Suppression of the cooperative Jahn-Teller distortion and its effect on the Raman octahedra-rotation modes of TbM n1 -xF exO3

NASA Astrophysics Data System (ADS)

Vilarinho, R.; Passos, D. J.; Queirós, E. C.; Tavares, P. B.; Almeida, A.; Weber, M. C.; Guennou, M.; Kreisel, J.; Moreira, J. Agostinho

2018-04-01

This work reports the changes in structure and lattice dynamics induced by substituting the Jahn-Teller-active M n3 + ion by the Jahn-Teller-inactive F e3 + in TbM n1 -xF exO3 over the full composition range. The structural analysis reveals that the amplitude of the cooperative Jahn-Teller distortion decreases linearly from x =0 (pure TbMn O3 ) to x =0.5 , where it is completely suppressed. We then correlate this evolution with the behavior of the Raman modes across the solid solution. In particular, we show that the Raman modes associated with the rotation of octahedra, whose wave number is commonly considered to scale linearly with the tilt angles in orthorhombic Pnma perovskites, are also sensitive to the amplitude of the Jahn-Teller distortion.

Ab initio EPR parameters for dangling-bond defect complexes in silicon: Effect of Jahn-Teller distortion

NASA Astrophysics Data System (ADS)

Pfanner, Gernot; Freysoldt, Christoph; Neugebauer, Jörg; Gerstmann, Uwe

2012-05-01

A dangling bond (db) is an important point defect in silicon. It is realized in crystalline silicon by defect complexes of the monovacancy V with impurities. In this work, we present spin-polarized density-functional theory calculations of EPR parameters (g and hyperfine tensors) within the GIPAW formalism for two kinds of db defect complexes. The first class characterizes chemically saturated db systems, where three of the four dangling bonds of the isolated vacancy are saturated by hydrogen (VH3) or hydrogen and oxygen (hydrogen-oxygen complex, VOH). The second kind of db consists of systems with a Jahn-Teller distortion, where the vacancy includes either a substitutional phosphorus atom (the E center, VP) or a single hydrogen atom (VH). For all systems we obtain excellent agreement with available experimental data, and we are therefore able to quantify the effect of the Jahn-Teller distortion on the EPR parameters. Furthermore we study the influence of strain to obtain further insights into the structural and electronic characteristics of the considered defects.

Observation of a quadrupole interaction for cubic imperfections exhibiting a dynamic Jahn-Teller effect.

NASA Technical Reports Server (NTRS)

Herrington, J. R.; Estle, T. L.; Boatner, L. A.

1972-01-01

The observation and interpretation of weak EPR transitions, identified as 'forbidden' transitions, establish the existence of a new type of quadrupole interaction for cubic-symmetry imperfections. This interaction is simply a consequence of the ground-vibronic-state degeneracy. The signs as well as the magnitudes of the quadrupole-coupling coefficients are determined experimentally. These data agree well with the predictions of crystal field theory modified to account for a weak-to-moderate vibronic interaction (i.e., a dynamic Jahn-Teller effect).

Teaching the Jahn-Teller Theorem: A Simple Exercise That Illustrates How the Magnitude of Distortion Depends on the Number of Electrons and Their Occupation of the Degenerate Energy Level

ERIC Educational Resources Information Center

Johansson, Adam Johannes

2013-01-01

Teaching the Jahn-Teller theorem offers several challenges. For many students, the first encounter comes in coordination chemistry, which can be difficult due to the already complicated nature of transition-metal complexes. Moreover, a deep understanding of the Jahn-Teller theorem requires that one is well acquainted with quantum mechanics and…

Rotational Parameters from Vibronic Eigenfunctions of Jahn-Teller Active Molecules

NASA Astrophysics Data System (ADS)

Garner, Scott M.; Miller, Terry A.

2017-06-01

The structure in rotational spectra of many free radical molecules is complicated by Jahn-Teller distortions. Understanding the magnitudes of these distortions is vital to determining the equilibrium geometric structure and details of potential energy surfaces predicted from electronic structure calculations. For example, in the recently studied {\\widetilde{A}^2E^{''} } state of the NO_3 radical, the magnitudes of distortions are yet to be well understood as results from experimental spectroscopic studies of its vibrational and rotational structure disagree with results from electronic structure calculations of the potential energy surface. By fitting either vibrationally resolved spectra or vibronic levels determined by a calculated potential energy surface, we obtain vibronic eigenfunctions for the system as linear combinations of basis functions from products of harmonic oscillators and the degenerate components of the electronic state. Using these vibronic eigenfunctions we are able to predict parameters in the rotational Hamiltonian such as the Watson Jahn-Teller distortion term, h_1, and compare with the results from the analysis of rotational experiments.

EPR Studies of orthorhombic Jahn-Teller effect in single crystal of ferroelectric Cu(II):Cd2(NH4)2 (SO4)3

NASA Astrophysics Data System (ADS)

Benson, Yerima; de, Dilip

In this paper we report the first EPR observation and theoretical explanation of orthorhombic Jahn-Teller effect in Cu(II) doped single crystal of ferroelectric cadmium ammonium sulphate: Cu(II):Cd2(NH4)2 (SO4)3 . The isotropic EPR spectra of the 2D ion (in regular octahedral symmetry) at higher temperature becomes anisotropic at low temperature with clear manifestation of orthorhombic g and hyperfine tensors at 15 K. The static Jahn-Teller(JT) effect can only be explained theoretically by assuming the three JT potential wells energetically inequivalent, unlike the potential wells in most of the Cu(II) doped crystalline materials where JT effect manifests. The measured splitting of the JT potential wells in this ferroelectric crystal fall in the sub millimeter wave region pointing to possible application of the material.

Vibrational and Nonadiabatic Coherence in 2D Electronic Spectroscopy, the Jahn-Teller Effect, and Energy Transfer

NASA Astrophysics Data System (ADS)

Jonas, David M.

2018-04-01

Femtosecond two-dimensional (2D) Fourier transform spectroscopy generates and probes several types of coherence that characterize the couplings between vibrational and electronic motions. These couplings have been studied in molecules with Jahn-Teller conical intersections, pseudo-Jahn-Teller funnels, dimers, molecular aggregates, photosynthetic light harvesting complexes, and photosynthetic reaction centers. All have closely related Hamiltonians and at least two types of vibrations, including one that is decoupled from the electronic dynamics and one that is nonadiabatically coupled. Polarized pulse sequences can often be used to distinguish these types of vibrations. Electronic coherences are rapidly obscured by inhomogeneous dephasing. The longest-lived coherences in these systems arise from delocalized vibrations on the ground electronic state that are enhanced by a nonadiabatic Raman excitation process. These characterize the initial excited-state dynamics. 2D oscillation maps are beginning to isolate the medium lifetime vibronic coherences that report on subsequent stages of the excited-state dynamics.

Quantifying the effects of higher order coupling terms on fits using a second order Jahn-Teller Hamiltonian

NASA Astrophysics Data System (ADS)

Tran, Henry K.; Stanton, John F.; Miller, Terry A.

2018-01-01

The limitations associated with the common practice of fitting a quadratic Hamiltonian to vibronic levels of a Jahn-Teller system have been explored quantitatively. Satisfactory results for the prototypical X∼2E‧ state of Li3 are obtained from fits to both experimental spectral data and to an "artificial" spectrum calculated by a quartic Hamiltonian which accurately reproduces the adiabatic potential obtained from state-of-the-art quantum chemistry calculations. However the values of the Jahn-Teller parameters, stabilization energy, and pseudo-rotation barrier obtained from the quadratic fit differ markedly from those associated with the ab initio potential. Nonetheless the RMS deviations of the fits are not strikingly different. Guidelines are suggested for comparing parameters obtained from fits to experiment to those obtained by direct calculation, but a principal conclusion of this work is that such comparisons must be done with a high degree of caution.

The effect of band Jahn-Teller distortion on the magnetoresistivity of manganites: a model study.

PubMed

Rout, G C; Panda, Saswati; Behera, S N

2011-10-05

We present a model study of magnetoresistance through the interplay of magnetisation, structural distortion and external magnetic field for the manganite systems. The manganite system is described by the Hamiltonian which consists of the s-d type double exchange interaction, Heisenberg spin-spin interaction among the core electrons, and the static and dynamic band Jahn-Teller (JT) interaction in the e(g) band. The relaxation time of the e(g) electron is found from the imaginary part of the Green's function using the total Hamiltonian consisting of the interactions due to the electron and phonon. The calculated resistivity exhibits a peak in the pure JT distorted insulating phase separating the low temperature metallic ferromagnetic phase and the high temperature paramagnetic phase. The resistivity is suppressed with the increase of the external magnetic field. The e(g) electron band splitting and its effect on magnetoresistivity is reported here. © 2011 IOP Publishing Ltd

First-Principles Study of the Jahn-Teller Distortion in the Ti1-XVXH2 and Zr1-XNbxH2 Alloys

NASA Astrophysics Data System (ADS)

Quijano, Ramiro; de Coss, Romeo; Singh, David

2008-03-01

The transition metal dihydrides TiH2 and ZrH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Electronic band structure calculations have shown that TiH2 and ZrH2 in the cubic phase display a very flat band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. In order to understand the role of band filling in controlling the structural instability of the transition metal dihydrides, we have performed a first-principles total energy study of the Ti1-XVxH2 and Zr1-xNbxH2 alloys. The calculations were performed using FP-LAPW method within the (DFT) and we use the GGA for exchange correlation functional energy. The critical concentration for which the Jahn-Teller effect is suppressed, was determined from the evolution of the tetragonal-cubic energy barrier. We discuss the electronic mechanism of the structural-instability, in terms of the band filling. From the obtained results we conclude that the tetragonal distortion in TiH2 and ZrH2 is not produced only by a Jahn-Teller Effect. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 43830-F.

Jahn-Teller versus quantum effects in the spin-orbital material LuVO 3

DOE PAGES

Skoulatos, M.; Toth, S.; Roessli, B.; ...

2015-04-13

In this article, we report on combined neutron and resonant x-ray scattering results, identifying the nature of the spin-orbital ground state and magnetic excitations in LuVO 3 as driven by the orbital parameter. In particular, we distinguish between models based on orbital-Peierls dimerization, taken as a signature of quantum effects in orbitals, and Jahn-Teller distortions, in favor of the latter. In order to solve this long-standing puzzle, polarized neutron beams were employed as a prerequisite in order to solve details of the magnetic structure, which allowed quantitative intensity analysis of extended magnetic-excitation data sets. The results of this detailed studymore » enabled us to draw definite conclusions about the classical versus quantum behavior of orbitals in this system and to discard the previous claims about quantum effects dominating the orbital physics of LuVO 3 and similar systems.« less

The temperature dependence of the pressure switching of Jahn Teller deformation in the deuterated ammonium copper Tutton salt

NASA Astrophysics Data System (ADS)

Augustyniak, Maria A.; Krupski, Marcin

1999-09-01

The pressure switch of the Jahn-Teller deformation direction in (ND 4) 2Cu(SO 4) 2·6D 2O was investigated in the temperature range 130-320 K. Below 295 K, the new, pressure-induced phase, is stable under ambient pressure. Switching back is observed on heating to above 297 K. In the range 150-295 K a strong temperature dependence of the switching pressure (from 24 to 450 MPa) is observed. Below 150 K, the switching process is slow and a coexistence of two phases is observed. We conclude that the switch of the Cu(D 2O) 6 complex deformation direction is the Jahn-Teller response to the changes in the hydrogen bond system.

Jahn-Teller distortion of Mn3+-occupied octahedra in red beryl from Utah indicated by optical spectroscopy

NASA Astrophysics Data System (ADS)

Fridrichová, Jana; Bačík, Peter; Ertl, Andreas; Wildner, Manfred; Dekan, Július; Miglierini, Marcel

2018-01-01

Red beryl from Utah is chemically homogeneous and contains only Fe < 0.163, Mn < 0.018, and Mg < 0.016 apfu. Channel sites contain only up to Cs 0.011, K 0.009, Rb 0.004, and Na 0.004 apfu. This suggests only very slight tetrahedral (Cs,K,Rb)Li□-1Be-1 substitution, octahedral Na(Fe2+,Mg)□-1Al-1 substitution can be excluded. Fe and Mn are trivalent as documented by Mössbauer spectroscopy and optical absorption spectroscopy. Red beryl optimized formula is ∼[(Cs,Rb,K)0.02□0.98]Σ1.00□1.00(Al1.79Fe3+0.16Mn3+0.02Ti4+0.02Mg0.01)Σ2.00Be3(Si6O18). Location of Mn3+ was estimated to the octahedral Al3+ site, other choices are improbable due to the bond-length requirements. No Mn3+-induced Jahn-Teller structural distortion was detected due to site symmetry restrictions and small Mn3+ content. However, optical spectroscopy shows broad band at ∼7190 cm-1 assigned to the excited level of the spin-allowed pseudo-tetragonal split E ground state of elongated six-fold Mn3+ coordination. Crystal field calculations indicate that the local Mn3+ environment complies well with crystal chemical expectations for Jahn-Teller distorted Mn3+O6 octahedra.

Experimental investigation of the Jahn-Teller effect in the ground and excited electronic states of the tropyl radical. Part II. Vibrational analysis of the A 2E"3-X 2E"2 electronic transition.

PubMed

Sioutis, Ilias; Stakhursky, Vadim L; Tarczay, György; Miller, Terry A

2008-02-28

Laser-induced fluorescence (LIF) and laser-excited dispersed fluorescence (LEDF) spectra of the cycloheptatrienyl (tropyl) radical C7H7 have been observed under supersonic jet-cooling conditions. Assignment of the LIF excitation spectrum yields detailed information about the A-state vibronic structure. The LEDF emission was collected by pumping different vibronic bands of the A 2E"3<--X 2E"2 electronic spectrum. Analysis of the LEDF spectra yields valuable information about the vibronic levels of the X 2E"2 state. The X- and A-state vibronic structures characterize the Jahn-Teller distortion of the respective potential energy surfaces. A thorough analysis reveals observable Jahn-Teller activity in three of the four e'3 modes for the X 2E"2 state and two of the three e'1 modes for the A 2E"3 state and provides values for their deperturbed vibrational frequencies as well as linear Jahn-Teller coupling constants. The molecular parameters characterizing the Jahn-Teller interaction in the X and A states of C7H7 are compared to theoretical results and to those previously obtained for C5H5 and C6H6+.

Pseudo Jahn-Teller effect in control and rationalization of chemical transformations in two-dimensional compounds

NASA Astrophysics Data System (ADS)

Gorinchoy, N. N.; Bersuker, I. B.

2017-05-01

We show that the pseudo Jahn-Teller effect (PJTE) is instrumental in predicting and rationalizing structural changes in chemical transformations of two-dimensional (2D) molecular systems by means of analyzing the symmetries and electron occupation of the ground and lowest excited electronic states and the energy gap between them, subject to their PJT coupling along the main distortion coordinates. Special attention is paid to rationalizing the PJTE origin of non-planarity of 2D compounds and to the restoration of their planar configurations. Examples of two series of 1,2- and 1,4-dithiin containing tricyclic compounds (carbon sulfide, thianthrene, and antracene and their derivatives) are used to demonstrate in detail the mechanism of (1) enhancement and suppression of the PJTE distortions (puckering) in redox processes, and (2) PJTE induced symmetry breaking and restoration of the planar configuration by chemical substitutions.

Thermal and composition driven phase transition in the co-operative Jahn-Teller distorted Zn1-xCuxCr2O4 spinel

NASA Astrophysics Data System (ADS)

Saraswathy, S.; Kalavathi, S.; Rajamadhavan, R.; Asuvathraman, R.

2018-04-01

Phase pure poly crystalline powder samples of spinel compounds with formula Zn1-xCuxCr2O4 have been synthesized. It is found that for a critical concentration of Cu with x=0.58 cubic structure of the parent ZnCr2O4 transforms into a tetragonal structure. The well-known co-operative Jahn-Teller effect induces the structural transition and the observed variation of lattice parameters as a function of Cu substitution displays the role of strain. Thermally driven destruction of the co-operative Jahn-Teller effect and the resultant reverting back to cubic structure is observed to complete at 850 K and 373 K in pristine CuCr2O4 and Zn0.4Cu0.6Cr2O4. A first order transition observed for Zn0.4Cu0.6Cr2O4 is at variance with the continuous transition observed in the literature for Mg0.46Cu0.54Cr2O4.

The Jahn-Teller effect in (hu+)2⊗hg systems

NASA Astrophysics Data System (ADS)

Hands, Ian D.; Diery, Wajood A.; Dunn, Janette L.; Bates, Colin A.

2007-07-01

A general consideration is made of the vibronic coupling in a (hu+)2⊗hg Jahn-Teller system, that is to say, a system in which two holes of Hu symmetry are coupled to vibrations of hg symmetry. We find that the resulting high-spin states may undergo spontaneous distortion into species exhibiting one of the following four possible symmetries: D5 d, D3 d, D2 h or C2 h. The system may be viewed as a first approximation to a C602+ ion, but our intention here is to make a general consideration of the model without application to any specific molecular system. Coulombic interactions between holes, which must be important in real systems, are therefore ignored throughout. However, they could be included in the model, if required, using the method described in an earlier work [I.D. Hands, J.L. Dunn, W.A. Diery, C.A. Bates, Phys. Rev. B 73 (2006) 115435]. For each of the different symmetry types, projection operators are used to create symmetry-adapted states (SASs) that give a good account of the states of the system over a wide range of coupling strengths. These SASs are used, in turn, to derive energies for the vibronic states.

Using Extended Huckel Theory as a Platform to Introduce Jahn-Teller Distortion: The Spontaneous Distortion of 1,3,5,7-Cyclooctatetraene from a Perfect Octagon

ERIC Educational Resources Information Center

Sohlberg, Karl; Liu, Xiang

2013-01-01

Herein, a slightly enhanced version of extended Huckel molecular orbital theory is applied to demonstrate the spontaneous distortion of 1,3,5,7-cyclooctatetraene from a perfect octagon, a consequence of the Jahn-Teller effect. The exercise is accessible to students who have been introduced to basic quantum mechanics and extended Huckel molecular…

Modulation of Jahn-Teller effect on magnetization and spontaneous electric polarization of CuFeO2

NASA Astrophysics Data System (ADS)

Xiao, Guiling; Xia, Zhengcai; Wei, Meng; Huang, Sha; Shi, Liran; Zhang, Xiaoxing; Wu, Huan; Yang, Feng; Song, Yujie; Ouyang, Zhongwen

2018-03-01

CuFe0.99Mn0.01O2 and CuFe0.99Co0.01O2 single crystal samples are grown by a floating zone technique and their magnetization and spontaneous electric polarization have been investigated. Similarly with pure CuFeO2, an obviously anisotropic magnetization and spontaneous electric polarization were observed in the both doped samples, and their phase transition critical fields and temperatures are directly doping ion dependent. Considering the different d-shell configuration and ionic size between Mn3+, Co3+ and Fe3+ ions, in which the Mn3+ ion with Jahn-Teller (J-T) effect has different distortion on the geometry frustration from both of Fe3+ and Co3+ ion. Since for Mn3+ ion, the orbital splitting results from the low-symmetry J-T distortion in a crystal-field environment leads to a distorted MnO6 octahedron, which different from undistorted FeO6 and CoO6 octahedrons. The strain between distorted and undistorted octahedrons produces different effects on the spin reorientation transition and spontaneous electric polarization. Although the pure CuFeO2 has a very strong and robust frustration, the presence of the strain due to the random distribution of distorted MnO6 octahedron and undistorted CoO6 (FeO6) octahedrons leads to its spin reorientation transitions and spontaneous electric polarization different from CuFeO2.

The Jahn-Teller distortion influenced ferromagnetic order in Pr1-xLaxMnO3

NASA Astrophysics Data System (ADS)

He, Feifei; Mao, Zhongquan; Tang, Lingyun; Zhang, Jiang; Chen, Xi

2018-06-01

The structural and magnetic properties of Pr1-xLaxMnO3 (0 ≤ x ≤ 1) polycrystalline powders are investigated. A structural phase transition from a large Jahn-Teller (J-T) distorted orthorhombic structure to a small J-T distorted orthorhombic phase is found at x = 0.70, while the LaMnO3 is showed to have a rhombohedral structure. All the samples exhibit ferromagnetic ordering, and meanwhile, a reentrant spin glass behavior at low temperature. The relationship between J-T distortions and the ferromagnetic order is discussed.

Absence of Jahn-Teller transition in the hexagonal Ba 3CuSb 2O 9 single crystal

DOE PAGES

Katayama, Naoyuki; Kimura, Kenta; Han, Yibo; ...

2015-07-13

With decreasing temperature, liquids generally freeze into a solid state, losing entropy in the process. However, exceptions to this trend exist, such as quantum liquids, which may remain unfrozen down to absolute zero owing to strong quantum entanglement effects that stabilize a disordered state with zero entropy. Examples of such liquids include Bose-Einstein condensation of cold atoms, superconductivity, quantum Hall state of electron systems, and quantum spin liquid state in the frustrated magnets. Furthermore, recent studies have clarified the possibility of another exotic quantum liquid state based on the spin-orbital entanglement in FeSc2S4. To confirm this exotic ground state, experimentsmore » based on single-crystalline samples are essential. However, no such single-crystal study has been reported to date. Here, we report, to our knowledge, the first single-crystal study on the spin-orbital liquid candidate, 6H-Ba3CuSb2O9, and we have confirmed the absence of an orbital frozen state. In strongly correlated electron systems, orbital ordering usually appears at high temperatures in a process accompanied by a lattice deformation, called a static Jahn-Teller distortion. By combining synchrotron X-ray diffraction, electron spin resonance, Raman spectroscopy, and ultrasound measurements, we find that the static Jahn-Teller distortion is absent in the present material, which indicates that orbital ordering is suppressed down to the lowest temperatures measured. Lastly, we discuss how such an unusual feature is realized with the help of spin degree of freedom, leading to a spin-orbital entangled quantum liquid state.« less

Cyclopropenyl Anions: Carbon Tunneling or Diradical Formation? A Contest between Jahn-Teller and Hund.

PubMed

Kozuch, Sebastian

2015-07-14

The π bond shifting (automerization) by carbon tunneling of cyclopropenyl anions was computationally analyzed by the small curvature tunneling methodology. Similar to other antiaromatic cases, the process is hindered by substituents departing from planarity, since these groups must be realigned along with the π bond shifting. With hydrogens as substituents the tunneling is extremely fast, in a case of both heavy and light atom tunneling. But, with more massive substituents (such as Me and F), and especially with longer groups (such as CN), the tunneling probability is reduced or even virtually canceled. The automerization of triphenylcyclopropyl anion by tunneling was supposed to be impossible due to the high mass of the phenyl groups. However, it was found that the ground state of this species is actually a D3h aromatic triplet, a single-well system that cannot undergo automerization. For this and other systems with π acceptor groups, the superposition of states that generates the second-order Jahn-Teller distortion is diminished, and by Hund's rule, the triplet results in the ground state.

Generalized Born-Oppenheimer treatment of Jahn-Teller systems in Hilbert spaces of arbitrary dimension: theory and application to a three-state model potential.

PubMed

Varandas, A J C; Sarkar, B

2011-05-14

Generalized Born-Oppenheimer equations including the geometrical phase effect are derived for three- and four-fold electronic manifolds in Jahn-Teller systems near the degeneracy seam. The method is readily extendable to N-fold systems of arbitrary dimension. An application is reported for a model threefold system, and the results are compared with Born-Oppenheimer (geometrical phase ignored), extended Born-Oppenheimer, and coupled three-state calculations. The theory shows unprecedented simplicity while depicting all features of more elaborated ones.

Contribution of Jahn-Teller and charge transfer excitations to the photovoltaic effect of manganite/titanite heterojunctions

NASA Astrophysics Data System (ADS)

Ifland, Benedikt; Hoffmann, Joerg; Kressdorf, Birte; Roddatis, Vladimir; Seibt, Michael; Jooss, Christian

2017-06-01

The effect of correlation effects on photovoltaic energy conversion at manganite/titanite heterojunctions is investigated. As a model system we choose a heterostructure consisting of the small polaron absorber Pr0.66Ca0.34MnO3 (PCMO) epitaxially grown on single-crystalline Nb-doped SrTi0.998Nb0.002O3 (STNO) substrates. The high structural and chemical quality of the interfaces is proved by detailed characterization using high-resolution transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) studies. Spectrally resolved and temperature-dependent photovoltaic measurements show pronounced contributions of both the Jahn-Teller (JT) excitations and the charge transfer (CT) transitions to the photovoltaic effect at different photon energies. A linear temperature dependence of the open-circuit voltage for an excitation in the PCMO manganite is only observed below the charge-ordering temperature, indicating that the diffusion length of the photocarrier exceeds the size of the space charge region. The photovoltaic response is compared to that of a heterojunction of lightly doped Pr0.05Ca0.95MnO3 (CMO)/STNO, where the JT transition is absent. Here, significant contributions of the CT transition to the photovoltaic effect set in below the Neel temperature. We conclude that polaronic correlations and ordering effects are essentials for photovoltaic energy conversion in manganites.

Dynamical Jahn Teller distortion in single crystals of Cu(II) doped magnesium potassium phosphate hexahydrate: a variable temperature EPR study

NASA Astrophysics Data System (ADS)

PrabhuKantan, A.; Velavan, K.; Venkatesan, R.; Sambasiva Rao, P.

2003-05-01

Single crystal electron paramagnetic resonance (EPR) studies on Cu(II)-doped magnesium potassium phosphate hexahydrate have been carried out at room temperature. The temperature dependence of g and A values has been obtained for the polycrystalline sample and the ground state is unambiguously identified. These results indicate the existence of a dynamic Jahn-Teller distortion for Cu(II) ion. The g and A tensor direction cosines are evaluated and compared with Mg-O directions, which confirms that Cu(II) enters substitutionally in the lattice.

Ab initio theory of spin-orbit coupling for quantum bits in diamond exhibiting dynamic Jahn-Teller effect

NASA Astrophysics Data System (ADS)

Gali, Adam; Thiering, Gergő

Dopants in solids are promising candidates for implementations of quantum bits for quantum computing. In particular, the high-spin negatively charged nitrogen-vacancy defect (NV) in diamond has become a leading contender in solid-state quantum information processing. The initialization and readout of the spin is based on the spin-selective decay of the photo-excited electron to the ground state which is mediated by spin-orbit coupling between excited states states and phonons. Generally, the spin-orbit coupling plays a crucial role in the optical spinpolarization and readout of NV quantum bit (qubit) and alike. Strong electron-phonon coupling in dynamic Jahn-Teller (DJT) systems can substantially influence the effective strength of spin-orbit coupling. Here we show by ab initio supercell density functional theory (DFT) calculations that the intrinsic spin-orbit coupling is strongly damped by DJT effect in the triplet excited state that has a consequence on the rate of non-radiative decay. This theory is applied to the ground state of silicon-vacancy (SiV) and germanium-vacancy (GeV) centers in their negatively charged state that can also act like qubits. We show that the intrinsic spin-orbit coupling in SiV and GeV centers is in the 100 GHz region, in contrast to the NV center of 10 GHz region. Our results provide deep insight in the nature of SiV and GeV qubits in diamond. EU FP7 DIADEMS project (Contract No. 611143).

An EPR investigation of the dynamic Jahn-Teller effect in SrCl2:y(2 plus) and SrCl2:Sc(2 plus)

NASA Technical Reports Server (NTRS)

Herrington, J. R.; Estle, T. L.; Boatner, L. A.

1972-01-01

EPR spectra have been observed for SrCl2:Y(2+) and SrCl2:Sc(2+) at liquid helium temperatures. At 1.2 K the spectra were dominated by anisotropic hyperfine patterns whose lineshapes and angular dependences were explained using second order solutions of the effective Hamiltonian for an isolated 2Eg state split by large random internal strains. Pronounced asymmetries in some of the strin produced lineshapes for Srcl2:Sc(2+) are shown to result from second order terms in the solution of the effective Hamiltonian. Coexisting with the anisotropic hyperfine patterns are weak nearly isotropic hyperfine patterns with typical lineshapes. Variations in the apparent intensity of lines in these weak hyperfine patterns as functions of the applied magnetic field direction and temperature imply that these lines result from averaging by vibronic relaxation of a portion of the anisotropic pattern. The effective Hamiltonian parameters for SrCl2:La(2+), SrCl2:y(2+), and SrCl2:SC(2+) are analyzed in terms of crystal field theory modified to include a dynamic Jahn-Teller effect.

Jahn-Teller distortion in the phosphorescent excited state of three-coordinate Au(I) phosphine complexes.

PubMed

Barakat, Khaldoon A; Cundari, Thomas R; Omary, Mohammad A

2003-11-26

DFT calculations were used to optimize the phosphorescent excited state of three-coordinate [Au(PR3)3]+ complexes. The results indicate that the complexes rearrange from their singlet ground-state trigonal planar geometry to a T-shape in the lowest triplet luminescent excited state. The optimized structure of the exciton contradicts the structure predicted based on the AuP bonding properties of the ground-state HOMO and LUMO. The rearrangement to T-shape is a Jahn-Teller distortion because an electron is taken from the degenerate e' (5dxy, 5dx2-y2) orbital upon photoexcitation of the ground-state D3h complex. The calculated UV absorption and visible emission energies are consistent with the experimental data and explain the large Stokes' shifts while such correlations are not possible in optimized models that constrained the exciton to the ground-state trigonal geometry.

Jahn-Teller transition in TiF3 investigated using density-functional theory

NASA Astrophysics Data System (ADS)

Perebeinos, Vasili; Vogt, Tom

2004-03-01

We use first-principles density-functional theory to calculate the electronic and magnetic properties of TiF3 using the full-potential-linearized augmented-plane-wave method. The local density approximation (LDA) predicts a fully saturated ferromagnetic metal and finds degenerate energy minima for high- and low-symmetry structures. The experimentally observed Jahn-Teller phase transition at Tc=370 K cannot be driven by the electron-phonon interaction alone, which is usually described accurately by the LDA. Electron correlations beyond the LDA are essential to lift the degeneracy of the singly occupied Ti t2g orbital. Although the on-site Coulomb correlations are important, the direction of the t2g-level splitting is determined by dipole-dipole interactions. The LDA+U functional predicts an aniferromagnetic insulator with an orbitally ordered ground state. The input parameters U=8.1 eV and J=0.9 eV for the Ti 3d orbital were found by varying the total charge on the TiF2-6 ion using the molecular NRLMOL code. We estimate the Heisenberg exchange constant for spin 1/2 on a cubic lattice to be approximately 24 K. The symmetry lowering energy in LDA+U is about 900 K per TiF3 formula unit.

Acoustic Properties of Crystals with Jahn-Teller Impurities: Elastic Moduli and Relaxation Time. Application to SrF2:Cr2+

NASA Astrophysics Data System (ADS)

Averkiev, Nikita S.; Bersuker, Isaac B.; Gudkov, Vladimir V.; Zhevstovskikh, Irina V.; Sarychev, Maksim N.; Zherlitsyn, Sergei; Yasin, Shadi; Shakurov, Gilman S.; Ulanov, Vladimir A.; Surikov, Vladimir T.

2017-11-01

A new approach to evaluate the relaxation contribution to the total elastic moduli for crystals with Jahn-Teller (JT) impurities is worked out and applied to the analysis of the experimentally measured ultrasound velocity and attenuation in SrF2:Cr2+. Distinguished from previous work, the background adiabatic contribution to the moduli, important for revealing the impurity relaxation contribution, is taken into account. The temperature dependence of the relaxation time for transitions between the equivalent configurations of the JT centers has been obtained, and the activation energy for the latter in SrF2:Cr2+, as well as the linear vibronic coupling constant have been evaluated.

High-pressure behavior of cuprospinel CuFe 2O 4: Influence of the Jahn-Teller effect on the spinel structure

DOE PAGES

Kyono, Atsushi; Gramsch, Stephen A.; Nakamoto, Yuki; ...

2015-08-14

The Jahn-Teller-effect at Cu 2+ in cuprospinel CuFe 2O 4 was investigated using high-pressure, single crystal synchrotron x-ray diffraction (XRD) techniques at beamline BL10A at the Photon Factory, KEK, Japan. Six data sets were collected in the pressure range from ambient to 5.9 GPa at room temperature. Structural refinements based on the data were performed at 0.0, 1.8, 2.7, and 4.6 GPa. The unit cell volume of cuprospinel decreases continuously from 590.8 (6) Å 3 to 579.5 (8) Å 3 up to 3.8 GPa. Leastsquares fitting to a third-order Birch-Murnaghan equation of state yields zero-pressure volume V 0 = 590.7more » (1) Å 3 and bulk modulus K 0 = 188.1 (4.4) GPa with K’ fixed at 4.0. The crystal chemical composition determined by electron-probe analysis and x-ray site-occupancy refinement is represented as [Cu 0.526Fe 0.474] [6][Cu 0.074Fe 1.926]O 4. Most of the Cu 2+ are preferentially distributed onto the tetrahedral (T) site of the spinel structure. At 4.6 GPa, a cubic-tetragonal phase transition is indicated by a splitting of the a axis of the cubic structure into a smaller a axis and a longer c axis, with unit cell parameters a = 5.882 (1) Å and c = 8.337 (1) Å. The tetragonal crystal structure with space group I4 1/amd was refined to R1 = 0.0182 and wR2 = 0.0134 using observed 35 x-ray reflections. At the T site, the tetrahedral O-T-O bond angles along the c-axis direction of the unit cell decreases slightly from 109.47 ° to 108.7 (4) °, which generates a stretched tetrahedral geometry along the c-axis. The cubic-totetragonal transition induced by the Jahn-Teller effect at Cu 2+ is attributable to the angular distortion at the tetrahedral site. At the octahedral (M) site, on the other hand, the two M-O bonds parallel to the caxis are shortened with respect to the four M-O bonds parallel to the ab-plane, which are lengthened as a result of the phase transition, leading to a compressed octahedral geometry along the c-axis. With the competing distortions

On the Mechanism of D-Wave High TC Superconductivity by the Interplay of Jahn-Teller Physics and Mott Physics

NASA Astrophysics Data System (ADS)

Ushio, H.; Matsuno, S.; Kamimura, H.

2011-01-01

In the present paper we will discuss two important roles of the interplay of Jahn-Teller physics and Mott physics. One is the small Fermi surface. The "Fermi arcs" observed in ARPES should be one of the edges of small Fermi pockets, based on the Kamimura-Suwa model (K-S model). This prediction is consistent with ARPES results by Tanaka et al. Another is the mechanism of superconductivity in cuprates. This can be explained by the interplay of strong electron-phonon interactions and local AF order. It is shown that the characteristic phase difference of wave functions between up- and down-spin carriers in the presence of the local AF order leads to the superconducting gap of dx2-y2 symmetry even in the phonon-involved mechanism.

Bcc and Fcc transition metals and alloys: a central role for the Jahn-Teller effect in explaining their ideal and distorted structures.

PubMed

Lee, Stephen; Hoffmann, Roald

2002-05-01

Transition metal elements, alloys, and intermetallic compounds often adopt the body centered cubic (bcc) and face centered cubic (fcc) structures. By comparing quantitative density functional with qualitative tight-binding calculations, we analyze the electronic factors which make the bcc and fcc structures energetically favorable. To do so, we develop a tight-binding function, DeltaE(star), a function that measures the energetic effects of transferring electrons within wave vector stars. This function allows one to connect distortions in solids to the Jahn-Teller effect in molecules and to provide an orbital perspective on structure determining deformations in alloys. We illustrate its use by considering first a two-dimensional square net. We then turn to three-dimensional fcc and bcc structures, and distortions of these. Using DeltaE(star), we rationalize the differences in energy of these structures. We are able to deduce which orbitals are responsible for instabilities in seven to nine valence electron per atom (e(-)/a) bcc systems and five and six e(-)/a fcc structures. Finally we demonstrate that these results account for the bcc and fcc type structures found in both the elements and binary intermetallic compounds of group 4 through 9 transition metal atoms. The outline of a theory of metal structure deformations based on loss of point group operation rather than translational symmetry is presented.

Pseudo Jahn-Teller coupling in trioxides XO3(0,1,-1) with 22 and 23 valence electrons

NASA Astrophysics Data System (ADS)

Grein, Friedrich

2013-05-01

D3h and C2v geometries and energies, vertical excitation energies, as well as minimal energy paths as function of the O1(z)-X-O2 angle α were obtained for XO3(0,1,-1) (X = B, Al, Ga; C, Si, Ge; N, P, As; S, Se) molecules and ions with 22 and 23 valence electrons (VE), using density functional theory (DFT), coupled cluster with single and double substitutions with noniterative triple excitations (CCSD(T)), equation of motion (EOM)-CCSD, time-dependent DFT, and multi-reference configuration interaction methods. It is shown that pseudo Jahn-Teller (PJT) coupling increases as the central atom X becomes heavier, due to decreases in excitation energies. As is well known for CO3, the excited 1E' states of the 22 VE systems SiO3, GeO3; NO_3 ^ +, PO3+, AsO3+; BO3-, AlO3-, GaO3- have strong vibronic coupling with the 1A1' ground state via the e' vibrational modes, leading to a C2v minimum around α = 145°. For first and second row X atoms, there is an additional D3h minimum (α = 120°). Interacting excited states have minima around 135°. In the 23 VE systems CO3-, SiO3-; NO3, PO3; SO3+, coupling of the excited 2E' with the 2A2' ground state via the e' mode does not generate a C2v state. Minima of interacting excited states are close to 120°. However, due to very strong PJT coupling, a double-well potential is predicted for GeO3-, AsO3, and SeO3+, with a saddle point at D3h symmetry. Interaction of the b2 highest occupied molecular orbital with the b2 lowest unoccupied molecular orbital, both oxygen lone pair molecular orbitals, is seen as the reason for the C2v stabilization of 22 VE molecules.

Theoretical Study of the Jahn-Teller effect in CH3CN+ (X2E) and CD3CN+ (X2E): multimode spin-vibronic energy level calculations.

PubMed

Zhang, Shiyang; Mo, Yuxiang

2009-10-15

The spin-vibronic energy levels for CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) have been calculated using a diabatic model including multimode vibronic couplings and spin-orbit interaction without adjusting any parameter. The diabatic potential energy surfaces are represented by the Taylor expansions including linear, quadratic and bilinear vibronic coupling terms. The normal coordinates used in the Taylor expansion were expressed by the mass-weighted Cartesian coordinates. The adiabatic potential energy surfaces for CH(3)CN(+) and CD(3)CN(+) were calculated at the level of CASPT2/cc-pvtz, and the spin-orbit coupling constant was calculated at the level of MRCI/CAS/cc-pvtz. The spin-orbit energy splittings for the ground vibrational states of CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) are 20 and 16 cm(-1), respectively, which are resulted from the quenching of the spin-orbit coupling strength of 51 cm(-1). The calculated spin-vibronic levels are in good agreement with the experimental data. The calculation results show that the Jahn-Teller effects in CH(3)CN(+)(X(2)E) and CD(3)CN(+)(X(2)E) are essential to understand their spin-vibronic energy structure.

Underlying theory of a model for the Renner-Teller effect in tetra-atomic molecules: X(2)Πu electronic state of C2H2(+).

PubMed

Perić, M; Jerosimić, S; Mitić, M; Milovanović, M; Ranković, R

2015-05-07

In the present study, we prove the plausibility of a simple model for the Renner-Teller effect in tetra-atomic molecules with linear equilibrium geometry by ab initio calculations of the electronic energy surfaces and non-adiabatic matrix elements for the X(2)Πu state of C2H2 (+). This phenomenon is considered as a combination of the usual Renner-Teller effect, appearing in triatomic species, and a kind of the Jahn-Teller effect, similar to the original one arising in highly symmetric molecules. Only four parameters (plus the spin-orbit constant, if the spin effects are taken into account), which can be extracted from ab initio calculations carried out at five appropriate (planar) molecular geometries, are sufficient for building up the Hamiltonian matrix whose diagonalization results in the complete low-energy (bending) vibronic spectrum. The main result of the present study is the proof that the diabatization scheme, hidden beneath the apparent simplicity of the model, can safely be carried out, at small-amplitude bending vibrations, without cumbersome computation of non-adiabatic matrix elements at large number of molecular geometries.

Symmetry breaking in the planar configurations of disilicon tetrahalides: Pseudo-Jahn-Teller effect parameters, hardness and electronegativity.

PubMed

Kouchakzadeh, Ghazaleh; Nori-Shargh, Davood

2015-11-21

CCSD(T), MP2, LC-BLYP, LC-ωPBE and B3LYP methods with the Def2-TZVPP basis set and natural bond orbital (NBO) interpretations were performed to investigate the correlations between the Pseudo-Jahn-Teller Effect (PJTE) parameters [i.e. vibronic coupling constant values (F), energy gaps between reference states (Δ) and the primary force constant (K0)], structural and configurational properties, global hardness, global electronegativity, natural bond orders, stabilization energies associated with electron delocalizations and natural atomic charges of disilicon tetrafluoride (1), disilicon tetrachloride (2), disilicon tetrabromide (3) and disilicon tetraiodide (4). All levels of theory showed the trans-bent (C2h) configurations as the energy minimum structures of compounds 1-4, and the flap angles between the X2Si planes and the Si=Si bonds in the distorted (C2h) configurations decrease from compound 1 to compound 4. The negative curvatures of the ground state electronic configurations and the positive curvatures of the excited states of the adiabatic potential energy surfaces (APESs) which resulted from the mixing of the ground Ag and excited B2g states are due to the PJTE (i.e. PJT(Ag + B2g) ⊗ b2g problem). Contrary to the usual expectation, with the decrease of the energy gaps between reference states (Δ), the PJTE stabilization energy, E(PJT), decreases from compound 1 to compound 4. The canonical molecular orbital (CMO) analysis revealed that the contributions of the ψ(HOMO)(b3u) and ψL(UMO)(b1u) molecular orbitals in the vibronic coupling constant (F) decrease from compound 1 to compound 4. This fact clearly justifies the decrease of the vibronic coupling constant (F) and the primary force constant (the force constant without the PJTE) values on going from compound 1 to compound 4, leading to the decrease of the negative curvatures of the ground state electronic configuration curves of their corresponding APESs. The results obtained showed that the

Ab initio study of dynamical E × e Jahn-Teller and spin-orbit coupling effects in the transition-metal trifluorides TiF3, CrF3, and NiF3

NASA Astrophysics Data System (ADS)

Mondal, Padmabati; Opalka, Daniel; Poluyanov, Leonid V.; Domcke, Wolfgang

2012-02-01

Multiconfiguration ab initio methods have been employed to study the effects of Jahn-Teller (JT) and spin-orbit (SO) coupling in the transition-metal trifluorides TiF3, CrF3, and NiF3, which possess spatially doubly degenerate excited states (ME) of even spin multiplicities (M = 2 or 4). The ground states of TiF3, CrF3, and NiF3 are nondegenerate and exhibit minima of D3h symmetry. Potential-energy surfaces of spatially degenerate excited states have been calculated using the state-averaged complete-active-space self-consistent-field method. SO coupling is described by the matrix elements of the Breit-Pauli operator. Linear and higher order JT coupling constants for the JT-active bending and stretching modes as well as SO-coupling constants have been determined. Vibronic spectra of JT-active excited electronic states have been calculated, using JT Hamiltonians for trigonal systems with inclusion of SO coupling. The effect of higher order (up to sixth order) JT couplings on the vibronic spectra has been investigated for selected electronic states and vibrational modes with particularly strong JT couplings. While the weak SO couplings in TiF3 and CrF3 are almost completely quenched by the strong JT couplings, the stronger SO coupling in NiF3 is only partially quenched by JT coupling.

Vibronic Analysis for widetilde{B} - widetilde{X} Transition of Isopropoxy Radical

NASA Astrophysics Data System (ADS)

Chhantyal-Pun, Rabi; Miller, Terry A.

2013-06-01

Alkoxy radicals are important intermediates in combustion and atmospheric chemistry. Alkoxy radicals are also of significant spectroscopic interest for the study of Jahn Teller and pseudo Jahn Teller effects, involving the widetilde{X} and widetilde{A} states. The Jahn Teller effect has been studied in methoxy. Substitution of one or two hydrogens by methyl groups transforms the interaction to a pseudo Jahn Teller effect in ethoxy and isopropoxy. Previously, moderate resolution scans have been obtained for widetilde{B} - widetilde{X} and widetilde{B} - widetilde{A} transition systems, the latter observable at higher temperature. These measurements have shown that the widetilde{X} and widetilde{A} states of isopropoxy are separated by only 60.7(7) cm^{-1} which indicates a strong pseudo Jahn Teller effect in the widetilde{X} state. Such pseduo Jahn Teller coupling should also introduce additional bands into the widetilde{B} - widetilde{X} spectrum and a number of weaker transitions have been observed which may be caused by such effects. In this talk we present a vibronic analysis for the widetilde{B} - widetilde{X} transition based on the experimental results and also the results from recent quantum chemistry calculations.

Pseudo-Jahn-Teller Distortion in Two-Dimensional Phosphorus: Origin of Black and Blue Phases of Phosphorene and Band Gap Modulation by Molecular Charge Transfer.

PubMed

Chowdhury, Chandra; Jahiruddin, Sheik; Datta, Ayan

2016-04-07

Phosphorene (Pn) is stabilized as a layered material like graphite, yet it possess a natural direct band gap (Eg = 2.0 eV). Interestingly, unlike graphene, Pn exhibits a much richer phase diagram which includes distorted forms like the stapler-clip (black Pn, α form) and chairlike (blue Pn, β form) structures. The existence of these phases is attributed to pseudo-Jahn-Teller (PJT) instability of planar hexagonal P6(6-) rings. In both cases, the condition for vibronic instability of the planar P6(6-) rings is satisfied. Doping with electron donors like tetrathiafulvalene and tetraamino-tetrathiafulvalene and electron acceptors like tetracyanoquinodimethane and tetracyanoethylene convert blue Pn into N-type and black Pn into efficient P-type semiconductors, respectively. Interestingly, pristine blue Pn, an indirect gap semiconductor, gets converted into a direct gap semiconductor on electron or hole doping. Because of comparatively smaller undulation in blue Pn (with respect to black Pn), the van der Waals interactions between the dopants and blue Pn is stronger. PJT distortions for two-dimensional phosphorus provides a unified understanding of structural features and chemical reactivity in its different phases.

Aggregate frequency width, nuclear hyperfine coupling and Jahn-Teller effect of Cu2+ impurity ion ESR in SrLaAlO4 dielectric resonator at 20 millikelvin

NASA Astrophysics Data System (ADS)

Hosain, M. A.; Le Floch, J.-M.; Krupka, J.; Tobar, M. E.

2018-01-01

The impurity paramagnetic ion, Cu2+ substitutes Al in the SrLaAlO4 single crystal lattice, this results in a CuO6 elongated octahedron, and the resulting measured g-factors satisfy four-fold axes variation condition. The aggregate frequency width of the electron spin resonance with the required minimum level of impurity concentration has been evaluated in this single crystal SrLaAlO4 at 20 millikelvin. Measured parallel hyperfine constants, A\\Vert Cu , were determined to be -155.7×10-4~cm-1, ~ -163.0×10-4~cm-1, ~ -178.3×10-4~cm-1 and -211.1×10-4~cm-1 at 9.072~GHz~(WGH4, 1, 1) for the nuclear magnetic quantum number M_I=+\\frac{3}{2}, +\\frac{1}{2}, -\\frac{1}{2} , and -\\frac{3}{2} respectively. The anisotropy of the hyperfine structure reveals the characteristics of the static Jahn-Teller effect. The second-order-anisotropy term, ˜ (\\fracspin{-orbit~coupling}{10D_q}){\\hspace{0pt}}2 , is significant and cannot be disregarded, with the local strain dominating over the observed Zeeman-anisotropy-energy difference. The Bohr electron magneton, β=9.23× 10-24 JT-1 , (within -0.43% so-called experimental error) has been found using the measured spin-Hamiltonian parameters. Measured nuclear dipolar hyperfine structure parameter P\\Vert=12.3×10-4~cm-1 shows that the mean inverse third power of the electron distance from the nucleus is < r-3_q>≃ 5.23 a.u. for Cu2+ ion in the substituted Al3+ ion site assuming nuclear electric quadruple moment Q=-0.211 barn.

Free H₂ rotation vs Jahn-Teller constraints in the nonclassical trigonal (TPB)Co-H₂ complex.

PubMed

Gunderson, William A; Suess, Daniel L M; Fong, Henry; Wang, Xiaoping; Hoffmann, Christina M; Cutsail, George E; Peters, Jonas C; Hoffman, Brian M

2014-10-22

Proton exchange within the M-H2 moiety of (TPB)Co(H2) (Co-H2; TPB = B(o-C6H4P(i)Pr2)3) by 2-fold rotation about the M-H2 axis is probed through EPR/ENDOR studies and a neutron diffraction crystal structure. This complex is compared with previously studied (SiP(iPr)3)Fe(H2) (Fe-H2) (SiP(iPr)3 = [Si(o-C6H4P(i)Pr2)3]). The g-values for Co-H2 and Fe-H2 show that both have the Jahn-Teller (JT)-active (2)E ground state (idealized C3 symmetry) with doubly degenerate frontier orbitals, (e)(3) = [|mL ± 2>](3) = [x(2) - y(2), xy](3), but with stronger linear vibronic coupling for Co-H2. The observation of (1)H ENDOR signals from the Co-HD complex, (2)H signals from the Co-D2/HD complexes, but no (1)H signals from the Co-H2 complex establishes that H2 undergoes proton exchange at 2 K through rotation around the Co-H2 axis, which introduces a quantum-statistical (Pauli-principle) requirement that the overall nuclear wave function be antisymmetric to exchange of identical protons (I = 1/2; Fermions), symmetric for identical deuterons (I = 1; Bosons). Analysis of the 1-D rotor problem indicates that Co-H2 exhibits rotor-like behavior in solution because the underlying C3 molecular symmetry combined with H2 exchange creates a dominant 6-fold barrier to H2 rotation. Fe-H2 instead shows H2 localization at 2 K because a dominant 2-fold barrier is introduced by strong Fe(3d)→ H2(σ*) π-backbonding that becomes dependent on the H2 orientation through quadratic JT distortion. ENDOR sensitively probes bonding along the L2-M-E axis (E = Si for Fe-H2; E = B for Co-H2). Notably, the isotropic (1)H/(2)H hyperfine coupling to the diatomic of Co-H2 is nearly 4-fold smaller than for Fe-H2.

a Zero-Order Picture of the Infrared Spectrum for the Methoxy Radical: Assignment of States

NASA Astrophysics Data System (ADS)

Johnson, Britta; Sibert, Edwin

2016-06-01

The ground tilde{X}^2E vibrations of the methoxy radical have intrigued both experimentalists and theorists alike due to the presence of a conical intersection at the C3v molecular geometry. This conical intersection causes methoxy's vibrational spectrum to be strongly influenced by Jahn-Teller vibronic coupling which leads to large amplitude vibrations and extensive mixing of the two lowest electronic states. This coupling combined with spin-orbit and Fermi couplings greatly complicates the assignments of states. Using the potential force field and calculated spectra of Nagesh and Sibert1,2, we assign quantum numbers to the infrared spectrum. When the zero-order states are the diabatic normal mode states, there is sufficient mode mixing that the normal mode quantum numbers are poor labels for the final states. We define a series of zero-order Hamiltonians which include additional coupling elements beyond the normal mode picture but still allow for the assignment of Jahn-Teller quantum numbers. In methoxy, the two lowest frequency e} modes, the bend (q_5) and the rock (q_6), are the modes with the strongest Jahn-Teller coupling. In general, a zero-order Hamiltonian which includes first-order Jahn-Teller coupling in q_6 is sufficient for most states of interest. Working in a representation which includes first-order Jahn-Teller coupling in q_6, we identify states in which additional coupling elements must be included; these couplings include first-order Jahn-Teller coupling in q_5, higher order Jahn-Teller coupling in q_5 and q_6, and, in the dueterated case, Jahn-Teller coupling which is modulated by the corresponding a modes. [^1] Nagesh, J.; Sibert, E. L. J. Phys. Chem. A 2012, 116, 3846-3855. Lee, Y.F.; Chou, W.T.; Johnson, B.A.; Tabor, D.P. ; Sibert, E.L.; Lee, Y.P. J. Mol. Spectrosc. 2015, 310, 57-67. Barckholtz, T. A.; Miller, T. A. Int. Revs. in Phys. Chem. 1998, 17, 435-524.

Nodeless vibrational amplitudes and quantum nonadiabatic dynamics in the nested funnel for a pseudo Jahn-Teller molecule or homodimer

NASA Astrophysics Data System (ADS)

Peters, William K.; Tiwari, Vivek; Jonas, David M.

2017-11-01

The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between

Nodeless vibrational amplitudes and quantum nonadiabatic dynamics in the nested funnel for a pseudo Jahn-Teller molecule or homodimer.

PubMed

Peters, William K; Tiwari, Vivek; Jonas, David M

2017-11-21

The nonadiabatic states and dynamics are investigated for a linear vibronic coupling Hamiltonian with a static electronic splitting and weak off-diagonal Jahn-Teller coupling through a single vibration with a vibrational-electronic resonance. With a transformation of the electronic basis, this Hamiltonian is also applicable to the anti-correlated vibration in a symmetric homodimer with marginally strong constant off-diagonal coupling, where the non-adiabatic states and dynamics model electronic excitation energy transfer or self-exchange electron transfer. For parameters modeling a free-base naphthalocyanine, the nonadiabatic couplings are deeply quantum mechanical and depend on wavepacket width; scalar couplings are as important as the derivative couplings that are usually interpreted to depend on vibrational velocity in semiclassical curve crossing or surface hopping theories. A colored visualization scheme that fully characterizes the non-adiabatic states using the exact factorization is developed. The nonadiabatic states in this nested funnel have nodeless vibrational factors with strongly avoided zeroes in their vibrational probability densities. Vibronic dynamics are visualized through the vibrational coordinate dependent density of the time-dependent dipole moment in free induction decay. Vibrational motion is amplified by the nonadiabatic couplings, with asymmetric and anisotropic motions that depend upon the excitation polarization in the molecular frame and can be reversed by a change in polarization. This generates a vibrational quantum beat anisotropy in excess of 2/5. The amplitude of vibrational motion can be larger than that on the uncoupled potentials, and the electronic population transfer is maximized within one vibrational period. Most of these dynamics are missed by the adiabatic approximation, and some electronic and vibrational motions are completely suppressed by the Condon approximation of a coordinate-independent transition dipole between

Eu/RG absorption and excitation spectroscopy in the solid rare gases: state dependence of crystal field splitting and Jahn-Teller coupling.

PubMed

Byrne, Owen; McCaffrey, John G

2011-03-28

Absorption spectroscopy recorded for annealed samples of matrix-isolated atomic europium reveals a pair of thermally stable sites in Ar and Kr while a single site exists in Xe. Plots of the matrix shifts of the visible s → p bands versus host polarizability, allowed the association of the single site in Xe and the blue sites in Ar and Kr. On the basis of the similar ground state bond lengths expected for the Eu-rare gas (RG) diatomics and the known Na-RG molecules, the blue sites are attributed to Eu occupancy in the smaller tetra-vacancy while the red sites are proposed to arise from hexa-vacancy sites. Both sites are of cubic symmetry, consistent with the pronounced Jahn-Teller structure present on the y(8)P ← a(8)S(7/2) transition for these bands in the three hosts studied. Site-selective excitation spectroscopy has been used to reanalyze complex absorption spectra previously published by Jakob et al. [Phys. Lett. A 57, 67 (1976)] for the near-UV f → d transitions. On the basis that a pair of thermally stable sites exist in solid argon, the occurrence of crystal field splitting has been identified to occur for the J ≥ 5/2 level of the (8)P state when isolated in these two sites with cubic symmetry. From a detailed lineshape analysis, the magnitude of the crystal field splittings on the J = 5/2 level in Ar is found to be 105 and 123 cm(-1) for the red and blue sites, respectively.

Jahn–Teller Assisted Na Diffusion for High Performance Na Ion Batteries

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

Li, Xin; Wang, Yan; Wu, Di

2016-08-30

Na energy storage technology is strategically attractive for large scale applications such as grid energy storage. Here, we show in this paper that there is a clear relation between the Jahn$-$Teller activity of a transition metal ion at the end of charge and the mobility of Na in a cathode material. This is particularly important as mobility at the end of charge limits the capacity of current materials. Consequently, by using this classical piece of physics in the battery world, it is possible to create higher capacity Na-cathode materials. Even more exciting is that the ideal element to impart thismore » effect on cathodes is Fe, which is the least expensive of the transition metal oxides and can therefore enable low cost cathode materials.« less

α-ScVSe2O8, β-ScVSe2O8, and ScVTe2O8: new quaternary mixed metal oxides composed of only second-order Jahn-Teller distortive cations.

PubMed

Kim, Yeong Hun; Lee, Dong Woo; Ok, Kang Min

2013-10-07

Three new quaternary scandium vanadium selenium/tellurium oxides, α-ScVSe2O8, β-ScVSe2O8, and ScVTe2O8 have been synthesized through hydrothermal and standard solid-state reactions. Although all three reported materials are stoichiometrically similar, they exhibit different crystal structures: α-ScVSe2O8 has a three-dimensional framework structure consisting of ScO6, VO6, and SeO3 groups. β-ScVSe2O8 reveals another three-dimensional framework composed of ScO7, VO5, and SeO3 polyhedra. ScVTe2O8 shows a layered structure with ScO6, VO4, and TeO4 polyhedra. Interestingly, the constituent cations, that is, Sc(3+), V(5+), Se(4+), and Te(4+) are all in a distorted coordination environment attributable to second-order Jahn-Teller (SOJT) effects. Complete characterizations including infrared spectroscopy, elemental analyses, thermal analyses, dipole moment calculation, and the magnitudes of out-of-center distortions for the compounds are reported. Transformation reactions suggest that α-ScVSe2O8 may change to β-ScVSe2O8, and then to Sc2(SeO3)3·H2O under hydrothermal conditions.

Multiconfiguration Self-Consistent Field Study on Formonitrile Imine and N-Substituted Nitrile Imines HCN2-R: Energy Component Analysis of the Pseudo-Jahn-Teller Effect.

PubMed

Toyota, Azumao; Muramatsu, Takashi; Koseki, Shiro

2017-03-23

Stable geometrical structures for formonitrile imine (1) and N-substituted nitrile imines HCN 2 -R (R = Li, BeH, BH 2 , CH 3 , CN, CCH, C 6 H 5 , NH 2 , OH, and F) (2-11) were examined by using the multiconfiguration self-consistent-field (MCSCF) method followed by second-order configuration interaction (SOCI) calculations and second-order multiconfiguration quasi-degenerate perturbation theory (MCQDPT2) calculations, together with the aug-cc-pVTZ basis sets. The results show that 1 suffers a pseudo-Jahn-Teller (JT) distortion from a linear C ∞v structure to a C 1 structure via a planar bent C s structure. Each of the others is found to undergo pseudo-JT distortion from a symmetrical structure to a planar bent C s structure for 2, 3, and 7 and to a C 1 structure for 4, 5, 6, 8, 9, 10, and 11. At the stationary structures of 1-11, the structural characteristics were briefly discussed in terms of allenic and propargylic. To elucidate the nature of pseudo-JT distortions, energy component analyses were carried out at the MCSCF+SOCI level of theory at all of the stationary structures for the relevant molecules. In most of the molecules examined, pseudo-JT stabilizations were classified into two groups, one in which the stability arises from a lowering of the energy of the attractive term V en and the other in which the stability results from a lowering of the energy of the repulsive terms V nn and V ee . In addition to the above two groups, it was also found that the following three groups are responsible for the pseudo-JT stabilizations in a certain stage of the structural changes. Namely, one is a lowering of the energy of the term V ee observed in 6, another is a lowering of the energy of the terms V ee and V en observed in 9-11, and the other is a lowering of the energy of the terms V en and V nn observed in 10. These energetic behaviors were accounted in terms of an elongation or a contraction of the molecular skeleton, a migration of electrons from one part of

Assigning the low lying vibronic states of CH3O and CD3O

NASA Astrophysics Data System (ADS)

Johnson, Britta A.; Sibert, Edwin L.

