cognitive status, clinical and demographic data, as well as the MoCA with a weighted and unweighted score. Receiver operating characteristic (ROC) curve analysis was used to evaluate discriminative ability of the MoCA. Group comparisons and ROC analysis were performed for PD-MCI classifications with a cut-off ≤ 1, 1.5, and 2 standard deviation (SD) below appropriate norms. PD-MCI patients scored lower on the weighted than the original MoCA version (p < 0.001) compared to PD patients with normal cognitive function. Areas under the curve only differed significantly for the 2 SD cut-off, leading to an increased sensitivity of the weighted MoCA score (72.9% vs. 70.5%) and specificity compared to the original version (79.0% vs. 65.4%). Our results indicate better discriminant power for the weighted MoCA compared to the original for more advanced stages of PD-MCI (2 SD cut-off). Future studies are needed to evaluate the predictive value of the weighted MoCA for PDD.

Preparation of MoO2/g-C3N4 composites with a high surface area and its application in deep desulfurization from model oil

NASA Astrophysics Data System (ADS)

Hou, Liang-pei; Zhao, Rong-xiang; Li, Xiu-ping; Gao, Xiao-han

2018-03-01

A series of catalysts of composition X-MoO2/g-C3N4 (X = 0, 0.5, 1, 3, 5 wt.%) were successfully synthesized by calcination of a mixture of (NH4)6Mo7O24·4H2O and g-C3N4. Oxidative desulfurization experiments were conducted using X-MoO2/g-C3N4 as a catalyst, H2O2 as an oxidant, and ionic liquids (ILs) as extraction agents. Catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared (FT-IR), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), and Brunauer-Emmett-Teller analysis (BET). Characterization results suggested that MoO2 was present in the catalyst and its crystallinity improved with increased Mo-loading. The catalysts had a larger specific surface area due to the presence of MoO2 dispersed on g-C3N4. Experimental results showed that 3%-MoO2/g-C3N4 had the highest catalytic activity among all the catalysts tested. A desulfurization rate of 96.0% was achieved under optimal conditions. Through gas chromatography-mass spectrometry (GC-MS) analysis, it was shown that dibenzothoiphene sulfone was the sole product of the oxidation desulfurization reaction. An apparent activation energy of 61.1 kJ/mol was estimated based on Arrhenius equation. The activity of 3%-MoO2/g-C3N4 slightly decreased after six runs. A possible mechanism for the reaction has been proposed.

Effect of Temperature on the Desorption of Lithium from Molybdenum(110) Surfaces: Implications for Fusion Reactor First Wall Materials

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

Chen, Mohan; Roszell, John; Scoullos, Emanuel V.

2016-03-30

Determining the strength of Li binding to Mo is critical to assessing the survivability of Li as a potential first wall material in fusion reactors. Here, we present the results of a joint experimental and theoretical investigation into how Li desorbs from Mo(110) surfaces, based on what can be deduced from temperature-programmed desorption measurements and density functional theory (DFT). Li desorption peaks measured at temperatures ranging from 711 K (1 monolayer, ML) to 1030 K (0.04 ML), with corresponding desorption onsets from 489 to 878 K, follow a trend similar to predicted Gibbs free energies for Li adsorption. Bader chargemore » analysis of DFT densities reveals that repulsive forces between neighboring positively charged Li atoms increase with coverage and thus reduce the bond strength between Mo and Li, thereby lowering the desorption temperature as the coverage increases. In addition, DFT predicts that Li desorbs at higher temperatures from a surface with vacancies than from a perfect surface, offering an explanation for the anomalously high desorption temperatures for the last Li to desorb from Mo(110). Analysis of simulated local densities of states indicates that the stronger binding to the defective surface is correlated with enhanced interaction between Li and Mo, involving the Li 2s electrons and not only the Mo 4d electrons as in the case of the pristine surface, but also the Mo 5s electrons in the case with surface vacancies. We suggest that steps and kinks present on the Mo(110) surface behave similarly and contribute to the high desorption temperatures. These findings imply that roughened Mo surfaces may strengthen Li film adhesion at higher temperatures.« less

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

Devaraj, Arun; Jana, Saumyadeep; McInnis, Colleen A.

During eutectoid transformation of U-10Mo alloy, uniform metastable γ UMo phase is expected to transform to a mixture of α-U and γ’-U 2Mo phase. The presence of transformation products in final U-10Mo fuel, especially the α phase is considered detrimental for fuel irradiation performance, so it is critical to accurately evaluate the extent of transformation in the final U-10Mo alloy. This phase transformation can cause a volume change that induces a density change in final alloy. To understand this density and volume change, we developed a theoretical model to calculate the volume expansion and resultant density change of U-10Mo alloymore » as a function of the extent of eutectoid transformation. Based on the theoretically calculated density change for 0 to 100% transformation, we conclude that an experimental density measurement system will be challenging to employ to reliably detect and quantify the extent of transformation. Subsequently, to assess the ability of various methods to detect the transformation in U-10Mo, we annealed U-10Mo alloy samples at 500°C for various times to achieve in low, medium, and high extent of transformation. After the heat treatment at 500°C, the samples were metallographically polished and subjected to optical microscopy and x-ray diffraction (XRD) methods. Based on our assessment, optical microscopy and image processing can be used to determine the transformed area fraction, which can then be correlated with the α phase volume fraction measured by XRD analysis. XRD analysis of U-10Mo aged at 500°C detected only α phase and no γ’ was detected. To further validate the XRD results, atom probe tomography (APT) was used to understand the composition of transformed regions in U-10Mo alloys aged at 500°C for 10 hours. Based on the APT results, the lamellar transformation product was found to comprise α phase with close to 0 at% Mo and γ phase with 28–32 at% Mo, and the Mo concentration was highest at the α/γ interface.« less

Extraordinary selectivity of CoMo{sub 3}S{sub 13} chalcogel for C{sub 2}H{sub 6} and CO{sub 2} adsorption.

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

Shafaei-Fallah, M.; Rothenberger, Z.; Katsoulidis, A. P.

The chalcogel CoMo{sub 3}S{sub 13} is obtained from the reaction of (NH{sub 4}){sub 2}[Mo{sub 3}S{sub 13}] with cobalt acetate in solution. The chalcogel has a BET surface area of 570 m{sup 2} g{sup -1}, and pair distribution function analysis (PDF) and infrared spectroscopy indicate that the [Mo{sub 3}S{sub 13}]{sup 2-} cluster is a building block in the porous network. The CoMo{sub 3}S{sub 13} chalcogel exhibits high selectivity for separating ethane and carbon dioxide from hydrogen and methane.

Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH 3 Complex

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

Bhattacharya, Papri; Heiden, Zachariah M.; Wiedner, Eric S.

We report ammonia oxidation by homolytic cleavage of all three H atoms from a Mo-15NH3 complex using the 2,4,6-tri-tert-butylphenoxyl radical to afford a Mo-alkylimido (Mo=15NR) complex (R = 2,4,6-tri-t-butylcyclohexa-2,5-dien-1-one). Reductive cleavage of Mo=15NR generates a terminal Mo≡N nitride, and a [Mo-15NH]+ complex is formed by protonation. Computational analysis describes the energetic profile for the stepwise removal of three H atoms from the Mo-15NH3 complex and the formation of Mo=15NR. Acknowledgment. This work was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Re-search Center funded by the U.S. Department of Energy (U.S. DOE), Office of Science, Officemore » of Basic Energy Sciences. EPR and mass spectrometry experiments were performed using EMSL, a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at PNNL. The authors thank Dr. Eric D. Walter and Dr. Rosalie Chu for assistance in performing EPR and mass spectroscopy analysis, respectively. Computational resources provided by the National Energy Re-search Scientific Computing Center (NERSC) at Lawrence Berkeley National Laboratory. Pacific North-west National Laboratory is operated by Battelle for the U.S. DOE.« less

Complex-valued time-series correlation increases sensitivity in FMRI analysis.

PubMed

Kociuba, Mary C; Rowe, Daniel B

2016-07-01

To develop a linear matrix representation of correlation between complex-valued (CV) time-series in the temporal Fourier frequency domain, and demonstrate its increased sensitivity over correlation between magnitude-only (MO) time-series in functional MRI (fMRI) analysis. The standard in fMRI is to discard the phase before the statistical analysis of the data, despite evidence of task related change in the phase time-series. With a real-valued isomorphism representation of Fourier reconstruction, correlation is computed in the temporal frequency domain with CV time-series data, rather than with the standard of MO data. A MATLAB simulation compares the Fisher-z transform of MO and CV correlations for varying degrees of task related magnitude and phase amplitude change in the time-series. The increased sensitivity of the complex-valued Fourier representation of correlation is also demonstrated with experimental human data. Since the correlation description in the temporal frequency domain is represented as a summation of second order temporal frequencies, the correlation is easily divided into experimentally relevant frequency bands for each voxel's temporal frequency spectrum. The MO and CV correlations for the experimental human data are analyzed for four voxels of interest (VOIs) to show the framework with high and low contrast-to-noise ratios in the motor cortex and the supplementary motor cortex. The simulation demonstrates the increased strength of CV correlations over MO correlations for low magnitude contrast-to-noise time-series. In the experimental human data, the MO correlation maps are noisier than the CV maps, and it is more difficult to distinguish the motor cortex in the MO correlation maps after spatial processing. Including both magnitude and phase in the spatial correlation computations more accurately defines the correlated left and right motor cortices. Sensitivity in correlation analysis is important to preserve the signal of interest in fMRI data sets with high noise variance, and avoid excessive processing induced correlation. Copyright © 2016 Elsevier Inc. All rights reserved.

Photocatalytic wastewater purification with simultaneous hydrogen production using MoS2 QD-decorated hierarchical assembly of ZnIn2S4 on reduced graphene oxide photocatalyst.

PubMed

Zhang, Shuqu; Wang, Longlu; Liu, Chengbin; Luo, Jinming; Crittenden, John; Liu, Xia; Cai, Tao; Yuan, Jili; Pei, Yong; Liu, Yutang

2017-09-15

It is attractive to photocatalytically purify wastewater and simultaneously convert solar energy into clean hydrogen energy. However, it is still a challenge owing to the relatively low photocatalytic efficiency of photocatalysts. In this study, we synthesized a molybdenum disulfide (MoS 2 ) quantum dot-decorated 3D nanoarchitecture (MoS 2 QDs) of indium zinc sulfide (ZnIn 2 S 4 ) and reduced grapheme oxide (MoS 2 QDs@ZnIn 2 S 4 @RGO) photocatalyst using a simple solvothermal method. The RGO promotes the electron transfer, and the highly dispersed MoS 2 QDs provides numerous catalytic sites. The photocatalytic purification of rhodamine B (RhB), eosin Y (EY), fulvic acid (FA), methylene blue (MB) and p-nitrophenol (PNP) in simulated wastewaters were further tested. The degradation efficiencies and TOC removal were 91% and 75% for PNP, 92.2% and 72% for FA, 98.5% and 80% for MB, 98.6% and 84% for EY, and 98.8% and 88% for RhB, respectively (C organics  = 20 mg/L, C catalyst  = 1.25 g/L, t = 12 h, I light  = 3.36 × 10 -5  E L -1  s -1 ). Among these tests, the highest hydrogen production was achieved (45 μmol) during RhB degradation. Both experimental and calculational results prove that lower LUMO (lowest unoccupied molecular orbit) level of organic molecules was available for transferring electrons to catalysts, resulting in more efficient hydrogen production. Significantly, the removal efficiencies of natural organic substances in actual river water reached 76.3-98.4%, and COD reduced from 32 to 16 mg/L with 13.8 μmol H 2 production after 12 h. Copyright © 2017 Elsevier Ltd. All rights reserved.

Continuous infusion of low-dose unfractionated heparin after aneurysmal subarachnoid hemorrhage: a preliminary study of cognitive outcomes.

PubMed

James, Robert F; Khattar, Nicolas K; Aljuboori, Zaid S; Page, Paul S; Shao, Elaine Y; Carter, Lacey M; Meyer, Kimberly S; Daniels, Michael W; Craycroft, John; Gaughen, John R; Chaudry, M Imran; Rai, Shesh N; Everhart, D Erik; Simard, J Marc

2018-05-11

OBJECTIVE Cognitive dysfunction occurs in up to 70% of aneurysmal subarachnoid hemorrhage (aSAH) survivors. Low-dose intravenous heparin (LDIVH) infusion using the Maryland protocol was recently shown to reduce clinical vasospasm and vasospasm-related infarction. In this study, the Montreal Cognitive Assessment (MoCA) was used to evaluate cognitive changes in aSAH patients treated with the Maryland LDIVH protocol compared with controls. METHODS A retrospective analysis of all patients treated for aSAH between July 2009 and April 2014 was conducted. Beginning in 2012, aSAH patients were treated with LDIVH in the postprocedural period. The MoCA was administered to all aSAH survivors prospectively during routine follow-up visits, at least 3 months after aSAH, by trained staff blinded to treatment status. Mean MoCA scores were compared between groups, and regression analyses were performed for relevant factors. RESULTS No significant differences in baseline characteristics were observed between groups. The mean MoCA score for the LDIVH group (n = 25) was 26.4 compared with 22.7 in controls (n = 22) (p = 0.013). Serious cognitive impairment (MoCA ≤ 20) was observed in 32% of controls compared with 0% in the LDIVH group (p = 0.008). Linear regression analysis demonstrated that only LDIVH was associated with a positive influence on MoCA scores (β = 3.68, p =0.019), whereas anterior communicating artery aneurysms and fevers were negatively associated with MoCA scores. Multivariable linear regression analysis resulted in all 3 factors maintaining significance. There were no treatment complications. CONCLUSIONS This preliminary study suggests that the Maryland LDIVH protocol may improve cognitive outcomes in aSAH patients. A randomized controlled trial is needed to determine the safety and potential benefit of unfractionated heparin in aSAH patients.

Screening an elderly hearing impaired population for mild cognitive impairment using Mini-Mental State Examination (MMSE) and Montreal Cognitive Assessment (MoCA).

PubMed

Lim, Magdalene Yeok Leng; Loo, Jenny Hooi Yin

2018-07-01

To determine if there is an association between hearing loss and poorer cognitive scores on Mini-Mental State Examination (MMSE) and Montreal Cognitive Assessment (MoCA) and to determine if poor hearing acuity affects scoring on the cognitive screening tests of MMSE and MoCA. One hundred fourteen elderly patients (Singapore residents) aged between 55 and 86 years were sampled. Participants completed a brief history questionnaire, pure tone audiometry, and 2 cognitive screening tests-the MMSE and MoCA. Average hearing thresholds of the better ear in the frequencies of 0.5, 1, 2, and 4 kHz were used for data analysis. Hearing loss was significantly associated with poorer cognitive scores in Poisson regression models adjusted for age. Mini-Mental State Examination scores were shown to decrease by 2.8% (P = .029), and MoCA scores by 3.5% (P = .013) for every 10 dB of hearing loss. Analysis of hearing-sensitive components of "Registration" and "Recall" in MMSE and MoCA using chi-square tests showed significantly poorer performance in the hearing loss group as compared to the normal hearing group. Phonetic analysis of target words with high error rates shows that the poor performance was likely contributed by decreased hearing acuity, on top of a possible true deficit in cognition in the hearing impaired. Hearing loss is associated with poorer cognitive scores on MMSE and MoCA, and cognitive scoring is likely confounded by poor hearing ability. This highlights an important, often overlooked aspect of sensory impairment during cognitive screening. Provisions should be made when testing for cognition in the hearing-impaired population to avoid over-referral and subsequent misdiagnoses of cognitive impairment. Copyright © 2018 John Wiley & Sons, Ltd.

Photophysics of a coumarin based Schiff base in solvents of varying polarities

NASA Astrophysics Data System (ADS)

Ghosh, Saptarshi; Roy, Nayan; Singh, T. Sanjoy; Chattopadhyay, Nitin

2018-01-01

The present work reports detailed photophysics of a coumarin based Schiff base, namely, (E)-7-(((8-hydroxyquinolin-2-yl)methylene)amino)-4-methyl-2H-chromen-2-one (HMC) in different solvents of varying polarity exploiting steady state absorption, fluorescence and time resolved fluorescence spectroscopy. The dominant photophysical features of HMC are discussed in terms of emission from an intramolecular charge transfer (ICT) excited state. Molecular orbital (MO) diagrams as obtained from DFT based computational analysis confirms the occurrence of charge transfer from 8‧-hydroxy quinoline moiety of the molecule to the coumarin part. The notable difference in the photophysical response of HMC from its analogous coumarin (C480) lies in a lower magnitude of fluorescence quantum yield of the former, particularly in the solvents of low polarity, which is rationalized by considering the higher rate of non-radiative decay of HMC in apolar solvents. Phosphorescence emission as well as phosphorescence lifetime of HMC has also been reported in 77 K frozen matrix.

Benzothiazole analogues: Synthesis, characterization, MO calculations with PM6 and DFT, in silico studies and in vitro antimalarial as DHFR inhibitors and antimicrobial activities.

PubMed

Thakkar, Sampark S; Thakor, Parth; Ray, Arabinda; Doshi, Hiren; Thakkar, Vasudev R

2017-10-15

Benzothiazole analogues are of interest due to their potential activity against malarial and microbial infections. In search of suitable antimicrobial and antimalarial agents, we report here the synthesis, characterization and biological activities of benzothiazole analogues (J 1-J 10). The molecules were characterized by IR, Mass, 1 H NMR, 13 C NMR and elemental analysis. The in vitro antimicrobial activity was investigated against pathogenic strains; the results were explained with the help of DFT and PM6 molecular orbital calculations. In vitro cytotoxicity and genotoxicity of the molecules were studied against S. pombe cells. In vitro antimalarial activity was studied. The active compounds J 1, J 2, J 3, J 5 and J 6 were further evaluated for enzyme inhibition efficacy against the receptor Pf-DHFR, computational and in vitro studies were carried out to examine their candidatures as lead dihydrofolate reductase inhibitors. Copyright © 2017 Elsevier Ltd. All rights reserved.

Origin of the Surface-Induced First Hyperpolarizability in the C60/SiO2 System: SCC-DFTB Insight.

PubMed

Nénon, Sébastien; Champagne, Benoît

2014-01-02

Using the self-consistent charge density functional tight binding (SCC-DFTB) method, C60 molecules physisorbed on an α-quartz slab are shown to display a first hyperpolarizability, whereas, owing to their symmetry, both the α-quartz slab and C60 molecule have no first hyperpolarizabilities. A larger first hyperpolarizability is achieved when the lowest-lying (five- or six-membered) ring is situated in between two hydroxyl rows, rather than on top, because this situation favors orbital overlaps and charge transfer. Further analysis has demonstrated that (i) the first hyperpolarizability originates from the MO overlap and field-induced charge transfers from the neighboring substrate/adsorbate moieties but not to geometric relaxation of the C60 molecules at the interface and that (ii) larger first hyperpolarizabilities are associated with low surface coverage and with small distances between C60 and the surface. This contribution is a clear illustration of the emergence of second-order nonlinear optical responses (first hyperpolarizability) as a result of breaking the centrosymmetry.

Neutronic and thermal-hydraulic analysis of fission molybdenum-99 production at Tehran Research Reactor using LEU plate targets.

PubMed

Abedi, Ebrahim; Ebrahimkhani, Marzieh; Davari, Amin; Mirvakili, Seyed Mohammad; Tabasi, Mohsen; Maragheh, Mohammad Ghannadi

2016-12-01

Efficient and safe production of molybdenum-99 ( 99 Mo) radiopharmaceutical at Tehran Research Reactor (TRR) via fission of LEU targets is studied. Neutronic calculations are performed to evaluate produced 99 Mo activity, core neutronic safety parameters and also the power deposition values in target plates during a 7 days irradiation interval. Thermal-hydraulic analysis has been also carried out to obtain thermal behavior of these plates. Using Thermal-hydraulic analysis, it can be concluded that the safety parameters are satisfied in the current study. Consequently, the present neutronic and thermal-hydraulic calculations show efficient 99 Mo production is accessible at significant activity values in TRR current core configuration. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cytotoxicity of the coagulant Moringa oleifera lectin (cMoL) to B16-F10 melanoma cells.

PubMed

de Andrade Luz, Luciana; Rossato, Franco Aparecido; Costa, Rute Alves Pereira E; Napoleão, Thiago Henrique; Paiva, Patrícia Maria Guedes; Coelho, Luana Cassandra Breitenbach Barroso

2017-10-01

Moringa oleifera seeds are used in alternative medicine to treat inflammation, tumors and bacterial and protozoan infections, for example. The seeds contain lectins, which are carbohydrate-binding proteins with several biological properties including cytotoxicity to cancer cells. In this work, we examined the cytotoxicity of the coagulant M. oleifera lectin (cMoL) on B16-F10 murine melanoma cells. cMoL cytotoxic effects were evaluated through trypan blue assay and flow cytometry analysis. Mitochondrial superoxide levels and activation of caspases 3, 8 and 9 were measured. cMoL (1.5-16μM) reduced viability and caused cell death of B16-F10 cells with an IC 50 of 9.72μM. Flow cytometry analysis indicated induction of necrosis and suggested the presence of cells in late apoptosis. Specificity for tumor cells was observed since death of normal human fibroblasts (GN) was not higher than 20% in treatments with cMoL from 1.5 to 16μM. Microscopy images revealed rounded shape and reduction of volume in B16-F10 cells treated with cMoL. cMoL increased mitochondrial ROS production and promoted caspases 3, 8 and 9 activation in B16-F10 cells, indicating the activation of apoptosis-related pathway. In conclusion, this study demonstrates that cMoL is cytotoxic to B16-F10 cells, which stimulates more investigation on the anticancer potential of this lectin. Copyright © 2017 Elsevier Ltd. All rights reserved.

A novel route for the synthesis of nanotubes and fullerene-like nanostructures of molybdenum disulfide

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

Panigrahi, Pravas Kumar, E-mail: pravas.iit@gmail.com; Pathak, Amita, E-mail: ami@chem.iitkgp.ernet.in

Graphical abstract: Nanotubes and fullerene-like nanostructures of MoS{sub 2} were synthesized via a microwave-assisted route in solution phase. Highlights: Black-Right-Pointing-Pointer Microwave-assisted route for synthesis of nanotube and fullerene-like nanostructures of MoS{sub 2}. Black-Right-Pointing-Pointer Morphological analysis of the synthesized products. Black-Right-Pointing-Pointer Solvent plays important role in the modification of morphology of MoS{sub 2}. -- Abstract: The paper described the synthesis of nanotubes and fullerene-like nanostructures of MoS{sub 2} through a technically simple, rapid, and energy-efficient microwave-assisted synthesis technique, which involved the use of elemental sulfur dissolved in a mixture of monoethanolamine and hydrazine hydrate as the sulfide source. The microwave inducedmore » reaction between the molybdate with sulfide ions, in the presence of hydrazine hydrate in the reaction medium, resulted in the formation of gray colored powders of amorphous MoS{sub 2}. The as-obtained powders were calcined at 600 Degree-Sign C for 2 h and characterized by different techniques. HRTEM analysis of the calcined samples indicated the formation of fullerene-like MoS{sub 2} structures when the starting solution mixture was irradiated with microwave for a period of 200 s, while on 600 s of irradiation of the same revealed the formation of folded sheets like MoS{sub 2} nanotubes. BET surface areas of the calcined samples have been measured and a plausible reaction mechanism for the formation of nanotubes and fullerene-like nanostructures of MoS{sub 2} has been proposed.« less

Enabling Colloidal Synthesis of Edge-Oriented MoS2 with Expanded Interlayer Spacing for Enhanced HER Catalysis.

PubMed

Sun, Yugang; Alimohammadi, Farbod; Zhang, Dongtang; Guo, Guangsheng

2017-03-08

By selectively promoting heterogeneous nucleation/growth of MoS 2 on graphene monolayer sheets, edge-oriented (EO) MoS 2 nanosheets with expanded interlayer spacing (∼9.4 Å) supported on reduced graphene oxide (rGO) sheets were successfully synthesized through colloidal chemistry, showing the promise in low-cost and large-scale production. The number and edge length of MoS 2 nanosheets per area of graphene sheets were tuned by controlling the reaction time in the microwave-assisted solvothermal reduction of ammonium tetrathiomolybdate [(NH 4 ) 2 MoS 4 ] in dimethylformamide. The edge-oriented and interlayer-expanded (EO&IE) MoS 2 /rGO exhibited significantly improved catalytic activity toward hydrogen evolution reaction (HER) in terms of larger current density, lower Tafel slope, and lower charge transfer resistance compared to the corresponding interlayer-expanded MoS 2 sheets without edge-oriented geometry, highlighting the importance of synergistic effect between edge-oriented geometry and interlayer expansion on determining HER activity of MoS 2 nanosheets. Quantitative analysis clearly shows the linear dependence of current density on the edge length of MoS 2 nanosheets.

Metal complexes of fluorophosphines. 13. Reaction of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with (methylamino)bis(difluorophosphine). X-ray crystal structure analysis of a novel binuclear molybdenum fluorophosphine carbonyl complex with a bridging chlorine atom: (CO)/sub 2/Mo(/sup +/-CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/(. mu. -PF/sub 2/)(. mu. -Cl)Mo(CO)(PF/sub 2/NHCH/sub 3/)

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

King, R.B.; Shimura, M.; Brown, G.M.

1984-01-01

Reaction of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with CH/sub 3/N(PF/sub 2/)/sub 2/ in acetonitrile solution at room temperature gives white, volatile, crystalline fac-(CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/Mo(CO)/sub 3/, containing one monodentate and one bidentate CH/sub 3/N(PF/sub 2/)/sub 2/ ligand. The same reactants in boiling acetonitrile give yellow (CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 4/Mo/sub 2/(CO)/sub 3/ in considerably better yield than the previously reported preparation of this binuclear complex from the cycloheptatriene complex C/sub 7/H/sub 8/Mo(CO)/sub 3/ and CH/sub 3/N(PF/sub 2/)/sub 2/ in boiling methylcyclohexane. Reaction in acetonitrile solution of fac-(CH/sub 3/CN)/sub 3/Mo(CO)/sub 3/ with CH/sub 3/N(PF/sub 2/)/sub 2/ containing about 0.2% HClmore » gives brown-red, volatile (CO)/sub 2/Mo(/sup +/-CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 2/(..mu..-PF/sub 2/)(..mu..-Cl)-Mo(CO)(PF/sub 2/NHCH/sub 3/), whose composition and structure were established by single-crystal X-ray structure analysis. This novel quadruply bridged binuclear complex is obtained in considerably better yield from the reaction of (CH/sub 3/N(PF/sub 2/)/sub 2/)/sub 3/Mo/sub 2/(CO)/sub 5/ with ((C/sub 2/H/sub 5/)/sub 3/NH)Cl in acetonitirle solution. The complex has a Mo-Mo bond 2.975 A in length. Crystal data: monoclinic, space group P2/sub 1//c, a = 17.546 (4) A, b = 9.725 (2) A, c = 14.558 (3), ..beta.. = 107.20 (2)/sup 0/, Z = 4. 30 references, 2 figures, 3 tables.« less

Revealing the microscopic CVD growth mechanism of MoSe2 and the role of hydrogen gas during the growth procedure.