2017-05-01

The assignment of lines in vibrational spectra in strongly mixing systems is considered. Several low lying vibrational states of the ground electronic X˜ 2E state of the CH3O and CD3O radicals are assigned. Jahn-Teller, spin-orbit, and Fermi couplings mix the normal mode states. The mixing complicates the assignment of the infrared spectra using a zero-order normal mode representation. Alternative zero-order representations, which include specific Jahn-Teller couplings, are explored. These representations allow for definitive assignments. In many instances it is possible to plot the wavefunctions on which the assignments are based. The plots, which are shown in the adiabatic representation, allow one to visualize the effects of various higher order couplings. The plots also enable one to visualize the conical seam and its effect on the wavefunctions. The first and the second order Jahn-Teller couplings in the rocking motion dominate the spectral features in CH3O, while first order and modulated first order couplings dominate the spectral features in CD3O. The methods described here are general and can be applied to other Jahn-Teller systems.

Unconventional high-Tc superconductivity in fullerides.

PubMed

Takabayashi, Yasuhiro; Prassides, Kosmas

2016-09-13

A3C60 molecular superconductors share a common electronic phase diagram with unconventional high-temperature superconductors such as the cuprates: superconductivity emerges from an antiferromagnetic strongly correlated Mott-insulating state upon tuning a parameter such as pressure (bandwidth control) accompanied by a dome-shaped dependence of the critical temperature, Tc However, unlike atom-based superconductors, the parent state from which superconductivity emerges solely by changing an electronic parameter-the overlap between the outer wave functions of the constituent molecules-is controlled by the C60 (3-) molecular electronic structure via the on-molecule Jahn-Teller effect influence of molecular geometry and spin state. Destruction of the parent Mott-Jahn-Teller state through chemical or physical pressurization yields an unconventional Jahn-Teller metal, where quasi-localized and itinerant electron behaviours coexist. Localized features gradually disappear with lattice contraction and conventional Fermi liquid behaviour is recovered. The nature of the underlying (correlated versus weak-coupling Bardeen-Cooper-Schrieffer theory) s-wave superconducting states mirrors the unconventional/conventional metal dichotomy: the highest superconducting critical temperature occurs at the crossover between Jahn-Teller and Fermi liquid metal when the Jahn-Teller distortion melts.This article is part of the themed issue 'Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene'. © 2016 The Author(s).

Structure and Stability of Carboxylate Complexes. 20. Diaqua Bis(methoxyacetato) Complexes of Nickel(II), Copper(II), and Zinc(II): A Structural Study of the Dynamic Pseudo-Jahn-Teller Effect.

PubMed

Prout, Keith; Edwards, Alison; Mtetwa, Victor; Murray, Jon; Saunders, John F.; Rossotti, Francis J. C.

1997-06-18

The crystal structure of trans-diaquabis(methoxyacetato)copper(II), C(6)H(14)O(8)Cu, has been determined by neutron diffraction at 4.2 K (monoclinic, P2(1)/n, a = 6.88(1), b = 7.19(1), c = 9.77(2) Å, gamma = 95.7(1) degrees, (Z = 2)) and by X-ray diffraction at 125, 165, 205, 240, 265, 295, and 325 K. These measurements show that there is no phase change in the temperature range 4.2-325 K. The copper(II) coordination at 4.2 K is a tetragonally distorted elongated rhombic octahedron (Cu-OOC 1.955(1), Cu-OMe 2.209(1), and Cu-OH(2) 2.031(2) Å). As the temperature increases to 325 K, the Cu-OOC bonds shorten slightly to 1.934(5) Å, the Cu-OMe bonds shorten more markedly to 2.137(4) Å, and Cu-OH(2) lengthens to 2.155(6) Å to give a tetragonally distorted compressed rhombic octahedron. For comparison the structure of the isomorphous nickel(II) complex (monoclinic, P2(1)/n, a = 6.633(1), b = 7.192(1), c = 10.016(2) Å, gamma = 98.30(2) degrees, (Z = 2)) has been redetermined at 295 K and the structure of the analogous zinc(II) complex (orthorhombic, F2dd, a = 7.530(1), b = 13.212(1), c = 21.876(2) Å (Z = 8)) has also been determined. The nickel(II) complex has an almost regular trans (centrosymmetric) octahedral coordination (Ni-OOC 2.022(1), Ni-OMe 2.043(1), and Ni-OH(2) 2.077(2) Å). However, zinc(II) has a very distorted octahedral coordination with the zinc atom on a 2-fold axis with the water molecules and the methoxy ligators cis and the carboxylate ligators trans (Zn-OOC 1.985(1), Zn-OMe 2.304(2), and Zn-OH(2) 2.038(2) Å). The variation in the dimensions of the copper(II) coordination sphere is discussed in terms of static (low temperature) and planar dynamic (high temperature) pseudo-Jahn-Teller effects.

Anisotropic orbital occupation and Jahn-Teller distortion of orthorhombic YMnO{sub 3} epitaxial films: A combined experimental and theoretical study on polarization-dependent x-ray absorption spectroscopy

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

Haw, Shu-Chih; Chen, Shin-Ann; National Synchrotron Radiation Research Center

2014-04-21

The b-axis oriented orthorhombic YMnO{sub 3} (o-YMnO{sub 3}) epitaxial films on a YAlO{sub 3} (010) substrate were fabricated with pulsed-laser deposition. The anisotropic orbital occupation and Jahn-Teller (JT) distortion of an o-YMnO{sub 3} film were investigated with polarization-dependent x-ray absorption spectra and configuration-interaction multiplet-cluster calculations. A significant energy difference, ∼3.8 eV, for the main white line along E//b and E//a in polarization-dependent Mn K-edge spectra of o-YMnO{sub 3} indicates an extraordinary JT distortion and significant anisotropic Mn–O bonding within the ab plane in the o-YMnO{sub 3} film. Most importantly, although the orbital occupation of 3d electrons in o-YMnO{sub 3} filmsmore » is almost the same as that in single crystalline o-DyMnO{sub 3}, the JT distortion of o-YMnO{sub 3} films is larger than that of single crystalline o-DyMnO{sub 3}, deduced from the multiplet calculations. We speculate that this JT distortion predominantly contributes to the origin of the cycloidal spin deformation in bulk o-YMnO{sub 3}, because of a suppressed nearest-neighbor superexchange interaction and an enhanced next-nearest-neighbor superexchange interaction. These complementary results provide insight into the origin of the E-type magnetic configuration of o-YMnO{sub 3}.« less

Magneto-structural correlation in Co0.8Cu0.2Cr2O4 cubic spinel

NASA Astrophysics Data System (ADS)

Kumar, Ram; Rayaprol, S.; Siruguri, V.; Xiao, Y.; Ji, W.; Pal, D.

2018-05-01

Neutron and X-ray diffraction, magnetic susceptibility, and specific heat measurements have been used to investigate the magneto-structural phase transitions in 20% Cu substituted multiferroic CoCr2O4 spinel. The Jahn-Teller active Cu2+ ion in the tetrahedral A-site of the spinel configuration induces the Jahn-Teller distortion slightly above the Néel temperature. In this compound, we observe a Jahn-Teller distortion of the crystal structure at 90 K. It was further observed that the high temperature cubic (Fd 3 ‾ m) structure coexists with the low temperature orthorhombic (Fddd) structure till the lowest temperature of measurement.

Phase Separation and d Electronic Orbitals on Cyclic Degradation in Li-Mn-O Compounds: First-Principles Multiscale Modeling and Experimental Observations.

PubMed

Kim, Duho; Lim, Jin-Myoung; Park, Min-Sik; Cho, Kyeongjae; Cho, Maenghyo

2016-07-06

A combined study involving experiments and multiscale computational approaches is conducted to propose a theoretical solution for the suppression of the Jahn-Teller distortion which causes severe cyclic degradation. As-synthesized pristine and Al-doped Mn spinel compounds are the focus to understand the mechanism of the cyclic degradation in terms of the Jahn-Teller distortion, and the electrochemical performance of the Al-doped sample shows enhanced cyclic performance compared with that of the pristine one. Considering the electronic structures of the two systems using first-principles calculations, the pristine spinel suffers entirely from the Jahn-Teller distortion by Mn(3+), indicating an anisotropic electronic structure, but the Al-doped spinel exhibits an isotropic electronic structure, which means the suppressed Jahn-Teller distortion. A multiscale phase field model in nanodomain shows that the phase separation of the pristine spinel occurs to inactive Li0Mn2O4 (i.e., fully delithiated) gradually during cycles. In contrast, the Al-doped spinel does not show phase separation to an inactive phase. This explains why the Al-doped spinel maintains the capacity of the first charge during the subsequent cycles. On the basis of the mechanistic understanding of the origins and mechanism of the suppression of the Jahn-Teller distortion, fundamental insight for making tremendous cuts in the cyclic degradation could be provided for the Li-Mn-O compounds of Li-ion batteries.

Magnetostructural Properties of Colossal Magnetoresistance Manganites Under External Magnetic Fields and Uniaxial Pressure

NASA Astrophysics Data System (ADS)

Kaplan, Michael; Zimmerman, George

2002-03-01

In the colossal magnetoresistance manganites the transport and magnetostructural properties are tightly connected [1,2]. Many magnetic field induced structural phase transitions and anomalous magnetoacoustical properties continue to be discovered in various manganite derivatives. Nevertheless the mechanism of structural transitions and microscopic theory of corresponding anomalous properties are still to be completely understood. Here we present a microscopic model of magnetic field and uniaxial pressure induced structural phase transitions in lightly doped manganites. The model is based on the cooperative Jahn-Teller effect which takes into account the Mn3+-ground doublet and excited triplet electronic states. Numerous calculations for different orientation magnetic field suggest the explanations of the origin of the structural transitions and of the measured magnetostriction data. The calculations for the two-sublattice antiferrodistortive crystals under uniaxial pressure support the idea of metaelasticity - a property typical for Jahn-Teller antiferroelastics. 1.Y. Tokura, ed. Colossal Magnetoresistance Oxides. Gordon & Breach, London, 2000. 2.M. Kaplan, G. Zimmerman, eds. Vibronic Interactions: Jahn-Teller Effect in Crystal and Molecules. NATO Science Series, Dordrecht/Boston/London, 2001

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

Bhattacharyya, Swarnendu, E-mail: swarnendu.bhattacharyya@ch.tum.de; Domcke, Wolfgang, E-mail: wolfgang.domcke@ch.tum.de; Dai, Zuyang

A diabatic three-sheeted six-dimensional potential-energy surface has been constructed for the ground state and the lowest excited state of the PH{sub 3}{sup +} cation. Coupling terms of Jahn-Teller and pseudo-Jahn-Teller origin up to eighth order had to be included to describe the pronounced anharmonicity of the surface due to multiple conical intersections. The parameters of the diabatic Hamiltonian have been optimized by fitting the eigenvalues of the potential-energy matrix to ab initio data calculated at the CASSCF/MRCI level employing the correlation-consistent triple-ζ basis. The theoretical photoelectron spectrum of phosphine and the non-adiabatic nuclear dynamics of the phosphine cation have beenmore » computed by propagating nuclear wave packets with the multiconfiguration time-dependent Hartree method. The theoretical photoelectron bands obtained by Fourier transformation of the autocorrelation function agree well with the experimental results. It is shown that the ultrafast non-radiative decay dynamics of the first excited state of PH{sub 3}{sup +} is dominated by the exceptionally strong Jahn-Teller coupling of the asymmetric bending vibrational mode together with a hyperline of conical intersections with the electronic ground state induced by the umbrella mode. Time-dependent population probabilities have been computed for the three adiabatic electronic states. The non-adiabatic Jahn-Teller dynamics within the excited state takes place within ≈5 fs. Almost 80% of the excited-state population decay to the ground state within about 10 fs. The wave packets become highly complex and delocalized after 20 fs and no further significant transfer of electronic population seems to occur up to 100 fs propagation time.« less

Non percolative nature of the metal-insulator transition and persistence of local Jahn-Teller distortions in the rhombohedral regime of La 1-xCa xMnO 3

DOE PAGES

Shatnawi, Mouath; Bozin, Emil S.; Mitchell, J. F.; ...

2016-04-25

Evolution of the average and local crystal structure of Ca-doped LaMnO 3 has been studied across the metal to insulator (MI) and the orthorhombic to rhombohedral (OR) structural phase transitions over a broad temperature range for two Ca concentrations (x = 0.18,0.22). Combined Rietveld and high real space resolution atomic pair distribution function (PDF) analysis of neutron total scattering data was carried out with aims of exploring the possibility of nanoscale phase separation (PS) in relation to MI transition, and charting the evolution of local Jahn-Teller (JT) distortion of MnO 6 octahedra across the OR transition at T S~720 K.more » The study utilized explicit two-phase PDF structural modeling, revealing that away from T MI there is no evidence for nanoscale phase coexistence. The local JT distortions disappear abruptly upon crossing into the metallic regime both with doping and temperature, with only a small temperature-independent signature of quenched disorder being observable at low temperature as compared to CaMnO 3. The results hence do not support the percolative scenario for the MI transition in La 1–xCa xMnO 3 based on PS, and question its ubiquity in the manganites. In contrast to LaMnO 3 that exhibits long-range orbital correlations and sizable octahedral distortions at low temperature, the doped samples with compositions straddling the MI boundary exhibit correlations (in the insulating regime) limited to only ~1 nm with observably smaller distortions. In the x = 0.22 sample local JT distortions are found to persist across the OR transition and deep into the R phase (up to ~1050 K), where they are crystallographically prohibited. As a result, their magnitude and subnanometer spatial extent remain unchanged.« less

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

Jian, Tian; Lopez, Gary V.; Wang, Lai-Sheng, E-mail: Lai-Sheng-Wang@brown.edu

We report the observation of a manganese-centered tubular boron cluster (MnB{sub 16}{sup −}), which is characterized by photoelectron spectroscopy and ab initio calculations. The relatively simple pattern of the photoelectron spectrum indicates the cluster to be highly symmetric. Ab initio calculations show that MnB{sub 16}{sup −} has a Mn-centered tubular structure with C{sub 4v} symmetry due to first-order Jahn-Teller effect, while neutral MnB{sub 16} reduces to C{sub 2v} symmetry due to second-order Jahn-Teller effect. In MnB{sub 16}{sup −}, two unpaired electrons are observed, one on the Mn 3d{sub z{sup 2}} orbital and another on the B{sub 16} tube, making itmore » an unusual biradical. Strong covalent bonding is found between the Mn 3d orbitals and the B{sub 16} tube, which helps to stabilize the tubular structure. The current result suggests that there may exist a whole class of metal-stabilized tubular boron clusters. These metal-doped boron clusters provide a new bonding modality for transition metals, as well as a new avenue to design boron-based nanomaterials.« less

The vibronic level structure of the cyclopentadienyl radical

NASA Astrophysics Data System (ADS)

Ichino, Takatoshi; Wren, Scott W.; Vogelhuber, Kristen M.; Gianola, Adam J.; Lineberger, W. Carl; Stanton, John F.

2008-08-01

The 351.1 nm photoelectron spectrum of the cyclopentadienide ion has been measured, which reveals the vibronic structure of the X~ 2E1'' state of the cyclopentadienyl radical. Equation-of-motion ionization potential coupled-cluster (EOMIP-CCSD) calculations have been performed to construct a diabatic model potential of the X~ 2E1'' state, which takes into account linear Jahn-Teller effects along the e2' normal coordinates as well as bilinear Jahn-Teller effects along the e2' and ring-breathing a1' coordinates. A simulation based on this ab initio model potential reproduces the spectrum very well, identifying the vibronic levels with linear Jahn-Teller angular momentum quantum numbers of +/-1/2. The angular distributions of the photoelectrons for these vibronic levels are highly anisotropic with the photon energies used in the measurements. A few additional weak photoelectron peaks are observed when photoelectrons ejected parallel to the laser polarization are examined. These peaks correspond to the vibronic levels for out-of-plane modes in the ground X~ 2E1'' state, which arise due to several pseudo-Jahn-Teller interactions with excited states of the radical and quadratic Jahn-Teller interaction in the X~ 2E1'' state. A variant of the first derivative of the energy for the EOMIP-CCSD method has been utilized to evaluate the strength of these nonadiabatic couplings, which have subsequently been employed to construct the model potential of the X~ 2E1'' state with respect to the out-of-plane normal coordinates. Simulations based on the model potential successfully reproduce the weak features that become conspicuous in the 0° spectrum. The present study of the photoelectron spectrum complements a previous dispersed fluorescence spectroscopic study Miller and co-workers [J. Chem. Phys. 114, 4855 (2001); 4869 (2001) Miller and co-workers [J. Chem. Phys.114, 4869 (2001)] to provide a detailed account of the vibronic structure of X~ 2E1'' cyclopentadienyl. The electron

Ne matrix spectra of the sym-C6Br3F3+ radical cation

USGS Publications Warehouse

Bondybey, V.E.; Sears, T.J.; Miller, T.A.; Vaughn, C.; English, J.H.; Shiley, R.S.

1981-01-01

The electronic absorption and laser excited, wavelength resolved fluorescence spectra of the title cation have been observed in solid Ne matrix and vibrationally analysed. The vibrational structure of the excited B2A2??? state shows close similarity to the parent compound. The X2E??? ground state structure is strongly perturbed and irregular owing to a large Jahn-Teller distortion. The data are analysed in terms of a recently developed, sophisticated multimode Jahn-Teller theoretical model. We have generated the sym-C6Br3F3+ cations in solid Ne matrix and obtained their wavelength resolved emission and absorption spectra. T ground electronic X2E??? state exhibits an irregular and strongly perturbed vibrational structure, which can be successfully modeled using sophisticated multimode Jahn-Teller theory. ?? 1981.

Orbital effects in cobaltites by neutron scattering

NASA Astrophysics Data System (ADS)

Louca, Despina

2005-03-01

The orbital degree of freedom can play a central role in the physics of transition metal perovskite oxides because of its intricate coupling with other degrees of freedom such as spin, charge and lattice. In this talk the case of La1-xSrxCoO3 will be presented. Using elastic and inelastic neutron scattering, we investigated the thermal evolution of the local atomic structure and lattice dynamics in the pure sample and with the addition of charge carriers as the system crosses over from a paramagnetic insulator to a ferromagnetic metal. In LaCoO3, the thermal activation of the Co ions from a nonmagnetic ground state to an intermediate spin state gives rise to orbital degeneracy. This leads to Jahn-Teller distortions that are dynamical in nature. Doping stabilizes the intermediate spin configuration of the Co ions in the paramagnetic insulating phase. Evidence for local static Jahn-Teller distortions is observed but without long-range ordering. The size of the JT lattice is proportional to the amount of charge. However, with cooling to the metallic phase, static JT distortions disappear for x <= 30 %, the percolation limit. This coincides with narrowing of two modes at φ=22,nd,4,eV in the phonon spectrum in which we argue is due to localized dynamical JT fluctuations^1. The implications of the orbital effects to the structural and magnetic properties will be discussed. ^1D. Louca and J. L. Sarrao, Phys. Rev. Lett. 91, 155501 (2003).

Jet cooled cavity ringdown spectroscopy of the A ˜ 2 E ″ ← X ˜ 2 A2 ' transition of the NO3 radical

NASA Astrophysics Data System (ADS)

Codd, Terrance; Chen, Ming-Wei; Roudjane, Mourad; Stanton, John F.; Miller, Terry A.

2015-05-01

The A ˜ 2 E ″ ← X ˜ 2 A2 ' spectrum of NO3 radical from 7550 cm-1 to 9750 cm-1 has been recorded and analyzed. Our spectrum differs from previously recorded spectra of this transition due to jet-cooling, which narrows the rotational contours and eliminates spectral interference from hot bands. Assignments of numerous vibronic features can be made based on both band contour and position including the previously unassigned 30 1 band and several associated combination bands. We have analyzed our spectrum first with an independent anharmonic oscillator model and then by a quadratic Jahn-Teller vibronic coupling model. The fit achieved with the quadratic Jahn-Teller model is excellent, but the potential energy surface obtained with the fitted parameters is in only qualitative agreement with one obtained from ab initio calculations.

Tensile Strain Effects on the Magneto-transport in Calcium Manganese Oxide Thin Films: Comparison with its Hole-doped Counterpart

NASA Astrophysics Data System (ADS)

Lawson, Bridget; Neubauer, Samuel; Chaudhry, Adeel; Hart, Cacie; Ferrone, Natalie; Houston, David; Yong, Grace; Kolagani, Rajeswari

Magnetoresistance properties of the epitaxial thin films of doped rare earth manganites are known to be influenced by the effect of bi-axial strain induced by lattice mismatch with the substrate. In hole-doped manganites, the effect of both compressive and tensile strain is qualitatively consistent with the expected changes in unit cell symmetry from cubic to tetragonal, leading to Jahn-Teller strain fields that affect the energy levels of Mn3 + energy levels. Recent work in our laboratory on CaMnO3 thin films has pointed out that tetragonal distortions introduced by tensile lattice mismatch strain may also have the effect of modulating the oxygen content of the films in agreement with theoretical models that propose such coupling between strain and oxygen content. Our research focuses on comparing the magneto-transport properties of hole-doped manganite LaCaMnO3 thin films with that of its electron doped counter parts, in an effort to delineate the effects of oxygen stoichiometry changes on magneto-transport from the effects of Jahn-Teller type strain. Towson University Office of Undergraduate Research, Fisher Endowment Grant and Undergraduate Research Grant from the Fisher College of Science and Mathematics, Seed Funding Grant from the School of Emerging technologies and the NSF Grant ECCS 112856.

Evidence of Photo-induced Dynamic Competition of Metallic and Insulating Phase in a Layered Manganite.

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

Li, Yuelin; Walko, Donald A.; Li, Qing'an

2015-12-16

We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr2Mn2O7, can be manipulated using ultrafast optical excitation. The time- dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario whereby the lasermore » excitation modulates the local competition between the metallic and the insulating phases.« less

Evidence of photo-induced dynamic competition of metallic and insulating phase in a layered manganite

DOE PAGES

Li, Yuelin; Walko, Daonld A.; Li, Qing'an; ...

2015-11-17

We show evidence that the competition between the antiferromagetic metallic phase and the charge- and orbital-ordered insulating phase at the reentrant phase boundary of a layered manganite, LaSr 2Mn 2O 7, can be manipulated using ultrafast optical excitation. The time-dependent evolution of the Jahn-Teller superlattice reflection, which indicates the formation of the charge and orbital order, was measured at different laser fluences. The laser-induced enhancement and reduction the Jahn-Teller reflection intensity shows a reversal of sign between earlier (~10 ns) and later (~150 ns) time delays during the relaxation after photo excitation. This effect is consistent with a scenario wherebymore » the laser excitation modulates the local competition between the metallic and the insulating phases.« less

Vibronic eigenstates and the geometric phase effect in the 2E″ state of NO3.

PubMed

Eisfeld, Wolfgang; Viel, Alexandra

2017-01-21

The 2 E″ state of NO 3 , a prototype for the Jahn-Teller effect, has been an enigma and a challenge for a long time for both experiment and theory. We present a detailed theoretical study of the vibronic quantum dynamics in this electronic state, uncovering the effects of tunnelling, geometric phase, and symmetry. To this end, 45 vibronic levels of NO 3 in the 2 E″ state are determined accurately and analyzed thoroughly. The computation is based on a high quality diabatic potential representation of the two-sheeted surface of the 2 E″ state developed by us [W. Eisfeld et al., J. Chem. Phys. 140, 224109 (2014)] and on the multi-configuration time dependent Hartree approach. The vibrational eigenstates of the NO 3 - anion are determined and analyzed as well to gain a deeper understanding of the symmetry properties of such D 3h symmetric systems. To this end, 61 eigenstates of the NO 3 - anion ground state are computed using the single sheeted potential surface of the 1 A 1 state published in the same reference quoted above. The assignments of both the vibrational and vibronic levels are discussed. A simple model is proposed to rationalize the computed NO 3 spectrum strongly influenced by the Jahn-Teller couplings, the associated geometric phase effect, and the tunnelling. Comparison with the available spectroscopic data is also presented.

Group III Acceptors with Shallow and Deep Levels in Silicon Carbide: ESR and ENDOR Studies

NASA Astrophysics Data System (ADS)

Il'in, I. V.; Uspenskaya, Yu. A.; Kramushchenko, D. D.; Muzafarova, M. V.; Soltamov, V. A.; Mokhov, E. N.; Baranov, P. G.

2018-04-01

Results of investigations of Group III acceptors (B, Al, and Ga) in crystals of silicon carbide using the most informative electron spin resonance and electron nuclear double resonance methods are presented. Structural models of the acceptors with shallow and deep levels are considered. In addition to the data obtained earlier, studies using high-frequency magnetic resonance were obtained, which allowed revealing orthorhombic deviations from the axial symmetry for the deep acceptors; theoretical analysis explains experimentally found shifts of g factors for the deep acceptors arising due to the orthorhombic deviations, which appear probably due to the Jahn-Teller effect.

Effects of Mn substitution on the thermoelectric properties of the electron-doped perovskite Sr1-xLaxTiO3

NASA Astrophysics Data System (ADS)

Okuda, T.; Hata, H.; Eto, T.; Nishina, K.; Kuwahara, H.; Nakamura, M.; Kajimoto, R.

2014-12-01

We have tried to improve the n-type thermoelectric properties of the electron- doped Perovskite Sr1-xLaxTiO3 by a Mn substitution. The 1 ~ 2 % Mn substitution enhances the Seebeck coefficient (S) and reduces the thermal conductivity (κ) by about 50 % at room temperature (RT) without largely increasing the resistivity for the 5 % electron-doped SrTiO3. Consequently, the power factor at RT keeps a large value comparable to that of Bi2Te3 and the dimensionless figure-of-merits at RT increases twofold by the slight Mn substitution. Such a large reduction of κ at RT is perhaps due to the effect of Jahn-Teller active Mn3+ ions, around which dynamical local lattice distortion may occur.

The Synthesis and Characterization of Some Fluoride Perovskites: An Undergraduate Experiment in Solid State Chemistry.

ERIC Educational Resources Information Center

Langley, Richard H.; And Others

1984-01-01

Describes a senior-level experiment dealing with the synthesis and characterization of a perovskite. Since most perovskites are cubic, their characterization by x-ray diffraction is simplified. In addition, magnetic ordering may be observed and the effects of a Jahn-Teller distortion seen. (JN)

Novel effect of spin dynamics with suppression of charge and orbital ordering in Nd0.5Ca0.5MnO3 under the influence of ac electric field

NASA Astrophysics Data System (ADS)

Sarwar, T.; Qamar, A.; Nadeem, M.

2017-07-01

Dynamics of spin ordering in the manganite Nd0.5Ca0.5MnO3 have been investigated in this paper. It was observed that the complex mixed magnetic ordering in pellets is comprised of antiferromagnetic ordering at 160 K (TN) and complete charge ordering at 250 K (TCO). Under ac field, appearance of unstable ferromagnetic correlations is observed above TCO, which is badly frustrated due to strong spin disorder induced by Jahn Teller distortions. Impedance measurements reveal the spin glass like scenario, suppressing the strong antiferromagnetic and charge ordering states below TN.

Simultaneous effects of pressure and temperature on donor binding energy in Pöschl-Teller quantum well

NASA Astrophysics Data System (ADS)

Hakimyfard, Alireza; Barseghyan, M. G.; Duque, C. A.; Kirakosyan, A. A.

2009-12-01

In the frame of the variational method and the effective-mass approximation, the effects of hydrostatic pressure and temperature on the binding energy for donor impurities in the Pöschl-Teller quantum well are studied. The binding energy dependencies on the width of the quantum well, the hydrostatic pressure, the impurity position, the temperature, and the parameters of the confining potential are reported. The results show that the binding energy increases (decreases) with the increasing of the hydrostatic pressure (temperature). It is also found that, associated with the symmetry breaking in the Pöschl-Teller quantum well, and depending on the impurity position, the binding energy can increase or decrease.

Molecular geometry of vanadium dichloride and vanadium trichloride: a gas-phase electron diffraction and computational study.

PubMed

Varga, Zoltán; Vest, Brian; Schwerdtfeger, Peter; Hargittai, Magdolna

2010-03-15

The molecular geometries of VCl2 and VCl3 have been determined by computations and gas-phase electron diffraction (ED). The ED study is a reinvestigation of the previously published analysis for VCl2. The structure of the vanadium dichloride dimer has also been calculated. According to our joint ED and computational study, the evaporation of a solid sample of VCl2 resulted in about 66% vanadium trichloride and 34% vanadium dichloride in the vapor. Vanadium dichloride is unambiguously linear in its 4Sigma(g)+ ground electronic state. For VCl3, all computations yielded a Jahn-Teller-distorted ground-state structure of C(2v) symmetry. However, it lies merely less than 3 kJ/mol lower than the 3E'' state (D(3h) symmetry). Due to the dynamic nature of the Jahn-Teller effect in this case, rigorous distinction cannot be made between the planar models of either D(3h) symmetry or C(2v) symmetry for the equilibrium structure of VCl3. Furthermore, the presence of several low-lying excited electronic states of VCl3 is expected in the high-temperature vapor. To our knowledge, this is the first experimental and computational study of the VCl3 molecule.

Structural change and charge ordering correlated ultrasonic anomalies in La1-xCaxMnO3 (x=0.5,0.83) perovskite

NASA Astrophysics Data System (ADS)

Zheng, R. K.; Zhu, C. F.; Xie, J. Q.; Li, X. G.

2001-01-01

Ultrasonic sound velocity and attenuation have been measured in polycrystalline manganese oxide La1-xCaxMnO3 (x=0.5,0.83,1.0) at a frequency of 10 MHz. For x=0.5, on cooling down from high temperature, a slight softening of the sound velocity above the charge ordering transition temperature TCO and dramatic stiffening below TCO coincided with big attenuation peaks for both longitudinal and transverse waves were observed. It was found that these ultrasonic anomalies near TCO are correlated with the fine structure (i.e., the lattice parameters) change caused by the Jahn-Teller effect. For x=0.83, the sound velocity starts to soften dramatically with decreasing temperature from higher temperature to TS (180 K), and stiffens dramatically below TS. The large softening and stiffening of the sound velocity accompanied by a big attenuation peak are strongly correlated with a cubic-to-tetragonal structural phase transition at TS, which is confirmed by the low-temperature powder x-ray diffraction measurements. It is suggested that this structural phase transition be due to the Jahn-Teller distortion of the Mn3+O6 octahedra and related to the charge ordering transition. For CaMnO3, the anomaly in sound velocity is small.

Rotational and Fine Structure of Pseudo-Jahn Molecules with C_1 Symmetry

NASA Astrophysics Data System (ADS)

Liu, Jinjun

2016-06-01

It has been found in our previous works that rotational and fine-structure analysis of spectra involving nearly degenerate electronic states may aid in interpretation and analysis of the vibronic structure, specifically in the case of pseudo-Jahn-Teller (pJT) molecules with C_s symmetry. The spectral analysis of pJT derivatives (isopropoxy and cyclohexoxy of a prototypical JT molecule (the methoxy radical) allowed for quantitative determination of various contributions to the energy separation between the nearly degenerate electronic states, including the relativistic spin-orbit (SO) effect, the electrostatic interaction, and their zero-point energy difference. These states are coupled by SO and Coriolis interactions, which can also be determined accurately in rotational and fine structure analysis. Most recently, the spectroscopic model for rotational analysis of pJT molecules has been extended for analysis of molecules with C_1 symmetry, i.e., no symmetry. This model includes the six independently determinable components of the spin-rotation (SR) tensor and the three components of the SO and Coriolis interactions. It has been employed to simulate and fit high-resolution laser-induced fluorescence (LIF) spectra of jet-cooled alkoxy radicals with C_1 symmetry, including the 2-hexoxy and the 2-pentoxy radicals, as well as previously recorded LIF spectrum of the trans-conformer (defined by its OCCC dihedral angle) of the 2-butoxy radical. Although the LIF spectra can be reproduced by using either the SR constants or SO and Coriolis constants, the latter simulation offers results that are physically more meaningful whereas the SR constants have to be regarded as effective constants. Furthermore, we will review the SO and Coriolis constants of alkoxy radicals that have been investigated, starting from the well-studied methoxy radical (CH_3O). J. Liu, D. Melnik, and T. A. Miller, J. Chem. Phys. 139, 094308 (2013) J. Liu and T. A. Miller, J. Phys. Chem. A 118, 11871

Research on the optical spectra, g factors and defect structures for two tetragonal Y²+ centers in the irradiated CaF₂: Y crystal.

PubMed

Zheng, Wen-Chen; Mei, Yang; Yang, Yu-Guang; Liu, Hong-Gang

2012-11-01

Based on the defect models that the tetragonal Y(2+) (1) center in the irradiated CaF(2): Y crystal is due to Y(2+) at Ca(2+) site associated with a nearest interstitial F(-) ion along C(4) axis and the tetragonal Y(2+) (2) center is Y(2+) at Ca(2+) site where the tetragonal distortion is caused by the static Jahn-Teller effect, the two optical spectral bands and anisotropic g factors for both tetragonal Y(2+) centers are calculated. The calculations are made by using two methods based on the cluster approach, one is the complete diagonalization (of energy matrix) method (CDM) and another is the perturbation theory method (PTM). The calculated results for each Y(2+) center from CDM and PTM coincide and show reasonable agreement with the experimental values. The calculated isotropic g factor for Y(2+) (2) center at higher temperature owing to the dynamical Jahn-Teller effect is also consistent with the observed value. The defect structures (i.e., tetragonal distortion) of the two Y(2+) centers are obtained from the calculation. It appears that both theoretical methods can be applied to explain the optical and EPR data, to study the defect model and to determine the defect structures for d(1) ions in crystals. Copyright © 2012 Elsevier B.V. All rights reserved.

Vibrational overtone spectra of metallocenes: effect of the coordinating metal on the CH bond lengths

NASA Astrophysics Data System (ADS)

Billinghurst, Brant E.; Gough, Kathleen M.

2003-03-01

The first through third overtone spectra of ferrocene, ruthenocene, nickelocene, cobaltocene, dicyclopentadienyl magnesium and sodium cyclopentadienyl are examined with particular attention to the CH stretching of the cyclopentadienyl. Using semi-empirical correlations between CH bond length and CH stretching frequencies in each overtone region, we have determined that the type of metal atom within a metallocene complex has little effect on the CH bond length in the cyclopentadienyl. The only exception is cobaltocene where there is evidence that the Jahn-Teller effect results in several different CH bond lengths. Evidence that bis(cyclopentadienyl) magnesium is not ionic has been observed.

Edward Teller

Science.gov Websites

physics, astrophysics, and statistical mechanics. Lawrence Livermore [National Laboratory] physicist Mort towering figures of 20th-century physics. ... Although his early training was in chemical physics and spectroscopy, Teller has made substantial contributions to such diverse fields as nuclear physics, plasma

Effect of temperature on the electronic instability and the crystalline phase change at low temperature of V3Si type compounds

NASA Technical Reports Server (NTRS)

Labbe, J.; Friedel, J.

1977-01-01

Equations assuming a Jahn-Teller type effect for the d band electrons in V3Si compounds are given, and the results of free-energy change calculations by using some approximations based on these equations are depicted. The tetragonal structure is converted to cubic as the temperature rises past T sub m which is calculated as 13 K. by the Batterman-Barrett method and is measured to be 20-5 K. Other parameters such as change of C sub p with temperature are predicted better.

Angle-resolved photoelectron spectroscopy of cyclopropane

NASA Astrophysics Data System (ADS)

Keller, P. R.; Taylor, J. W.; Carlson, Thomas A.; Whitley, T. A.; Grimm, F. A.

1985-10-01

The angular distribution parameter, β, determined for the valence orbitals (IP < 18 eV) of cyclopropane in the 10-30 eV photon energy range using dispersed polarized synchrotron radiation. The energy dependence of β for photoelectron energies between, 2 and 10 eV above threshold was found to be similar to those found previously for other σ orbitals. The effects of Jahn-Teller splitting on β for the 3e' orbital were found to be small but definitely present. The overall shape and magnitude of the β( hv) curve are, however, sufficiently for the different Jahn-Teller components that, for purposes of orbital assignments using β( hv) curves the shape and magnitude of the curves can be considered associated only with the initial state. Resonance photoionization features at a photon ener of ≈ 18 eV were observed in the 3e' and 3a' 1 orbitals and tentatively assigned to autoionization.

Near-infrared photoabsorption by C60 dianions in a storage ring.

PubMed

Kadhane, U; Andersen, J U; Bonderup, E; Concina, B; Hvelplund, P; Suhr Kirketerp, M-B; Liu, B; Nielsen, S Brøndsted; Panja, S; Rangama, J; Støchkel, K; Tomita, S; Zettergren, H; Hansen, K; Sundén, A E K; Canton, S E; Echt, O; Forster, J S

2009-07-07

We present a detailed study of the electronic structure and the stability of C(60) dianions in the gas phase. Monoanions were extracted from a plasma source and converted to dianions by electron transfer in a Na vapor cell. The dianions were then stored in an electrostatic ring, and their near-infrared absorption spectrum was measured by observation of laser induced electron detachment. From the time dependence of the detachment after photon absorption, we conclude that the reaction has contributions from both direct electron tunneling to the continuum and vibrationally assisted tunneling after internal conversion. This implies that the height of the Coulomb barrier confining the attached electrons is at least approximately 1.5 eV. For C(60)(2-) ions in solution electron spin resonance measurements have indicated a singlet ground state, and from the similarity of the absorption spectra we conclude that also the ground state of isolated C(60)(2-) ions is singlet. The observed spectrum corresponds to an electronic transition from a t(1u) lowest unoccupied molecular orbital (LUMO) of C(60) to the t(1g) LUMO+1 level. The electronic levels of the dianion are split due to Jahn-Teller coupling to quadrupole deformations of the molecule, and a main absorption band at 10,723 cm(-1) corresponds to a transition between the Jahn-Teller ground states. Also transitions from pseudorotational states with 200 cm(-1) and (probably) 420 cm(-1) excitation are observed. We argue that a very broad absorption band from about 11,500 cm(-1) to 13,500 cm(-1) consists of transitions to so-called cone states, which are Jahn-Teller states on a higher potential-energy surface, stabilized by a pseudorotational angular momentum barrier. A previously observed, high-lying absorption band for C(60)(-) may also be a transition to a cone state.

High-Resolution Laser Spectroscopy of Free Radicals in Nearly Degenerate Electronic States

NASA Astrophysics Data System (ADS)

Liu, Jinjun

2017-06-01

Rovibronic structure of molecules in orbitally degenerate electronic states including Renner-Teller (RT) and Jahn-Teller (JT) active molecules has been extensively studied. Less is known about rotational structure of polyatomic molecules in nearly degenerate states, especially those with low (e.g., C_s) symmetry that are subject to the pseudo-Jahn-Teller (pJT) effect. In the case of free radicals, the unpaired electron further complicates energy levels by inducing spin-orbit (SO) and spin-rotation (SR) splittings. Asymmetric deuteration or methyl substitution of C_{3v} free radicals such as CH_3O, CaCH_3, and CaOCH_3 lowers the molecular symmetry, lifts the vibronic degeneracy, and reduces the JT effect to the pJT effect. New spectroscopic models are required to reproduce the rovibronic structure and simulate the experimentally obtained spectra of pJT-active free radicals. It has been found that rotational and fine-structure analysis of spectra involving nearly degenerate states may aid in vibronic analysis and interpretation of effective molecular constants. Especially, SO and Coriolis interactions that couple the two states can be determined accurately from fitting the experimental spectra. Coupling between the two electronic states also affects the intensities of rotational and vibronic transitions. The study on free radicals in nearly degenerate states provides a promising avenue of research which may bridge the gap between symmetry-induced degenerate states and the Born-Oppenheimer (BO) limit of unperturbed electronic states.

Spontaneous symmetry breaking by double lithium adsorption in polyacenes

NASA Astrophysics Data System (ADS)

Ortiz, Yenni. P.; Seligman, Thomas H.

2010-12-01

We show that adsorption of one lithium atom to polyacenes, i.e. chains of linearly fused benzene rings, will cause such chains to be slightly deformed. If we adsorb a second identical atom on the opposite side of the same ring, this deformation is dramatically enhanced despite the fact that a symmetric configuration seems possible. We argue, that this may be due to an instability of the Jahn-Teller type possibly indeed to a Peierls instability.

Spontaneous symmetry breaking by double lithium adsorption in polyacenes

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

Ortiz, Yenni. P.; Seligman, Thomas H.; Centro Internacional de Ciencias, Cuernavaca, Morelos

2010-12-23

We show that adsorption of one lithium atom to polyacenes, i.e. chains of linearly fused benzene rings, will cause such chains to be slightly deformed. If we adsorb a second identical atom on the opposite side of the same ring, this deformation is dramatically enhanced despite the fact that a symmetric configuration seems possible. We argue, that this may be due to an instability of the Jahn-Teller type possibly indeed to a Peierls instability.

Reconnaissance for radioactive deposits in the vicinity of Teller and Cape Nome, Seward Peninsula, Alaska, 1946-47

USGS Publications Warehouse

White, Max Gregg; West, W.S.; Matzko, J.J.

1953-01-01

Placer-mining areas and bedrock exposures near Teller on the Seward Peninsula, Alaska, were investigated in June and July, 1946, for possible sources of radioactive materials. The areas that were investigated are: Dese Creek, southeast of Teller; Bluestone River basin, south and southeast of Teller; Sunset Creek and other small streams flowing south into Grantley Harbor, northeast of Teller; and, also northeast of Teller, Swanson Creek and its tributaries, which flow north into the Agiapuk River basin. No significant amount of radioactive material was found, either in the stream gravels or in the bedrock of any of the areas. A heavy-mineral fraction obtained from a granite boulder probably derived from a bench gravel on Gold Run contains 0. 017 percent equivalent uranium, but the radioactivity is due to allanite and zircon. The types of bedrock tested include schist, slate, and greenstone. Readings on fresh surfaces of rock were the same as, or only slightly above the background count. The maximum radioactivity in stream concentrates is 0. 004 percent equivalent uranium in a sluice concentrate from Sunset Creek.

The effect of external magnetic field on the Raman peaks in manganites

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

Sahu, A. K., E-mail: ajitsahu@seemantaengg.ac.in; Rout, G. C.

2014-04-24

We report here a microscopic theoretical model study exhibiting the effect of external magnetic field on the Raman excitation peaks in the CMR manganite system. The Hamiltonian consists of Jahn-Teller (J-T) distortion in e{sub g} band, the double exchange interaction and the Heisenberg spin-spin interaction. Further the phonons are coupled to e{sub g} band electrons, J-T distorted e{sub g} band and the double exchange interaction. The Raman spectral intensity is calculated from the imaginary part of the phonon Green function. The spectra exhibits three peaks besides a very weak high energy peak. The magnetic field effect on these peaks aremore » reported.« less

Visual Display Terminal use in Iranian bank tellers: Effects on job stress and insomnia.

PubMed

Giahi, Omid; Shahmoradi, Behzad; Barkhordari, Abdullah; Khoubi, Jamshid

2015-01-01

Visual Display Terminals (VDTs) are equipments in many workplaces which their use may increase the risk of visual, musculoskeletal and mental problems including insomnia. To determine the relationship between duration of daily VDT use and insomnia among the Iranian bank tellers. We randomly selected 382 bank tellers working with VDT. Quality of sleep and stress information were collected by Athens Insomnia Scales (AIS) and Demand-Control Model (DCM) model respectively. Out of 382 participants, 127 (33.2%) had sleep complaints and 255 (66.8%) had no sleep disorders. Moreover, the insomnia symptoms' score were significantly high in the participants having more than 6 hours of daily VDT use after adjusting for multiple confounding factors (P <  0.001). There was no significant relationship between stress and insomnia. It seems that the low levels of stress and job satisfaction reduce the impact of VDT on sleep quality in tellers who worked less than 6 hours per day.

Task clarification, performance feedback, and social praise: Procedures for improving the customer service of bank tellers

PubMed Central

Crowell, Charles R.; Anderson, D. Chris; Abel, Dawn M.; Sergio, Joseph P.

1988-01-01

Customer service for bank tellers was defined in terms of 11 verbal behavior categories. An audio-recording system was used to track the occurrence of behaviors in these categories for six retail banking tellers. Three behavior management interventions (task clarification, performance feedback, and social praise), applied in sequence, were designed to improve overall teller performance with regard to the behavioral categories targeted. Clarification was accomplished by providing clear delineation of the various target categories, with specific examples of the behaviors in each. Feedback entailed presentation of ongoing verbal and visual information regarding teller performance. Praise consisted of verbal recognition of teller performance by branch managers. Results showed that clarification effects emerged quickly, producing an overall increase in desired behaviors of 12% over baseline. Feedback and praise effects occurred more gradually, resulting in overall increases of 6% and 7%, respectively. A suspension of all procedures led to a decline in overall performance, whereas reinstatement of feedback and praise was again accompanied by performance improvement. These findings extend the generality of behavior management applications and help to distinguish between possible antecedent and consequent effects of performance feedback. PMID:16795713

Renner-Teller effects in the photoelectron spectra of CNC, CCN, and HCCN.

PubMed

Coudert, Laurent H; Gans, Bérenger; Garcia, Gustavo A; Loison, Jean-Christophe

2018-02-07

The line intensity of photoelectron spectra when either the neutral or cationic species display a Renner-Teller coupling is derived and applied to the modeling of the photoelectron spectra of CNC, CCN, and HCCN. The rovibronic energy levels of these three radicals and of their cations are investigated starting from ab initio results. A model treating simultaneously the bending mode and the overall rotation is developed to deal with the quasilinearity problem in CNC + , CCN + , and HCCN and accounts for the large amplitude nature of their bending mode. This model is extended to treat the Renner-Teller coupling in CNC, CCN, and HCCN + . Based on the derived photoelectron line intensity, the photoelectron spectra of all three molecules are calculated and compared to the experimental ones.

Zero kinetic energy photoelectron spectroscopy of triphenylene.

PubMed

Harthcock, Colin; Zhang, Jie; Kong, Wei

2014-06-28

We report vibrational information of both the first electronically excited state and the ground cationic state of jet-cooled triphenylene via the techniques of resonantly enhanced multiphoton ionization (REMPI) and zero kinetic energy (ZEKE) photoelectron spectroscopy. The first excited electronic state S1 of the neutral molecule is of A1' symmetry and is therefore electric dipole forbidden in the D3h group. Consequently, there are no observable Franck-Condon allowed totally symmetric a1' vibrational bands in the REMPI spectrum. All observed vibrational transitions are due to Herzberg-Teller vibronic coupling to the E' third electronically excited state S3. The assignment of all vibrational bands as e' symmetry is based on comparisons with calculations using the time dependent density functional theory and spectroscopic simulations. When an electron is eliminated, the molecular frame undergoes Jahn-Teller distortion, lowering the point group to C2v and resulting in two nearly degenerate electronic states of A2 and B1 symmetry. Here we follow a crude treatment by assuming that all e' vibrational modes resolve into b2 and a1 modes in the C2v molecular frame. Some observed ZEKE transitions are tentatively assigned, and the adiabatic ionization threshold is determined to be 63 365 ± 7 cm(-1). The observed ZEKE spectra contain a consistent pattern, with a cluster of transitions centered near the same vibrational level of the cation as that of the intermediate state, roughly consistent with the propensity rule. However, complete assignment of the detailed vibrational structure due to Jahn-Teller coupling requires much more extensive calculations, which will be performed in the future.

The strength of electron electron correlation in Cs3C60

NASA Astrophysics Data System (ADS)

Baldassarre, L.; Perucchi, A.; Mitrano, M.; Nicoletti, D.; Marini, C.; Pontiroli, D.; Mazzani, M.; Aramini, M.; Riccó, M.; Giovannetti, G.; Capone, M.; Lupi, S.

2015-10-01

Cs3C60 is an antiferromagnetic insulator that under pressure (P) becomes metallic and superconducting below Tc = 38 K. The superconducting dome present in the T - P phase diagram close to a magnetic state reminds what found in superconducting cuprates and pnictides, strongly suggesting that superconductivity is not of the conventional Bardeen-Cooper-Schrieffer (BCS) type We investigate the insulator to metal transition induced by pressure in Cs3C60 by means of infrared spectroscopy supplemented by Dynamical Mean-Field Theory calculations. The insulating compound is driven towards a metallic-like behaviour, while strong correlations survive in the investigated pressure range. The metallization process is accompanied by an enhancement of the Jahn-Teller effect. This shows that electronic correlations are crucial in determining the insulating behaviour at ambient pressure and the bad metallic nature for increasing pressure. On the other hand, the relevance of the Jahn-Teller coupling in the metallic state confirms that phonon coupling survives in the presence of strong correlations.

Griffiths' inequalities for Ashkin-Teller model

NASA Technical Reports Server (NTRS)

Lee, C. T.

1973-01-01

The two Griffiths' (1967) inequalities for the correlation functions of Ising ferromagnets with two-body interactions, and two other inequalities obtained by Kelly and Sherman (1968) and by Sherman (1969) are shown to hold not only for the Ashkin-Teller (1943) model but also for a generalized Ashkin-Teller model (Kihara et al., 1954) with many-body interactions involving arbitrary clusters of particles. A cluster of particles is understood to mean a collection of pairs of particles rather than a group of particles. The four generalized inequalities under consideration are presented in the form of theorems, and a new inequality is obtained.

Magnetization and heat-capacity measurements on Zn1-xCrxTe

NASA Astrophysics Data System (ADS)

Pekarek, T. M.; Luning, J. E.; Miotkowski, I.; Crooker, B. C.

1994-12-01

We have taken magnetization and calorimetric measurements on Zn1-xCrxTe (x=0.003). The heat-capacity measurements show a Schottky peak indicating an energy-level splitting of 3.1 K between the ground and first excited states. Above 1.5 K we observe additional heat capacity, which indicates the presence of additional low-energy vibronic excitations. The magnetization data reveal a small anisotropy (~7%) with the (111) direction giving the largest value. The magnetization data were fit with a model including a static Jahn-Teller distortion proposed previously in these materials [J. T. Vallin, G. A. Slack, S. Roberts, and A. E. Hughes, Phys. Rev. B 2, 4313 (1970)]. Reasonable agreement was found with the data for a spin-orbit parameter of -59 cm-1 and a Jahn-Teller energy of 320 cm-1.

Frequency effects on charge ordering in Y0.5Ca0.5MnO3 by impedance spectroscopy

NASA Astrophysics Data System (ADS)

Sarwar, Tuba; Qamar, Afzaal; Nadeem, Muhammad

2015-02-01

In this work, structural and electrical properties of Y0.5Ca0.5MnO3 are investigated by employing X-ray diffraction and impedance spectroscopy, respectively. Applied ac electric field showed the charge ordering transition temperature around 265 K and below this temperature the heteromorphic behavior of the sample is discussed in the proximity of TCO. With frequency effects the volume of robust charge orbital ordering (COO) domains diminishes due to different competing phases along with Jahn Teller distortions. Comprehensive melting and collapse of charge orbital ordering occurs below TN(125 K), where a colossal drop in the value of impedance is observed. The change in profile of modulus plane plots determines the spreading of relaxation time of intermingled phases. Hopping mechanism is elaborated in terms of strong electron phonon coupling. Variable range hopping model and Arrhenius model are used to discuss the short and long range hopping between Mn3+ and Mn4+ channels assessing the activation energy Ea.

Teller Award Acceptance Speech (LIRPP Vol. 12)

NASA Astrophysics Data System (ADS)

McCrory, Robert L.

2016-10-01

It is indeed an honor to receive an award named for such an accomplished and famous physicist who is present with us today, Dr. Edward Teller. In thinking over what to say on this occasion, I noted that the Teller Award was given for pioneering research in controlled fusion, in controlling fusion for the benefit of mankind. I think everyone in this audience certainly would agree that this lofty goal is truly one of the unconquered, grand challenges in applied physics...

Occupational Noise Exposure among Toll Tellers at Toll Plaza in Malaysia

NASA Astrophysics Data System (ADS)

Azmi, Sharifah Nadya Syed; Dawal, Siti Zawiah Md; Ya, Tuan Mohammad Yusoff Shah Tuan; Saidin, Hamidi

2010-10-01

Toll tellers working at toll plaza have potential of exposure to high noise from the vehicles especially for the peak level of sound emitted by the heavy vehicles. However, occupational exposures in this workplace have not been adequately characterized and identified. Occupational noise exposure among toll tellers at toll plaza was assessed using Sound Level Meter, Noise Dosimeter and through questionnaire survey. These data were combined to estimate the work shift exposure level and health impacts to the toll tellers by using statistical analysis. Noise Dosimeter microphone was located at the hearing zone of the toll teller which working inside the toll booth and full-period measurements were collected for each work shift. The measurements were taken at 20 toll booths from 6.00 am to 2.00 pm for 5 days. 71 respondents participated in the survey to identify the symptoms of noise induced hearing loss and other health related problems among toll tellers. Results of this study indicated that occupational noise exposure among toll tellers for Mean Continuous Equivalent Level, Leq was 79.2±1.4 dB(A), Mean Maximum Level, Lmax was 107.8±3.6 dB(A) and Mean Peak Level, Lpeak was 136.6±9.9 dB. The Peak Level reported statistically significantly at 140 dB, the level of TLV recommended by ACGIH. The research findings indicated that the primary risk exposure to toll tellers comes from noise that emitted from heavy vehicles. Most of the toll tellers show symptoms of noise induced hearing loss and annoyed by the sources of noise at the toll plaza.

12 CFR 205.16 - Disclosures at automated teller machines.

Code of Federal Regulations, 2011 CFR

2011-01-01

... 12 Banks and Banking 2 2011-01-01 2011-01-01 false Disclosures at automated teller machines. 205.16 Section 205.16 Banks and Banking FEDERAL RESERVE SYSTEM BOARD OF GOVERNORS OF THE FEDERAL RESERVE SYSTEM ELECTRONIC FUND TRANSFERS (REGULATION E) § 205.16 Disclosures at automated teller machines. (a...

Occasional Addresses by Edward Teller at Conferences of Laser Interaction and Related Plasma Phenomena (LIRPP)

NASA Astrophysics Data System (ADS)

Hora, Heinrich; Miley, George H.

2016-10-01

The following sections are included: * Futurology of High Intensity Lasers (LIRPP Vol. 3A) * Lecture in Connection with the Edward Teller Medal Award (LIRPP Vol. 10) * Photo of the First Recipients of the Edward Teller Medal in 1991 * Photos from the Edward Teller Medal Celebration in 1997 * Photo with Participants of the LIRPP No. 12 Conference, 1995 * Photo with Edward Teller Medalists at IFSA01, Kyoto, 2001 * Keynote Address: The Edward Teller Lecture (LIRPP Vol. 11) * Keynote Address: Dr. Edward Teller (LIRPP Vol. 12) * Teller Award Presentation and Keynote Address (LIRPP Vol. 13) * Laudations of Awardees 1991-1995 (LIRPP Vol. 13) * Laudations of Awardees 1999-2003

Universal Teller Curriculum Guide.

ERIC Educational Resources Information Center

DuPage Area Vocational Education Authority, Addison, IL.

This curriculum guide has been designed to provide the teacher with a basis for planning a comprehensive program in the career field of universal teller, and to allow the teacher and learner maximum flexibility. The teaching or instruction, in both educational and financial institutions, can be accomplished through large formal groups, small…

Two-Channel Kondo Physics due to As Vacancies in the Layered Compound ZrAs1.58Se0.39

NASA Astrophysics Data System (ADS)

Kirchner, Stefan; Cichorek, T.; Bochenek, L.; Schmidt, M.; Niewa, R.; Czuluccki, A.; Auffermann, G.; Steglich, F.; Kniep, R.

We address the origin of the magnetic-field independent - | A | T 1 / 2 term observed in the low-temperature resistivity of several As-based metallic systems of the PbFCl structure type. For the layered compound ZrAs1.58Se0.39, we show that vacancies in the square nets of As give rise to the low-temperature transport anomaly over a wide temperature regime of almost two decades in temperature. This low-temperature behavior is in line with the non-magnetic version of the two-channel Kondo effect, whose origin we ascribe to a dynamic Jahn-Teller effect operating at the vacancy-carrying As layer with a C4 symmetry. The pair-breaking nature of the dynamical defects in the square nets of As explains the low superconducting transition temperature Tc 0 . 14 K of ZrAs1.58Se0.39, as compared to the free-of-vacancies homologue ZrP1.54S0.46 (Tc 3 . 7 K). Our findings should be relevant to a wide class of metals with disordered pnictogen layers.

Two-Channel Kondo Physics due to As Vacancies in the Layered Compound ZrAs1.58 Se0.39

NASA Astrophysics Data System (ADS)

Cichorek, T.; Bochenek, L.; Schmidt, M.; Czulucki, A.; Auffermann, G.; Kniep, R.; Niewa, R.; Steglich, F.; Kirchner, S.

2016-09-01

We address the origin of the magnetic-field-independent -|A |T1 /2 term observed in the low-temperature resistivity of several As-based metallic systems of the PbFCl structure type. For the layered compound ZrAs1.58 Se0.39 , we show that vacancies in the square nets of As give rise to the low-temperature transport anomaly over a wide temperature regime of almost two decades in temperature. This low-temperature behavior is in line with the nonmagnetic version of the two-channel Kondo effect, whose origin we ascribe to a dynamic Jahn-Teller effect operating at the vacancy-carrying As layer with a C4 symmetry. The pair-breaking nature of the dynamical defects in the square nets of As explains the low superconducting transition temperature Tc≈0.14 K of ZrAs1.58 Se0.39 compared to the free-of-vacancies homologue ZrP1.54 S0.46 (Tc≈3.7 K ). Our findings should be relevant to a wide class of metals with disordered pnictogen layers.

Nanoscale strain mapping in battery nanostructures

NASA Astrophysics Data System (ADS)

Ulvestad, A.; Cho, H. M.; Harder, R.; Kim, J. W.; Dietze, S. H.; Fohtung, E.; Meng, Y. S.; Shpyrko, O. G.

2014-02-01

Coherent x-ray diffraction imaging is used to map the local three dimensional strain inhomogeneity and electron density distribution of two individual LiNi0.5Mn1.5O4-δ cathode nanoparticles in both ex-situ and in-situ environments. Our reconstructed images revealed a maximum strain of 0.4%. We observed different variations in strain inhomogeneity due to multiple competing effects. The compressive/tensile component of the strain is connected to the local lithium content and, on the surface, interpreted in terms of a local Jahn-Teller distortion of Mn3+. Finally, the measured strain distributions are discussed in terms of their impact on competing theoretical models of the lithiation process.

Elastic properties of iron-based superconductor SrFe2(As1-xPx)2

NASA Astrophysics Data System (ADS)

Horikoshi, Keita; Imai, Jo; Nakanishi, Yoshiki; Nakamura, Mitsuteru; Kobayashi, Tatsuya; Adachi, Toru; Miyasaka, Shigeki; Tajima, Setsuko; Yoshizawa, Masahito

2018-05-01

We have measured the transverse elastic constants C44 and C66 of iron-based superconductor SrFe2(As1-xPx)2 (Sr122) single crystals as a function of temperature. Under-doped samples show elastic anomalies towards the structural/magnetic transition temperature. Optimal sample shows an upturn at the superconducting transition temperature in both C44 and C66. These behavior is similar to Ba122, while only C66 shows anomaly for Ba122. The elastic anomalies were analyzed by Jahn-Teller formula, and it was found that the Jahn-Teller energy of C44 is much larger than that of C66. This indicates that monoclinic structural fluctuations exist inherently in Sr122 in addition to the known tetragonal fluctuations. Co-existence of these diverse fluctuations and their cooperation are a key to investigate the mechanism and properties of superconductivity in iron based superconductors.

Effect of dynamics on the elastic softening of vacancies in Si

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

Shirai, Koun; Ishisada, Jun

2014-02-21

Recently, elastic softening at temperatures below 20 K has been observed in nondoped floating zone silicon. From the experimental analysis, it has been suggested that this softening is caused by an intrinsic vacancy defect through the Jahn-Teller (JT) effect. We have theoretically studied the relations between softening and the vacancies. The ground state of the JT distortion is stiff. However, by considering atomistic dynamical and anharmonic effects, it is found that low-energy excitations exist in the E-mode distortion and that different polarizations of the E-distortion can be easily interchanged. The calculated energy barriers for the reorientation of JT distortions aremore » consistent with other experiments and calculations. This low-lying mode can be the cause of softening in the elastic responses.« less

Surface Meteorology at Teller Site Stations, Seward Peninsula, Alaska, Ongoing from 2016

DOE Data Explorer

Bob Busey; Bob Bolton; Cathy Wilson; Lily Cohen

2017-12-05

Meteorological data are currently being collected at two locations at the Teller Site, Seward Peninsula. Teller Creek Station near TL_BSV (TELLER BOTTOM METEOROLOGICAL STATION) Station is located in the lower watershed in a tussock / willow transition zone and co-located with continuous snow depth measurements and subsurface measurements. Teller Creek Station near TL_IS_5 (TELLER TOP METEOROLOGICAL STATION) Station is located in the upper watershed and co-located with continuous snow depth measurements and subsurface measurements. Two types of data products are provided for these stations: First, meteorological and site characterization data grouped by sensor/measurement type (e.g., radiation or soil pit temperature and moisture). These are *.csv files. Second, a Data Visualization tool is provided for quick visualization of measurements over time at a station. Download the *_Visualizer.zip file, extract, and click on the 'index.html' file. Data values are the same in both products.