PubMed

Wang, Hulian; Zhu, Dancheng; Jiang, Feng; Zhao, Pei; Wang, Hongtao; Zhang, Ze; Chen, Xin; Jin, Chuanhong

2018-08-03

Understanding the microscopic mechanisms for the nucleation and growth of two-dimensional molybdenum diselenide (2D MoSe 2 ) via chemical vapor deposition (CVD) is crucial towards the precisely controlled growth of the 2D material. In this work, we employed a joint use of transmission electron microscopy and CVD, in which the 2D MoSe 2 were directly grown on a graphene membrane based on grids, that enables the microstructural characterization of as-grown MoSe 2 flakes. We further explore the role of hydrogen gas and find: in an argon ambient, the primary products are few-layer MoSe 2 flakes, along with MoO x nanoparticles; while with the introduction of H 2 , single-layer MoSe 2 became the dominant product during the CVD growth. Quantitative analysis of the effects of H 2 flow rate on the flake sizes, and areal coverage was also given. Nevertheless, we further illuminated the evolution of shape morphology and edge structures of single-layer MoSe 2 , and proposed the associated growth routes during a typical CVD process.

Desulfurization of 4-methyl dibenzothiophene using titanium supported Keggin type polyoxometalate

NASA Astrophysics Data System (ADS)

Lesbani, Aldes; Anggraini, Ana; Mohadi, Risfidian; Rohendi, Dedi; Said, Muhammad

2017-03-01

Titanium supported Keggin type polyoxometalate H5PV2Mo10O40.nH2O has been prepared using tetra isopropyl orthotitanate by sol-gel method and microemulsion to form H5PV2Mo10O40/TiO2. Compound H5PV2Mo10O40.nH2O/TiO2 was characterized using FTTR spectroscopy, X-Ray analysis, and acidity measurement. FTTR spectrum showed that all vibration of titanium and polyoxometalate were appeared in H5PV2Mo10O40.nH2O/TiO2 with decreasing crystallinity. The acidity of H5PV2Mo10O40.nH2O/TiO2 was higher than H5PV2Mo10O40.nH2O. Desulfurization of 4-methyl dibenzothiophene (4-MDBT) using H5PV2Mo10O40.nH2O/TiO2 as catalyst resulted conversion of 4-MDBT was 99% and higher than desulfurization using H5PV2Mo10O40.nH2O under mild conditions.

Recombinant protein expression of Moringa oleifera lectin in methylotrophic yeast as active coagulant for sustainable high turbid water treatment.

PubMed

Abd Wahid, Muhamad Azhar; Megat Mohd Noor, Megat Johari; Goto, Masafumi; Sugiura, Norio; Othman, Nor'azizi; Zakaria, Zuriati; Ahmad Mohammed, Thamer; Jusoh, Ahmad; Hara, Hirofumi

2017-08-01

The natural coagulant Moringa oleifera lectin (MoL) as cationic protein is a promising candidate in coagulation process of water treatment plant. Introducing the gene encoding MoL into a host, Pichia pastoris, to secrete soluble recombinant protein is assessed in this study. Initial screening using PCR confirmed the insertion of MoL gene, and SDS-PAGE analysis detected the MoL protein at 8 kDa. Cultured optimization showed the highest MoL protein at 520 mg/L was observed at 28 °C for 144 h of culturing by induction in 1% methanol. Approximately, 0.40 mg/mL of recombinant MoL protein showed 95 ± 2% turbidity removal of 1% kaolin suspension. In 0.1% kaolin suspension, the concentration of MoL at 10 μg/mL exhibits the highest turbidity reduction at 68 ± 1%. Thus, recombinant MoL protein from P. pastoris is an effective coagulant for water treatment.

Design of an X -band electron linear accelerator dedicated to decentralized 99Mo/99mTc supply: From beam energy selection to yield estimation

NASA Astrophysics Data System (ADS)

Jang, Jaewoong; Yamamoto, Masashi; Uesaka, Mitsuru

2017-10-01

The most frequently used radionuclide in diagnostic nuclear medicine, 99mTc, is generally obtained by the decay of its parent radionuclide, 99Mo. Recently, concerns have been raised over shortages of 99Mo/99mTc, owing to aging of the research reactors which have been supplying practically all of the global demand for 99Mo in a centralized fashion. In an effort to prevent such 99Mo/99mTc supply disruption and, furthermore, to ameliorate the underlying instability of the centralized 99Mo/99mTc supply chain, we designed an X -band electron linear accelerator which can be distributed over multiple regions, whereby 99Mo/99mTc can be supplied with improved accessibility. The electron beam energy was designed to be 35 MeV, at which an average beam power of 9.1 kW was calculated by the following beam dynamics analysis. Subsequent radioactivity modeling suggests that 11 of the designed electron linear accelerators can realize self-sufficiency of 99Mo/99mTc in Japan.

MoS2 @HKUST-1 Flower-Like Nanohybrids for Efficient Hydrogen Evolution Reactions.

PubMed

Wang, Chengli; Su, Yingchun; Zhao, Xiaole; Tong, Shanshan; Han, Xiaojun

2018-01-24

A novel MoS 2 -based flower-like nanohybrid for hydrogen evolution was fabricated through coating the Cu-containing metal-organic framework (HKUST-1) onto MoS 2 nanosheets. It is the first time that MoS 2 @HKUST-1 nanohybrids have been reported for the enhanced electrochemical performance of HER. The morphologies and components of the MoS 2 @HKUST-1 flower-like nanohybrids were characterized by scanning electron microscopy, X-ray diffraction analysis and Fourier transform infrared spectroscopy. Compared with pure MoS 2 , the MoS 2 @HKUST-1 hybrids exhibit enhanced performance on hydrogen evolution reaction with an onset potential of -99 mV, a smaller Tafel slope of 69 mV dec -1 , and a Faradaic efficiency of nearly 100 %. The MoS 2 @HKUST-1 flower-like nanohybrids exhibit excellent stability in acidic media. This design opens new possibilities to effectively synthesize non-noble metal catalysts with high performance for the hydrogen evolution reaction (HER). © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation on nonlinear optical properties of MoS2 nanoflake, grown on silicon and quartz substrates

NASA Astrophysics Data System (ADS)

Bayesteh, S.; Mortazavi, S. Z.; Reyhani, A.

2018-03-01

In this study, MoS2 was directly synthesized by one-step thermal chemical vapour deposition (TCVD), on different substrates including Si/SiO2 and quartz, using MoO3 and sulfide powders as precursor. The XRD patterns demonstrate the high crystallinity of MoS2 on Si/SiO2 and quartz substrates. SEM confirmed the formation of MoS2 grown on both substrates. According to line width and frequency difference between the E1 2g and A1g in Raman spectroscopy, it is inferred that the MoS2 grown on Si/SiO2 substrate is monolayer and the MoS2 grown on quartz substrate is multilayer. Moreover, by assessment of MoS2 nanoflake band gap via UV-visible analysis, it verified the formation of few layer structures. In addition, the open-aperture and close-aperture Z-scan techniques were employed to study the nonlinear optical properties including nonlinear absorption and nonlinear refraction of the synthesized MoS2. All experiments were performed using a diode laser with a wavelength of 532 nm as light source. The monolayer MoS2 synthesized on Si/SiO2, display considerable two-photon absorption. However, the multilayer MoS2 synthesized on quartz displayed saturable absorption (SA). It is noticeable that both samples demonstrate obvious self-defocusing behaviour.

A Bayesian network model for predicting aquatic toxicity mode ...

EPA Pesticide Factsheets

The mode of toxic action (MoA) has been recognized as a key determinant of chemical toxicity, but development of predictive MoA classification models in aquatic toxicology has been limited. We developed a Bayesian network model to classify aquatic toxicity MoA using a recently published dataset containing over one thousand chemicals with MoA assignments for aquatic animal toxicity. Two dimensional theoretical chemical descriptors were generated for each chemical using the Toxicity Estimation Software Tool. The model was developed through augmented Markov blanket discovery from the dataset of 1098 chemicals with the MoA broad classifications as a target node. From cross validation, the overall precision for the model was 80.2%. The best precision was for the AChEI MoA (93.5%) where 257 chemicals out of 275 were correctly classified. Model precision was poorest for the reactivity MoA (48.5%) where 48 out of 99 reactive chemicals were correctly classified. Narcosis represented the largest class within the MoA dataset and had a precision and reliability of 80.0%, reflecting the global precision across all of the MoAs. False negatives for narcosis most often fell into electron transport inhibition, neurotoxicity or reactivity MoAs. False negatives for all other MoAs were most often narcosis. A probabilistic sensitivity analysis was undertaken for each MoA to examine the sensitivity to individual and multiple descriptor findings. The results show that the Markov blank

Rejection of randomly coinciding events in ZnMoO scintillating bolometers

NASA Astrophysics Data System (ADS)

Chernyak, D. M.; Danevich, F. A.; Giuliani, A.; Mancuso, M.; Nones, C.; Olivieri, E.; Tenconi, M.; Tretyak, V. I.

2014-06-01

Random coincidence of events (particularly from two neutrino double beta decay) could be one of the main sources of background in the search for neutrinoless double beta decay with cryogenic bolometers due to their poor time resolution. Pulse-shape discrimination by using front edge analysis, mean-time and methods were applied to discriminate randomly coinciding events in ZnMoO cryogenic scintillating bolometers. These events can be effectively rejected at the level of 99 % by the analysis of the heat signals with rise-time of about 14 ms and signal-to-noise ratio of 900, and at the level of 92 % by the analysis of the light signals with rise-time of about 3 ms and signal-to-noise ratio of 30, under the requirement to detect 95 % of single events. These rejection efficiencies are compatible with extremely low background levels in the region of interest of neutrinoless double beta decay of Mo for enriched ZnMoO detectors, of the order of counts/(y keV kg). Pulse-shape parameters have been chosen on the basis of the performance of a real massive ZnMoO scintillating bolometer. Importance of the signal-to-noise ratio, correct finding of the signal start and choice of an appropriate sampling frequency are discussed.

Surface plasmon-enhanced optical absorption in monolayer MoS2 with one-dimensional Au grating

NASA Astrophysics Data System (ADS)

Song, Jinlin; Lu, Lu; Cheng, Qiang; Luo, Zixue

2018-05-01

The optical absorption of a composite photonic structure, namely monolayer molybdenum disulfide (MoS2)-covered Au grating, is theoretically investigated using a rigorous coupled-wave analysis algorithm. The enhancement of localized electromagnetic field due to surface plasmon polaritons supported by Au grating can be utilized to enhance the absorption of MoS2. The remarkable enhancement of absorption due to exciton transition can also be realized. When the period of grating is 600 nm, the local absorption of the monolayer MoS2 on Au grating is nearly 7 times higher than the intrinsic absorption due to B exciton transition. A further study reveals that the absorption properties of Au grating can be tailored by altering number of MoS2 layers, changing to a MoS2 nanoribbon array, and inserting a hafnium dioxide (HfO2) spacer. This work will contribute to the design of MoS2-based optical and optoelectronic devices.

Fabrication of a temperature-responsive and recyclable MoS2 nanocatalyst through composting with poly (N-isopropylacrylamide)

NASA Astrophysics Data System (ADS)

Liu, Yan; Chen, Pengpeng; Nie, Wangyan; Zhou, Yifeng

2018-04-01

A temperature-responsive, recyclable nanocatalyst was fabricated by composting the exfoliated molybdenum disulfide (MoS2) nanosheets with poly (N-isopropylacry lamide) (PNIPAM). The structure and morphology of MoS2/PNIPAM nanocatalyst was fully characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), Thermogravimetry analysis (TGA), Scanning electron microscope (SEM) and Transmission electron microscopy (TEM). The temperature-responsive properties of the MoS2/PNIPAM nanocatalyst were confirmed by Dynamic Light Scattering (DLS) and Ultraviolet-visible ((UV-vis)) absorption spectroscopy. The catalytic activities of the MoS2/PNIPAM nanocatalyst were studied using the reduction reaction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) as the model reaction. Results showed that the catalytic activity of the MoS2/PNIPAM nanocatalyst could be regulated by temperature. Furthermore, when the temperature went higher than the low critical solution temperature (LCST) of PNIPAM, the MoS2/PNIPAM nanocatalyst tended to aggregated to form bulk materials from homogeneous suspension.

Functionalization of liquid-exfoliated two-dimensional 2H-MoS2.

PubMed

Backes, Claudia; Berner, Nina C; Chen, Xin; Lafargue, Paul; LaPlace, Pierre; Freeley, Mark; Duesberg, Georg S; Coleman, Jonathan N; McDonald, Aidan R

2015-02-23

Layered two-dimensional (2D) inorganic transition-metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS2 . We found that the reaction of liquid-exfoliated 2D MoS2 , with M(OAc)2 salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS2 -M(OAc)2 materials. Importantly, this method furnished the 2H-polytype of MoS2 which is a semiconductor. X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT-IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS2 surface sulfur atoms to the M(OAc)2 salt. Interestingly, functionalization of 2H-MoS2 allows for its dispersion/processing in more conventional laboratory solvents. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetics of Molybdenum Adsorption and Desorption in Soils.

PubMed

Sun, Wenguang; Selim, H Magdi

2018-05-01

Much uncertainty exists in mechanisms and kinetics controlling the adsorption and desorption of molybdenum (Mo) in the soil environment. To investigate the characteristics of Mo adsorption and desorption and predict Mo behavior in the vadose zone, kinetic batch experiments were performed using three soils: Webster loam, Windsor sand and Mahan sand. Adsorption isotherms for Mo were strongly nonlinear for all three soils. Strong kinetic adsorption of Mo by all soils was also observed, where the rate of retention was rapid initially and was followed by slow retention behavior with time. The time-dependent Mo sorption rate was not influenced when constant pH was maintained. Desorption or release results indicated that there were significant fractions of Mo that appeared to be irreversible or slowly reversibly sorbed by Windsor and Mahan. X-ray absorption near edge structure (XANES) analysis for Windsor and Mahan soils indicated that most of Mo had been bound to kaolinite, whereas Webster had similar XANES features to those of Mo sorbed to montmorillonite. A sequential extraction procedure provided evidence that a significant amount of Mo was irreversibly sorbed. A multireaction model (MRM) with nonlinear equilibrium and kinetic sorption parameters was used to describe the adsorption-desorption kinetics of Mo on soils. Our results demonstrated that a formulation of MRM with two sorption sites (equilibrium and reversible) successfully described Mo adsorption-desorption data for Webster loam, and an additional irreversible reaction phase was recommended to describe Mo desorption or release with time for Windsor and Mahan soils. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Effects of hydrogen on the structural and optical properties of MoSe2 grown by hot filament chemical vapor deposition

NASA Astrophysics Data System (ADS)

Wang, B. B.; Zhu, M. K.; Levchenko, I.; Zheng, K.; Gao, B.; Xu, S.; Ostrikov, K.

2017-10-01

The role of reactive environment and hydrogen specifically in growth and structure of molybdenum selenide (MoSe2) nanomaterials is presently debated, and it is not clear whether hydrogen can promote the growth of MoSe2 sheets and alter their electronic properties. To find efficient, convenient methods for controlling the nucleation, growth and resultant properties of MoSe2 nanomaterials, MoSe2 nanoflakes were synthesized on silicon substrates by hot filament chemical vapor deposition using molybdenum trioxide and selenium powders in pure hydrogen, nitrogen gases and hydrogen-nitrogen mixtures. The structures and composition of synthesized MoSe2 nanoflakes were studied using the advanced characterization instruments including field emission scanning electron microscopy, micro-Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy and energy dispersive X-ray spectrometry. The analysis of the growth process indicates that hydrogen can improve the formation of MoSe2 nanoflakes and significantly alter their properties due to the high reduction capacity of hydrogen and the creation of more nucleation centers of MoSe2 nanoflakes on the silicon surface. The study of photoluminescent (PL) properties reveals that the MoSe2 nanoflakes can generate a strong PL band at about 631 nm, differently from the plain MoSe2 nanoflakes. The major difference in the PL properties may be related to the edges of MoSe2 nanoflakes. These results can be used to control the growth and structure of MoSe2-based nanomaterials and contribute to the development of advanced MoSe2-based optoelectronic devices.

The Earth-Moon system as a typical binary in the Solar System

NASA Astrophysics Data System (ADS)

Ipatov, S.

2014-07-01

In recent years new arguments in favor of the formation of solid planetesimals by contraction of rarefied preplanetesimals (RPPs) have been found. It is often considered that masses of some RPPs can correspond to masses of solid bodies of diameter about 1000 km. [1] showed that in the vortices launched by the Rossby wave instability in the borders of the dead zone, the solids quickly achieve critical densities and undergo gravitational collapse into protoplanetary embryos in the mass range 0.1-0.6M_E (where M_E is the mass of the Earth). [2] and [3] supposed that transneptunian binaries were formed from RPPs. It was shown in [2] that the angular momenta acquired at collisions of RPPs moving in circular heliocentric orbits could have the same values as the angular momenta of discovered transneptunian and asteroid binaries. [4] obtained that the angular momenta used in [3] as initial data in calculations of the contraction of RPPs leading to formation of transneptunian binaries could be acquired at collisions of two RPPs moving in circular heliocentric orbits. I supposed that the fraction of RPPs collided with other RPPs during their contraction can be about the fraction of small bodies of diameter d>100 km with satellites (among all such small bodies), i.e., it can be about 0.3 for objects formed in the transneptunian belt. The model of collisions of RPPs explains negative angular momenta of some observed binaries, as about 20 percent of collisions of RPPs moving in circular heliocentric orbits lead to retrograde rotation. Note that if all RPPs got their angular momenta at their formation without mutual collisions, then the angular momenta of small bodies without satellites and those with satellites could be similar (but actually they differ considerably). Most of rarefied preasteroids could turn into solid asteroids before they collided with other preasteroids. Some present asteroids can be debris of larger solid bodies, and the formation of many binaries with primaries with d<100 km can be explained by other models (not by contraction of RPPs). [5] noted that the giant impact concept, which is a popular model of the Moon formation, has several weaknesses. In particular, they calculated formation of the Earth-Moon system from a rarefied protoplanet which mass equaled to the mass of the Earth-Moon system. Using the formulas presented in [2], we obtained that the ratio r_K=K_{EM}/K_{s2} of the angular momentum K_{EM} of the Earth-Moon system to the angular momentum K_{s2} at a typical collision of two identical RPPs - Hill spheres, which masses m_2 are equal to 0.5\\cdot1.0123M_E and heliocentric orbits are circular, is about 0.0335. As K_{s2} ∝ (m_2)^{3/5} [2], then K_{s2}=K_{EM} at 2 m_2=0.0335^{3/5}\\cdot 1.0123M_E=0.13M_E. For circular heliocentric orbits, the maximum value of K_{s2} is greater by a factor of 0.6^{-1} than the above typical value. In this case, r_K=0.02 and 0.02^{3/5}=0.096. Therefore, the angular momentum of the Earth-Moon system can be acquired at a collision of two RPPs with a total mass not smaller than the mass of Mars. We suppose that solid proto-Earth and proto-Moon (with masses m_{Eo} and m_{Mo}) could be formed from a RPP (e.g., according to the models of contraction of a RPP [3,5]). Let us consider the model of the growth of proto-Earth and proto-Moon to the present masses of the Earth and the Moon (M_E and 0.0123M_E, respectively) by accumulation of smaller planetesimals for the case when the effective radii of proto-Earth and proto-Moon are proportional to r (where r is a radius of a considered object). Such proportionality can be considered for large enough eccentricities of planetesimals. In this case, r_{Mo}=m_{Mo}/M_E = [ (0.0123)^{-2/3} - k + k \\cdot (m_{Eo}/M_E)^{-2/3})]^{-3/2}, where k=(k_d)^{-2/3}, and k_d is the ratio of the density of the growing Moon to that of the growing Earth (k_d=0.6 for the present Earth and Moon). For r_{Eo}=m_{Eo}/M_E=0.1, we have r_{Mo}=0.0094 at k=1 and r_{Mo}=0.0086 at k=0.6^{-2/3}. At these values of r_{Mo}, the ratio f_M=(0.0123-r_{Mo})/0.0123 of the mass of planetesimals that were accreted by the Moon at the stage of the solid body accumulation to the present mass of the Moon is 0.24 and 0.30, respectively. If we consider that effective radii of the objects are proportional to r^2 (the case of relatively small relative velocities of planetesimals), then at r_{Eo}=0.1 for k_d equal 1 and 0.6, we obtain f_M equal to 0.04 and 0.05, respectively. In the above model, the Moon could acquire up to 1/3 of its mass at the stage of accumulation of solid bodies, while the mass of the growing Earth increased by a factor of ten, but probably the initial mass of a solid proto-Earth exceeded 0.1M_E. Probably, the RPPs that contracted and formed the embryos of other terrestrial planets did not collide with massive RPPs, and therefore they did not get large enough angular momentum needed to form massive satellites.

Li 3Mo 4P 5O 24: A two-electron cathode for lithium-ion batteries with three-dimensional diffusion pathways

DOE PAGES

Wen, Bohua; Khalifah, Peter G.; Liu, Jue; ...

2016-04-12

The structure of the novel compound Li 3Mo 4P 5O 24 has been solved from single crystal X-ray diffraction data. The Mo cations in Li 3Mo 4P 5O 24 are present in four distinct types of MoO 6 octahedra, each of which has one open vertex at the corner participating in a Mo=O double bond and whose other five corners are shared with PO 4 tetrahedra. On the basis of a bond valence sum difference map (BVS-DM) analysis, this framework is predicted to support the facile diffusion of Li + ions, a hypothesis that is confirmed by electrochemical testing data,more » which show that Li 3Mo 4P 5O 24 can be utilized as a rechargeable battery cathode material. It is found that Li can both be removed from and inserted into Li 3Mo 4P 5O 24. The involvement of multiple redox processes occurring at the same Mo site is reflected in electrochemical plateaus around 3.8 V associated with the Mo 6+/Mo 5+ redox couple and 2.2 V associated with the Mo 5+/Mo 4+ redox couple. The two-electron redox properties of Mo cations in this structure lead to a theoretical capacity of 198 mAh/g. When cycled between 2.0 and 4.3 V versus Li +/Li, an initial capacity of 113 mAh/g is observed with 80% of this capacity retained over the first 20 cycles. Lastly, this compound therefore represents a rare example of a solid state cathode able to support two-electron redox capacity and provides important general insights about pathways for designing next-generation cathodes with enhanced specific capacities.« less

RBS Depth Profiling Analysis of (Ti, Al)N/MoN and CrN/MoN Multilayers.

PubMed

Han, Bin; Wang, Zesong; Devi, Neena; Kondamareddy, K K; Wang, Zhenguo; Li, Na; Zuo, Wenbin; Fu, Dejun; Liu, Chuansheng

2017-12-01

(Ti, Al)N/MoN and CrN/MoN multilayered films were synthesized on Si (100) surface by multi-cathodic arc ion plating system with various bilayer periods. The elemental composition and depth profiling of the films were investigated by Rutherford backscattering spectroscopy (RBS) using 2.42 and 1.52 MeV Li 2+ ion beams and different incident angles (0°, 15°, 37°, and 53°). The microstructures of (Ti, Al)N/MoN multilayered films were evaluated by X-ray diffraction. The multilayer periods and thickness of the multilayered films were characterized by scanning electron microscopy (SEM) and high-resolution transmission electron microscopy (HR-TEM) and then compared with RBS results.

Research Update: Nanoscale surface potential analysis of MoS2 field-effect transistors for biomolecular detection using Kelvin probe force microscopy

NASA Astrophysics Data System (ADS)

Kim, Min Hyung; Park, Heekyeong; Lee, Hyungbeen; Nam, Kihwan; Jeong, Seokhwan; Omkaram, Inturu; Yoon, Dae Sung; Lee, Sei Young; Kim, Sunkook; Lee, Sang Woo

2016-10-01

We used high-resolution Kelvin probe force microscopy (KPFM) to investigate the immobilization of a prostate specific antigen (PSA) antibody by measuring the surface potential (SP) on a MoS2 surface over an extensive concentration range (1 pg/ml-100 μg/ml). After PSA antibody immobilization, we demonstrated that the SP on the MoS2 surface characterized by KPFM strongly correlated to the electrical signal of a MoS2 bioFET. This demonstration can not only be used to optimize the immobilization conditions for captured molecules, but can also be applied as a diagnostic tool to complement the electrical detection of a MoS2 FET biosensor.

Microstructural analysis of as-processed U-10 wt.%Mo monolithic fuel plate in AA6061 matrix with Zr diffusion barrier

NASA Astrophysics Data System (ADS)

Perez, E.; Yao, B.; Keiser, D. D., Jr.; Sohn, Y. H.

2010-07-01

For higher U-loading in low-enriched U-10 wt.%Mo fuels, monolithic fuel plate clad in AA6061 is being developed as a part of Reduced Enrichment for Research and Test Reactor (RERTR) program. This paper reports the first characterization results from a monolithic U-10 wt.%Mo fuel plate with a Zr diffusion barrier that was fabricated as part of a plate fabrication campaign for irradiation testing in the Advanced Test Reactor (ATR). Both scanning and transmission electron microscopy (SEM and TEM) were employed for analysis. At the interface between the Zr barrier and U-10 wt.%Mo, going from Zr to U(Mo), UZr 2, γ-UZr, Zr solid-solution and Mo 2Zr phases were observed. The interface between AA6061 cladding and Zr barrier plate consisted of four layers, going from Al to Zr, (Al, Si) 2Zr, (Al, Si)Zr 3 (Al, Si) 3Zr, and AlSi 4Zr 5. Irradiation behavior of these intermetallic phases is discussed based on their constituents. Characterization of as-fabricated phase constituents and microstructure would help understand the irradiation behavior of these fuel plates, interpret post-irradiation examination, and optimize the processing parameters of monolithic fuel system.