Evaluation of Spin Hamiltonian Parameters and Local Structure of Cu2+-doped Ion in xK2SO4-(50 - x)Na2SO4-50ZnSO4 Glasses with Various K2SO4 Concentrations

NASA Astrophysics Data System (ADS)

Ding, Ch.-Ch.; Wu, Sh.-Y.; Xu, Y.-Q.; Zhang, L.-J.; He, J.-J.

2018-03-01

The spin Hamiltonian parameters (SHPs), i.e., g factors and hyperfine structure constants, and local structures are theoretically studied by analyzing tetragonally elongated 3d9 clusters for Cu2+ in xK2SO4-(50 - x)Na2SO4-50ZnSO4 glasses with various K2SO4 concentrations x. The concentration dependences of the SHPs are attributed to the parabolic decreases of the cubic field parameter Dq, orbital reduction factor k, relative tetragonal elongation ratio τ, and core polarization constant κ with x. The [CuO6]10- clusters are found to undergo significant elongations of about 17% due to the Jahn-Teller effect. The calculated cubic field splittings and the SHPs at various concentrations agree well with the experimental data.

Concomitant Ordering and Symmetry Lowering

ERIC Educational Resources Information Center

Boo, William O. J.; Mattern, Daniell L.

2008-01-01

Examples of concomitant ordering include magnetic ordering, Jahn-Teller cooperative ordering, electronic ordering, ionic ordering, and ordering of partially-filled sites. Concomitant ordering sets in when a crystal is cooled and always lowers the degree of symmetry of the crystal. Concomitant ordering concepts can also be productively applied to…

Nonequilibrium phase transitions in isotropic Ashkin-Teller model

NASA Astrophysics Data System (ADS)

Akıncı, Ümit

2017-03-01

Dynamic behavior of an isotropic Ashkin-Teller model in the presence of a periodically oscillating magnetic field has been analyzed by means of the mean field approximation. The dynamic equation of motion has been constructed with the help of a Glauber type stochastic process and solved for a square lattice. After defining the possible dynamical phases of the system, phase diagrams have been given and the behavior of the hysteresis loops has been investigated in detail. The hysteresis loop for specific order parameter of isotropic Ashkin-Teller model has been defined and characteristics of this loop in different dynamical phases have been given.

GeneStoryTeller: a mobile app for quick and comprehensive information retrieval of human genes

PubMed Central

Eleftheriou, Stergiani V.; Bourdakou, Marilena M.; Athanasiadis, Emmanouil I.; Spyrou, George M.

2015-01-01

In the last few years, mobile devices such as smartphones and tablets have become an integral part of everyday life, due to their software/hardware rapid development, as well as the increased portability they offer. Nevertheless, up to now, only few Apps have been developed in the field of bioinformatics, capable to perform fast and robust access to services. We have developed the GeneStoryTeller, a mobile application for Android platforms, where users are able to instantly retrieve information regarding any recorded human gene, derived from eight publicly available databases, as a summary story. Complementary information regarding gene–drugs interactions, functional annotation and disease associations for each selected gene is also provided in the gene story. The most challenging part during the development of the GeneStoryTeller was to keep balance between storing data locally within the app and obtaining the updated content dynamically via a network connection. This was accomplished with the implementation of an administrative site where data are curated and synchronized with the application requiring a minimum human intervention. Database URL: http://bioserver-3.bioacademy.gr/Bioserver/GeneStoryTeller/. PMID:26055097

Response functions for dimers and square-symmetric molecules in four-wave-mixing experiments with polarized light

NASA Astrophysics Data System (ADS)

Smith, Eric Ryan; Farrow, Darcie A.; Jonas, David M.

2005-07-01

Four-wave-mixing nonlinear-response functions are given for intermolecular and intramolecular vibrations of a perpendicular dimer and intramolecular vibrations of a square-symmetric molecule containing a doubly degenerate state. A two-dimensional particle-in-a-box model is used to approximate the electronic wave functions and obtain harmonic potentials for nuclear motion. Vibronic interactions due to symmetry-lowering distortions along Jahn-Teller active normal modes are discussed. Electronic dephasing due to nuclear motion along both symmetric and asymmetric normal modes is included in these response functions, but population transfer between states is not. As an illustration, these response functions are used to predict the pump-probe polarization anisotropy in the limit of impulsive excitation.

Note: Is it symmetric or not?

PubMed

Stanton, John F

2013-07-28

The reasons by which a molecule might distort from an idealized high symmetry configuration (for example, D3h for the nitrate radical) in a quantum-chemical computation are well-known, but briefly reviewed here in light of considerable recent debate on the BNB molecule. The role of the pseudo-Jahn-Teller effect in such cases is emphasized, as is the ultimate relevance and proper interpretation of the title question in cases where the adiabatic potential energy surface is extremely flat.

Theoretical formulation of optical conductivity of La0.7Ca0.3MnO3 exhibiting paramagnetic insulator - ferromagnetic metal transition

NASA Astrophysics Data System (ADS)

Satiawati, L.; Majidi, M. A.

2017-07-01

A theory of high-energy optical conductivity of La0.7Ca0.3MnO3 has been proposed previously. The proposed theory works to explain the temperature-dependence of the optical conductivity for the photon energy region above ˜0.5 eV for up to ˜22 eV, but fails to capture the correct physics close to the dc limit in which metal-insulator transition occurs. The missing physics at the low energy has been acknowledged as mainly due to not incorporating phonon degree of freedom and electron-phonon interactions. In this study, we aim to complete the above theory by proposing a more complete Hamiltonian incorporating additional terms such as crystal field, two modes of Jahn-Teller vibrations, and coupling between electrons and the two Jahn-Teller vibrational modes. We solve the model by means of dynamical mean-field theory. At this stage, we aim to derive the analytical formulae involved in the calculation, and formulate the algorithmic implementation for the self-consistent calculation process. Our final goal is to compute the density of states and the optical conductivity for the complete photon energy range from 0 to 22 eV at various temperatures, and compare them with the experimental data. We expect that the improved model preserves the correct temperature-dependent physics at high photon energies, as already captured by the previous model, while it would also reveal ferromagnetic metal - paramagnetic insulator transition at the dc limit.

Star wars and strategic defense initiatives: work activity and health symptoms of unionized bank tellers during work reorganization.

PubMed

Seifert, A M; Messing, K; Dumais, L

1997-01-01

Work activity and health symptoms of bank tellers whose work was undergoing reorganization were examined during a university-union study of the health effects of work in women's traditional jobs. Data were gathered through collective and individual interviews, analysis of work activity, and a questionnaire administered to 305 tellers. Employees worked in a standing posture over 80 percent of the time. More than two-thirds frequently suffered pain in back, legs, and feet. The average teller had been involved in 3.7 robberies as a direct victim and six as a witness. Work required feats of memory and concentration. In order to meet job demands, tellers engaged in supportive activities and teamwork. The introduction of individualized objectives threatened the employees' ability to collaborate and induced distress. More than twice as many tellers as other female workers in Québec experience psychological distress (Ilfeld scale), related to: robbery during the past two years (odds ratio = 1.7; confidence interval = 1.0-2.9); difficult relations with superiors (O.R. = 2.6; C.I. = 1.3-5.3); and full-time work (O.R. = 2.3; C.I. = 1.3-3.9). Diverse methods enriched the analysis, and union participation allowed the proposal of concrete correction measures.

Superconductivity and fast proton transport in nanoconfined water

NASA Astrophysics Data System (ADS)

Johnson, K. H.

2018-04-01

A real-space molecular-orbital density-wave description of Cooper pairing in conjunction with the dynamic Jahn-Teller mechanism for high-Tc superconductivity predicts that electron-doped water confined to the nanoscale environment of a carbon nanotube or biological macromolecule should superconduct below and exhibit fast proton transport above the transition temperature, Tc ≅ 230 K (-43 °C).

Proton NMR studies of the electronic structure of ZrH/sub x/

NASA Technical Reports Server (NTRS)

Attalla, A.; Bowman, R. C., Jr.; Craft, B. D.; Venturini, E. L.; Rhim, W. K.

1982-01-01

The proton spin lattice relaxation times and Knight shifts were measured in f.c.c. (delta-phase) and f.c.t. (epsilon-phase) ZrH/sub x/ for 1.5 or = to x or = to 2.0. Both parameters indicate that N(E/sub F/) is very dependent upon hydrogen content with a maximum occurring at ZrH1 83. This behavior is ascribed to modifications in N(E/sub F/) through a fcc/fct distortion in ZrH/sub x/ associated with a Jahn-Teller effect.

12 CFR 328.4 - Prohibition against receiving deposits at same teller station or window as noninsured institution.

Code of Federal Regulations, 2010 CFR

2010-01-01

... teller station or window as noninsured institution. 328.4 Section 328.4 Banks and Banking FEDERAL DEPOSIT... Prohibition against receiving deposits at same teller station or window as noninsured institution. (a) Prohibition. An insured depository institution may not receive deposits at any teller station or window where...

Study of Topological Effects Concerning the Lowest A″ and the Three A' States for the CO2(+) Ion.

PubMed

Dhindhwal, Vikash; Baer, Michael; Sathyamurthy, N

2016-05-19

A study of the topological effects, viz., the Jahn-Teller (JT) and Renner-Teller (RT) effects, in CO2(+) has been carried out by calculating nonadiabatic coupling terms (NACTs) at the state-averaged CASSCF level using the cc-pVTZ basis set for the lowest three A' states and one A″ state along a circular contour. Using the NACTs, the privileged adiabatic-to-diabatic transformation (ADT) angles (γ12) for 1A' and 2A' states of CO2(+) have been calculated along various circular contours. Employing one of the oxygen atoms as the test particle exposed two conical intersections (ci) located on each side of the CO diatom. The main purpose of this study is to explore the possibility of forming reliable diabatic potential energy surfaces for this system. Success in achieving this goal is guaranteed by the ability to calculate quantized privileged ADT angles along closed contours covering large regions in configuration space (see, e.g., J. Phys. Chem. A 2014 , 118 , 6361 ). The calculations were carried out for two and three JT states. In most cases very nice quantization has been achieved although the calculations were frequently done, as required, for large regions in configuration space (sometimes ≥18 Å(2)). In one case, for which the quantization was not gratifying, the inclusion of the RT effect modified it considerably.

Electronic instability and change of crystalline phase in compounds of the V3Si type at low temperature

NASA Technical Reports Server (NTRS)

Labbe, J.; Friedel, J.

1978-01-01

In V3Si, the V atoms form an array of dense linear chains; a tight-binding approximation in one dimension was used to describe the d electrons. The electronic energy calculated by this method was reduced when the lattice is deformed. This lead to a band type of the Jahn Teller effect, which may explain the cubic to tetragonal transition which was observed at low temperatures. The theory can be extended to other superconductors of the V3X type when X=Ga, Ge, Sn, etcetera, or NB3SN.

Self-trapping of the d- d charge transfer exciton in bulk NiO evidenced by X-ray excited luminescence

NASA Astrophysics Data System (ADS)

Sokolov, V. I.; Pustovarov, V. A.; Churmanov, V. N.; Ivanov, V. Yu.; Gruzdev, N. B.; Sokolov, P. S.; Baranov, A. N.; Moskvin, A. S.

2012-07-01

Soft X-ray (XUV) excitation did make it possible to avoid the predominant role of the surface effects in luminescence of NiO and revealed a bulk luminescence with a puzzling well isolated doublet of very narrow lines with close energies near 3.3 eV which is assigned to recombination transitions in self-trapped d- d charge transfer (CT) excitons formed by coupled Jahn-Teller Ni+ and Ni3+ centers. The conclusion is supported both by a comparative analysis of the CT luminescence spectra for NiO and solid solutions Ni x Zn1 - x O, and by a comprehensive cluster model assignment of different p- d and d- d CT transitions, their relaxation channels. To the best of our knowledge, it is the first observation of the luminescence due to self-trapped d- d CT excitons.

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

Sissa, Cristina; Delchiaro, Francesca; Di Maiolo, Francesco

Essential-state models efficiently describe linear and nonlinear spectral properties of different families of charge-transfer chromophores. Here, the essential-state machinery is applied to the calculation of the early-stage dynamics after ultrafast (coherent) excitation of polar and quadrupolar chromophores. The fully non-adiabatic treatment of coupled electronic and vibrational motion allows for a reliable description of the dynamics of these intriguing systems. In particular, the proposed approach is reliable even when the adiabatic and harmonic approximations do not apply, such as for quadrupolar dyes that show a multistable, broken-symmetry excited state. Our approach quite naturally leads to a clear picture for a dynamicalmore » Jahn-Teller effect in these systems. The recovery of symmetry due to dynamical effects is however disrupted in polar solvents where a static symmetry lowering is observed. More generally, thermal disorder in polar solvents is responsible for dephasing phenomena, damping the coherent oscillations with particularly important effects in the case of polar dyes.« less

Off-Centre Effects in the Triplet Relaxed Excited State of Ga+ Centres in CsBr:Ga Crystal

NASA Astrophysics Data System (ADS)

Kalder, K.; Korrovits, V.; Nagirnyi, V.; Stolovits, A.; Zazubovich, S.; Babin, V.

1997-06-01

Spectra, polarization and decay kinetics of the triplet and singlet emission of Ga+ centres in CsBr:Ga crystals have been studied in the temperature range of 0.1 to 400 K. It has been found that the triplet AX and AT emission bands coincide. Two slow components have been observed in the decay kinetics of each emission at T < 1.5 K and explained by the tunnel splitting of the metastable minima of the corresponding triplet relaxed excited state. It points to the off-centre displacement of a Ga+ ion from a crystal lattice site both in the tetragonal (T) and in the trigonal (X) Jahn-Teller minima.

Structural evolution of the methane cation in subfemtosecond photodynamics

NASA Astrophysics Data System (ADS)

Mondal, T.; Varandas, A. J. C.

2015-07-01

An ab initio quantum dynamics study has been performed to explore the structural rearrangement of ground state CH 4+ in subfemtosecond resolved photodynamics. The method utilizes time-dependent wave-packet propagation on the X ˜ 2 T 2 electronic manifold of the title cation in full dimensionality, including nonadiabatic coupling of the three electronic sheets. Good agreement is obtained with recent experiments [Baker et al., Science 312, 424 (2006)] which use high-order harmonic generation to probe the attosecond proton dynamics. The novel results provide direct theoretical support of the observations while unravelling the underlying details. With the geometrical changes obtained by calculating the expectation values of the nuclear coordinates as a function of time, the structural evolution is predicted to begin through activation of the totally symmetric a1 and doubly degenerate e modes. While the former retains the original Td symmetry of the cation, the Jahn-Teller active e mode conducts it to a D2d structure. At ˜1.85 fs, the intermediate D2d structure is further predicted to rearrange to local C2v minimum geometry via Jahn-Teller active bending vibrations of t2 symmetry.

Giant ferrimagnetism and polarization in a mixed metal perovskite metal-organic framework

NASA Astrophysics Data System (ADS)

Rout, Paresh C.; Srinivasan, Varadharajan

2018-01-01

Perovskite metal-organic frameworks (MOFs) have recently emerged as potential candidates for multiferroicity. However, the compounds synthesized so far possess only weak ferromagnetism and low polarization. Additionally, the very low magnetic transition temperatures (Tc) also pose a challenge to the application of the materials. We have computationally designed a mixed metal perovskite MOF—[C(NH2)3] [(Cu0.5Mn0.5) (HCOO) 3] —that is predicted to have magnetization two orders of magnitude larger than its parent ([C (NH2)3] [Cu (HCOO) 3] ), a significantly larger polarization (9.9 μ C /cm2), and an enhanced Tc of up to 56 K, unprecedented in perovskite MOFs. A detailed study of the magnetic interactions revealed a mechanism leading to the large moments as well as the increase in the Tc. Mixing a non-Jahn-Teller ion (Mn2 +) into a Jahn-Teller host (Cu2 +) leads to competing lattice distortions which are directly responsible for the enhanced polarization. The MOF is thermodynamically stable as evidenced by the computed enthalpy of formation and can likely be synthesized. Our work represents a first step towards rational design of multiferroic perovskite MOFs through the largely unexplored mixed metal approach.

Science and Technology Review, July-August 1998: Celebrating Edward Teller at 90

DOE R&D Accomplishments Database

Smart, J.

1998-07-01

On the occasion of Edward Teller's 90th birthday, Science and Technology Review (S&TR) has the pleasure of honoring Lawrence Livermore's co-founder and most influential scientist. Teller is known for his inventive work in physics, his concepts leading to thermonuclear explosions, and his strong stands on such issues as science education, the nation's strategic defense, the needs for science in the future, and sharing scientific information. The articles in this issue also show him, as always, tirelessly moving forward with his new and changing interests.

Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 : in Search of Jahn–Teller Distorted Cr(II) Oxide

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

Li, Man-Rong; Deng, Zheng; Lapidus, Saul H.

2016-10-17

A novel 6H - type hexagonal perovskite Ba 3 (Cr 0.97(1) Te 0.03 (1 ) ) 2 TeO 9 was prepared at high pressure (6 GPa) and temperature ( 1 773 K). Both transmission electron microscopy and synchrotron powder x - ray diffraction data demonstrate that Ba 3 (Cr 0.97(1) Te 0.03(1) ) 2 TeO 9 crystallize s in P6 3 / mmc with face - shared (Cr 0.97(1) Te 0.03(1) )O 6 octahedral pairs interconnected with TeO 6 octahedra via corner - sharing. Structure analysis shows a mixed Cr 2+ /Cr 3+ valence state with ~ 10% Cr 2+more » . The existence of Cr 2+ in Ba 3 (Cr 2+ 0.10(1) Cr 3+ 0.87(1) Te 6+ 0.03 ) 2 TeO 9 is further evidenced by x - ray absorption near edge spectr oscopy . Magnetic properties measurements show a paramagnetic response down to 4 K and a small glassy - state curvature at low temperature. In this work, the o ctahedral Cr 2+ O 6 component is stabilized in an oxide material for the first time ; the expected Jahn - Teller distortion of high - spin ( d 4 ) Cr 2+ is not found , which is attributed to the small proportion of Cr 2+ (~ 10%) and the face - sharing arrangement of CrO 6 octahedral pairs, that structu rally dis favor axial distortion.« less

Anisotropic mechanoresponse of energetic crystallites: a quantum molecular dynamics study of nano-collision

NASA Astrophysics Data System (ADS)

Li, Ying; Kalia, Rajiv K.; Misawa, Masaaki; Nakano, Aiichiro; Nomura, Ken-Ichi; Shimamura, Kohei; Shimojo, Fuyuki; Vashishta, Priya

2016-05-01

At the nanoscale, chemistry can happen quite differently due to mechanical forces selectively breaking the chemical bonds of materials. The interaction between chemistry and mechanical forces can be classified as mechanochemistry. An example of archetypal mechanochemistry occurs at the nanoscale in anisotropic detonating of a broad class of layered energetic molecular crystals bonded by inter-layer van der Waals (vdW) interactions. Here, we introduce an ab initio study of the collision, in which quantum molecular dynamic simulations of binary collisions between energetic vdW crystallites, TATB molecules, reveal atomistic mechanisms of anisotropic shock sensitivity. The highly sensitive lateral collision was found to originate from the twisting and bending to breaking of nitro-groups mediated by strong intra-layer hydrogen bonds. This causes the closing of the electronic energy gap due to an inverse Jahn-Teller effect. On the other hand, the insensitive collisions normal to multilayers are accomplished by more delocalized molecular deformations mediated by inter-layer interactions. Our nano-collision studies provide a much needed atomistic understanding for the rational design of insensitive energetic nanomaterials and the detonation synthesis of novel nanomaterials.At the nanoscale, chemistry can happen quite differently due to mechanical forces selectively breaking the chemical bonds of materials. The interaction between chemistry and mechanical forces can be classified as mechanochemistry. An example of archetypal mechanochemistry occurs at the nanoscale in anisotropic detonating of a broad class of layered energetic molecular crystals bonded by inter-layer van der Waals (vdW) interactions. Here, we introduce an ab initio study of the collision, in which quantum molecular dynamic simulations of binary collisions between energetic vdW crystallites, TATB molecules, reveal atomistic mechanisms of anisotropic shock sensitivity. The highly sensitive lateral collision

Gamow–Teller resonances in the {sup 118}Sb compound nucleus: Puzzles of an experiment in Sarov

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

Urin, M. H., E-mail: urin@theor.mephi.ru

2016-03-15

Contradictory data on the observation of Gamow–Teller resonances in the {sup 118}Sb compound nucleus are discussed along with the available interpretation of these data and planned experimental and theoretical investigations into Gamow–Teller resonances in a number of antimony isotopes.

Magnetic phase transition in layered inorganic-organic hybrid (C12H25NH3)2CuCl4

NASA Astrophysics Data System (ADS)

Bochalya, Madhu; Kumar, Sunil; Kanaujia, Pawan K.; Prakash, G. Vijaya

2018-05-01

Inorganic-organic (IO) hybrids are material systems which have become an interesting theme of research for physicist and chemists recently due to the possibility of engineering specific magnetic, thermal or optoelectronic properties by playing around with the transition metal, halides and the organic components. Our experiments on (C12H25NH3)2CuCl4 show that the system exhibits a long range ferromagnetic order below ˜11 K. In such an inorganic-organic hybrid system, Jahn-Teller distortion of the copper ions results into a weak ferromagnetic order as compared to the antiferromagnetic spin-spin exchange in the pure inorganic CuCl2 compound. Moreover, this particular hybrid system also exhibits photoluminescence when excited below absorption maximum related to charge transfer peak though the effect is much weaker as compared to that in extensively studied other MX4-based (M = Sn, Pb; X = Cl, Br, I) counterparts.

One of My Favorite Assignments: Automated Teller Machine Simulation.

ERIC Educational Resources Information Center

Oberman, Paul S.

2001-01-01

Describes an assignment for an introductory computer science class that requires the student to write a software program that simulates an automated teller machine. Highlights include an algorithm for the assignment; sample file contents; language features used; assignment variations; and discussion points. (LRW)

Comment on 'Ground state of octahedral platinum hexafluoride'

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

Gabuda, S. P.; Kozlova, S. G.

2009-05-15

It is shown that the principal results of a recent work by Alvarez-Thon et al. [Phys. Rev. A 77, 034502 (2008)] are in conflict with earlier work of the present authors [JETP Lett. 73, 35 (2001)] and also with a well known result concerning magnetic properties, NMR, and Jahn-Teller effect in the systems possessing even number of d electrons. This can be attributed to the fact that Alvarez-Thon et al. did not account for the influence of {sup 19}F and {sup 195}Pt nuclear magnetic moments and vibronic interactions on the wave function of PtF{sub 6} molecules.

Speckle in the diffraction patterns of Hendricks-Teller and icosahedral glass models

NASA Technical Reports Server (NTRS)

Garg, Anupam; Levine, Dov

1988-01-01

It is shown that the X-ray diffraction patterns from the Hendricks-Teller model for layered systems and the icosahedral glass models for the icosahedral phases show large fluctuations between nearby scattering wave vectors and from sample to sample, that are quite analogous to laser speckle. The statistics of these fluctuations are studied analytically for the first model and via computer simulations for the second. The observability of these effects is discussed briefly.

Atomic-scale understanding of non-stoichiometry effects on the electrochemical performance of Ni-rich cathode materials

NASA Astrophysics Data System (ADS)

Kong, Fantai; Liang, Chaoping; Longo, Roberto C.; Zheng, Yongping; Cho, Kyeongjae

2018-02-01

As the next-generation high energy capacity cathode materials for Li-ion batteries, Ni-rich oxides face the problem of obtaining near-stoichiometric phases due to excessive Ni occupying Li sites. These extra-Ni-defects drastically affect the electrochemical performance. Despite of its importance, the fundamental correlation between such defects and the key electrochemical properties is still poorly understood. In this work, using density-functional-theory, we report a comprehensive study on the effects of non-stoichiometric phases on properties of Ni-rich layered oxides. For instance, extra-Ni-defects trigger charge disproportionation reaction within the system, alleviating the Jahn-Teller distortion of Ni3+ ions, which constitutes an important reason for their low formation energies. Kinetic studies of these defects reveal their immobile nature, creating a "pillar effect" that increases the structural stability. Ab initio molecular dynamics revealed Li depletion regions surrounding extra-Ni-defects, which are ultimate responsible for the arduous Li diffusion and re-intercalation, resulting in poor rate performance and initial capacity loss. Finally, the method with combination of high valence cation doping and ion-exchange synthesis is regarded as the most promising way to obtain stoichiometric oxides. Overall, this work not only deepens our understanding of non-stoichiometric Ni-rich layered oxides, but also enables further optimizations of high energy density cathode materials.

GeneStoryTeller: a mobile app for quick and comprehensive information retrieval of human genes.

PubMed

Eleftheriou, Stergiani V; Bourdakou, Marilena M; Athanasiadis, Emmanouil I; Spyrou, George M

2015-01-01

In the last few years, mobile devices such as smartphones and tablets have become an integral part of everyday life, due to their software/hardware rapid development, as well as the increased portability they offer. Nevertheless, up to now, only few Apps have been developed in the field of bioinformatics, capable to perform fast and robust access to services. We have developed the GeneStoryTeller, a mobile application for Android platforms, where users are able to instantly retrieve information regarding any recorded human gene, derived from eight publicly available databases, as a summary story. Complementary information regarding gene-drugs interactions, functional annotation and disease associations for each selected gene is also provided in the gene story. The most challenging part during the development of the GeneStoryTeller was to keep balance between storing data locally within the app and obtaining the updated content dynamically via a network connection. This was accomplished with the implementation of an administrative site where data are curated and synchronized with the application requiring a minimum human intervention. © The Author(s) 2015. Published by Oxford University Press.

The Renner-Teller effect in HCCCl(+)(X̃(2)Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations.

PubMed

Sun, Wei; Dai, Zuyang; Wang, Jia; Mo, Yuxiang

2015-05-21

The spin-vibronic energy levels of the chloroacetylene cation up to 4000 cm(-1) above the ground state have been measured using the one-photon zero-kinetic energy photoelectron spectroscopic method. The spin-vibronic energy levels have also been calculated using a diabatic model, in which the potential energy surfaces are expressed by expansions of internal coordinates, and the Hamiltonian matrix equation is solved using a variational method with harmonic basis functions. The calculated spin-vibronic energy levels are in good agreement with the experimental data. The Renner-Teller (RT) parameters describing the vibronic coupling for the H-C≡C bending mode (ε4), Cl-C≡C bending mode (ε5), the cross-mode vibronic coupling (ε45) of the two bending vibrations, and their vibrational frequencies (ω4 and ω5) have also been determined using an effective Hamiltonian matrix treatment. In comparison with the spin-orbit interaction, the RT effect in the H-C≡C bending (ε4) mode is strong, while the RT effect in the Cl-C≡C bending mode is weak. There is a strong cross-mode vibronic coupling of the two bending vibrations, which may be due to a vibronic resonance between the two bending vibrations. The spin-orbit energy splitting of the ground state has been determined for the first time and is found to be 209 ± 2 cm(-1).

Orbital symmetry fingerprints for magnetic adatoms in graphene

NASA Astrophysics Data System (ADS)

Uchoa, Bruno; Yang, Ling; Tsai, S.-W.; Peres, N. M. R.; Castro Neto, A. H.

2014-01-01

In this paper, we describe the formation of local resonances in graphene in the presence of magnetic adatoms containing localized orbitals of arbitrary symmetry, corresponding to any given angular momentum state. We show that quantum interference effects which are naturally inbuilt in the honeycomb lattice in combination with the specific orbital symmetry of the localized state lead to the formation of fingerprints in differential conductance curves. In the presence of Jahn-Teller distortion effects, which lift the orbital degeneracy of the adatoms, the orbital symmetries can lead to distinctive signatures in the local density of states. We show that those effects allow scanning tunneling probes to characterize adatoms and defects in graphene.

Comment on "Histories and Horoscopes: The Ethnographer as Fortune-Teller."

ERIC Educational Resources Information Center

Luttrell, Wendy

1998-01-01

Explores the analogy of the researcher as fortune teller and the parallels between research histories and horoscopes and discusses the tension between what the subject is and what he or she is imagined to be by others. (SLD)

Effects of strain on ferroelectric polarization and magnetism in orthorhombic HoMnO3

NASA Astrophysics Data System (ADS)

Iuşan, Diana; Yamauchi, Kunihiko; Barone, Paolo; Sanyal, Biplab; Eriksson, Olle; Profeta, Gianni; Picozzi, Silvia

2013-01-01

We explore how the ferroelectric polarization of antiferromagnetic E-type orthorhombic HoMnO3 can be increased, by investigating the effects of in-plane strain on both the magnetic properties and the ferroelectric polarization, using combined density functional theory calculations and a model Hamiltonian technique. Our results show that the net polarization is strongly enhanced under compressive strain, due to an increase of the elec-tronic contribution to the polarization. In contrast, the ionic contribution is found to decrease. We identify the electron-lattice coupling, due to Jahn-Teller (JT) distortions, and its response to strain, to be responsible for the observed behavior. The JT-induced orbital ordering of occupied Mn-eg1 electrons in alternating 3x2-r23y2-r2 orbital states in the unstrained structure, changes under in-plane compressive strain to a mixture with x2-z2y2-z2 states. The asymmetric hopping of eg electrons between Mn ions along zigzag spin chains (typical of the AFM-E spin configuration) is therefore enhanced under strain, explaining the large value of the polarization. Using a degenerate double-exchange model including electron-phonon interaction, we reproduce the change in the orbital ordering pattern. In this picture, the orbital ordering change is related to a change of the Berry phase of the eg electrons. This causes an increase of the electronic contribution to the polarization.

Perspectives of disproportionation driven superconductivity in strongly correlated 3d compounds.

PubMed

Moskvin, A S

2013-02-27

Disproportionation in 3d compounds can give rise to an unconventional electron-hole Bose liquid with a very rich phase diagram, from a Bose metal, to a charge ordering insulator and an inhomogeneous Bose-superfluid. Optimal conditions for disproportionation driven high-T(c) superconductivity are shown to be realized only for several Jahn-Teller d(n) configurations that permit the formation of well defined local composite bosons. These are the high-spin d(4), low-spin d(7), and d(9) configurations given the octahedral crystal field, and the d(1), high-spin d(6) configurations given the tetrahedral crystal field. The disproportionation reaction has a peculiar 'anti-Jahn-Teller' character lifting the bare orbital degeneracy. Superconductivity in the d(4) and d(6) systems at variance with d(1), d(7), and d(9) systems implies unavoidable coexistence of the spin-triplet composite bosons and the magnetic lattice. We argue that unconventional high-T(c) superconductivity, observed in quasi-2d cuprates with tetragonally distorted CuO(6) octahedra and iron-based layered pnictides/chalcogenides with tetrahedrally coordinated Fe(2+) ions presents a key argument to support the fact that the disproportionation scenario is at work in these compounds.

On the nature of the phase transition in uranium dioxide

NASA Astrophysics Data System (ADS)

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

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

Soil Physical, Chemical, and Thermal Characterization, Teller Road Site, Seward Peninsula, Alaska, 2016

DOE Data Explorer

Graham, David; Kholodov, Alexander; Wilson, Cathy; Moon, Ji-Won; Romanovsky, Vladimir; Busey, Bob

2018-02-05

This dataset provides the results of physical, chemical, and thermal characterization of soils at the Teller Road Site, Seward Peninsula, Alaska. Soil pits were dug from 7-14 September 2016 at designated Intensive Stations 2 through 9 at the Teller Road MM 27 Site. This dataset includes field observations and descriptions of soil layers or horizons, field measurements of soil volumetric water content, soil temperature, thermal conductivity, and heat capacity. Laboratory measurements of soil properties include gravimetric water content, bulk density, volumetric water content, and total carbon and nitrogen.

Anomalous double-stripe charge ordering in β -NaFe2O3 with double triangular layers consisting of almost perfect regular Fe4 tetrahedra

NASA Astrophysics Data System (ADS)

Kobayashi, Shintaro; Ueda, Hiroaki; Michioka, Chishiro; Yoshimura, Kazuyoshi; Nakamura, Shin; Katsufuji, Takuro; Sawa, Hiroshi

2018-05-01

The physical properties of the mixed-valent iron oxide β -NaFe2O3 were investigated by means of synchrotron radiation x-ray diffraction, magnetization, electrical resistivity, differential scanning calorimetry, 23Na NMR, and 57FeM o ̈ssbauer measurements. This compound has double triangular layers consisting of almost perfect regular Fe4 tetrahedra, which suggests geometrical frustration. We found that this compound exhibits an electrostatically unstable double-stripe-type charge ordering, which is stabilized by the cooperative compression of Fe3 +O6 octahedra, owing to a valence change and Fe2 +O6 octahedra due to Jahn-Teller distortion. Our results indicate the importance of electron-phonon coupling for charge ordering in the region of strong charge frustration.

Spontaneous electric polarization in the B-site magnetic spinel GeCu2O4

NASA Astrophysics Data System (ADS)

Yanda, Premakumar; Ghara, Somnath; Sundaresan, A.

2018-04-01

We report the observation of a spontaneous electric polarization at the antiferromagnetic ordering temperature (TN ∼ 33 K) of Cu2+ ions in the B-site magnetic spinel GeCu2O4, synthesized at high pressure and high temperature. This compound is known to crystallize in a tetragonal structure (space group I41/amd) due to Jahn-Teller distortion of Cu2+ ions and exhibit a collinear up-up-down-down (↑↑↓↓) antiferromagnetic spin configuration below TN. We found a clear dielectric anomaly at TN, where an electric polarization appears in the absence of applied magnetic field. The electric polarization is suppressed by applied magnetic fields, which demonstrates that the compound GeCu2O4 is a type-II multiferroic.

One Dimensional(1D)-to-2D Crossover of Spin Correlations in the 3D Magnet ZnMn 2O 4

DOE PAGES

Disseler, S. M.; Chen, Y.; Yeo, S.; ...

2015-12-08

In this paper we report on the intriguing evolution of the dynamical spin correlations of the frustrated spinel ZnMn 2O 4. Inelastic neutron scattering and magnetization studies reveal that the dynamical correlations at high temperatures are 1D. At lower temperature, these dynamical correlations become 2D. Surprisingly, the dynamical correlations condense into a quasi 2D Ising-like ordered state, making this a rare observation of two dimensional order on the spinel lattice. Remarkably, 3D ordering is not observed down to temperatures as low as 300 mK. This unprecedented dimensional crossover stems from frustrated exchange couplings due to the huge Jahn-Teller distortions aroundmore » Mn 3+ ions on the spinel lattice.« less

Effect of pressure on the tetragonal distortion in TiH2: a first-principles study

NASA Astrophysics Data System (ADS)

de Coss, R.; Quijano, R.; Singh, D. J.

2009-03-01

The transition metal dihydride TiH2 present the fluorite structure (CaF2) at high temperature but undergoes a tetragonal distortion with c/a<1 at low temperature. Early electronic band structure calculations have shown that TiH2 in the cubic phase display a nearly flat double degenerated band at the Fermi level. Thus the low temperature tetragonal distortion has been associated to a Jahn-Teller effect. Nevertheless, recently we have show that the instability of fcc-TiH2 is likely to be related with a van Hove singularity. In the present work, we have performed ab-initio calculations of the electronic structure and the tetragonal distortion for TiH2 under pressure (0-30 GPa). We found that the fcc-fct energy barrier and the tetragonal distortion increases with pressure. The evolution of the tetragonal distortion is analyzed in terms of the electronic band structure. This research was supported by Consejo Nacional de Ciencia y Tecnolog'ia (Conacyt) under Grant No. 49985.

First iron and cobalt(II) hexabromoclathrochelates: structural, magnetic, redox, and electrocatalytic behavior.

PubMed

Dolganov, Alexander V; Belov, Alexander S; Novikov, Valentin V; Vologzhanina, Anna V; Romanenko, Galina V; Budnikova, Yulia G; Zelinskii, Genrikh E; Buzin, Michail I; Voloshin, Yan Z

2015-02-07

Template condensation of dibromoglyoxime with n-butylboronic acid on the corresponding metal ion as a matrix under vigorous reaction conditions afforded iron and cobalt(ii) hexabromoclathrochelates. The paramagnetic cobalt clathrochelate was found to be a low-spin complex at temperatures below 100 K, with a gradual increase in the effective magnetic moment at higher temperatures due to the temperature 1/2↔3/2 spin crossover and a gap caused by the structure phase transition. The multitemperature X-ray and DSC studies of this complex and its iron(ii)-containing analog also showed temperature structural transitions. The variation of an encapsulated metal ion's radius, electronic structure and spin state caused substantial differences in the geometry of its coordination polyhedron; these differences increase with the decrease in temperature due to Jahn-Teller distortion of the encapsulated cobalt(ii) ion with an electronic configuration d(7). As follows from CV and GC data, these cage iron and cobalt complexes undergo both oxidation and reduction quasireversibly, and showed an electrocatalytic activity for hydrogen production in different producing systems.

Theoretical studies of the EPR parameters and local structures for Cu2+-doped cobalt ammonium phosphate hexahydrate

NASA Astrophysics Data System (ADS)

Li, Chao-Ying; Liu, Shi-Fei; Fu, Jin-Xian

2015-11-01

High-order perturbation formulas for a 3d9 ion in rhombically elongated octahedral was applied to calculate the electron paramagnetic resonance (EPR) parameters (the g factors, gi, and the hyperfine structure constants Ai, i = x, y, z) of the rhombic Cu2+ center in CoNH4PO4.6H2O. In the calculations, the required crystal-field parameters are estimated from the superposition model which enables correlation of the crystal-field parameters and hence the EPR parameters with the local structure of the rhombic Cu2+ center. Based on the calculations, the ligand octahedral (i.e. [Cu(H2O)6]2+ cluster) are found to experience the local bond length variations ΔZ (≈0.213 Å) and δr (≈0.132 Å) along axial and perpendicular directions due to the Jahn-Teller effect. Theoretical EPR parameters based on the above local structure are in good agreement with the observed values; the results are discussed.

Impact of hole doping on spin transition in perovskite-type cobalt oxides.

PubMed

Che, Xiangli; Li, Liping; Hu, Wanbiao; Li, Guangshe

2016-06-28

Series of perovskite PrCo1-xNixO3-δ (x = 0-0.4) were prepared and carefully investigated to understand the spin state transition driven by hole doping and further to reveal the effect of spin state transition on electronic conduction. It is shown that with increasing doping level, the transition temperature Ts for Co(3+) ions from low-spin (LS) to intermediate-spin (IS) reduces from 211.9 K for x = 0 to 190.5 K for x = 0.4. XPS and FT-IR spectra demonstrate that hole doping promoted this transition due to a larger Jahn-Teller distortion. Moreover, a thermal activation of spin disorder caused by thermal population of the spin states for Co ions has a great impact on the electrical transport of these perovskite samples. This work may shed light on the comprehension of spin transition in cobalt oxides through hole doping, which is promising for finding new strategies of enhancing electronic conduction, especially for energy and catalysis applications.

Lattice dynamics of A Sb2O6 (A =Cu , Co) with trirutile structure

NASA Astrophysics Data System (ADS)

Maimone, D. T.; Christian, A. B.; Neumeier, J. J.; Granado, E.

2018-03-01

Raman spectroscopy experiments on single crystals of CuSb2O6 and CoSb2O6 quasi-one-dimensional antiferromagnets with trirutile crystal structure were performed, with a focus on the first material. The observed Raman-active phonon modes and previously reported infrared-active modes were identified with the aid of ab initio lattice dynamics calculations. The structural transition between monoclinic β -CuSb2O6 and tetragonal α -CuSb2O6 phases at Ts=400 K is manifested in our spectra by a "repulsion" of two accidentally quasidegenerate symmetric modes below Ts, caused by a phonon mixing effect that is only operative in the monoclinic β -CuSb2O6 phase due to symmetry restrictions. Also, two specific phonons, associated with CuO6 octahedra rotation and with a Jahn-Teller elongation mode, soften and broaden appreciably as T →Ts . A crossover from a displacive to an order-disorder transition at Ts is inferred.

Designing shape-memory Heusler alloys from first-principles

NASA Astrophysics Data System (ADS)

Siewert, M.; Gruner, M. E.; Dannenberg, A.; Chakrabarti, A.; Herper, H. C.; Wuttig, M.; Barman, S. R.; Singh, S.; Al-Zubi, A.; Hickel, T.; Neugebauer, J.; Gillessen, M.; Dronskowski, R.; Entel, P.

2011-11-01

The phase diagrams of magnetic shape-memory Heusler alloys, in particular, ternary Ni-Mn-Z and quarternary (Pt, Ni)-Mn-Z alloys with Z = Ga, Sn, have been addressed by density functional theory and Monte Carlo simulations. Finite temperature free energy calculations show that the phonon contribution stabilizes the high-temperature austenite structure while at low temperatures magnetism and the band Jahn-Teller effect favor the modulated monoclinic 14M or the nonmodulated tetragonal structure. The substitution of Ni by Pt leads to a series of magnetic shape-memory alloys with very similar properties to Ni-Mn-Ga but with a maximal eigenstrain of 14%.

Spin and orbital disordering by hole doping in P r1 -xC axV O3

NASA Astrophysics Data System (ADS)

Reehuis, M.; Ulrich, C.; Abdala, P. M.; Pattison, P.; Khaliullin, G.; Fujioka, J.; Miyasaka, S.; Tokura, Y.; Keimer, B.

2016-09-01

High-resolution powder x-ray diffraction and single-crystal neutron diffraction were used to investigate the crystal structure and magnetic ordering of the compound P r1 -xC axV O3 (0 ≤x ≤0.3 ), which undergoes an insulator-to-metal transition for x ˜0.23 . Since the ionic radii of P r3 + and C a2 + are almost identical and structural disorder is minimal, P r1 -xC axV O3 is a good model system for the influence of hole doping on the spin and orbital correlations in transition metal oxides. The end member PrV O3 is a Mott-Hubbard insulator, which exhibits a structural phase transition at TS=180 K from an orthorhombic to a monoclinic structure with space groups Pbnm and P 21/b , respectively. This transition is associated with the onset of orbital ordering and strong Jahn-Teller distortions of the V O6 octahedra. Antiferromagnetic C -type order with vanadium moments oriented in the a b plane is observed below TN=140 K . Upon cooling, the vanadium moments induce a progressive magnetic polarization of the praseodymium sublattice, resulting in a ferrimagnetic structure with coexisting modes (Cx, Fy) and (Fx, Cy). In the insulating range of the P r1 -xC axV O3 phase diagram, Ca doping reduces both the orbital and magnetic transition temperatures so that TS=108 K and TN=95 K for x =0.20 . The Jahn-Teller distortions and ordered vanadium moments also decrease upon doping. In a metallic sample with x =0.30 , Jahn-Teller distortions and long-range orbital ordering are no longer observable, and the average crystal structure remains orthorhombic down to low temperature. However, broadening of some lattice Bragg reflections indicate a significant increase in lattice strain. Antiferromagnetic short-range order with a weak ordered moment of 0.14(3) μB per vanadium atom could still be observed on the vanadium site below T ˜60 K . We discuss these observations in terms of doping-induced spin-orbital polaron formation.

Teller Training Module: Off-Line Banking System. High-Technology Training Module.

ERIC Educational Resources Information Center

Lund, Candyce J.

This teller training module on offline banking systems is intended to be part of a postsecondary financial applications course. The module contains the following sections: module objective; specific objective; content--electronic audit machine key functions, practice packet--sample bank transactions and practicing procedures, and…

Bis(6-meth-oxy-2-{[tris-(hydroxy-meth-yl)-meth-yl]-imino-meth-yl}phenolato)-copper(II) dihydrate.

PubMed

Zhang, Xiutang; Wei, Peihai; Dou, Jianmin; Li, Bin; Hu, Bo

2009-01-08

In the title compound, [Cu(C(12)H(16)NO(5))(2)]·2H(2)O, the Cu(II) ion adopts a trans-CuN(2)O(4) octa-hedral geometry arising from two N,O,O'-tridentate 6-meth-oxy-2-{[tris-(hydroxy-meth-yl)meth-yl]-imino-meth-yl}phenolate ligands. The Jahn-Teller distortion of the copper centre is unusally small. In the crystal structure, O-H⋯O hydrogen bonds, some of which are bifurcated, link the component species.

Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches

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

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

The phases of A 2Mn 8O 16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3d electrons are more explicitly considered with the DFT + Umore » approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn 3+ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Lastly, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.« less

Charge localization and ordering in A 2 Mn 8 O 16 hollandite group oxides: Impact of density functional theory approaches

DOE PAGES

Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

2017-12-01

The phases of A 2Mn 8O 16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3d electrons are more explicitly considered with the DFT + Umore » approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn 3+ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Lastly, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.« less

Charge localization and ordering in A2Mn8O16 hollandite group oxides: Impact of density functional theory approaches

NASA Astrophysics Data System (ADS)

Kaltak, Merzuk; Fernández-Serra, Marivi; Hybertsen, Mark S.

2017-12-01

The phases of A2Mn8O16 hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in density functional theory. Three examples (A = Ag, Li, and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn 3 d electrons are more explicitly considered with the DFT + U approach. Finally, selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low-U and a high-U approach. In the low-U case, the materials are described as band metals with a high-symmetry, tetragonal crystal structure. In the high-U case, the electrons donated by A result in formation of local Mn3 + centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low-temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. Finally, while competing effects in the local magnetic coupling are subtle, the fully anisotropic implementation of DFT + U gives the best overall agreement with results from the hybrid functional.

Exotic s-wave superconductivity in alkali-doped fullerides.

PubMed

Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro

2016-04-20

Alkali-doped fullerides (A3C60 with A = K, Rb, Cs) show a surprising phase diagram, in which a high transition-temperature (Tc) s-wave superconducting state emerges next to a Mott insulating phase as a function of the lattice spacing. This is in contrast with the common belief that Mott physics and phonon-driven s-wave superconductivity are incompatible, raising a fundamental question on the mechanism of the high-Tc superconductivity. This article reviews recent ab initio calculations, which have succeeded in reproducing comprehensively the experimental phase diagram with high accuracy and elucidated an unusual cooperation between the electron-phonon coupling and the electron-electron interactions leading to Mott localization to realize an unconventional s-wave superconductivity in the alkali-doped fullerides. A driving force behind the exotic physics is unusual intramolecular interactions, characterized by the coexistence of a strongly repulsive Coulomb interaction and a small effectively negative exchange interaction. This is realized by a subtle energy balance between the coupling with the Jahn-Teller phonons and Hund's coupling within the C60 molecule. The unusual form of the interaction leads to a formation of pairs of up- and down-spin electrons on the molecules, which enables the s-wave pairing. The emergent superconductivity crucially relies on the presence of the Jahn-Teller phonons, but surprisingly benefits from the strong correlations because the correlations suppress the kinetic energy of the electrons and help the formation of the electron pairs, in agreement with previous model calculations. This confirms that the alkali-doped fullerides are a new type of unconventional superconductors, where the unusual synergy between the phonons and Coulomb interactions drives the high-Tc superconductivity.

Electron-spin-resonance studies of 12CH3F + , 13CH3F + , and 12CH2DF + in neon matrices at 4 K: Comparison with theoretical calculations

NASA Astrophysics Data System (ADS)

Knight, Lon B., Jr.; Gregory, Brian W.; Hill, Devon W.; Arrington, C. A.; Momose, Takamasa; Shida, Tadamasa

1991-01-01

Various isotopic forms of the methyl fluoride cation 12CH3F+, 13CH3F+, and 12CH2DF+ have been generated by photoionization at 16.8 eV and separately by electron bombardment at 50 eV. The first electron-spin-resonance (ESR) results are reported for this radical cation which was isolated in neon matrices at 4 K. The measured A tensors or nuclear hyperfine parameters were compared with the results obtained from various computational approaches. Surprising observations were the large amounts of spin density on the methyl group, especially the hydrogen atoms, and the extreme differences in the deuterated spectra compared to the nondeuterated case. The presence of a single D atom apparently acts to prevent dynamic Jahn-Teller averaging which makes the methyl hydrogens equivalent on the ESR time scale. Such a dramatic Jahn-Teller effect has been previously observed for the similar methane cations CH+4 and CH2D+2. The magnetic parameters for CH2DF+ in neon at 4 K are gX=2.0032(5), gY=2.0106(8), and gZ=2.0120(5); for H: AX = 483(1), AY=476(1), and AZ=483(1) MHz; for D: ‖AX‖=5.0(3), ‖AY‖<3, and ‖AZ‖=7.1(3) MHz; for 19F : AX=965(1), AY=-130(2), and AZ=-166(1) MHz. For CH3F+, the g tensor and 19F A tensor were similar to those above but the H atoms were equivalent with values of AX=317(1), AY=323(2), and AZ=312 MHz.

Distorted allotropes of bi-benzene: vibronic interactions and electronic excitations

NASA Astrophysics Data System (ADS)

Krasnenko, V.; Boltrushko, V.; Hizhnyakov, V.

2017-05-01

Bi-benzene - chemically bound two benzene molecules in stuck position is studied both analytically and numerically. There are several allotropes of bi-benzene having different geometry. The reason of the existence of sundry distorted structures is the pseudo-Jahn-Teller effect. The parameters of vibronic couplings causing distortions are found. For the calculation of these parameters both, the vibronic coupling of carbon atoms in different C6 rings and the vibronic coupling in the rings are considered. The contribution of the distortion of C6-planes to the latter coupling is also found. The energies of all the electronic states of π-electrons in all bi-benzene allotropes are determined by using the calculated vibronic interaction parameters.

Large-scale phase separation with nano-twin domains in manganite spinel (Co,Fe,Mn){sub 3}O{sub 4}

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

Horibe, Y., E-mail: horibe@post.matsc.kyutech.ac.jp; Takeyama, S.; Mori, S.

The effect of Mn concentration on the formation of nano-domain structures in the spinel oxide (Co,Fe,Mn){sub 3}O{sub 4} was investigated by electron diffraction, bright-, and dark-field imaging technique with transmission electron microscopy. Large scale phase separation with nano-twin domains was observed in Co{sub 0.6}Fe{sub 1.0}Mn{sub 1.4}O{sub 4}, in contrast to the highly aligned checkerboard nano-domains in Co{sub 0.6}Fe{sub 0.9}Mn{sub 1.5}O{sub 4}. Diffusion of the Mn{sup 3+} ions with the Jahn-Teller distortions is suggested to play an important role in the formation of checkerboard nano-domain structure.

Theoretical studies of the local structures and spin Hamiltonian parameters for Cu2+ in alkaline earth alumino borate glasses

NASA Astrophysics Data System (ADS)

Guo, Jia-Xing; Wu, Shao-Yi; Kuang, Min-Quan; Peng, Li; Wu, Li-Na

2018-01-01

The local structures and spin Hamiltonian parameters are theoretically studied for Cu2+ in alkaline earth alumino borate (XAB, X = Mg, Ca and Sr) glasses by using the perturbation calculations for tetragonally elongated octahedral 3d9 groups. The [CuO6]10- groups are subject to the large relative tetragonal elongation ratios of 15.4%, 13.4% and 13.0% for MgAB, CaAB and SrAB glasses, respectively, arising from the Jahn-Teller effect. The decreasing cubic field parameter Dq, orbital reduction factor k and relative elongation ratio with the increase of the radius of alkaline earth ion X from Mg to Ca or Sr are analyzed for the studied systems in a uniform way.

Controlling the orbital sequence in individual Cu-phthalocyanine molecules.

PubMed

Uhlmann, C; Swart, I; Repp, J

2013-02-13

We report on the controlled change of the energetic ordering of molecular orbitals. Negatively charged copper(II)phthalocyanine on NaCl/Cu(100) undergoes a Jahn-Teller distortion that lifts the degeneracy of two frontier orbitals. The energetic order of the levels can be controlled by Au and Ag atoms in the vicinity of the molecule. As only one of the states is occupied, the control of the energetic order is accompanied by bistable changes of the charge distribution inside the molecule, rendering it a bistable switch.

Influence of the Renner-Teller Coupling in CO+H Collision Dynamics

NASA Astrophysics Data System (ADS)

Ndengue, Steve Alexandre; Dawes, Richard

2017-06-01

Carbon monoxide is after molecular hydrogen the second most abundant molecule in the universe and an important molecule for processes occurring in the atmosphere, hydrocarbon combustion and the interstellar medium. The rate coefficients of CO in collision with dominant species like H, H_2, He, etc are necessary to understand the CO emission spectrum or to model combustion chemistry processes. The inelastic scattering of CO with H has been intensively studied theoretically in the past decades,^1 mostly using the so-called WKS PES^6 developed by Werner et al. or recently a modified version by Song et al.^2 Though the spectroscopic agreement of the WKS surface with experiment is quite good, so far the studies of scattering dynamics have neglected coupling to an electronic excited state. We present new results on a set of HCO surfaces of the ground and the excited Renner-Teller coupled electronic states^3 with the principal objective of studying the influence of the Renner-Teller coupling on the inelastic scattering of CO+H. Our calculations done using the MCTDH^4 algorithm in the 0-2 eV energy range allow evaluation of the contribution of the Renner-Teller coupling on the rovibrationally inelastic scattering and discuss the relevance and reliability of the calculations. References:} 1. N. Balakrishnan, M. Yan and A. Dalgarno, Astrophys. J. 568, 443 (2002); B.C. Shepler et al, Astron. & Astroph. 475, L15 (2007); L. Song et al, J. Chem. Phys. 142, 204303 (2015); K.M. Walker et al, Astroph. J. 811, 27 (2015). 2. L. Song et al, Astrophys. J. 813, 96 (2015). 3. H.-M. Keller et al, J. Chem. Phys. 105, 4983 (1996). 4. S. Ndengue, R. Dawes and H. Guo, J. Chem. Phys. 144, 244301 (2016). 5. M.H. Beck et al., Phys. Rep. 324, 1 (2000).

Nilsson diagrams for light neutron-rich nuclei with weakly-bound neutrons

NASA Astrophysics Data System (ADS)

Hamamoto, Ikuko

2007-11-01

Using Woods-Saxon potentials and the eigenphase formalism for one-particle resonances, one-particle bound and resonant levels for neutrons as a function of quadrupole deformation are presented, which are supposed to be useful for the interpretation of spectroscopic properties of some light neutron-rich nuclei with weakly bound neutrons. Compared with Nilsson diagrams in textbooks that are constructed using modified oscillator potentials, we point out a systematic change of the shell structure in connection with both weakly bound and resonant one-particle levels related to small orbital angular momenta ℓ. Then, it is seen that weakly bound neutrons in nuclei such as C15-19 and Mg33-37 may prefer being deformed as a result of the Jahn-Teller effect, due to the near degeneracy of the 1d5/2-2s1/2 levels and the 1f7/2-2p3/2 levels in the spherical potential, respectively. Furthermore, the absence of some one-particle resonant levels compared with the Nilsson diagrams in textbooks is illustrated.

Spontaneous symmetry breaking and strong deformations in metal adsorbed graphene sheets

NASA Astrophysics Data System (ADS)

Jalbout, A. F.; Ortiz, Y. P.; Seligman, T. H.

2013-03-01

We study the adsorption of Li to graphene flakes simulated as aromatic molecules. Surprisingly the out of plane deformation is much stronger for the double adsorption from both sides to the same ring than for a single adsorption, although a symmetric solution seems possible. We thus have an interesting case of spontaneous symmetry breaking. While we cannot rule out a Jahn Teller deformation with certainty, this explanation seems unlikely and other options are discussed. We find a similar behavior for boron-nitrogen sheets, and also for other light alkalines as adsorbants.

A tight binding model study of tunneling conductance spectra of spin and orbitally ordered CMR manganites

NASA Astrophysics Data System (ADS)

Panda, Saswati; Sahoo, D. D.; Rout, G. C.

2018-04-01

We report here a tight binding model for colossal magnetoresistive (CMR) manganites to study the pseudo gap (PG) behavior near Fermi level. In the Kubo-Ohata type DE model, we consider first and second nearest neighbor interactions for transverse spin fluctuations in core band and hopping integrals in conduction band, in the presence of static band Jahn-Teller distortion. The model Hamiltonian is solved using Zubarev's Green's function technique. The electron density of states (DOS) is found out from the Green's functions. We observe clear PG near Fermi level in the electron DOS.

A binuclear Mn(III) complex of a scorpiand-like ligand displaying a single unsupported Mn(III)-O-Mn(III) bridge.

PubMed

Blasco, Salvador; Cano, Joan; Clares, M Paz; García-Granda, Santiago; Doménech, Antonio; Jiménez, Hermas R; Verdejo, Begoña; Lloret, Francesc; García-España, Enrique

2012-11-05

The crystal structure of a binuclear Mn(III) complex of a scorpiand-like ligand (L) displays an unsupported single oxo bridging ligand with a Mn(III)-O-Mn(III) angle of 174.7°. Magnetic susceptibility measurements indicate strong antiferromagnetic coupling between the two metal centers. DFT calculations have been carried out to understand the magnetic behavior and to analyze the nature of the observed Jahn-Teller distortion. Paramagnetic (1)H NMR has been applied to rationalize the formation and magnetic features of the complexes formed in solution.

Origin of Spinel Nanocheckerboards via First Principles

NASA Astrophysics Data System (ADS)

Kornbluth, Mordechai; Marianetti, Chris A.

2015-06-01

Self-organizing nanocheckerboards have been experimentally fabricated in Mn-based spinels but have not yet been explained with first principles. Using density-functional theory, we explain the phase diagram of the ZnMnxGa2 -xO4 system and the origin of nanocheckerboards. We predict total phase separation at zero temperature and then show the combination of kinetics, thermodynamics, and Jahn-Teller physics that generates the system's observed behavior. We find that the {011 } surfaces are strongly preferred energetically, which mandates checkerboard ordering by purely geometrical considerations.

Investigation of Gamow Teller transition properties in 56-64Ni isotopes using QRPA methods

NASA Astrophysics Data System (ADS)

Cakmak, Sadiye; Nabi, Jameel-Un; Babacan, Tahsin

2018-02-01

Weak rates in nickel isotopes play an integral role in the dynamics of supernovae. Electron capture and β-decay of nickel isotopes, dictated by Gamow-Teller transitions, significantly alter the lepton fraction of the stellar matter. In this paper we calculate Gamow-Teller (GT) transitions for isotopes of nickel, Ni6456-, using QRPA methods. The GT strength distributions were calculated using four different QRPA models. Our results are also compared with previous theoretical calculations and measured strength distributions wherever available. Our investigation concluded that amongst all RPA models, the pn-QRPA(C) model best described the measured GT distributions (including total GT strength and centroid placement). It is hoped that the current investigation of GT properties would prove handy and may lead to a better understanding of the presupernova evolution of massive stars.

Formal verification of automated teller machine systems using SPIN

NASA Astrophysics Data System (ADS)

Iqbal, Ikhwan Mohammad; Adzkiya, Dieky; Mukhlash, Imam

2017-08-01

Formal verification is a technique for ensuring the correctness of systems. This work focuses on verifying a model of the Automated Teller Machine (ATM) system against some specifications. We construct the model as a state transition diagram that is suitable for verification. The specifications are expressed as Linear Temporal Logic (LTL) formulas. We use Simple Promela Interpreter (SPIN) model checker to check whether the model satisfies the formula. This model checker accepts models written in Process Meta Language (PROMELA), and its specifications are specified in LTL formulas.

Investigating the Human Computer Interaction Problems with Automated Teller Machine Navigation Menus

ERIC Educational Resources Information Center

Curran, Kevin; King, David

2008-01-01

Purpose: The automated teller machine (ATM) has become an integral part of our society. However, using the ATM can often be a frustrating experience as people frequently reinsert cards to conduct multiple transactions. This has led to the research question of whether ATM menus are designed in an optimal manner. This paper aims to address the…

Old Father Story Teller: Grandfather Stories of the Pueblo Native American Indians.