Stellar Laboratories . [VI. New Mo IV - VII Oscillator Strengths and the Molybdenum Abundance in the Hot White Dwarfs G191-B2B and RE 0503-289

NASA Technical Reports Server (NTRS)

Rauch, T.; Quinet, T.; Hoyer, D.; Werner, K.; Demleitner, M.; Kruk, J. W.

2016-01-01

For the spectral analysis of high-resolution and high signal-to-noise (SN) spectra of hot stars, state-of-the-art non-local thermodynamic equilibrium (NLTE) model atmospheres are mandatory. These are strongly dependent on the reliability of the atomic data that is used for their calculation. Aims: To identify molybdenum lines in the ultraviolet (UV) spectra of the DA-type white dwarf G191B2B and the DO-type white dwarf RE 0503289 and, to determine their photospheric Mo abundances, reliable Mo iv-vii oscillator strengths are used. Methods: We newly calculated Mo iv-vii oscillator strengths to consider their radiative and collisional bound-bound transitions indetail in our NLTE stellar-atmosphere models for the analysis of Mo lines exhibited in high-resolution and high SN UV observations of RE 0503289.Results. We identified 12 Mo v and nine Mo vi lines in the UV spectrum of RE 0503289 and measured a photospheric Mo abundance of 1.2 3.0 104(mass fraction, 22 500 56 400 times the solar abundance). In addition, from the As v and Sn iv resonance lines,we measured mass fractions of arsenic (0.51.3 105, about 300 1200 times solar) and tin (1.33.2 104, about 14 300 35 200 times solar). For G191B2B, upper limits were determined for the abundances of Mo (5.3 107, 100 times solar) and, in addition, for Kr (1.1106, 10 times solar) and Xe (1.7107, 10 times solar). The arsenic abundance was determined (2.35.9 107, about 21 53 times solar). A new, registered German Astrophysical Virtual Observatory (GAVO) service, TOSS, has been constructed to provide weighted oscillator strengths and transition probabilities.Conclusions. Reliable measurements and calculations of atomic data are a prerequisite for stellar-atmosphere modeling. Observed Mo v-vi line profiles in the UV spectrum of the white dwarf RE 0503289 were well reproduced with our newly calculated oscillator strengths. For the first time, this allowed the photospheric Mo abundance in a white dwarf to be determined.

Electroluminescence and Photocurrent Generation from Atomically Sharp WSe2/MoS2 Heterojunction p–n Diodes

PubMed Central

2015-01-01

The p–n diodes represent the most fundamental device building blocks for diverse optoelectronic functions, but are difficult to achieve in atomically thin transition metal dichalcogenides (TMDs) due to the challenges in selectively doping them into p- or n-type semiconductors. Here, we demonstrate that an atomically thin and sharp heterojunction p–n diode can be created by vertically stacking p-type monolayer tungsten diselenide (WSe2) and n-type few-layer molybdenum disulfide (MoS2). Electrical measurements of the vertically staked WSe2/MoS2 heterojunctions reveal excellent current rectification behavior with an ideality factor of 1.2. Photocurrent mapping shows rapid photoresponse over the entire overlapping region with a highest external quantum efficiency up to 12%. Electroluminescence studies show prominent band edge excitonic emission and strikingly enhanced hot-electron luminescence. A systematic investigation shows distinct layer-number dependent emission characteristics and reveals important insight about the origin of hot-electron luminescence and the nature of electron–orbital interaction in TMDs. We believe that these atomically thin heterojunction p–n diodes represent an interesting system for probing the fundamental electro-optical properties in TMDs and can open up a new pathway to novel optoelectronic devices such as atomically thin photodetectors, photovoltaics, as well as spin- and valley-polarized light emitting diodes, on-chip lasers. PMID:25157588

Exact solutions to the Mo-Papas and Landau-Lifshitz equations

NASA Astrophysics Data System (ADS)

Rivera, R.; Villarroel, D.

2002-10-01

Two exact solutions of the Mo-Papas and Landau-Lifshitz equations for a point charge in classical electrodynamics are presented here. Both equations admit as an exact solution the motion of a charge rotating with constant speed in a circular orbit. These equations also admit as an exact solution the motion of two identical charges rotating with constant speed at the opposite ends of a diameter. These exact solutions allow one to obtain, starting from the equation of motion, a definite formula for the rate of radiation. In both cases the rate of radiation can also be obtained, with independence of the equation of motion, from the well known fields of a point charge, that is, from the Maxwell equations. The rate of radiation obtained from the Mo-Papas equation in the one-charge case coincides with the rate of radiation that comes from the Maxwell equations; but in the two-charge case the results do not coincide. On the other hand, the rate of radiation obtained from the Landau-Lifshitz equation differs from the one that follows from the Maxwell equations in both the one-charge and two-charge cases. This last result does not support a recent statement by Rohrlich in favor of considering the Landau-Lifshitz equation as the correct and exact equation of motion for a point charge in classical electrodynamics.

Analysis of Femoral Components of Cemented Total Hip Arthroplasty

NASA Astrophysics Data System (ADS)

Singh, Shantanu; Harsha, A. P.

2016-10-01

There have been continuous on-going revisions in design of prosthesis in Total Hip Arthroplasty (THA) to improve the endurance of hip replacement. In the present work, Finite Element Analysis was performed on cemented THA with CoCrMo trapezoidal, CoCrMo circular, Ti6Al4V trapezoidal and Ti6Al4V circular stem. It was observed that cross section and material of femoral stem proved to be critical parameters for stress distribution in femoral components, distribution of interfacial stress and micro movements. In the first part of analysis, designs were investigated for micro movements and stress developed, for different stem materials. Later part of the analysis focused on investigations with respect to different stem cross sections. Femoral stem made of Titanium alloy (Ti6Al4V) resulted in larger debonding of stem at cement-stem interface and increased stress within the cement mantle in contrast to chromium alloy (CoCrMo) stem. Thus, CoCrMo proved to be a better choice for cemented THA. Comparison between CoCrMo femoral stem of trapezium and circular cross section showed that trapezoidal stem experiences lesser sliding and debonding at interfaces than circular cross section stem. Also, trapezium cross section generated lower peak stress in femoral stem and cortical femur. In present study, femur head with diameter of 36 mm was considered for the analysis in order to avoid dislocation of the stem. Also, metallic femur head was coupled with cross linked polyethylene liner as it experiences negligible wear compared to conventional polyethylene liner and unlike metallic liner it is non carcinogenic.

Ancillary ligand effects upon dithiolene redox noninnocence in tungsten bis(dithiolene) complexes.

PubMed

Yan, Yong; Keating, Christopher; Chandrasekaran, Perumalreddy; Jayarathne, Upul; Mague, Joel T; DeBeer, Serena; Lancaster, Kyle M; Sproules, Stephen; Rubtsov, Igor V; Donahue, James P

2013-06-03

An expanded set of compounds of the type [W(S2C2Me2)2L1L2](n) (n = 0: L1 = L2 = CO, 1; L1 = L2 = CN(t)Bu, 2; L1 = CO, L2 = carbene, 3; L1 = CO, L2 = phosphine, 4; L1 = L2 = phosphine, 5. n = 2-: L1 = L2 = CN(-), [6](2-)) has been synthesized and characterized. Despite isoelectronic formulations, the compound set reveals gradations in the dithiolene ligand redox level as revealed by intraligand bond lengths, υ(CCchelate), and rising edge energies in the sulfur K-edge X-ray absorption spectra (XAS). Differences among the terminal series members, 1 and [6](2-), are comparable to differences seen in homoleptic dithiolene complexes related by full electron transfer to/from a dithiolene-based MO. The key feature governing these differences is the favorable energy of the CO π* orbitals, which are suitably positioned to overlap with tungsten d orbitals and exert an oxidizing effect on both metal and dithiolene ligand via π-backbonding. The CN(-) π* orbitals are too high in energy to mix effectively with tungsten and thus leave the filled dithiolene π* orbitals unperturbed. This work shows how, and the degree to which, the redox level of a noninnocent ligand can be modulated by the choice of ancillary ligands(s).

Molybdenum isotope fractionation in scleractinian corals and its implications on biological activities

NASA Astrophysics Data System (ADS)

Wei, G.; Wang, Z.; Li, J.; Deng, W.; Chen, X.; Ma, J.; Zeng, T.

2017-12-01

Molybdenum can actively involve in many biological processes on coral reefs, and its isotope fractionation in coral skeleton is possibly linked to some biological activities. We have performed a 3-days' time-series observation in a time interval of 4 hours on both Mo concentrations and δ98/85Mo of the seawater of the Luhuitou Reef in Sanya of Southern Hainan Islands in the northern South China Sea. Both Mo concentrations and δ98/85Mo show in pace diurnal variations with temperature, pH, dissolved oxygen (DO) contents, dissolved inorganic carbon (DIC) contents and its δ13C. High Mo concentrations and low δ98/85Mo generally occur during day time, and low Mo concentrations and high δ98/85Mo occur at night, suggesting that respiration of coral dominated at night tends to uptake more Mo from seawater. A further analysis on the Mo isotopic compositions of 6 different coral species on the Luhuitou Reef indicates that different coral species has different δ98/85Mo values in their skeleton. The lowest δ98/85Mo value occurs in Fungia of 0.34 ‰, and the highest occurs in Acropora sp of 1.91 ‰. These are all lower than that of the seawater, 2.04 ‰, suggesting a specie-depended Mo fractionation on coral skeleton. Meanwhile, we measured a 32-year time series of both Mo concentrations and δ98/85Mo of a Porites coral from the Great Barrier Reefs of Australia in annual resolution. The Mo concentrations vary from 12.5 to 78.0 ng/g, with an average of 21.4 ± 0.02 ng/g, and the δ98/95Mo values change from 0.46 to 1.83‰, with an average of 1.34 ± 0.09‰. A significant negative correlation occurs between the δ98/95Mo and the Mo concentration, and a positive correlation occurs between the δ98/95Mo and the seawater surface temperature. All these suggest that Mo isotope fractionation in coral skeleton is associated with biological activities of coral, such as respiration, and the δ98/95Mo values may be used to indicate changes in the related biological activities.

Block correlated second order perturbation theory with a generalized valence bond reference function.

PubMed

Xu, Enhua; Li, Shuhua

2013-11-07

The block correlated second-order perturbation theory with a generalized valence bond (GVB) reference (GVB-BCPT2) is proposed. In this approach, each geminal in the GVB reference is considered as a "multi-orbital" block (a subset of spin orbitals), and each occupied or virtual spin orbital is also taken as a single block. The zeroth-order Hamiltonian is set to be the summation of the individual Hamiltonians of all blocks (with explicit two-electron operators within each geminal) so that the GVB reference function and all excited configuration functions are its eigenfunctions. The GVB-BCPT2 energy can be directly obtained without iteration, just like the second order Mo̸ller-Plesset perturbation method (MP2), both of which are size consistent. We have applied this GVB-BCPT2 method to investigate the equilibrium distances and spectroscopic constants of 7 diatomic molecules, conformational energy differences of 8 small molecules, and bond-breaking potential energy profiles in 3 systems. GVB-BCPT2 is demonstrated to have noticeably better performance than MP2 for systems with significant multi-reference character, and provide reasonably accurate results for some systems with large active spaces, which are beyond the capability of all CASSCF-based methods.

RadNet Air Data From Springfield, MO

EPA Pesticide Factsheets

This page presents radiation air monitoring and air filter analysis data for Springfield, MO from EPA's RadNet system. RadNet is a nationwide network of monitoring stations that measure radiation in air, drinking water and precipitation.

Evaluation of border traps and interface traps in HfO2/MoS2 gate stacks by capacitance–voltage analysis

NASA Astrophysics Data System (ADS)

Zhao, Peng; Khosravi, Ava; Azcatl, Angelica; Bolshakov, Pavel; Mirabelli, Gioele; Caruso, Enrico; Hinkle, Christopher L.; Hurley, Paul K.; Wallace, Robert M.; Young, Chadwin D.

2018-07-01

Border traps and interface traps in HfO2/few-layer MoS2 top-gate stacks are investigated by C–V characterization. Frequency dependent C–V data shows dispersion in both the depletion and accumulation regions for the MoS2 devices. The border trap density is extracted with a distributed model, and interface traps are analyzed using the high-low frequency and multi-frequency methods. The physical origins of interface traps appear to be caused by impurities/defects in the MoS2 layers, performing as band tail states, while the border traps are associated with the dielectric, likely a consequence of the low-temperature deposition. This work provides a method of using multiple C–V measurements and analysis techniques to analyze the behavior of high-k/TMD gate stacks and deconvolute border traps from interface traps.

Electronic Structure and Multisite Basicity of the Pyramidal Phosphinidene-Bridged Dimolybdenum Complex [Mo2(η(5)-C5H5)(μ-κ(1):κ(1),η(5)-PC5H4)(η(6)-C6H3(t)Bu3)(CO)2(PMe3)].

PubMed

Albuerne, Isabel G; Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Ruiz, Miguel A

2015-10-19

The title phosphinidene complex could be sequentially protonated with HBF4·OEt2 or [H(OEt2)2](BAr'4) to give the phosphido-bridged derivatives [Mo2Cp(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X and then the hydrides [Mo2Cp(H)(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X2 (X = BF4, BAr'4; Ar' = 3,5-C6H3(CF3)2; Mes* = 2,4,6-C6H2(t)Bu3). Density functional theory (DFT) calculations revealed that the most favored site for initial electrophilic attack is the metallocene Mo atom, but attachment of the electrophile to the phosphinidene P atom gives more stable products. This was in agreement with all other reactions investigated, which invariably involved the attachment of the added electrophile at the P site. Thus, the title compound reacted with S8 at 223 K to give the thiophosphinidene-bridged complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(S)C5H4}(η(6)-HMes*)(CO)2(PMe3)], a poorly stable molecule which reacted with MeI at room temperature to give the corresponding thiolatophosphido derivative, isolated as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(SMe)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4) (P-S = 2.128(4) Å) after anion exchange with Na(BAr'4). Reaction of the title compound with MeI proceeded smoothly to give the corresponding methylphosphido derivative, isolated analogously as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4). The related complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe2Ph)](BAr'4) (P-C(Me) = 1.841(5) Å) could be prepared analogously from the neutral precursor [Mo2Cp{μ-κ(1):κ(1),η(5)-PC5H4}(η(6)-HMes*)(CO)2(PMe2Ph)]. In contrast, reaction of the title complex with ethylene sulfide involved opening of the C2S ring and formation of new P-C and Mo-S bonds (1.886(7) and 2.493(2) Å, respectively), with displacement of the PMe3 ligand, to give the phosphido-thiolato complex [Mo2Cp{μ-κ(2)(P,S):κ(1)P,η(5)-P(C2H4S)C5H4}(η(6)-HMes*)(CO)2]. All these derivatives of the title complex displayed an unusual trigonal pyramidal-like environment around the bridging P atom, with the added electrophile placed in the Mo2P plane as a result of the directionality of the relevant frontier orbital of the phosphinidene complex, according to DFT calculations.

Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers

PubMed Central

2017-01-01

Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (SN2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the SN2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside SN2 Cl– + CH3Cl with similar Cl– substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that SN2@N and SN2@O have similar PES to the prototypical SN2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The SN2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ*A–Cl) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn–Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction. PMID:28045531

Activation Strain Analysis of SN2 Reactions at C, N, O, and F Centers.

PubMed

Kubelka, Jan; Bickelhaupt, F Matthias

2017-02-02

Fundamental principles that determine chemical reactivity and reaction mechanisms are the very foundation of chemistry and many related fields of science. Bimolecular nucleophilic substitutions (S N 2) are among the most common and therefore most important reaction types. In this report, we examine the trends in the S N 2 reactions with respect to increasing electronegativity of the reaction center by comparing the well-studied backside S N 2 Cl - + CH 3 Cl with similar Cl - substitutions on the isoelectronic series with the second period elements N, O, and F in place of C. Relativistic (ZORA) DFT calculations are used to construct the gas phase reaction potential energy surfaces (PES), and activation strain analysis, which allows decomposition of the PES into the geometrical strain and interaction energy, is employed to analyze the observed trends. We find that S N 2@N and S N 2@O have similar PES to the prototypical S N 2@C, with the well-defined reaction complex (RC) local minima and a central barrier, but all stationary points are, respectively, increasingly stable in energy. The S N 2@F, by contrast, exhibits only a single-well PES with no barrier. Using the activation strain model, we show that the trends are due to the interaction energy and originate mainly from the decreasing energy of the empty acceptor orbital (σ* A-Cl ) on the reaction center A in the order of C, N, O, and F. The decreasing steric congestion around the central atom is also a likely contributor to this trend. Additional decomposition of the interaction energy using Kohn-Sham molecular orbital (KS-MO) theory provides further support for this explanation, as well as suggesting electrostatic energy as the primary reason for the distinct single-well PES profile for the FCl reaction.

Individual and collective modes of surface magnetoplasmon in thiolate-protected silver nanoparticles studied by MCD spectroscopy.

PubMed

Yao, Hiroshi; Shiratsu, Taisuke

2016-06-07

Large magneto-optical (MO) responses at the energy of localized surface plasmon resonance (LSPR), namely, surface magnetoplasmons, are demonstrated for the first time in thiolate-protected silver nanoparticles with magnetic circular dichroism (MCD) spectroscopy. The samples examined are decanethiol (DT)-, azobenzenethiol (ABT)-, and ABT/DT mixed-monolayer-protected Ag nanoparticles. ABT-protected Ag nanoparticles are somewhat aggregated and thus exhibit a broad, collective mode of plasmonic absorption, whereas other samples with highly-dispersed nanoparticles show an individual mode of LSPR absorption. In all Ag nanoparticles, a derivative-like MCD signal is observed under an applied magnetic field of 1.6 T, which can be explained in terms of two circular modes of magnetoplasmon caused by the increase (or decrease) in the Lorentz force imparted on the free electrons that oscillate in the left (or right) circular orbits in the nanosphere. For the Ag nanoparticles exhibiting an individual LSPR mode, in particular, simultaneous deconvolution analysis of UV-vis absorption and MCD spectra reveal that (i) the amplitude of the magnetoplasmonic component with lower frequency (ω-), resulting from the reduction in the confinement strength of collective electrons by the Lorentz force, is stronger than that with a higher frequency (ω+); (ii) the accurate shift or cyclotron frequency between two magnetoplasmonic modes (ωc = ω+-ω-) is size-dependent, and presents a very large value with implications for the apparent enhancement of the local magnetic-field in the Ag nanoparticles. These results strongly suggest that the Ag-thiolate layer or Ag-S bonding on the nanoparticle surface plays a significant role in the MO enhancement.

Isolation and identification of a lethal rhabdovirus from farmed rice field eels Monopterus albus.

PubMed

Ou, Tong; Zhu, Ruo-Lin; Chen, Zhong-Yuan; Zhang, Qi-Ya

2013-11-06

We provide the first description of a virus responsible for a systemic hemorrhagic disease causing high mortality in farmed rice field eels Monopterus albus in China. Typical signs exhibited by the diseased fish were extensive hemorrhages in the skin and viscera and some neurological signs, such as loss of equilibrium and disorganized swimming. Histopathological examination revealed various degrees of necrosis within the spleen and liver. Virus isolation was attempted from visceral tissues of diseased fish by inoculation on 6 fish cell lines. Typical cytopathic effects (CPE) were produced in bluegill fry (BF2) cells, so this cell line was chosen for further isolation and propagation of the virus. Electron microscopy observation showed that the negative stained viral particles had the characteristic bullet shape of rhabdoviruses and an estimated size of 60 × 120 nm. We therefore tentatively refer to this virus as Monopterus albus rhabdovirus (MoARV). Molecular characterization of MoARV, including sequence analysis of the nucleoprotein (N), phosphoprotein (P), and glycoprotein (G) genes, revealed 94.5 to 97.3% amino acid similarity to that of Siniperca chuatsi rhabdovirus. Phylogenetic analysis based on the amino acid sequences of N and G proteins indicated that MoARV should be a member of the genus Vesiculovirus. Koch's postulates were fulfilled by infecting healthy rice field eels with MoARV, which produced an acute infection. RT-PCR analysis demonstrated that MoARV RNA could be detected in both naturally and experimentally infected fish. The data suggest that MoARV was the causative pathogen of the disease.

Hypothesis-based weight-of-evidence evaluation and risk assessment for naphthalene carcinogenesis

PubMed Central

Bailey, Lisa A.; Nascarella, Marc A.; Kerper, Laura E.; Rhomberg, Lorenz R.

2016-01-01

Inhalation of naphthalene causes olfactory epithelial nasal tumors in rats (but not in mice) and benign lung adenomas in mice (but not in rats). The limited available human data have not identified an association between naphthalene exposure and increased respiratory cancer risk. Assessing naphthalene's carcinogenicity in humans, therefore, depends entirely on experimental evidence from rodents. We evaluated the respiratory carcinogenicity of naphthalene in rodents, and its potential relevance to humans, using our Hypothesis-Based Weight-of-Evidence (HBWoE) approach. We systematically and comparatively reviewed data relevant to key elements in the hypothesized modes of action (MoA) to determine which is best supported by the available data, allowing all of the data from each realm of investigation to inform interpretation of one another. Our analysis supports a mechanism that involves initial metabolism of naphthalene to the epoxide, followed by GSH depletion, cytotoxicity, chronic inflammation, regenerative hyperplasia, and tumor formation, with possible weak genotoxicity from downstream metabolites occurring only at high cytotoxic doses, strongly supporting a non-mutagenic threshold MoA in the rat nose. We also conducted a dose–response analysis, based on the likely MoA, which suggests that the rat nasal MoA is not relevant in human respiratory tissues at typical environmental exposures. Our analysis illustrates how a thorough WoE evaluation can be used to support a MoA, even when a mechanism of action cannot be fully elucidated. A non-mutagenic threshold MoA for naphthalene-induced rat nasal tumors should be considered as a basis to determine human relevance and to guide regulatory and risk-management decisions. PMID:26202831

Oxidation process of MoO xC y to MoO 3: kinetics and mechanism

NASA Astrophysics Data System (ADS)

Aleman-Vázquez, L. O.; Torres-García, E.; Rodríguez-Gattorno, G.; Ocotlán-Flores, J.; Camacho-López, M. A.; Cano, J. L.

2004-10-01

A non-isothermal kinetic study of the oxidation of "carbon-modified MoO3" in the temperature range of 150-550°C by simultaneous TGA-DTA was investigated. During the oxidation process, two thermal events were detected, which are associated with the oxidation of carbon in MoOxCy and MoO2 to MoO3. The model-free and model-fitting kinetic approaches have been applied to TGA experimental data. The solid state-kinetics of the oxidation of MoOxCy to MoO3 is governed by F1 (unimolecular decay), which suggests that the reaction is of the first order with respect to oxygen concentration. The constant (Ea)α value (about 115±5 kJ/mol) for this first stage can be related to the nature of the reaction site in the MoO3 matrix. This indicates that oxidation occurs in well-defined lattice position sites (energetically equivalent). On the other hand, for the second stage of oxidation, MoO2 to MoO3, the isoconversional analysis shows a complex (Ea)α dependence on (α) and reveals a typical behavior for competitive reaction. A D2 (two-dimensional diffusion) mechanism with a variable activation energy value in the range 110-200 kJ/mol was obtained. This can be interpreted as an inter-layer oxygen diffusion in the solid bulk, which does not exclude other simultaneous mechanism reactions.

A Bayesian network model for predicting aquatic toxicity mode ...

EPA Pesticide Factsheets

The mode of toxic action (MoA) has been recognized as a key determinant of chemical toxicity but MoA classification in aquatic toxicology has been limited. We developed a Bayesian network model to classify aquatic toxicity mode of action using a recently published dataset containing over one thousand chemicals with MoA assignments for aquatic animal toxicity. Two dimensional theoretical chemical descriptors were generated for each chemical using the Toxicity Estimation Software Tool. The model was developed through augmented Markov blanket discovery from the data set with the MoA broad classifications as a target node. From cross validation, the overall precision for the model was 80.2% with a R2 of 0.959. The best precision was for the AChEI MoA (93.5%) where 257 chemicals out of 275 were correctly classified. Model precision was poorest for the reactivity MoA (48.5%) where 48 out of 99 reactive chemicals were correctly classified. Narcosis represented the largest class within the MoA dataset and had a precision and reliability of 80.0%, reflecting the global precision across all of the MoAs. False negatives for narcosis most often fell into electron transport inhibition, neurotoxicity or reactivity MoAs. False negatives for all other MoAs were most often narcosis. A probabilistic sensitivity analysis was undertaken for each MoA to examine the sensitivity to individual and multiple descriptor findings. The results show that the Markov blanket of a structurally

Improvement of the coagulation/flocculation process using a combination of Moringa oleifera lam with anionic polymer in water treatment.

PubMed

Bongiovani, Milene Carvalho; Camacho, Franciele Pereira; Nishi, Letícia; Coldebella, Priscila Ferri; Valverde, Karina Cardoso; Vieira, Angélica Marquetotti Salcedo; Bergamasco, Rosângela

2014-01-01

The objective of this study is to investigate the impacts of anionic polymer as a flocculant aid on the coagulation/flocculation performance with a saline solution of Moringa oleifera as a coagulant to provide larger flocs and decrease the time sedimentation. For the tests, raw water was used from Pirapó River Basin (Maringá, Paraná, Brazil). Optimization of coagulation/flocculation tests was initially performed in a jar-test with a dosage of M. oleifera Lam (crude extract--MO, oil-extracted with ethanol--MO (et) and hexane--MO (hex) 1% m/v) as the coagulant that ranged from 10 to 60 mg L(-1) and of the anionic polymer 0.1% as a flocculant aid with a dosage that ranged from 0 to 0.4 mg L(-1). The parameters analysed were colour, turbidity and compounds with absorption in UV254nm. In view of the statistical analysis results, MO (hex) with a dosage of 30 mg L(-1) was chosen as a coagulant for the next tests of coagulation/flocculation. When anionic polymer was used alone (0.0 mg L(-1) of MO (hex)), parameters were not removed and there was no generation of heavy flocs as compared with the combination of MO (hex) with the anionic polymer. Statistical analysis showed that MO (hex) obtained the highest removals of the parameters analysed in lower dosages and no significant increase in parameters removal was observed when the polymer dosage was increased. The efficacy of the coagulant +/- anionic polymer was optimal when 30mg L(-1) of MO (hex) was used as a coagulant and 0.1 mg L(-1) of the anionic polymer was used as a flocculant aid, decreasing the time sedimentation from 1 h to 15 min.