ERIC Educational Resources Information Center

Velarde, Pablita

Pablita Velarde, renowned artist and lecturer, recalls some of the Tewa legends handed down orally through the generations. She heard her grandfather and great-grandfather relate these tales on cold winter evenings at Santa Clara Pueblo when she was a child. The six stories told by Old Father Story Teller are "The Stars," which ties the…

Excitations and relaxation dynamics in multiferroic GeV4S8 studied by terahertz and dielectric spectroscopy

NASA Astrophysics Data System (ADS)

Reschke, S.; Wang, Zhe; Mayr, F.; Ruff, E.; Lunkenheimer, P.; Tsurkan, V.; Loidl, A.

2017-10-01

We report on THz time-domain spectroscopy on multiferroic GeV4S8 , which undergoes orbital ordering at a Jahn-Teller transition at 30.5 K and exhibits antiferromagnetic order below 14.6 K. The THz experiments are complemented by dielectric experiments at audio and radio frequencies. We identify a low-lying excitation close to 0.5 THz, which is only weakly temperature dependent and probably corresponds to a molecular excitation within the electronic level scheme of the V4 clusters. In addition, we detect complex temperature-dependent behavior of a low-lying phononic excitation, closely linked to the onset of orbitally driven ferroelectricity. In the high-temperature cubic phase, which is paramagnetic and orbitally disordered, this excitation is of relaxational character becomes an overdamped Lorentzian mode in the orbitally ordered phase below the Jahn-Teller transition, and finally appears as well-defined phonon excitation in the antiferromagnetic state. Abrupt changes in the real and imaginary parts of the complex dielectric permittivity show that orbital ordering appears via a structural phase transition with strong first-order character and that the onset of antiferromagnetic order is accompanied by significant structural changes, which are of first-order character, too. Dielectric spectroscopy documents that at low frequencies, significant dipolar relaxations are present in the orbitally ordered, paramagnetic phase only. In contrast to the closely related GaV4S8 , this relaxation dynamics that most likely mirrors coupled orbital and polar fluctuations does not seem to be related to the dynamic processes detected in the THz regime.

Perovskite-structure TlMnO₃: a new manganite with new properties.

PubMed

Yi, Wei; Kumagai, Yu; Spaldin, Nicola A; Matsushita, Yoshitaka; Sato, Akira; Presniakov, Igor A; Sobolev, Alexey V; Glazkova, Yana S; Belik, Alexei A

2014-09-15

We synthesize a new member of the AMnO3 perovskite manganite family (where A is a trivalent cation)--thallium manganite, TlMnO3--under high-pressure (6 GPa) and high-temperature (1500 K) conditions and show that the structural and magnetic properties are distinct from those of all other AMnO3 manganites. The crystal structure of TlMnO3 is solved and refined using single-crystal X-ray diffraction data. We obtain a triclinically distorted structure with space group P1̅ (No. 2), Z = 4, and lattice parameters a = 5.4248(2) Å, b = 7.9403(2) Å, c = 5.28650(10) Å, α = 87.8200(10)°, β = 86.9440(10)°, and γ = 89.3130(10)° at 293 K. There are four crystallographic Mn sites in TlMnO3 forming two groups based on the degree of their Jahn-Teller distortions. Physical properties of insulating TlMnO3 are investigated with Mössbauer spectroscopy and resistivity, specific heat, and magnetization measurements. The orbital ordering, which persists to the decomposition temperature of 820 K, suggests A-type antiferromagnetic ordering with the ferromagnetic planes along the [-101] direction, consistent with the measured collinear antiferromagnetism below the Néel temperature of 92 K. Hybrid density functional calculations are consistent with the experimentally identified structure, insulating ground state, and suggested magnetism, and show that the low symmetry originates from the strongly Jahn-Teller distorted Mn(3+) ions combined with the strong covalency of the Tl(3+)-O bonds.

Structural analysis of LaVO3 thin films under epitaxial strain

NASA Astrophysics Data System (ADS)

Meley, H.; Karandeep, Oberson, L.; de Bruijckere, J.; Alexander, D. T. L.; Triscone, J.-M.; Ghosez, Ph.; Gariglio, S.

2018-04-01

Rare earth vanadate perovskites exhibit a phase diagram in which two different types of structural distortions coexist: the strongest, the rotation of the oxygen octahedra, comes from the small tolerance factor of the perovskite cell (t = 0.88 for LaVO3) and the smaller one comes from inter-site d-orbital interactions manifesting as a cooperative Jahn-Teller effect. Epitaxial strain acts on octahedral rotations and crystal field symmetry to alter this complex lattice-orbit coupling. In this study, LaVO3 thin film structures have been investigated by X-ray diffraction and scanning transmission electron microscopy. The analysis shows two different orientations of octahedral tilt patterns, as well as two distinct temperature behaviors, for compressive and tensile film strain states. Ab initio calculations capture the strain effect on the tilt pattern orientation in agreement with experimental data.

Perturbatively deformed defects in Pöschl-Teller-driven scenarios for quantum mechanics

NASA Astrophysics Data System (ADS)

Bernardini, Alex E.; da Rocha, Roldão

2016-07-01

Pöschl-Teller-driven solutions for quantum mechanical fluctuations are triggered off by single scalar field theories obtained through a systematic perturbative procedure for generating deformed defects. The analytical properties concerning the quantum fluctuations in one-dimension, zero-mode states, first- and second-excited states, and energy density profiles are all obtained from deformed topological and non-topological structures supported by real scalar fields. Results are firstly derived from an integrated λϕ4 theory, with corresponding generalizations applied to starting λχ4 and sine-Gordon theories. By focusing our calculations on structures supported by the λϕ4 theory, the outcome of our study suggests an exact quantitative correspondence to Pöschl-Teller-driven systems. Embedded into the perturbative quantum mechanics framework, such a correspondence turns into a helpful tool for computing excited states and continuous mode solutions, as well as their associated energy spectrum, for quantum fluctuations of perturbatively deformed structures. Perturbative deformations create distinct physical scenarios in the context of exactly solvable quantum systems and may also work as an analytical support for describing novel braneworld universes embedded into a 5-dimensional gravity bulk.

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

NASA Astrophysics Data System (ADS)

Schoepp, Juergen

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

Possible origin of photoconductivity in La0.7Ca0.3MnO3

NASA Astrophysics Data System (ADS)

Sagdeo, P. R.; Choudhary, R. J.; Phase, D. M.

2010-01-01

The effect of photon energy on the density of states near Fermi level of pulsed laser deposited La0.7Ca0.3MnO3 thin film has been studied to investigate the possible origin of change in the conductivity of these manganites upon photon exposure. For this purpose the photoelectron spectroscopy measurements were carried out using CSR beamline (BL-2) on Indus-1 synchrotron radiation source. The valance band spectra were measured at room temperature with photon energy ranging from 40 to 60 eV. We could see huge change in the density of states near Fermi level and this change is observed to be highest at 56 eV which is due to the resonance between Mn 3p to Mn 3d level. Our results suggest that the probability of electron transfer from deep Mn 3p level to Mn 3d-eg level is higher than that of Mn 3d-t2g level. It appears that this transfer of electron from deep Mn level to Mn 3d-eg level not only modifies the density of state near Fermi level but also changes the mobility of electrons by modifying the electron lattice coupling due to presence of Mn+3 Jahn-Teller ion.

Ferromagnetism in LaCoO3 nanoparticles

NASA Astrophysics Data System (ADS)

Zhou, Shiming; Shi, Lei; Zhao, Jiyin; He, Laifa; Yang, Haipeng; Zhang, Shangming

2007-11-01

We have investigated the structural and magnetic properties of LaCoO3 nanoparticles prepared by a sol-gel method. A ferromagnetic order with TC˜85K has been observed in the nanoparticles. The infrared spectra give evidence for a stabilizing of higher spin state and a reduced Jahn-Teller distortion in the nanoparticles with respect to the bulk LaCoO3 , which is consistent with the recent reports in the strained films [Phys. Rev. B 75, 144402 (2007)] and proposed to be the possible origin of the observed ferromagnetic order in LaCoO3 .

Spin dynamics and orbital state in LaTiO3

PubMed

Keimer; Casa; Ivanov; Lynn; Zimmermann; Hill; Gibbs; Taguchi; Tokura

2000-10-30

A neutron scattering study of the Mott-Hubbard insulator LaTiO3 ( T(N) = 132 K) reveals a spin wave spectrum that is well described by a nearest-neighbor superexchange constant J = 15.5 meV and a small Dzyaloshinskii-Moriya interaction ( D = 1.1 meV). The nearly isotropic spin wave spectrum is surprising in view of the absence of a static Jahn-Teller distortion that could quench the orbital angular momentum, and it may indicate strong orbital fluctuations. A resonant x-ray scattering study has uncovered no evidence of orbital order in LaTiO3.

The trigonal prism in coordination chemistry.

PubMed

Cremades, Eduard; Echeverría, Jorge; Alvarez, Santiago

2010-09-10

Herein we analyze the accessibility of the trigonal-prismatic geometry to metal complexes with different electron configurations, as well as the ability of several hexadentate ligands to favor that coordination polyhedron. Our study combines i) a structural database analysis of the occurrence of the prismatic geometry throughout the transition-metal series, ii) a qualitative molecular orbital analysis of the distortions expected for a trigonal-prismatic geometry, and iii) a computational study of complexes of several transition-metal ions with different hexadentate ligands. Also the tendency of specific electron configurations to present a cis bond-stretch Jahn-Teller distortion is analyzed.

Specific features of the structural and magnetic states of a Zn1 - x Ni x Se crystal ( x = 0.0025) at low temperatures

NASA Astrophysics Data System (ADS)

Dubinin, S. F.; Sokolov, V. I.; Parkhomenko, V. D.; Teploukhov, S. G.; Gruzdev, N. B.

2008-12-01

The magnetic state and the structure of a Zn1 - x Ni x Se ( x = 0.0025) bulk crystal were studied at low temperatures. It is revealed that the magnetic and crystal structures below T ≅ 15 K are dependent on the cooling rate of this dilute semiconductor. For example, on fast cooling to 4.2 K, about 10% hexagonal ferromagnetic phase is formed in the crystal. During heating, the phase disappears at T ≅ 15 K. The results obtained are discussed with allowance for the specific features of the Jahn-Teller distortions in this compound.

Evidence for Jahn-Teller distortions at the antiferromagnetic transition in LaTiO3.

PubMed

Hemberger, J; Krug von Nidda, H-A; Fritsch, V; Deisenhofer, J; Lobina, S; Rudolf, T; Lunkenheimer, P; Lichtenberg, F; Loidl, A; Bruns, D; Büchner, B

2003-08-08

LaTiO3 is known as a Mott insulator which orders antiferromagnetically at T(N)=146 K. We report on results of thermal expansion and temperature dependent x-ray diffraction together with measurements of the heat capacity, electrical transport measurements, and optical spectroscopy in untwinned single crystals. At T(N) significant structural changes appear, which are volume conserving. Concomitant anomalies are also observed in the dc resistivity, in bulk modulus, and optical reflectivity spectra. We interpret these experimental observations as evidence of orbital order.

Transition from orbital liquid to Jahn-Teller insulator in orthorhombic perovskites RTiO3.

PubMed

Cheng, J-G; Sui, Y; Zhou, J-S; Goodenough, J B; Su, W H

2008-08-22

Following the same strategy used for RVO3, thermal conductivity measurements have been made on a series of single-crystal perovskites RTiO3 (R=La,Nd,...,Yb). Results reveal explicitly a transition from an orbital liquid to an orbitally ordered phase at a magnetic transition temperature, which is common for both the antiferromagnetic and ferromagnetic phases in the phase diagram of RTiO3. This spin/orbital transition is consistent with the mode softening at T_{N} in antiferromagnetic LaTiO3 and is supported by an anomalous critical behavior at T_{c} in ferromagnetic YTiO3.

Vibronic spectra of Cu(2+) in ZnTe

NASA Technical Reports Server (NTRS)

Volz, M. P.; Su, C.-H.; Lehoczky, S. L.; Szofran, F. R.

1992-01-01

Infrared-absorption spectra of substitutional Cu(2+) ions in ZnTe have been measured at 4.6 K. Several distinct absorption peaks are observed between 800 and 2000/cm. Absorption peaks at 1002 and 1069/cm are identified as zero-phonon lines arising from 2T2-2E transitions. Between 1069 and 2000/cm, several sets of sharp absorption lines are seen to recur regularly at an interval of 210/cm, corresponding to the LO phonon energy. Within each set distinct vibronic sidebands that cannot be identified with critical-point energies of TA, LA, TO or LO phonon modes are observed. A dynamic Jahn-Teller effect, involving coupling between a single-phonon mode and the electronic states of the 2E level, is proposed to account for the observed spectra.

Ab initio study of the ground state surface of Cu3

NASA Technical Reports Server (NTRS)

Langhoff, Stephen R.; Bauschlicher, Charles W., Jr.; Walch, Stephen P.; Laskowski, Bernard C.

1986-01-01

The ground state surface of the metallic trimer Cu3 is investigated theoretically. Relativistic and correlation effects are taken into account in ab initio computations, which are calibrated against analogous computations for the 1Sigma(g)+ state of Cu2; the results are presented in tables and analyzed. The Cu3 ground state is found to have a 2B2 C(2v) structure with angle greater than 60 deg, lying 59/cm below a 2A1 C(2v) geometry and 280/cm below the D(3h) equilateral geometry. These findings are shown to be in good agreement with the experimental measurements of Rohlfing and Valentini (1986) and their analysis (in terms of a Jahn-Teller distortion of 2E-prime equilateral-triangle geometry) by Truhlar et al. (1986).

Giant Optical Polarization Rotation Induced by Spin-Orbit Coupling in Polarons

NASA Astrophysics Data System (ADS)

Casals, Blai; Cichelero, Rafael; García Fernández, Pablo; Junquera, Javier; Pesquera, David; Campoy-Quiles, Mariano; Infante, Ingrid C.; Sánchez, Florencio; Fontcuberta, Josep; Herranz, Gervasi

2016-07-01

We have uncovered a giant gyrotropic magneto-optical response for doped ferromagnetic manganite La2 /3Ca1 /3MnO3 around the near room-temperature paramagnetic-to-ferromagnetic transition. At odds with current wisdom, where this response is usually assumed to be fundamentally fixed by the electronic band structure, we point to the presence of small polarons as the driving force for this unexpected phenomenon. We explain the observed properties by the intricate interplay of mobility, Jahn-Teller effect, and spin-orbit coupling of small polarons. As magnetic polarons are ubiquitously inherent to many strongly correlated systems, our results provide an original, general pathway towards the generation of magnetic-responsive gigantic gyrotropic responses that may open novel avenues for magnetoelectric coupling beyond the conventional modulation of magnetization.

Beyond mean-field description of Gamow-Teller resonances and β-decay

NASA Astrophysics Data System (ADS)

Niu, Yifei; Colò, Gianluca; Vigezzi, Enrico; Bai, Chunlin; Niu, Zhongming; Sagawa, Hiroyuki

2018-02-01

β-decay half-lives set the time scale of the rapid neutron capture process, and are therefore essential for understanding the origin of heavy elements in the universe. The random-phase approximation (RPA) based on Skyrme energy density functionals is widely used to calculate the properties of Gamow-Teller (GT) transitions, which play a dominant role in β-decay half-lives. However, the RPA model has its limitations in reproducing the resonance width and often overestimates β-decay half-lives. To overcome these problems, effects beyond mean-field can be included on top of the RPA model. In particular, this can be obtained by taking into account the particle-vibration coupling (PVC). Within the RPA+PVC model, we successfully reproduce the experimental GT resonance width and β-decay half-lives in magic nuclei. We then extend the formalism to superfluid nuclei and apply it to the GT resonance in 120Sn, obtaining a good reproduction of the experimental strength distribution. The effect of isoscalar pairing is also discussed.

Chemical Pressure Effects in Layered Manganites

NASA Astrophysics Data System (ADS)

Moritomo, Yutaka; Maruyama, Yousuke; Nakamura, Arao

1998-03-01

Lattice effects on the magnetic and transport properties have been investigated for layered-type doped mangaites. The insulator-to-metal transition temperature for La_1.2Sr_1.8Mn_2O7 (T_C=130 K) is significantly suppressed with chemical substitution of the trivalent La^3+ ions to smaller Nd^3+ (or Sm^3+) ions(Y. Moritomo et al), Phys. Rev. B56(1997)R7057. Similarly, the charge-ordering temperature for La_0.5Sr_1.5MnO4 (T_CO=230 K) is suppresses with chemical substitution(Y. Moritomo et al), Phys. Rev. B56, in press. Systematic x-ray as well as neutron diffraction measurements have revealed that above chemical pressure enhances the static Jahn-Teller distortion of the MnO6 octahedra in both the system. We will explain the suppressions of TC and T_CO in terms of the increasing d_3z^2-r^2 character in the occupied eg state. Our observation indicates that the chemical pressure effects are qualitatively different between the cubic and layered manganites systems. The authors are grateful to K. Ohoyama and M. Ohashi for their help in neutron diffraction measurements, and to S. Mori for his help in electron diffraction measurements. This work was supported by a Grant-In-Aid for Scientific Research from the Ministry of Education, Science, Sport and Culture and from PRESTO, Japan Scienece and Technology Corporation (JST), Japan.

The giant Gamow-Teller resonance states

NASA Astrophysics Data System (ADS)

Suzuki, Toshio

1982-04-01

The mean energy of the giant Gamow-Teller resonance state (GTS) is studied, which is defined by the non-energy-weighted and the linearly energy-weighted sum of the strengths for ΣAi = 1 τi- σi- Using Bohr and Mottelson's hamiltonian with the ξl· σ force, the difference between the mean energies of GTS and the isobaric analog state (IAS) is expressed as E GTS -E IAS,≈ 2<π¦Σ Ai=1ξ il i· σ i¦π>/ (3T 0-4(k τ-k στ) T 0. The observed energy systematics is well explained by kτ- kστ≈ 4/ A MeV . The relationship between the mean energies and the excitation energies of the collective states in the random phase approximation for charge-exchange excitations is discussed in a simple model. From the excitation energy systematics of GTS, the values of kστ and the Migdal parameter g' are estimated to be about k στ = {(16-24)}/{A}MeV and g' = 0.49-0.72 , respectively.

Systematic shell-model study of β -decay properties and Gamow-Teller strength distributions in A ≈40 neutron-rich nuclei

NASA Astrophysics Data System (ADS)

Yoshida, Sota; Utsuno, Yutaka; Shimizu, Noritaka; Otsuka, Takaharu

2018-05-01

We perform large-scale shell-model calculations of β -decay properties for neutron-rich nuclei with 13 ≤Z ≤18 and 22 ≤N ≤34 , taking the first-forbidden transitions into account. The natural-parity and unnatural-parity states are calculated in the 0 ℏ ω and 1 ℏ ω model spaces, respectively, within the full s d +p f +s d g valence shell. The calculated β -decay half-lives and β -delayed neutron emission probabilities show good agreement with the experimental data. The first-forbidden transitions make a non-negligible contribution to the half-lives of N ≳28 nuclei. The low-lying Gamow-Teller strengths of even-even nuclei are considerably larger than those of the neighboring odd-A and odd-odd nuclei, strongly affecting the half-lives and neutron emission probabilities. It is shown that this even-odd effect is caused by the Jπ=1+ proton-neutron pairing interaction. We derive a formula to represent the positions of the Gamow-Teller giant resonances from the calculated strength distributions.

A robust and effective time-independent route to the calculation of Resonance Raman spectra of large molecules in condensed phases with the inclusion of Duschinsky, Herzberg-Teller, anharmonic, and environmental effects

PubMed Central

Egidi, Franco; Bloino, Julien; Cappelli, Chiara; Barone, Vincenzo

2015-01-01

We present an effective time-independent implementation to model vibrational resonance Raman (RR) spectra of medium-large molecular systems with the inclusion of Franck-Condon (FC) and Herzberg-Teller (HT) effects and a full account of the possible differences between the harmonic potential energy surfaces of the ground and resonant electronic states. Thanks to a number of algorithmic improvements and very effective parallelization, the full computations of fundamentals, overtones, and combination bands can be routinely performed for large systems possibly involving more than two electronic states. In order to improve the accuracy of the results, an effective inclusion of the leading anharmonic effects is also possible, together with environmental contributions under different solvation regimes. Reduced-dimensionality approaches can further enlarge the range of applications of this new tool. Applications to imidazole, pyrene, and chlorophyll a1 in solution are reported, as well as comparisons with available experimental data. PMID:26550003

Investigations on the Local Structures and the Spin Hamiltonian Parameters for Cu2+ in (90-x)TeO2-10GeO2-xWO3 Glasses

NASA Astrophysics Data System (ADS)

Feng, Chun-Rong; Jian, Jun; Chen, Xiao-Hong; Du, Quan; Wang, Ling

2017-12-01

The local structures and the spin Hamiltonian parameters (SHPs) for Cu2+ in (90-x)TeO2-10GeO2-xWO3 glasses are theoretically investigated at various WO3 concentrations (x=7.5, 15, 22.5 and 30 mol%). Subject to the Jahn-Teller effect, the [CuO6]10- groups are found to experience the small or moderate tetragonal elongation distortions (characterised by the relative tetragonal elongation ratios ρ≈0.35-3.09%) in C4 axis. With only three adjusted coefficients a, b and ω, the relevant model parameters (Dq, k and ρ) are described by the Fourier type and linear functions, respectively, and the measured concentration dependences of the d-d transition bands and SHPs are reproduced. The maximum of g∥ and the minimum of |A∥| at x=15 mol% are illustrated from the abrupt decrease of the copper-oxygen electron cloud admixtures or covalency and the obvious decline of the copper 3d-3s (4s) orbital admixtures due to the decreasing electron cloud density around oxygen ligands spontaneously bonding with Cu2+ and Te4+ (W6+), respectively.

AES Cardless Automatic Teller Machine (ATM) Biometric Security System Design Using FPGA Implementation

NASA Astrophysics Data System (ADS)

Ahmad, Nabihah; Rifen, A. Aminurdin M.; Helmy Abd Wahab, Mohd

2016-11-01

Automated Teller Machine (ATM) is an electronic banking outlet that allows bank customers to complete a banking transactions without the aid of any bank official or teller. Several problems are associated with the use of ATM card such card cloning, card damaging, card expiring, cast skimming, cost of issuance and maintenance and accessing customer account by third parties. The aim of this project is to give a freedom to the user by changing the card to biometric security system to access the bank account using Advanced Encryption Standard (AES) algorithm. The project is implemented using Field Programmable Gate Array (FPGA) DE2-115 board with Cyclone IV device, fingerprint scanner, and Multi-Touch Liquid Crystal Display (LCD) Second Edition (MTL2) using Very High Speed Integrated Circuit Hardware (VHSIC) Description Language (VHDL). This project used 128-bits AES for recommend the device with the throughput around 19.016Gbps and utilized around 520 slices. This design offers a secure banking transaction with a low rea and high performance and very suited for restricted space environments for small amounts of RAM or ROM where either encryption or decryption is performed.

High pressure effects on a trimetallic Mn(II/III) SMM.

PubMed

Prescimone, Alessandro; Sanchez-Benitez, Javier; Kamenev, Konstantin V; Moggach, Stephen A; Lennie, Alistair R; Warren, John E; Murrie, Mark; Parsons, Simon; Brechin, Euan K

2009-09-28

A combined study of the high pressure crystallography and high pressure magnetism of the complex [Mn3(Hcht)2(bpy)4](ClO4)3.Et2O.2MeCN (1.Et2O.2MeCN) (H3cht is cis,cis-1,3,5-cyclohexanetriol) is presented in an attempt to observe and correlate pressure induced changes in its structural and physical properties. At 0.16 GPa the complex 1.Et2O.2MeCN loses all associated solvent in the crystal lattice, becoming 1. At higher pressures structural distortions occur changing the distances between the metal centres and the bridging oxygen atoms making the magnetic exchange between the manganese ions weaker. No significant variations are observed in the Jahn-Teller axis of the only Mn(III) present in the structure. High pressure dc chiMT plots display a gradual decrease in both the low temperature value and slope. Simulations show a decrease in J with increasing pressure although the ground state is preserved. Magnetisation data do not show any change in |D|.

Bond-length fluctuations and the spin-state transition in LCoO3 (L=La, Pr, and Nd)

NASA Astrophysics Data System (ADS)

Yan, J.-Q.; Zhou, J.-S.; Goodenough, J. B.

2004-04-01

The temperature dependence of thermal conductivity, κ(T), and magnetic susceptibility, χ(T), have been measured on single crystals of LCoO3 (L=La, Pr, Nd) grown by the floating-zone method. The susceptibility measurement shows a progressive stabilization of the low-spin (LS) state of Co(III) with decreasing size of the L3+ ion, and the population of excited intermediate-spin (IS) or high-spin (HS) state Co(III) ions begins to increase at 200 K and 300 K for PrCoO3 and NdCoO3 compared with 35 K in LaCoO3. The low-temperature Curie-Weiss paramagnetic susceptibility of LCoO3 is an intrinsic property arising from surface cobalt and, possibly, a LS ground state bearing some IS character caused by the virtual excitation to the IS state. The transition from a LS to a IS/HS state introduces bond-length fluctuations that suppress the phonon contribution to κ(T) below 300 K. The suppressed κ(T) could be further reduced by dynamic Jahn-Teller distortions associated with the IS/HS species. A smooth transition in ρ(T) and α(T) and a nearly temperature independent α(T)≈20 μV/K above 600 K do not support a thermally induced, homogeneous Mott-Hubbard transition model for the high-temperature transition of LaCoO3 from an insulating to a conductive state. A two-phase process is proposed for the interval 300 KJahn-Teller distortions that may be dynamic.

Elastic and anelastic relaxations associated with the incommensurate structure of Pr0.48Ca0.52MnO3

NASA Astrophysics Data System (ADS)

Carpenter, Michael A.; Howard, Christopher J.; McKnight, Ruth E. A.; Migliori, Albert; Betts, Jon B.; Fanelli, Victor R.

2010-10-01

The elastic and anelastic properties of a polycrystalline sample of Pr0.48Ca0.52MnO3 have been investigated by resonant ultrasound spectroscopy, as a function of temperature (10-1130 K) and magnetic field strength (0-15 T). Marked softening of the shear modulus as the Pnma↔incommensurate phase transition at ˜235K in zero field is approached from either side is consistent with pseudoproper ferroelastic character, driven by an order parameter with Γ3+ symmetry associated with Jahn-Teller ordering. This is accompanied by an increase in attenuation just below the transition point. The attenuation remains relatively high down to ˜80K , where there is a distinct Debye peak. It is attributed to coupling of shear strain with the Γ3+ order parameter which, in turn, controls the repeat distance of the incommensurate structure. Kinetic data extracted from the Debye peak suggest that the rate-controlling process could be related to migration of polarons. Elastic softening and stiffening as a function of magnetic field at constant temperatures between 177 and ˜225K closely resembles the behavior as a function of temperature at 0, 5, and 10 T and is consistent with thermodynamically continuous behavior for the phase transition in both cases. This overall pattern can be rationalized in terms of linear/quadratic coupling between the Γ3+ order parameter and an order parameter with Σ1 or Σ2 symmetry. It is also consistent with a dominant role for spontaneous strains in determining the strength of coupling, evolution of the incommensurate microstructure, and equilibrium evolution of the Jahn-Teller ordered structure through multicomponent order-parameter space.

The ÖX˜ absorption of vinoxy radical revisited: Normal and Herzberg-Teller bands observed via cavity ringdown spectroscopy

NASA Astrophysics Data System (ADS)

Thomas, Phillip S.; Chhantyal-Pun, Rabi; Kline, Neal D.; Miller, Terry A.

2010-03-01

The ÖX˜ electronic absorption spectrum of vinoxy radical has been investigated using room temperature cavity ringdown spectroscopy. Analysis of the observed bands on the basis of computed vibrational frequencies and rotational envelopes reveals that two distinct types of features are present with comparable intensities. The first type corresponds to "normal" allowed electronic transitions to the origin and symmetric vibrations in the à state. The second type is interpreted in terms of excitations to asymmetric à state vibrations, which are only vibronically allowed by Herzberg-Teller coupling to the B˜ state. Results of electronic structure calculations indicate that the magnitude of the Herzberg-Teller coupling is appropriate to produce vibronically induced transitions with intensities comparable to those of the normal bands.

Thermo physical Properties of Multiferroic Rare Earth Manganite GdMnO3

NASA Astrophysics Data System (ADS)

Choithrani, Renu; Gaur, N. K.

2008-04-01

We have investigated the thermophysical properties of multiferroic rare earth manganite GdMnO3 in the temperature range 15 K⩽T⩽300 K. We have applied interatomic potential to study the Specific heat (C) as a function of temperature. The calculated Specific heat values are closer to the available experimental data. At room temperature, the orthorhombic GdMnO3 phase is indicative of a strong Jahn-Teller distortion. In addition, we have reported the cohesive energy (φ), molecular force constant (f), compressibility (β), Restrahalen frequency (ν0), Debye temperature (ΘD) and Groneisen parameter (γ) at temperature 15 K⩽T⩽300 K.

Isotropic Kink and Quasiparticle Excitations in the Three-Dimensional Perovskite Manganite La_{0.6}Sr_{0.4}MnO_{3}.

PubMed

Horiba, Koji; Kitamura, Miho; Yoshimatsu, Kohei; Minohara, Makoto; Sakai, Enju; Kobayashi, Masaki; Fujimori, Atsushi; Kumigashira, Hiroshi

2016-02-19

In order to reveal the many-body interactions in three-dimensional perovskite manganites that show colossal magnetoresistance, we performed an in situ angle-resolved photoemission spectroscopy on La_{0.6}Sr_{0.4}MnO_{3} and investigated the behavior of quasiparticles. We observed quasiparticle peaks near the Fermi momentum in both the electron and the hole bands, and clear kinks throughout the entire hole Fermi surface in the band dispersion. This isotropic behavior of quasiparticles and kinks suggests that polaronic quasiparticles produced by the coupling of electrons with Jahn-Teller phonons play an important role in the colossal magnetoresistance properties of the ferromagnetic metallic phase of three-dimensional manganites.

Ultrafast optically induced ferromagnetic/anti-ferromagnetic phase transition in GdTiO3 from first principles

NASA Astrophysics Data System (ADS)

Khalsa, Guru; Benedek, Nicole A.

2018-03-01

Epitaxial strain and chemical substitution have been the workhorses of functional materials design. These static techniques have shown immense success in controlling properties in complex oxides through the tuning of subtle structural distortions. Recently, an approach based on the excitation of an infrared active phonon with intense midinfrared light has created an opportunity for dynamical control of structure through special nonlinear coupling to Raman phonons. We use first-principles techniques to show that this approach can dynamically induce a magnetic phase transition from the ferromagnetic ground state to a hidden antiferromagnetic phase in the rare earth titanate GdTiO3 for realistic experimental parameters. We show that a combination of a Jahn-Teller distortion, Gd displacement, and infrared phonon motion dominate this phase transition with little effect from the octahedral rotations, contrary to conventional wisdom.

A crossover in anisotropic nanomechanochemistry of van der Waals crystals

NASA Astrophysics Data System (ADS)

Shimamura, Kohei; Misawa, Masaaki; Li, Ying; Kalia, Rajiv K.; Nakano, Aiichiro; Shimojo, Fuyuki; Vashishta, Priya

2015-12-01

In nanoscale mechanochemistry, mechanical forces selectively break covalent bonds to essentially control chemical reactions. An archetype is anisotropic detonation of layered energetic molecular crystals bonded by van der Waals (vdW) interactions. Here, quantum molecular dynamics simulations reveal a crossover of anisotropic nanomechanochemistry of vdW crystal. Within 10-13 s from the passage of shock front, lateral collision produces NO2 via twisting and bending of nitro-groups and the resulting inverse Jahn-Teller effect, which is mediated by strong intra-layer hydrogen bonds. Subsequently, as we transition from heterogeneous to homogeneous mechanochemical regimes around 10-12 s, shock normal to multilayers becomes more reactive, producing H2O assisted by inter-layer N-N bond formation. These time-resolved results provide much needed atomistic understanding of nanomechanochemistry that underlies a wider range of technologies.

Ab initio study of MF2 (M=Mn, Fe, Co, Ni) rutile-type compounds using the periodic unrestricted Hartree-Fock approach

NASA Astrophysics Data System (ADS)

de P. R. Moreira, Ibério; Dovesi, Roberto; Roetti, Carla; Saunders, Victor R.; Orlando, Roberto

2000-09-01

The ab initio periodic unrestricted Hartree-Fock method has been applied in the investigation of the ground-state structural, electronic, and magnetic properties of the rutile-type compounds MF2 (M=Mn, Fe, Co, and Ni). All electron Gaussian basis sets have been used. The systems turn out to be large band-gap antiferromagnetic insulators; the optimized geometrical parameters are in good agreement with experiment. The calculated most stable electronic state shows an antiferromagnetic order in agreement with that resulting from neutron scattering experiments. The magnetic coupling constants between nearest-neighbor magnetic ions along the [001], [111], and [100] (or [010]) directions have been calculated using several supercells. The resulting ab initio magnetic coupling constants are reasonably satisfactory when compared with available experimental data. The importance of the Jahn-Teller effect in FeF2 and CoF2 is also discussed.

Specific features of nonvalent interactions in orthorhombic perovskites

NASA Astrophysics Data System (ADS)

Serezhkin, V. N.; Pushkin, D. V.; Serezhkina, L. B.

2014-07-01

It is established that isostructural orthorhombic perovskites ABO3 (sp. gr. Pnma in different systems, no. 62, Z = 4), depending on the specificity of nonvalent interactions (which determine the combinatorial-topological type of the Voronoi-Dirichlet polyhedra (VDPs) of four basis atoms), are divided into ten different stereotypes. It is shown by the example of 259 perovskites belonging to the DyCrO3 stereotype that VDP characteristics can be used to quantitatively estimate the distortion of BO6 octahedra, including that caused by the Jahn-Teller effect. It is found that one of the causes of the distortion of the coordination polyhedra of atoms in the structure of orthorhombic perovskites is heteroatomic metal-metal interactions, for which the interatomic distances are much shorter than the sum of the Slater radii of A and B atoms.

Anharmonic rattling vibrations effects in the ESR of Er 3+ doped SmB 6 Kondo insulator

DOE PAGES

Lesseux, G. G.; Rosa, P. F. S.; Fisk, Z.; ...

2017-01-23

We report X-band Electron Spin Resonance (ESR) experiments on ≈ 0.2% and ≈ 0.7 % Er 3+ doped SmB 6 at low temperature (4 K - 40 K). The crystal field ground state of Er 3+ in SmB 6 is a Γ 8 quartet with a nearby Γ 6 excited doublet. The angular dependence of the resonances is not consistent with transitions between pure cubic crystal field states. The data were interpreted in terms of a dynamic Jahn-Teller (JT) effect by a coupling to Γ 3 vibrational modes, which we propose to originate from the rattling of the small Ermore » 3+ ions in the large SmB6 cage. Our data show an anisotropic pair of E and E’ resonances at g ≈ 4.4 and two nearly isotropic signals at g ≈ 5.8, one intense and narrow (A vibrational mode) and the other broad and faint, which we attribute to Er 3+ ions at lattice sites which are strongly affected by strain, defects and/or extrinsic Al impurities that inhibits the JT effects. Our results are in general consistent with those previously reported by Sturm et al. In addition to the angular dependence of the lines, we discuss the intensities, g-values and the linewidths of the Er 3+ transitions as a function of temperature.« less

Gamow-Teller Strength in the Continuum Studied via the (p,n) Reaction

NASA Astrophysics Data System (ADS)

Wakasa, T.; Hatanaka, K.; Sakai, H.; Fujita, S.; Nonaka, T.; Ohnishi, T.; Yako, K.; Sekiguchi, K.; Okamura, H.; Otsu, H.; Ishida, S.; Sakamoto, N.; Uesaka, T.; Satou, Y.; Greenfield, M. B.

2002-09-01

The double differential cross sections for θ1ab between 0.0° and 14.7° and the polarization transfer coefficient DNN(0°) for the 27 Al(vec {p},vec {n}) reaction have been measured at a bombarding energy of 295 MeV. A multipole decomposition technique is applied for the cross section data to extract L = 0, 1, 2, and 3 contributions. The Gamow-Teller (GT) strength B(GT) deduced from the L = 0 contribution is compared with the B(GT) values calculated in a full sd shell-model space. The sum of B(GT) values up to 20 MeV excitation is Sβ- = 4.0 ± 0.1 ± 0.1. A fairly large L = 0 contribution is observed in the continuum region up to 50 MeV, which could be in part ascribed to the quenched GT strength. A limit on the effect that the Δ(1232)-isobar nucleon-hole admixture has upon the GT strength is estimated.

New Baxter phase in the Ashkin-Teller model on a cubic lattice

NASA Astrophysics Data System (ADS)

Santos, J. P.; Rosa, D. S.; Sá Barreto, F. C.

2018-02-01

The mean field theory results are obtained from the Bogoliubov inequality for the spin-1/2 Ashkin-Teller model on a cubic lattice for different cluster sizes. The phase diagram, magnetization and free energy are obtained. From those expressions we observed a new phase in the model. Denoted in the course of this work by Baxter(2) this new phase presents 〈 S 〉 ≠ 〈 σ 〉 ≠ 0. The phase transitions between the Baxter(2) and the others well known phases for the model are studied and classified.

Enhanced charge ordering transition in doped CaFeO3 through steric templating

NASA Astrophysics Data System (ADS)

Jiang, Lai; Saldana-Greco, Diomedes; Schick, Joseph T.; Rappe, Andrew M.

2014-06-01

We report a density functional theory investigation of B-site doped CaFeO3, a prototypical charge ordered perovskite. At 290 K, CaFeO3 undergoes a metal-insulator transition and a charge disproportionation reaction 2Fe4+→Fe5++Fe3+. We observe that when Zr dopants occupy a (001) layer, the band gap of the resulting solid solution increases to 0.93 eV due to a two-dimensional Jahn-Teller-type distortion, where FeO6 cages on the xy plane elongate along x and y alternatively between neighboring Fe sites. Furthermore, we show that the rock-salt ordering of the Fe5+ and Fe3+ cations can be enhanced when the B-site dopants are arranged in a (111) plane due to a collective steric effect that facilitates the size discrepancy between the Fe5+O6 and Fe3+O6 octahedra and therefore gives rise to a larger band gap. The enhanced charge disproportionation in these solid solutions is verified by rigorously calculating the oxidation states of the Fe cations with different octahedral cage sizes. We therefore predict that the corresponding transition temperature will increase due to the enhanced charge ordering and larger band gap. The compositional, structural, and electrical relationships exploited in this paper can be extended to a variety of perovskites and nonperovskite oxides, providing guidance in the structural manipulation of electrical properties of functional materials.

A survey of ab initio conical intersections for the H+H2 system

NASA Astrophysics Data System (ADS)

Halász, Gábor; Vibók, Ágnes; Mebel, Alexander M.; Baer, Michael

2003-02-01

In this article we present a survey of the various conical intersections which govern potential transitions between the three lower electronic states for the title molecular system. It was revealed that these three states, for a given fixed HH distance, RHH, usually form four conical intersections: two, between the two lower states and two, between the two upper states. One of the four is the well known equilateral D3h ci and the others are, essentially, C2v cis: One of them is located on the symmetry line perpendicular to the HH axis (just like the D3h ci) and the other two are located on both sides of this symmetry line and in this way form the ci-twins. The study was carried out for four RHH-values, namely, RHH=0.74, 0.5417, 0.52, and 0.4777 Å. It was also established that there exists one single RHH-value designated as R˜HH, located in the interval {0.52, 0.53 Å}, for which all four cis coalesce to become one kind of "super" ci which couples the three states. The numerical study was carried out employing the line integral approach for groups of two and three states. As for the two-state calculations we found that all D3h-cis, at close proximity, are circular (ordinary) Jahn-Teller-type cis, whereas all C2v-cis, at close proximity, are elliptic Jahn-Teller cis [Chem. Phys. Lett 354, 243 (2002)]. Particular attention is given to the 3-state quantization of the nonadiabatic coupling matrix. The quantization is found to be fulfilled in all situations as long as the regions in configuration space are not too far from the relevant cis. In the Discussion and Conclusion we discuss, among other subjects, the possibility to diabatize the adiabatic potential matrix.

Spin-phonon coupling and high-pressure phase transitions of RMnO 3 (R=Ca and Pr): An inelastic neutron scattering and first-principles study

DOE PAGES

Mishra, S. K.; Gupta, M. K.; Mittal, R.; ...

2016-06-22

Here, we report inelastic neutron scattering measurements over 7–1251 K in CaMnO 3 covering various phase transitions, and over 6–150 K in PrMnO 3 covering the magnetic transition. The excitations around 20 meV in CaMnO 3 and at 17 meV in PrMnO 3 at low temperatures are found to be associated with magnetic origin. We observe coherent magnetic neutron scattering in localized regions in reciprocal space and show it to arise from long-range correlated magnetic spin-waves below the magnetic transition temperature (TN) and short-range stochastic spin-spin fluctuations above T N. In spite of the similarity of the structure of themore » two compounds, the neutron inelastic spectrum of PrMnO 3 exhibits broad features at 150 K unlike well-defined peaks in the spectrum of CaMnO 3. This might result from the difference in the nature of interactions in the two compounds (magnetic and Jahn-Teller distortion). Ab initio phonon calculations have been used to interpret the observed phonon spectra. The ab initio calculations at high pressures show that the variations of Mn-O distances are isotropic for CaMnO 3 and highly anisotropic for PrMnO 3. The calculation in PrMnO 3 shows the suppression of Jahn-Teller distortion and simultaneous insulator-to-metal transition. It appears that this transition may not be associated with the occurrence of the tetragonal phase above 20 GPa as reported in the literature, since the tetragonal phase is found to be dynamically unstable, although it is found to be energetically favored over the orthorhombic phase above 20 GPa. CaMnO 3 does not show any phase transition up to 60 GPa.« less

Magnetic properties of the Fe{sup II} spin crossover complex in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol)

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

Suzuki, Atsushi, E-mail: suzuki@mat.usp.ac.j; Iguchi, Motoi; Oku, Takeo

2010-04-15

Influence of chemical substitution in the Fe{sup II} spin crossover complex on magnetic properties in emulsion polymerization of trifluoroethylmethacrylate using poly(vinyl alcohol) as a protective colloid was investigated near its high spin/low spin (HS/LS) phase transition. The obvious bi-stability of the HS/LS phase transition was considered by the identification of multiple spin states between the quintet (S=2) states to single state (S=0) across the excited triplet state (S=1). Magnetic parameters of gradual shifts of anisotropy g-tensor supported by the molecular distortion of the spin crossover complex would arise from a Jahn-Teller effect regarding ligand field theory on the basis ofmore » a B3LYP density functional theory using electron spin resonance (ESR) spectrum and X-ray powder diffraction. - Graphical abstract: AFM surface image of the emulsion particles with the spin crossover complex.« less

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

Krasnenko, V.; Boltrushko, V.; Hizhnyakov, V.

Chemically bound states of benzene molecules with graphene are studied both analytically and numerically. The states are formed by switching off intrabonds of π-electrons in C{sub 6} rings to interbonds. A number of different undistorted and distorted structures are established both with aligned and with transversal mutual orientation of benzene and graphene. The vibronic interactions causing distortions of bound states are found, by using a combination of analytical and numerical considerations. This allows one to determine all electronic transitions of π-electrons without explicit numerical calculations of excited states, to find the conical intersections of potentials, and to show that themore » mechanism of distortions is the pseudo-Jahn-Teller effect. It is found that the aligned distorted benzene molecule placed between two graphene sheets makes a chemical bond with both of them, which may be used for fastening of graphene sheets together.« less

Excited States of the divacancy in SiC

NASA Astrophysics Data System (ADS)

Bockstedte, Michel; Garratt, Thomas; Ivady, Viktor; Gali, Adam

2014-03-01

The divacancy in SiC - a technologically mature material that fulfills the necessary requirements for hosting defect based quantum computing - is a good candidate for implementing a solid state quantum bit. Its ground state is isovalent to the NV center in diamond as demonstrated by density functional theory (DFT). Furthermore, coherent manipulation of divacancy spins in SiC has been demonstrated. The similarities to NV might indicate that the same inter system crossing (ICS) from the high to the low spin state is responsible for its spin-dependent fluorescent signal. By DFT and a DFT-based multi-reference hamiltonian we analyze the excited state spectrum of the defects. In contrast to the current picture of the spin dynamics of the NV center, we predict that a static Jahn-Teller effect in the first excited triplet states governs an ICS both with the excited and ground state of the divacancy.

Experimental and theoretical identification of the Fe(vii) oxidation state in FeO4.

PubMed

Lu, Jun-Bo; Jian, Jiwen; Huang, Wei; Lin, Hailu; Li, Jun; Zhou, Mingfei

2016-11-16

The experimentally known highest oxidation state of iron has been determined to be Fe(vi) so far. Here we report a combined matrix-isolation infrared spectroscopic and theoretical study of two interconvertible iron oxide anions: a dioxoiron peroxide complex [(η 2 -O 2 )FeO 2 ] - with a C 2v -structure and a tetroxide FeO 4 - with a D 2d tetrahedral structure, which are formed by co-condensation of laser-ablated iron atoms and electrons with O 2 /Ar mixtures at 4 K. Quantum chemistry theoretical studies indicate that the Jahn-Teller distorted tetroxide FeO 4 - anion is a d 1 species with hereto the highest iron formal oxidation state Fe(vii).

DFT calculations of the structures and vibrational spectra of the [Fe(bpy) 3] 2+ and [Ru(bpy) 3] 2+ complexes

NASA Astrophysics Data System (ADS)

Alexander, Bruce D.; Dines, Trevor J.; Longhurst, Rayne W.

2008-09-01

Structures of the [M(bpy) 3] 2+ complexes (M = Fe and Ru) have been calculated at the B3-LYP/DZVP level. IR and Raman spectra were calculated using the optimised geometries, employing a scaled quantum chemical force field, and compared with an earlier normal coordinate analysis of [Ru(bpy) 3] 2+ which was based upon experimental data alone, and the use of a simplified model. The results of the calculations provide a highly satisfactory fit to the experimental data and the normal coordinate analyses, in terms of potential energy distributions, allow a detailed understanding of the vibrational spectra of both complexes. Evidence is presented for Jahn-Teller distortion in the 1E MLCT excited state.

Tunneling Splittings in Vibronic Structure of CH_3F^+ ( X^2E): Studied by High Resolution Photoelectron Spectra and AB Initio Theoretical Method

NASA Astrophysics Data System (ADS)

Mo, Yuxiang; Gao, Shuming; Dai, Zuyang; Li, Hua

2013-06-01

We report a combined experimental and theoretical study on the vibronic structure of CH_3F^+. The results show that the tunneling splittings of vibrational energy levels occur in CH_3F^+ due to the Jahn-Teller effect. Experimentally, we have measured a high resolution ZEKE spectrum of CH_3F up to 3500 cm^-^1 above the ground state. Theoretically, we performed an ab initio calculation based on the diabatic model. The adiabatic potential energy surfaces (APES) of CH_3F^+ have been calculated at the MRCI/CAS/avq(t)z level and expressed by Taylor expansions with normal coordinates as variables. The energy gradients for the lower and upper APES, the derivative couplings between them and also the energies of the APES have been used to determine the coefficients in the Taylor expansion. The spin-vibronic energy levels have been calculated by accounting all six vibrational modes and their couplings. The experimental ZEKE spectra were assigned based on the theoretical calculations. W. Domcke, D. R. Yarkony, and H. Köpple (Eds.), Conical Intersections: Eletronic Structure, Dynamics and Spectroscopy (World Scientific, Singapore, 2004). M. S. Schuurman, D. E. Weinberg, and D. R. Yarkony, J. Chem. Phys. 127, 104309 (2007).

Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

NASA Astrophysics Data System (ADS)

Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

2016-08-01

The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Badue to the decreasing crystal-field strength Dq and hence the decreasing force constant of the Cu2+-O2- bonds. The present studies would be helpful to understand local structures and the influences on the optical properties of RPPZ glasses containing copper dopants.

Leaf Mass Area, Leaf Carbon and Nitrogen Content, Kougarok Road and Teller Road, Seward Peninsula, Alaska, 2016

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

Shawn Serbin; Alistair Rogers; Kim Ely

Carbon, Nitrogen and Leaf Mass Area of leaves sampled from locations on the Kougarok Rd (transect A) and Teller Rd NGEE Arctic study sites, Seward Peninsula, Alaska. Species include: Alnus viridis spp. fruticosa, Arctostaphylos rubra, Betula glandulosa, Chamerion latifolium, Petasites frigidus, Salix alaxensis, Salix glauca, Salix pulchra, Salix richardsonii and Vaccinium uliginosum.

Electronic structures and geometries of the XF{sub 3} (X = Cl, Br, I, At) fluorides

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

Sergentu, Dumitru-Claudiu; CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3; Amaouch, Mohamed

The potential energy surfaces of the group 17 XF{sub 3} (X = Cl, Br, I, At) fluorides have been investigated for the first time with multiconfigurational wave function theory approaches. In agreement with experiment, bent T-shaped C{sub 2v} structures are computed for ClF{sub 3}, BrF{sub 3}, and IF{sub 3}, while we predict that an average D{sub 3h} structure would be experimentally observed for AtF{sub 3}. Electron correlation and scalar relativistic effects strongly reduce the energy difference between the D{sub 3h} geometry and the C{sub 2v} one, along the XF{sub 3} series, and in the X = At case, spin-orbit couplingmore » also slightly reduces this energy difference. AtF{sub 3} is a borderline system where the D{sub 3h} structure becomes a minimum, i.e., the pseudo-Jahn-Teller effect is inhibited since electron correlation and scalar-relativistic effects create small energy barriers leading to the global C{sub 2v} minima, although both types of effects interfere.« less

Unusual Ferroelectricity in Two-Dimensional Perovskite Oxide Thin Films.

PubMed

Lu, Jinlian; Luo, Wei; Feng, Junsheng; Xiang, Hongjun

2018-01-10

Two-dimensional (2D) ferroelectricity have attracted much attention due to their applications in novel miniaturized devices such as nonvolatile memories, field effect transistors, and sensors. Since most of the commercial ferroelectric (FE) devices are based on ABO 3 perovskite oxides, it is important to investigate the properties of 2D ferroelectricity in perovskite oxide thin films. Here, based on density functional theory (DFT) calculations, we find that there exist three kinds of in-plane FE states that originate from different microscopic mechanisms: (i) a proper FE state with the polarization along [110] due to the second-order Jahn-Teller effect related to the B ion with empty d-orbitals; (ii) a robust FE state with the polarization along [100] induced by the surface effect; (iii) a hybrid improper FE state with the polarization along [110] that is induced by the trilinear coupling between two rotational modes and the A-site displacement. Interestingly, the ferroelectricity in the latter two cases becomes stronger along with decreasing the thin film thickness, in contrast to the usual behavior. Moreover, the latter two FE states are compatible with magnetism since their stability does not depend on the occupation of the d-orbitals of the B-ion. These two novel 2D FE mechanisms provide new avenues to design 2D multiferroics, as we demonstrated in SrVO and CaFeO thin film cases. Our work not only reveals new physical mechanisms of 2D ferroelectricity in perovskite oxide thin films but also provides a new route to design the high-performance 2D FE and multiferroics.

Time-of-flight neutron powder diffraction study on the third row transition metal hexafluorides WF6, OsF6, and PtF6

NASA Astrophysics Data System (ADS)

Marx, R.; Seppelt, K.; Ibberson, R. M.

1996-05-01

A neutron diffraction study on the third-row transition metal hexafluorides MF6 (M≡W, Os, Pt) has been performed using the high resolution neutron powder diffractometer (HRPD) at the spallation source ISIS, England. The previously unknown structures of the low-temperature phases of OsF6 and PtF6 are reported. WF6, OsF6, and PtF6, which exhibit a (5dt2g)0, (5dt2g)2, and (5dt2g)4 electronic configuration, respectively, are found to be isostructural and crystallize in the UF6 structure, space group Pmnb, (No. 62). The geometry of the MF6 molecules is to good approximation octahedral for each compound, the mean M-F bond length increasing only slightly from 182.5 (W) to 185.0 (Pt). For WF6 deviations from ideal octahedral geometry are only marginally significant [181.8(2) to 183.2(2) pm] and may be interpreted on the basis of packing effects. Deviations for the d2 complex OsF6 are somewhat larger [181.5(2) to 184.4(3) pm] and may be assumed to be caused by packing effects essentially the same as for WF6, in addition to a first-order Jahn-Teller effect arising from the (5dt2g)2 electronic configuration. While eliminating the effects of packing by a comparison of individual M-F bond lengths for WF6 and OsF6, the OsF6 molecule shows to have D4h symmetry with two apical M-F bonds about 1.8 pm longer than the four equatorial bonds as a result of the Jahn-Teller distortion. Only small deviations from ideal octahedral geometry [184.4(3) to 185.8(3) pm] are found for the d4 complex PtF6. Within the series W to Pt a substantial shortening of the F...F van der Waals contact distances is observed. This shortening more than compensates for the increase in the M-F bond lengths and leads to unit cell volumes and cell parameters decreasing continuously from W to Pt. The variation of F...F contact distances and M-F bond lengths may be rationalized in terms of polarization of the F-ligands in the field of the highly charged nuclei of the central atoms which are only incompletely

Composition-dependent properties and phase stability of Fe-Pd ferromagnetic shape memory alloys: A first-principles study

NASA Astrophysics Data System (ADS)

Li, Chun-Mei; Hu, Yan-Fei

2017-12-01

The composition-dependent properties and their correlation with the phase stability of Fe75+xPd25-x (- 10.0 ≤x ≤10.0 ) alloys are systematically investigated by using first-principles exact muffin-tin orbitals (EMTO)-coherent potential approximation (CPA) calculations. It is shown that the martensitic transformation (MT) from L 12 to body-centered-tetragonal (bct) occurs in the ordered alloys with about -5.0 ≤x ≤10.0 . In both the L 12 and bct phases, the evaluated a and c/a agree well with the available experimental data; the average magnetic moment per atom increases whereas the local magnetic moments of Fe atoms, dependent on both their positions and the structure of the alloy, decrease with increasing x. The tetragonal shear elastic constant of the L 12 phase ( C ' ) decreases whereas that of the bct phase (Cs) increases with x. The tetragonality of the martensite ( |1 -c /a | ) increases whereas its energy relative to the austenite with a negative value decreases with Fe addition. All these effects account for the increase of MT temperature (TM) with x. The MT from L 12 to bct is finally confirmed originating from the splitting of Fe 3d Eg and T2 g bands upon tetragonal distortion due to the Jahn-Teller effect.

Effect of Jahn-Teller ion in zinc sodium sulphate hexahydrate: a case of low hyperfine coupling constant for Cu(II) ion

NASA Astrophysics Data System (ADS)

Naidu, K. C.; Shiyamala, C.; Mithira, S.; Natarajan, B.; Venkatesan, R.; Rao, P. S.

2005-06-01

Single crystal electron paramagnetic resonance (EPR) studies of Cu(II) doped zinc sodium sulphate hexahydrate are carried out from room temperature (RT) to 123 K. The RT spectra show unresolved hyperfine lines and hence angular variation studies are also carried out at 123 K to obtain spin Hamiltonian parameters. The spin Hamiltonian parameters calculated from the 123 K spectra are: g(11)=2.039, g(22)=2.232, g(33)=2.394, A(11)=5.64 mT, A(22)=4.20 mT, and A(33)=7.94 mT. The g-matrix values at RT and 123 K have matched fairly well with each other. The low hyperfine value (A(33)), obtained at 123 K, has been explained by considering considerable admixture of d(x 2-y 2) ground state with d(z 2) excited state and the delocalization of the unpaired spin density onto the ligands. The admixture coefficients of ground state wave function are: a=0.346, b=0.935, c=0.055, d=0.040, e=-0.040, where a and b correspond to admixture coefficients for d(z 2) and d(x 2-y 2), respectively. Angular variation of Cu(II) resonances in the three orthogonal axes shows that the impurity has entered a substitutional site in the host lattice in place of Zn(II). Bonding parameters, kappa=0.295, P=245.4x10(-4), alpha(2)=0.709, alpha=0.8421 and alpha'=0.6034, have also been calculated to fully characterize the EPR.

Gamow-Teller transitions and neutron-proton-pair transfer reactions

NASA Astrophysics Data System (ADS)

Van Isacker, P.; Macchiavelli, A. O.

2018-05-01

We propose a schematic model of nucleons moving in spin-orbit partner levels, j = l ± 1/2, to explain Gamow-Teller and two-nucleon transfer data in N = Z nuclei above 40Ca. Use of the LS coupling scheme provides a more transparent approach to interpret the structure and reaction data. We apply the model to the analysis of charge-exchange, 42Ca(3He,t)42Sc, and np-transfer, 40Ca(3He,p)42Sc, reactions data to define the elementary modes of excitation in terms of both isovector and isoscalar pairs, whose properties can be determined by adjusting the parameters of the model (spin-orbit splitting, isovector pairing strength and quadrupole matrix element) to the available data. The overall agreement with experiment suggests that the approach captures the main physics ingredients and provides the basis for a boson approximation that can be extended to heavier nuclei. Our analysis also reveals that the SU(4)-symmetry limit is not realized in 42Sc.

What is the valence of Mn in GaMnN?

NASA Astrophysics Data System (ADS)

Nelson, Ryky; Berlijn, Tom; Moreno, Juana; Jarrell, Mark; Ku, Wei

2014-03-01

Motivated by the potential high Curie temperature of GaMnN, we investigate the controversial Mn-valence in this diluted magnetic semiconductor. From a first-principles Wannier functions analysis of the high energy Hilbert space we find unambiguously the charge state of Mn to be close to 2 + (d5), but in a mixed spin configuration with average magnetic moments of 4 μB. Using more extended Wannier orbitals to capture the lower-energy physics, we further demonstrate the feasibility of both the effective d4 description (appropriate to deal with the local magnetic moment and Jahn-Teller distortion), and the effective d5 description (relevant to study long-range magnetic order). Our derivation highlights the general richness of low-energy sectors in interacting many-body systems and the generic need for multiple effective descriptions, and advocates for a diminished relevance of atomic valence measured by various experimental probes. This research is supported in part by LA-SiGMA, NSF Award Number #EPS-1003897. TB was supported by DOE CMCSN and as a Wigner Fellow at the Oak Ridge National Laboratory.

High-resolution study of Gamow-Teller excitations in the 42Ca(3He,t )42Sc reaction and the observation of a "low-energy super-Gamow-Teller state"

NASA Astrophysics Data System (ADS)

Fujita, Y.; Fujita, H.; Adachi, T.; Susoy, G.; Algora, A.; Bai, C. L.; Colò, G.; Csatlós, M.; Deaven, J. M.; Estevez-Aguado, E.; Guess, C. J.; Gulyás, J.; Hatanaka, K.; Hirota, K.; Honma, M.; Ishikawa, D.; Krasznahorkay, A.; Matsubara, H.; Meharchand, R.; Molina, F.; Nakada, H.; Okamura, H.; Ong, H. J.; Otsuka, T.; Perdikakis, G.; Rubio, B.; Sagawa, H.; Sarriguren, P.; Scholl, C.; Shimbara, Y.; Stephenson, E. J.; Suzuki, T.; Tamii, A.; Thies, J. H.; Yoshida, K.; Zegers, R. G. T.; Zenihiro, J.

2015-06-01

To study the Gamow-Teller (GT) transitions from the Tz=+1 nucleus 42Ca to the Tz=0 nucleus 42Sc, where Tz is the z component of isospin T , we performed a (p ,n )-type (3He,t ) charge-exchange reaction at 140 MeV/nucleon and scattering angles around 0∘. With an energy resolution of 29 keV, states excited by GT transitions (GT states) could be studied accurately. The reduced GT transition strengths B (GT) were derived up to the excitation energy of 13 MeV, assuming the proportionality between the cross sections at 0∘ and B (GT) values. The main part of the observed GT transition strength is concentrated in the lowest 0.611-MeV, Jπ=1+ GT state. All the other states at higher energies are weakly excited. Shell-model calculations could reproduce the gross feature of the experimental B (GT) distribution, and random-phase-approximation calculations including an attractive isoscalar interaction showed that the 0.611-MeV state has a collective nature. It was found that this state has all of the properties of a "low-energy super-Gamow-Teller state." It is expected that low-lying Jπ=1+ GT states have T =0 in the Tz=0 nucleus 42Sc. However, T =1 states are situated in a higher energy region. Assuming an isospin-analogous structure in A =42 isobars, analogous T =1 , 1+ states are also expected in 42Ca. Comparing the (3He 42,tCa) 42Sc and 42Ca(p ,p') spectra measured at 0∘, candidates for T =1 GT states could be found in the 10 -12 -MeV region of 42Sc. They were all weakly excited. The mass dependence of the GT strength distributions in Sc isotopes is also discussed.

A Theoretical Investigation of the Structure and Reactivity of the Molecular Constituents of Oil Sand and Oil Shale

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

Parish, Carol A.

molecular-based energy storage devices as well as magnetically controllable liquid marbles. 3-5 We have been investigating the small molecule encapsulation properties of POSS and discovered some interesting symmetry breaking processes that need to be better understood in order to use POSS in advanced materials. We have investigated this symmetry breaking mechanism in POSS monocations Si8O12(C(CH3)3)8+ and Si8O12Cl8+, using density functional theory (DFT) and group theory. Under Oh symmetry, these ions possess 2T2g and 2Eg electronic states, respectively, and undergo different symmetry breaking mechanisms. The ground states of Si 8O 12(C(CH 3) 3) 8 + and Si 8O 12Cl 8 + belong to the C 3v and D 4h point groups and are characterized by Jahn-Teller stabilization energies of 3959 and 1328 cm-1, respectively, at the B3LYP/def2-SVP level of theory. The symmetry distortion mechanism in Si 8O 12Cl 8 + is Jahn-Teller type, whereas in Si 8O 12(C(CH 3) 3) 8 + the distortion is a combination of both Jahn-Teller and pseudo-Jahn-Teller effects. The distortion force acting in Si 8O 12(C(CH 3) 3) 8 + is mainly localized on one Si-(tert-butyl) group while in Si 8O 12Cl 8 + it is distributed over the oxygen atoms. The main distortion forces acting on the Si8O12 core arise from the coupling between the electronic state and the vibrational modes; identified as 9t 2g+1e g+3a 2u for the Si 8O 12(C(CH 3) 3) 8 + and 1e g+2e g for Si 8O 12Cl 8 +. This work was published in the Journal of Physical Chemistry A, 2015, 119, 4237-4243.« less

Effects of rare-earth size on the electronic structure of La1−xLuxVO3.

PubMed

Chen, B; Laverock, J; Newby, D; McNulty, J F; Smith, K E; Glans, P-A; Guo, J-H; Qiao, R-M; Yang, W-L; Lees, M R; Tung, L D; Singh, R P; Balakrishnan, G

2015-03-18

The electronic structure of La(1-x)Lu(x)VO(3)(x = 0, 0.2, 0.6 and 1) single crystals has been investigated using soft x-ray absorption spectroscopy, soft x-ray emission spectroscopy, and resonant soft x-ray inelastic scattering to study the effects of rare-earth size. The x-ray absorption and emission spectra at the O K-edge present a progressive evolution with R-site cation, in agreement with local spin density approximation calculations. This evolution with R, together with the temperature dependence of the O K-edge spectra, is attributed to changes in the crystal structure of La(1-x)Lu(x)VO(3). The crystal-field dd. excitations probed by resonant inelastic x-ray scattering at the V L(3)-edge exhibit an increase in energy and enhanced intensity with the decrease of R-site ionic radius, which is mainly attributed to the increased tilting magnitude of the VO(6) octahedra. Upon cooling to ~95 K, the dd* excitations are prominently enhanced in relative Intensity, in agreement with the formation of the Jahn.Teller distortion int he orbital ordering phase. Additionally, the dd* transitions of the mixed compounds are noticeably suppressed with respect to those of the pure compounds, possibly owing to the formation of C-type orbital ordering induced by large R-site size variances.

Hybrid density functional study of structural, bonding, and electronic properties of the manganite series La1-xCaxMnO3 (x =0,1/4,1)

NASA Astrophysics Data System (ADS)

Korotana, R.; Mallia, G.; Gercsi, Z.; Liborio, L.; Harrison, N. M.

2014-05-01

Hybrid-exchange density functional theory calculations are carried out to determine the effects of A-site doping on the electronic and magnetic properties of the manganite series La1-xCaxMnO3. This study focuses on the ground state of an ordered Ca occupancy in a periodic structure. It is shown that the hybrid-exchange functional, Becke three-parameter Lee-Yang-Parr (B3LYP), provides an accurate and consistent description of the electronic structure for LaMnO3, CaMnO3, and La0.75Ca0.25MnO3. We have quantified the relevant structural, magnetic, and electronic energy contributions to the stability of the doped compound. An insight into the exchange coupling mechanism for the low hole density region of the phase diagram, where a polaron (anti-Jahn-Teller) forms, is also provided. This study completes a microscopic description of the lightly doped insulator with an antiferromagnetic-to-ferromagnetic and metal-to-insulator transition.

Enhanced way of securing automated teller machine to track the misusers using secure monitor tracking analysis

NASA Astrophysics Data System (ADS)

Sadhasivam, Jayakumar; Alamelu, M.; Radhika, R.; Ramya, S.; Dharani, K.; Jayavel, Senthil

2017-11-01

Now a days the people's attraction towards Automated Teller Machine(ATM) has been increasing even in rural areas. As of now the security provided by all the bank is ATM pin number. Hackers know the way to easily identify the pin number and withdraw money if they haven stolen the ATM card. Also, the Automated Teller Machine is broken and the money is stolen. To overcome these disadvantages, we propose an approach “Automated Secure Tracking System” to secure and tracking the changes in ATM. In this approach, while creating the bank account, the bank should scan the iris known (a part or movement of our eye) and fingerprint of the customer. The scanning can be done with the position of the eye movements and fingerprints identified with the shortest measurements. When the card is swiped then ATM should request the pin, scan the iris and recognize the fingerprint and then allow the customer to withdraw money. If somebody tries to break the ATM an alert message is given to the nearby police station and the ATM shutter is automatically closed. This helps in avoiding the hackers who withdraw money by stealing the ATM card and also helps the government in identifying the criminals easily.

Synchrotron radiation-based 61Ni Mössbauer spectroscopic study of Li(Ni1/3Mn1/3Co1/3)O2 cathode materials of lithium ion rechargeable battery

NASA Astrophysics Data System (ADS)

Segi, Takashi; Masuda, Ryo; Kobayashi, Yasuhiro; Tsubota, Takayuki; Yoda, Yoshitaka; Seto, Makoto

2016-12-01

Layered rocksalt type oxides, such as Li(Ni1/3Mn1/3Co1/3)O2, are widely used as the cathode active materials of lithium-ion rechargeable batteries. Because the nickel ions are associated with the role of the charge compensation at discharge and charge, the 61Ni Mössbauer measurements at 6 K using synchrotron radiation were performed to reveal the role of Ni. The Ni ions of the active materials play two roles for the redox process between the charge and discharge states of lithium-ion batteries. Half of the total Ni ions change to the low-spin Ni3+ with Jahn-Teller distortion from the Ni2+ ions of the discharge state. The remainder exhibit low-spin state divalent Ni ions.

High pressure synthesis, crystal growth and magnetic properties of TiOF

NASA Astrophysics Data System (ADS)

Cumby, J.; Burchell, M. B.; Attfield, J. P.

2018-06-01

Polycrystalline samples of TiOF have been prepared at 1300 °C and 8 GPa, with small single crystals grown at the same conditions. The crystal structure remains tetragonal rutile-type down to at least 90 K (space group P42/mnm, a = 4.6533 (2) Å and c = 3.0143 (2) Å at 90 K) and the Ti(O,F)6 octahedra are slightly compressed, consistent with Jahn-Teller distortion of 3d1 Ti3+. Diffuse scattering reveals disordered structural correlations that may arise from local cis-order of oxide anions driven by covalency. TiOF is paramagnetic down to 5 K and observation of a small paramagnetic moment and a substantial Pauli term indicates that the d-electrons are partially delocalised.

Structures and chemical properties of silicene: unlike graphene.

PubMed

Jose, Deepthi; Datta, Ayan

2014-02-18

The discovery of graphene and its remarkable and exotic properties have aroused interest in other elements and molecules that form 2D atomic layers, such as metal chalcogenides, transition metal oxides, boron nitride, silicon, and germanium. Silicene and germanene, the Si and Ge counterparts of graphene, have interesting fundamental physical properties with potential applications in technology. For example, researchers expect that silicene will be relatively easy to incorporate within existing silicon-based electronics. In this Account, we summarize the challenges and progress in the field of silicene research. Theoretical calculations have predicted that silicene possesses graphene-like properties such as massless Dirac fermions that carry charge and the quantum spin Hall effect. Researchers are actively exploring the physical and chemical properties of silicene and tailoring it for wide variety of applications. The symmetric buckling in each of the six-membered rings of silicene differentiates it from graphene and imparts a variety of interesting properties with potential technological applications. The pseudo-Jahn-Teller (PJT) distortion breaks the symmetry and leads to the buckling in silicenes. In graphene, the two sublattice structures are equivalent, which does not allow for the opening of the band gap by an external electric field. However, in silicene where the neighboring Si atoms are displaced alternatively perpendicular to the plane, the intrinsic buckling permits a band gap opening in silicene in the presence of external electric field. Silicene's stronger spin orbit coupling than graphene has far reaching applications in spintronic devices. Because silicon prefers sp(3) hybridization over sp(2), hydrogenation is much easier in silicene. The hydrogenation of silicene to form silicane opens the band gap and increases the puckering angle. Lithiation can suppress the pseudo-Jahn-Teller distortion in silicene and hence can flatten silicene's structure

What makes an automated teller machine usable by blind users?

PubMed

Manzke, J M; Egan, D H; Felix, D; Krueger, H

1998-07-01

Fifteen blind and sighted subjects, who featured as a control group for acceptance, were asked for their requirements for automated teller machines (ATMs). Both groups also tested the usability of a partially operational ATM mock-up. This machine was based on an existing cash dispenser, providing natural speech output, different function menus and different key arrangements. Performance and subjective evaluation data of blind and sighted subjects were collected. All blind subjects were able to operate the ATM successfully. The implemented speech output was the main usability factor for them. The different interface designs did not significantly affect performance and subjective evaluation. Nevertheless, design recommendations can be derived from the requirement assessment. The sighted subjects were rather open for design modifications, especially the implementation of speech output. However, there was also a mismatch of the requirements of the two subject groups, mainly concerning the key arrangement.

76 FR 6640 - Advantage Life Products, Inc., and B-Teller, Inc. (n/k/a CA Goldfields, Inc.), Order of...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-02-07

..., Inc. (n/k/a CA Goldfields, Inc.), Order of Suspension of Trading February 3, 2011. It appears to the... current and accurate information concerning the securities of B-Teller, Inc. (n/k/a CA Goldfields, Inc...(k) of the Securities Exchange Act of 1934, that trading in the securities of the above-listed...

Strain broadening of the 1042-nm zero phonon line of the NV- center in diamond: A promising spectroscopic tool for defect tomography

NASA Astrophysics Data System (ADS)

Biktagirov, T. B.; Smirnov, A. N.; Davydov, V. Yu.; Doherty, M. W.; Alkauskas, A.; Gibson, B. C.; Soltamov, V. A.

2017-08-01

The negatively charged nitrogen-vacancy (NV-) center in diamond is a promising candidate for many quantum applications. Here, we examine the splitting and broadening of the center's infrared (IR) zero-phonon line (ZPL). We develop a model for these effects that accounts for the strain induced by photodependent microscopic distributions of defects. We apply this model to interpret observed variations of the IR ZPL shape with temperature and photoexcitation conditions. We identify an anomalous temperature-dependent broadening mechanism and that defects other than the substitutional nitrogen center significantly contribute to strain broadening. The former conclusion suggests the presence of a strong Jahn-Teller effect in the center's singlet levels and the latter indicates that major sources of broadening are yet to be identified. These conclusions have important implications for the understanding of the center and the engineering of diamond quantum devices. Finally, we propose that, once the major sources of broadening are identified, the IR ZPL has the potential to be a sensitive spectroscopic tool for probing microscopic strain fields and performing defect tomography.

Structural and magnetic properties of Nd0.67Ba0.33MnO3 manganites with partial replacement of Fe and Cu at Mn-site

NASA Astrophysics Data System (ADS)

Sudakshina, B.; Arun, B.; Chandrasekhar, K. Devi; Yang, H. D.; Vasundhara, M.

2018-06-01

We have investigated the structural and magnetic properties of Nd0.67Ba0.33MnO3 manganite and partial replacement of Mn with Fe and Cu compounds followed by X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS) and vibrating sample magnetometer (VSM). The Rietveld refinement of XRD indicates orthorhombic crystal structure with I-mma space group for all the compounds and thus obtained lattice parameters confirm the presence of co-operative Jahn-Teller effect. XRD and XAS spectra results suggests the existence of Fe3+ in Fe-substituted compound where as a mixed state of Cu2+ and Cu3+ ions in the Cu-substituted compound. The ferromagnetic (FM) to paramagnetic (PM) transition and magnetic moment is found to decrease upon the substitution of Fe and Cu atoms because of the suppression of double exchange interaction. The theoretically obtained and experimentally determined values of effective PM moment and saturation magnetic moment confirms the presence of inhomogeneous magnetic states containing FM and antiferromagnetic clusters in all the studied compounds.

Strain doping: Reversible single-axis control of a complex oxide lattice via helium implantation

DOE PAGES

Guo, Hangwen; Dong, Shuai; Rack, Philip D.; ...

2015-06-25

We report on the use of helium ion implantation to independently control the out-of-plane lattice constant in epitaxial La 0.7Sr 0.3MnO 3 thin films without changing the in-plane lattice constants. The process is reversible by a vacuum anneal. Resistance and magnetization measurements show that even a small increase in the out-of-plane lattice constant of less than 1% can shift the metal-insulator transition and Curie temperatures by more than 100 °C. Unlike conventional epitaxy-based strain tuning methods which are constrained not only by the Poisson effect but by the limited set of available substrates, the present study shows that strain canmore » be independently and continuously controlled along a single axis. This permits novel control over orbital populations through Jahn-Teller effects, as shown by Monte Carlo simulations on a double-exchange model. As a result, the ability to reversibly control a single lattice parameter substantially broadens the phase space for experimental exploration of predictive models and leads to new possibilities for control over materials’ functional properties.« less

Application of polynomial su(1, 1) algebra to Pöschl-Teller potentials

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

Zhang, Hong-Biao, E-mail: zhanghb017@nenu.edu.cn; Lu, Lu

2013-12-15

Two novel polynomial su(1, 1) algebras for the physical systems with the first and second Pöschl-Teller (PT) potentials are constructed, and their specific representations are presented. Meanwhile, these polynomial su(1, 1) algebras are used as an algebraic technique to solve eigenvalues and eigenfunctions of the Hamiltonians associated with the first and second PT potentials. The algebraic approach explores an appropriate new pair of raising and lowing operators K-circumflex{sub ±} of polynomial su(1, 1) algebra as a pair of shift operators of our Hamiltonians. In addition, two usual su(1, 1) algebras associated with the first and second PT potentials are derivedmore » naturally from the polynomial su(1, 1) algebras built by us.« less

Excitation Dependent Phosphorous Property and New Model of the Structured Green Luminescence in ZnO

NASA Astrophysics Data System (ADS)

Ye, Honggang; Su, Zhicheng; Tang, Fei; Wang, Mingzheng; Chen, Guangde; Wang, Jian; Xu, Shijie

2017-02-01

The copper induced green luminescence (GL) with two sets of fine structures in ZnO crystal has been found for several decades (i.e., R. Dingle, Phys. Rev. Lett. 23, 579 (1969)), but the physical origin of the doublet still remains as an open question up to now. In this paper, we provide new insight into the mechanism of the structured GL band in terms of new experimental findings and theoretical calculations. It is found, for the first time, that the GL signal exhibits persistent afterglow for tens of minutes after the switch-off of below-band-gap excitation light but it cannot occur under above-band-gap excitation. Such a phosphorous property may be interpreted as de-trapping and feeding of electrons from a shallow trapping level via the conduction band to the Cu-related luminescence centers where the Cu3+ ion is proposed to work as the final state of the GL emission. From first-principles calculation, such a Cu3+ ion in wurtzite ZnO prefers a high spin 3d8 state with two non-degenerated half-filled orbitals due to the Jahn-Teller effect, probably leading to the double structures in photoluminescence spectrum. Therefore, this model gives a comprehensively new understanding on the mechanism of the structured GL band in ZnO.

Ligand field photofragmentation spectroscopy of [Ag(L)N]2+ complexes in the gas phase: experiment and theory.

PubMed

Guan, Jingang; Puskar, Ljiljana; Esplugas, Ricardo O; Cox, Hazel; Stace, Anthony J

2007-08-14

Experiments have been undertaken to record photofragmentation spectra from a series of [Ag(L)N]2+ complexes in the gas phase. Spectra have been obtained for silver(II) complexed with the ligands (L): acetone, 2-pentanone, methyl-vinyl ketone, pyridine, and 4-methyl pyridine (4-picoline) with N in the range of 4-7. A second series of experiments using 1,1,1,3-fluoroacetone, acetonitrile, and CO2 as ligands failed to show any evidence of photofragmentation. Interpretation of the experimental data has come from time-dependent density functional theory (TDDFT), which very successfully accounts for trends in the spectra in terms of subtle differences in the properties of the ligands. Taking a sample of three ligands, acetone, pyridine, and acetonitrile, the calculations show all the spectral transitions to involve ligand-to-metal charge transfer, and that wavelength differences (or lack of spectra) arise from small changes in the energies of the molecular orbitals concerned. The calculations account for an absence in the spectra of any effects due to Jahn-Teller distortion, and they also reveal structural differences between complexes where the coordinating atom is either oxygen or nitrogen that have implications for the stability of silver(II) compounds. Where possible, comparisons have also been made with the physical properties of condensed phase silver(II) complexes.

Mixed valence transition metal 2D-oxides: Comparison between delafossite and crednerite compounds

NASA Astrophysics Data System (ADS)

Martin, Christine; Poienar, Maria

2017-08-01

Transition metal oxides offer large opportunities to study relationships between structures and properties. Indeed these compounds crystallize in numerous frameworks corresponding to different dimensionalities and, accordingly, show a huge variety of properties (as high Tc superconductivity, colossal magnetoresistivity, multiferroicity..). The control of the oxidation state of the transition metal, via the monitoring of the oxygen content, is of prime importance to understand and optimize the properties, due to the strong coupling that exists between the lattice and the charges and spins of the transition metals. In this large playground for chemists, we reinvestigated several 2D-compounds derived from delafossite structure. Considering this paper as a very short review, we report here the results obtained on CuMO2 compounds (with M = Cr, Mn or Mn+Cu) by using a combination of techniques, as X-ray, neutrons and/or electrons diffraction on poly-crystals for structural characterisations that are correlated with electrical and/or magnetic properties. The complementarity of studies is also addressed by the synthesis and characterization of single crystals in addition to poly-crystals. Moreover the comparison of the structures of similar Cr and Mn based oxides highlights the crucial role of the Jahn-Teller effect of trivalent manganese to lift the degeneracy, which is responsible of the magnetic frustration in CuCrO2.

Jahn-Teller effect on the [TiF 4F 4F int] 6-(C 4v) and [NiF 4F 4F int] 7-(C 4v) clusters embedded into SrF 2 crystals

NASA Astrophysics Data System (ADS)

Ulanov, V. A.; Zhiteitcev, E. R.; Varlamov, A. G.

2007-07-01

By means of EPR method the associative [TiF 4F 4F int] 6-(C 4v) and [NiF 4F 4F int] 7-(C 4v) centers were revealed in the fluorite type SrF 2:Ti and SrF 2:Ni crystals grown by Bridgman method in helium atmosphere containing some amount of a fluorine gas. It was found that at low temperatures the local structures of these associative centers were exposed to a static rhombic distortion. The reasons of such distortions were accounted for by the assumption that the E ⊗ ( b1 + b2) vibronic interaction became effective due to that the ground orbital states of the [TiF 4F 4F int] 6-(C 4v) and [NiF 4F 4F int] 7-(C 4v) centers occurred to be doubly degenerated.

Maximally localized Wannier functions in LaMnO3 within PBE + U, hybrid functionals and partially self-consistent GW: an efficient route to construct ab initio tight-binding parameters for eg perovskites.

PubMed

Franchini, C; Kováčik, R; Marsman, M; Murthy, S Sathyanarayana; He, J; Ederer, C; Kresse, G

2012-06-13

Using the newly developed VASP2WANNIER90 interface we have constructed maximally localized Wannier functions (MLWFs) for the e(g) states of the prototypical Jahn-Teller magnetic perovskite LaMnO(3) at different levels of approximation for the exchange-correlation kernel. These include conventional density functional theory (DFT) with and without the additional on-site Hubbard U term, hybrid DFT and partially self-consistent GW. By suitably mapping the MLWFs onto an effective e(g) tight-binding (TB) Hamiltonian we have computed a complete set of TB parameters which should serve as guidance for more elaborate treatments of correlation effects in effective Hamiltonian-based approaches. The method-dependent changes of the calculated TB parameters and their interplay with the electron-electron (el-el) interaction term are discussed and interpreted. We discuss two alternative model parameterizations: one in which the effects of the el-el interaction are implicitly incorporated in the otherwise 'noninteracting' TB parameters and a second where we include an explicit mean-field el-el interaction term in the TB Hamiltonian. Both models yield a set of tabulated TB parameters which provide the band dispersion in excellent agreement with the underlying ab initio and MLWF bands.

Two-channel Kondo physics from arsenic bond oscillations in zirconium arsenide selenide

NASA Astrophysics Data System (ADS)

Kirchner, Stefan; Cichorek, Tomasz; Bochenek, L.; Schmidt, Marcus; Niewa, Rainer; Czulucki, A.; Auffermann, G.; Steglich, Frank; Kniep, Ruediger

2015-03-01

The two-channel Kondo effect is a fascinating but extremely fragile many-body state that has been theoretically discussed extensively. we address metallic compounds of a specific (PbFCl) structure for which a - AT 1 / 2 term to ρ (T) is frequently observed, in line with the two-channel Kondo effect. The origin of this anomalous behavior has remained enigmatic since here, solely the interaction between electrons may account for this behavior, and the two-channel Kondo state is not expected to occur. By combining chemical and structural investigations with various physical property measurements we show that the magnetic field-independent - AT 1 / 2 term to the low-T resistivity observed over two decades in ZrAsxSey with 1.90 <= x + y <= 1.99 originates from vacancies in the layer exclusively built up by As. Furthermore, we can trace back the two-channel Kondo effect in this material to a dynamic Jahn-Teller effect operating at these vacancies. All physical properties of the investigated compounds support this conclusion. Our findings will be relevant also for other metallic systems with pnictogen-pnictogen bondings, e.g., cage-forming compounds like the skutterudites.

P2-type Na2/3Mn1-xAlxO2 cathode material for sodium-ion batteries: Al-doped enhanced electrochemical properties and studies on the electrode kinetics

NASA Astrophysics Data System (ADS)

Pang, Wei-Lin; Zhang, Xiao-Hua; Guo, Jin-Zhi; Li, Jin-Yue; Yan, Xin; Hou, Bao-Hua; Guan, Hong-Yu; Wu, Xing-Long

2017-07-01

Recently, sodium-ion batteries (SIBs) have been considered as the promising alternative for lithium-ion batteries. Although layered P2-type transition metal oxides are an important class of cathode materials for SIBs, there are still some hurdles for the practical applications, including low specific capacity as well as poor cycling and rate properties. In this study, the electrochemical properties of layered Mn-based oxides have been effectively improved via Al doping, which cannot only promote the formation of layered P2-type structure in the preparation processes but also stabilize the lattice during the successive Na-intercalation/deintercalation due to suppression of the Jahn-Teller distortion of Mn3+. Among the as-prepared series of Na2/3Mn1-xAlxO2 (x = 0, 1/18, 1/9, and 2/9), Na2/3Mn8/9Al1/9O2 with x = 1/9 exhibits the optimal doping effect with the best electrochemical properties, in terms of the highest specific capacity of 162.3 mA h g-1 at 0.1 C, the highest rate capability, and the best cycling stability in comparison to the undoped Na2/3MnO2 and the other two materials with different Al-doped contents. Both cyclic voltammetry at varied scan rates and galvanostatic intermittent titration technique disclose the optimal electrode kinetics (the highest Na-diffusion coefficient) of the best Na2/3Mn8/9Al1/9O2.

Lattice-mediated magnetic order melting in TbMnO 3

DOE PAGES

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.; ...

2018-03-15

Recent ultrafast magnetic-sensitive measurements have revealed a delayed melting of the long-range cycloid spin order in TbMnO 3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting andmore » is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. In conclusion, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.« less

Structural phase transition, Néel temperature enhancement, and persistent magneto-dielectric coupling in Cr-substituted Mn3O4

NASA Astrophysics Data System (ADS)

Dwivedi, G. D.; Kumar, Abhishek; Yang, K. S.; Chen, B. Y.; Liu, K. W.; Chatterjee, Sandip; Yang, H. D.; Chou, H.

2016-05-01

Structural phase transition and Néel temperature (TN) enhancement were observed in Cr-substituted Mn3O4 spinels. Structural, magnetic, and dielectric properties of (Mn1-xCrx)3O4 (where x = 0.00, 0.10, 0.20, 0.25, 0.30, 0.40, and 0.50) were investigated. Cr-substitution induces room temperature structural phase transition from tetragonally distorted I41/amd (x = 0.00) to cubic Fd 3 ¯ m (x = 0.50). TN is found to increase from 43 K (x = 0.00) to 58 K (x = 0.50) with Cr-substitution. The spin ordering-induced dielectric anomaly near TN ensures that magneto-dielectric coupling persists in the cubic x = 0.50 system. X-ray absorption spectra reveal that Cr exists in a trivalent oxidation state and prefers the octahedral (Oh)-site, replacing Mn3+. Due to a reduction in the Jahn-Teller active Mn3+ cation and an increase in the smaller Cr3+ cation, the system begins to release the geometrical frustration by lowering its degeneracy. Consequently, a phase transition, from distorted tetragonal structure to the more symmetric cubic phase, occurs.

Lattice-mediated magnetic order melting in TbMnO 3

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

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.

Recent ultrafast magnetic-sensitive measurements have revealed a delayed melting of the long-range cycloid spin order in TbMnO 3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting andmore » is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. In conclusion, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.« less

Gamow-Teller strength observed in the 48Ti(n, p) 48Sc reaction: Implications for the double beta decay of 48Ca

NASA Astrophysics Data System (ADS)

Alford, W. P.; Helmer, R. L.; Abegg, R.; Celler, A.; Frekers, D.; Green, P.; Häusser, O.; Henderson, R.; Hicks, K.; Jackson, K. P.; Jeppesen, R.; Miller, C. A.; Trudel, A.; Vetterli, M.; Yen, S.; Pourang, R.; Watson, J.; Brown, B. A.; Engel, J.

1990-07-01

Cross sections for the 48Ti(n, p) reaction have been measured at angles of 0°, 6°, and 12° at an energy of 200 MeV. The measurements are compared with results of DWIA calculations to obtain estimates of transition strengths for L = 0, 1, and ⩾2 up to an excitation energy of 25 MeV. Gamow-Teller strength ( L = 0) is peaked between 3 and 4 MeV excitation energy, with a significant distribution extending to about 12 MeV. The L = 1 strength is found mainly between 6 and 20 MeV while the cross section for transitions with L ⩾2 increases from 10 MeV to the upper limit of the measurements. The distribution of Gamow-Teller strength is in poor agreement with theoretical distributions used to calculate the lifetime for double beta decay of 48Ca.

An Anomaly in the Inglis-Teller Limits of the C VI Lyman and Balmer Series in Laser-Produced Plasmas

NASA Astrophysics Data System (ADS)

Elton, R.; Iglesias, E.; Griem, H.; Weaver, J.; Pien, G.; Mancini, R.

2002-11-01

Soft x-ray spectra from thin carbon layers heated by the OMEGA and NIKE lasers have been obtained with both spherical and planar targets, respectively, using a flat-field grazing incidence spectrograph equipped with a gated microchannel plate for temporal resolution. In both experiments, late-time (recombining) hydrogenic C VI spectra show an n-to-1 Lyman spectral series blending with the continuum at n=4, contrary to n=9 in the n-to-2 Balmer series. It appears unlikely that plasma inhomogeneities are the sole cause of this anomaly, given the difference in the experimental configurations. Other explanations for the line-to-continuum merging (other than the usual Stark-broadened Inglis-Teller effect) under consideration include non-thermal Doppler broadening, deviations from statistical sublevel population distributions, and opacity effects. Collisional-radiative and hydrodynamic modeling, including cascades, is employed to further understand this phenomenon.

The Electronic Ground State of the Nitrate Radical: a Decade of Controversy

NASA Astrophysics Data System (ADS)

Stanton, John F.

2017-06-01

In the ten years since the traditional assignment of its degenerate stretching fundamental became controversial, a great deal of work - both theoretical and experimental - has been done on the NO_3 molecule. A brief review of these developments will be given, and results of very high-level calculations of the dispersed fluorescence and negative ion photoelectron spectra of this molecule will be presented together with the corresponding experimental results. In addition, the question of "what is next to do" on the ground state - from a theoretical point of view - will be addressed. Time permitting, some discussion will also be devoted to the strongly Jahn-Teller active ^2E^{''} (first excited) electronic state, where the level of understanding and agreement thus far obtained from experiment and theory is still at a rather primitive stage.

Structural and dynamical properties of the V(3+) ion in dilute aqueous solution: An ab initio QM/MM molecular dynamics simulation.

PubMed

Kritayakornupong, Chinapong

2009-12-01

A hybrid ab initio QM/MM molecular dynamics simulation at the Hartree-Fock level has been performed to investigate structural and dynamical parameters of the V(3+) ion in dilute aqueous solution. A distorted octahedral structure with the average V(3+)-O distance of 1.99 A is evaluated from the QM/MM simulation, which is in good agreement with the X-ray data. Several structural parameters such as angular distribution functions, theta- and tilt-angle distributions have been determined to obtain the full description of the hydration structure of the hydrated V(3+). The Jahn-Teller distortions of the V(3+) ion are pronounced in the QM/MM simulation. The mean residence time of 14.5 ps is estimated for the ligand exchange processes in the second hydration shell. (c) 2009 Wiley Periodicals, Inc.

Coupled Electronic and Magnetic Phase Transition in the Infinite-Layer Phase LaSrNiRuO4.

PubMed

Patino, Midori Amano; Zeng, Dihao; Bower, Ryan; McGrady, John E; Hayward, Michael A

2016-09-06

Topochemical reduction of the ordered double perovskite LaSrNiRuO6 with CaH2 yields LaSrNiRuO4, an extended oxide phase containing infinite sheets of apex-linked, square-planar Ni(1+)O4 and Ru(2+)O4 units ordered in a checkerboard arrangement. At room temperature the localized Ni(1+) (d(9), S = (1)/2) and Ru(2+) (d(6), S = 1) centers behave paramagnetically. However, on cooling below 250 K the system undergoes a cooperative phase transition in which the nickel spins align ferromagnetically, while the ruthenium cations appear to undergo a change in spin configuration to a diamagnetic spin state. Features of the low-temperature crystal structure suggest a symmetry lowering Jahn-Teller distortion could be responsible for the observed diamagnetism of the ruthenium centers.

Analysis of the workload of bank tellers of a Brazilian public institution.

PubMed

Serikawa, Simoni S; Albieri, Ana Carolina S; Bonugli, Gustavo P; Greghi, Marina F

2012-01-01

During the last decades there have been many changes in the banking sector organization. It has been also observed the mutual growing of musculoskeletal and mental disorders. This study investigated the workload of bank tellers at a Brazilian public institution. It was performed the Ergonomic Work Analysis (EWA). Three employees participated in this study. During the analysis process, three research instruments were applied: Inventory of Work and Risk of Illness, Yoshitake Fatigue Questionnaire and Nordic Musculoskeletal Questionnaire, beyond the realization of footage recordings and the self-confrontation. The results indicated the existence of an excess of workload on the evaluated workstations, mainly in relation to mental order constraints, that overlaps the physical aspects. Thereby it was found that the employees tend to adopt strategies trying to reduce the impacts of the excess of workload, in order to regulate it.

Potential energy surface of cyclooctatetraene

NASA Astrophysics Data System (ADS)

Andrés, José L.; Castaño, Obis; Morreale, Antonio; Palmeiro, Raul; Gomperts, Roberto

1998-01-01

We present a theoretical study of the cyclooctatetraene (COT) molecule. Seven COT structures are located on the singlet ground state potential energy surface. Four of them, which present D2d (tub), Cs (bicyclo[4.2.0]octa-2,4,7-triene or BOT), C2h (chair) and D4 (crown) symmetries are stable species, and the other three are transition state structures showing Cs, D4h, and D8h symmetry. We discuss the symmetry of wave functions for these stationary points. Geometries, energies, and harmonic vibrational frequencies of these structures, and energy gaps between singlet-triplet states and low-lying singlets are presented. For the planar D4h and D8h structures, Jahn-Teller and tunneling effects have also been discussed. Ring inversion, bond shifting and valence isomerization reactive channels from the tub COT conformer are discussed from the point of view of the corresponding transition state structures. Where possible, in order to lend support to this theoretical information comparisons with recent transition state spectroscopy data are made.

Advisor-Teller Money Manager (ATM) Therapy for Substance Use Disorders

PubMed Central

Rosen, Marc I.; Rounsaville, Bruce J.; Ablondi, Karen; Black, Anne C.; Rosenheck, Robert A.

2011-01-01

Objective Patients with concomitant psychiatric and substance use disorders are commonly assigned representative payees or case managers to help manage their funds, but money management has not been conceptualized as a theory-based treatment. This randomized clinical trial was conducted to determine the effect of a money management–based therapy, advisor-teller money manager (ATM), on substance abuse or dependence. Methods Ninety patients at a community mental health center who had a history of cocaine or alcohol abuse or dependence were assessed after random assignment to 36 weeks of ATM (N=47) or a control condition in which use of a financial workbook was reviewed (N=43). Patients assigned to ATM were encouraged to deposit their funds into a third-party account, plan weekly expenditures, and negotiate monthly budgets. Substance use calendars and urine toxicology tests were collected every other week for 36 weeks and again 52 weeks after randomization. Results Patients assigned to ATM had significantly more negative toxicologies for cocaine metabolite over time than patients in the control group, and treating clinicians rated ATM patients as significantly more likely to be abstinent from illicit drugs. Self-reported abstinence from alcohol did not significantly differ between groups. Unexpectedly, patients assigned to ATM were more likely to be assigned a representative payee or a conservator than control participants during the follow-up period (ten of 47 versus two of 43). One patient in ATM assaulted the therapist when his check had not arrived. Conclusions ATM is an efficacious therapy for the treatment of cocaine abuse or dependence among people with concomitant psychiatric illness but requires protection of patient autonomy and staff safety. PMID:20592006

Advisor-Teller Money Manager (ATM) therapy for substance use disorders.

PubMed

Rosen, Marc I; Rounsaville, Bruce J; Ablondi, Karen; Black, Anne C; Rosenheck, Robert A

2010-07-01

Patients with concomitant psychiatric and substance use disorders are commonly assigned representative payees or case managers to help manage their funds, but money management has not been conceptualized as a theory-based treatment. This randomized clinical trial was conducted to determine the effect of a money management-based therapy, advisor-teller money manager (ATM), on substance abuse or dependence. Ninety patients at a community mental health center who had a history of cocaine or alcohol abuse or dependence were assessed after random assignment to 36 weeks of ATM (N=47) or a control condition in which use of a financial workbook was reviewed (N=43). Patients assigned to ATM were encouraged to deposit their funds into a third-party account, plan weekly expenditures, and negotiate monthly budgets. Substance use calendars and urine toxicology tests were collected every other week for 36 weeks and again 52 weeks after randomization. Patients assigned to ATM had significantly more negative toxicologies for cocaine metabolite over time than patients in the control group, and treating clinicians rated ATM patients as significantly more likely to be abstinent from illicit drugs. Self-reported abstinence from alcohol did not significantly differ between groups. Unexpectedly, patients assigned to ATM were more likely to be assigned a representative payee or a conservator than control participants during the follow-up period (ten of 47 versus two of 43). One patient in ATM assaulted the therapist when his check had not arrived. ATM is an efficacious therapy for the treatment of cocaine abuse or dependence among people with concomitant psychiatric illness but requires protection of patient autonomy and staff safety.

Impact of New Gamow-Teller Strengths on Explosive Type Ia Supernova Nucleosynthesis

NASA Astrophysics Data System (ADS)

Mori, Kanji; Famiano, Michael A.; Kajino, Toshitaka; Suzuki, Toshio; Hidaka, Jun; Honma, Michio; Iwamoto, Koichi; Nomoto, Ken'ichi; Otsuka, Takaharu

2016-12-01

Recent experimental results have confirmed a possible reduction in the Gamow-Teller (GT+) strengths of pf-shell nuclei. These proton-rich nuclei are of relevance in the deflagration and explosive burning phases of SNe Ia. While prior GT strengths result in nucleosynthesis predictions with a lower-than-expected electron fraction, a reduction in the GT+ strength can result in a slightly increased electron fraction compared to previous shell model predictions, though the enhancement is not as large as previous enhancements in going from rates computed by Fuller, Fowler, and Newman based on an independent particle model. A shell model parametrization has been developed that more closely matches experimental GT strengths. The resultant electron-capture rates are used in nucleosynthesis calculations for carbon deflagration and explosion phases of SNe Ia, and the final mass fractions are compared to those obtained using more commonly used rates.

Effect of Fe and Co substitution on the martensitic stability and the elastic, electronic, and magnetic properties of Mn2NiGa : Insights from ab initio calculations

NASA Astrophysics Data System (ADS)

Kundu, Ashis; Ghosh, Sheuly; Ghosh, Subhradip

2017-11-01

We investigate the effects of Fe and Co substitutions on the phase stability of the martensitic phase and mechanical, electronic, and magnetic properties of the magnetic shape memory system Mn2NiGa by first-principles density functional theory calculations. The evolution of these aspects upon substitution of Fe and Co at different crystallographic sites is investigated by computing the electronic structure, mechanical properties (tetragonal shear constant, Pugh ratio, and Cauchy pressure), and magnetic exchange parameters. We find that the austenite phase of Mn2NiGa gradually stabilizes with increase in concentration of Fe/Co due to the weakening of the minority spin hybridization of Ni and Mn atoms occupying crystallographically equivalent sites. The interplay between relative structural stability and the compositional changes is understood from the variations in the elastic moduli and electronic structures. We find that like in the Ni2MnGa -based systems, the elastic shear modulus C' can be considered as a predictor of composition dependence of martensitic transformation temperature Tm in substituted Mn2NiGa , thus singling it out as the universally acceptable predictor for martensitic transformation in Ni-Mn-Ga compounds over a wide composition range. The magnetic properties of Mn2NiGa are found to be greatly improved by the substitutions due to stronger ferromagnetic interactions in the compounds. The gradually weaker (stronger) Jahn-Teller distortion (covalent bonding) in the minority spin densities of states due to substitutions leads to a half-metallic-like gap in these compounds resulting in materials with high spin polarization when the substitutions are complete. The substitutions at the Ga site result in the two compounds Mn2NiFe and Mn2NiCo with very high magnetic moments and Curie temperatures. Thus, our work indicates that although the substitutions destroy the martensitic transformation and thus the possibility of realization of shape memory

Direct and real time probe of photoinduced structure transition in colossal magnetoresistive material

DOE PAGES

Li, Junjie; Wang, Xuan; Zhou, Haidong; ...

2016-07-29

Here, we report a direct and real time measurement of photoinduced structure phase transition in single crystal La 0.84Sr 0.16MnO 3 using femtosecond electron diffraction. The melting of orthorhombic lattice ordering under femtosecond optical excitation is found involving two distinct processes with different time scales, an initial fast melting of orthorhombic phase in about 4 ps and a subsequent slower transformation in 90 ps and longer timescales. Furthermore, the fast process is designated as the initial melting of orthorhombic phase induced by the Mn-O bond change that is most likely driven by the quenching of the dynamic Jahn-Teller distortion followingmore » the photo-excitation. We attribute the slow process to the growing of newly formed structure domain from the photo-excited sites to the neighboring non-excited orthorhombic sites.« less

Further characterization of spectral features attributable to titanium on the moon

NASA Technical Reports Server (NTRS)

Burns, R. G.; Parkin, K. M.; Loeffler, B. M.; Leung, I. S.; Abu-Eid, R. M.

1976-01-01

The following transitions are observed in the electronic absorption spectra of lunar titanaugites: Fe(2+) spin-allowed and spin-forbidden crystal field; Ti(3+) spin allowed and Jahn-Teller split crystal field; Ti(3+)-Ti(4+) CT; Fe(2+)-Ti(4+) CT; and O(2-)-Fe(2+), Ti(3+), Ti(4+) CT. Of these, the transitions involving Ti(3+) are unique to lunar or nonferric-bearing titanaugites. All titanaugites have the Fe(2+) crystal field and Fe(2+)-Ti(4+) CT transitions in common. These features in the diffuse reflectance spectra of lunar materials give rise to the '1.0 band' and to the observed absorption around 0.5-0.6 micron, respectively. Since regolith contains a variety of phases with coexisting Fe(2+), Ti(3+), and Ti(4+) ions, several metal-metal charge transfer processes are possible.

Structural instability of the CoO 4 tetrahedral chain in SrCoO 3-δ thin films

DOE PAGES

Glamazda, A.; Choi, Kwang-yong; Lemmens, P.; ...

2015-08-31

Raman scattering experiments together with detailed lattice dynamic calculations are performed to elucidate crystallographic and electronic peculiarities of SrCoO 3-δ films. We observe that the 85 cm -1 phonon mode involving the rotation of a CoO 4 tetrahedron undergoes a hardening by 21 cm -1 when the temperature is decreased. In addition, new phonon modes appear at 651.5 and 697.6 cm -1 . The latter modes are attributed to the Jahn-Teller activated modes. Upon cooling from room temperature, all phonons exhibit an exponential-like increase of intensity with a characteristic energy of about 103–107 K. We attribute this phenomenon to anmore » instability of the CoO 4 tetrahedral chain structure, which constitutes a key ingredient to understand the electronic and structural properties of the brownmillerite SrCoO 2.5.« less

Characterization and frequency-thermal response of electrical properties of Cu nanoferrite prepared by sol-gel method

NASA Astrophysics Data System (ADS)

Moghadasi, Fatemeh S.; Daadmehr, Vahid; Kashfi, Monire

2016-10-01

In this paper, we have synthesized copper ferrite nanocrystals using sol-gel method. X-ray diffraction (XRD) analysis confirms that the ferrite has cubic spinal structure and shows Jahn-Teller effect. Also, scan electron microscope (SEM) image demonstrates that grains are nano size order. We showed that the dielectric properties are compatible with the Maxwell-Wagner model and phenomenological Koop's theory. Loss tangent and conductivity of the ferrite have been measured to have small values of 2.4 and 2×10-7 S/m, respectively at room temperature and at 12 Hz. Conductivity has been investigated in terms of localized hopping mechanism and good obedience of Jonscher's law was observed. Variation of activation energy was studied and showed a transition temperature of 443 °K. The electrical modulus shows relaxation of interfacial polarization with relaxation time of 0.318 ms at 24 °C and 15.9 μs at 72 °C. In Impedance spectroscopy, we observed the effects of grain and grain boundary. By increasing temperature, capacity and conduction would increase which show easier polarization process and a semiconducting behavior. Also, relaxation times are shifted to smaller values to represent increasing the electrons mobility.

Two-dimensional La2/3Sr4/3MnO4 Manganite Films Probed by Epitaxial Strain and Cation Ordering

NASA Astrophysics Data System (ADS)

Nelson-Cheeseman, Brittany; Santos, Tiffany; Bhattacharya, Anand

2010-03-01

Dimensionality is known to play a central role in the properties of strongly correlated systems. Here we investigate magnetism and transport in thin films of the Ruddlesden-Popper n=1 phase, La1-xSr1+xMnO4. Within this material, the MnO6-octahedra form two-dimensional perovskite sheets separated by an extra rocksalt layer. By fabricating high quality thin films with ozone-assisted molecular beam epitaxy, we study how the effects of epitaxial strain and intentional cation ordering, known as digital synthesis, influence the properties of this 2-dimensional manganite. For example, at the same Mn^3+:Mn^4+ ratio (2:1) as its fully spin-polarized 3D manganite counterpart, this two dimensional analog at x=1/3 only displays a spin glass phase below 20K in bulk. This is believed to result from a competition between superexchange and double exchange, as well as disordered Jahn-Teller distortions. However, in our films we find weak ferromagnetic order up to much higher temperatures in addition to a low temperature spin glass phase. We will discuss how strain and cation order effect the presence of this weak ferromagnetism.

Variational Principles, Occam Razor and Simplicity Paradox

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

2004-05-01

Variational minimum principles (VMP) refer to energy (statics, Thomson and Earnshaw theorems in electrostatics), action (Maupertuis, Euler, Lagrange, Hamilton), light (Fermat), quantum paths (Feynman), etc. Historically, VMP appeal to some economy in nature, similarly to Occam Razor Parsimony (ORP) principle. Version of ORP are "best world" (Leibniz), Panglossianism (Voltaire), and "most interesting world" (Dyson). Conceptually, VMP exemplify curious fact that infinite set is often simpler than its subsets (e.g., set of all integers is simpler than set of primes). Algorithmically very simple number 0.1234567... (Champernowne constant) contains Library of Babel of "all books" (Borges) and codes (infinitely many times) everything countably possible. Likewise, full Megaverse (Everett, Deutsch, Guth, Linde) is simpler than our specific ("Big Bang") universe. Dynamically, VMP imply memory effects akin to hysteresis. Similar ideas are "water memory" (Benveniste, Josephson) and isotopic biology (Berezin). Paradoxically, while ORP calls for economy (simplicity), unfolding of ORP in VMP seemingly works in the opposite direction allowing for complexity emergence (e.g., symmetry breaking in Jahn-Teller effect). Metaphysical extrapolation of this complimentarity may lead to "it-from-bit" (Wheeler) reflection of why there is something rather than nothing.

IMPACT OF NEW GAMOW–TELLER STRENGTHS ON EXPLOSIVE TYPE IA SUPERNOVA NUCLEOSYNTHESIS

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

Mori, Kanji; Famiano, Michael A.; Kajino, Toshitaka

2016-12-20

Recent experimental results have confirmed a possible reduction in the Gamow–Teller (GT{sub +}) strengths of pf-shell nuclei. These proton-rich nuclei are of relevance in the deflagration and explosive burning phases of SNe Ia. While prior GT strengths result in nucleosynthesis predictions with a lower-than-expected electron fraction, a reduction in the GT{sub +} strength can result in a slightly increased electron fraction compared to previous shell model predictions, though the enhancement is not as large as previous enhancements in going from rates computed by Fuller, Fowler, and Newman based on an independent particle model. A shell model parametrization has been developed thatmore » more closely matches experimental GT strengths. The resultant electron-capture rates are used in nucleosynthesis calculations for carbon deflagration and explosion phases of SNe Ia, and the final mass fractions are compared to those obtained using more commonly used rates.« less

Size- and pressure-controlled ferromagnetism in LaCoO3 nanoparticles

NASA Astrophysics Data System (ADS)

Fita, I.; Markovich, V.; Mogilyansky, D.; Puzniak, R.; Wisniewski, A.; Titelman, L.; Vradman, L.; Herskowitz, M.; Varyukhin, V. N.; Gorodetsky, G.

2008-06-01

Magnetic properties of nanocrystalline LaCoO3 with particle size of 25, 30, 32, and 38 nm, prepared by the citrate method, were investigated in temperature range 2-320 K, magnetic field up to 50 kOe, and under hydrostatic pressure up to 11 kbar. All nanoparticles exhibit weak ferromagnetism below TC≈85K , in agreement with recent observation on LaCoO3 particles and tensile thin films. It was found that with decreasing particle size, i.e., with increasing the surface to volume ratio, the unit-cell volume increases monotonically due to the surface effect. The ferromagnetic moment increases as well, simultaneously with lattice expansion, whereas TC remains nearly unchanged. On the other hand, an applied hydrostatic pressure suppresses strongly the ferromagnetic phase leading to its full disappearance at 10 kbar, while the TC does not change visibly under pressure. It appears that the ferromagnetism in LaCoO3 nanoparticles is controlled by the unit-cell volume. This clear correlation suggests that the nature of ferromagnetic ground state of LaCoO3 is likely related to orbitally ordered Jahn-Teller active Co3+ ions with intermediate-spin (IS) state, which may persist in the expanded lattice at low temperatures. A robust orbital order presumed among the IS Co3+ species can explain the very stable TC observed for LaCoO3 samples prepared under different conditions: single crystal powders, nanoparticles, and thin films.

Lattice-mediated magnetic order melting in TbMnO3

NASA Astrophysics Data System (ADS)

Baldini, Edoardo; Kubacka, Teresa; Mallett, Benjamin P. P.; Ma, Chao; Koohpayeh, Seyed M.; Zhu, Yimei; Bernhard, Christian; Johnson, Steven L.; Carbone, Fabrizio

2018-03-01

Recent ultrafast magnetic-sensitive measurements [Johnson et al., Phys. Rev. B 92, 184429 (2015), 10.1103/PhysRevB.92.184429; Bothschafter et al., Phys. Rev. B 96, 184414 (2017), 10.1103/PhysRevB.96.184414] have revealed a delayed melting of the long-range cycloid spin order in TbMnO3 following photoexcitation across the fundamental Mott-Hubbard gap. The microscopic mechanism behind this slow transfer of energy from the photoexcited carriers to the spin degrees of freedom is still elusive and not understood. Here, we address this problem by combining spectroscopic ellipsometry, ultrafast broadband optical spectroscopy, and ab initio calculations. Upon photoexcitation, we observe the emergence of a complex collective response, which is due to high-energy coherent optical phonons coupled to the out-of-equilibrium charge density. This response precedes the magnetic order melting and is interpreted as the fingerprint of the formation of anti-Jahn-Teller polarons. We propose that the charge localization in a long-lived self-trapped state hinders the emission of magnons and other spin-flip mechanisms, causing the energy transfer from the charge to the spin system to be mediated by the reorganization of the lattice. Furthermore, we provide evidence for the coherent excitation of a phonon mode associated with the ferroelectric phase transition.

Nanoclustering phase competition induces the resistivity hump in colossal magnetoresistive manganites

NASA Astrophysics Data System (ADS)

Pradhan, Kalpataru; Yunoki, Seiji

2017-12-01

Using a two-band double-exchange model with Jahn-Teller lattice distortions and superexchange interactions, supplemented by quenched disorder, at an electron density n =0.65 , we explicitly demonstrate the coexistence of the n =1 /2 -type (π ,π ) charge-ordered and the ferromagnetic nanoclusters above the ferromagnetic transition temperature Tc in colossal magnetoresistive (CMR) manganites. The resistivity increases due to the enhancement of the volume fraction of the charge-ordered and the ferromagnetic nanoclusters upon decreasing the temperature down to Tc. The ferromagnetic nanoclusters start to grow and merge, and the volume fraction of the charge-ordered nanoclusters decreases below Tc, leading to the sharp drop in the resistivity. By applying a small external magnetic field h , we show that the resistivity above Tc increases, as compared with the case when h =0 , a fact that further confirms the coexistence of the charge-ordered and the ferromagnetic nanoclusters. In addition, we show that the volume fraction of the charge-ordered nanoclusters decreases upon increasing the bandwidth, and consequently the resistivity hump diminishes for large bandwidth manganites, in good qualitative agreement with experiments. The obtained insights from our calculations provide a complete pathway to understand the phase competition in CMR manganites.

Gamow-Teller transitions in the 64Ni(3He, t)64Cu reaction

NASA Astrophysics Data System (ADS)

Popescu, L.; Adachi, T.; Berg, G. P. A.; von Brentano, P.; De Frenne, D.; Fujita, K.; Fujita, Y.; Hatanaka, K.; Jacobs, E.; Negret, A.; Nakanishi, K.; Sakemi, Y.; Shimbara, Y.; Shimizu, Y.; Tameshige, Y.; Tamii, A.; Uchida, M.; Yosoi, M.

2005-10-01

In order to study the Gamow-Teller (GT) transitions in the fp-shell nucleus 64Cu, the 64Ni(3He, t)64Cu charge-exchange reaction was investigated at E3He= 140 MeV/nucleon [1]. The outgoing tritons were momentum analysed by the Grand Raiden spectrometer at 0°. The very high energy resolution of 35 keV (FWHM) allowed the separation of individual levels in the excitation energy region from 0 to 3.5 MeV. An angular distribution analysis was performed for the observed transitions to these states. In addition to the ground state (g.s.), known to be a Jπ = 1+ GT state, several excited states showed L = 0 nature, making them candidates of GT states. At higher excitation energies, the level density becomes very high and a bump-like structure, the so-called GT Giant Resonance, dominates the spectrum.

Bethe, Oppenheimer, Teller and the Fermi Award: Norris Bradbury Speaks

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

Meade, Roger Allen

In 1956 the Enrico Fermi Presidential Award was established to recognize scientists, engineers, and science policymakers who gave unstintingly over their careers to advance energy science and technology. The first recipient was John von Neumann. .1 Among those scientists who were thought eligible for the award were Hans Bethe, J. Robert Oppenheimer, and Edward Teller. In 1959 Norris Bradbury was asked to comment on the relative merits of each these three men, whom he knew well from their affiliation with Los Alamos. Below is a reproduction of the letter Bradbury sent to Dr. Warren C. Johnson of the AEC’s Generalmore » Advisory Committee(GAC) containing his evaluation of each man. The letter might surprise those not accustomed to Bradbury’s modus operandi of providing very detailed and forthright answers to the AEC. The letter, itself, was found in cache of old microfilm. Whether because of the age of the microfilm or the quality of the filming process, portions of the letter are not legible. Where empty brackets appear, the word or words could not be read or deduced. Words appearing in brackets are guesses that appear, from the image, to be what was written. These guesses, of course, are just that – guesses.« less

Is talking to an automated teller machine natural and fun?

PubMed

Chan, F Y; Khalid, H M

Usability and affective issues of using automatic speech recognition technology to interact with an automated teller machine (ATM) are investigated in two experiments. The first uncovered dialogue patterns of ATM users for the purpose of designing the user interface for a simulated speech ATM system. Applying the Wizard-of-Oz methodology, multiple mapping and word spotting techniques, the speech driven ATM accommodates bilingual users of Bahasa Melayu and English. The second experiment evaluates the usability of a hybrid speech ATM, comparing it with a simulated manual ATM. The aim is to investigate how natural and fun can talking to a speech ATM be for these first-time users. Subjects performed the withdrawal and balance enquiry tasks. The ANOVA was performed on the usability and affective data. The results showed significant differences between systems in the ability to complete the tasks as well as in transaction errors. Performance was measured on the time taken by subjects to complete the task and the number of speech recognition errors that occurred. On the basis of user emotions, it can be said that the hybrid speech system enabled pleasurable interaction. Despite the limitations of speech recognition technology, users are set to talk to the ATM when it becomes available for public use.

Enhanced vibronic interaction caused by local lattice symmetry lowering in the (Fe, Mg)As2 ternary system

NASA Astrophysics Data System (ADS)

Pishtshev, A.; Rubin, P.

2018-04-01

By means of periodic density functional theory (DFT) electronic structure calculations, we investigate iron-site doping effects in a structural model of bulk FeAs2. Simulations performed within the projector augmented-wave method-Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) functional scheme reveal that the impacts of the two stoichiometric substitutions Fe → Mg and Fe → Ni are radically different with respect to the structural and electronic behavior of the dopants. In particular, unlike the Ni dopant, the Mg dopant incorporated in FeAs2 occupies a noncentral equilibrium position characterized by an off-center displacement from the reference higher-symmetry position. Analysis of the respective electron and vibrational factors allows us to explain this result in terms of the local pseudo Jahn-Teller effect (pJTE). On the basis of DFT calculations, we deduce which electron orbitals and lattice vibrational modes are appropriate for promoting the local instability at the origin of the pJTE. Quantitative evaluations of the pJTE parameters performed within the polyatomic formalism of an effective tight-binding model show that it is just the enhanced vibronic interaction in the Mg-[FeAs6] cluster that is responsible for the local lattice symmetry breaking.

Molecular properties of metal difluorides and their interactions with CO2 and H2O molecules: a DFT investigation.

PubMed

Arokiyanathan, Agnes Lincy; Lakshmipathi, Senthilkumar

2017-11-18

A computational study of metal difluorides (MF 2 ; M = Ca to Zn) and their interactions with carbon dioxide and water molecules was performed. The structural parameter values obtained and the results of AIM analysis and energy decomposition analysis indicated that the Ca-F bond is weaker and less ionic than the bonds in the transition metal difluorides. A deformation density plot revealed the stablizing influence of the Jahn-Teller effect in nonlinear MF 2 molecules (e.g., where M= Sc, Ti, Cr). An anaysis of the metal K-edge peaks of the difluorides showed that shifts in the edge energy were due to the combined effects of the ionicity, effective nuclear charge, and the spin state of the metal. The interactions of CO 2 with ScF 2 (Scc3 geometry) and TiF 2 (Tic2 geometry) caused CO 2 to shift from its usual linear geometry to a bent geometry (η 2 (C=O) binding mode), while it retained its linear geometry (η 1 (O) binding mode) when it interacted with the other metal difluorides. Energy decomposition analysis showed that, among the various geometries considered, the Scc3 and Tic2 geometries possessed the highest interaction energies and orbital interaction energies. Heavier transition metal difluorides showed stronger affinities for H 2 O, whereas the lighter transition metal (Sc and Ti) difluorides preferred CO 2 . Overall, the results of this study suggest that fluorides of lighter transition metals with partially filled d orbitals (e.g., Sc and Ti) could be used for CO 2 capture under moist conditions. Graphical abstract Interaction of metal difluorides with carbon dioxide and water.

Nematic phase in the CE-regime of colossal magnetoresistive manganites

NASA Astrophysics Data System (ADS)

Ochoa, Emily; Sen, Cengiz; Dagotto, Elbio; Lamar/UTK Collaboration

We report nematic phase tendencies around the first order CE transition in the two-orbital double exchange model with Jahn-Teller phonons at electronic density n = 0 . 5 . Starting with a random state at high temperatures, we employ a careful cool-down method using a Monte Carlo algorithm. We then monitor the spin structure factor S (q) of the CE phase as a function of temperature. Near the critical temperature, S (q) grows with decreasing temperature for both right- and left-ordered CE ladders, followed by a spontaneous symmetry breaking into one or the other as the critical temperature is achieved. Below the critical temperature a pure CE state with a staggered charge order is obtained. Our results are similar to those observed in pnictides in earlier studies. Lamar University Office of Undergraduate Research, and U.S. Department of Energy, Office of Basic Energy Sciences, Materials Sciences and Engineering Division.

A2TiF 5· nH 2O ( A=K, Rb, or Cs; n=0 or 1): Synthesis, structure, characterization, and calculations of three new uni-dimensional titanium fluorides

NASA Astrophysics Data System (ADS)

Jo, Vinna; Woo Lee, Dong; Koo, Hyun-Joo; Ok, Kang Min

2011-04-01

Three new uni-dimensional alkali metal titanium fluoride materials, A2TiF 5· nH 2O ( A=K, Rb, or Cs; n=0 or 1) have been synthesized by hydrothermal reactions. The structures of A2TiF 5· nH 2O have been determined by single-crystal X-ray diffraction. The Ti 4+ cations have been reduced to Ti 3+ during the synthesis reactions. All three A2TiF 5· nH 2O materials contain novel 1-D chain structures that are composed of the slightly distorted Ti 3+F 6 corner-sharing octahedra attributable to the Jahn-Teller distortion. The coordination environment of the alkali metal cations plays an important role to determine the degree of turning in the chain structures. Complete structural analyses, Infrared and UV-vis diffuse reflectance spectra, and thermal analyses are presented, as are electronic structure calculations.