Carbon-based coating containing ultrafine MoO2 nanoparticles as an integrated anode for high-performance lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Quanyi; Yang, Qi; Zhao, Yanhong; Wan, Bin

2017-10-01

Copper-supported MoO2-C composite as an integrated anode with excellent battery performance was synthesized by a facile knife coating technique followed by heat treatment in a vacuum. The obtained samples were characterized by X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), thermal analysis, nitrogen adsorption and desorption analysis, field emission scanning microscopy (FESEM), and transmission electron microscopy (TEM). The results show the MoO2-C composite coating is comprised of a porous carbon matrix with a pore size of 1-3 nm and ultrafine MoO2 nanoparticles with a size of 5-10 nm encapsulated inside, the coating is tightly attached on the surface of copper foil, and the interface between them is free of cracks. Stable PAN-DMF-H2O system containing ammonium molybdate suitable for knife coating technique and the MoO2-C composite with ultrafine MoO2 nanoparticles encapsulated in the carbon matrix can be prepared through controlling amount of added ammonium molybdate solution. The copper-supported MoO2-C composite coating can be directly utilized as the integrated anode for lithium-ion batteries (LIBs). It delivers a capacity of 814 mA h g-1 at a current density of 100 mA g-1 after 100 cycles without apparent capacity fading. Furthermore, with increase of current densities to 200, 500, 1000, 2000, and 5000 mA g-1, it exhibits average capacities of 809, 697, 568, 383, and 188 mA h g-1. Its outstanding electrochemical performance is attributed to combined merits of integrated anode and structure with ultrafine MoO2 nanoparticles embedded in the porous carbon matrix.

Reaction of BH4- with [Mo2Cp2(mu-SMe)n] species to give tetrahydroborato, hydrido or dimetallaborane compounds: control of product by ancillary ligands.

PubMed

Cabon, Nolwenn; Petillon, Francois Y; Schollhammer, Philippe; Talarmin, Jean; Muir, Kenneth W

2004-09-07

The reaction of mono- or dichloro-dimolybdenum(III) complexes [Mo2Cp2(mu-SMe)2(mu-Cl)(mu-Y)] (Cp=eta5-C5H5; 1, Y=SMe; 2, Y=PPh2; 3, Y=Cl) with NaBH4 at room temperature gave in high yields tetrahydroborato (8), hydrido (9) or metallaborane (12) complexes depending on the ancillary ligands. The correct formulation of derivatives and has been unambigously determined by X-ray diffraction methods. That of the hydrido compound 9 has been established in solution by NMR analysis and confirmed by an X-ray study of the mu-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-PPh2)(mu-N=CHMe)] (10) obtained from the insertion of acetonitrile into the Mo-H bond of 9. Reaction of NaBH4 with nitrile derivatives, [Mo2Cp2(mu-SMe)4-n(CH3CN)2n]n+(5, n=1; 6 n=2), afforded the tetrahydroborato compound 8, together with a mu-azavinylidene species [Mo2Cp2(mu-SMe)3(mu-N=CHMe)](14), when n=1, and the metallaborane complex 12, together with a mixed borohydrato-azavinylidene derivative [Mo2Cp2(mu-SMe)2(mu-BH4)(mu-N=CHMe)] (13), when n=2. The molecular structures of these complexes have been confirmed by X-ray analysis. Preparations of some of the starting complexes (3 and 4) are also described, as are the molecular structures of the precursors [Mo2Cp2(mu-SMe)2(mu-X)(mu-Y)] (1, X/Y=Cl/SMe; 2, X/Y=Cl/PPh2; 4, X/Y=SMe/PPh2).

Structural, morphological, and optical characterizations of Mo, CrN and Mo:CrN sputtered coatings for potential solar selective applications

NASA Astrophysics Data System (ADS)

Ibrahim, Khalil; Mahbubur Rahman, M.; Taha, Hatem; Mohammadpour, Ehsan; Zhou, Zhifeng; Yin, Chun-Yang; Nikoloski, Aleksandar; Jiang, Zhong-Tao

2018-05-01

Mo, CrN, and Mo:CrN sputtered coatings synthesized onto silicon Si(100) substrates were investigated as solar selective surfaces and their potential applications in optical devices. These coatings were characterized using XRD, SEM, UV-vis, and FTIR techniques. XRD investigation, showed a change in CrN thin film crystallite characteristic due to Mo doping. Compared to the CrN coating, the Mo:CrN film has a higher lattice parameter and lower grain size of 4.19 nm and 106.18 nm, respectively. FESEM morphology confirmed the decrement in Mo:CrN crystal size due to Mo doping. Optical analysis showed that in the visible range of the solar spectrum, the CrN coatings exhibit the highest solar absorptance of 66% while the lowest thermal emittance value of 5.67 was recorded for the CrN coating doped with Mo. Consequently, the highest solar selectivity of 9.6, and the energy band-gap of 2.88 eV were achieved with the Mo-doped CrN coatings. Various optical coefficients such as optical absorption coefficient, refractive index, extinction coefficient, real and imaginary parts of dielectric constants, and energy loss functions of these coatings were also estimated from the optical reflectance data recorded in the wavelength range of 190-2300 nm.

Investigation on nonlinear optical properties of MoS2 nanoflakes grown on silicon and quartz substrates

NASA Astrophysics Data System (ADS)

Bayesteh, Samaneh; Zahra Mortazavi, Seyedeh; Reyhani, Ali

2018-05-01

In this study, MoS2 nanoflakes were directly grown on different substrates—Si/SiO2 and quartz—by one-step thermal chemical vapor deposition using MoO3 and sulfide powders as precursors. Scanning electron microscopy and x-ray diffraction patterns demonstrated the formation of MoS2 structures on both substrates. Moreover, UV-visible and photoluminescence analysis confirmed the formation of MoS2 few-layer structures. According to Raman spectroscopy, by assessment of the line width and frequency shift differences between the and A 1g, it was inferred that the MoS2 grown on the silicon substrate was monolayer and that grown on the quartz substrate was multilayer. In addition, open-aperture and close-aperture Z-scan techniques were employed to study the nonlinear optical properties including nonlinear absorption and nonlinear refraction of the grown MoS2. All experiments were performed using a diode laser with a wavelength of 532 nm as the light source. It is noticeable that both samples demonstrate obvious self-defocusing behavior. The monolayer MoS2 grown on the silicon substrate displayed considerable two-photon absorption while, the multilayer MoS2 synthesized on the quartz exhibited saturable absorption. In general, few-layered MoS2 would be useful for the development of nanophotonic devices like optical limiters, optical switchers, etc.

Analysis of optical and electronic properties of MoS2 for optoelectronics and FET applications

NASA Astrophysics Data System (ADS)

Ullah, Muhammad S.; Yousuf, Abdul Hamid Bin; Es-Sakhi, Azzedin D.; Chowdhury, Masud H.

2018-04-01

Molybdenum disulfide (MoS2) is considered as a promising alternative to conventional semiconductor materials that used in the IC industry because of its novel properties. In this paper, we explore the optical and electronic properties of MoS2 for photodetector and transistors applications. This simulation is done using `DFT materials properties simulator'. Our findings show that mono- and multi-layer MoS2 is suitable for conventional and tunnel FET applications due to direct and indirect band-gap respectively. The bulk MoS2 crystal, which are composed of stacked layers have indirect bandgap and mono-layer MoS2 crystal form direct bandgap at the K-point of Brillouin zone. Indirect bandgap of bulk MoS2 crystal implies that phonons need to be involved in band-to-band tunneling (BTBT) process. Degenerately doped semiconductor, which is basically spinning the Fermi level, changing the DOS profile, and thinning the indirect bandgap that allow tunneling from valence band to conduction band. The optical properties of MoS2 is explored in terms of Absorption coefficient, extinction coefficient and refractive index. Our results shows that a MoS2 based photodetector can be fabricate to detect light in the visible range (below 500nm). It is also observed that the MoS2 is most sensitive for the light of wavelength 450nm.

Adsorption of DNA/RNA nucleobases onto single-layer MoS2 and Li-Doped MoS2: A dispersion-corrected DFT study

NASA Astrophysics Data System (ADS)

Sadeghi, Meisam; Jahanshahi, Mohsen; Ghorbanzadeh, Morteza; Najafpour, Ghasem

2018-03-01

The kind of sensing platform in nano biosensor plays an important role in nucleic acid sequence detection. It has been demonstrated that graphene does not have an intrinsic band gap; therefore, transition metal dichalcogenides (TMDs) are desirable materials for electronic base detection. In the present work, a comparative study of the adsorption of the DNA/RNA nucleobases [Adenine (A), Cytosine (C) Guanine (G), Thymine (T) and Uracil (U)] onto the single-layer molybdenum disulfide (MoS2) and Li-doped MoS2 (Li-MoS2) as a sensing surfaces was investigated by using Dispersion-corrected Density Functional Theory (D-DFT) calculations and different measure of equilibrium distances, charge transfers and binding energies for the various nucleobases were calculated. The results revealed that the interactions between the nucleobases and the MoS2 can be strongly enhanced by introducing metal atom, due to significant charge transfer from the Li atom to the MoS2 when Lithium is placed on top of the MoS2. Furthermore, the binding energies of the five nucleobases were in the range of -0.734 to -0.816 eV for MoS2 and -1.47 to -1.80 eV for the Li-MoS2. Also, nucleobases were adsorbed onto MoS2 sheets via the van der Waals (vdW) force. This high affinity and the renewable properties of the biosensing platform demonstrated that Li-MoS2 nanosheet is biocompatible and suitable for nucleic acid analysis.

Large-area, continuous and high electrical performances of bilayer to few layers MoS2 fabricated by RF sputtering via post-deposition annealing method

PubMed Central

Hussain, Sajjad; Singh, Jai; Vikraman, Dhanasekaran; Singh, Arun Kumar; Iqbal, Muhammad Zahir; Khan, Muhammad Farooq; Kumar, Pushpendra; Choi, Dong-Chul; Song, Wooseok; An, Ki-Seok; Eom, Jonghwa; Lee, Wan-Gyu; Jung, Jongwan

2016-01-01

We report a simple and mass-scalable approach for thin MoS2 films via RF sputtering combined with the post-deposition annealing process. We have prepared as-sputtered film using a MoS2 target in the sputtering system. The as-sputtered film was subjected to post-deposition annealing to improve crystalline quality at 700 °C in a sulfur and argon environment. The analysis confirmed the growth of continuous bilayer to few-layer MoS2 film. The mobility value of ~29 cm2/Vs and current on/off ratio on the order of ~104 were obtained for bilayer MoS2. The mobility increased up to ~173–181 cm2/Vs, respectively, for few-layer MoS2. The mobility of our bilayer MoS2 FETs is larger than any previously reported values of single to bilayer MoS2 grown on SiO2/Si substrate with a SiO2 gate oxide. Moreover, our few-layer MoS2 FETs exhibited the highest mobility value ever reported for any MoS2 FETs with a SiO2 gate oxide. It is presumed that the high mobility behavior of our film could be attributed to low charged impurities of our film and dielectric screening effect by an interfacial MoOxSiy layer. The combined preparation route of RF sputtering and post-deposition annealing process opens up the novel possibility of mass and batch production of MoS2 film. PMID:27492282

Urine Odor

MedlinePlus

... doctor. Brunzel NA. Physical examination of urine. In: Fundamentals of Urine and Body Fluid Analysis. 3rd ed. St. Louis, Mo.: Saunders Elsevier; 2013:97. McPherson RA, et al., eds. Henry's Clinical Diagnosis and Management by Laboratory Methods. 23rd ed. St. Louis, Mo.: ...

RadNet Air Data From Jefferson City, MO

EPA Pesticide Factsheets

This page presents radiation air monitoring and air filter analysis data for Jefferson City, MO from EPA's RadNet system. RadNet is a nationwide network of monitoring stations that measure radiation in air, drinking water and precipitation.

RadNet Air Data From St. Louis, MO

EPA Pesticide Factsheets

This page presents radiation air monitoring and air filter analysis data for St. Louis, MO from EPA's RadNet system. RadNet is a nationwide network of monitoring stations that measure radiation in air, drinking water and precipitation.

Effect of Mo contents on corrosion behaviors of welded duplex stainless steel

NASA Astrophysics Data System (ADS)

Bae, Seong Han; Lee, Hae Woo

2013-05-01

The corrosion behaviour and change of the phase fraction in welded 24Cr Duplex stainless steel was investigated for different chemical composition ranges of Mo contents. Filler metal was produced by fixing the contents of Cr, Ni, N, and Mn while adjusting the Mo content to 0.5, 1.4, 2.5, 3.5 wt%. The δ-ferrite fraction was observed to increase as the content of Mo increased. A polarisation test conducted in a salt solution, indicated the pitting corrosion potential increased continuously to 3.5 wt% Mo, while the corrosion potential changed most between 0.5 and 1.41 wt% Mo. The location of the pitting corrosion in 0.5 wt% Mo steel was randomly distributed, but it occurred selectively at the grain boundary between the γ- and δ-ferrite phases in 1.4, 2.5 and 3.5 wt% Mo steel. Energy dispersive X-ray spectroscopy mapping analysis showed that areas deficient in Cr, Mo, and Ni occurred around the grain boundary of the γ- and δ-ferrite phases. Non-metallic inclusions are thought to act as initiation points for the pitting corrosion that occurs in the salt solution initially as a result of the potential difference between the matrix structure and the incoherent inclusions.

The Magnaporthe oryzae Alt A 1-like protein MoHrip1 binds to the plant plasma membrane.

PubMed

Zhang, Yi; Liang, Yingbo; Dong, Yijie; Gao, Yuhan; Yang, Xiufen; Yuan, Jingjing; Qiu, Dewen

2017-10-07

MoHrip1, a protein isolated from Magnaporthe oryzae, belongs to the Alt A 1 (AA1) family. mohrip1 mRNA levels showed inducible expression throughout the infection process in rice. To determine the location of MoHrip1 in M. oryzae, a mohrip1-gfp mutant was generated. Fluorescence microscopy observations and western blotting analysis showed that MoHrip1 was both present in the secretome and abundant in the fungal cell wall. To obtain MoHrip1 protein, we carried out high-yield expression of MoHrip1 in Pichia pastoris. Treatment of tobacco plants with MoHrip1 induced the formation of necrosis, accumulation of reactive oxygen species and expression of several defense-related genes, as well as conferred disease resistance. By fusion to green fluorescent protein, we showed that MoHrip1 was able to bind to the tobacco and rice plant plasma membrane, causing rapid morphological changes at the cellular level, such as cell shrinkage and chloroplast disorganization. These findings indicate that MoHrip1 is a microbe-associated molecular pattern that is perceived by the plant immune system. This is the first study on an AA1 family protein that can bind to the plant plasma membrane. Copyright © 2017 Elsevier Inc. All rights reserved.

Fullerene-like (IF) Nb(x)Mo(1-x)S2 nanoparticles.

PubMed

Deepak, Francis Leonard; Cohen, Hagai; Cohen, Sidney; Feldman, Yishay; Popovitz-Biro, Ronit; Azulay, Doron; Millo, Oded; Tenne, Reshef

2007-10-17

IF-Mo1-xNbxS2 nanoparticles have been synthesized by a vapor-phase reaction involving the respective metal halides with H2S. The IF-Mo1-xNbxS2 nanoparticles, containing up to 25% Nb, were characterized by a variety of experimental techniques. Analysis of the powder X-ray powder diffraction, X-ray photoelectron spectroscopy, and different electron microscopy techniques shows that the majority of the Nb atoms are organized as nanosheets of NbS2 within the MoS2 host lattice. Most of the remaining Nb atoms (3%) are interspersed individually and randomly in the MoS2 host lattice. Very few Nb atoms, if any, are intercalated between the MoS2 layers. A sub-nanometer film of niobium oxide seems to encoat the majority of the nanoparticles. X-ray photoelectron spectroscopy in the chemically resolved electrical measurement mode (CREM) and scanning probe microscopy measurements of individual nanoparticles show that the mixed IF nanoparticles are metallic independent of the substitution pattern of the Nb atoms in the lattice of MoS2 (whereas unsubstituted IF-MoS2 nanoparticles are semiconducting). Furthermore the IF-Mo1-xNbxS2 nanoparticles are found to exhibit interesting single electron tunneling effects at low temperatures.

First-principles study on the electronic structure and elastic properties of Mo2NiB2 doped with V

NASA Astrophysics Data System (ADS)

Li, Jinming; Li, Xiaobo; Gao, Haiyun; Peng, Dian

2018-04-01

The content of this study is to analyze the electronic structure and elastic properties that the different structures of Mo2NiB2 and doping with V of the tetragonal M3B2 (Mo2Ni1‑xVxB2 and Mo2‑yNi1‑yV2yB2) (x = 0.25, 0.5, 0.75 and y = 0.125, 0.25, 0.375) by first-principles calculations based on density functional theory (DFT) combined with the projection-plus-wave method. But the calculated formation energy shows that V atoms prefer to substitute the Mo and Ni atoms of the tetragonal Mo2NiB2. Moreover, with the increase of V content, the formation enthalpy of tetragonal Mo2NiB2 is reduced, and the formation enthalpy of Mo1.625Ni0.625V0.75B2 is the least as ‑53.23 kJ/mol. The calculated elastic constant suffices the condition of mechanical stability, indicate that they are stable. The calculated elastic modulus illustrates that Mo2NiB2 having better mechanical properties when V elements are at Mo and Ni sites instead of Ni sites. The calculated and analyzed density of states of Mo1.625Ni0.625V0.75B2 has the smallest the density of states at the Fermi level indicating that it has the more stable structure. For the theoretical analysis of the first-principles calculations, the addition of 15 atom% of the V and V doping modes of Mo and Ni are preferentially replaced by V atoms of Mo2NiB2 ternary boride has the best performance.

Crystallization of a barium-aluminosilicate glass

NASA Technical Reports Server (NTRS)

Drummond, C. H., III; Lee, W. E.; Bansal, N. P.; Hyatt, M. J.

1989-01-01

The crystallization of a celsian glass composition was investigated as a possible high-temperature ceramic matrix material. Heat treatments invariably resulted in crystallization of the hexaclesian phase unless a flux, such as lithia, was added or a nucleating agent used (e.g., celsian seeds). TEM analysis revealed complex microstructures. Glasses with Mo additions contained hexacelsian, mullite, and an Mo-rich glass. Li2O additions stabilized celsian but mullite and Mo-rich glass were still present.

An efficient linear-scaling CCSD(T) method based on local natural orbitals.

PubMed

Rolik, Zoltán; Szegedy, Lóránt; Ladjánszki, István; Ladóczki, Bence; Kállay, Mihály

2013-09-07

An improved version of our general-order local coupled-cluster (CC) approach [Z. Rolik and M. Kállay, J. Chem. Phys. 135, 104111 (2011)] and its efficient implementation at the CC singles and doubles with perturbative triples [CCSD(T)] level is presented. The method combines the cluster-in-molecule approach of Li and co-workers [J. Chem. Phys. 131, 114109 (2009)] with frozen natural orbital (NO) techniques. To break down the unfavorable fifth-power scaling of our original approach a two-level domain construction algorithm has been developed. First, an extended domain of localized molecular orbitals (LMOs) is assembled based on the spatial distance of the orbitals. The necessary integrals are evaluated and transformed in these domains invoking the density fitting approximation. In the second step, for each occupied LMO of the extended domain a local subspace of occupied and virtual orbitals is constructed including approximate second-order Mo̸ller-Plesset NOs. The CC equations are solved and the perturbative corrections are calculated in the local subspace for each occupied LMO using a highly-efficient CCSD(T) code, which was optimized for the typical sizes of the local subspaces. The total correlation energy is evaluated as the sum of the individual contributions. The computation time of our approach scales linearly with the system size, while its memory and disk space requirements are independent thereof. Test calculations demonstrate that currently our method is one of the most efficient local CCSD(T) approaches and can be routinely applied to molecules of up to 100 atoms with reasonable basis sets.

DESIGN ANALYSIS FOR THE NAVAL SNF WASTE PACKAGE

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

T.L. Mitchell

2000-05-31

The purpose of this analysis is to demonstrate the design of the naval spent nuclear fuel (SNF) waste package (WP) using the Waste Package Department's (WPD) design methodologies and processes described in the ''Waste Package Design Methodology Report'' (CRWMS M&O [Civilian Radioactive Waste Management System Management and Operating Contractor] 2000b). The calculations that support the design of the naval SNF WP will be discussed; however, only a sub-set of such analyses will be presented and shall be limited to those identified in the ''Waste Package Design Sensitivity Report'' (CRWMS M&O 2000c). The objective of this analysis is to describe themore » naval SNF WP design method and to show that the design of the naval SNF WP complies with the ''Naval Spent Nuclear Fuel Disposal Container System Description Document'' (CRWMS M&O 1999a) and Interface Control Document (ICD) criteria for Site Recommendation. Additional criteria for the design of the naval SNF WP have been outlined in Section 6.2 of the ''Waste Package Design Sensitivity Report'' (CRWMS M&O 2000c). The scope of this analysis is restricted to the design of the naval long WP containing one naval long SNF canister. This WP is representative of the WPs that will contain both naval short SNF and naval long SNF canisters. The following items are included in the scope of this analysis: (1) Providing a general description of the applicable design criteria; (2) Describing the design methodology to be used; (3) Presenting the design of the naval SNF waste package; and (4) Showing compliance with all applicable design criteria. The intended use of this analysis is to support Site Recommendation reports and assist in the development of WPD drawings. Activities described in this analysis were conducted in accordance with the technical product development plan (TPDP) ''Design Analysis for the Naval SNF Waste Package (CRWMS M&O 2000a).« less

Spectroscopic Characterization of YedY: The Role of Sulfur Coordination in a Mo(V) Sulfite Oxidase Family Enzyme Form

PubMed Central

Yang, Jing; Rothery, Richard; Sempombe, Joseph

2011-01-01

Electronic paramagnetic resonance, electronic absorption, and magnetic circular dichroism spectroscopies have been performed on YedY, a SUOX fold protein with a Mo domain that is remarkably similar to that found in chicken sulfite oxidase, A. thaliana plant sulfite oxidase, and the bacterial sulfite dehydrogenase from S. novella. Low-energy dithiolene→Mo and cysteine thiolate→Mo charge transfer bands have been assigned for the first time in a Mo(V) form of a SUOX fold protein, and the spectroscopic data have been used to interpret the results of bonding calculations. The analysis shows that second coordination sphere effects modulate dithiolene and cysteine sulfur covalency contributions to the Mo bonding scheme. Namely, a more acute Ooxo-Mo-SCys-C dihedral angle results in increased cysteine thiolate S→Mo charge transfer and a high g1 in the EPR spectrum. The spectrosocopic results, coupled with the available structural data, indicate that these second coordination sphere effects may play key roles in modulating the active site redox potential, facilitating hole superexchange pathways for electron transfer regeneration, and affecting the type of reactions catalyzed by sulfite oxidase family enzymes. PMID:19860477

One-dimensional growth of hexagonal rods of metastable h-MoO3 using one-pot, rapid and environmentally benign supercritical fluid processing

NASA Astrophysics Data System (ADS)

Thangasamy, Pitchai; Shanmugapriya, Vadivel; Sathish, Marappan

2018-05-01

A facile and one-pot supercritical fluid method was demonstrated for the synthesis of phase pure crystalline h-MoO3 microrods within a short reaction time of 5 min at 400 °C. The formation of h-MoO3 was confirmed by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) and Raman spectroscopic analysis. Scanning electron microscopy (SEM) and Transmission electron microscopy (TEM) images clearly revealed the formation of hexagonal h-MoO3 rods. Further, photoluminescence emission peaks corresponding to band to band transition was observed in the h-MoO3 microrods. It was observed that when increasing the reaction time from 5 min to 30 min at 400 °C, h-MoO3 microrods undergoes disintegration to α-MoO3 thin nanorods. Interestingly, h-MoO3 microrods were also formed in a reaction time of 30 min at 400 °C when reducing the volume of nitric acid from 1 mL to ∼0.5 mL. The short reaction time and simple synthetic strategy makes this method can be suitable for the synthesis of other semiconductor nanomaterials for diverse applications.

Experimental and theoretical characterization of ordered MAX phases Mo{sub 2}TiAlC{sub 2} and Mo{sub 2}Ti{sub 2}AlC{sub 3}

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

Anasori, Babak; A.J. Drexel Nanomaterials Institute, Drexel University, Philadelphia, Pennsylvania 19104; Dahlqvist, Martin

2015-09-07

Herein, we report on the phase stabilities and crystal structures of two newly discovered ordered, quaternary MAX phases—Mo{sub 2}TiAlC{sub 2} and Mo{sub 2}Ti{sub 2}AlC{sub 3}—synthesized by mixing and heating different elemental powder mixtures of mMo:(3-m)Ti:1.1Al:2C with 1.5 ≤ m ≤ 2.2 and 2Mo: 2Ti:1.1Al:2.7C to 1600 °C for 4 h under Ar flow. In general, for m ≥ 2 an ordered 312 phase, (Mo{sub 2}Ti)AlC{sub 2}, was the majority phase; for m < 2, an ordered 413 phase (Mo{sub 2}Ti{sub 2})AlC{sub 3}, was the major product. The actual chemistries determined from X-ray photoelectron spectroscopy (XPS) are Mo{sub 2}TiAlC{sub 1.7} and Mo{sub 2}Ti{sub 1.9}Al{sub 0.9}C{sub 2.5}, respectively. High resolution scanning transmissionmore » microscopy, XPS and Rietveld analysis of powder X-ray diffraction confirmed the general ordered stacking sequence to be Mo-Ti-Mo-Al-Mo-Ti-Mo for Mo{sub 2}TiAlC{sub 2} and Mo-Ti-Ti-Mo-Al-Mo-Ti-Ti-Mo for Mo{sub 2}Ti{sub 2}AlC{sub 3}, with the carbon atoms occupying the octahedral sites between the transition metal layers. Consistent with the experimental results, the theoretical calculations clearly show that M layer ordering is mostly driven by the high penalty paid in energy by having the Mo atoms surrounded by C in a face-centered configuration, i.e., in the center of the M{sub n+1}X{sub n} blocks. At 331 GPa and 367 GPa, respectively, the Young's moduli of the ordered Mo{sub 2}TiAlC{sub 2} and Mo{sub 2}Ti{sub 2}AlC{sub 3} are predicted to be higher than those calculated for their ternary end members. Like most other MAX phases, because of the high density of states at the Fermi level, the resistivity measurement over 300 to 10 K for both phases showed metallic behavior.« less

Internal stresses in wear and corrosion resistant amorphous metallic coatings of (W/0.6/Re/0.4/)76B24 and (Mo/0.6/Ru/0.4/)82B18

NASA Technical Reports Server (NTRS)

Thakoor, A. P.; Lamb, J. L.; Williams, R. M.; Khanna, S. K.