Neutron diffraction study of layered Ni dioxides: Ag2NiO2

NASA Astrophysics Data System (ADS)

Nozaki, Hiroshi; Sugiyama, Jun; Janoschek, Marc; Roessli, Bertrand; Pomjakushin, Vladimir; Keller, Lukas; Yoshida, Hiroyuki; Hiroi, Zenji

2008-03-01

In order to elucidate the antiferromagnetic (AF) nature of hexagonal Ag2NiO2 with TN = 56 K and to know the mechanism of the structural phase transition of TS~270 K, neutron powder diffraction patterns have been measured in the temperature range between 1.5 and 330 K. One magnetic Bragg peak indexed as \\frac {1}{3}~\\frac {1}{3}~0 is clearly observed below TN, confirming the formation of long-range AF order, reported by a muon-spin spectroscopy measurement. The weak intensity of the magnetic peak also suggests the two-dimensional nature of the AF order, but the spin structure is still unknown. In addition, the precise structural analysis of the data between 160 and 330 K shows that only the cH-axis length changes drastically at TS, which suggests the appearance of local Jahn-Teller distortion below TS.

Present knowledge of electronic properties and charge transport of icosahedral boron-rich solids

NASA Astrophysics Data System (ADS)

Werheit, Helmut

2009-06-01

B12 icosahedra or related structure elements determine the different modifications of elementary boron and numerous boron-rich compounds from α-rhombohedral boron with 12 to YB66 type with about 1584 atoms per unit cell. Typical are well-defined high density intrinsic defects: Jahn-Teller distorted icosahedra, vacancies, incomplete occupancies, statistical occupancies and antisite defects. The correlation between intrinsic point defects and electron deficiencies solves the discrepancy between theoretically predicted metal and experimentally proved semiconducting character. The electron deficiencies generate split-off valence states, which are decisive for the electronic transport, a superposition of band-type and hopping-type conduction. Their share depends on actual conditions like temperature or pre-excitation. The theoretical model of bipolaron hopping is incompatible with numerous experiments. Technical application of the typically p-type icosahedral boron-rich solids requires suitable n-type counterparts; doping and other possibilities are discussed.

Double Gamow-Teller Transitions and its Relation to Neutrinoless β β Decay

NASA Astrophysics Data System (ADS)

Shimizu, Noritaka; Menéndez, Javier; Yako, Kentaro

2018-04-01

We study the double Gamow-Teller (DGT) strength distribution of 48Ca with state-of-the-art large-scale nuclear shell model calculations. Our analysis shows that the centroid energy of the DGT giant resonance depends mostly on the isovector pairing interaction, while the resonance width is more sensitive to isoscalar pairing. Pairing correlations are also key in neutrinoless β β (0 ν β β ) decay. We find a simple relation between the centroid energy of the 48Ca DGT giant resonance and the 0 ν β β decay nuclear matrix element. More generally, we observe a very good linear correlation between the DGT transition to the ground state of the final nucleus and the 0 ν β β decay matrix element. The correlation, which originates on the dominant short-range character of both transitions, extends to heavier systems including several β β emitters and also holds in energy-density functional results. Our findings suggest that DGT experiments can be a very valuable tool to obtain information on the value of 0 ν β β decay nuclear matrix elements.

Shape coexistence, shape evolution and Gamow-Teller {beta}-decay of neutron-rich A Asymptotically-Equal-To 100 nuclei

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

Petrovici, A.; Schmid, K. W.; Faessler, A.

The structure of neutron-rich nuclei in the A Asymptotically-Equal-To 100 mass region relevant for the astrophysical r process manifests drastic changes in some isotopic chains and often sudden variations of particular nuclear properties have been identified. For a realistic description of the evolution in structure with increasing energy, spin, and isospin determined by shape coexistence and mixing beyond-mean-field approaches are required. Our recent studies represent an attempt to the self-consistent description of the shape coexistence phenomena in neutron-rich A Asymptotically-Equal-To 100 nuclei within the complex Excited Vampir variational model with symmetry projection before variation using a realistic effective interaction basedmore » on the Bonn A potential in a large model space. Results concerning the triple shape coexistence and the shape evolution in the N=58 Sr and Zr isotopes, the shape evolution in a chain of Zr nuclei, as well as the Gamow-Teller {beta}-decay properties of neutron-rich Zr and Tc nuclei are presented.« 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.

Piezomagnetism and magnetoelastic memory in uranium dioxide

DOE PAGES

Jaime, M.; Saul, A.; Salamon, M.; ...

2017-07-24

Uranium dioxide (UO 2) is a prime nuclear fuel and perhaps the most thoroughly studied actinide material to date. Its thermal and magnetic properties remain, however, a puzzle resulting from strong couplings between magnetism and lattice vibrations. The magnetic state of this cubic material is characterized by a non- collinear antiferromagnetic structure and multidomain Jahn-Teller distortions that could be behind novel thermal properties. Here we show that single crystals of UO 2, subjected to magnetic fields up to 95 T in the magnetic state, exhibit the abrupt appearance of positive linear magnetostriction leading to a trigonal distortion. Upon reversal ofmore » the field the linear term also reverses sign, a hallmark of piezomagnetism. The switching phenomenon occurs at ± 18 T and persists during subsequent field reversals, demonstrating robust magneto-elastic memory. This is the first example of piezomagnetism in an actinide spin system and the magneto-elastic memory loop here is nearly an order of magnitude wider in field than those previously observed, making UO 2 the hardest piezomagnet known. The possibility of an inverse phase with reduced magnetocrystalline anisotropy is considered to explain these effects.« less

Piezomagnetism and magnetoelastic memory in uranium dioxide

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

Jaime, M.; Saul, A.; Salamon, M.

Uranium dioxide (UO 2) is a prime nuclear fuel and perhaps the most thoroughly studied actinide material to date. Its thermal and magnetic properties remain, however, a puzzle resulting from strong couplings between magnetism and lattice vibrations. The magnetic state of this cubic material is characterized by a non- collinear antiferromagnetic structure and multidomain Jahn-Teller distortions that could be behind novel thermal properties. Here we show that single crystals of UO 2, subjected to magnetic fields up to 95 T in the magnetic state, exhibit the abrupt appearance of positive linear magnetostriction leading to a trigonal distortion. Upon reversal ofmore » the field the linear term also reverses sign, a hallmark of piezomagnetism. The switching phenomenon occurs at ± 18 T and persists during subsequent field reversals, demonstrating robust magneto-elastic memory. This is the first example of piezomagnetism in an actinide spin system and the magneto-elastic memory loop here is nearly an order of magnitude wider in field than those previously observed, making UO 2 the hardest piezomagnet known. The possibility of an inverse phase with reduced magnetocrystalline anisotropy is considered to explain these effects.« less

Topological magnetic phase in LaMnO3 (111) bilayer

NASA Astrophysics Data System (ADS)

Weng, Yakui; Huang, Xin; Yao, Yugui; Dong, Shuai

Candidates for correlated topological insulators, originated from the spin-orbit coupling as well as Hubbard type correlation, are expected in the (111) bilayer of perovskite-structural transition-metal oxides. Based on the first-principles calculation and tight-binding model, the electronic structure of a LaMnO3 (111) bilayer sandwiched in LaScO3 barriers has been investigated. For the ideal undistorted perovskite structure, the Fermi energy of LaMnO3 (111) bilayer just stays at the Dirac point, rendering a semi-metal (graphene-like) which is also a half-metal (different from graphene nor previous studied LaNiO3 (111) bilayer). The Dirac cone can be opened by the spin-orbit coupling, giving rise to nontrivial topological bands corresponding to the (quantized) anomalous Hall effect. For the realistic orthorhombic distorted lattice, the Dirac point moves with increasing Hubbard repulsion (or equivalent Jahn-Teller distortion). Finally, a Mott gap opens, establishing a phase boundary between the Mott insulator and topological magnetic insulator. Our calculation finds that the gap opened by spin-orbit coupling is much smaller in the orthorhombic distorted lattice (~ 1 . 7 meV) than the undistorted one (~11 meV).

Simulation Of Wave Function And Probability Density Of Modified Poschl Teller Potential Derived Using Supersymmetric Quantum Mechanics

NASA Astrophysics Data System (ADS)

Angraini, Lily Maysari; Suparmi, Variani, Viska Inda

2010-12-01

SUSY quantum mechanics can be applied to solve Schrodinger equation for high dimensional system that can be reduced into one dimensional system and represented in lowering and raising operators. Lowering and raising operators can be obtained using relationship between original Hamiltonian equation and the (super) potential equation. In this paper SUSY quantum mechanics is used as a method to obtain the wave function and the energy level of the Modified Poschl Teller potential. The graph of wave function equation and probability density is simulated by using Delphi 7.0 programming language. Finally, the expectation value of quantum mechanics operator could be calculated analytically using integral form or probability density graph resulted by the programming.

Diminished CAGE Effect in {p}-H2: Infrared Spectra of CH3S Observed from Photolysis of CH3SH, CH3SCH3, and CH3SSCH3 Isolated in {p}-H2

NASA Astrophysics Data System (ADS)

Lee, Yuan-Pern; Bahou, Mohammed

2010-06-01

We report infrared absorption spectrum of the methylthio (or thiomethoxy) radical, CH3S, isolated in solid {p}-H2. CH3S was produced by in situ UV photodissociation of three precursors: CH3SH, CH3SH3, and CH3SSCH3 isolated in solid {p}-H2. New absorption features commonly observed with similar intensity ratios in experiments using these precursors are assigned as absorption of CH3S. In Addition to the previously assigned transitions of ν 3 (a1) at 727.1 cm-1, fundamental transitions ν 6 (a1) at 771.1, ν 6 (e) at 1056.6, ν 5 (a1) at 1400.0, and &nu 4 (a1) at 2898.0 cm-1 were observed. The wavenumbers of these features agree satisfactorily with those predicted with a spin-vibronic Hamiltonian accounting for the anharmonic effects and the Jahn-Teller effects to the qu rtic term; the corresponding wavenumbers predicted from theory are ν 6 (a1) at 793, ν 6 (e) at 1105, ν 5 (a1) at 1436, and ν 4 (a1) at 2938 cm-1, with deviations of 14-4.6 % from experiments. Previous attempts of UV photolysis of CH3SCH3 and CH3SSCH3 isolated in an Ar matrix failed to produce CH3S. These results serve as an excellent example that the diminished cae effect of solid {p}-H2 makes production of free radicals via photolysis in situ feasible. If time permits, other examples will be discussed. A. V. Marenich and J. E. Boggs, J. Chem. Theory Comput., 1, 1162 (2005).

Investigations of the local distortions and EPR parameters for Cu2+ in xNa2 O-(30-x)K2 O-70B2 O3 (5 ≤ x ≤ 25 mol%) glasses.

PubMed

Zhang, Zhen-Ya; Wu, Shao-Yi; Zhang, Fu; Zhang, Cheng-Xi; Qin, Rui-Jie; Gao, Han

2018-03-01

The local distortions and electron paramagnetic resonance parameters for Cu 2+ in the mixed alkali borate glasses xNa 2 O-(30-x)K 2 O-70B 2 O 3 (5 ≤ x ≤ 25 mol%) are theoretically studied with distinct modifier Na 2 O compositions x. Owing to the Jahn-Teller effect, the octahedral [CuO 6 ] 10- clusters show significant tetragonal elongation ratios p ~19% along the C 4 axis. With the increase of composition x, the cubic field parameter Dq and the orbital reduction factor k exhibit linearly and quasi-linearly decreasing tendencies, respectively, whereas the relative tetragonal elongation ratio p has quasi-linearly increasing rule with some fluctuations, leading to the minima of g factors at x = 10 mol%. The composition dependences of the optical spectra and the electron paramagnetic resonance parameters are suitably reproduced by the linear or quasi-linear relationships of the relevant quantities (i.e., Dq, k, and p) with x. The above composition dependences are analyzed from mixed alkali effect, which brings forward the modifications of the local crystal-fields and the electronic cloud distribution around Cu 2+ with the variation of the composition of Na 2 O. Copyright © 2017 John Wiley & Sons, Ltd.

Contamination Effects Due to Space Environmental Interactions

NASA Technical Reports Server (NTRS)

Chen, Philip T.; Paquin, Krista C. (Technical Monitor)

2001-01-01

Molecular and particulate contaminants are commonly generated from the orbital spacecraft operations that are under the influence of the space environment. Once generated, these contaminants may attach to the surfaces of the spacecraft or may remain in the vicinity of the spacecraft. In the event these contaminants come to rest on the surfaces of the spacecraft or situated in the line-of-sight of the observation path, they will create various degrees of contamination effect which may cause undesirable effects for normal spacecraft operations, There will be circumstances in which the spacecraft may be subjected to special space environment due to operational conditions. Interactions between contaminants and special space environment may alter or greatly increase the contamination effect due to the synergistic effect. This paper will address the various types of contamination generation on orbit, the general effects of the contamination on spacecraft systems, and the typical impacts on the spacecraft operations due to the contamination effect. In addition, this paper will explain the contamination effect induced by the space environment and will discuss the intensified contamination effect resulting from the synergistic effect with the special space environment.

Greenhouse effect due to atmospheric nitrous oxide

NASA Technical Reports Server (NTRS)

Yung, Y. L.; Wang, W. C.; Lacis, A. A.

1976-01-01

The greenhouse effect due to nitrous oxide in the present atmosphere is about 0.8 K. Increase in atmospheric N2O due to perturbation of the nitrogen cycle by man may lead to an increase in surface temperature as large as 0.5 K by 2025, or 1.0 K by 2100. Other climatic effects of N2O are briefly discussed.

Theoretical study of the local structures and the EPR parameters for RLNKB glasses with VO2+ and Cu2+ dopants

NASA Astrophysics Data System (ADS)

Ding, Chang-Chun; Wu, Shao-Yi; Wu, Li-Na; Zhang, Li-Juan; Peng, Li; Wu, Ming-He; Teng, Bao-Hua

2018-02-01

The electron paramagnetic resonance (EPR) parameters and local structures for impurities VO2+ and Cu2+ in RO-Li2O-Na2O-K2O-B2O3 (RLNKB; R = Zn, Mg, Sr and Ba) glasses are theoretically investigated by using the perturbation formulas of the EPR parameters for tetragonally compressed octahedral 3d1 and tetragonally elongated octahedral 3d9 clusters, respectively. The VO2+ and Cu2+ dopants are found to undergo the tetragonal compression (characterized by the negative relative distortion ratios ρ ≈ -3%, -0.98%, -1% and -0.8% for R = Zn, Mg, Sr and Ba) and elongation (characterized by the positive relative distortion ratios ρ ≈ 29%, 17%, 16% and 28%), respectively, due to the Jahn-Teller effect. Both dopants show similar overall decreasing trends of cubic field parameter Dq and covalency factor N with decreasing electronegativity of alkali earth cation R. The conventional optical basicities Λth and local optical basicities Λloc are calculated for both systems, and the local Λloc are higher for Cu2+ than for VO2+ in the same RLNKB glass, despite the opposite relationship for the conventional Λth. This point is supported by the weaker covalency or stronger ionicity for Cu2+ than VO2+ in the same RLNKB system, characterized by the larger N in the former. The above comparative analysis on the spectral and local structural properties would be helpful to understand structures and spectroscopic properties for the similar oxide glasses with transition-metal dopants of complementary electronic configurations.

Shell-model method for Gamow-Teller transitions in heavy deformed odd-mass nuclei

NASA Astrophysics Data System (ADS)

Wang, Long-Jun; Sun, Yang; Ghorui, Surja K.

2018-04-01

A shell-model method for calculating Gamow-Teller (GT) transition rates in heavy deformed odd-mass nuclei is presented. The method is developed within the framework of the projected shell model. To implement the computation requirement when many multi-quasiparticle configurations are included in the basis, a numerical advancement based on the Pfaffian formula is introduced. With this new many-body technique, it becomes feasible to perform state-by-state calculations for the GT nuclear matrix elements of β -decay and electron-capture processes, including those at high excitation energies in heavy nuclei which are usually deformed. The first results, β- decays of the well-deformed A =153 neutron-rich nuclei, are shown as the example. The known log(f t ) data corresponding to the B (GT- ) decay rates of the ground state of 153Nd to the low-lying states of 153Pm are well described. It is further shown that the B (GT) distributions can have a strong dependence on the detailed microscopic structure of relevant states of both the parent and daughter nuclei.

Heptacopper(II) and dicopper(II)-adenine complexes: synthesis, structural characterization, and magnetic properties

DOE PAGES

Leite Ferreira, B. J. M.; Brandão, Paula; Dos Santos, A. M.; ...

2015-07-13

The syntheses, crystal structures, and magnetic properties of two new copper(II) complexes with molecular formulas [Cu 7(μ 2-OH 2) 6(μ 3-O) 6(adenine) 6(NO 3) 26H 2O (1) and [Cu 2(μ 2-H 2O) 2(adenine) 2(H 2O) 4](NO 3) 42H 2O (2) are reported. We composed the heptanuclear compound of a central octahedral CuO 6 core sharing edges with six adjacent copper octahedra. In 2, the copper octahedra shares one equatorial edge. In both compounds, these basic copper cluster units are further linked by water bridges and bridging adenine ligands through N3 and N9 donors. All copper(II) centers exhibit Jahn-Teller distorted octahedralmore » coordination characteristic of a d 9 center. Our study of the magnetic properties of the heptacopper complex revealed a dominant ferromagnetic intra-cluster interaction, while the dicopper complex exhibits antiferromagnetic intra-dimer interactions with weakly ferromagnetic inter-dimer interaction.« less

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.

Dynamically fluctuating electric dipole moments in fullerene-based magnets.

PubMed

Kambe, Takashi; Oshima, Kokichi

2014-09-19

We report here the direct evidence of the existence of a permanent electric dipole moment in both crystal phases of a fullerene-based magnet--the ferromagnetic α-phase and the antiferromagnetic α'-phase of tetra-kis-(dimethylamino)-ethylene-C60 (TDAE-C60)--as determined by dielectric measurements. We propose that the permanent electric dipole originates from the pairing of a TDAE molecule with surrounding C60 molecules. The two polymorphs exhibit clear differences in their dielectric responses at room temperature and during the freezing process with dynamically fluctuating electric dipole moments, although no difference in their room-temperature structures has been previously observed. This result implies that two polymorphs have different local environment around the molecules. In particular, the ferromagnetism of the α-phase is founded on the homogeneous molecule displacement and orientational ordering. The formation of the different phases with respect to the different rotational states in the Jahn-Teller distorted C60s is also discussed.

Evolution of the magnetic and structural properties of Fe 1 - x Co x V 2 O 4

DOE PAGES

Sinclair, R.; Ma, Jie; Cao, H. B.; ...

2015-10-12

The magnetic and structural properties of single-crystal Fe 1-xCo xV 2O 4 samples have been investigated by performing specific heat, susceptibility, neutron diffraction, and x-ray diffraction measurements. As the orbital-active Fe 2+ ions with larger ionic size are gradually substituted by the orbital-inactive Co 2+ ions with smaller ionic size, the system approaches the itinerant electron limit with decreasing V-V distance. Then, various factors such as the Jahn-Teller distortion and the spin-orbital coupling of the Fe 2+ ions on the A sites and the orbital ordering and electronic itinerancy of the V 3+ ions on the B sites compete withmore » each other to produce a complex magnetic and structural phase diagram. Finally, this phase diagram is compared to those of Fe 1-xMn xV 2O 4 and Mn 1-xCo xV 2O 4 to emphasize several distinct features.« less

Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer

NASA Astrophysics Data System (ADS)

Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

2018-04-01

The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr3 monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr - Br6 units. As an example, we further show that (CrBr3)2Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

Correlation between microstructure and electrical transport properties of La0.7(Ba1-xCax)0.3MnO3 (x = 0 and 0.03) synthesized by sol-gel

NASA Astrophysics Data System (ADS)

Kurniawan, Budhy; Winarsih, Suci; Imaduddin, Agung; Manaf, Azwar

2018-03-01

In this paper, we reported the correlation of structure, microstructure, and electrical transport properties of polycrystalline La0.7(Ba1-xCax)0.3MnO3 (x = 0 and 0.03). The materials were synthesized by sol-gel method. These materials have interesting electronic and magnetic properties which are heavily affected by the degree of crystallographic mismatch between the La and Mn sites. By tuning these sites, the double exchange (DE) and Coulomb interactions among Mn ions can be artificially controlled. La0.7Ba0.3MnO3 is one of the strong candidates for application because it has high magnetoresistance and magnetocaloric properties. Doped Ca to the La0.7Ba0.3MnO3 is aimed for reducing its transition temperature to near room temperature and increasing the magnetoresistance and magnetocaloric properties of this material. Jahn-Teller distortion can be linked to core-shell model with the result of percolation model.

Pinning of topological solitons at extrinsic defects in a quasi one-dimensional charge density wave

NASA Astrophysics Data System (ADS)

Razzaq, Samad; Wippermann, Stefan; Tae Hwan Kim Collaboration; Han Woong Yeom Collaboration

Quasi one-dimensional (1D) electronic systems are known to exhibit exotic physical phenomena, such as, e.g., Jahn Teller distortions, charge density wave (CDW) formation and non-Fermi liquid behavior. Solitonic excitations of the charge density wave ordered ground state and associated topological edge states in atomic wires are presently the focus of increasing attention. We carried out a combined ab initio and scanning tunneling microscopy (STM) study of solitonic and non-solitonic phase defects in the In/Si(111) atomic wire array. While free solitons move too fast to be imaged directly in STM, they can become trapped at extrinsic de- fects within the wire. We discuss the detailed atomistic structure of the responsible extrinsic defects and trapped solitons. Our study highlights the key role of coupled theory-experimental investigations in order to understand also the elusive fast moving solitons. S. W. gratefully acknowledges financial support from the German Research Foundation (DFG), Grant No. FOR1700.

Prediction of Intrinsic Ferromagnetic Ferroelectricity in a Transition-Metal Halide Monolayer.

PubMed

Huang, Chengxi; Du, Yongping; Wu, Haiping; Xiang, Hongjun; Deng, Kaiming; Kan, Erjun

2018-04-06

The realization of multiferroics in nanostructures, combined with a large electric dipole and ferromagnetic ordering, could lead to new applications, such as high-density multistate data storage. Although multiferroics have been broadly studied for decades, ferromagnetic ferroelectricity is rarely explored, especially in two-dimensional (2D) systems. Here we report the discovery of 2D ferromagnetic ferroelectricity in layered transition-metal halide systems. On the basis of first-principles calculations, we reveal that a charged CrBr_{3} monolayer exhibits in-plane multiferroicity, which is ensured by the combination of orbital and charge ordering as realized by the asymmetric Jahn-Teller distortions of octahedral Cr─Br_{6} units. As an example, we further show that (CrBr_{3})_{2}Li is a ferromagnetic ferroelectric multiferroic. The explored phenomena and mechanism of multiferroics in this 2D system not only are useful for fundamental research in multiferroics but also enable a wide range of applications in nanodevices.

Influence of the manganese and cobalt content on the electrochemical performance of P2-Na0.67MnxCo1-xO2 cathodes for sodium-ion batteries.

PubMed

Hemalatha, K; Jayakumar, M; Prakash, A S

2018-01-23

The resurgence of sodium-ion batteries in recent years is due to their potential ability to form intercalation compounds possessing a high specific capacity and energy density comparable to existing lithium systems. To comprehend the role of cobalt substitution in the structure and electrochemical performance of Na 0.67 MnO 2 , the solid solutions of P2-Na 0.67 Mn x Co 1-x O 2 (x = 0.25, 0.5, 0.75) are synthesized and characterized. The XRD-Rietveld analysis revealed that the Co-substitution in Na 0.67 MnO 2 decreases lattice parameters 'a' and 'c' resulting in the contraction of MO 6 octahedra and the enlargement of inter-layer 'd' spacing. XPS indicates that the isovalent cobalt substitution in Na 0.67 MnO 2 results in the partial/complete replacement of Jahn-Teller active trivalent manganese to form low-spin complexes of better structural stability. The Na-ion diffusion coefficient, D Na + , derived from cyclic voltammetry and impedance spectroscopy, confirmed the enhanced mass transport in Co-rich phases compared to Mn-rich phases. Furthermore, higher diffusion coefficient values are observed for Co 3+ /Co 4+ than for their Mn 3+ /Mn 4+ redox processes. In addition, Co-rich phases exhibit a high structural stability and superior capacity retention, whereas Mn-rich phases discharge higher capacities.

An unusual stable mononuclear Mn(III) bis-terpyridine complex exhibiting Jahn-Teller compression: electrochemical synthesis, physical characterisation and theoretical study.

PubMed

Romain, Sophie; Duboc, Carole; Neese, Frank; Rivière, Eric; Hanton, Lyall R; Blackman, Allan G; Philouze, Christian; Leprêtre, Jean-Claude; Deronzier, Alain; Collomb, Marie-Noëlle

2009-01-01

The mononuclear manganese bis-terpyridine complex [Mn(tolyl-terpy)(2)](X)(3) (1(X)(3); X=BF(4), ClO(4), PF(6); tolyl-terpy=4'-(4-methylphenyl)-2,2':6',2"-terpyridine), containing Mn in the unusual +III oxidation state, has been isolated and characterised. The 1(3+) ion is a rare example of a mononuclear Mn(III) complex stabilised solely by neutral N ligands. Complex 1(3+) is obtained by electrochemical oxidation of the corresponding Mn(II) compound 1(2+) in anhydrous acetonitrile. Under these conditions the cyclic voltammogram of 1(2+) exhibits not only the well-known Mn(II)/Mn(III) oxidation at E(1/2)=+0.91 V versus Ag/Ag(+) (+1.21 V vs. SCE) but also a second metal-based oxidation process corresponding to Mn(III)/Mn(IV) at E(1/2)=+1.63 V (+1.93 V vs. SCE). Single crystals of 1(PF(6))(3)2 CH(3)CN were obtained by an electrocrystallisation procedure. X-ray analysis unambiguously revealed its tetragonally compressed octahedral geometry and high-spin character. The electronic properties of 1(3+) were investigated in detail by magnetic measurements and theoretical calculations, from which a D value of +4.82 cm(-1) was precisely determined. Density functional and complete active space self consistent field ab initio calculations both correctly predict a positive sign of D, in agreement with the compressed tetragonal distortion observed in the X-ray structure of 1(PF(6))(3)2 CH(3)CN. The different contributions to D were calculated, and the results show that 1) the spin-orbit coupling part (+2.593 cm(-1)) is predominant compared to the spin-spin interaction (+1.075 cm(-1)) and 2) the excited triplet states make the dominant contribution to the total D value.

Hour-Glass Neural Network Based Daily Money Flow Estimation for Automatic Teller Machines

NASA Astrophysics Data System (ADS)

Karungaru, Stephen; Akashi, Takuya; Nakano, Miyoko; Fukumi, Minoru

Monetary transactions using Automated Teller Machines (ATMs) have become a normal part of our daily lives. At ATMs, one can withdraw, send or debit money and even update passbooks among many other possible functions. ATMs are turning the banking sector into a ubiquitous service. However, while the advantages for the ATM users (financial institution customers) are many, the financial institution side faces an uphill task in management and maintaining the cash flow in the ATMs. On one hand, too much money in a rarely used ATM is wasteful, while on the other, insufficient amounts would adversely affect the customers and may result in a lost business opportunity for the financial institution. Therefore, in this paper, we propose a daily cash flow estimation system using neural networks that enables better daily forecasting of the money required at the ATMs. The neural network used in this work is a five layered hour glass shaped structure that achieves fast learning, even for the time series data for which seasonality and trend feature extraction is difficult. Feature extraction is carried out using the Akamatsu Integral and Differential transforms. This work achieves an average estimation accuracy of 92.6%.

Isoscalar neutron-proton pairing and SU(4)-symmetry breaking in Gamow-Teller transitions

NASA Astrophysics Data System (ADS)

Kaneko, K.; Sun, Y.; Mizusaki, T.

2018-05-01

The isoscalar neutron-proton pairing is thought to be important for nuclei with equal number of protons and neutrons but its manifestation in structure properties remains to be understood. We investigate the Gamow-Teller (GT) transitions for the f7 /2-shell nuclei in large-scale shell-model calculations with the realistic Hamiltonian. We show that the isoscalar T =0 ,Jπ=1+ neutron-proton pairing interaction plays a decisive role for the concentration of GT strengths at the first-excited 11+ state in 42Sc, and that the suppression of these strengths in 46V, 50Mn, and 54Co is mainly caused by the spin-orbit force supplemented by the quadrupole-quadrupole interaction. Based on the good reproduction of the charge-exchange reaction data, we further analyze the interplay between the isoscalar and isovector pairing correlations. We conclude that even for the most promising A =42 nuclei where the SU(4) isoscalar-isovector-pairing symmetry is less broken, the probability of forming an isoscalar neutron-proton pairing condensation is less than 60% as compared to the expectation at the SU(4)-symmetry limit.

Nonequilibrium critical dynamics of the two-dimensional Ashkin-Teller model at the Baxter line

NASA Astrophysics Data System (ADS)

Fernandes, H. A.; da Silva, R.; Caparica, A. A.; de Felício, J. R. Drugowich

2017-04-01

We investigate the short-time universal behavior of the two-dimensional Ashkin-Teller model at the Baxter line by performing time-dependent Monte Carlo simulations. First, as preparatory results, we obtain the critical parameters by searching the optimal power-law decay of the magnetization. Thus, the dynamic critical exponents θm and θp, related to the magnetic and electric order parameters, as well as the persistence exponent θg, are estimated using heat-bath Monte Carlo simulations. In addition, we estimate the dynamic exponent z and the static critical exponents β and ν for both order parameters. We propose a refined method to estimate the static exponents that considers two different averages: one that combines an internal average using several seeds with another, which is taken over temporal variations in the power laws. Moreover, we also performed the bootstrapping method for a complementary analysis. Our results show that the ratio β /ν exhibits universal behavior along the critical line corroborating the conjecture for both magnetization and polarization.

Local probe studies on lattice distortions and electronic correlations in manganites

NASA Astrophysics Data System (ADS)

Lopes, Armandina Maria Lima

Nesta tese apresenta-se um estudo experimental das distorcoes locais e correlacoes electronicas em oxidos magneticos com magnetoresistencia colossal. A tecnica de sonda local - Correlacao Angular Perturbada - e utilizada em amostras caracterizadas quanto as suas propriedades macroscopicas nomeadamente propriedades estruturais, magneticas e electricas, tendo em vista a obtencao de informacao microscopica relevante via gradiente de campo electrico e campo magnetico hiperfino, focando em particular os seguintes aspectos: -Distorcoes de rede e agregados de polaroes no sistema LaMnO3+Delta. E apresentado um estudo dos gradientes de campo electrica e campo magnetico hiperfino em amostras representativas do sistema LaMnO3+Delta, correlacionando estas propriedades locais com a caracterizacao das propriedades macroscopicas, efectuada nas mesmas amostras. Desta forma, foi possivel estudar a natureza microscopica das distorcoes polaronicas. Foi dada especial atencao ao composto com composicao LaMnO3.12 uma vez que este e um sistema padrao de uma manganite ferromagnetica-isoladora que apresenta uma transicao estrutural romboedrica (R)-ortorrombica (O) perto da temperatura ambiente. O estudo revelou que agregados de distorcoes locais sobrevivem ate 776 K, na fase de estrutura media mais simetrica (romboedrica), onde, por simetria, os octaedros MnO6 deveriam ser regulares. Estas distorcoes sao semelhantes as observadas no sistema LaMnO3 onde os octaedros MnO6 apresentam uma distorcao Jahn-Teller colectiva. Com a diminuicao da temperatura observa-se um aumento continuo destes agregados. Abaixo de uma temperatura critica estas distorcoes relaxam acomodando-se numa estrutura com reduzidas distorcoes Jahn-teller. Verificou-se tambem que a transicao estrutural (macroscopica) pode ser entendida como uma transicao de percolacao dos ambientes microscopicos. -Coexistencia das ordens electrica e magnetica no sistema Pr1-xCaxMnO3. E apresentado o primeiro estudo de gradiente de campo

Watching the electronic motions driven by a conical intersection

NASA Astrophysics Data System (ADS)

Jonas, David

2007-03-01

In chemistry, the fastest electronic rearrangements proceed through ``conical intersections'' between electronic potential energy surfaces. With sufficiently short pulses, the electronic motion can be isolated by polarized excitation of aligned electronic wavepackets at a conical intersection. Polarized femtosecond probing reveals signatures of electronic wavepacket motion (due to the energy gaps) and of electron transfer between orbitals (due to the couplings) driven by the conical intersection. After exciting a D4h symmetry silicon naphthalocyanine molecule onto a Jahn-Teller conical intersection in the first excited state, electronic motions cause a ˜100 fs drop in the pump-probe polarization anisotropy. The polarized vibrational modulations of the signal can be used to deduce the symmetry and stabilization energies for each vibration. The initial decay of the polarization anisotropy can be quantitatively predicted from these vibrational parameters. Both coupling and energy gap variations are important on the ˜100 fs timescale. A 1 meV stabilization drives electrons from orbital to orbital in 100 fs, and the theory indicates that a chemically reactive conical intersection with 1000x greater stabilization energy could cause electronic equilibration within 2 fs. We have recently carried out experiments on a nominally D2h symmetry free-base naphthalocyanine for which the splitting between x and y polarized transitions is not resolved in the linear spectrum. For this molecule, the anisotropy also decays on a similar timescale and exhibits damped modulations whose origin (vibrational or electronic) has not yet been determined. The role of the central protons and nominal D2h symmetry in the electronic dynamics will be discussed.

Microbial Community Patterns Associated with Automated Teller Machine Keypads in New York City.

PubMed

Bik, Holly M; Maritz, Julia M; Luong, Albert; Shin, Hakdong; Dominguez-Bello, Maria Gloria; Carlton, Jane M

2016-01-01

In densely populated urban environments, the distribution of microbes and the drivers of microbial community assemblages are not well understood. In sprawling metropolitan habitats, the "urban microbiome" may represent a mix of human-associated and environmental taxa. Here we carried out a baseline study of automated teller machine (ATM) keypads in New York City (NYC). Our goal was to describe the biodiversity and biogeography of both prokaryotic and eukaryotic microbes in an urban setting while assessing the potential source of microbial assemblages on ATM keypads. Microbial swab samples were collected from three boroughs (Manhattan, Queens, and Brooklyn) during June and July 2014, followed by generation of Illumina MiSeq datasets for bacterial (16S rRNA) and eukaryotic (18S rRNA) marker genes. Downstream analysis was carried out in the QIIME pipeline, in conjunction with neighborhood metadata (ethnicity, population, age groups) from the NYC Open Data portal. Neither the 16S nor 18S rRNA datasets showed any clustering patterns related to geography or neighborhood demographics. Bacterial assemblages on ATM keypads were dominated by taxonomic groups known to be associated with human skin communities ( Actinobacteria , Bacteroides , Firmicutes , and Proteobacteria ), although SourceTracker analysis was unable to identify the source habitat for the majority of taxa. Eukaryotic assemblages were dominated by fungal taxa as well as by a low-diversity protist community containing both free-living and potentially pathogenic taxa ( Toxoplasma , Trichomonas ). Our results suggest that ATM keypads amalgamate microbial assemblages from different sources, including the human microbiome, eukaryotic food species, and potentially novel extremophilic taxa adapted to air or surfaces in the built environment. DNA obtained from ATM keypads may thus provide a record of both human behavior and environmental sources of microbes. IMPORTANCE Automated teller machine (ATM) keypads represent

Microbial Community Patterns Associated with Automated Teller Machine Keypads in New York City

PubMed Central

Maritz, Julia M.; Luong, Albert

2016-01-01

ABSTRACT In densely populated urban environments, the distribution of microbes and the drivers of microbial community assemblages are not well understood. In sprawling metropolitan habitats, the “urban microbiome” may represent a mix of human-associated and environmental taxa. Here we carried out a baseline study of automated teller machine (ATM) keypads in New York City (NYC). Our goal was to describe the biodiversity and biogeography of both prokaryotic and eukaryotic microbes in an urban setting while assessing the potential source of microbial assemblages on ATM keypads. Microbial swab samples were collected from three boroughs (Manhattan, Queens, and Brooklyn) during June and July 2014, followed by generation of Illumina MiSeq datasets for bacterial (16S rRNA) and eukaryotic (18S rRNA) marker genes. Downstream analysis was carried out in the QIIME pipeline, in conjunction with neighborhood metadata (ethnicity, population, age groups) from the NYC Open Data portal. Neither the 16S nor 18S rRNA datasets showed any clustering patterns related to geography or neighborhood demographics. Bacterial assemblages on ATM keypads were dominated by taxonomic groups known to be associated with human skin communities (Actinobacteria, Bacteroides, Firmicutes, and Proteobacteria), although SourceTracker analysis was unable to identify the source habitat for the majority of taxa. Eukaryotic assemblages were dominated by fungal taxa as well as by a low-diversity protist community containing both free-living and potentially pathogenic taxa (Toxoplasma, Trichomonas). Our results suggest that ATM keypads amalgamate microbial assemblages from different sources, including the human microbiome, eukaryotic food species, and potentially novel extremophilic taxa adapted to air or surfaces in the built environment. DNA obtained from ATM keypads may thus provide a record of both human behavior and environmental sources of microbes. IMPORTANCE Automated teller machine (ATM) keypads

β -decay scheme of 140Te to I 140 : Suppression of Gamow-Teller transitions between the neutron h9 /2 and proton h11 /2 partner orbitals

NASA Astrophysics Data System (ADS)

Moon, B.; Moon, C.-B.; Odahara, A.; Lozeva, R.; Söderström, P.-A.; Browne, F.; Yuan, C.; Yagi, A.; Hong, B.; Jung, H. S.; Lee, P.; Lee, C. S.; Nishimura, S.; Doornenbal, P.; Lorusso, G.; Sumikama, T.; Watanabe, H.; Kojouharov, I.; Isobe, T.; Baba, H.; Sakurai, H.; Daido, R.; Fang, Y.; Nishibata, H.; Patel, Z.; Rice, S.; Sinclair, L.; Wu, J.; Xu, Z. Y.; Yokoyama, R.; Kubo, T.; Inabe, N.; Suzuki, H.; Fukuda, N.; Kameda, D.; Takeda, H.; Ahn, D. S.; Shimizu, Y.; Murai, D.; Bello Garrote, F. L.; Daugas, J. M.; Didierjean, F.; Ideguchi, E.; Ishigaki, T.; Morimoto, S.; Niikura, M.; Nishizuka, I.; Komatsubara, T.; Kwon, Y. K.; Tshoo, K.

2017-07-01

We report for the first time the β -decay scheme of 140Te (Z =52 ) to 140I (Z =53 ), with a specific focus on the Gamow-Teller strength along N =87 isotones. These results were obtained in an experiment performed at the Radioactive Ion Beam Factory (RIBF), RIKEN, where the parent nuclide, 140Te, was produced through the in-flight fission of a 238U beam at 345 MeV per nucleon impinging on a 9Be target. Based on data from the high-efficiency γ -ray spectrometer, EUROBALL-RIKEN Cluster Array (EURICA), we constructed a decay scheme of 140I. The half-life of 140Te has been determined to be 350(5) ms. A level at 926 keV has been assigned as a (1+) state based on the logf t value of 4.89(6). This (1+) state, commonly observed in odd-odd nuclei, can be interpreted in terms of the π h11 /2ν h9 /2 configuration formed by the Gamow-Teller transition between a neutron in the h9 /2 orbital and a proton in the h11 /2 orbital. We observe a sharp contrast to this type of β -decay branching to the lower-lying 1+ states between 140I and 136I, where we see a large reduction as the number of neutrons increases. This is in contrast to the prediction by large-scale shell model calculations. To investigate this type of the suppression, results of the Nilsson model calculations will be discussed. Along the isotones with N =87 , we discuss a characteristic feature of the Gamow-Teller distributions at 1+ states with respect to the isospin difference.

Born-Oppenheimer and Renner-Teller coupled-channel quantum reaction dynamics of O((3)P) + H2(+)(X(2)Σg(+)) collisions.

PubMed

Gamallo, Pablo; Defazio, Paolo; González, Miguel; Paniagua, Miguel; Petrongolo, Carlo

2015-09-28

We present Born-Oppenheimer (BO) and Renner-Teller (RT) time dependent quantum dynamics studies of the reactions O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) and OH(X(2)Π) + H(+). We consider the OH2(+) X[combining tilde](2)A'' and Ã(2)A' electronic states that correlate with a linear (2)Π species. The electronic angular momenta operators L[combining circumflex] and L[combining circumflex](2) are considered in nonadiabatic coupled-channel calculations, where the associated RT effects are due to diagonal V(RT) potentials that add up to the PESs and to off-diagonal C(RT) couplings between the potential energy surfaces (PESs). Initial-state-resolved reaction probabilities PI, integral cross sections σI, and rate constants kI are obtained using recent ab initio PESs and couplings and the real wavepacket formalism. Because the PESs are strongly attractive, PI have no threshold energy and are large, σI decrease with collision energy, and kI depend little on the temperature. The X[combining tilde](2)A'' PES is up to three times more reactive than the Ã(2)A' PES and H2(+) rotational effects (j0 = 0, 1) are negligible. The diagonal V(RT) potentials are strongly repulsive at the collinearity and nearly halve all low-energy observables with respect to the BO ones. The off-diagonal C(RT) couplings are important at low partial waves, where they mix the X[combining tilde](2)A'' and Ã(2)A' states up to ∼20%. However, V(RT) effects predominate over the C(RT) ones that change at most by ∼19% the BO values of σI and kI. The reaction O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) is probably one of the most reactive atom + diatom collisions because its RT rate constant at room temperature is equal to 2.26 × 10(-10) cm(3) s(-1). Within the BO approximation, the present results agree rather well with recent quasiclassical and centrifugal-sudden data using the same PESs.

Electronic Structure of Ethynyl Substituted Cyclobutadienes

NASA Astrophysics Data System (ADS)

Emmert, Frank Lee Emmert, III; Thompson, Stephanie J.; Slipchenko, Lyudmila V.

2011-06-01

We investigated the effects of ethynyl substitution on the electronic structure of cyclobutadiene. These species are involved in Bergman Cyclization reactionsand are possible intermediates in the formation of fullerenes and graphite sheets. Prediction of the electronic energy of cyclobutadiene is challenging for single-reference ab initio methods such as HF, MP2 or DFT because of Jahn-Teller distortions and the diradical character of the singlet state. We determined the vertical and adiabatic singlet-triplet energy splittings, the natural charges and spin densities in substituted cyclobutadienes, using the equations of motion spin flip coupled cluster with single and double excitations (EOM-SF-CCSD) method that accurately describes diradical states. The adiabatic singlet-triplet gaps decrease upon substituent addition, but the singlet state is always lower in energy. However, we found that the results are affected by spin-contamination of the reference state and deteriorate when an unrestricted HF reference is employed. O. L. Chapman, C. L. McIntosh, J. Pacansky, "Cyclobutadiene" J. Am. Chem. Soc. 1973, 95, (2), 614-617. N. S. Goroff, "Mechanism of Fullerene Formation." Acc. Chem. Res. 1996, 29, (2), 77-83. L.V. Slipchenko and A.I. Krylov, "Singlet-triplet gaps in diradicals by the Spin-Flip approach: A benchmark study", J. Chem. Phys. 2002, 117, 4694-4708.

Perils of Neglecting Lattice Relaxation in the Pressure Dependence of Deep Luminescence Bands in Wide Gap Semiconductors

NASA Astrophysics Data System (ADS)

Iota, V.; Weinstein, B. A.

1998-03-01

Deep defect states are often assumed to be insensitive to pressure because of their localized atomic-like character. In apparent conflict with this, experiments on widegap II-VI materials find that the pressure shifts of many 'midgap' photoluminescence (PL) bands associated with large-lattice-relaxation defects are more rapid than the shift of the bandgap(B. Weinstein, T. Ritter, et. al., Phys. Stat. Sol. (b) 198), 167 (1996). To study this, we measured the effects of pressure on the PL and PL-excitation (PLE) bands arising from the Zn-vacancy (V_Zn) and the P_Se deep acceptor centers in ZnSe. Using the observed pressure variation of the Stokes shifts and the established 1 atm. configuration coordinate (CC) models( D.Y. Jeon, H.P Gislason, G.D. Watkins, Phys. Rev. B 48), 7872 (1993), we were able to infer quantitative CC-diagrams at any pressure. Our results show that the pressure dependence of the lattice relaxation contributes a substantial fraction (several meV/kbar) to the overall shift of the PL-bands, and, hence, must be included. For the case of the V_Zn, simple calculations of the Jahn-Teller splitting using dangling-bond orbitals support this conclusion. figures

The influence of temperature on a nutty-cake structural material: LiMn1-xFexPO4 composite with LiFePO4 core and carbon outer layer for lithium-ion battery

NASA Astrophysics Data System (ADS)

Huo, Zhen-Qing; Cui, Yu-Ting; Wang, Dan; Dong, Yue; Chen, Li

2014-01-01

The extremely low electronic conductivity, slow ion diffusion kinetics, and the Jahn-Teller effect of LiMnPO4 limit its electrochemical performance. In this work, a nutty-cake structural C-LiMn1-xFexPO4-LiFePO4 cathode material is synthesized by hydrothermal method and further calcined at different temperatures. The influence of calcination temperature on the electrochemical behavior is investigated by X-ray diffractometer, scanning electron microscope, field-emission high-resolution transmission electron microscope, energy-dispersive X-ray spectroscopy, electrochemical impedance spectroscopy and charge-discharge tests. And the performance of C-LiMn1-xFexPO4-LiFePO4 materials has a relationship with its crystal structure. The well-crystallized Sample-600 calcined at 600 °C shows the smallest charge transfer resistance, the largest lithium ion diffusion coefficient (DLi) and the best cycling stability. The discharge capacity of Sample-600 holds around 112 mAh g-1 after the 3rd cycle at 0.1 C rate. The performances improvement of C-LiMn1-xFexPO4-LiFePO4 material can be mainly attributed to the iron diffusion from the LiFePO4 core to the outer LiMnPO4 layer under appropriate calcination temperature.

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

PubMed Central

Lee, Byeongchan; Lee, Geun Woo

2016-01-01

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

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

Bazante, Alexandre P., E-mail: abazante@chem.ufl.edu; Bartlett, Rodney J.; Davidson, E. R.

The benzene radical anion is studied with ab initio coupled-cluster theory in large basis sets. Unlike the usual assumption, we find that, at the level of theory investigated, the minimum energy geometry is non-planar with tetrahedral distortion at two opposite carbon atoms. The anion is well known for its instability to auto-ionization which poses computational challenges to determine its properties. Despite the importance of the benzene radical anion, the considerable attention it has received in the literature so far has failed to address the details of its structure and shape-resonance character at a high level of theory. Here, we examinemore » the dynamic Jahn-Teller effect and its impact on the anion potential energy surface. We find that a minimum energy geometry of C{sub 2} symmetry is located below one D{sub 2h} stationary point on a C{sub 2h} pseudo-rotation surface. The applicability of standard wave function methods to an unbound anion is assessed with the stabilization method. The isotropic hyperfine splitting constants (A{sub iso}) are computed and compared to data obtained from experimental electron spin resonance experiments. Satisfactory agreement with experiment is obtained with coupled-cluster theory and large basis sets such as cc-pCVQZ.« less

Structure-related frustrated magnetism of nanosized polyoxometalates: aesthetics and properties in harmony.

PubMed

Kögerler, Paul; Tsukerblat, Boris; Müller, Achim

2010-01-07

The structural versatility characterizing polyoxometalate chemistry, in combination with the option to deliberately use well-defined building blocks, serves as the foundation for the generation of a large family of magnetic clusters, frequently comprising highly symmetric spin arrays. If the spin centers are coupled by antiferromagnetic exchange, some of these systems exhibit spin frustration, which can result in novel magnetic properties of purely molecular origins. We discuss here the magnetic properties of selected nanosized polyoxometalate clusters featuring spin triangles as their magnetic 'building blocks' or fragments. This includes unique porous Keplerate clusters of the type {(Mo)Mo(5)}(12)M(30) (M = Fe(III), Cr(III), V(IV)) with the spin centers defining a regular icosidodecahedron and the {V(15)As(6)}-type cluster sphere containing a single equilateral spin triangle; these species are widely discussed and studied in the literature for their role in materials science as molecular representations of Kagomé lattices and in relation to quantum computing, respectively. Exhibiting fascinating and unique structural features, these magnetic molecules allow the study of the implications of frustrated spin ordering. Furthermore, this perspective covers the impact of spin frustration on the degeneracy of the ground state and related problems, namely strong magnetic anisotropy and the interplay of antisymmetric exchange and structural Jahn-Teller effects.

Search for multipolar instability in URu2Si2 studied by ultrasonic measurements under pulsed magnetic field

NASA Astrophysics Data System (ADS)

Yanagisawa, T.; Mombetsu, S.; Hidaka, H.; Amitsuka, H.; Cong, P. T.; Yasin, S.; Zherlitsyn, S.; Wosnitza, J.; Huang, K.; Kanchanavatee, N.; Janoschek, M.; Maple, M. B.; Aoki, D.

2018-04-01

The elastic properties of URu2Si2 in the high magnetic field region above 40 T, over a wide temperature range from 1.5 to 120 K, were systematically investigated by means of high-frequency ultrasonic measurements. The investigation was performed at high magnetic fields to better investigate the innate bare 5 f -electron properties, since the unidentified electronic thermodynamic phase of unknown origin, the so-called "hidden order" (HO), and associated hybridization of conduction and f electrons (c -f hybridization) are suppressed at high magnetic fields. From the three different transverse modes we find contrasting results; both the Γ4(B2 g) and Γ5(Eg) symmetry modes C66 and C44 show elastic softening that is enhanced above 30 T, while the characteristic softening of the Γ3(B1 g) symmetry mode (C11-C12)/2 is suppressed in high magnetic fields. These results underscore the presence of a hybridization-driven Γ3(B1 g) lattice instability in URu2Si2 . However, the results from this work cannot be explained by using existing crystalline electric field schemes applied to the quadrupolar susceptibility in a local 5 f2 configuration. Instead, we present an analysis based on a band Jahn-Teller effect.

Optical conductivity of Nd_0.7Sr_0.3MnO_3-δ in the infrared-UV range

NASA Astrophysics Data System (ADS)

Quijada, M. A.; Drew, H. D.; Kwon, C.; Ramesh, R.; Venkatesan, T.

1997-03-01

We have measured the infrared-UV (2000-40,000 cm-1) transmittance and reflectance of thin films of Nd_0.7Sr_0.3MnO_3-δ at temperatures in the range of 15-300 K.(S.G. Kaplan et al., Phys. Rev. Lett. 77), 2081 (1996). The optical properties are derived by inverting the full Fresnel equations for a thin film on a thick substrate. The real part of the optical conductivity shows a broad peak feature near 10,000 cm-1 which shifts to lower frequency as the temperature is lowered or the magnetic field is increased. In addition, there is a redistribution of spectral weight from high to low energies as the temperature is lowered through the paramagnetic/ferromagnetic phase transition. The optical data are found to be consistent with models that include both the double-exchange interaction and the dynamic Jahn-Teller (J-T) effect on the Mn^3+ d(e_g) levels. Within these models, the conductivity peak represents the optical charge transfer transition from the lower J-T split Mn^3+ level to a neighboring Mn^4+ ion. We will also report on the sum rule analysis of the optical conductivity up to 40,000 cm-1.

Ab initio DFT+U study of He atom incorporation into UO(2) crystals.

PubMed

Gryaznov, Denis; Heifets, Eugene; Kotomin, Eugene

2009-09-07

We present and discuss results of the density functional theory (DFT) for perfect UO(2) crystals with He atoms in octahedral interstitial positions therein. We have calculated basic bulk crystal properties and He incorporation energies into the low temperature anti-ferromagnetic UO(2) phase using several exchange-correlation functionals within the spin-polarized local density (LDA) and generalized gradient (GGA) approximations. In all DFT calculations we included the on-site correlation corrections using the Hubbard model (DFT+U approach). We analysed a potential crystalline symmetry reduction from tetragonal down to orthorhombic structure and confirmed the presence of the Jahn-Teller effect in a perfect UO(2). We discuss also the problem of a conducting electronic state arising when He is placed into a tetragonal antiferromagnetic phase of UO(2) commonly used in defect modelling. Consequently, we found a specific monoclinic lattice distortion which allowed us to restore the semiconducting state and properly estimate He incorporation energies. Unlike the bulk properties, the He incorporation energy strongly depends on several factors, including the supercell size, the use of spin polarization, the exchange-correlation functionals and on-site correlation corrections. We compare our results for the He incorporation with the previous shell model and ab initio DFT calculations.

Investigation of the charge-orbital ordering mechanism in single-layered Pr0.5Ca1.5MnO4

NASA Astrophysics Data System (ADS)

Rangkuti, C. N.; Majidi, M. A.

2018-04-01

Motivated by the experimental study of half-doped single-layered Pr0.5Ca1.5MnO4 showing charge, orbital, and spin orderings [1], we propose a model to theoretically study the system to explain such ordering phenomena. The ground state electron configuration reveals that the charges form a checkerboard pattern with alternating Mn3+/Mn4+ sites, while the orbitals are aligned in zigzag chains [1, 2]. We calculate the ground state energy of this system to find the most preferable configuration by comparing three types of configurations (charge-unordered, charge-ordered, and charge-orbital-ordered states). The calculations are based on a tight-binding model representing effective electron hoppings among Mn ions in MnO2-plane. We take into account the horizontally- and vertically-oriented orbital and spin degrees of freedom at Mn sites. We assume that the hopping integral values depend on the relative orientation between the corresponding orbitals of adjacent Mn ions. The interaction terms we incorporate into our effective Hamiltonian include inter-orbital, intra-orbital Hubbard repulsions, and Jahn-Teller distortion [2]. We absorb the exchange interaction between spins into local self-energy that we calculate within dynamical mean field algorithm [2]. Within our model we show a circumstance in which the charge-orbital ordered configuration has the lowest energy, consistent with the ground state ordering revealed by the experimental data.

Cooling quasiparticles in A 3C 60 fullerides by excitonic mid-infrared absorption

NASA Astrophysics Data System (ADS)

Nava, Andrea; Giannetti, Claudio; Georges, Antoine; Tosatti, Erio; Fabrizio, Michele

2018-02-01

Long after its discovery, superconductivity in alkali fullerides A3C60 still challenges conventional wisdom. The freshest inroad in such ever-surprising physics is the behaviour under intense infrared excitation. Signatures attributable to a transient superconducting state extending up to temperatures ten times higher than the equilibrium Tc ~ 20 K have been discovered in K3C60 after ultra-short pulsed infrared irradiation--an effect which still appears as remarkable as mysterious. Motivated by the observation that the phenomenon is observed in a broad pumping frequency range that coincides with the mid-infrared electronic absorption peak still of unclear origin, rather than to transverse optical phonons as has been proposed, we advance here a radically new mechanism. First, we argue that this broad absorption peak represents a `super-exciton' involving the promotion of one electron from the t1u half-filled state to a higher-energy empty t1g state, dramatically lowered in energy by the large dipole-dipole interaction acting in conjunction with the Jahn-Teller effect within the enormously degenerate manifold of (t1u)2(t1g)1 states. Both long-lived and entropy-rich because they are triplets, the infrared-induced excitons act as a sort of cooling mechanism that permits transient superconductive signals to persist up to much higher temperatures.

Neutron diffraction study of the inverse spinels Co2TiO4 and Co2SnO4

NASA Astrophysics Data System (ADS)

Thota, S.; Reehuis, M.; Maljuk, A.; Hoser, A.; Hoffmann, J.-U.; Weise, B.; Waske, A.; Krautz, M.; Joshi, D. C.; Nayak, S.; Ghosh, S.; Suresh, P.; Dasari, K.; Wurmehl, S.; Prokhnenko, O.; Büchner, B.

2017-10-01

We report a detailed single-crystal and powder neutron diffraction study of Co2TiO4 and Co2SnO4 between the temperature 1.6 and 80 K to probe the spin structure in the ground state. For both compounds the strongest magnetic intensity was observed for the (111)M reflection due to ferrimagnetic ordering, which sets in below TN=48.6 and 41 K for Co2TiO4 and Co2SnO4 , respectively. An additional low intensity magnetic reflection (200)M was noticed in Co2TiO4 due to the presence of an additional weak antiferromagnetic component. Interestingly, from both the powder and single-crystal neutron data of Co2TiO4 , we noticed a significant broadening of the magnetic (111)M reflection, which possibly results from the disordered character of the Ti and Co atoms on the B site. Practically, the same peak broadening was found for the neutron powder data of Co2SnO4 . On the other hand, from our single-crystal neutron diffraction data of Co2TiO4 , we found a spontaneous increase of particular nuclear Bragg reflections below the magnetic ordering temperature. Our data analysis showed that this unusual effect can be ascribed to the presence of anisotropic extinction, which is associated to a change of the mosaicity of the crystal. In this case, it can be expected that competing Jahn-Teller effects acting along different crystallographic axes can induce anisotropic local strain. In fact, for both ions Ti3 + and Co3 +, the 2 tg levels split into a lower dx y level yielding a higher twofold degenerate dx z/dy z level. As a consequence, one can expect a tetragonal distortion in Co2TiO4 with c /a <1 , which we could not significantly detect in the present work.

Density functional theory study on Herzberg-Teller contribution in Raman scattering from 4-aminothiophenol-metal complex and metal-4-aminothiophenol-metal junction

NASA Astrophysics Data System (ADS)

Liu, Shasha; Zhao, Xiuming; Li, Yuanzuo; Zhao, Xiaohong; Chen, Maodu

2009-06-01

Density functional theory (DFT) and time-dependent DFT calculations have been performed to investigate the Raman scattering spectra of metal-molecule complex and metal-molecule-metal junction architectures interconnected with 4-aminothiophenol (PATP) molecule. The simulated profiles of normal Raman scattering (NRS) spectra for the two complexes (Ag2-PATP and PATP-Au2) and the two junctions (Ag2-PATP-Au2 and Au2-PATP-Ag2) are similar to each other, but exhibit obviously different Raman intensities. Due to the lager static polarizabilities of the two junctions, which directly influence the ground state chemical enhancement in NRS spectra, the calculated normal Raman intensities of them are stronger than those of two complexes by the factor of 102. We calculate preresonance Raman scattering (RRS) spectra with incident light at 1064 nm, which is much lower than the S1 electronic transition energy of complexes and junctions. Ag2-PATP-Au2 and Au2-PATP-Ag2 junctions yield higher Raman intensities than those of Ag2-PATP and PATP-Au2 complexes, especially for b2 modes. This effect is mainly attributed to charge transfer (CT) between the metal gap and the PAPT molecule which results in the occurrence of CT resonance enhancement. The calculated pre-RRS spectra strongly depend on the electronic transition state produced by new structures. With excitation at 514.5 nm, the calculated pre-RRS spectra of two complexes and two junctions are stronger than those of with excitation at 1064 nm. A charge difference densities methodology has been used to visually describe chemical enhancement mechanism of RRS spectrum. This methodology aims at visualizing intermolecular CT which provides direct evidence of the Herzberg-Teller mechanism.

Mechanisms of spin-flipping and metal-insulator transition in nano-Fe3O4

NASA Astrophysics Data System (ADS)

Dito Fauzi, Angga; Aziz Majidi, Muhammad; Rusydi, Andrivo

2017-04-01

Fe3O4 is a half-metallic ferrimagnet with {{T}\\text{C}}˜ 860 K exhibiting metal-insulator transition (MIT) at  ˜120 K. In bulk form, the saturation magnetization is 0.6 Tesla (˜471 emu cm-3). A recent experimental study has shown that the saturation magnetization of nano-Fe3O4 thin films can achieve up to  ˜760 emu cm-3, attributed to spin-flipping of Fe ions at tetrahedral sites assisted by oxygen vacancies (V O). Such a system has shown to have higher MIT temperature (˜150 K). The spin-flipping is a new phenomenon in Fe3O4, while the MIT is a long-standing one. Here, we propose a model and calculations to investigate the mechanisms of both phenomena. Our results show that, for the system without V O, the ferrimagnetic configuration is energetically favorable. Remakably, upon inclusion of V O, the ground-state configuration switches into ferromagnetic. As for the MIT, by proposing temperature dependences of some hopping integrals in the model, we demonstrate that the system without and with V O undergo the MIT in slightly different ways, leading to higher MIT temperature for the system with V O, in agreement with the experimental data. Our results also show that the MIT in both systems occur concomitantly with the redistribution of electrons among the three Fe ions in each Fe3O4 formula unit. As such temperature dependences of hopping integrals may arise due to dynamic Jahn-Teller effects, our phenomenological theory may provide a way to reconcile existing theories relating the MIT to the structural transition and the charge ordering.