1985-01-01

Hard protective coatings in the W-Re-B and Mo-Ru-B alloy systems have been deposited by magnetron sputtering onto soda-lime glass and heat-treated AISI 52100 steel substrates. X-ray diffraction has confirmed the amorphous nature of the as-deposited coatings, and their crystallization temperatures were determined by differential thermal analysis to be 1000 and 790 C for W-Re-B and Mo-Ru-B coatings, respectively. Both coatings exhibit high microhardness; Mo-Ru-B, in addition, has excellent corrosion resistance by comparison with pure Mo at high anodic potentials. Attention is given to the influence of internal stresses on the protective properties of the coatings deposited under different conditions.

Enhanced hydrogen evolution reaction on hybrids of cobalt phosphide and molybdenum phosphide

NASA Astrophysics Data System (ADS)

Fang, Si-Ling; Chou, Tsu-Chin; Samireddi, Satyanarayana; Chen, Kuei-Hsien; Chen, Li-Chyong; Chen, Wei-Fu

2017-03-01

Production of hydrogen from water electrolysis has stimulated the search of sustainable electrocatalysts as possible alternatives. Recently, cobalt phosphide (CoP) and molybdenum phosphide (MoP) received great attention owing to their superior catalytic activity and stability towards the hydrogen evolution reaction (HER) which rivals platinum catalysts. In this study, we synthesize and study a series of catalysts based on hybrids of CoP and MoP with different Co/Mo ratio. The HER activity shows a volcano shape and reaches a maximum for Co/Mo = 1. Tafel analysis indicates a change in the dominating step of Volmer-Hyrovský mechanism. Interestingly, X-ray diffraction patterns confirmed a major ternary interstitial hexagonal CoMoP2 crystal phase is formed which enhances the electrochemical activity.

The Electrochemical Behavior of Mo-Ta Alloy in Phosphoric Acid Solution for TFT-LCD Application.

PubMed

Lee, Sang-Hyuk; Kim, Byoung O; Seo, Jong Hyun

2015-10-01

Molybdenum-tantalum alloy thin film is a suitable material for the higher corrosion resistance and low resistivity for gate and data metal lines. In this study, Mo-Ta alloy thin films were prepared by using a DC magnetron co-sputtering system on a glass substrate. An abrupt increase in the etching rates of low Mo-Ta alloys was observed. From the observed impedance analysis, the defect densities in the MoTa oxide films increased from 5.4 x 10(21) (cm(-3)) to 8.02 x 10(21) (cm(-3)) up to the 6 at% of tantalum level; and above the 6 at% of tantalum level, the defect densities decreased. This electrochemical behavior is explained by the mechanical instability of the MoTa oxide film.

Effect of Mo-doping concentration on the physical behaviour of sprayed ZnO layers

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

Reddy, T. Sreenivasulu; Reddy, M. Vasudeva; Reddy, K. T. Ramakrishna, E-mail: ktrkreddy@gmail.com

2015-06-24

Mo-doped zinc oxide layers (MZO) have been prepared on cleaned glass substrates by chemical spray pyrolysis technique by varying Mo-doping concentration in the range, 0 – 5 at. %. The X-ray diffraction studies revealed that all the as prepared layers were polycrystalline in nature and exhibited wurtzite structure. The layers prepared with lower Mo-doping concentration (<2 at. %) were preferably oriented along the (100) plane, whereas in the case of higher Mo-doping concentration (>2 at. %), the films showed the (002) plane as the dominant peak. The optical analysis indicated that all the layers had an average optical transmittance ofmore » 80% in the visible region and the evaluated band gap varied in the range, 3.28 - 3.50 eV.« less

Tune color of single-phase LiGd(MoO4)2-X(WO4)X: Sm3+, Tb3+ via adjusting the proportion of matrix and energy transfer to create white-light phosphor

NASA Astrophysics Data System (ADS)

Wu, Hongyue; Yang, Junfeng; Wang, Xiaoxue; Gan, Shucai; Li, Linlin

2018-03-01

A series of LiGd(MO4)2: Sm3+, Tb3+ (M = Mo, W) phosphors was prepared by a conventional solid state reaction method. Powder X-Ray diffraction (XRD) analysis reveals that the compounds are of the same structure type. Their luminescent properties have been studied. The optimal doping concentrations are 8% for Sm3+ and 18% for Tb3+ in the LiGd(MoO4)2 host. Sm3+ and Tb3+ have different sensitivity to the Mo/W ratio. For LiGd(MoO4)2-X(WO4)X: Sm3+ (X = 0, 0.4, 0.8, 1.2, 1.6, 2.0), the strongest emission intensity is 1.766 times than that of the weakest, while 171 times for LiGd(MoO4)2-X(WO4)X: Tb3+. The experimental results show that Mo/W ratio strong influences on the properties of LiGd(MoO4)2-X(WO4)X: Tb3+. With the increasing of WO42- groups concentration, the shape of characteristic excitation peaks of Tb3+ is almost the same and the excitation intensity gradually increase. Moreover, the energy transfer from Tb3+ to Sm3+ has been realized in the co-doped phosphors. The experimental analysis and theoretical calculations reveal that the quadrupole-quadrupole interaction is the dominant mechanism for the Tb3+→Sm3+ energy transfer. Therefore, luminous intensity can be adjusted by different sensitivities to matrix composition and energy transfer from Tb3+→Sm3+. By this tuning color method, white-light-emitting phosphor has been prepared. The excitation wavelength is 378 nm, and this indicates that the white-light-emitting phosphor could be pumped by near-UV light.

Structures, thermal expansion properties and phase transitions of Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (0.0 {le} x {le} 2.0).

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

Cheng, Y. Z.; Wu, M. M.; Peng, J.

2007-05-03

Structures, thermal expansion properties and phase transitions of Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (0.0 {le} x {le} 2.0) have been investigated by X-ray diffraction and differential thermal analysis. The partial substitution of Er{sup 3+} for Fe{sup 3+} induces pronounced decreases in the phase transition temperature from monoclinic to orthorhombic structure. Rietveld analysis of the XRD data shows that both the monoclinic and orthorhombic Fe{sub 2}(MoO{sub 4}){sub 3}, as well as the orthorhombic Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (x {le} 0.8) have positive thermal expansion coefficients. However, the linear thermal expansion coefficients of Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} (x = 0.6-2.0)more » decrease with increasing content of Er{sup 3+} and for x {ge} 1.0, compounds Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} show negative thermal expansion properties. Attempts for making zero thermal expansion coefficient materials result in that very low negative thermal expansion coefficient of -0.60 x 10{sup -6} C in Er{sub 1.0}Fe{sub 1.0}(MoO{sub 4}){sub 3} is observed in the temperature range of 180-400 C, and zero thermal expansion is observed in Er{sub 0.8}Fe{sub 1.2}(MoO{sub 4}){sub 3} in the temperature range of 350-450 C. In addition, anisotropic thermal expansions are found for all the orthorhombic Er{sub x}Fe{sub 2-x}(MoO{sub 4}){sub 3} compounds, with negative thermal expansion coefficients along the a axes.« less

The Influence of Plasma-Based Nitriding and Oxidizing Treatments on the Mechanical and Corrosion Properties of CoCrMo Biomedical Alloy

NASA Astrophysics Data System (ADS)

Noli, Fotini; Pichon, Luc; Öztürk, Orhan

2018-04-01

Plasma-based nitriding and/or oxidizing treatments were applied to CoCrMo alloy to improve its surface mechanical properties and corrosion resistance for biomedical applications. Three treatments were performed. A set of CoCrMo samples has been subjected to nitriding at moderate temperatures ( 400 °C). A second set of CoCrMo samples was oxidized at 395 °C in pure O2. The last set of CoCrMo samples was nitrided and subsequently oxidized under the experimental conditions of previous sets (double treatment). The microstructure and morphology of the layers formed on the CoCrMo alloy were investigated by X-ray diffraction, Atomic Force Microscopy, and Scanning Electron Microscopy. In addition, nitrogen and oxygen profiles were determined by Glow Discharge Optical Emission Spectroscopy, Rutherford Backscattering Spectroscopy, Energy-Dispersive X-ray, and Nuclear Reaction Analysis. Significant improvement of the Vickers hardness of the CoCrMo samples after plasma nitriding was observed due to the supersaturated nitrogen solution and the formation of an expanded FCC γ N phase and CrN precipitates. In the case of the oxidized samples, Vickers hardness improvement was minimal. The corrosion behavior of the samples was investigated in simulated body fluid (0.9 pct NaCl solution at 37 °C) using electrochemical techniques (potentiodynamic polarization and cyclic voltammetry). The concentration of metal ions released from the CoCrMo surfaces was determined by Instrumental Neutron Activation Analysis. The experimental results clearly indicate that the CoCrMo surface subjected to the double surface treatment consisting in plasma nitriding and plasma oxidizing exhibited lower deterioration and better resistance to corrosion compared to the nitrided, oxidized, and untreated samples. This enhancement is believed to be due to the formation of a thicker and more stable layer.

A Descriptive Analysis of Studies on Behavioural Treatment of Drooling (1970-2005)

ERIC Educational Resources Information Center

Van der Burg, Jan J. W.; Didden, Robert; Jongerius, Peter H.; Rotteveel, Jan J.

2007-01-01

A descriptive analysis was conducted on studies on the behavioural treatment of drooling (published between 1970 and 2005). The 17 articles that met the inclusion criteria described 53 participants (mean age 14y 7mo, [SD 4y 9mo]; range 6-28y). Sex of 87% of the participants was reported: 28 male, 18 female. For 60% of the participants the degree…

Authigenic molybdenum formation in marine sediments: A link to pore water sulfide in the Santa Barbara Basin

USGS Publications Warehouse

Zheng, Yen; Anderson, Robert F.; VanGeen, A.; Kuwabara, J.

2000-01-01

Pore water and sediment Mo concentrations were measured in a suite of multicores collected at four sites along the northeastern flank of the Santa Barbara Basin to examine the connection between authigenic Mo formation and pore water sulfide concentration. Only at the deepest site (580 m), where pore water sulfide concentrations rise to >0.1 ??M right below the sediment water interface, was there active authigenic Mo formation. At shallower sites (550,430, and 340 m), where pore water sulfide concentrations were consistently <0.05 ??M, Mo precipitation was not occuring at the time of sampling. A sulfide concentration of ???0.1 ??M appears to be a threshold for the onset of Mo-Fe-S co-precipitation. A second threshold sulfide concentration of ???100 ??M is required for Mo precipitation without Fe, possibly as Mo-S or as particle-bound Mo. Mass budgets for Mo were constructed by combining pore water and sediment results for Mo with analyses of sediment trap material from Santa Barbara Basin as well as sediment accumulation rates derived from 210Pb. The calculations show that most of the authigenic Mo in the sediment at the deepest site is supplied by diffusion from overlying bottom waters. There is, however, a non-lithogenic particulate Mo associated with sinking particles that contributes ???15% to the total authigenic Mo accumulation. Analysis of sediment trap samples and supernant brine solutions indicates the presence of non-lithogenic particulate Mo, a large fraction of which is easily remobilized and, perhaps, associated with Mn-oxides. Our observations show that even with the very high flux of organic carbon reaching the sediment of Santa Barbara Basin, active formation of sedimentary authigenic Mo requires a bottom water oxygen concentration below 3 ??M. However, small but measurable rates of authigenic Mo accumulation were observed at sites where bottom water oxygen ranged between 5 and 23 ??M, indicating that the formation of authigenic Mo occured in the recent past, but not at the time of sampling. Copyright ?? 2000 Elsevier Science Ltd.

First-principles characterization of potassium intercalation in the hexagonal 2H-MoS2

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

Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.

2012-01-12

Periodic density functional theory calculations were performed to study the structural and electronic properties of potassium intercalated into hexagonal MoS{sub 2} (2H-MoS{sub 2}). Metallic potassium (K) atoms are incrementally loaded in the hexagonal sites of the interstitial spaces between MoS2 sheets of the 2H-MoS{sub 2} bulk structure generating 2H-KxMoS2 (0.125 {<=} x {<=} 1.0) structures. To accommodate the potassium atoms, the interstitial spacing c parameter in the 2H-MoS{sub 2} bulk expands from 12.816 {angstrom} in 2H-MoS{sub 2} to 16.086 {angstrom} in 2H-K{sub 0.125}MoS{sub 2}. The second lowest potassium loading concentration (K{sub 0.25}MoS{sub 2}) results in the largest interstitial spacing expansionmore » (to c = 16.726 {angstrom}). Our calculations show that there is a small gradual contraction of the interstitial spacing as the potassium loading increases with c = 14.839 {angstrom} for KMoS{sub 2}. This interstitial contraction is correlated with an in-plane expansion of the MoS{sub 2} sheets, which is in good agreement with experimental X-ray diffraction (XRD) measurements. The electronic analysis shows that potassium readily donates its 4s electron to the conduction band of the 2H-K{sub x}MoS{sub 2}, and is largely ionic in character. As a result of the electron donation, the 2H-K{sub x}MoS{sub 2} system changes from a semiconductor to a more metallic system with increasing potassium intercalation. For loadings 0.25 {<=} x {<=} 0.625, triangular Mo-Mo-Mo moieties are prominent and tend to form rhombitrihexagonal motifs. Intercalation of H{sub 2}O molecules that solvate the K atoms is likely to occur in catalytic conditions. The inclusion of two H{sub 2}O molecules per K atom in the K{sub 0.25}MoS{sub 2} structure shows good agreement with XRD measurements.« less

Facile solution-processed aqueous MoOx for feasible application in organic light-emitting diode

NASA Astrophysics Data System (ADS)

Zheng, Qinghong; Qu, Disui; Zhang, Yan; Li, Wanshu; Xiong, Jian; Cai, Ping; Xue, Xiaogang; Liu, Liming; Wang, Honghang; Zhang, Xiaowen

2018-05-01

Solution-processed techniques attract increasing attentions in organic electronics for their low-cost and scalable manufacturing. We demonstrate the favorite hole injection material of solution-processed aqueous MoOx (s-MoOx) with facile fabrication process and cast successful application to constructing efficient organic light-emitting diodes (OLEDs). Atomic force microscopy and X-ray photoelectron spectroscopy analysis show that s-MoOx behaves superior film morphology and non-stoichiometry with slight oxygen deficiency. With tris(8-hydroxy-quinolinato)aluminium as emitting layer, s-MoOx based OLED shows maximum luminous efficiency of 7.9 cd/A and power efficiency of 5.9 lm/W, which have been enhanced by 43.6% and 73.5%, respectively, in comparison with the counterpart using conventional vacuum thermal evaporation MoOx. Current-voltage, impedance-voltage, phase-voltage and capacitance-voltage characteristics of hole-only devices indicate that s-MoOx with two processes of "spin-coating/annealing" shows mostly enhanced hole injection capacity and thus promoting device performance. Our experiments provide an alternative approach for constructing efficient OLED with solution process.

Thermal conduction properties of Mo/Si multilayers for extreme ultraviolet optics

NASA Astrophysics Data System (ADS)

Bozorg-Grayeli, Elah; Li, Zijian; Asheghi, Mehdi; Delgado, Gil; Pokrovsky, Alexander; Panzer, Matthew; Wack, Daniel; Goodson, Kenneth E.

2012-10-01

Extreme ultraviolet (EUV) lithography requires nanostructured optical components, whose reliability can be influenced by radiation absorption and thermal conduction. Thermal conduction analysis is complicated by sub-continuum electron and phonon transport and the lack of thermal property data. This paper measures and interprets thermal property data, and their evolution due to heating exposure, for Mo/Si EUV mirrors with 6.9 nm period and Mo/Si thickness ratios of 0.4/0.6 and 0.6/0.4. We use time-domain thermoreflectance and the 3ω method to estimate the thermal resistance between the Ru capping layer and the Mo/Si multilayers (RRu-Mo/Si = 1.5 m2 K GW-1), as well as the out-of-plane thermal conductivity (kMo/Si 1.1 W m-1 K-1) and thermal anisotropy (η = 13). This work also reports the impact of annealing on thermal conduction in a co-deposited MoSi2 layer, increasing the thermal conductivity from 1.7 W m-1 K-1 in the amorphous phase to 2.8 W m-1 K-1 in the crystalline phase.

Expression and localization of exocytic and recycling Rabs from Magnaporthe oryzae in mammalian cells

PubMed Central

Qi, Yaoyao; Marlin, M. Caleb; Liang, Zhimin; Zhang, Dongmei; Zhou, Jie; Wang, Zonghua; Lu, Guodong; Li, Guangpu

2018-01-01

Rab GTPases are master regulators of intracellular membrane trafficking along endocytic and exocytic pathways. In this chapter, we began to characterize the exocytic and recycling Rabs from the filamentous fungus Magnaporthe oryzae (M. oryzae) that causes the rice blast disease. Among the 11 putative Rabs identified from the M. oryzae genome database (MoRabs), MoRab1, MoRab8, and MoRab11 appear orthologs of mammalian Rab1, Rab8, and Rab11 and likely function in exocytosis and endosomal recycling. To test this contention, we cloned, expressed, and determined intracellular localization of the three MoRabs in mammalian cells, in comparison to their human counterparts (hRabs). The MoRabs were well expressed as GFP fusion proteins and colocalized with the tdTomato-labeled hRabs on exocytic and recycling organelles, as determined by immunoblot analysis and confocal fluorescence microscopy. The colocalization supports the contention that the MoRabs are indeed Rab orthologs and may play important roles in the development and pathogenicity of M. oryzae. PMID:26360026

Status of LUMINEU program to search for neutrinoless double beta decay of 100Mo with cryogenic ZnMoO4 scintillating bolometers

NASA Astrophysics Data System (ADS)

Danevich, F. A.; Bergé, L.; Boiko, R. S.; Chapellier, M.; Chernyak, D. M.; Coron, N.; Devoyon, L.; Drillien, A.-A.; Dumoulin, L.; Enss, C.; Fleischmann, A.; Gastaldo, L.; Giuliani, A.; Gray, D.; Gros, M.; Hervé, S.; Humbert, V.; Ivanov, I. M.; Juillard, A.; Kobychev, V. V.; Koskas, F.; Loidl, M.; Magnier, P.; Makarov, E. P.; Mancuso, M.; de Marcillac, P.; Marnieros, S.; Marrache-Kikuchi, C.; Navick, X.-F.; Nones, C.; Olivieri, E.; Paul, B.; Penichot, Y.; Pessina, G.; Plantevin, O.; Poda, D. V.; Redon, T.; Rodrigues, M.; Shlegel, V. N.; Strazzer, O.; Tenconi, M.; Torres, L.; Tretyak, V. I.; Vasiliev, Ya. V.; Velazquez, M.; Viraphong, O.

2015-10-01

The LUMTNEU program aims at performing a pilot experiment on 0ν2β decay of 100Mo using radiopure ZnMoO4 crystals enriched in 100Mo operated as cryogenic scintillating bolometers. Large volume ZnMoO4 crystal scintillators (˜ 0.3 kg) were developed and tested showing high performance in terms of radiopurity, energy resolution and α/β particle discrimination capability. Zinc molybdate crystal scintillators enriched in 100Mo were grown for the first time by the low-thermal-gradient Czochralski technique with a high crystal yield and an acceptable level of enriched molybdenum irrecoverable losses. A background level of ˜ 0.5 counts/(yr keV ton) in the region of interest can be reached in a large detector array thanks to the excellent detectors radiopurity and particle discrimination capability, suppression of randomly coinciding events by pulse-shape analysis, and anticoincidence cut. These results pave the way to future sensitive searches based on the LUMTNEU technology, capable of approachingand exploring the inverted hierarchy region of the neutrino mass pattern.

SolarSoft Web Services

NASA Astrophysics Data System (ADS)

Freeland, S.; Hurlburt, N.

2005-12-01

The SolarSoft system (SSW) is a set of integrated software libraries, databases, and system utilities which provide a common programming and data analysis environment for solar physics. The system includes contributions from a large community base, representing the efforts of many NASA PI team MO&DA teams,spanning many years and multiple NASA and international orbital and ground based missions. The SSW general use libraries include Many hundreds of utilities which are instrument and mission independent. A large subset are also SOLAR independent, such as time conversions, digital detector cleanup, time series analysis, mathematics, image display, WWW server communications and the like. PI teams may draw on these general purpose libraries for analysis and application development while concentrating efforts on instrument specific calibration issues rather than reinvention of general use software. By the same token, PI teams are encouraged to contribute new applications or enhancements to existing utilities which may have more general interest. Recent areas of intense evolution include space weather applications, automated distributed data access and analysis, interfaces with the ongoing Virtual Solar Observatory efforts, and externalization of SolarSoft power through Web Services. We will discuss the current status of SSW web services and demonstrate how this facilitates accessing the underlying power of SolarSoft in more abstract terms. In this context, we will describe the use of SSW services within the Collaborative Sun Earth Connector environment.

Chemistry of the oxophosphinidene ligand. 2. Reactivity of the anionic complexes [MCp{P(O)R*}(CO)(2)](-) (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3)) toward electrophiles based on elements different from carbon.

PubMed

Alonso, María; Alvarez, M Angeles; García, M Esther; Ruiz, Miguel A; Hamidov, Hayrullo; Jeffery, John C

2010-12-20

The anionic oxophosphinidene complexes (H-DBU)[MCp{P(O)R*}(CO)(2)] (M = Mo, W; R* = 2,4,6-C(6)H(2)(t)Bu(3); Cp = η(5)-C(5)H(5), DBU = 1,8-diazabicyclo [5.4.0] undec-7-ene) displayed multisite reactivity when faced with different electrophilic reagents. The reactions with the group 14 organochloride compounds ER(4-x)Cl(x) (E = Si, Ge, Sn, Pb) led to either phosphide-like, oxophosphinidene-bridged derivatives [MCp{P(OE')R*}(CO)(2)] (E' = SiMe(3), SiPh(3), GePh(3), GeMe(2)Cl) or to terminal oxophosphinidene complexes [MCp{P(O)R*}(CO)(2)(E')] (E' = SnPh(3), SnPh(2)Cl, PbPh(3); Mo-Pb = 2.8845(4) Å for the MoPb compound). A particular situation was found in the reaction with SnMe(3)Cl, this giving a product existing in both tautomeric forms, with the phosphide-like complex [MCp{P(OSnMe(3))R*}(CO)(2)] prevailing at room temperature and the tautomer [MCp{P(O)R*}(CO)(2)(SnMe(3))] being the unique species present below 203 K in dichloromethane solution. The title anions also showed a multisite behavior when reacting with transition-metal based electrophiles. Thus, the reactions with the complexes [M'Cp(2)Cl(2)] (M' = Ti, Zr) gave phosphide-like derivatives [MCp{P(OM')R*}(CO)(2)] (M = Mo, M' = TiCp(2)Cl, ZrCp(2)Cl; M = W, M' = ZrCp(2)Cl), displaying a bridging κ(1),κ(1)-P,O- oxophosphinidene ligand connecting MCp(CO)(2) and M'Cp(2)Cl metal fragments (W-P = 2.233(1) Å, O-Zr = 2.016(4) Å for the WZr compound]. In contrast, the reactions with the complex [AuCl{P(p-tol)(3)}] gave the metal-metal bonded derivatives trans-[MCp{P(O)R*}(CO)(2){AuP(p-tol)(3)}] (M = Mo, W; Mo-Au = 2.7071(7) Å). From all the above results it was concluded that the terminal oxophosphinidene complexes are preferentially formed under conditions of orbital control, while charge-controlled reactions tend to give derivatives with the electrophilic fragment bound to the oxygen atom of the oxophosphinidene ligand (phosphide-like, oxophosphinidene-bridged derivatives).

Re-assessing the Molybdenum Isotope Composition of Pre-GOE Seawater: Evidence for Dynamic Ocean Redox

NASA Astrophysics Data System (ADS)

Ostrander, C. M.; Kendall, B.; Roy, M.; Romaniello, S. J.; Nunn, S. J.; Gordon, G. W.; Olson, S. L.; Lyons, T. W.; Zheng, W.; Anbar, A. D.

2016-12-01

Molybdenum (Mo) isotope compositions of Archean shales can provide important insights into ocean and atmosphere redox dynamics prior to the Great Oxidation Event (GOE). Unfortunately, the relatively limited Mo isotope database and small number of sample sets for Archean shales do not allow for in-depth reconstructions and specifically make it difficult to differentiate global from local effects. To accurately estimate the Mo isotope composition of Archean seawater and better investigate the systematics of local and global redox, more complete sample sets are needed. We carried out a Mo isotope analysis of the euxinic 2.65 Ga Roy Hill Shale sampled in two stratigraphically correlated cores, and revisited the well-studied euxinic 2.5 Ga Mt. McRae Shale in higher resolution. Our data show contrasting Mo isotope values in the 2.65 Ga Roy Hill Shale between near- and offshore depositional environments, with systematically heavier isotope values in the near-shore environment. High-resolution analysis of the Mt. McRae Shale yields oscillating Mo concentrations and isotope values at the cm- to dm-scale during the well-characterized "whiff of O2" interval, with the heaviest isotope values measured during euxinic deposition. Variations in the measured isotope values within each section are primarily associated with redox changes in the local depositional environment and amount of detrital content. Both non-quantitative removal of Mo associated with incorporation into non-euxinic sediments and large detrital Mo contributions shift some measured isotopic compositions toward lighter values. This is readily apparent in the near-shore Roy Hill Shale section and the Mt. McRae Shale, but may not fully explain variations observed in the offshore Roy Hill Shale deposit. Here, euxinic deposition is not accompanied by Mo enrichments or isotopic compositions as heavy as the near-shore equivalent, even after detrital correction. This disparity between the near- and offshore environment could signify spatial variation in the Mo isotope composition of 2.65 Ga seawater and highlights the need for multi-site and high-resolution studies in order to best assess paleoenvironmental conditions.

Surface morphology of molybdenum silicide films upon low-energy ion beam sputtering.

PubMed

Gago, R; Jaafar, M; Palomares, F J

2018-07-04

The surface morphology of molybdenum silicide (Mo x Si 1-x ) films has been studied after low-energy Ar + ion beam sputtering (IBS) to explore eventual pattern formation on compound targets and, simultaneously, gather information about the mechanisms behind silicide-assisted nanopatterning of silicon surfaces by IBS. For this purpose, Mo x Si 1-x films with compositions below, equal and above the MoSi 2 stoichiometry (x  =  0.33) have been produced by magnetron sputtering, as assessed by Rutherford backscattering spectrometry (RBS). The surface morphology of silicon and silicide films before and after IBS has been imaged by atomic force microscopy (AFM), comprising conditions where typical nanodot or ripple patterns emerge on the former. In the case of irradiated Mo x Si 1-x surfaces, AFM shows a marked surface smoothing at normal incidence with and without additional Mo incorporation (the former results in nanodot patterns on Si). The morphological analysis also provides no evidence of ion-induced phase separation in irradiated Mo x Si 1-x . Contrary to silicon, Mo x Si 1-x surfaces also do not display ripple formation for (impurity free) oblique irradiations, except at grazing incidence conditions where parallel ripples emerge in a more evident fashion than in the Si counterpart. By means of RBS, irradiated Mo x Si 1-x films with 1 keV Ar + at normal incidence have also been used to measure experimentally the (absolute) sputtering yield and rate of Si and Mo x Si 1-x materials. The analysis reveals that, under the present working conditions, the erosion rate of silicides is larger than for silicon, supporting simulations from the TRIDYN code. This finding questions the shielding effect from silicide regions as roughening mechanism in metal-assisted nanopatterning of silicon. On the contrary, the results highlight the relevance of in situ silicide formation. Ripple formation on Mo x Si 1-x under grazing incidence is also attributed to the dominance of sputtering effects under this geometry. In conclusion, our work provides some insights into the complex morphological evolution of compound surfaces and solid experimental evidences regarding the mechanisms behind silicide-assisted nanopatterning.

Analysing the Stewardship Function in Botswana’s Health System: Reflecting on the Past, Looking to the Future

PubMed Central

Seitio-Kgokgwe, Onalenna; Gauld, Robin DC; Hill, Philip C.; Barnett, Pauline

2016-01-01

Background: In many parts of the world, ongoing deficiencies in health systems compromise the delivery of health interventions. The World Health Organization (WHO) identified four functions that health systems need to perform to achieve their goals: Efforts to strengthen health systems focus on the way these functions are carried out. While a number of studies on health systems functions have been conducted, the stewardship function has received limited attention. In this article, we evaluate the extent to which the Botswana Ministry of Health (MoH) undertook its stewardship role. Methods: We used the WHO Health Systems Performance Assessment Frame (HSPAF) to guide analysis of the stewardship function of the Botswana’s MoH focusing on formulation of national health policies, exerting influence through health regulation, and coalition building. Data were abstracted from published and unpublished documents. We interviewed 54 key informants comprising staff of the MoH (N = 40) and stakeholder organizations (N = 14). Data from documents was analyzed through content analysis. Interviews were transcribed and analyzed through thematic analysis. Results: A lack of capacity for health policy development was identified. Significant policy gaps existed in some areas. Challenges were reported in policy implementation. While the MoH made efforts in developing various statutes that regulated different aspects of the health system, some gaps existed in the regulatory framework. Poor enforcement of legislation was a challenge. Although the MoH had a high number of stakeholders, the mechanisms for stakeholder engagement in the planning processes were weak. Conclusion: Problems in the exercise of the stewardship function posed challenges in ensuring accountability and limited the health system’s ability to benefit from its stakeholders. Ongoing efforts to establish a District Health System under control of the MoH, attempts to improve service delivery at a national level and political will to strengthen public-private engagement mechanisms are some of the prospects that can improve the MoH’s stewardship function. PMID:28005550

Discontinuous precipitation in a nickel-free high nitrogen austenitic stainless steel on solution nitriding

NASA Astrophysics Data System (ADS)

Mohammadzadeh, Roghayeh; Akbari, Alireza; Grumsen, Flemming B.; Somers, Marcel A. J.

2017-10-01

Chromium-rich nitride precipitates in production of nickel-free austenitic stainless steel plates via pressurised solution nitriding of Fe-22.7Cr-2.4Mo ferritic stainless steel at 1473 K (1200 °C) under a nitrogen gas atmosphere was investigated. The microstructure, chemical and phase composition, morphology and crystallographic orientation between the resulted austenite and precipitates were investigated using optical microscopy, X-ray Diffraction (XRD), Scanning and Transmission Electron Microscopy (TEM) and Electron Back Scatter Diffraction (EBSD). On prolonged nitriding, Chromium-rich nitride precipitates were formed firstly close to the surface and later throughout the sample with austenitic structure. Chromium-rich nitride precipitates with a rod or strip-like morphology was developed by a discontinuous cellular precipitation mechanism. STEM-EDS analysis demonstrated partitioning of metallic elements between austenite and nitrides, with chromium contents of about 80 wt.% in the precipitates. XRD analysis indicated that the Chromium-rich nitride precipitates are hexagonal (Cr, Mo)2N. Based on the TEM studies, (Cr, Mo)2N precipitates presented a (1 1 1)γ//(0 0 2)(Cr, Mo)2N, ?γ//?(Cr, Mo)2N orientation relationship with respect to the austenite matrix. EBSD studies revealed that the austenite in the regions that have transformed into austenite and (Cr, Mo)2N have no orientation relation to the untransformed austenite.

Out-of-Plane Electromechanical Response of Monolayer Molybdenum Disulfide Measured by Piezoresponse Force Microscopy.

PubMed

Brennan, Christopher J; Ghosh, Rudresh; Koul, Kalhan; Banerjee, Sanjay K; Lu, Nanshu; Yu, Edward T

2017-09-13

Two-dimensional (2D) materials have recently been theoretically predicted and experimentally confirmed to exhibit electromechanical coupling. Specifically, monolayer and few-layer molybdenum disulfide (MoS 2 ) have been measured to be piezoelectric within the plane of their atoms. This work demonstrates and quantifies a nonzero out-of-plane electromechanical response of monolayer MoS 2 and discusses its possible origins. A piezoresponse force microscope was used to measure the out-of-plane deformation of monolayer MoS 2 on Au/Si and Al 2 O 3 /Si substrates. Using a vectorial background subtraction technique, we estimate the effective out-of-plane piezoelectric coefficient, d 33 eff , for monolayer MoS 2 to be 1.03 ± 0.22 pm/V when measured on the Au/Si substrate and 1.35 ± 0.24 pm/V when measured on Al 2 O 3 /Si. This is on the same order as the in-plane coefficient d 11 reported for monolayer MoS 2 . Interpreting the out-of-plane response as a flexoelectric response, the effective flexoelectric coefficient, μ eff * , is estimated to be 0.10 nC/m. Analysis has ruled out the possibility of elastic and electrostatic forces contributing to the measured electromechanical response. X-ray photoelectron spectroscopy detected some contaminants on both MoS 2 and its substrate, but the background subtraction technique is expected to remove major contributions from the unwanted contaminants. These measurements provide evidence that monolayer MoS 2 exhibits an out-of-plane electromechanical response and our analysis offers estimates of the effective piezoelectric and flexoelectric coefficients.

Clinical and histological evaluation of laser therapy in the treatment of oral mucositis in an animal model

NASA Astrophysics Data System (ADS)

Vitória, L. A.; Machado, R. M.; Oliveira, C. R. B.; Rodriguez, T. T.; Cangussu, M. C. T.; Mathias, C. C.; Ramalho, L. M. P.

2018-04-01

Oral mucositis (MO) is considered to be the most severe stomatologic complication associated with antineoplastic treatment, which may lead to its interruption. Several current clinical protocols have aproven the benefits of Laser Photobiomodulation (LP) in the prevention and control of MO, due to its analgesic and anti-inflammatory effects and its stimulation of mesenchymal cells proliferation. The objective of this study was to evaluate the action of laser in initial events of chemo-induced MO. Eight Hamsters were divided into 2 groups (G): GI positive control (induction of MO) and GII Laser (induction of MO + Laser therapy). MO was induced by two injections of 5-Fluorouracil followed by grooves in the mucosa of the cheek pouch. The PL (Diode Laser of Gallium and Aluminum Arsenide, λ660nm, 40mW, 2,4J/cm2 ) was performed on day 0 of the experiment and every 48 hours until day 6. On day 7 the mucosa was photographed for clinical analysis according to Lima et al., 2005 and the animals were killed, for bag removal and histological processing for Hematoxylin and Eosin (H / E) staining. After statistical analysis (Fischer's Exact) with a significance level 0.5%, it was concluded that the LP, according to the adopted protocol, was able to prevent MO, and most hamsters showed no visible clinical changes in the cheek pouch. Histologically, it was observed that LP reduced angiogenesis and recruitment of inflammatory cells in G2. According to the results obtained LP was effective in preventing and reducing the severity of oral mucositis.

Investigation on structural, thermal, optical and sensing properties of meta-stable hexagonal MoO(3) nanocrystals of one dimensional structure.

PubMed

Chithambararaj, Angamuthuraj; Bose, Arumugam Chandra

2011-01-01

Hexagonal molybdenum oxide (h-MoO(3)) was synthesized by a solution based chemical precipitation technique. Analysis by X-ray diffraction (XRD) confirmed that the as-synthesized powder had a metastable hexagonal structure. The characteristic vibrational band of Mo-O was identified from Fourier transform infrared spectroscopy (FT-IR). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) images clearly depicted the morphology and size of h-MoO(3.) The morphology study showed that the product comprises one-dimensional (1D) hexagonal rods. From the electron energy loss spectroscopy (EELS) measurement, the elemental composition was investigated and confirmed from the characteristic peaks of molybdenum and oxygen. Thermogravimetric (TG) analysis on metastable MoO(3) revealed that the hexagonal phase was stable up to 430 °C and above this temperature complete transformation into a highly stable orthorhombic phase was achieved. The optical band gap energy was estimated from the Kubelka-Munk (K-M) function and was found to be 2.99 eV. Finally, the ethanol vapor-sensing behavior was investigated and the sensing response was found to vary linearly as a function of ethanol concentration in the parts per million (ppm) range.

Prediction of the First Variceal Haemorrhage

PubMed Central

1997-01-01

We followed 87 cirrhotic patients with esophageal varices and without previous hemorrhage for a mean period of 24 mo to prospectively evaluate the occurance of variceal bleeding within (early) or after (late) 6 mo from entry and the contribution of portal Doppler ultrasound parameters to the prediction of early and late hemorrhage. Clinical, biochemical, endoscopic and portal Doppler ultrasound parameters were recorded at entry. Variceal bleeding occurred in 22 patients (25.3%). Nine (40.9%) bled within the first 6 mo. Cox regression analysis identified variceal size, cherry-red spots, serum bilirubin and congestion index of the portal vein (the ratio of portal vein [cross-sectional area] and portal blood flow velocity) as the only independent predictors of first variceal hemorrhage. Discriminant analysis was used to find the prognostic index cut off points to identify patients who bled within 6 mo (prognostic group 1) or after 6 mo (prognostic group 2) or remained free of bleeding (prognostic group 3). The cumulative proportion of patients correctly classified was 73% in prognostic group 1, 47% in prognostic group 2 and more than 80% in prognostic group 3. The addition of Doppler ultrasound flowmetry to clinical, biochemical and endoscopic parameter only improved the classification of patients with early bleeding. PMID:9184882

Diverging biological roles among human monocyte subsets in the context of tuberculosis infection.

PubMed

Balboa, Luciana; Barrios-Payan, Jorge; González-Domínguez, Erika; Lastrucci, Claire; Lugo-Villarino, Geanncarlo; Mata-Espinoza, Dulce; Schierloh, Pablo; Kviatcovsky, Denise; Neyrolles, Olivier; Maridonneau-Parini, Isabelle; Sánchez-Torres, Carmen; Sasiain, María del Carmen; Hernández-Pando, Rogelio

2015-08-01

Circulating monocytes (Mo) play an essential role in the host immune response to chronic infections. We previously demonstrated that CD16(pos) Mo were expanded in TB (tuberculosis) patients, correlated with disease severity and were refractory to dendritic cell differentiation. In the present study, we investigated whether human Mo subsets (CD16(neg) and CD16(pos)) differed in their ability to influence the early inflammatory response against Mycobacterium tuberculosis. We first evaluated the capacity of the Mo subsets to migrate and engage a microbicidal response in vitro. Accordingly, CD16(neg) Mo were more prone to migrate in response to different mycobacteria-derived gradients, were more resistant to M. tuberculosis intracellular growth and produced higher reactive oxygen species than their CD16(pos) counterpart. To assess further the functional dichotomy among the human Mo subsets, we carried out an in vivo analysis by adapting a hybrid mouse model (SCID/Beige, where SCID is severe combined immunodeficient) to transfer each Mo subset, track their migratory fate during M. tuberculosis infection, and determine their impact on the host immune response. In M. tuberculosis-infected mice, the adoptively transferred CD16(neg) Mo displayed a higher lung migration index, induced a stronger pulmonary infiltration of murine leucocytes expressing pro- and anti-inflammatory cytokines, and significantly decreased the bacterial burden, in comparison with CD16(pos) Mo. Collectively, our results indicate that human Mo subsets display divergent biological roles in the context of M. tuberculosis infection, a scenario in which CD16(neg) Mo may contribute to the anti-mycobacterial immune response, whereas CD16(pos) Mo might promote microbial resilience, shedding light on a key aspect of the physiopathology of TB disease.

XAS Study at Mo and Co K-Edges of the Sulfidation of a CoMo / Al2O3 Hydrotreating Catalyst

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

Pichon, C.; Gandubert, A. D.; Legens, C.

2007-02-02

Because of its impact on environment, the removal of sulfur is an indispensable step, called hydrotreatment, in the refining of petroleum. One of the most commonly used hydrotreating catalysts is CoMo-type catalyst which is composed of molybdenum disulfide slabs promoted by cobalt atoms (CoMoS phase) and well dispersed on a high specific area alumina. As far as the highest sulfur content allowed in gasoline and diesel is continually decreasing, more and more efficient and active hydrotreating catalysts are required. In order to optimize the reactivity of the CoMo-type catalyst in hydrotreatment, a better understanding of the processes used to producemore » the active phase (CoMoS slabs) of the catalyst is necessary. The study reported here deals with the sulfiding mechanism of the slabs and the influence of temperature on the phenomenon. Ex situ X-ray absorption spectroscopy (XANES and EXAFS) was used to study the evolution of the structure of CoMo-type catalyst sulfided at various temperatures (from 293 to 873 K). XAS analysis was performed at both molybdenum and cobalt K-edges to obtain a cross-characterization of the sulfidation of the slabs. It evidenced the formation of various compounds, including two molybdenum oxides, MoS3 (or MoS3-like compound) and Co9S8, at specific steps of the sulfiding process. It showed the role of intermediate played by MoS3 (or MoS3-like compound) during the formation of the slabs and the competition between the appearance of promoted slabs (CoMoS phase) and Co9S8. At last, it leaded to the proposal of a mechanism for the sulfidation of the catalyst.« less

Physical properties of monolithic U8 wt.%-Mo

NASA Astrophysics Data System (ADS)

Hengstler, R. M.; Beck, L.; Breitkreutz, H.; Jarousse, C.; Jungwirth, R.; Petry, W.; Schmid, W.; Schneider, J.; Wieschalla, N.

2010-07-01

As a possible high density fuel for research reactors, monolithic U8 wt.%-Mo ("U8Mo") was examined with regard to its structural, thermal and electric properties. X-ray diffraction by the Bragg-Brentano method was used to reveal the tetragonal lattice structure of rolled U8Mo. The specific heat capacity of cast U8Mo was determined by differential scanning calorimetry, its thermal diffusivity was measured by the laser flash method and its mass density by Archimedes' principle. From these results, the thermal conductivity of U8Mo in the temperature range from 40 °C to 250 °C was calculated; in the measured temperature range, it is in good accordance with literature data for UMo with 8 and 9 wt.% Mo, is higher than for 10 wt.% Mo and lower than for 5 wt.% Mo. The electric conductivity of rolled and cast U8Mo was measured by a four-wire method and the electron based part of the thermal conductivity calculated by the Wiedemann-Frantz law. Rolled and cast U8Mo was irradiated at about 150 °C with 80 MeV 127I ions to receive the same iodine ion density in the damage peak region as the fission product density in the fuel of a typical high flux reactor after the targeted nuclear burn-up. XRD analysis of irradiated U8Mo showed a change of the lattice parameters as well as the creation of UO 2 in the superficial sample regions; however, a phase change by irradiation was not observed. The determination of the electron based part of the thermal conductivity of the irradiated samples failed due to high measurement errors which are caused by the low thickness of the damage region in the ion irradiated samples.

GOATS - Orbitology Component

NASA Technical Reports Server (NTRS)

Haber, Benjamin M.; Green, Joseph J.

2010-01-01

The GOATS Orbitology Component software was developed to specifically address the concerns presented by orbit analysis tools that are often written as stand-alone applications. These applications do not easily interface with standard JPL first-principles analysis tools, and have a steep learning curve due to their complicated nature. This toolset is written as a series of MATLAB functions, allowing seamless integration into existing JPL optical systems engineering modeling and analysis modules. The functions are completely open, and allow for advanced users to delve into and modify the underlying physics being modeled. Additionally, this software module fills an analysis gap, allowing for quick, high-level mission analysis trades without the need for detailed and complicated orbit analysis using commercial stand-alone tools. This software consists of a series of MATLAB functions to provide for geometric orbit-related analysis. This includes propagation of orbits to varying levels of generalization. In the simplest case, geosynchronous orbits can be modeled by specifying a subset of three orbit elements. The next case is a circular orbit, which can be specified by a subset of four orbit elements. The most general case is an arbitrary elliptical orbit specified by all six orbit elements. These orbits are all solved geometrically, under the basic problem of an object in circular (or elliptical) orbit around a rotating spheroid. The orbit functions output time series ground tracks, which serve as the basis for more detailed orbit analysis. This software module also includes functions to track the positions of the Sun, Moon, and arbitrary celestial bodies specified by right ascension and declination. Also included are functions to calculate line-of-sight geometries to ground-based targets, angular rotations and decompositions, and other line-of-site calculations. The toolset allows for the rapid execution of orbit trade studies at the level of detail required for the early stage of mission concept development.

Mo(V) co-ordination in the periplasmic nitrate reductase from Paracoccus pantotrophus probed by electron nuclear double resonance (ENDOR) spectroscopy.

PubMed Central

Butler, Clive S; Fairhurst, Shirley A; Ferguson, Stuart J; Thomson, Andrew J; Berks, Ben C; Richardson, David J; Lowe, David J

2002-01-01

The first electron nuclear double resonance (ENDOR) study of a member of the Mo-bis-molybdopterin guanine dinucleotide family of molybdoenzymes is presented, using the periplasmic nitrate reductase from Paracoccus pantotrophus. Rapid freeze-quenched time-resolved EPR revealed that during turnover the intensity of a Mo(V) EPR signal known as High-g [resting] increases. This signal is split by two interacting protons that are not solvent-exchangeable. X-band proton-ENDOR analysis resolved broad symmetrical resonance features that arose from four classes of protons weakly coupled to the Mo(V). Signals from two of these were lost upon exchange into deuterated buffer, suggesting that they may originate from OH(-) or H(2)O groups. One of these signals was also lost when the enzyme was redox-cycled in the presence of azide. Since these protons are very weakly coupled OH/H(2)O groups, they are not likely to be ligated directly to the Mo(V). This suggests that protonation of a Mo(VI)zO group does not occur on reduction to Mo(V), but most probably accompanies reduction of Mo(V) to Mo(IV). A resonance feature from a more strongly coupled proton, that was not lost following exchange into deuterated buffer, could also be resolved at 22-24 MHz. The anisotropy of this feature, determined from ENDOR spectra collected at a range of field positions, indicated a Mo-proton distance of approx. 3.2 A, consistent with this being one of the beta-methylene protons of a Mo-Cys ligand. PMID:11964184

Supported molybdenum oxides as effective catalysts for the catalytic fast pyrolysis of lignocellulosic biomass

DOE PAGES

Murugappan, Karthick; Mukarakate, Calvin; Budhi, Sridhar; ...

2016-07-12

The catalytic fast pyrolysis (CFP) of pine was investigated over 10 wt% MoO 3/TiO 2 and MoO 3/ZrO 2 at 500 °C and H 2 pressures ≤ 0.75 bar. The product distributions were monitored in real time using a molecular beam mass spectrometer (MBMS). Both supported MoO 3 catalysts show different levels of deoxygenation based on the cumulative biomass to MoO 3 mass ratio exposed to the catalytic bed. For biomass to MoO 3 mass ratios <1.5, predominantly olefinic and aromatic hydrocarbons are produced with no detectable oxygen-containing species. For ratios ≥ 1.5, partially deoxygenated species comprised of furans andmore » phenols are observed, with a concomitant decrease of olefinic and aromatic hydrocarbons. For ratios ≥ 5, primary pyrolysis vapours break through the bed, indicating the onset of catalyst deactivation. Product quantification with a tandem micropyrolyzer-GCMS setup shows that fresh supported MoO 3 catalysts convert ca. 27 mol% of the original carbon into hydrocarbons comprised predominantly of aromatics (7 C%), olefins (18 C%) and paraffins (2 C%), comparable to the total hydrocarbon yield obtained with HZSM-5 operated under similar reaction conditions. In conclusion, post-reaction XPS analysis on supported MoO 3/ZrO 2 and MoO 3/TiO 2 catalysts reveal that ca. 50% of Mo surface species exist in their partially reduced forms (i.e., Mo 5+ and Mo 3+), and that catalyst deactivation is likely associated to coking.« less

The structure, thermal expansion and phase transition properties of Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} (x = 0, 1.0, 2.0) solid solutions

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

Liu, X.Z.; Hao, L.J.; Wu, M.M.

Graphical abstract: A polymorph with Gd{sub 2}Mo{sub 3}O{sub 12}-type structure (space group: Pba2) for negative thermal expansion material Ho{sub 2}Mo{sub 3}O{sub 12} is observed above 700 °C, this polymorphism could be effectively supressed by W-substiution for Mo, the give the temperature dependence of Pba2 phase contents for Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} (x = 0.0, 1.0, 2.0). - Highlights: • The solid solution Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12} was investigated by in situ X-ray diffraction. • It is found that the substitution slightly influence thermal expansion property. • A polymorph of Ho{sub 2}Mo{sub 3}O{sub 12} with Pba2 space group wasmore » observed above 700 °C. • The W-substitution for Mo effectively suppresses this transformation. - Abstract: Three solid solutions of Ho{sub 2}Mo{sub 3−x}W{sub x}O{sub 12}(x = 0, 1.0, 2.0) were prepared by solid state reaction method, the temperature dependent in-situ X-ray diffraction and thermal analysis were performed to investigate their structure and thermal expansion. All samples have orthorhombic structure(space group Pbcn# 60) with negative thermal expansion at the room temperature. the substitution of W for Mo enlarges the lattice constant and slightly influences the negative thermal expansion. An irreversible phase transformation to the Pba2 phase(Tb{sub 2}Mo{sub 3}O{sub 12} structure) was observed at high temperature for Mo-rich samples. This ploymorphism could be effectively suppressed by the W-substitution for Mo, this phenomenon could be explained by the lower electronegativity of W{sup 6+} than Mo{sup 6+}.« less

Detecting mammographically occult cancer in women with dense breasts using Radon Cumulative Distribution Transform: a preliminary analysis

NASA Astrophysics Data System (ADS)

Lee, Juhun; Nishikawa, Robert M.; Rohde, Gustavo K.

2018-02-01

We propose using novel imaging biomarkers for detecting mammographically-occult (MO) cancer in women with dense breast tissue. MO cancer indicates visually occluded, or very subtle, cancer that radiologists fail to recognize as a sign of cancer. We used the Radon Cumulative Distribution Transform (RCDT) as a novel image transformation to project the difference between left and right mammograms into a space, increasing the detectability of occult cancer. We used a dataset of 617 screening full-field digital mammograms (FFDMs) of 238 women with dense breast tissue. Among 238 women, 173 were normal with 2 - 4 consecutive screening mammograms, 552 normal mammograms in total, and the remaining 65 women had an MO cancer with a negative screening mammogram. We used Principal Component Analysis (PCA) to find representative patterns in normal mammograms in the RCDT space. We projected all mammograms to the space constructed by the first 30 eigenvectors of the RCDT of normal cases. Under 10-fold crossvalidation, we conducted quantitative feature analysis to classify normal mammograms and mammograms with MO cancer. We used receiver operating characteristic (ROC) analysis to evaluate the classifier's output using the area under the ROC curve (AUC) as the figure of merit. Four eigenvectors were selected via a feature selection method. The mean and standard deviation of the AUC of the trained classifier on the test set were 0.74 and 0.08, respectively. In conclusion, we utilized imaging biomarkers to highlight differences between left and right mammograms to detect MO cancer using novel imaging transformation.

Effects of composition modulation on the luminescence properties of Eu(3+) doped Li1-xAgxLu(MoO4)2 solid-solution phosphors.

PubMed

Cheng, Fangrui; Xia, Zhiguo; Molokeev, Maxim S; Jing, Xiping

2015-11-07

Double molybdate scheelite-type solid-solution phosphors Li1-xAgxLu1-y(MoO4)2:yEu(3+) were synthesized by the solid state reaction method, and their crystal structures and luminescence properties were investigated in detail. The composition modulation and structural evolution of this series of samples were studied and the selected AgEu(MoO4)2, AgLu(MoO4)2, LiLu(MoO4)2 and LiEu(MoO4)2 phases were analyzed based on the Rietveld refinement. Depending on the variation of the Li/Ag ratio in Li1-xAgxLu1-y(MoO4)2:yEu(3+) phosphors, the difference in the luminescence properties of Li1-xAgxLu1-y(MoO4)2:yEu(3+) phosphors was ascribed to two factors, one reason could be assigned to the coupling effect and the nonradiative transition between the energy levels of LixAg1-xLu(MoO4)2 matrices and the activator Eu(3+), another could be due to the near ultraviolet energy absorption and transmission efficiency between the charge-transfer (CT) band of O(2-)-Mo(6+) and the 4f → 4f emissive transitions of Eu(3+). The ultraviolet-visible diffuse reflection spectra (UV-vis DRS) and Raman spectra analysis were also used to verify the above mechanism.

Effect of alloying on screw dislocation structure in Mo: atomistic modelling approach with ab-initio parametrization

NASA Astrophysics Data System (ADS)

Gornostyrev, Yu. N.