Structural, vibrational, and electronic properties of an uncoordinated pseudoephedrine derivative and its mononuclear and trinuclear copper(II)-coordinated compounds: A combined theoretical and experimental study

NASA Astrophysics Data System (ADS)

Valencia, Israel; Ávila-Torres, Yenny; Barba-Behrens, Norah; Garzón, Ignacio L.

2014-11-01

Multicopper oxidases are fundamental in a variety of biological processes in bacteria, fungi and vertebrates. The catalytic center in these enzymes is formed basically by three copper ions, bridged by oxygen bonds. In order to get insights into the reactivity of these complex systems, biomimetic compounds are usually synthesized. Accordingly, in this work, we studied structural, vibrational, and electronic properties of an uncoordinated pseudoephedrine derivative, as well as its corresponding mononuclear and trinuclear copper(II)-coordinated complexes by means of density functional theory. The calculations are compared with experimental results using measurements of the infrared spectra. It is obtained that the molecular configuration of the pseudoephedrine amino-alcohol derivative is stabilized by hydrogen bonding Osbnd H⋯N and by Csbnd H⋯π interactions that are not present in the mononuclear and trinuclear compounds. The coordination compounds show octahedral and square pyramid geometries, respectively, which are slightly distorted by Jahn-Teller effects. The analysis of their theoretical and experimental IR spectra reveals signals related with hydrogen bonding as well as metal-ligand vibrational modes. Regarding the electronic structure, the density of states was calculated in order to analyze the atomic orbital contributions present in these compounds. This analysis would provide useful insights about the optical behavior, for example, in the visible region of the spectrum of the coordinated compounds. At these energies, the optical absorption would be influenced by the orbital interaction of the Cu2+d orbitals with sp ones of the ligand, reflecting a decrease of the HOMO-LUMO gap of the organic ligand due to the presence of the copper(II) ions.

Fast computation of the Gauss hypergeometric function with all its parameters complex with application to the Pöschl Teller Ginocchio potential wave functions

NASA Astrophysics Data System (ADS)

Michel, N.; Stoitsov, M. V.

2008-04-01

The fast computation of the Gauss hypergeometric function F12 with all its parameters complex is a difficult task. Although the F12 function verifies numerous analytical properties involving power series expansions whose implementation is apparently immediate, their use is thwarted by instabilities induced by cancellations between very large terms. Furthermore, small areas of the complex plane, in the vicinity of z=e, are inaccessible using F12 power series linear transformations. In order to solve these problems, a generalization of R.C. Forrey's transformation theory has been developed. The latter has been successful in treating the F12 function with real parameters. As in real case transformation theory, the large canceling terms occurring in F12 analytical formulas are rigorously dealt with, but by way of a new method, directly applicable to the complex plane. Taylor series expansions are employed to enter complex areas outside the domain of validity of power series analytical formulas. The proposed algorithm, however, becomes unstable in general when |a|, |b|, |c| are moderate or large. As a physical application, the calculation of the wave functions of the analytical Pöschl-Teller-Ginocchio potential involving F12 evaluations is considered. Program summaryProgram title: hyp_2F1, PTG_wf Catalogue identifier: AEAE_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEAE_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 6839 No. of bytes in distributed program, including test data, etc.: 63 334 Distribution format: tar.gz Programming language: C++, Fortran 90 Computer: Intel i686 Operating system: Linux, Windows Word size: 64 bits Classification: 4.7 Nature of problem: The Gauss hypergeometric function F12, with all its parameters complex, is uniquely

Quasi-Particle Relaxation and Quantum Femtosecond Magnetism in Non-Equilibrium Phases of Insulating Manganites

NASA Astrophysics Data System (ADS)

Perakis, Ilias; Kapetanakis, Myron; Lingos, Panagiotis; Barmparis, George; Patz, A.; Li, T.; Wang, Jigang

We study the role of spin quantum fluctuations driven by photoelectrons during 100fs photo-excitation of colossal magneto-resistive manganites in anti-ferromagnetic (AFM) charge-ordered insulating states with Jahn-Teller distortions. Our mean-field calculation of composite fermion excitations demonstrates that spin fluctuations reduce the energy gap by quasi-instantaneously deforming the AFM background, thus opening a conductive electronic pathway via FM correlation. We obtain two quasi-particle bands with distinct spin-charge dynamics and dependence on lattice distortions. To connect with fs-resolved spectroscopy experiments, we note the emergence of fs magnetization in the low-temperature magneto-optical signal, with threshold dependence on laser intensity characteristic of a photo-induced phase transition. Simultaneously, the differential reflectivity shows bi-exponential relaxation, with fs component, small at low intensity, exceeding ps component above threshold for fs AFM-to-FM switching. This suggests the emergence of a non-equilibrium metallic FM phase prior to establishment of a new lattice structure, linked with quantum magnetism via spin/charge/lattice couplings for weak magnetic fields.

Structure and reactivity of a mononuclear gold(II) complex

NASA Astrophysics Data System (ADS)

Preiß, Sebastian; Förster, Christoph; Otto, Sven; Bauer, Matthias; Müller, Patrick; Hinderberger, Dariush; Hashemi Haeri, Haleh; Carella, Luca; Heinze, Katja

2017-12-01

Mononuclear gold(II) complexes are very rare labile species. Transient gold(II) species have been suggested in homogeneous catalysis and in medical applications, but their geometric and electronic structures have remained essentially unexplored: even fundamental data, such as the ionic radius of gold(II), are unknown. Now, an unprecedentedly stable neutral gold(II) complex of a porphyrin derivative has been isolated, and its structural and spectroscopic features determined. The gold atom adopts a 2+2 coordination mode in between those of gold(III) (four-coordinate square planar) and gold(I) (two-coordinate linear), owing to a second-order Jahn-Teller distortion enabled by the relativistically lowered 6s orbital of gold. The reactivity of this gold(II) complex towards dioxygen, nitrosobenzene and acids is discussed. This study provides insight on the ionic radius of gold(II), and allows it to be placed within the homologous series of nd9 Cu/Ag/Au divalent ions and the 5d8/9/10 Pt/Au/Hg 'relativistic' triad in the periodic table.

Structural and catalytic characterization of a heterovalent Mn(II)Mn(III) complex that mimics purple acid phosphatases.

PubMed

Smith, Sarah J; Riley, Mark J; Noble, Christopher J; Hanson, Graeme R; Stranger, Robert; Jayaratne, Vidura; Cavigliasso, Germán; Schenk, Gerhard; Gahan, Lawrence R

2009-11-02

The binuclear heterovalent manganese model complex [Mn(II)Mn(III)(L1)(OAc)(2)] ClO(4) x H(2)O (H(2)L1 = 2-(((3-((bis(pyridin-2-ylmethyl)amino)methyl)-2-hydroxy-5-methylbenzyl)(pyridin-2-ylmethyl)amino)-methyl)phenol) has been prepared and studied structurally, spectroscopically, and computationally. The magnetic and electronic properties of the complex have been related to its structure. The complex is weakly antiferromagnetically coupled (J approximately -5 cm(-1), H = -2J S(1) x S(2)) and the electron paramagnetic resonance (EPR) and magnetic circular dichroism (MCD) spectra identify the Jahn-Teller distortion of the Mn(III) center as predominantly a tetragonal compression, with a significant rhombic component. Electronic structure calculations using density functional theory have confirmed the conclusions derived from the experimental investigations. In contrast to isostructural M(II)Fe(III) complexes (M = Fe, Mn, Zn, Ni), the Mn(II)Mn(III) system is bifunctional possessing both catalase and hydrolase activities, and only one catalytically relevant pK(a) (= 8.2) is detected. Mechanistic implications are discussed.

Structural transition in Mg-doped LiMn 2O 4: a comparison with other M-doped Li-Mn spinels

NASA Astrophysics Data System (ADS)

Capsoni, Doretta; Bini, Marcella; Chiodelli, Gaetano; Massarotti, Vincenzo; Mozzati, Maria Cristina; Azzoni, Carlo B.

2003-01-01

The charge distribution in the Mg-doped lithium manganese spinel Li 1.02Mg xMn 1.98- xO 4 with 0.00< x≤0.20 is discussed and compared to those pertinent to other M-doped samples (M=Ni 2+, Co 3+, Cr 3+, Al 3+ and Ga 3+). EPR spectra, low temperature X-ray diffraction and conductivity data are related to the cooperative Jahn-Teller (J-T) transition occurring at about 280 K in the undoped sample. The sensitivity of the cationic sublattice in displaying electronic and magnetic changes after substitution is remarked. The inhibition of the J-T transition is related to the ratio r=|Mn 4+|/|Mn 3+| as deduced from the charge distribution model [Li 1- xt+Mg xt2+] tetr[Li y+ xt+Mg xo2+Mn 1-3 y-2 x3+Mn 1+2 y+ x4+] octa where x= xo+ xt. For y=0.02 and x=0.02, a value r=1.177 is obtained, very close to rlim=1.18, the limit value beyond which the transition is inhibited.

Crystal Growth of the S =1/2 Antiferromagnet K2PbCu(NO2)6 Elpasolite

NASA Astrophysics Data System (ADS)

Dong, Lianyang; Besara, Tiglet; Siegrist, Theo

The elpasolite K2PbCu(NO2)6is known for its two structural transitions at 281 K and 273 K. Single crystals of K2PbCu(NO2)6 have been grown in aqueous solution, but the rapid nucleation rate and convective transport renders it difficult to obtain large high quality single crystals. We developed a gel method to grow K2PbCu(NO2)6 Elpasolite with sizes up to 5x5x5 mm3, suitable for neutron diffraction measurements. Susceptibility measurements clearly show that the Jahn-Teller distortions at 286K and 273K with associated orbital ordering produce a linear chain Heisenberg antiferromagnetic system. The intrachain interaction strength has been derived from a Bonner-Fisher analysis that yielded a value of 5.4K. This work was supported by the National Science Foundation, under award DMR-1534818. A portion of this work has been performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement.

Habit plane-driven P2-type manganese-based layered oxide as long cycling cathode for Na-ion batteries

NASA Astrophysics Data System (ADS)

Luo, Rui; Wu, Feng; Xie, Man; Ying, Yao; Zhou, Jiahui; Huang, Yongxin; Ye, Yusheng; Li, Li; Chen, RenJie

2018-04-01

Layered transition metal oxides are considered to be promising candidates as cathode materials for sodium-ion batteries. Herein, a facile solid-state reaction is developed to synthesize hexagons plate-like Na0.67Ni0.25Mn0.75O2+δ (denoted as P2-NNM) material with habit plane formed. The structure of this layered oxide is characterized by XRD, HR-TEM and SAED. The layered material delivers a high reversible capacity of 91.8 mAh g-1 at 0.2 C with a capacity retention of 94.4 % after 280 cycles, superior rate capability and long cycle life (84.2 % capacity retention after 1000 cycle). Ni2+ is an active ion and Ni doping alleviates the Jahn-Teller distortion, and Mn3+/Mn4+ coexist as Mn4+ is desired from the stability perspective. Particularly, CV and XPS results confirm these results. Moreover, the electrode exhibits a quasi-solid-solution reaction during the sodium extraction and insertion. This contribution demonstrates that P2-NNM is a promising cathode electrode for rechargeable long-life sodium-ion batteries.

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

NASA Astrophysics Data System (ADS)

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

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

Structure-activity correlations in a nickel-borate oxygen evolution catalyst.

PubMed

Bediako, D Kwabena; Lassalle-Kaiser, Benedikt; Surendranath, Yogesh; Yano, Junko; Yachandra, Vittal K; Nocera, Daniel G

2012-04-18

An oxygen evolution catalyst that forms as a thin film from Ni(aq)(2+) solutions containing borate electrolyte (Ni-B(i)) has been studied by in situ X-ray absorption spectroscopy. A dramatic increase in catalytic rate, induced by anodic activation of the electrodeposited films, is accompanied by structure and oxidation state changes. Coulometric measurements correlated with X-ray absorption near-edge structure spectra of the active catalyst show that the nickel centers in activated films possess an average oxidation state of +3.6, indicating that a substantial proportion of nickel centers exist in a formal oxidation state of Ni(IV). In contrast, nickel centers in nonactivated films exist predominantly as Ni(III). Extended X-ray absorption fine structure reveals that activated catalyst films comprise bis-oxo/hydroxo-bridged nickel centers organized into sheets of edge-sharing NiO(6) octahedra. Diminished long-range ordering in catalyst films is due to their ostensibly amorphous nature. Nonactivated films display a similar oxidic nature but exhibit a distortion in the local coordination geometry about nickel centers, characteristic of Jahn-Teller distorted Ni(III) centers. Our findings indicate that the increase in catalytic activity of films is accompanied by changes in oxidation state and structure that are reminiscent of those observed for conversion of β-NiOOH to γ-NiOOH and consequently challenge the long-held notion that the β-NiOOH phase is a more efficient oxygen-evolving catalyst. © 2012 American Chemical Society

Role of 5f electrons in the structural stability of light actinide (Th-U) mononitrides under pressure.

PubMed

Modak, P; Verma, Ashok K

2016-03-28

Pressure induced structural sequences and their mechanism for light actinide (Th-U) mononitrides were studied as a function of 5f-electron number using first-principles total energy and electronic structure calculations. Zero pressure lattice constants, bulk module and C11 elastic module vary systematically with 5f-electron number implying its direct role on crystal binding. There is a critical 5f-electron number below which the system makes B1-B2 and above it B1-R3̄m-B2 structural sequence under pressure. Also, the B1-B2 transition pressure increases with increasing 5f-electron number whereas an opposite trend is obtained for the B1-R3̄m transition pressure. The ascending of N p anti-bonding states through the Fermi level at high pressure is responsible for the structural instability of the system. Above the critical 5f-electron number in the system a narrow 5f-band occurs very close to the Fermi level which allows the system to lower its symmetry via band Jahn-Teller type lattice distortion and the system undergoes a B1-R3̄m phase transition. However, below the critical 5f-electron number this mechanism is not favorable due to a lack of sufficient 5f-state occupancy and thus the system undergoes a B1-B2 phase transition like other ionic solids.

Redox non-innocence of thioether crowns: spectroelectrochemistry and electronic structure of formal nickel(III) complexes of aza-thioether macrocycles.

PubMed

Stephen, Emma; Huang, Deguang; Shaw, Jennifer L; Blake, Alexander J; Collison, David; Davies, E Stephen; Edge, Ruth; Howard, Judith A K; McInnes, Eric J L; Wilson, Claire; Wolowska, Joanna; McMaster, Jonathan; Schröder, Martin

2011-09-05

The Ni(II) complexes [Ni([9]aneNS(2)-CH(3))(2)](2+) ([9]aneNS(2)-CH(3)=N-methyl-1-aza-4,7-dithiacyclononane), [Ni(bis[9]aneNS(2)-C(2)H(4))](2+) (bis[9]aneNS(2)-C(2)H(4)=1,2-bis-(1-aza-4,7-dithiacyclononylethane) and [Ni([9]aneS(3))(2)](2+) ([9]aneS(3)=1,4,7-trithiacyclononane) have been prepared and can be electrochemically and chemically oxidized to give the formal Ni(III) products, which have been characterized by X-ray crystallography, UV/Vis and multi-frequency EPR spectroscopy. The single-crystal X-ray structure of [Ni(III)([9]aneNS(2)-CH(3))(2)](ClO(4))(6)·(H(5)O(2))(3) reveals an octahedral co-ordination at the Ni centre, while the crystal structure of [Ni(III)(bis[9]aneNS(2)-C(2)H(4))](ClO(4))(6)·(H(3)O)(3)·3H(2)O exhibits a more distorted co-ordination. In the homoleptic analogue, [Ni(III)([9]aneS(3))(2)](ClO(4))(3), structurally characterized at 30 K, the Ni-S distances [2.249(6), 2.251(5) and 2.437(2) Å] are consistent with a Jahn-Teller distorted octahedral stereochemistry. [Ni([9]aneNS(2)-CH(3))(2)](PF(6))(2) shows a one-electron oxidation process in MeCN (0.2 M NBu(4)PF(6), 293 K) at E(½)=+1.10 V versus Fc(+)/Fc assigned to a formal Ni(III)/Ni(II) couple. [Ni(bis[9]aneNS(2)-C(2)H(4))](PF(6))(2) exhibits a one-electron oxidation process at E(½)=+0.98 V and a reduction process at E(½)=-1.25 V assigned to Ni(II)/Ni(III) and Ni(II)/Ni(I) couples, respectively. The multi-frequency X-, L-, S-, K-band EPR spectra of the 3+ cations and their 86.2% (61)Ni-enriched analogues were simulated. Treatment of the spin Hamiltonian parameters by perturbation theory reveals that the SOMO has 50.6%, 42.8% and 37.2% Ni character in [Ni([9]aneNS(2)-CH(3))(2)](3+), [Ni(bis[9]aneNS(2)-C(2)H(4))](3+) and [Ni([9]aneS(3))(2)](3+), respectively, consistent with DFT calculations, and reflecting delocalisation of charge onto the S-thioether centres. EPR spectra for [(61)Ni([9]aneS(3))(2)](3+) are consistent with a dynamic Jahn-Teller distortion in this compound. Copyright �

Microstructural, Magnetic, and Optical Properties of Pr-Doped Perovskite Manganite La0.67Ca0.33MnO3 Nanoparticles Synthesized via Sol-Gel Process

NASA Astrophysics Data System (ADS)

Xia, Weiren; Wu, Heng; Xue, Piaojie; Zhu, Xinhua

2018-05-01

We report on microstructural, magnetic, and optical properties of Pr-doped perovskite manganite (La1 - xPrx)0.67Ca0.33MnO3 (LPCMO, x = 0.0-0.5) nanoparticles synthesized via sol-gel process. Structural characterizations (X-ray and electron diffraction patterns, (high resolution) TEM images) provide information regarding the phase formation and the single-crystalline nature of the LPCMO systems. X-ray and electron diffraction patterns reveal that all the LPCMO samples crystallize in perovskite crystallography with an orthorhombic structure ( Pnma space group), where the MnO6 octahedron is elongated along the b axis due to the Jahn-Teller effect. That is confirmed by Raman spectra. Crystallite sizes and grain sizes were calculated from XRD and TEM respectively, and the lattice fringes resolved in the high-resolution TEM images of individual LPCMO nanoparticle confirmed its single-crystalline nature. FTIR spectra identify the characteristic Mn-O bond stretching vibration mode near 600 cm- 1, which shifts towards high wavenumbers with increasing post-annealing temperature or Pr-doping concentration, resulting in further distortion of the MnO6 octahedron. XPS revealed dual oxidation states of Mn3+ and Mn4+ in the LPCMO nanoparticles. UV-vis absorption spectra confirm the semiconducting nature of the LPCMO nanoparticles with optical bandgaps of 2.55-2.71 eV. Magnetic measurements as a function of temperature and magnetic field at field cooling and zero-field cooling modes, provided a Curie temperature around 230 K, saturation magnetization of about 81 emu/g, and coercive field of 390 Oe at 10 K. Such magnetic properties and the semiconducting nature of the LPCMO nanoparticles will make them as suitable candidate for magnetic semiconductor spintronics.

Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

PubMed

Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

2013-03-06

Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface.

Tuning the Curie temperature of epitaxial Nd0.6Sr0.4MnO3 thin films

NASA Astrophysics Data System (ADS)

Bhat, Shwetha G.; Kumar, P. S. Anil

2018-02-01

NdxSr1-xMnO3 (0.2 ≤ x ≤ 0.5) systems are widely studied in magnetism, popular for high colossal magnetoresistance and are ferromagnetic oxides with TC ranging from 200 K to 300 K. Recently, many of such compounds are re-visited for exploring the correlation of spin, charge and lattice degrees of freedom. Although, manganite thin films are the ideal candidates for studying the electron-correlation effects, the puzzle of obtaining a high quality epitaxial thin films of NdxSr1-xMnO3 are still unsolved contrary to its sister compound LaxSr1-xMnO3. Hence, in this study, we demonstrate the growth of best quality of Nd0.6Sr0.4MnO3 (NSMO) epitaxial thin films. This is evident from the TC and a sharp insulator-to-metal transition (IMT) coinciding at as high as ∼255 K against the bulk TC (∼270 K). It is the highest reported TC in Nd0.6Sr0.4MnO3 thin films to date. Moreover, as-deposited films with in situ oxygen annealing are not enough to relax the lattice of NSMO films due to the significant Jahn-Teller distortion in the film. With ex situ annealing processes alongside the various deposition and in situ annealing conditions, we have extensively studied the growth of epitaxial NSMO thin films on LaAlO3 (0 0 1) and SrTiO3 (0 0 1) to investigate the evolution of lattice and its one-to-one correspondence with the magnetism and the electrical properties of thin films. Accordingly, the enhanced magnetization, reduced resistivity and the higher TC and IMT of the NSMO films obtained from our extensive growth analysis looks promising for the future applications across the TC and IMT.

Synthesis, structure, properties and immobilization on a gold surface of the monoribbed-functionalized tris-dioximate cobalt(II) clathrochelates and an electrocatalytic hydrogen production from H+ ions.

PubMed

Voloshin, Y Z; Belov, A S; Vologzhanina, A V; Aleksandrov, G G; Dolganov, A V; Novikov, V V; Varzatskii, O A; Bubnov, Y N

2012-05-28

The cycloaddition of the mono- and dichloroglyoximes to the cobalt(II) bis-α-benzyldioximate afforded the cobalt(II) mono- and dichloroclathrochelates in moderate yields (40-60%). These complexes undergo nucleophilic substitution of their reactive chlorine atoms with aliphatic amines, alcohols and thiolate anions. In the case of ethylenediamine and 1,2-ethanedithiol, only the macrobicyclic products with α,α'-N(2)- and α,α'-S(2)-alicyclic six-numbered ribbed fragments were obtained. The cobalt(II) cage complexes with terminal mercapto groups were synthesized using aliphatic dithiols. The crystal and molecular structures of the six cobalt(II) clathrochelates were obtained by X-ray diffraction. Their CoN(6)-coordination polyhedra possess a geometry intermediate between a trigonal prism and a trigonal antiprism, and the encapsulated cobalt(II) ions are shifted from their centres due to the structural Jahn-Teller effect with the Co-N distances varying significantly (by 0.10-0.26 Å). The electrochemistry of the complexes obtained was studied by cyclic voltammetry (CV). The anodic waves correspond to the quasi-reversible Co(2+/3+) oxidations, whereas the cathodic ranges contain the quasi-reversibile waves assigned to the Co(2+/+) reductions; all the cobalt(i)-containing clathrochelate anions formed are stable in the CV time scale. The electrocatalytic properties of the cobalt complexes obtained were studied in the production of hydrogen from H(+) ions: the addition of HClO(4) resulted in the formation of the same catalytic cathodic reduction Co(2+/+) waves. The controlled-potential electrolysis with gas chromatography analysis confirmed the production of H(2) in high Faraday yields. The efficiency of this electrocatalytic process was enhanced by an immobilization of the complexes with terminal mercapto groups on a surface of the working gold electrode.

Microstructural, Magnetic, and Optical Properties of Pr-Doped Perovskite Manganite La0.67Ca0.33MnO3 Nanoparticles Synthesized via Sol-Gel Process.

PubMed

Xia, Weiren; Wu, Heng; Xue, Piaojie; Zhu, Xinhua

2018-05-04

We report on microstructural, magnetic, and optical properties of Pr-doped perovskite manganite (La 1 - x Pr x ) 0.67 Ca 0.33 MnO 3 (LPCMO, x = 0.0-0.5) nanoparticles synthesized via sol-gel process. Structural characterizations (X-ray and electron diffraction patterns, (high resolution) TEM images) provide information regarding the phase formation and the single-crystalline nature of the LPCMO systems. X-ray and electron diffraction patterns reveal that all the LPCMO samples crystallize in perovskite crystallography with an orthorhombic structure (Pnma space group), where the MnO 6 octahedron is elongated along the b axis due to the Jahn-Teller effect. That is confirmed by Raman spectra. Crystallite sizes and grain sizes were calculated from XRD and TEM respectively, and the lattice fringes resolved in the high-resolution TEM images of individual LPCMO nanoparticle confirmed its single-crystalline nature. FTIR spectra identify the characteristic Mn-O bond stretching vibration mode near 600 cm - 1 , which shifts towards high wavenumbers with increasing post-annealing temperature or Pr-doping concentration, resulting in further distortion of the MnO 6 octahedron. XPS revealed dual oxidation states of Mn 3+ and Mn 4+ in the LPCMO nanoparticles. UV-vis absorption spectra confirm the semiconducting nature of the LPCMO nanoparticles with optical bandgaps of 2.55-2.71 eV. Magnetic measurements as a function of temperature and magnetic field at field cooling and zero-field cooling modes, provided a Curie temperature around 230 K, saturation magnetization of about 81 emu/g, and coercive field of 390 Oe at 10 K. Such magnetic properties and the semiconducting nature of the LPCMO nanoparticles will make them as suitable candidate for magnetic semiconductor spintronics.

Cu2+ Dual-Doped Layer-Tunnel Hybrid Na0.6Mn1- xCu xO2 as a Cathode of Sodium-Ion Battery with Enhanced Structure Stability, Electrochemical Property, and Air Stability.

PubMed

Chen, Ting-Ru; Sheng, Tian; Wu, Zhen-Guo; Li, Jun-Tao; Wang, En-Hui; Wu, Chun-Jin; Li, Hong-Tai; Guo, Xiao-Dong; Zhong, Ben-He; Huang, Ling; Sun, Shi-Gang

2018-03-28

Sodium-ion batteries (SIBs) have been regarded as a promising candidate for large-scale renewable energy storage system. Layered manganese oxide cathode possesses the advantages of high energy density, low cost and natural abundance while suffering from limited cycling life and poor rate capacity. To overcome these weaknesses, layer-tunnel hybrid material was developed and served as the cathode of SIB, which integrated high capacity, superior cycle ability, and rate performance. In the current work, the doping of copper was adopted to suppress the Jahn-Teller effect of Mn 3+ and to affect relevant structural parameters. Multifunctions of the Cu 2+ doping were carefully investigated. It was found that the structure component ratio is varied with the Cu 2+ doping amount. Results demonstrated that Na + /vacancy rearrangement and phase transitions were suppressed during cycling without sacrificing the reversible capacity and enhanced electrochemical performances evidenced with 96 mA h g -1 retained after 250 cycles at 4 C and 85 mA h g -1 at 8 C. Furthermore, ex situ X-ray diffraction has demonstrated high reversibility of the Na 0.6 Mn 0.9 Cu 0.1 O 2 cathode during Na + extraction/insertion processes and superior air stability that results in better storage properties. This study reveals that the Cu 2+ doping could be an effective strategy to tune the properties and related performances of Mn-based layer-tunnel hybrid cathode.

Enhancement of tetragonal anisotropy and stabilisation of the tetragonal phase by Bi/Mn-double-doping in BaTiO3 ferroelectric ceramics

PubMed Central

Yabuta, Hisato; Tanaka, Hidenori; Furuta, Tatsuo; Watanabe, Takayuki; Kubota, Makoto; Matsuda, Takanori; Ifuku, Toshihiro; Yoneda, Yasuhiro

2017-01-01

To stabilise ferroelectric-tetragonal phase of BaTiO3, the double-doping of Bi and Mn up to 0.5 mol% was studied. Upon increasing the Bi content in BaTiO3:Mn:Bi, the tetragonal crystal-lattice-constants a and c shrank and elongated, respectively, resulting in an enhancement of tetragonal anisotropy, and the temperature-range of the ferroelectric tetragonal phase expanded. X-ray absorption fine structure measurements confirmed that Bi and Mn were located at the A(Ba)-site and B(Ti)-site, respectively, and Bi was markedly displaced from the centrosymmetric position in the BiO12 cluster. This A-site substitution of Bi also caused fluctuations of B-site atoms. Magnetic susceptibility measurements revealed a change in the Mn valence from +4 to +3 upon addition of the same molar amount of Bi as Mn, probably resulting from a compensating behaviour of the Mn at Ti4+ sites for donor doping of Bi3+ into the Ba2+ site. Because addition of La3+ instead of Bi3+ showed neither the enhancement of the tetragonal anisotropy nor the stabilisation of the tetragonal phase, these phenomena in BaTiO3:Mn:Bi were not caused by the Jahn-Teller effect of Mn3+ in the MnO6 octahedron, but caused by the Bi-displacement, probably resulting from the effect of the 6 s lone-pair electrons in Bi3+. PMID:28367973

Theory and experimental evidence of phonon domains and their roles in pre-martensitic phenomena

NASA Astrophysics Data System (ADS)

Jin, Yongmei M.; Wang, Yu U.; Ren, Yang

2015-12-01

Pre-martensitic phenomena, also called martensite precursor effects, have been known for decades while yet remain outstanding issues. This paper addresses pre-martensitic phenomena from new theoretical and experimental perspectives. A statistical mechanics-based Grüneisen-type phonon theory is developed. On the basis of deformation-dependent incompletely softened low-energy phonons, the theory predicts a lattice instability and pre-martensitic transition into elastic-phonon domains via 'phonon spinodal decomposition.' The phase transition lifts phonon degeneracy in cubic crystal and has a nature of phonon pseudo-Jahn-Teller lattice instability. The theory and notion of phonon domains consistently explain the ubiquitous pre-martensitic anomalies as natural consequences of incomplete phonon softening. The phonon domains are characterised by broken dynamic symmetry of lattice vibrations and deform through internal phonon relaxation in response to stress (a particular case of Le Chatelier's principle), leading to previously unexplored new domain phenomenon. Experimental evidence of phonon domains is obtained by in situ three-dimensional phonon diffuse scattering and Bragg reflection using high-energy synchrotron X-ray single-crystal diffraction, which observes exotic domain phenomenon fundamentally different from usual ferroelastic domain switching phenomenon. In light of the theory and experimental evidence of phonon domains and their roles in pre-martensitic phenomena, currently existing alternative opinions on martensitic precursor phenomena are revisited.

Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2

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

Trease, Nicole M.; Seymour, Ieuan D.; Radin, Maxwell D.

2016-11-22

The doping of Al into layered Li transition metal (TM) oxide cathode materials, LiTMO 2, is known to improve the structural and thermal stability, although the origin of the enhanced properties is not well understood. The effect of aluminum doping on layer stabilization has been investigated using a combination of techniques to measure the aluminum distribution in layered LiNi 0.8Co 0.15Al 0.05O 2 (NCA) over multiple length scales with 27Al and 7Li MAS NMR, local electrode atom probe (APT) tomography, X-ray and neutron diffraction, DFT, and SQUID magnetic susceptibility measurements. APT ion maps show a homogenous distribution of Ni, Co,more » Al and O 2 throughout the structure at the single particle level in agreement with the high-temperature phase diagram. 7Li and 27Al NMR indicates that the Ni 3+ ions undergo a dynamic Jahn-Teller (JT) distortion. 27Al NMR spectra indicate that the Al reduces the strain associated with the JT distortion, by preferential electronic ordering of the JT long bonds directed toward the Al 3+ ion. The ability to understand the complex atomic and orbital ordering around Al 3+ demonstrated in the current method will be useful for studying the local environment of Al 3+ in a range of transition metal oxide battery materials.« less

Identifying the Distribution of Al 3+ in LiNi 0.8 Co 0.15 Al 0.05 O 2

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

Trease, Nicole M.; Seymour, Ieuan D.; Radin, Maxwell D.

2016-10-07

The doping of Al into layered Li transition metal (TM) oxide cathode materials, LiTMO 2, is known to improve the structural and thermal stability, although the origin of the enhanced properties is not well understood. We have investigated the effect of aluminum doping on layer stabilization using a combination of techniques to measure the aluminum distribution in layered LiNi 0.8Co 0.15Al 0.05O 2 (NCA) over multiple length scales with 27Al and 7Li MAS NMR, local electron atom probe (LEAP) tomography, X-ray and neutron diffraction, DFT, and SQUID magnetic susceptibility measurements. LEAP tomographic maps show a homogenous distribution of Ni, Co,more » Al and O 2 throughout the structure at the particle level in agreement with the hightemperature phase diagram. 7Li and 27Al NMR indicates that the Ni 3+ ions undergo a dynamic Jahn-Teller (JT) distortion. 27Al NMR spectra indicate that the Al reduces the strain associated with the JT distortion, by preferential electronic ordering of the JT long bonds directed toward the Al 3+ ion. Our ability to understand the complex atomic and orbital ordering around Al 3+ demonstrated in the current method will be useful for studying the local environment of Al 3+ in a range of transition metal oxide battery materials.« less

Twinned low-temperature structures of tris(ethylenediamine)zinc(II) sulfate and tris(ethylenediamine)copper(II) sulfate.

PubMed

Lutz, Martin

2010-11-01

Tris(ethylenediamine)zinc(II) sulfate, [Zn(C(2)H(8)N(2))(3)]SO(4), (I), undergoes a reversible solid-solid phase transition during cooling, accompanied by a lowering of the symmetry from high-trigonal P31c to low-trigonal P3 and by merohedral twinning. The molecular symmetries of the cation and anion change from 32 (D(3)) to 3 (C(3)). This lower symmetry allows an ordered sulfate anion and generates in the complex cation two independent N atoms with significantly different geometries. The twinning is the same as in the corresponding Ni complex [Jameson et al. (1982). Acta Cryst. B38, 3016-3020]. The low-temperature phase of tris(ethylenediamine)copper(II) sulfate, [Cu(C(2)H(8)N(2))(3)]SO(4), (II), has only triclinic symmetry and the unit-cell volume is doubled with respect to the room-temperature structure in P31c. (II) was refined as a nonmerohedral twin with five twin domains. The asymmetric unit contains two independent formula units, and all cations and anions are located on general positions with 1 (C(1)) symmetry. Both molecules of the Cu complex are in elongated octahedral geometries because of the Jahn-Teller effect. This is in contrast to an earlier publication, which describes the complex as a compressed octahedron [Bertini et al. (1979). J. Chem. Soc. Dalton Trans. pp. 1409-1414].

Topological magnetic phase in LaMnO3 (111) bilayer

NASA Astrophysics Data System (ADS)

Weng, Yakui; Huang, Xin; Yao, Yugui; Dong, Shuai

2015-11-01

Candidates for correlated topological insulators, originated from the spin-orbit coupling as well as the Hubbard-type correlation, are expected in the (111) bilayer of perovskite-structural transition-metal oxides. Based on the first-principles calculation and tight-binding model, the electronic structure of a LaMnO3 (111) bilayer sandwiched in LaScO3 barriers has been investigated. For the ideal undistorted perovskite structure, the Fermi energy of LaMnO3 (111) bilayer just stays at the Dirac point, rendering a semimetal (graphenelike) which is also a half metal [different from graphene or the previously studied LaNiO3 (111) bilayer]. The Dirac cone can be opened by the spin-orbit coupling, giving rise to nontrivial topological bands corresponding to the (quantized) anomalous Hall effect. For the realistic orthorhombic distorted lattice, the Dirac point moves with increasing Hubbard repulsion (or equivalent Jahn-Teller distortion). Finally, a Mott gap opens, establishing a phase boundary between the Mott insulator and topological magnetic insulator. Our calculation finds that the gap opened by spin-orbit coupling is much smaller in the orthorhombic distorted lattice (˜1.7 meV) than the undistorted one (˜11 meV). Therefore, to suppress the lattice distortion can be helpful to enhance the robustness of the topological phase in perovskite (111) bilayers.

Different Effects of Al Substitution for Mn or Fe on the Structure and Electrochemical Properties of Na0.67Mn0.5Fe0.5O2 as a Sodium Ion Battery Cathode Material.

PubMed

Wang, Huibo; Gao, Rui; Li, Zhengyao; Sun, Limei; Hu, Zhongbo; Liu, Xiangfeng

2018-05-07

P2-type layered oxides based on the elements Fe and Mn have attracted great interest as sodium ion battery (SIB) cathode materials owing to their inexpensive metal constituents and high specific capacity. However, they suffer from rapid capacity fading and complicated phase transformations. In this study, we modulate the crystal structure and optimize the electrochemical performances of Na 0.67 Mn 0.5 Fe 0.5 O 2 by Al doping for Mn or Fe, respectively, and the roles of Al in the enhancement of the rate capability and cycling performance are unraveled. (1) The substitution of Al for Mn or Fe decreases the lattice parameters a and c but enlarges d spacing and lengthens Na-O bonds, which enhances Na + diffusion and rate capability especially for Na 0.67 Mn 0.5 Fe 0.47 Al 0.03 O 2 . (2) Al doping reduces the thickness of TMO 2 and strengthens TM-O/O-O bonding. This enhances the layered structure stability and the capacity retention. (3) Al doping mitigates Mn 3+ and Jahn-Teller distortion, mitigating the irreversible phase transition. (4) Al doping also alleviates the lattice volume variation and the structure strain. This further improves the stability of the layered structure and the cycling performances particularly in the case of Al doping for Fe. The in-depth insights into the roles of Al substitution might be also useful for designing high-performance cathode materials for SIBs through appropriate lattice doping.

Analysis of Rotationally Resolved Spectra to Non-Degenerate (a''_1) Upper-State Vibronic Levels in the tilde{A} ^2E''-tilde{X}^2A^'_2 Electronic Transition of NO_3

NASA Astrophysics Data System (ADS)

Roudjane, Mourad; Codd, Terrance Joseph; Chen, Ming-Wei; Tran, Henry; Melnik, Dmitry G.; Miller, Terry A.; Stanton, John F.

2015-06-01

The vibronic structure of the tilde{A}-tilde{X} electronic spectrum of NO_3 has been observed using both room-temperature and jet-cooled samples. A recent analysis of this structure is consistent with the Jahn-Teller effect (JTE) in the e^' ν_3 vibrational mode (N-O stretch) being quite strong while the JTE in the e^' ν_4 mode (O-N-O) bend) is rather weak. Electronic structure calculations qualitatively predict these results but the calculated magnitude of the JTE is quantitatively inconsistent with the spectral analysis. Rotationally resolved spectra have been obtained for over a dozen vibronic bands of the tilde{A}-tilde{X} electronic transition in NO_3. An analysis of these spectra should provide considerably more experimental information about the JTE in the tilde{A} state of NO_3 as the rotational structure should be quite sensitive to the geometric distortion of the molecule due to the JTE. This talk will focus upon the parallel bands, which terminate on tilde{A} state levels of a''_1 vibronic symmetry, which were the subject of a preliminary analysis reported at this meeting in 2014. We have now recorded the rotational structure of over a half-dozen parallel bands and have completed analysis on the 3^1_0 and 3^1_0 4^1_0 transitions with several other bands being reasonably well understood. Two general conclusions emerge from this work. (i) All the spectral bands show evidence of perturbations which can reasonably be assumed to result from interactions of the observed tilde{A} state levels with high vibrational levels of the tilde{X} state. The perturbations range from severe in some bands to quite modest in others. (ii) Analyses of observed spectra, insofar as the perturbations permit, have all been performed with an oblate symmetric top model including only additional spin-rotation effects. This result is, of course, consistent with an effective, undistorted geometry for NO_3 of D3h symmetry on the rotational timescale.

Antibiogram of bacteria isolated from automated teller machines in Hamadan, West Iran

PubMed Central

Mahmoudi, Hassan; Arabestani, Mohammad Reza; Alikhani, Mohammad Yousef; Sedighi, Iraj; Kohan, Hamed Farhadi; Molavi, Mohammad

2017-01-01

Aim: Bacteria are ubiquitous in the environment. In keeping with the continued expansion of urbanization and the growing population, an increasing number of people use automated banking, i.e. automated teller machines (ATMs). The aim of this study was to investigate the bacterial contamination and its antibiotic sensitivity on computer keyboards located at ATMs in Hamadan province, Iran. Method: Out of 360 ATMs at four locations in Hamadan, 96 were randomly selected for this study. The antibiotic susceptibility pattern of all isolates was determined by the agar disk diffusion method using gentamicin (10 µg), vancomycin (30 µg), trimethoprim/sulfamethoxazole (25 µg), amikacin (30 µg), tobramycin (10 µg), cephalotin (30 µg), norfloxacin (5 µg), and ceftizoxim (30 µg) disks. Results: Melli and Saderat Banks had the most frequently contaminated ATMS, with 18 (27.7%) and 12 (18.5%), respectively. The most frequently isolated bacteria were Staphylococcus epidermidis in 12 (18.5%) ATMs, Pseudomonas aeruginosa in 12 (18.5%), Bacillus subtilis in 11 (16.9%), Escherichia coli in 6 (9.2%), Klebsiella spp. in 8 (12.3%), Enterobacter spp. in 2 (3.1%), Bacillus cereus in 6 (9.2%), Staphylococcus aureus in 3 (4.6%), and Micrococcaceae spp. in 5 (7.69%) cases. All isolated bacteria were susceptible to gentamicin, cephalotin, tobramycin, amikacin, norfloxacin, and vancomycin. The S. aureus resistance rate to trimethoprim/sulfamethoxazole was 50%. Conclusion: All tested ATM keyboards were contaminated with at least one species of bacteria. Based on these findings, it is recommendable to disinfect the hands after entering one’s own apartment, work area or a hospital, in order to hinder the spread of critical pathogens in the personal environment or in the hospital. PMID:28197394

Gamow-Teller transitions between proton h11/2 and neutron h9/2 partner orbitals in 140I

NASA Astrophysics Data System (ADS)

Moon, B.; Moon, C.-B.; Odahara, A.; Lozeva, R.; Söderström, P.-A.; Nishimura, S.; Yuan, C.; Hong, B.; for theNP1112-RIBF87 Collaboration

2018-04-01

The excited states of the neutron-rich nucleus 140I were, for the first time, investigated by a β-delayed γ-ray spectroscopy. The parent nuclide 140Te was produced through the in-flight fission of the 238U beam at 345 MeV per nucleon on a 9Be target at the Radioactive Isotope Beam Factory (RIBF), RIKEN in Japan. The half-life of 140Te was measured to be 350(5) ms and the spin-parity of ground state of 140I was found to be 2-. The spin-parities of three levels at 926, 1188, and 1787 keV were assigned as 1+ based on log f t values. These allowed Gamow-Teller (G-T) transition-states could be interpreted as the transformation of a neutron in the h9/2 orbital into a proton in the h11/2 orbital. Systematic features of level structures and G-T transitions are discussed in the frameworks of the large-scale shell model and deformed shell model.

Ashkin-Teller criticality and weak first-order behavior of the phase transition to a fourfold degenerate state in two-dimensional frustrated Ising antiferromagnets

NASA Astrophysics Data System (ADS)

Liu, R. M.; Zhuo, W. Z.; Chen, J.; Qin, M. H.; Zeng, M.; Lu, X. B.; Gao, X. S.; Liu, J.-M.

2017-07-01

We study the thermal phase transition of the fourfold degenerate phases (the plaquette and single-stripe states) in the two-dimensional frustrated Ising model on the Shastry-Sutherland lattice using Monte Carlo simulations. The critical Ashkin-Teller-like behavior is identified both in the plaquette phase region and the single-stripe phase region. The four-state Potts critical end points differentiating the continuous transitions from the first-order ones are estimated based on finite-size-scaling analyses. Furthermore, a similar behavior of the transition to the fourfold single-stripe phase is also observed in the anisotropic triangular Ising model. Thus, this work clearly demonstrates that the transitions to the fourfold degenerate states of two-dimensional Ising antiferromagnets exhibit similar transition behavior.

Orbital ordering-driven ferromagnetism in LaCoO3 nanowires

NASA Astrophysics Data System (ADS)

Wang, Yang; Fan, Hong Jin

2010-09-01

The structure and magnetic properties of LaCoO3 nanowires are investigated as a function of the diameter in the temperature range of 5-300 K. Ferromagnetism below 85 K is observed in these nanowires, in agreement with the recent observations in LaCoO3 epitaxial thin films and nanoparticles. With the diameter of nanowires decreasing, the unit-cell volume increases, while both the global and local structural distortions lessen, accompanied by the gradual enhancement of ferromagnetism. The structure analysis reveals that LaCoO3 nanowires exhibit a monoclinic distorted structure with I2/a space group in the entire investigated temperature range. Different from bulks, there is no clear spin-state transition occurring with temperature in LaCoO3 nanowires. There exists a noticeable Jahn-Teller (JT) distortion in the nanowires even at the lowest temperature, namely, orbital-ordered JT active Co3+ ions with intermediate-spin (IS) state persist at low temperatures, which is not observed in bulk LaCoO3. These results indicate that the ferromagnetism in the nanowires is driven by the orbital ordering of IS Co3+.

Coupled ferroelectric polarization and magnetization in spinel FeCr2S4

PubMed Central

Lin, L.; Zhu, H. X.; Jiang, X. M.; Wang, K. F.; Dong, S.; Yan, Z. B.; Yang, Z. R.; Wan, J. G.; Liu, J.-M.

2014-01-01

One of the core issues for multiferroicity is the strongly coupled ferroelectric polarization and magnetization, while so far most multiferroics have antiferromagnetic order with nearly zero magnetization. Magnetic spinel compounds with ferrimagnetic order may be alternative candidates offering large magnetization when ferroelectricity can be activated simultaneously. In this work, we investigate the ferroelectricity and magnetism of spinel FeCr2S4 in which the Fe2+ sublattice and Cr3+ sublattice are coupled in antiparallel alignment. Well defined ferroelectric transitions below the Fe2+ orbital ordering termperature Too = 8.5 K are demonstrated. The ferroelectric polarization has two components. One component arises mainly from the noncollinear conical spin order associated with the spin-orbit coupling, which is thus magnetic field sensitive. The other is probably attributed to the Jahn-Teller distortion induced lattice symmetry breaking, occuring below the orbital ordering of Fe2+. Furthermore, the coupled ferroelectric polarization and magnetization in response to magnetic field are observed. The present work suggests that spinel FeCr2S4 is a multiferroic offering both ferroelectricity and ferrimagnetism with large net magnetization. PMID:25284432

Spin-state blockade in Te6+-substituted electron-doped LaCoO3

NASA Astrophysics Data System (ADS)

Tomiyasu, Keisuke; Koyama, Shun-Ichi; Watahiki, Masanori; Sato, Mika; Nishihara, Kazuki; Onodera, Mitsugi; Iwasa, Kazuaki; Nojima, Tsutomu; Yamasaki, Yuuichi; Nakao, Hironori; Murakami, Youichi

2015-03-01

Perovskite-type LaCoO3 (Co3+: d6) is a rare inorganic material with sensitive and characteristic responses among low, intermediate, and high spin states. For example, in insulating nonmagnetic low-spin states below about 20 K, light hole doping (Ni substitution) induces much larger magnetization than expected; over net 10μB/hole (5μB/Ni) for 1μB/hole (1μB/Ni), in which the nearly isolated dopants locally change the surrounding Co low-spin states to magnetic ones and form spin molecules with larger total spin. Further, the former is isotropic, whereas the latter exhibits characteristic anisotropy probably because of Jahn-Teller distortion. In contrast, for electron doping, relatively insensitive spin-state responses were reported, as in LaCo(Ti4+) O3, but are not clarified, and are somewhat controversial. Here, we present macroscopic measurement data of another electron-doped system LaCo(Te6+) O3 and discuss the spin-state responses. This study was financially supported by Grants-in-Aid for Young Scientists (B) (No. 22740209 and 26800174) from the MEXT of Japan.

Mapping chemical/structural order in double perovskite Sr2-xGdxMnTiO6 by atomic resolution electron microscopy

NASA Astrophysics Data System (ADS)

Alvarez, Inmaculada; Biskup, Neven; Lopez, Maria; Garcia-Hernandez, Mar; Veiga, Luisa; Varela, Maria; UCM Collaboration; ORNL Collaboration; CSIC Collaboration

2013-03-01

We report on visualizing the chemical and structural order of double perovskite Sr2-xGdxMnTiO6. The antisite disorder of Mn and Ti is detected even at atomic scale at all x, resulting in Mn-rich and Ti-rich regions. For x ?0.75, the majority of manganese ions are in Mn3+ state and are centered in Jahn-Teller distorted MnO6octahedra. The Fourier transformation of atomic resolution images along the [110] zone axis reveals a superstructure that corresponds to the tilting of oxygen octahedra and that doubles the unit cell along [001]c. This superstructure is spatially inhomogeneous and coincides with the regions where B-site ion (Mn/Ti) is displaced along the [110] direction. We discuss these findings in the frame of possible local ferroelectricity and in the light of strong electroresistance observed in Sr1.25Gd0.75MnTiO6. Research at ORNL supported by the U.S. DOE-BES, Materials Sciences and Engineering Division, and also by ORNL's ShaRE User Program (sponsored by DOE-BES). Research at UCM supported by the ERC Starting Investigator Award and MAT2010-20117.

Orbital Dimer Model for the Spin-Glass State in Y_{2}Mo_{2}O_{7}.

PubMed

Thygesen, Peter M M; Paddison, Joseph A M; Zhang, Ronghuan; Beyer, Kevin A; Chapman, Karena W; Playford, Helen Y; Tucker, Matthew G; Keen, David A; Hayward, Michael A; Goodwin, Andrew L

2017-02-10

The formation of a spin glass generally requires that magnetic exchange interactions are both frustrated and disordered. Consequently, the origin of spin-glass behavior in Y_{2}Mo_{2}O_{7}-in which magnetic Mo^{4+} ions occupy a frustrated pyrochlore lattice with minimal compositional disorder-has been a longstanding question. Here, we use neutron and x-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously reported PDF, extended x-ray-absorption fine structure spectroscopy, and NMR studies, and provides a new and physical explanation of the exchange disorder responsible for spin-glass formation. We show that Mo^{4+} ions displace according to a local "two-in-two-out" rule on each Mo_{4} tetrahedron, driven by orbital dimerization of Jahn-Teller active Mo^{4+} ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O^{2-} displacements yield a distribution of Mo-O-Mo angles, which in turn introduces disorder into magnetic interactions. Our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition.

Dispersed-Fluorescence Spectroscopy of Jet-Cooled Calcium Ethoxide Radical (CaOC_2H_5)

NASA Astrophysics Data System (ADS)

Paul, Anam C.; Reza, Md Asmaul; Liu, Jinjun

2016-06-01

Metal-containing free radicals are important intermediates in metal-surface reactions and in the interaction between metals and organic molecules. In the present work, dispersed fluorescence (DF) spectra of the calcium ethoxide radical (CaOC_2H_5) have been obtained by pumping the {tilde A^2}{A}' ← {tilde X^2}{A}' and the {tilde B^2}{A}'' ← {tilde X^2}{A}' origin bands in its laser-induced fluorescence (LIF) spectrum. CaOC_2H_5 radicals were produced by 1064 nm laser ablation of calcium grains in the presence of ethanol under jet-cooled conditions. Dominant transitions in the vibrationally resolved DF spectra are well reproduced using Franck-Condon factors predicted by complete active space self-consistent (CASSCF) calculations. Differences in transition intensities between the {tilde A^2}{A}' → {tilde X^2}{A}' and the {tilde B^2}{A}'' → {tilde X^2}{A}' DF spectra are attributed to the pseudo-Jahn-Teller interaction between the tilde A ^2 A' and the tilde B ^2 A'' states. Collision-induced population transfer between these two excited electronic states results in additional peaks in the DF spectra.

Design of Mott and topological phases on buckled 3d-oxide honeycomb lattices

NASA Astrophysics Data System (ADS)

Pentcheva, Rossitza

The honeycomb lattice, as realized e.g. in graphene, has rendered a robust platform for innovative science and potential applications. A much richer generalization of this lattice arises in (111)-oriented bilayers of perovskites, adding the complexity of the strongly correlated, multiorbital nature of electrons in transition metal oxides. Based on first principles calculations with an on-site Coulomb repulsion, here we provide trends in the evolution of ground states versus band filling in (111)-oriented (La XO3)2 /(LaAlO3)4 superlattices, with X spanning the entire 3d transition metal series. The competition between local quasi-cubic and global triangular symmetry triggers unanticipated broken symmetry phases, with mechanisms ranging from Jahn-Teller distortion, to charge-, spin-, and orbital-ordering. LaMnO3 and LaCoO3 bilayers, where spin-orbit coupling opens a sizable gap in the Dirac-point Fermi surface, emerge as much desired oxide-based Chern insulators, the latter displaying a gap capable of supporting room-temperature applications Further realizations of the honeycomb lattice and geometry patterns beyond the perovskite structure will be addressed. Research supported by the DFG, SFB/TR80.

Nonadiabatic dynamics of O(1D) + N2(X1Σg+) → O(3P) + N2(X1Σg+) on three coupled potential surfaces: symmetry, Coriolis, spin-orbit, and Renner-Teller effects.

PubMed

Defazio, Paolo; Gamallo, Pablo; Petrongolo, Carlo

2012-02-07

We present the spin-orbit (SO) and Renner-Teller (RT) quantum dynamics of the spin-forbidden quenching O((1)D) + N(2)(X(1)Σ(g)(+)) → O((3)P) + N(2)(X(1)Σ(g)(+)) on the N(2)O X(1)A', ã(3)A", and b(3)A' coupled PESs. We use the permutation-inversion symmetry, propagate coupled-channel (CC) real wavepackets, and compute initial-state-resolved probabilities and cross sections σ(j(0)) for the ground vibrational and the first two rotational states of N(2), j(0) = 0 and 1. Labeling symmetry angular states by j and K, we report selection rules for j and for the minimum K value associated with any electronic state, showing that ã(3)A" is uncoupled in the centrifugal-sudden (CS) approximation at j(0) = 0. The dynamics is resonance-dominated, the probabilities are larger at low K, σ(j(0)) decrease with the collision energy and increase with j(0), and the CS σ(0) is lower than the CC one. The nonadiabatic interactions play different roles on the quenching dynamics, because the X(1)A'-b(3)A' SO effects are those most important while the ã(3)A"-b(3)A' RT ones are negligible.

Gamow-Teller response in the configuration space of a density-functional-theory-rooted no-core configuration-interaction model

NASA Astrophysics Data System (ADS)

Konieczka, M.; Kortelainen, M.; Satuła, W.

2018-03-01

Background: The atomic nucleus is a unique laboratory in which to study fundamental aspects of the electroweak interaction. This includes a question concerning in medium renormalization of the axial-vector current, which still lacks satisfactory explanation. Study of spin-isospin or Gamow-Teller (GT) response may provide valuable information on both the quenching of the axial-vector coupling constant as well as on nuclear structure and nuclear astrophysics. Purpose: We have performed a seminal calculation of the GT response by using the no-core configuration-interaction approach rooted in multireference density functional theory (DFT-NCCI). The model treats properly isospin and rotational symmetries and can be applied to calculate both the nuclear spectra and transition rates in atomic nuclei, irrespectively of their mass and particle-number parity. Methods: The DFT-NCCI calculation proceeds as follows: First, one builds a configuration space by computing relevant, for a given physical problem, (multi)particle-(multi)hole Slater determinants. Next, one applies the isospin and angular-momentum projections and performs the isospin and K mixing in order to construct a model space composed of linearly dependent states of good angular momentum. Eventually, one mixes the projected states by solving the Hill-Wheeler-Griffin equation. Results: The method is applied to compute the GT strength distribution in selected N ≈Z nuclei including the p -shell 8Li and 8Be nuclei and the s d -shell well-deformed nucleus 24Mg. In order to demonstrate a flexibility of the approach we present also a calculation of the superallowed GT β decay in doubly-magic spherical 100Sn and the low-spin spectrum in 100In. Conclusions: It is demonstrated that the DFT-NCCI model is capable of capturing the GT response satisfactorily well by using a relatively small configuration space, exhausting simultaneously the GT sum rule. The model, due to its flexibility and broad range of applicability, may

Effective axial-vector strength and β-decay systematics

NASA Astrophysics Data System (ADS)

Delion, D. S.; Suhonen, J.

2014-09-01

We use the weak axial-vector coupling strength g_{\\text{A}} as a key parameter to reproduce simultaneously the available data for both the Gamow-Teller \\beta^- and \\beta^+/\\text{EC} decay rates in nine triplets of isobars with mass numbers A=70,78,100,104,106,110,116,128,130 . We use the proton-neutron quasiparticle random-phase approximation (pnQRPA) with schematic dipole interaction containing particle-particle and particle-hole parts with mass-dependent strengths. Our analysis points to a strongly quenched effective value g_{\\text{A}}\\approx 0.3 , with a relative error of 28%. We then perform a systematic computation of 218 experimentally known \\beta^- and \\beta^+/\\text{EC} decays with quite a remarkable success. The presently extracted value of g_{\\text{A}} should be taken as an effective one, specific for a given nuclear theory framework. Present studies suggest that the effective g_{\\text{A}} is suitable for the description of decay transitions to 1^+ states at moderate excitation, below the Gamow-Teller giant resonance region.

Solvent effects on the vibronic one-photon absorption profiles of dioxaborine heterocycles

NASA Astrophysics Data System (ADS)

Wang, Yan-Hua; Halik, Marcus; Wang, Chuan-Kui; Marder, Seth R.; Luo, Yi

2005-11-01

The vibronic profiles of one-photon absorption spectra of dioxaborine heterocycles in gas phase and solution have been calculated at the Hartree-Fock and density-functional-theory levels. The polarizable continuum model has been applied to simulate the solvent effect, while the linear coupling model is used to compute the Franck-Condon and Herzberg-Teller contributions. It is found that a good agreement between theory and experiment can be achieved when the solvent effect and electron correlation are taken into account simultaneously. For the first excited charge-transfer state, the maximum of its Herzberg-Teller profile is blueshifted from that of the Franck-Condon profile. The shifted energy is found to be around 0.2eV, which agrees well with the measured energy difference between two- and one-photon absorptions of the first excited state.

Born-Oppenheimer and Renner-Teller Quantum Dynamics of CH(X(2)Π) + D((2)S) Reactions on Three CHD Potential Surfaces.

PubMed

Gamallo, Pablo; Akpinar, Sinan; Defazio, Paolo; Petrongolo, Carlo

2015-11-19

The quantum dynamics of three CH(X(2)Π) + D((2)S) reactions is studied by means of the coupled-channel time-dependent real-wavepacket (WP) and flux methods at collision energy Ecol ≤ 0.6 eV and on three potential energy surfaces (PESs): the Born-Oppenheimer (BO) ground PES X̃(3)A″ and the excited ones ã(1)A' and b̃(1)A″, coupled by nonadiabatic (NA) Renner-Teller (RT) effects. This three-state model is suitable for obtaining initial-state-resolved observables, is based on a complete analysis of the correlation diagram of the lowest electronic states of the CHD intermediate and of their NA interactions, and neglects the smaller coupling effects due to the asymptotic electronic angular momenta that become important in state-to-state dynamics. WPs are propagated on each PES at total angular momentum values J ≤ 70, with CH in the two lowest vibrational states v0 and in the ground rotational state j0 = 1. Reaction probabilities are obtained for three possible final products (f): (dP) CH decay and C((3)P) + HD(X(1)Σ(+)) formation that occurs on the uncoupled ground PES, (dD) CH decay and C((1)D) + HD(X(1)Σ(+)) formation that depends on the RT-coupled singlet species, and (ex) exchange to CD(X(2)Π) + H((2)S) available adiabatically from the X̃(3)A″ PES and nonadiabatically from ã(1)A' and b̃(1)A″. Observable cross sections σf,v0j0 and rate constants kf,v0j0 in the temperature range T = 100-2000 K are obtained for (dP), (dD), and (ex) channels. Comparing BO with RT probabilities, we show that NA effects are important at high J values for the (ex) channel at v0 = 1. Real time mechanisms on the three PESs show that RT couplings are opened after some time and clearly point out the formation of the product channels. Both cross sections and rate constants present the same sequence, for example σex,11 > σdP,01 ∼ σex,01 > σdP,11 ≫ σdD,11 ≫ σdD,01, and the CH vibrational excitation enhances the total removal CH+D reactivity by a factor of ∼1

Climatic effects due to halogenated compounds in the earth's atmosphere

NASA Technical Reports Server (NTRS)

Wang, W.-C.; Pinto, J. P.; Yung, Y. L.