2005-03-01

The plastic deformation in bcc metals is realized by the motion of screw dislocations with a complex star-like non-planar core. In this case, the direct investigation of the solute effect by first principles electronic structure calculations is a challenging problem for which we follow a combined approach that includes atomistic dislocation modelling with ab-initio parametrization of interatomic interactions. The screw dislocation core structure in Mo alloys is described within the model of atomic row displacements along a dislocation line with the interatomic row potential estimated from total energy full-potential linear muffin-tin orbital (FLMTO) calculations with the generalized gradient approximation (GGA) for the exchange-correlation potential. We demonstrate (1) that the solute effect on the dislocation structure is different for ``hard'' and ``easy'' cores and (2) that the softener addition in a ``hard'' core gives rise to a structural transformation into a configuration with a lower energy through an intermediate state. The softener solute is shown to disturb locally the three-fold symmetry of the dislocation core and the dislocation structure tends to the split planar core.

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.

Electronic and magnetic ordering induced by Mo- and Ru doping of the Mn site in CaMnO3 perovskite: EMR probing

NASA Astrophysics Data System (ADS)

Shames, A. I.; Auslender, M.; Rozenberg, E.; Gorodetsky, G.; Martin, C.; Maignan, A.

2005-05-01

X-band electron magnetic-resonance (EMR) measurements of polycrystalline CaMn1-yMoyO3 (0⩽y ⩽0.14) samples were performed at 120K⩽T⩽540K. The data obtained are compared with those of another electron-doped manganite system, CaMn1-xRuxO3 (0⩽x ⩽0.40). The observed anomalies of the EMR parameters correlate pretty well with the temperatures of antiferro-, ferromagneticlike, and orbital/charge-ordering transitions in these systems. However, a strong difference is observed between the resonant properties of Mo- and Ru doped series at both paramagnetic (PM) and magnetically ordered states. To describe such a difference, the energy-band diagrams, which comprise the deep impurity t2g-like states +eg-like conductive band for CaMn1-xRuxO3 and shallow impurity states+conductive band, both having eg-like symmetry, for CaMn1-yMoyO3, are proposed. Specific electrons' contribution to the EMR linewidth at PM temperatures is introduced for the considered systems.

Characterization of an Irradiated RERTR-7 Fuel Plate Using Transmission Electron Microscopy

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

J. Gan; D. D. Keiser, Jr.; B. D. Miller

2010-03-01

Transmission electron microscopy (TEM) has been used to characterize an irradiated fuel plate with Al-2Si matrix from the RERTR-7 experiment that was irradiated under moderate reactor conditions. The results of this work showed the presence of a bubble superlattice within the U-7Mo grains that accommodated fission gases (e.g., Xe). The presence of this structure helps the U-7Mo exhibit a stable swelling behaviour during irradiation. Furthermore, TEM analysis showed that the Si-rich interaction layers that develop around the fuel particles at the U-7Mo/matrix interface during fuel plate fabrication and irradiation become amorphous during irradiation, and in regions of the interaction layermore » that have relatively high Si concentrations the fission gas bubbles remain small and contained within the layer but in areas with lower Si concentrations the bubbles grow in size. An important question that remains to be answered about the irradiation behaviour of U-Mo dispersion fuels, is how do more aggressive irradiation conditions affect the behaviour of fission gases within the U-7Mo fuel particles and in the amorphous interaction layers on the microstructural scale that can be characterized using TEM? This paper discusses the results of TEM analysis that was performed on a sample taken from an irradiated RERTR-7 fuel plate with Al-2Si matrix. This plate was exposed to more aggressive irradiation conditions than was the sample taken from the RERTR-6 plate. The microstructural features present within the U-7Mo and the amorphous interaction layers will be discussed. The results of this analysis will be compared to what was observed in the earlier RERTR-6 fuel plate characterization.« less

Modulating capacitive response of MoS2 flake by controlled nanostructuring through focused laser irradiation.

PubMed

Rani, Renu; Kundu, Anirban; Balal, Mohammad; Sheet, Goutam; Hazra, Kiran Shankar

2018-08-24

Unlike graphene nanostructures, various physical properties of nanostructured MoS 2 have remained unexplored due to the lack of established fabrication routes. Herein, we have reported unique electrostatic properties of MoS 2 nanostructures, fabricated in a controlled manner of different geometries on 2D flake by using focused laser irradiation technique. Electrostatic force microscopy has been carried out on MoS 2 nanostructures by varying tip bias voltage and lift height. The analysis depicts no contrast flip in phase image of the patterned nanostructure due to the absence of free surface charges. However, prominent change in phase shift at the patterned area is observed. Such contrast changes signify the capacitive interaction between tip and nanostructures at varying tip bias voltage and lift height, irrespective of their shape and size. Such unperturbed capacitive behavior of the MoS 2 nanostructures offer modulation of capacitance in periodic array on 2D MoS 2 flake for potential application in capacitive devices.

Murine Leukemia Virus Reverse Transcriptase: Structural Comparison with HIV-1 Reverse Transcriptase

PubMed Central

Coté, Marie L.; Roth, Monica J.

2008-01-01

Recent X-ray crystal structure determinations of Moloney murine leukemia virus reverse transcriptase (MoMLV RT) have allowed for more accurate structure/function comparisons to HIV-1 RT than were formerly possible. Previous biochemical studies of MoMLV RT in conjunction with knowledge of sequence homologies to HIV-1 RT and overall fold similarities to RTs in general, provided a foundation upon which to build. In addition, numerous crystal structures of the MoMLV RT fingers/palm subdomain had also shed light on one of the critical functions of the enzyme, specifically polymerization. Now in the advent of new structural information, more intricate examination of MoMLV RT in its entirety can be realized, and thus the comparisons with HIV-1 RT may be more critically elucidated. Here, we will review the similarities and differences between MoMLV RT and HIV-1 RT via structural analysis, and propose working models for the MoMLV RT based upon that information. PMID:18294720

Thermophysical properties of heat-treated U-7Mo/Al dispersion fuel

NASA Astrophysics Data System (ADS)

Cho, Tae Won; Kim, Yeon Soo; Park, Jong Man; Lee, Kyu Hong; Kim, Sunghwan; Lee, Chong Tak; Yang, Jae Ho; Oh, Jang Soo; Sohn, Dong-Seong

2018-04-01

In this study, the effects of interaction layer (IL) on thermophysical properties of U-7Mo/Al dispersion fuel were examined. Microstructural analyses revealed that ILs were formed uniformly on U-Mo particles during heating of U-7Mo/Al samples. The IL volume fraction was measured by applying image analysis methods. The uranium loadings of the samples were calculated based on the measured meat densities at 298 K. The density of the IL was estimated by using the measured density and IL volume fraction. Thermal diffusivity and heat capacity of the samples after the heat treatment were measured as a function of temperature and volume fractions of U-Mo and IL. The thermal conductivity of IL-formed U-7Mo/Al was derived by using the measured thermal diffusivity, heat capacity, and density. The thermal conductivity obtained in the present study was lower than that predicted by the modified Hashin-Shtrikman model due to the theoretical model's inability to consider the thermal resistance at interfaces between the meat constituents.

Effects of adding metals to MoS2 in a ytterbium doped Q-switched fiber laser

NASA Astrophysics Data System (ADS)

Khaleque, Abdul; Liu, Liming

2018-03-01

Molybdenum disulfide (MoS2) is widely used in lubricants, metallic alloys and in electronic and optical components. It is also used as saturable absorbers (SAs) in lasers (e.g. fiber lasers): a simple deposition of MoS2 on the fiber end can create a saturable absorber without the necessity of extensive alignment of the optical beam. In this article, we study the effects of adding different metals (Cr, Au, and Al) to MoS2 in a ytterbium (Yb)-doped Q-switched fiber laser. Experimental results show that the addition of a thin layer of gold and aluminium can reduce pulse durations to about 5.8 μs and 8.5 μs, respectively, compared with pure MoS2 with pulse duration of 12 μs. Experimental analysis of the combined metal and MoS2 based composite SAs can be useful in fiber laser applications where it may also find applications in medical, three dimensional (3D) active imaging and dental applications.

Structural and electronic properties of Li-ion battery cathode material MoF{sub 3} from first-principles

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

Li, A.Y.; Wu, S.Q.; Yang, Y.

2015-07-15

The transition metal fluorides have been extensively investigated recently as the electrode materials with high working voltage and large capacity. The structural, electronic and magnetic properties of MoF{sub 3} are studied by the first-principles calculations within both the generalized gradient approximation (GGA) and GGA+U frameworks. Our results show that the antiferromagnetic configuration of MoF{sub 3} is more stable than the ferromagnetic one, which is consistent with experimental results. The analysis of the electronic density of states shows that MoF{sub 3} is a Mott–Hubbard insulator with a d–d type band gap, which is similar to the case of FeF{sub 3}. Moreover,more » small spin polarizations were found on the sites of fluorine ions, which accords with a fluorine-mediated superexchange mechanism for the Mo–Mo magnetic interaction. - Graphical abstract: Deformation charge density and spin-density for MoF{sub 3} in the AF configuration. - Highlights: • The ground state of MoF{sub 3} is shown to be antiferromagnetic, in consistent with experiments. • The electronic states show that MoF{sub 3} is a Mott–Hubbard insulator with a d–d type band gap. • A fluorine-mediated super-exchange mechanism for the Mo–Mo magnetic interaction is shown.« less

Tellurite‐Squarate Driven Assembly of a New Family of Nanoscale Clusters Based on (Mo2O2S2)2+

PubMed Central

Purcell, Jamie W.; Miras, Haralampos N.; Long, De‐Liang; Markopoulou, Panagiota

2017-01-01

Abstract The preparation and characterization of a new family of four polyoxothiometalate (POTM) clusters are reported, with varying size and complexity, based upon the dimeric [Mo2O2S2(H2O)6]2+ cation with the general formula (NMe4)aKb[(Mo2O2S2)c(TeO4)d(C4O4)e(OH)f] where a,b,c,d,e,f={1,7,14,2,4,10}=1, {Mo28Te2}; {2,26,36,12,10,48}=2, {Mo72Te12}; {0,11,15,3,3,21}=3, {Mo30Te3}; {2,6,12,2,4,16}=4, {Mo24Te2}. The incorporation of tellurite anions allowed the fine tuning of the templating and bridging of the available building blocks, leading to new topologies of increased complexity. The structural diversity of this family of compounds ranges from the highly symmetrical cross‐shaped {Mo24Te2} to the stacked ring structure of {Mo72Te12}, which is the largest tellurium‐containing POTM cluster reported so far. Also a detailed experimental analysis revealed that the pH isolation window extends from acidic to basic values. ESI‐MS analyses not only confirmed the stability of this family in solution but also revealed the stability of the observed virtual building blocks. PMID:28548217

Reduction of Net Erosion of High-Z Divertor Surface by Local Redeposition in DIII-D

NASA Astrophysics Data System (ADS)

Stangeby, P. C.

2012-10-01

Utilizing the unique capability to expose material samples to well characterized diverted plasmas, recent DIII-D measurements have confirmed theoretical expectations of the relative net and gross erosion rates of molybdenum in the divertor region. Knowledge of these erosion rates is important for predicting first wall lifetime in future fusion devices. Theory suggests that the net erosion rate will be much less than gross erosion due to prompt local deposition of eroded ions by gyro-orbit motion, the strong E-field toward the target and friction with the fast plasma flow toward the target. However, experimental evidence to date has been contradictory. The results here, which are the most definitive to date, are consistent with the basic theoretical predictions. The net and gross erosion rates were measured utilizing 1-cm and 1-mm diameter Mo samples that are mounted on the DIII-D Divertor Material Evaluation System (DiMES) system and simultaneously exposed near the attached outer strike point of an L-mode plasma for 4 s. Due to the spatial extent of the re-deposition, the larger sample gives the net erosion while the smaller sample is indicative of the gross erosion. Post-mortem ion beam analysis (RBS) of the larger sample, indicates a 2.9 nm film thickness reduction (or 0.72 nm/s net erosion rate). Similar analysis of the smaller sample yields a 1.3 nm/s gross erosion rate, consistent with spectroscopic measurements of Mo I emission. The net to gross erosion ratio of 0.56 is consistent with calculations using a modeling package including REDEP/WBS and OEDGE codes. Using as input the measured plasma density and temperature profiles from divertor Langmuir probes, these codes estimate a net to gross erosion ratio of 0.46. Details of the modeling and implications for future devices will be discussed.

Atomic scale imaging of magnetic circular dichroism by achromatic electron microscopy.

PubMed

Wang, Zechao; Tavabi, Amir H; Jin, Lei; Rusz, Ján; Tyutyunnikov, Dmitry; Jiang, Hanbo; Moritomo, Yutaka; Mayer, Joachim; Dunin-Borkowski, Rafal E; Yu, Rong; Zhu, Jing; Zhong, Xiaoyan

2018-03-01

In order to obtain a fundamental understanding of the interplay between charge, spin, orbital and lattice degrees of freedom in magnetic materials and to predict and control their physical properties 1-3 , experimental techniques are required that are capable of accessing local magnetic information with atomic-scale spatial resolution. Here, we show that a combination of electron energy-loss magnetic chiral dichroism 4 and chromatic-aberration-corrected transmission electron microscopy, which reduces the focal spread of inelastically scattered electrons by orders of magnitude when compared with the use of spherical aberration correction alone, can achieve atomic-scale imaging of magnetic circular dichroism and provide element-selective orbital and spin magnetic moments atomic plane by atomic plane. This unique capability, which we demonstrate for Sr 2 FeMoO 6 , opens the door to local atomic-level studies of spin configurations in a multitude of materials that exhibit different types of magnetic coupling, thereby contributing to a detailed understanding of the physical origins of magnetic properties of materials at the highest spatial resolution.

Theoretical Study of Effect of Introducing π-Conjugation on Efficiency of Dye-Sensitized Solar Cell.

PubMed

Lee, Geon Hyeong; Kim, Young Sik

2018-09-01

In this study, phenoxazine (PXZ)-based dye sensitizers with triphenylamine (TPA) as a dual-electron donor and thiophen and benzothiadiazole (BTD) or 4,7-diethynylbenzo[c][1,2,5]thiadiazole (DEBT) as an electron acceptor (dye1, dye2, and dye3) were designed and investigated. dye3 can significantly stabilize the lowest unoccupied molecular orbital (LUMO) energy level of an organic dye. We used density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations to better understand the factors responsible for the photovoltaic performance. The absorption spectrum of the dyes showed different forms because of the different energy levels of the molecular orbital (MO) of each dye and the intramolecular energy transfer (EnT). Among the three dyes, dye3 showed greater red-shift, broader absorption spectra, and higher molar extinction coefficient. These results indicate that adding a withdrawing unit and π-conjugation to a dye can result in good photovoltaic properties for dye-sensitized solar cells (DSSCs).

Effects of Molybdenum Addition on Hydrogen Desorption of TiC Precipitation-Hardened Steel

NASA Astrophysics Data System (ADS)

Song, Eun Ju; Baek, Seung-Wook; Nahm, Seung Hoon; Suh, Dong-Woo

2018-05-01

The hydrogen-trap states in TiC and MoC that have coherent interfaces with ferrite were investigated using first-principles calculation. The trapping sites of TiC were the interfaces and interstitial sites of ferrite. On the other hand, the trapping sites of MoC were ferrite interstitial sites; the interface had a negative binding energy with H. Thermal desorption analysis confirms that the amounts of diffusible hydrogen were significantly reduced by addition of Mo in Ti-bearing steel.

Thermally activated rotational disorder in CaMoO 4 nanocrystals

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

Culver, Sean P.; Brutchey, Richard L.

2016-04-12

In this study, a dual-space approach, combining Rietveld and pair distribution function (PDF) analyses, has been applied to temperature-dependent synchrotron X-ray total scattering data collected on vapor diffusion sol–gel derived CaMoO 4 nanocrystals. A sharp transition in Ca–O bond distances in the range of 151–163 K was identified by PDF analysis, which is attributed to the thermal activation of rotational disorder associated with the rigid MoO 4 tetrahedra.

An Analysis of Changes in Threshold Limit Values Over Time

DTIC Science & Technology

1993-01-01

Metribuzin 21087-64-91 1984 1984 Mevinphos 7786-34-7 1982: 1982 _ _ Mica 12001-26-2 1 I987 1987 1 Mineral wool fiber _ 1987 1 1987 _ i t Molybdenum as Mo...1 _ _ i alpha-Methyl styrene _ __ 1968 6 Metribuzin Mevinphos t Mica _ _ _ Mineral wool fiber _ Molybdenum as Mo _ _ Soluble compounds I_...Metribuzin 0 0 i _ __ Mevinphos 0 0 Mica 0 10 ,0___ Mineral wool fiber 0 0 P _ _ Molybdenum as Mo _ ___ Soluble compounds 0 0 Insoluble compounds 1 j 00 _ i

Advanced simulation of mixed-material erosion/evolution and application to low and high-Z containing plasma facing components

NASA Astrophysics Data System (ADS)

Brooks, J. N.; Hassanein, A.; Sizyuk, T.

2013-07-01

Plasma interactions with mixed-material surfaces are being analyzed using advanced modeling of time-dependent surface evolution/erosion. Simulations use the REDEP/WBC erosion/redeposition code package coupled to the HEIGHTS package ITMC-DYN mixed-material formation/response code, with plasma parameter input from codes and data. We report here on analysis for a DIII-D Mo/C containing tokamak divertor. A DIII-D/DiMES probe experiment simulation predicts that sputtered molybdenum from a 1 cm diameter central spot quickly saturates (˜4 s) in the 5 cm diameter surrounding carbon probe surface, with subsequent re-sputtering and transport to off-probe divertor regions, and with high (˜50%) redeposition on the Mo spot. Predicted Mo content in the carbon agrees well with post-exposure probe data. We discuss implications and mixed-material analysis issues for Be/W mixing at the ITER outer divertor, and Li, C, Mo mixing at an NSTX divertor.

Electromagnetic scattering analysis of a three-dimensional-cavity-backed aperture in an infinite ground plane using a combined finite element method/method of moments approach

NASA Technical Reports Server (NTRS)

Reddy, C. J.; Deshpande, Manohar D.; Cockrell, C. R.; Beck, F. B.

1995-01-01

A combined finite element method/method of moments (FEM/MoM) approach is used to analyze the electromagnetic scattering properties of a three-dimensional-cavity-backed aperture in an infinite ground plane. The FEM is used to formulate the fields inside the cavity, and the MoM (with subdomain bases) in both spectral and spatial domains is used to formulate the fields above the ground plane. Fields in the aperture and the cavity are solved using a system of equations resulting from the combination of the FEM and the MoM. By virtue of the FEM, this combined approach is applicable to all arbitrarily shaped cavities with inhomogeneous material fillings, and because of the subdomain bases used in the MoM, the apertures can be of any arbitrary shape. This approach leads to a partly sparse and partly full symmetric matrix, which is efficiently solved using a biconjugate gradient algorithm. Numerical results are presented to validate the analysis.

Interface morphology of Mo/Si multilayer systems with varying Mo layer thickness studied by EUV diffuse scattering.

PubMed

Haase, Anton; Soltwisch, Victor; Braun, Stefan; Laubis, Christian; Scholze, Frank

2017-06-26

We investigate the influence of the Mo-layer thickness on the EUV reflectance of Mo/Si mirrors with a set of unpolished and interface-polished Mo/Si/C multilayer mirrors. The Mo-layer thickness is varied in the range from 1.7 nm to 3.05 nm. We use a novel combination of specular and diffuse intensity measurements to determine the interface roughness throughout the multilayer stack and do not rely on scanning probe measurements at the surface only. The combination of EUV and X-ray reflectivity measurements and near-normal incidence EUV diffuse scattering allows to reconstruct the Mo layer thicknesses and to determine the interface roughness power spectral density. The data analysis is conducted by applying a matrix method for the specular reflection and the distorted-wave Born approximation for diffuse scattering. We introduce the Markov-chain Monte Carlo method into the field in order to determine the respective confidence intervals for all reconstructed parameters. We unambiguously detect a threshold thickness for Mo in both sample sets where the specular reflectance goes through a local minimum correlated with a distinct increase in diffuse scatter. We attribute that to the known appearance of an amorphous-to-crystallization transition at a certain thickness threshold which is altered in our sample system by the polishing.

Energy for the interface system of (Nb, Mo)C/γ-Fe

NASA Astrophysics Data System (ADS)

Zhou, Yanyuan; Wang, Zhenqiang; Zhao, Jiaying; Leng, Zhe; Niu, Zhongyi; Guo, Chunhuan; Zhang, Zhengyan; Yang, Zhigang; Yao, Chunfa; Jiang, Fengchun

2017-08-01

The interfacial energies of MC/γ-Fe and formation energies of MC carbides have been investigated using first-principles calculations based on density functional theory (DFT). Results show that the replacement of Nb by Mo in the NbC lattice is unfavorable with respect to the formation energy. However, it reduces the lattice parameter of MC and decreases the σ_{{chemical}} (interfacial chemical energy) of MC/γ-Fe, thus favoring the formation of complex (Nb, Mo)C carbide. The substitution of Nb by Mo at the interface of MC/γ-Fe system promotes the hybridizations of Mo-1NNFe and C-1NNFe (or 2NNFe) (the first or second nearest neighboring Fe atoms), which leads to a decrease in σ_{{chemical}}. The influence of bond energy is estimated using the discrete lattice plane/nearest neighbor broken bond (DLP/NNBB) model. It is found that the reduced σ_{{chemical}} is attributed to the much smaller value of e_{{{{Fe-C}}}} - e_{{{{Mo-C}}}} (the difference between Fe-C and Mo-C interactions) compared to e_{{{{Fe-C}}}} - e_{{{{Nb-C}}}} (the difference between Fe-C and Nb-C interactions). The results obtained from the analysis of the precipitates in Nb- and Nb-Mo-bearing steels are in a good agreement with the calculations.

Calculation of correlation times for the. gamma. -alumina-supported molybdenum subcarbonyl, Mo(CO) sub 3 (ads)

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

Wagner, G.W.; Hanson, B.E.

1989-07-05

The theory of carbon-13 NMR line widths in the solid state for molecules with large chemical shift anisotropies is applied to the adsorbed molybdenum subcarbonyls Mo(CO){sub 3}(ads) and Mo(CO){sub 5}(ads). Correlation times for the rotation of the molybdenum subcarbonyl groups Mo(CO){sub 3}(ads) and Mo(CO){sub 5}(ads) on partially dehydroxylated alumina are calculated. Good agreement is obtained between data reported at observation frequencies of 15 to 75.5 MHz for carbon-13 for Mo(CO){sub 3}(ads). The correlation time for this adsorbed species is calculated to have a lower limit of 4.6 {plus minus} 0.5 ms. The presence of broad lines in the room temperaturemore » spectra for Mo(CO){sub 3}(ads) is thus explained by a slow molecular motion. Data for Mo(CO){sub 5}(ads) are available at observation frequencies of 15 to 90.5 MHz. A good fit to the experimental data is obtained assuming either long or short correlation times for this species. Thus literature estimates of <10{sup {minus}6}s for the correlation time for this species cannot be confirmed with certainty from the analysis presented here.« less

Feasibility analysis of cislunar flight using the Shuttle Orbiter

NASA Technical Reports Server (NTRS)

Haynes, Davy A.

1991-01-01

A first order orbital mechanics analysis was conducted to examine the possibility of utilizing the Space Shuttle Orbiter to perform payload delivery missions to lunar orbit. In the analysis, the earth orbit of departure was constrained to be that of Space Station Freedom. Furthermore, no enhancements of the Orbiter's thermal protection system were assumed. Therefore, earth orbit insertion maneuvers were constrained to be all propulsive. Only minimal constraints were placed on the lunar orbits and no consideration was given to possible landing sites for lunar surface payloads. The various phases and maneuvers of the mission are discussed for both a conventional (Apollo type) and an unconventional mission profile. The velocity impulses needed, and the propellant masses required are presented for all of the mission maneuvers. Maximum payload capabilities were determined for both of the mission profiles examined. In addition, other issues relating to the feasibility of such lunar shuttle missions are discussed. The results of the analysis indicate that the Shuttle Orbiter would be a poor vehicle for payload delivery missions to lunar orbit.

Stability of direct band gap under mechanical strains for monolayer MoS2, MoSe2, WS2 and WSe2

NASA Astrophysics Data System (ADS)

Deng, Shuo; Li, Lijie; Li, Min

2018-07-01

Single layer transition-metal dichalcogenides materials (MoS2, MoSe2, WS2 and WSe2) are investigated using the first-principles method with the emphasis on their responses to mechanical strains. All these materials display the direct band gap under a certain range of strains from compressive to tensile (stable range). We have found that this stable range is different for these materials. Through studying on their mechanical properties again using the first-principles approach, it is unveiled that this stable strain range is determined by the Young's modulus. More analysis on strains induced electronic band gap properties have also been conducted.

Homogeneous dispersion of organic p-dopants in an organic semiconductor as an origin of high charge generation efficiency

NASA Astrophysics Data System (ADS)

Lee, Jae-Hyun; Kim, Hyun-Mi; Kim, Ki-Bum; Kabe, Ryota; Anzenbacher, Pavel; Kim, Jang-Joo

2011-04-01

We report that an organic p-dopant tri[1,2-bis(trifluoromethyl)ethane-1,2-dithiolene] [Mo(tfd)3] resulted in higher density of holes than inorganic metal oxide dopants of ReO3 or MoO3 in 1,4-bis[N-(1-naphthyl)-N'-phenylamino]-4,4'-diamine even though the metal oxide dopants possess deeper work functions compared to Mo(tfd)3. Higher charge generation efficiency results largely from the homogeneous dispersion of Mo(tfd)3 in the host. In contradistinction, the transmission electron microscopy analysis revealed a formation of metal oxide nanoclusters. This highlights the importance of homogeneous dispersion for an efficient doping.

Synthesis and electrochemical property of few-layer molybdenum disulfide nanosheets

NASA Astrophysics Data System (ADS)

Fu, Yanjue; Wang, Chunrui; Wang, Linlin; Peng, Xia; Wu, Binhe; Sun, Xingqu; Chen, Xiaoshuang

2016-12-01

Large-scale few-layer MoS2 nanosheets have been fabricated via a simple hydrothermal route using molybdenum powder as precursors. The as-prepared MoS2 samples were characterized by X-ray powder diffraction (XRD) analysis, transmission electron microscopy (TEM), and Raman and photoluminescence (PL) spectral analyses at room temperature. The results confirm that the as-prepared MoS2 displays a sheet-like morphology with a thickness of few (bi- to tri-) layers. Electrochemical measurements showed that the as-prepared few-layer MoS2 exhibited the highest reversible capacity of 1127 mAh g-1 and a stable reversible capacity of 1057 mAh g-1 after 30 cycles.

Structural Analysis of MoS2 and other 2D layered materials using LEEM/LEED-I(V) and STM

NASA Astrophysics Data System (ADS)

Grady, Maxwell; Dai, Zhongwei; Jin, Wencan; Dadap, Jerry; Osgood, Richard; Sadowski, Jerzy; Pohl, Karsten

Layered two-dimensional materials, such as molybdenum disulfide, MoS2, are of interest for the development of many types of novel electronic devices. To fully understand the interfaces between these new materials, the atomic reconstructions at their surfaces must be understood. Low Energy Electron Microscopy and Diffraction, LEEM/ μLEED, present a unique method for rapid material characterization in real space and reciprocal space with high resolution. Here we present a study of the surface structure of 2H-MoS2 using μLEED intensity-voltage analysis. To aid this analysis, software is under development to automate the procedure of extracting I(V) curves from LEEM and LEED data. When matched with computational modeling, this data provides information with angstrom level resolution concerning the three dimensional atomic positions. We demonstrate that the surface structure of bulk MoS2 is distinct from the bulk crystal structure and exhibits a smaller surface relaxation at 320K compared to previous results at 95K. Furthermore, suspended monolayer samples exhibit large interlayer relaxations compared to the bulk surface termination. Further techniques for refining layer thickness determination are under development.

Vertical position of the orbits in nonsyndromic plagiocephaly in childhood and its relation to vertical strabismus.

PubMed

Eveleens, Jordi R J; Mathijssen, Irene M; Lequin, Maarten H; Polling, Jan-Roelof; Looman, Caspar W N; Simonsz, Huibert J

2011-01-01

To determine the existence of a correlation between the vertical angle of strabismus and the vertical angle between the orbital axes in nonsyndromic plagiocephaly in childhood. Patients were included when diagnosed with plagiocephaly. Orthoptic measurements showed a vertical strabismus and three-dimensional computed tomographic (CT) imaging of the skull was available. Patients were excluded if plagiocephaly was part of a syndrome or if any surgical intervention had taken place before our measurements. Three-dimensional CT imaging was used to calculate the vertical angle between the orbital axes in 3 reference planes (VAO) perpendicular to a line of reference through the lower borders of the maxilla (VAOmax), both auditory canals (VAOaud), and the lower points of the external occipital protuberances (VAOocc). Fourteen patients were included (mean age, 14 mo). Three-dimensional CT measurements showed a mean (SD) VAOmax of 1.70 (2.31) degrees, VAOaud of -1.54 (1.46) degrees, and VAOocc of -2.06 (4.29) degrees (a negative value indicates that the eye on the affected side was situated lower in the head). The mean vertical angle of strabismus was -2.39 (4.69) degrees in gaze toward the affected side, 3.66 (3.77) degrees in gaze ahead, and 8.14 (5.63) degrees in gaze toward the nonaffected side. The Pearson test showed no significant correlations. The clinical observation that vertical strabismus in adult plagiocephaly is correlated with the vertical angle of the orbital axes could not be confirmed in young children.

Study on Tribological Properties of CoCrMo Alloys against Metals and Ceramics as Bearing Materials for Artificial Cervical Disc

NASA Astrophysics Data System (ADS)

Xiang, Dingding; Song, Jian; Wang, Song; Liao, Zhenhua; Liu, Yuhong; Tyagi, Rajnesh; Liu, Weiqiang

2018-02-01

CoCrMo alloys are believed to be a kind of potential material for artificial cervical disc. However, the tribological properties of CoCrMo alloys against different metals and ceramics are not systematically studied. In this study, the tribological behaviors of CoCrMo alloys against metals (316L, Ti6Al4V) and ceramics (Si3N4, ZrO2) were focused under dry friction and 25 wt.% newborn calf serum (NCS)-lubricated conditions using a ball-on-disc apparatus under reciprocating motion. The microstructure, composition and hardness of CoCrMo alloys were characterized using x-ray diffraction, scanning electron microscopy (SEM) and hardness testers, respectively. The contact angles of the CoCrMo alloys with deionized water and 25 wt.% NCS were measured by the OCA contact angle measuring instrument. The maximum wear width, wear depth and wear volume were measured by three-dimensional white light interference. The morphology and the EDX analysis of the wear marks on CoCrMo alloys were examined by SEM to determine the basic mechanism of friction and wear. The dominant wear mechanism in dry friction for CoCrMo alloys against all pairings was severe abrasive wear, accompanied with a lot of material transfer. Under 25 wt.% NCS-lubricated condition, the wear mechanism for CoCrMo alloys against ceramics (Si3N4, ZrO2) was also mainly severe abrasive wear. However, severe abrasive wear and electrochemical corrosion occurred for the CoCrMo-316L pairing under lubrication. Severe abrasive wear, adhesive wear and electrochemical corrosion occurred for the CoCrMo-Ti6Al4V pairing under lubrication. According to the results, the tribological properties of CoCrMo alloys against ceramics were better than those against metals. The CoCrMo-ZrO2 pairing displayed the best tribological behaviors and could be taken as a potential candidate bearing material for artificial cervical disc.

Converting MMSE to MoCA and MoCA 5-minute protocol in an educationally heterogeneous sample with stroke or transient ischemic attack.

PubMed

Wong, Adrian; Black, Sandra E; Yiu, Stanley Y P; Au, Lisa W C; Lau, Alexander Y L; Soo, Yannie O Y; Chan, Anne Y Y; Leung, Thomas W H; Wong, Lawrence K S; Kwok, Timothy C Y; Cheung, Theodore C K; Leung, Kam-Tat; Lam, Bonnie Y K; Kwan, Joseph S K; Mok, Vincent C T

2018-05-01

The Montreal Cognitive Assessment (MoCA) is psychometrically superior over the Mini-mental State Examination (MMSE) for cognitive screening in stroke or transient ischemic attack (TIA). It is free for clinical and research use. The objective of this study is to convert scores from the MMSE to MoCA and MoCA-5-minute protocol (MoCA-5 min) and to examine the ability of the converted scores in detecting cognitive impairment after stroke or TIA. A total of 904 patients were randomly divided into training (n = 623) and validation (n = 281) samples matched for demography and cognition. MMSE scores were converted to MoCA and MoCA-5 min using (1) equipercentile method with log-linear smoothing and (2) Poisson regression adjusting for age and education. Receiver operating characteristics curve analysis was used to examine the ability of the converted scores in differentiating patients with cognitive impairment. The mean education was 5.8 (SD = 4.6; ranged 0-20) years. The entire spectrum of MMSE scores was converted to MoCA and MoCA-5 min using equipercentile method. Relationship between MMSE and MoCA scores was confounded by age and education, and a conversion equation with adjustment for age and education was derived. In the validation sample, the converted scores differentiated cognitively impaired patients with area under receiver operating characteristics curve 0.826 to 0.859. We provided 2 methods to convert scores from the MMSE to MoCA and MoCA-5 min based on a large sample of patients with stroke or TIA having a wide range of education and cognitive levels. The converted scores differentiated patients with cognitive impairment after stroke or TIA with high accuracy. Copyright © 2018 John Wiley & Sons, Ltd.

Quality of Life After Open Radical Prostatectomy Compared with Robot-assisted Radical Prostatectomy.

PubMed

Wallerstedt, Anna; Nyberg, Tommy; Carlsson, Stefan; Thorsteinsdottir, Thordis; Stranne, Johan; Tyritzis, Stavros I; Stinesen Kollberg, Karin; Hugosson, Jonas; Bjartell, Anders; Wilderäng, Ulrica; Wiklund, Peter; Steineck, Gunnar; Haglind, Eva

2018-01-20

Surgery for prostate cancer has a large impact on quality of life (QoL). To evaluate predictors for the level of self-assessed QoL at 3 mo, 12 mo, and 24 mo after robot-assisted laparoscopic (RALP) and open radical prostatectomy (ORP). The LAParoscopic Prostatectomy Robot Open study, a prospective, controlled, nonrandomised trial of more than 4000 men who underwent radical prostatectomy at 14 centres. Here we report on QoL issues after RALP and ORP. The primary outcome was self-assessed QoL preoperatively and at 3 mo, 12 mo, and 24 mo postoperatively. A direct validated question of self-assessed QoL on a seven-digit visual scale was used. Differences in QoL were analysed using logistic regression, with adjustment for confounders. QoL did not differ between RALP and ORP postoperatively. Men undergoing ORP had a preoperatively significantly lower level of self-assessed QoL in a multivariable analysis compared with men undergoing RALP (odds ratio: 1.21, 95% confidence interval: 1.02-1.43), that disappeared when adjusted for preoperative preparedness for incontinence, erectile dysfunction, and certainty of being cured (odds ratio: 1.18, 95% confidence interval: 0.99-1.40). Incontinence and erectile dysfunction increased the risk for poor QoL at 3 mo, 12 mo, and 24 mo postoperatively. Biochemical recurrence did not affect QoL. A limitation of the study is the nonrandomised design. QoL at 3 mo, 12 mo, and 24 mo after RALP or ORP did not differ significantly between the two techniques. Poor QoL was associated with postoperative incontinence and erectile dysfunction but not with early cancer relapse, which was related to thoughts of death and waking up at night with worry. We did not find any difference in quality of life at 3 mo, 12 mo, and 24 mo when open and robot-assisted surgery for prostate cancer were compared. Postoperative incontinence and erectile dysfunction were associated with poor quality of life. Copyright © 2017 European Association of Urology. Published by Elsevier B.V. All rights reserved.

Electronic and optical response of Cr-doped MoSe2 and WSe2: Compton measurements and first-principles strategies

NASA Astrophysics Data System (ADS)

Kumar, Kishor; Heda, N. L.; Jani, A. R.; Ahuja, B. L.

2017-08-01

In this paper, we present energy bands, density of states and Mulliken's population (MP) data using the linear combination of atomic orbitals (LCAO) method. To compare the theoretical momentum densities, we have also employed 100 mCi 241Am Compton spectrometer to measure the Compton profiles of Cr0.5X0.5Se2 (X=Mo and W). The experimental Compton data have been used to check the performance of various exchange and correlation energies for the present mixed dichalcogenides within the LCAO scheme. It is seen that CPs based on the hybridization of Hartree-Fock and density functional theory give a better agreement with the experimental data than other schemes employed in the present investigations. All theoretical approximations show an indirect band gap between the Γ and K points of the Brillouin zone. Further, equal-valence-electron-density scaled experimental data predict a more ionic character in Cr0.5W0.5Se2 than in Cr0.5Mo0.5Se2, which is in tune with our MP data. Going beyond the computation of electronic properties using LCAO, we have also reported accurate electronic and optical properties using the modified Becke-Johnson (mBJ) potential within the full potential augmented plane wave (FP-LAPW) method. Optical properties computed using the FP-LAPW-mBJ method show the feasibility of using both the mixed dichalcogenides in photovoltaic devices.

Roles of Bridging Ligand Topology and Conformation in Controlling Exchange Interactions between Paramagnetic Molybdenum Fragments in Dinuclear and Trinuclear Complexes.

PubMed

Ung VÂ, V&acaron;n Ân; Cargill Thompson, Alexander M. W.; Bardwell, David A.; Gatteschi, Dante; Jeffery, John C.; McCleverty, Jon A.; Totti, Federico; Ward, Michael D.

1997-07-30

The magnetic properties of two series of dinuclear complexes, and one trinuclear complex, have been examined as a function of the bridging pathway between the metal centers. The first series of dinuclear complexes is [{Mo(V)(O)(Tp)Cl}(2)(&mgr;-OO)], where "OO" is [1,4-O(C(6)H(4))(n)O](2)(-) (n = 1, 1; n = 2, 3), [4,4'-O(C(6)H(3)-2-Me)(2)O](2)(-) (4), or [1,3-OC(6)H(4)O](2)(-) (2) [Tp = tris(3,5-dimethylpyrazolyl)hydroborate]. The second series of dinuclear complexes is [{Mo(I)(NO)(Tp)Cl}(2)(&mgr;-NN)], where "NN" is 4,4'-bipyridyl (5), 3,3'-dimethyl-4,4'-bipyridine (6), 3,8-phenanthroline (7), or 2,7-diazapyrene (8). The trinuclear complex is [{Mo(V)(O)(Tp)Cl}(3)(1,3,5-C(6)H(3)O(3))] (9), whose crystal structure was determined [9.5CH(2)Cl(2): C(56)H(81)B(3)Cl(13)Mo(3)N(18)O(6); monoclinic, P2(1)/n; a = 13.443, b = 41.46(2), c = 14.314(6) Å; beta = 93.21(3) degrees; V = 7995(5) Å(3); Z = 4; R(1) = 0.106]. In these complexes, the sign and magnitude of the exchange coupling constant J is clearly related to both the topology and the conformation of the bridging ligand [where J is derived from H = -JS(1)().S(2)() for 1-8 and H = -J(S(1)().S(2)() + S(2)().S(3)() + S(1)().S(3)()) for 9]. The values are as follows: 1, -80 cm(-)(1); 2, +9.8 cm(-)(1); 3, -13.2 cm(-)(1); 4, -2.8 cm(-)(1); 5, -33 cm(-)(1); 6, -3.5 cm(-)(1); 7, -35.6 cm(-)(1); 8, -35.0 cm(-)(1); 9, +14.4 cm(-)(1). In particular the following holds: (1) J is negative (antiferromagnetic exchange) across the para-substituted bridges ligands of 1 and 3-8 but positive (ferromagnetic exchange) across the meta-substituted bridging ligands of 2 and 9. (2) J decreases in magnitude dramatically as the bridging ligand conformation changes from planar to twisted (compare 3 and 4, or 6 and 8). These observations are consistent with a spin-polarization mechanism for the exchange interaction, propagated across the pi-system of the bridging ligand by via overlap of bridging ligand p(pi) orbitals with the d(pi) magnetic orbitals of the metals. The EPR spectrum of 9 is characteristic of a quartet species and shows weak Deltam(s) = 2 and Deltam(s) = 3 transitions at one-half and one-third, respectively, of the field strength of the principal Deltam(s) = 1 component.

Disposable MoS2-Arrayed MALDI MS Chip for High-Throughput and Rapid Quantification of Sulfonamides in Multiple Real Samples.

PubMed

Zhao, Yaju; Tang, Minmin; Liao, Qiaobo; Li, Zhoumin; Li, Hui; Xi, Kai; Tan, Li; Zhang, Mei; Xu, Danke; Chen, Hong-Yuan

2018-04-27

In this work, we demonstrate, for the first time, the development of a disposable MoS 2 -arrayed matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) chip combined with an immunoaffinity enrichment method for high-throughput, rapid, and simultaneous quantitation of multiple sulfonamides (SAs). The disposable MALDI MS chip was designed and fabricated by MoS 2 array formation on a commercial indium tin oxide (ITO) glass slide. A series of SAs were analyzed, and clear deprotonated signals were obtained in negative-ion mode. Compared with MoS 2 -arrayed commercial steel plate, the prepared MALDI MS chip exhibited comparable LDI efficiency, providing a good alternative and disposable substrate for MALDI MS analysis. Furthermore, internal standard (IS) was previously deposited onto the MoS 2 array to simplify the experimental process for MALDI MS quantitation. 96 sample spots could be analyzed within 10 min in one single chip to perform quantitative analysis, recovery studies, and real foodstuff detection. Upon targeted extraction and enrichment by antibody conjugated magnetic beads, five SAs were quantitatively determined by the IS-first method with the linear range of 0.5-10 ng/mL ( R 2 > 0.990). Good recoveries and repeatability were obtained for spiked pork, egg, and milk samples. SAs in several real foodstuffs were successfully identified and quantified. The developed method may provide a promising tool for the routine analysis of antibiotic residues in real samples.

Quantitative in vivo biocompatibility of new ultralow-nickel cobalt-chromium-molybdenum alloys.

PubMed

Sonofuchi, Kazuaki; Hagiwara, Yoshihiro; Koizumi, Yuichiro; Chiba, Akihiko; Kawano, Mitsuko; Nakayama, Masafumi; Ogasawara, Kouetsu; Yabe, Yutaka; Itoi, Eiji

2016-09-01

Nickel (Ni) eluted from metallic biomaterials is widely accepted as a major cause of allergies and inflammation. To improve the safety of cobalt-chromium-molybdenum (Co-Cr-Mo) alloy implants, new ultralow-Ni Co-Cr-Mo alloys with and without zirconium (Zr) have been developed, with Ni contents of less than 0.01%. In the present study, we investigated the biocompatibility of these new alloys in vivo by subcutaneously implanting pure Ni, conventional Co-Cr-Mo, ultralow-Ni Co-Cr-Mo, and ultralow-Ni Co-Cr-Mo with Zr wires into the dorsal sides of mice. After 3 and 7 days, tissues around the wire were excised, and inflammation; the expression of IL-1β, IL-6, and TNF-α; and Ni, Co, Cr, and Mo ion release were analyzed using histological analyses, qRT-PCR, and inductively coupled plasma mass spectrometry (ICP-MS), respectively. Significantly larger amounts of Ni eluted from pure Ni wires than from the other wires, and the degree of inflammation depended on the amount of eluted Ni. Although no significant differences in inflammatory reactions were identified among new alloys and conventional Co-Cr-Mo alloys in histological and qRT-PCR analyses, ICP-MS analysis revealed that Ni ion elution from ultralow-Ni Co-Cr-Mo alloys with and without Zr was significantly lower than from conventional Co-Cr-Mo alloys. Our study, suggests that the present ultralow-Ni Co-Cr-Mo alloys with and without Zr have greater safety and utility than conventional Co-Cr-Mo alloys. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 34:1505-1513, 2016. © 2016 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.

Radical lymph node dissection and assessment: Impact on gallbladder cancer prognosis

PubMed Central

Liu, Gui-Jie; Li, Xue-Hua; Chen, Yan-Xin; Sun, Hui-Dong; Zhao, Gui-Mei; Hu, San-Yuan

2013-01-01

AIM: To investigate the lymph node metastasis patterns of gallbladder cancer (GBC) and evaluate the optimal categorization of nodal status as a critical prognostic factor. METHODS: From May 1995 to December 2010, a total of 78 consecutive patients with GBC underwent a radical resection at Liaocheng People’s Hospital. A radical resection was defined as removing both the primary tumor and the regional lymph nodes of the gallbladder. Demographic, operative and pathologic data were recorded. The lymph nodes retrieved were examined histologically for metastases routinely from each node. The positive lymph node count (PLNC) as well as the total lymph node count (TLNC) was recorded for each patient. Then the metastatic to examined lymph nodes ratio (LNR) was calculated. Disease-specific survival (DSS) and predictors of outcome were analyzed. RESULTS: With a median follow-up time of 26.50 mo (range, 2-132 mo), median DSS was 29.00 ± 3.92 mo (5-year survival rate, 20.51%). Nodal disease was found in 37 patients (47.44%). DSS of node-negative patients was significantly better than that of node-positive patients (median DSS, 40 mo vs 17 mo, χ2 = 14.814, P < 0.001), while there was no significant difference between N1 patients and N2 patients (median DSS, 18 mo vs 13 mo, χ2 = 0.741, P = 0.389). Optimal TLNC was determined to be four. When node-negative patients were divided according to TLNC, there was no difference in DSS between TLNC < 4 subgroup and TLNC ≥ 4 subgroup (median DSS, 37 mo vs 54 mo, χ2 = 0.715, P = 0.398). For node-positive patients, DSS of TLNC < 4 subgroup was worse than that of TLNC ≥ 4 subgroup (median DSS, 13 mo vs 21 mo, χ2 = 11.035, P < 0.001). Moreover, for node-positive patients, a new cut-off value of six nodes was identified for the number of TLNC that clearly stratified them into 2 separate survival groups (< 6 or ≥ 6, respectively; median DSS, 15 mo vs 33 mo, χ2 = 11.820, P < 0.001). DSS progressively worsened with increasing PLNC and LNR, but no definite cut-off value could be identified. Multivariate analysis revealed histological grade, tumor node metastasis staging, TNLC and LNR to be independent predictors of DSS. Neither location of positive lymph nodes nor PNLC were identified as an independent variable by multivariate analysis. CONCLUSION: Both TLNC and LNR are strong predictors of outcome after curative resection for GBC. The retrieval and examination of at least 6 nodes can influence staging quality and DSS, especially in node-positive patients. PMID:23964151

Radical lymph node dissection and assessment: Impact on gallbladder cancer prognosis.

PubMed

Liu, Gui-Jie; Li, Xue-Hua; Chen, Yan-Xin; Sun, Hui-Dong; Zhao, Gui-Mei; Hu, San-Yuan

2013-08-21

To investigate the lymph node metastasis patterns of gallbladder cancer (GBC) and evaluate the optimal categorization of nodal status as a critical prognostic factor. From May 1995 to December 2010, a total of 78 consecutive patients with GBC underwent a radical resection at Liaocheng People's Hospital. A radical resection was defined as removing both the primary tumor and the regional lymph nodes of the gallbladder. Demographic, operative and pathologic data were recorded. The lymph nodes retrieved were examined histologically for metastases routinely from each node. The positive lymph node count (PLNC) as well as the total lymph node count (TLNC) was recorded for each patient. Then the metastatic to examined lymph nodes ratio (LNR) was calculated. Disease-specific survival (DSS) and predictors of outcome were analyzed. With a median follow-up time of 26.50 mo (range, 2-132 mo), median DSS was 29.00 ± 3.92 mo (5-year survival rate, 20.51%). Nodal disease was found in 37 patients (47.44%). DSS of node-negative patients was significantly better than that of node-positive patients (median DSS, 40 mo vs 17 mo, χ² = 14.814, P < 0.001), while there was no significant difference between N1 patients and N2 patients (median DSS, 18 mo vs 13 mo, χ² = 0.741, P = 0.389). Optimal TLNC was determined to be four. When node-negative patients were divided according to TLNC, there was no difference in DSS between TLNC < 4 subgroup and TLNC ≥ 4 subgroup (median DSS, 37 mo vs 54 mo, χ² = 0.715, P = 0.398). For node-positive patients, DSS of TLNC < 4 subgroup was worse than that of TLNC ≥ 4 subgroup (median DSS, 13 mo vs 21 mo, χ² = 11.035, P < 0.001). Moreover, for node-positive patients, a new cut-off value of six nodes was identified for the number of TLNC that clearly stratified them into 2 separate survival groups (< 6 or ≥ 6, respectively; median DSS, 15 mo vs 33 mo, χ² = 11.820, P < 0.001). DSS progressively worsened with increasing PLNC and LNR, but no definite cut-off value could be identified. Multivariate analysis revealed histological grade, tumor node metastasis staging, TNLC and LNR to be independent predictors of DSS. Neither location of positive lymph nodes nor PNLC were identified as an independent variable by multivariate analysis. Both TLNC and LNR are strong predictors of outcome after curative resection for GBC. The retrieval and examination of at least 6 nodes can influence staging quality and DSS, especially in node-positive patients.

Interface structure and composition of MoO3/GaAs(0 0 1)

NASA Astrophysics Data System (ADS)

Sarkar, Anirban; Ashraf, Tanveer; Grafeneder, Wolfgang; Koch, Reinhold

2018-04-01

We studied growth, structure, stress, oxidation state as well as surface and interface structure and composition of thermally-evaporated thin MoO3 films on the technologically important III/V-semiconductor substrate GaAs(0 0 1). The MoO3 films grow with Mo in the 6+  oxidation state. The electrical resistance is tunable by the oxygen partial pressure during deposition from transparent insulating to semi-transparant halfmetallic. In the investigated growth temperature range (room temperature to 200 °C) no diffraction spots are detected by x-ray diffraction. However, high resolution transmission electron microscopy reveals the formation of MoO3 nanocrystal grains with diameters of 5–8 nm. At the interface a  ≈3 nm-thick intermediate layer has formed, where the single-crystal lattice of GaAs gradually transforms to the nanocrystalline MoO3 structure. This interpretation is corroborated by our in situ and real-time stress measurements evidencing a two-stage growth process as well as by elemental interface analysis revealing coexistance of Ga, As, Mo, and oxygen in a intermediate layer of 3–4 nm.

Single crystal growth and characterization of Na{sub x}Ln{sub 1−x}MoO{sub 4}, Ln=La, Ce, Pr, Nd, Sm, and Eu (x=0.397–0.499)

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

Cortese, Anthony J.; Abeysinghe, Dileka; Smith, Mark D.

Single crystals of La{sub 0.516(3)}Na{sub 0.484(3)}MoO{sub 4}, Ce{sub 0.512(2)}Na{sub 0.488(2)}MoO{sub 4}, Pr{sub 0.502(2)}Na{sub 0.498(2)}MoO{sub 4,} Nd{sub 0.501(2)}Na{sub 0.499(2)}MoO{sub 4}, Sm{sub 0.509(2)}Na{sub 0.491(2)}MoO{sub 4}, and Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} were grown for the first time out of an alkali metal halide eutectic flux. All compounds crystallize in the tetragonal space group I4{sub 1}/a. UV/Vis measurements show the presence of an absorption edge for all compounds except Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4}. The temperature dependence of the magnetic susceptibility was measured for all compounds and found to be paramagnetic across the entire 2–300 K temperature range measured. - Graphical abstract: Single crystals ofmore » La{sub 0.516(3)}Na{sub 0.484(3)}MoO{sub 4}, Ce{sub 0.512(2)}Na{sub 0.488(2)}MoO{sub 4}, Pr{sub 0.502(2)}Na{sub 0.498(2)}MoO{sub 4,} Nd{sub 0.501(2)}Na{sub 0.499(2)}MoO{sub 4}, Sm{sub 0.509(2)}Na{sub 0.491(2)}MoO{sub 4}, and Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} were grown for the first time out of an alkali metal halide eutectic flux. All compounds crystallize in the tetragonal space group I4{sub 1}/a. Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} was found to possess the highest Mo{sup 5+} content at 20.6%. UV/Vis, magnetic susceptibility, and a bond valence sum analysis were performed on all samples. Display Omitted - Highlights: • Six lanthanide sodium molybdates have been synthesized and characterized. • An in situ reduction was carried out using Mo as a metal reducing agent. • UV/Vis and magnetic susceptibility data were collected. • Eu{sub 0.603(2)}Na{sub 0.397(2)}MoO{sub 4} was found to possess the highest Mo{sup 5+} content at 20.6%.« less