1980-01-01

Using a one-dimensional radiative-convective model, a sensitivity study is performed of the effect of ozone depletion in the stratosphere on the surface temperature. There could be a cooling of the surface temperature by approximately 0.2 K due to chlorofluoromethane-induced ozone depletion at steady state (assuming 1973 release rates). This cooling reduces significantly the greenhouse effect due to the presence of chlorofluoromethanes. Carbon tetrafluoride has a strong nu sub 3 band at 7.8 microns, and the atmospheric greenhouse effect is shown to be 0.07 and 0.12 K/ppbv with and without taking into account overlap with CH4 and N2O bands. At concentrations higher than 1 ppbv, absorption by the nu sub 3 band starts to saturate and the greenhouse effect becomes less efficient.

Adult Competency Education Kit. Basic Skills in Speaking, Math, and Reading for Employment. Part N. ACE Competency Based Job Descriptions: #65--Typist I; #67--Grocery Checker; #68--File Clerk; #69--Receptionist; #70--Bank Teller; #71--Clerk, General Office.

ERIC Educational Resources Information Center

San Mateo County Office of Education, Redwood City, CA. Career Preparation Centers.

This eleventh of fifteen sets of Adult Competency Education (ACE) Competency Based Job Descriptions in the ACE kit contains job descriptions for Typist I, Grocery Checker, File Clerk, Receptionist; Bank Teller; and Clerk, General Office. Each begins with a fact sheet that includes this information: occupational title, D.O.T. code, ACE number,…

Storytelling as an age-dependent skill: oral recall of orally presented stories.

PubMed

Mergler, N L; Faust, M; Goldstein, M D

During experiment 1, three taped prose passages read by college student, middle-aged, or old tellers were orally recalled by college students in an incidental memory paradigm. More story units were remembered as the age of the teller increased (r = +.642, p less than .05). Comparison of these results, with prior research using written, as opposed to oral, presentation and recall of these stories, showed no differences in specific story units remembered. Teller age predicted recall on the two "storied" passages. These passages elicited more favorable comments from listeners when read by older tellers. The third, descriptive passage was less favorably regarded by listeners hearing older tellers. During experiment 2, taped storied passages read by middle-aged tellers were falsely attributed to young, middle-aged, or old persons before the college students listened. Incidental recall did not show an age of teller effect in this case, but the listener's evaluation of the speaker exhibited age-dependent stereotypes. It was concluded that 1) physical qualities of older voices lead to more effective oral transmission; 2) that one expects to receive certain types of oral information from older persons; and 3) that a mismatch between physical vocal quality and age attribution effects evaluation of the speaker, not recall of the information.

Electron temperature and de Hoffmann-Teller potential change across the Earth's bow shock: New results from ISEE 1

NASA Astrophysics Data System (ADS)

Hull, A. J.; Scudder, J. D.; Fitzenreiter, R. J.; Ogilvie, K. W.; Newbury, J. A.; Russell, C. T.

We present a survey of the trends between the electron temperature increase ΔTe and the de Hoffmann-Teller frame (HTF) electrostatic potential jump ΔΦHT and their correlation with other parameters that characterize the shock transition using a new ISEE 1 database of 129 Earth bow shock crossings. A fundamental understanding of the HTF potential is central to distinguishing the reversible and irreversible changes to electron temperature across collisionless shocks. The HTF potential is estimated using three different techniques: (1) integrating the steady state, electron fluid momentum equation across the shock layer using high time resolution plasma and field data from ISEE 1, (2) using the steady state, electron fluid energy equation, and (3) using an electron polytrope approximation. We find that ΔΦHT and ΔTe are strongly and positively correlated with |Δ(mpUn2/2)|, which is in good qualitative agreement with earlier experimental surveys [Thomsen et al., 1987b; Schwartz et al., 1988] that used bow shock model normals and used the flow in the spacecraft frame. There is a strong linear organization of the ΔTe with ΔΦHT, which suggests an average effective electron polytropic index of <γe>~2. In addition, ΔTe and ΔΦHT are organized by βe, although our results may be biased by our limited sampling of shock conditions. Comparisons indicate that the differentials in the HTF potential δΦHT are proportional to the differentials in the magnetic field intensity δB across the shock, with a proportionality constant κ that is a fixed constant for a given shock crossing.

An ab initio global potential-energy surface for NH2(A(2)A') and vibrational spectrum of the Renner-Teller A(2)A'-X(2)A" system.

PubMed

Zhou, Shulan; Li, Zheng; Xie, Daiqian; Lin, Shi Ying; Guo, Hua

2009-05-14

A global potential-energy surface for the first excited electronic state of NH(2)(A(2)A(')) has been constructed by three-dimensional cubic spline interpolation of more than 20,000 ab initio points, which were calculated at the multireference configuration-interaction level with the Davidson correction using the augmented correlation-consistent polarized valence quadruple-zeta basis set. The (J=0) vibrational energy levels for the ground (X(2)A(")) and excited (A(2)A(')) electronic states of NH(2) were calculated on our potential-energy surfaces with the diagonal Renner-Teller terms. The results show a good agreement with the experimental vibrational frequencies of NH(2) and its isotopomers.

Understanding Two Different Structures in the Dark Stable State of the Oxygen‐Evolving Complex of Photosystem II: Applicability of the Jahn–Teller Deformation Formula

PubMed Central

Shoji, Mitsuo; Isobe, Hiroshi; Tanaka, Ayako; Fukushima, Yoshimasa; Kawakami, Keisuke; Umena, Yasufumi; Kamiya, Nobuo; Nakajima, Takahito

2017-01-01

Abstract Tanaka et al. (J. Am. Chem. Soc., 2017, 139, 1718) recently reported the three‐dimensional (3D) structure of the oxygen evolving complex (OEC) of photosystem II (PSII) by X‐ray diffraction (XRD) using extremely low X‐ray doses of 0.03 and 0.12 MGy. They observed two different 3D structures of the CaMn4O5 cluster with different hydrogen‐bonding interactions in the S1 state of OEC keeping the surrounding polypeptide frameworks of PSII the same. Our Jahn–Teller (JT) deformation formula based on large‐scale quantum mechanics/molecular mechanics (QM/MM) was applied for these low‐dose XRD structures, elucidating important roles of JT effects of the MnIII ion for subtle geometric distortions of the CaMn4O5 cluster in OEC of PSII. The JT deformation formula revealed the similarity between the low‐dose XRD and damage‐free serial femtosecond X‐ray diffraction (SFX) structures of the CaMn4O5 cluster in the dark stable state. The extremely low‐dose XRD structures were not damaged by X‐ray irradiation. Implications of the present results are discussed in relation to recent SFX results and a blue print for the design of artificial photocatalysts for water oxidation. PMID:29577075

Moment analysis method as applied to the 2S --> 2P transition in cryogenic alkali metal/rare gas matrices.

PubMed

Terrill Vosbein, Heidi A; Boatz, Jerry A; Kenney, John W

2005-12-22

The moment analysis method (MA) has been tested for the case of 2S --> 2P ([core]ns1 --> [core]np1) transitions of alkali metal atoms (M) doped into cryogenic rare gas (Rg) matrices using theoretically validated simulations. Theoretical/computational M/Rg system models are constructed with precisely defined parameters that closely mimic known M/Rg systems. Monte Carlo (MC) techniques are then employed to generate simulated absorption and magnetic circular dichroism (MCD) spectra of the 2S --> 2P M/Rg transition to which the MA method can be applied with the goal of seeing how effective the MA method is in re-extracting the M/Rg system parameters from these known simulated systems. The MA method is summarized in general, and an assessment is made of the use of the MA method in the rigid shift approximation typically used to evaluate M/Rg systems. The MC-MCD simulation technique is summarized, and validating evidence is presented. The simulation results and the assumptions used in applying MA to M/Rg systems are evaluated. The simulation results on Na/Ar demonstrate that the MA method does successfully re-extract the 2P spin-orbit coupling constant and Landé g-factor values initially used to build the simulations. However, assigning physical significance to the cubic and noncubic Jahn-Teller (JT) vibrational mode parameters in cryogenic M/Rg systems is not supported.

Spin crossover in the CsFeII[CrIII(CN)6] Prussian blue analog: Phonons and thermodynamics from hybrid functionals

NASA Astrophysics Data System (ADS)

Middlemiss, Derek S.; Portinari, Damiano; Grey, Clare P.; Morrison, Carole A.; Wilson, Chick C.

2010-05-01

Solid-state lattice-dynamics calculations within the hybrid density-functional approach are applied to the study of the thermally induced Fe2+ lowspin(LS;S=0)↔highspin(HS;S=2) crossover (SCO) in the extended network of the CsFe[Cr(CN)6] Prussian blue analog. The variations in the thermodynamic parameters defining the SCO transition with the Fock exchange content (F0) of the functional are obtained and discussed, where, in keeping with the findings of previous studies of isolated complexes, it is found that an admixture F0≈14% provides reliable values. The transition is shown to be dominated by the entropy difference, ΔS , associated with the softening of low-frequency vibrational (vib) modes in the HS state, as has been suggested previously for a wide range of SCO materials, more than half of ΔSvib deriving from modes with wave numbers of 250cm-1 or less. Analysis of the influence of the spectroscopic selection rules upon the apparent SCO thermodynamics reveals that determinations based solely upon infrared or Raman frequencies, or upon their combination, lead to significant errors. The effect upon the SCO transition of the electronic entropy associated with the degenerate Fe2+ HS (eg2t2g4) configurations is also detailed, evidence for the existence of an associated dynamic Jahn-Teller distortion being presented. Optimized structures, bulk moduli, Γ -point vibrational frequencies, and crystal-field energy models are discussed for all relevant spin states.

Unusual x-ray excited luminescence spectra of NiO suggest self-trapping of the d-d charge-transfer exciton

NASA Astrophysics Data System (ADS)

Sokolov, V. I.; Pustovarov, V. A.; Churmanov, V. N.; Ivanov, V. Yu.; Gruzdev, N. B.; Sokolov, P. S.; Baranov, A. N.; Moskvin, A. S.

2012-09-01

Luminescence spectra of NiO have been investigated under vacuum ultraviolet (VUV) and soft x-ray (XUV) excitation (DESY, Hamburg). Photoluminescence (PL) spectra show broad emission violet and green bands centered at about 3.2 and 2.6 eV, respectively. The PL excitation (PLE) spectral evolution and lifetime measurements reveal that the two mechanisms with short and long decay times, attributed to the d(eg)-d(eg) and p(π)-d charge transfer (CT) transitions in the range 4-6 eV, respectively, are responsible for the observed emissions. The XUV excitation makes it possible to avoid the predominant role of the surface effects in luminescence and reveals a bulk violet luminescence with a puzzling well-isolated doublet of very narrow lines. These lines with close energies near 3.3 eV are attributed to recombination transitions in the self-trapped d-d CT excitons formed by the coupled Jahn-Teller Ni+ and Ni3+ centers. The conclusion is supported by a comparative analysis of the luminescence spectra for NiO and solid solution NixZn1-xO and by a comprehensive cluster model assignment of different p-d and d-d CT transitions and their relaxation channels. Our paper shows that the time-resolved luminescence measurements provide an instructive tool for the elucidation of the p-d and d-d CT excitations and their relaxation in 3d oxides.

Structural phase transition of as-synthesized Sr-Mn nanoferrites by annealing temperature

NASA Astrophysics Data System (ADS)

Amer, M. A.; Meaz, T. M.; Attalah, S. S.; Ghoneim, A. I.

2015-11-01

The Sr0.2Mn0.8Fe2O4 nanoparticle ferrites were synthesized by the co-precipitation method and annealed at different temperatures T. XRD, TEM, FT-IR, VSM and Mössbauer techniques were used to characterize the samples. This study proved that the structural phase of nanoferrites was transformed from cubic spinel for T≤500 °C to Z-type hexagonal for T≥700 °C. The structural transformation was attributed to Jahn-Teller effect of the Mn3+ ions and/or atomic disorder existed in the crystal lattice. The obtained spectra and parameters for the samples were affected by the transformation process. The lattice constant a showed a splitting to a and c for T>500 °C. The lattice constant c, grain and crystallite size R, strain, octahedral B-site band position and force constant, Debye temperature, coercivity Hc, remnant magnetization, squareness and magnetic moment, spontaneous magnetization and hyperfine magnetic fields showed increase against T. The lattice constant a, distortion and dislocation parameters, specific surface area, tetrahedral A-site band position and force constant, threshold frequency, Young's and bulk moduli, saturation magnetization Ms, area ratio of B-/A-sites, A-site line width were decreased with T. Experimental and theoretical densities, porosity, Poison ratio, stiffness constants, rigidity modulus, B-site line width and spontaneous magnetization showed dependence on T, whereas Ms and Hc proved dependence on R.

Discontinuities in effective permeability due to fracture percolation

DOE PAGES

Hyman, Jeffrey De'Haven; Karra, Satish; Carey, James William; ...

2018-01-31

Motivated by a triaxial coreflood experiment with a sample of Utica shale where an abrupt jump in permeability was observed, possibly due to the creation of a percolating fracture network through the sample, we perform numerical simulations based on the experiment to characterize how the effective permeability of otherwise low-permeability porous media depends on fracture formation, connectivity, and the contrast between the fracture and matrix permeabilities. While a change in effective permeability due to fracture formation is expected, the dependence of its magnitude upon the contrast between the matrix permeability and fracture permeability and the fracture network structure is poorlymore » characterized. We use two different high-fidelity fracture network models to characterize how effective permeability changes as percolation occurs. The first is a dynamic two-dimensional fracture propagation model designed to mimic the laboratory settings of the experiment. The second is a static three-dimensional discrete fracture network (DFN) model, whose fracture and network statistics are based on the fractured sample of Utica shale. Once the network connects the inflow and outflow boundaries, the effective permeability increases non-linearly with network density. In most networks considered, a jump in the effective permeability was observed when the embedded fracture network percolated. We characterize how the magnitude of the jump, should it occur, depends on the contrast between the fracture and matrix permeabilities. For small contrasts between the matrix and fracture permeabilities the change is insignificant. However, for larger contrasts, there is a substantial jump whose magnitude depends non-linearly on the difference between matrix and fracture permeabilities. A power-law relationship between the size of the jump and the difference between the matrix and fracture permeabilities is observed. In conclusion, the presented results underscore the importance of

Discontinuities in effective permeability due to fracture percolation

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

Hyman, Jeffrey De'Haven; Karra, Satish; Carey, James William

Motivated by a triaxial coreflood experiment with a sample of Utica shale where an abrupt jump in permeability was observed, possibly due to the creation of a percolating fracture network through the sample, we perform numerical simulations based on the experiment to characterize how the effective permeability of otherwise low-permeability porous media depends on fracture formation, connectivity, and the contrast between the fracture and matrix permeabilities. While a change in effective permeability due to fracture formation is expected, the dependence of its magnitude upon the contrast between the matrix permeability and fracture permeability and the fracture network structure is poorlymore » characterized. We use two different high-fidelity fracture network models to characterize how effective permeability changes as percolation occurs. The first is a dynamic two-dimensional fracture propagation model designed to mimic the laboratory settings of the experiment. The second is a static three-dimensional discrete fracture network (DFN) model, whose fracture and network statistics are based on the fractured sample of Utica shale. Once the network connects the inflow and outflow boundaries, the effective permeability increases non-linearly with network density. In most networks considered, a jump in the effective permeability was observed when the embedded fracture network percolated. We characterize how the magnitude of the jump, should it occur, depends on the contrast between the fracture and matrix permeabilities. For small contrasts between the matrix and fracture permeabilities the change is insignificant. However, for larger contrasts, there is a substantial jump whose magnitude depends non-linearly on the difference between matrix and fracture permeabilities. A power-law relationship between the size of the jump and the difference between the matrix and fracture permeabilities is observed. In conclusion, the presented results underscore the importance of

Neutron and X-ray investigations of the Jahn–Teller switch in partially deuterated ammonium copper Tutton salt, (NH 4 ) 2 [Cu(H 2 O) 6 ](SO 4 ) 2

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

Jørgensen, Mads R. V.; Piccoli, Paula M. B.; Hathwar, Venkatesha R.

2017-01-31

The structural phase transition accompanied by a Jahn–Teller switch has been studied over a range of H/D ratios in (NH 4) 2[Cu(H 2O) 6](SO 4) 2(ACTS). In particular, single-crystal neutron diffraction investigations of crystals with deuteration in the range 50 to 82% are shown to be consistent with previous electron paramagnetic resonance (EPR) experiments exhibiting a phase boundary at 50% deuteration under ambient pressure. Polycrystalline samples show that the two phases can co-exist. In addition, single-crystal neutron and polycrystalline X-ray diffraction pressure experiments show a shift to lower pressure at 60% deuterationversusprevious measurements at 100% deuteration.

Gamow-Teller strength and lepton captures rates on 66-71Ni in stellar matter

NASA Astrophysics Data System (ADS)

Nabi, Jameel-Un; Majid, Muhammad

Charge-changing transitions play a significant role in stellar weak-decay processes. The fate of the massive stars is decided by these weak-decay rates including lepton (positron and electron) captures rates, which play a consequential role in the dynamics of core collapse. As per previous simulation results, weak interaction rates on nickel (Ni) isotopes have significant influence on the stellar core vis-à-vis controlling the lepton content of stellar matter throughout the silicon shell burning phases of high mass stars up to the presupernova stages. In this paper, we perform a microscopic calculation of Gamow-Teller (GT) charge-changing transitions, in the β-decay and electron capture (EC) directions, for neutron-rich Ni isotopes (66-71Ni). We further compute the associated weak-decay rates for these selected Ni isotopes in stellar environment. The computations are accomplished by employing the deformed proton-neutron quasiparticle random phase approximation (pn-QRPA) model. A recent study showed that the deformed pn-QRPA theory is well suited for the estimation of GT transitions. The astral weak-decay rates are determined over densities in the range of 10-1011g/cm3 and temperatures in the range of 0.01 × 109-30 × 109K. The calculated lepton capture rates are compared with the previous calculation of Pruet and Fuller (PF). The overall comparison demonstrates that, at low stellar densities and high temperatures, our EC rates are bigger by as much as two orders of magnitude. Our results show that, at higher temperatures, the lepton capture rates are the dominant mode for the stellar weak rates and the corresponding lepton emission rates may be neglected.

Oral adverse effects due to the use of Nevirapine.

PubMed

Moura, Mariela Dutra Gontijo; Senna, Maria Inês Barreiros; Madureira, Davidson Fróis; Fonseca, Linaena Merícy Silva; Mesquita, Ricardo Alves

2008-01-01

The aim of this article is to present the clinical characteristics and management of an oral adverse effect stemming from the use of the antiretroviral medication Nevirapine (NVP). NVP is a non-nucleoside reverse transcriptase inhibitor used in the treatment of Human Immunodeficiency Virus (HIV) infection. A 29-year-old black man, HIV-infected since 1996, began highly active antiretroviral therapy (HAART) with zidovudine, lamivudine, and indinavir. From 1996 to 2002 several medications were changed due to their adverse effects: indinavir (renal colic and fever), nelfinavir (cutaneous rash), and efavirenz (nausea and temporary memory loss). When the patient presented to our service he was taking NVP, zidovudine, and lamivudine. A whitish plaque in the lips and bilateral buccal mucosa, burning, taste disturbance, and xerostomia were observed. The discontinuation of HAART led to the complete resolution of signs and symptoms. The patient has received follow-up treatment for three years and five months without local or systemic effects observed. Unfortunately, the clinical features of the oral adverse effect from NVP are not well known. This paper contributed to the identification of possible reactions in the oral cavity due to antiretroviral medication. Although HAART is very important in the treatment of HIV, its side effects are responsible for patients' non-adherence to medications. While more studies are needed to better understand the mechanism of action after suspending HAART, the complete resolution of the signs and symptoms was observed. Therefore, physicians and dentists alike must understand how to identify and prevent these adverse effects in order to further improve HIV patient treatments.

Are computers effective lie detectors? A meta-analysis of linguistic cues to deception.

PubMed

Hauch, Valerie; Blandón-Gitlin, Iris; Masip, Jaume; Sporer, Siegfried L

2015-11-01

This meta-analysis investigates linguistic cues to deception and whether these cues can be detected with computer programs. We integrated operational definitions for 79 cues from 44 studies where software had been used to identify linguistic deception cues. These cues were allocated to six research questions. As expected, the meta-analyses demonstrated that, relative to truth-tellers, liars experienced greater cognitive load, expressed more negative emotions, distanced themselves more from events, expressed fewer sensory-perceptual words, and referred less often to cognitive processes. However, liars were not more uncertain than truth-tellers. These effects were moderated by event type, involvement, emotional valence, intensity of interaction, motivation, and other moderators. Although the overall effect size was small, theory-driven predictions for certain cues received support. These findings not only further our knowledge about the usefulness of linguistic cues to detect deception with computers in applied settings but also elucidate the relationship between language and deception. © 2014 by the Society for Personality and Social Psychology, Inc.

Thermodynamics properties study of diatomic molecules with q-deformed modified Poschl-Teller plus Manning Rosen non-central potential in D dimensions using SUSYQM approach

NASA Astrophysics Data System (ADS)

Suparmi, A.; Cari, C.; Pratiwi, B. N.

2016-04-01

D-dimensional Dirac equation of q-deformed modified Poschl-Teller plus Manning Rosen non-central potential was solved using supersymmetric quantum mechanics (SUSY QM). The relativistic energy spectra were analyzed by using SUSY QM and shape invariant properties from radial part of D dimensional Dirac equation and the angular quantum numbers were obtained from angular part of D dimensional Dirac equation. The SUSY operators was used to generate the D dimensional relativistic wave functions both for radial and angular parts. In the non-relativistic limit, the relativistic energy equation was reduced to the non-relativistic energy. In the classical limit, the partition function of vibrational, the specific heat of vibrational, and the mean energy of vibrational of some diatomic molecules were calculated from the equation of non-relativistic energy with the help of error function and Mat-lab 2011.

Lactate as an insidious metabolite due to the Warburg effect.

PubMed

Luc, Raymond; Tortorella, Stephanie M; Ververis, Katherine; Karagiannis, Tom C

2015-04-01

Although oncogenetics remains a critical component of cancer biology and therapeutic research, recent interest has been taken towards the non-genetic features of tumour development and progression, such as cancer metabolism. Specifically, it has been observed that tumour cells are inclined to preferentially undergo glycolysis despite presence of adequate oxygen. First reported by Otto Warburg in the 1920s, and now termed the 'Warburg effect', this aberrant metabolism has become of particular interest due to the prevalence of the fermentation phenotype in a variety of cancers studied. Consequently, this phenotype has proven to play a pivotal role in cancer proliferation. As such Warburg's observations are now being integrated within the modern paradigms of cancer and in this review we explore the role of lactate as an insidious metabolite due to the Warburg effect.

Modified automatic teller machine prototype for older adults: a case study of participative approach to inclusive design.

PubMed

Chan, Chetwyn C H; Wong, Alex W K; Lee, Tatia M C; Chi, Iris

2009-03-01

The goal of this study was to enhance an existing automated teller machine (ATM) human-machine interface in order to accommodate the needs of older adults. Older adults were involved in the design and field test of the modified ATM prototype. The design of the user interface and functionality took the cognitive and physical abilities of older adults into account. The modified ATM system included only "cash withdrawal" and "transfer" functions based on the task demands and needs for services of older adults. One hundred and forty-one older adults (aged 60 or above) participated in the field test by operating modified or existing ATM systems. Those who operated the modified system were found to have significantly higher success rates than those who operated the existing system. The enhancement was most significant among older adults who had lower ATM-related abilities, a lower level of education, and no prior experience of using ATMs. This study demonstrates the usefulness of using a universal design and participatory approach to modify the existing ATM system for use by older adults. However, it also leads to a reduction in functionality of the enhanced system. Future studies should explore ways to develop a universal design ATM system which can satisfy the abilities and needs of all users in the entire population.

Seismoelectric effects due to mesoscopic heterogeneities

NASA Astrophysics Data System (ADS)

Jougnot, Damien; Rubino, J. GermáN.; Carbajal, Marina Rosas; Linde, Niklas; Holliger, Klaus

2013-05-01

While the seismic effects of wave-induced fluid flow due to mesoscopic heterogeneities have been studied for several decades, the role played by these types of heterogeneities on seismoelectric phenomena is largely unexplored. To address this issue, we have developed a novel methodological framework which allows for the coupling of wave-induced fluid flow, as inferred through numerical oscillatory compressibility tests, with the pertinent seismoelectric conversion mechanisms. Simulating the corresponding response of a water-saturated sandstone sample containing mesoscopic fractures, we demonstrate for the first time that these kinds of heterogeneities can produce measurable seismoelectric signals under typical laboratory conditions. Given that this phenomenon is sensitive to key hydraulic and mechanical properties, we expect that the results of this pilot study will stimulate further exploration on this topic in several domains of the Earth, environmental, and engineering sciences.

Orbital Dimer Model for the Spin-Glass State in Y 2 Mo 2 O 7

DOE PAGES

Thygesen, Peter M. M.; Paddison, Joseph A. M.; Zhang, Ronghuan; ...

2017-02-08

The formation of a spin glass generally requires that magnetic exchange interactions are both frustrated and disordered. Consequently, the origin of spin-glass behavior in Y 2Mo 2O 7-in which magnetic Mo 4+ ions occupy a frustrated pyrochlore lattice with minimal compositional disorder-has been a longstanding question. Here, we use neutron and x-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously reported PDF, extended x-rayabsorption fine structure spectroscopy, and NMR studies, and provides a new and physical explanation of the exchange disorder responsible for spin-glass formation. We show that Mo 4+ ions displace accordingmore » to a local "two-in-two-out" rule on each Mo 4 tetrahedron, driven by orbital dimerization of Jahn-Teller active Mo 4+ ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O 2- displacements yield a distribution of Mo-O-Mo angles, which in turn introduces disorder into magnetic interactions. In conclusion, our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition.« less

Structural and electronic transformations in substituted La-Sr manganites depending on cations and oxygen content

NASA Astrophysics Data System (ADS)

Karpasyuk, Vladimir; Badelin, Alexey; Merkulov, Denis; Derzhavin, Igor; Estemirova, Svetlana

2018-05-01

In the present research experimental data are obtained for the Jahn-Teller O‧ phase formation, phase transformation "orthorhombic-rhombohedral structure" and the change of the conductance type in the systems of manganites La3+1-c+xSr2+c-xMn3+1-c-x-2γMn4+c+2γZn2+xO3+γ, La3+1-c-xSr2+c+xMn3+1-c-x-2γMn4+c+2γGe4+xO3+γ, La3+1-cSr2+cMn3+1-x-c-2γMn4+c+2γ(Zn2+0.5Ge4+0.5)xO3+γ, where Mn4+ ions concentration is independent of "x". Ceramic samples were sintered in air at 1473 K. As-sintered samples had an excess of oxygen content. In order to provide stoichiometric oxygen content, the samples were annealed at 1223 K and partial pressure of oxygen PO2 = 10-1 Pа. Structural characteristics of the O‧ phase were obtained. The position of the phase boundary "orthorhombic-rhombohedral structure" and the temperature of the conductance type change depending on the cation composition of manganites and oxygen content were determined. Possible approaches to the interpretation of experimental results were suggested.

New functional materials AC3B4O12 (Review)

NASA Astrophysics Data System (ADS)

Vasil'ev, A. N.; Volkova, O. S.

2007-11-01

The physical properties of perovskites of the type AC3B4O12, whose structure derives from simple perovskites ABO3, are reviewed. The A position is subject to strong structural distortions and splits into two new positions A and C. In the structure of AC3B4O12 vacancies and any cations with a large radius, irrespective of their charge state, can be present in the icosahedral environment of A: Na +, Cd2+, Ca2+, Sr2+, Y3+, Ln3+, and Nd4+. The C position in the square environment of oxygen can be occupied only by the Jahn-Teller cations Cu2+ and Mn3+. Transition and nontransition metal ions—Mn3+, Fe3+, Al3+, Cr3+, Ti4+, Mn4+, Ge4+, Ru4+, Ir4+, Ta5+, Nb5+, Ta5+, Sb5+—can occupy the B position in an octahedral environment. Some members of the family of complex perovskites possess properties which are characteristic for systems with heavy fermions; collinear and noncollinear magnetic structures with high ordering temperatures occur in these materials; tunneling magnetoresistance and high permittivity are observed. The diversity and unique properties make these materials attractive for practical applications.

The Woodstock of Physics: The Hyped Future Then (1987)...The Actual Situation Now (2017)

NASA Astrophysics Data System (ADS)

Grant, Paul

In late January, 1986, Georg Bednorz stayed after work at the IBM Zurich Research Laboratory to measure the temperature dependence of the conductivity of a copper oxide perovskite whose preparation had recently been published by the CNRS group at the University of Caen. He had recognized that the Caen material composition matched that of the ``Jahn-Teller-Bipolaron'' high-temperature superconductivity pairing model speculated previously by his IBM mentor, Alex Mueller. One of his samples revealed trace superconductivity near 20-25 K, a stupendous result at the time1. In the late fall of 1986, Paul Chu and his collaborators at U. Huston and Alabama detected a sharp transition at 91 K in the same perovskite family. Subsequently, confirmation pandemonium ensued throughout the planet, resulting in the gathering termed ``The Woodstock of Physics'' convened at the New York Hilton the second week of March, 1987. Would HTSC thus embody the long sought ``energy deliverance of mankind?'' Not yet, despite obtaining materials reaching ambient pressure Tc's of 135 K, and after many successful demonstrations of power applications2 of these discoveries worldwide over the last three decades. Why not3 and when will its promise be fulfilled? That's the subject of this presentation.

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

Thygesen, Peter M. M.; Paddison, Joseph A. M.; Zhang, Ronghuan

The formation of a spin glass generally requires that magnetic exchange interactions are both frustrated and disordered. Consequently, the origin of spin-glass behavior in Y 2Mo 2O 7-in which magnetic Mo 4+ ions occupy a frustrated pyrochlore lattice with minimal compositional disorder-has been a longstanding question. Here, we use neutron and x-ray pair-distribution function (PDF) analysis to develop a disorder model that resolves apparent incompatibilities between previously reported PDF, extended x-rayabsorption fine structure spectroscopy, and NMR studies, and provides a new and physical explanation of the exchange disorder responsible for spin-glass formation. We show that Mo 4+ ions displace accordingmore » to a local "two-in-two-out" rule on each Mo 4 tetrahedron, driven by orbital dimerization of Jahn-Teller active Mo 4+ ions. Long-range orbital order is prevented by the macroscopic degeneracy of dimer coverings permitted by the pyrochlore lattice. Cooperative O 2- displacements yield a distribution of Mo-O-Mo angles, which in turn introduces disorder into magnetic interactions. In conclusion, our study demonstrates experimentally how frustration of atomic displacements can assume the role of compositional disorder in driving a spin-glass transition.« less

An Angular Overlap Model for Cu(II) Ion in the AMOEBA Polarizable Force Field

PubMed Central

Xiang, Jin Yu; Ponder, Jay W.

2014-01-01

An extensible polarizable force field for transition metal ion was developed based on AMOEBA and the angular overlap model (AOM) with consistent treatment of electrostatics for all atoms. Parameters were obtained by fitting molecular mechanics (MM) energies to various ab initio gas-phase calculations. The results of parameterization were presented for copper (II) ion ligated to water and model fragments of amino acid residues involved in the copper binding sites of type 1 copper proteins. Molecular dynamics (MD) simulations were performed on aqueous copper (II) ion at various temperatures, as well as plastocyanin (1AG6) and azurin (1DYZ). Results demonstrated that the AMOEBA-AOM significantly improves the accuracy of classical MM in a number of test cases when compared to ab initio calculations. The Jahn-Teller distortion for hexa-aqua copper (II) complex was handled automatically without specifically designating axial and in-plane ligands. Analyses of MD trajectories resulted in a 6-coordination first solvation shell for aqueous copper (II) ion and a 1.8ns average residence time of water molecules. The ensemble average geometries of 1AG6 and 1DYZ copper binding sites were in general agreement with X-ray and previous computational studies. PMID:25045338

Spin-state responses to light impurity substitution in low-spin perovskite LaCoO3

NASA Astrophysics Data System (ADS)

Tomiyasu, Keisuke; Kubota, Yuuki; Shimomura, Saya; Onodera, Mitsugi; Koyama, Syun-Ichi; Nojima, Tsutomu; Ishihara, Sumio; Nakao, Hironori; Murakami, Youichi

2013-06-01

We studied the spin-state responses to light impurity substitution in low-spin perovskite LaCoO3 (Co3+: d6) through magnetization, x-ray fluorescence, and electrical resistivity measurements of single-crystal LaCo0.99M0.01O3 (M = Cr, Mn, Fe, Ni). In the magnetization curves measured at 1.8 K, a change in the spin-state was not observed for Cr, Mn, or Fe substitution but was observed for Ni substitution. Strong magnetic anisotropy was also found in the Ni-substituted sample. The fluorescence measurements revealed that the valences were roughly estimated to be Cr3+, Mn(4-δ)+, Fe(3+δ')+, and Ni3+. From the observed chemical trends, we propose that the chemical potential is a key factor in inducing the change of the low-spin state. By expanding a model of the ferromagnetic spin-state heptamer generated by hole doping [Podlesnyak , Phys. Rev. Lett.PRLTAO0031-900710.1103/PhysRevLett.101.247603 101, 247603 (2008)], the emergence of highly anisotropic spin-state molecular ferromagnets induced by low-spin Ni3+ with Jahn-Teller activity is suggested. We also discuss applicability of the present results to other materials with Fe (d6).

Ba3CuOs2O9 and Ba3ZnOs2O9, a comparative study

NASA Astrophysics Data System (ADS)

Feng, Hai L.; Jansen, Martin

2018-02-01

Polycrystalline samples of Ba3CuOs2O9 and Ba3ZnOs2O9 were synthesized by solid-state reactions. Ba3CuOs2O9 crystallizes in Cmcm, while Ba3ZnOs2O9 adopts the hexagonal space group P63/mmc. Both the crystal structures consist of face-sharing Os-centered octahedra forming dimer-like Os2O9 units, which are interconnected by corner-sharing CuO6, or ZnO6 octahedra, respectively. In Ba3CuOs2O9, the CuO6 octahedra show a characteristic Jahn-Teller distortion. Both, Ba3CuOs2O9 and Ba3ZnOs2O9, are electrically insulating. Magnetic and specific heat measurements confirm that Ba3CuOs2O9 is antiferromagnetically ordered below 47 K. Analysis of the magnetic data indicated that its magnetic properties are dominated by Cu2+ ions. The magnetic susceptibility of Ba3ZnOs2O9 is weakly temperature-dependent with a broad maximum ≈ 280 K, indicating the presence of strong exchange interactions within the Os2O9 dimer. The residual magnetic susceptibility at low temperatures also suggests the presence of appreciable exchange coupling between the dimers.

Temperature-dependent and anisotropic optical response of layered Pr0.5Ca1.5MnO4 probed by spectroscopic ellipsometry

NASA Astrophysics Data System (ADS)

Majidi, M. A.; Thoeng, E.; Gogoi, P. K.; Wendt, F.; Wang, S. H.; Santoso, I.; Asmara, T. C.; Handayani, I. P.; van Loosdrecht, P. H. M.; Nugroho, A. A.; Rübhausen, M.; Rusydi, A.

2013-06-01

We study the temperature dependence as well as anisotropy of optical conductivity (σ1) in the pseudocubic single crystal Pr0.5Ca1.5MnO4 using spectrocopic ellipsometry. Three transition temperatures are observed and can be linked to charge-orbital (TCO/OO˜320 K), two-dimensional-antiferromagnetic (2D-AFM) (˜200 K), and three-dimensional AFM (TN˜125 K) orderings. Below TCO/OO, σ1 shows a charge-ordering peak (˜0.8 eV) with a significant blue shift as the temperature decreases. Calculations based on a model that incorporates a static Jahn-Teller distortion and assumes the existence of a local charge imbalance between two different sublattices support this assignment and explain the blue shift. This view is further supported by the partial spectral weight analysis showing the onset of optical anisotropy at TCO/OO in the charge-ordering region (0.5-2.5 eV). Interestingly, in the charge-transfer region (2.5-4 eV), the spectral weight shows anomalies around the T2D-AFM that we attribute to the role of oxygen-p orbitals in stabilizing the CE-type magnetic ordering. Our result shows the importance of spin, charge, orbital, and lattice degrees of freedom in this layered manganite.

Negative Ion Photoelectron Spectroscopy Confirms the Prediction that D-3h Carbontrioxide (CO 3) Has a Singlet Ground State

DOE PAGES

Hrovat, David; Hou, Gao-Lei; Chen, Bo; ...

2015-11-13

The CO 3 radical anion (CO 3 •–) has been formed by electrospraying carbonate dianion (CO 3 2–) into the gas phase. The negative ion photoelectron (NIPE) spectrum of CO 3 •– shows that, unlike trimethylenemethane [C(CH 2) 3], carbontrioxide (CO 3) has a singlet ground state. From the NIPE spectrum, the electron affinity of CO 3 was determined to be EA = 4.06 ± 0.03 eV, and the singlet-triplet energy difference was found to be ΔEST = - 17.8 ± 0.9 kcal/mol. B3LYP, CCSD(T), and CASPT2 calculations all find that the two lowest triplet states of CO 3 aremore » very close in energy, a prediction that is confirmed by the relative intensities of the bands in the NIPE spectrum of CO 3 •–. The 560 cm -1 vibrational progression, seen in the low energy region of the triplet band, enables the identification of the lowest, Jahn-Teller-distorted, triplet state as 3A 1, in which both unpaired electrons reside in σ MOs, rather than 3A 2, in which one unpaired electron occupies the b 2 σ MO, and the other occupies the b 1 π MO.« less

High-lying Gamow-Teller excited states in the deformed nuclei,76Ge,82Se and N = 20 nuclei in the island of inversion by the Deformed QRPA (DQRPA)

NASA Astrophysics Data System (ADS)

Cheoun, Myung-Ki; Ha, Eunja

2013-07-01

With the advent of high analysis technology in detecting the Gamow-Teller (GT) excited states beyond one nucleon emission threshold, the quenching of the GT strength to the Ikeda sum rule (ISR) seems to be recovered by the high-lying (HL) GT states. We address that these HL GT excited states result from the smearing of the Fermi surface by the increase of the chemical potential owing to the deformation within a framework of the deformed quasi-particle random phase approximation (DQRPA). Detailed mechanism leading to the smearing is discussed, and comparisons to the available experimental data on 76Ge,82Se and N = 20 nuclei are shown to explain the strong peaks on the HL GT excited states.

Molecular design of cage iron(II) and cobalt(II,III) complexes with a second fluorine-enriched superhydrophobic shell.

PubMed

Belov, Alexander S; Zelinskii, Genrikh E; Varzatskii, Oleg A; Belaya, Irina G; Vologzhanina, Anna V; Dolganov, Alexander V; Novikov, Valentin V; Voloshin, Yan Z

2015-02-28

Pentafluorophenylboron-capped iron and cobalt(II) hexachloroclathrochelate precursors were obtained by the one-pot template condensation of dichloroglyoxime with pentafluorophenylboronic acid on iron and cobalt(II) ions under vigorous reaction conditions in trifluoroacetic acid media. These reactive precursors easily undergo nucleophilic substitution with (per)fluoroarylthiolate anions, giving (per)fluoroarylsulfide macrobicyclic complexes with encapsulated iron and cobalt(II) ions; nucleophilic substitution of the cobalt(II) hexachloroclathrochelate precursor with a pentafluorophenylsulfide anion gave the target hexasulfide monoclathrochelate and the mixed-valence Co(III)Co(II)Co(III) bis-clathrochelate as a side product. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV-Vis, (57)Fe Mössbauer (for the X-rayed iron complexes), (1)H, (11)B, (13)C and (19)F NMR spectroscopies and by X-ray diffraction; their redox and electrocatalytic behaviors were studied using cyclic voltammetry and gas chromatography. As can be seen from the single-crystal X-ray diffraction data, the second superhydrophobic shell of such caged metal ions is formed by fluorine atoms of both the apical and ribbed (per)fluoroaryl peripheral groups. The main bond distances and chelate N=C-C=N angles in their molecules are similar, but rotational elongation (contraction) along the molecular C3-pseudoaxes, accompanied by changes in the geometry of the corresponding MN6-coordination polyhedra from a trigonal prism to a trigonal antiprism, allowed encapsulating Fe(2+), Co(2+) and Co(3+) ions. The nature of an encapsulated metal ion and its oxidation state affect the M-N bond lengths, and, for cobalt(ii) clathrochelate with an electronic configuration d(7) the Jahn-Teller structural effect is observed as an alternation of the Co-N distances. Pentafluorophenylboron-capped hexachloroclathrochelate precursors, giving stable catalytically active metal

Polaron melting and ordering as key mechanisms for colossal resistance effects in manganites

PubMed Central

Jooss, Ch.; Wu, L.; Beetz, T.; Klie, R. F.; Beleggia, M.; Schofield, M. A.; Schramm, S.; Hoffmann, J.; Zhu, Y.

2007-01-01

Polarons, the combined motion of electrons in a cloth of their lattice distortions, are a key transport feature in doped manganites. To develop a profound understanding of the colossal resistance effects induced by external fields, the study of polaron correlations and the resulting collective polaron behavior, i.e., polaron ordering and transition from polaronic transport to metallic transport is essential. We show that static long-range ordering of Jahn–Teller polarons forms a polaron solid which represents a new type of charge and orbital ordered state. The related noncentrosymmetric lattice distortions establish a connection between colossal resistance effects and multiferroic properties, i.e., the coexistence of ferroelectric and antiferromagnetic ordering. Colossal resistance effects due to an electrically induced polaron solid–liquid transition are directly observed in a transmission electron microscope with local electric stimulus applied in situ using a piezo-controlled tip. Our results shed light onto the colossal resistance effects in magnetic field and have a strong impact on the development of correlated electron-device applications such as resistive random access memory (RRAM). PMID:17699633

Study of Gamow-Teller strength and associated weak-rates on odd-A nuclei in stellar matter

NASA Astrophysics Data System (ADS)

Majid, Muhammad; Nabi, Jameel-Un; Riaz, Muhammad

In a recent study by Cole et al. [A. L. Cole et al., Phys. Rev. C 86 (2012) 015809], it was concluded that quasi-particle random phase approximation (QRPA) calculations show larger deviations and overestimate the total experimental Gamow-Teller (GT) strength. It was also concluded that QRPA calculated electron capture rates exhibit larger deviation than those derived from the measured GT strength distributions. The main purpose of this study is to probe the findings of the Cole et al. paper. This study gives useful information on the performance of QRPA-based nuclear models. As per simulation results, the capturing of electrons that occur on medium heavy isotopes have a significant role in decreasing the ratio of electron-to-baryon content of the stellar interior during the late stages of core evolution. We report the calculation of allowed charge-changing transitions strength for odd-A fp-shell nuclei (45Sc and 55Mn) by employing the deformed pn-QRPA approach. The computed GT transition strength is compared with previous theoretical calculations and measured data. For stellar applications, the corresponding electron capture rates are computed and compared with rates using previously calculated and measured GT values. Our finding shows that our calculated results are in decent accordance with measured data. At higher stellar temperature, our calculated electron capture rates are larger than those calculated by independent particle model (IPM) and shell model. It was further concluded that at low temperature and high density regions, the positron emission weak-rates from 45Sc and 55Mn may be neglected in simulation codes.

FEMALE SEX AND DISCONTINUATION OF ISONIAZID DUE TO ADVERSE EFFECTS DURING THE TREATMENT OF LATENT TUBERCULOSIS

PubMed Central

Pettit, April C.; Bethel, James; Hirsch-Moverman, Yael; Colson, Paul W.; Sterling, Timothy R.

2013-01-01

SUMMARY Objectives To determine the rate of and risk factors for discontinuation of isoniazid due to adverse effects during the treatment of latent tuberculosis infection in a large, multi-site study. Methods The Tuberculosis Epidemiologic Studies Consortium (TBESC) conducted a prospective study from March 2007–September 2008 among adults initiating isoniazid for treatment of LTBI at 12 sites in the US and Canada. The relative risk for isoniazid discontinuation due to adverse effects was determined using negative binomial regression. Adjusted models were constructed using forward stepwise regression. Results Of 1,306 persons initiating isoniazid, 617 (47.2%, 95% CI 44.5–50.0%) completed treatment and 196 (15.0%, 95% CI 13.1–17.1%) discontinued due to adverse effects. In multivariable analysis, female sex (RR 1.67, 95% CI 1.32–2.10, p<0.001) and current alcohol use (RR 1.41, 95% CI 1.13–1.77, p=0.003) were independently associated with isoniazid discontinuation due to adverse effects. Conclusions The rate of discontinuation of isoniazid due to adverse effects was substantially higher than reported earlier. Women were at increased risk of discontinuing isoniazid due to adverse effects; close monitoring of women for adverse effects may be warranted. Current alcohol use was also associated with isoniazid discontinuation; counseling patients to abstain from alcohol could decrease discontinuation due to adverse effects. PMID:23845828

Effect of intratympanic dexamethasone, memantine and piracetam on cellular apoptosis due to cisplatin ototoxicity.

PubMed

Topdag, M; Iseri, M; Gelenli, E; Yardimoglu, M; Yazir, Y; Ulubil, S A; Topdag, D O; Ustundag, E

2012-11-01

This study aimed to contribute to the literature on the prevention and treatment of ototoxicity due to various drugs and chemicals. This study compared the histological effects of intratympanic dexamethasone, memantine and piracetam on cellular apoptosis due to cisplatin ototoxicity, in 36 rats. Dexamethasone and memantine had significant effects on the stria vascularis, organ of Corti and spiral ganglion (p < 0.05). Although piracetam decreased the apoptosis rate, this effect was not statistically significant (p > 0.05). Dexamethasone and memantine were found superior to piracetam in reducing apoptosis due to cisplatin ototoxicity. Further studies of this subject are needed, incorporating electron microscopy and auditory brainstem response testing.

The inhibitory spillover effect: Controlling the bladder makes better liars *

PubMed Central

Fenn, Elise; Blandón-Gitlin, Iris; Coons, Jennifer; Pineda, Catherine; Echon, Reinalyn

2015-01-01

The Inhibitory-Spillover-Effect (ISE) on a deception task was investigated. The ISE occurs when performance in one self-control task facilitates performance in another (simultaneously conducted) self-control task. Deceiving requires increased access to inhibitory control. We hypothesized that inducing liars to control urination urgency (physical inhibition) would facilitate control during deceptive interviews (cognitive inhibition). Participants drank small (low-control) or large (high-control) amounts of water. Next, they lied or told the truth to an interviewer. Third-party observers assessed the presence of behavioral cues and made true/lie judgments. In the high-control, but not the low-control condition, liars displayed significantly fewer behavioral cues to deception, more behavioral cues signaling truth, and provided longer and more complex accounts than truth-tellers. Accuracy detecting liars in the high-control condition was significantly impaired; observers revealed bias toward perceiving liars as truth-tellers. The ISE can operate in complex behaviors. Acts of deception can be facilitated by covert manipulations of self-control. PMID:26366466

Structural characterization combined with the first principles simulations of barium/strontium cobaltite/ferrite as promising material for solid oxide fuel cells cathodes and high-temperature oxygen permeation membranes.

PubMed

Gangopadhayay, Shruba; Inerbaev, Talgat; Masunov, Artëm E; Altilio, Deanna; Orlovskaya, Nina

2009-07-01

Mixed ionic-electronic conducting perovskite type oxides with a general formula ABO(3) (where A = Ba, Sr, Ca and B = Co, Fe, Mn) often have high mobility of the oxygen vacancies and exhibit strong ionic conductivity. They are key materials that find use in several energy related applications, including solid oxide fuel cell (SOFC), sensors, oxygen separation membranes, and catalysts. Barium/strontium cobaltite/ferrite (BSCF) Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-delta) was recently identified as a promising candidate for cathode material in intermediate temperature SOFCs. In this work, we perform experimental and theoretical study of the local atomic structure of BSFC. Micro-Raman spectroscopy was performed to characterize the vibrational properties of BSCF. The Jahn-Teller distortion of octahedral coordination around Co(4+) cations was observed experimentally and explained theoretically. Different cations and oxygen vacancies ordering are examined using plane wave pseudopotential density functional theory. We find that cations are completely disordered, whereas oxygen vacancies exhibit a strong trend for aggregation in L-shaped trimer and square tetramer structure. On the basis of our results, we suggest a new explanation for BSCF phase stability. Instead of linear vacancy ordering, which must take place before the phase transition into brownmillerite structure, the oxygen vacancies in BSCF prefer to form the finite clusters and preserve the disordered cubic structure. This structural feature could be found only in the first-principles simulations and can not be explained by the effect of the ionic radii alone.

Ab Initio Ligand Field Molecular Mechanics and the Nature of Metal-Ligand π-Bonding in Fe(II) 2,6-di(pyrazol-1-yl)pyridine Spin Crossover Complexes.

PubMed

Deeth, Robert J; Halcrow, Malcolm A; Kershaw Cook, Laurence J; Raithby, Paul R

2018-04-06

A ligand field molecular mechanics (LFMM) force field has been constructed for the spin states of [Fe(bpp) 2 ] 2+ (bpp=2,6-di(pyrazol-1-yl)pyridine) and related complexes. A new charge scheme is employed which interpolates between partial charges for neutral bpp and protonated [H 3 bpp] 3+ to achieve a target metal charge. The LFMM angular overlap model (AOM) parameters are fitted to fully ab initio d orbital energies. However, several AOM parameter sets are possible. The ambiguity is resolved by calculating the Jahn-Teller distortion mode for high spin, which indicates that in [Fe(bpp) 2 ] 2+ pyridine is a π-acceptor and pyrazole a weak π-donor. The alternative fit, assumed previously, where both ligands act as π-donors leads to an inconsistent distortion. LFMM optimisations in the presence of [BF 4 ] - or [PF 6 ] - anions are in good agreement with experiment and the model also correctly predicts the spin state energetics for 3-pyrazolyl substituents where the interactions are mainly steric. However, for 4-pyridyl or 4-pyrazolyl substituents, LFMM only treats the electrostatic contribution which, for the pyridyl substituents, generates a fair correlation with the spin crossover transition temperatures, T 1/2 , but in the reverse sense to the dominant electronic effect. Thus, LFMM generates its smallest spin state energy difference for the substituent with the highest T 1/2 . One parameter set for all substituted bpp ligands is insufficient and further LFMM development will be required. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Renner-Teller quantum dynamics of NH(a(1)Delta) + H reactions on the NH(2) A(2)A(1) and X(2)B(1) coupled surfaces.

PubMed

Defazio, P; Gamallo, P; González, M; Petrongolo, C

2010-09-16

Four reactions NH(a1Delta) + H′(2S) are investigated by the quantum mechanical real wavepacket method, taking into account nonadiabatic Renner-Teller (RT) and rovibronic Coriolis couplings between the involved states. We consider depletion (d) to N(2D) + H2(X1Sigmag+), exchange (e) to NH′(a1Delta) + H(2S), quenching (q) to NH(X3Sigma-) + H′(2S), and exchange-quenching (eq) to NH′(X3Sigma-) + H(2S). We extend our RT theory to a general AB + C collision using a geometry-dependent but very simple and empirical RT matrix element. Reaction probabilities, cross sections, and rate constants are presented, and RT results are compared with Born-Oppenheimer (BO), experimental, and semiclassical data. The nonadiabatic couplings open two new channels, (q) and (eq), and increase the (d) and (e) reactivity with respect to the BO one, when NH(a1Delta) is rotationally excited. In this case, the quantum cross sections are larger than the semiclassical ones at low collision energies. The calculated rate constants at 300 K are k(d) = 3.06, k(e) = 3.32, k(q) = 1.44, and k(eq) = 1.70 in 10(-11) cm3 s(-1) compared with the measured values k(d) = (3.2 =/- 1.7), k(q + eq) = (1.7 +/- 0.3), and k(total) = (4.8 +/- 1.7). The theoretical depletion rate is thus in good agreement with the experimental value, but the quenching and total rates are overestimated, because the present RT couplings are too large. This discrepancy is probably due to our simple and empirical RT matrix element.

Effect of calcination temperatures on microstructures and photocatalytic activity of tungsten trioxide hollow microspheres.

PubMed

Yu, Jiaguo; Qi, Lifang; Cheng, Bei; Zhao, Xiufeng

2008-12-30

Tungsten trioxide hollow microspheres were prepared by immersing SrWO4 microspheres in a concentrated HNO3 solution, and then calcined at different temperatures. The prepared tungsten oxide samples were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Fourier transform infrared spectra, differential thermal analysis-thermogravimetry, UV-visible spectrophotometry, scanning electron microscopy, N2 adsorption/desorption measurements. The photocatalytic activity of the samples was evaluated by photocatalytic decolorization of rhodamine B aqueous solution under visible-light irradiation. It was found that with increasing calcination temperatures, the average crystallite size and average pore size increased, on the contrary, Brunauer-Emmett-Teller-specific surface areas decreased. However, pore volume and porosity increased firstly, and then decreased. Increasing calcination temperatures resulted in the changes of surface morphology of hollow microspheres. The un-calcined and 300 degrees C-calcined samples showed higher photocatalytic activity than other samples. At 400 degrees C, the photocatalytic activity decreased greatly due to the decrease of specific surface areas. At 500 degrees C, the photocatalytic activity of the samples increased again due to the junction effect of two phases.

Global earthquake casualties due to secondary effects: A quantitative analysis for improving PAGER losses

USGS Publications Warehouse

Wald, David J.

2010-01-01

This study presents a quantitative and geospatial description of global losses due to earthquake-induced secondary effects, including landslide, liquefaction, tsunami, and fire for events during the past 40 years. These processes are of great importance to the US Geological Survey’s (USGS) Prompt Assessment of Global Earthquakes for Response (PAGER) system, which is currently being developed to deliver rapid earthquake impact and loss assessments following large/significant global earthquakes. An important question is how dominant are losses due to secondary effects (and under what conditions, and in which regions)? Thus, which of these effects should receive higher priority research efforts in order to enhance PAGER’s overall assessment of earthquakes losses and alerting for the likelihood of secondary impacts? We find that while 21.5% of fatal earthquakes have deaths due to secondary (non-shaking) causes, only rarely are secondary effects the main cause of fatalities. The recent 2004 Great Sumatra–Andaman Islands earthquake is a notable exception, with extraordinary losses due to tsunami. The potential for secondary hazards varies greatly, and systematically, due to regional geologic and geomorphic conditions. Based on our findings, we have built country-specific disclaimers for PAGER that address potential for each hazard (Earle et al., Proceedings of the 14th World Conference of the Earthquake Engineering, Beijing, China, 2008). We will now focus on ways to model casualties from secondary effects based on their relative importance as well as their general predictability.

Solar Sail Topology Variations Due to On-Orbit Thermal Effects

NASA Technical Reports Server (NTRS)

Banik, Jeremy A.; Lively, Peter S.; Taleghani, Barmac K.; Jenkins, Chrostopher H.

2006-01-01

The objective of this research was to predict the influence of non-uniform temperature distribution on solar sail topology and the effect of such topology variations on sail performance (thrust, torque). Specifically considered were the thermal effects due to on orbit attitude control maneuvers. Such maneuvers are expected to advance the sail to a position off-normal to the sun by as much as 35 degrees; a solar sail initially deformed by typical pre-tension and solar pressure loads may suffer significant thermally induced strains due to the non-uniform heating caused by these maneuvers. This on-orbit scenario was investigated through development of an automated analytical shape model that iterates many times between sail shape and sail temperature distribution before converging on a final coupled thermal structural affected sail topology. This model utilizes a validated geometrically non-linear finite element model and a thermal radiation subroutine. It was discovered that temperature gradients were deterministic for the off-normal solar angle cases as were thermally induced strains. Performance effects were found to be moderately significant but not as large as initially suspected. A roll torque was detected, and the sail center of pressure shifted by a distance that may influence on-orbit sail control stability.

Substrate-dependent structural and CO sensing properties of LaCoO3 epitaxial films

NASA Astrophysics Data System (ADS)

Liu, Haifeng; Sun, Hongjuan; Xie, Ruishi; Zhang, Xingquan; Zheng, Kui; Peng, Tongjiang; Wu, Xiaoyu; Zhang, Yanping

2018-06-01

LaCoO3 thin films were grown on different (0 0 1) oriented LaAlO3, SrTiO3 and (LaAlO3)0.3(Sr2AlTaO6)0.7 by the polymer assisted deposition method, respectively. All the LaCoO3 thin films are in epitaxial growth on these substrates, with tetragonal distortion of CoO6 octahedrons. Due to different in-plane lattice mismatch, the LaCoO3 film on LaAlO3 has the largest tetragonal distortion of CoO6 octahedrons while the film grown on (LaAlO3)0.3(Sr2AlTaO6)0.7 has the smallest tetragonal distortion. The relative contents of the surface absorbed oxygen species are found to increase for the LaCoO3 epitaxial films grown on (0 0 1) oriented (LaAlO3)0.3(Sr2AlTaO6)0.7, SrTiO3 and LaAlO3 substrates, sequentially. The film sensors exhibit good CO sensing properties at 150 °C, and the LaCoO3 film on LaAlO3 shows the highest response but the film on (LaAlO3)0.3(Sr2AlTaO6)0.7 shows the lowest. It reveals that the larger degree of Jahn-Teller-like tetragonal distortion of CoO6 octahedrons may greatly improve the surface absorbing and catalytic abilities, corresponding to more excellent CO sensing performance. The present study suggests that the formation of epitaxial films is an efficient methodology for controlling the octahedral distortion and thereby improving the gas sensing performance of perovskite transition metal oxides.

Structure refinements of members in the brownmillerite solid solution series Ca{sub 2}Al{sub x}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}O{sub 5+{delta}} with 1/2{<=}x{<=}4/3

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

Stoeber, Stefan, E-mail: stefan.stoeber@geo.uni-halle.de; Redhammer, Guenther; Schorr, Susan

2013-01-15

Four different brownmillerite solid solutions Ca{sub 2}Al{sub x}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}O{sub 5+{delta}} with 1/2{<=}x{<=}4/3 were synthesized by a solid oxide ceramic method. The phases crystallize either in a primitive centered orthorhombic cell with space group Pnma or in a body centered cell with space group I2mb dependent on the aluminum concentration present in the solid solution. Mn{sup 3+} ions occupy exclusively site 4a coordinated by six oxygen anions. Increasing Mn{sup 3+} concentrations cause a remarkable distortion of the octahedron and indirectly of the tetrahedron, resulting in twisted and tilted octahedral layers as well as buckled tetrahedral chains. The influences aremore » discussed on the site 4a of trivalent manganese due to its Jahn-Teller activity, with regard to the occupation of octahedron and tetrahedron with different sized iron and aluminum ions. - Graphical Abstract: The coupled substitution Fe{sup 3+}>Mn{sup 3+}+Fe{sup 3+} <=>2 Al{sup 3+} in brownmillerite phases (Ca{sub 2}(Fe{sub 0.5}Mn{sub 0.5}){sub 2-x}Al{sub x}O{sub 5+{delta}}) changes predominantly their structural properties, which is essential for the hydration performance of the calcium aluminate cement, where brownmillerites occur as clinker phases. Highlights: Black-Right-Pointing-Pointer We present structural data of four Ca-Al-Fe-Mn-brownmillerites. Black-Right-Pointing-Pointer Mn{sup 3+}-ions occupy exclusively the octahedrally coordinated site 0,0,0. Black-Right-Pointing-Pointer Bonds and angles of the octahedrally coordinated site are distorted strongly. Black-Right-Pointing-Pointer Mn{sup 3+}-ions influence indirectly the shape of the tetrahedron. Black-Right-Pointing-Pointer Mn{sup 3+}-ions stabilize Pnma instead of I2mb in Ca-Al-Fe-Mn-brownmillerites.« less

Estimated probabilities and volumes of postwildfire debris flows—A prewildfire evaluation for the Pikes Peak area, El Paso and Teller Counties, Colorado

USGS Publications Warehouse

Elliott, John G.; Ruddy, Barbara C.; Verdin, Kristine L.; Schaffrath, Keelin R.

2012-01-01

Debris flows are fast-moving, high-density slurries of water, sediment, and debris that can have enormous destructive power. Although debris flows, triggered by intense rainfall or rapid snowmelt on steep hillsides covered with erodible material, are a common geomorphic process in some unburned areas, a wildfire can transform conditions in a watershed with no recent history of debris flows into conditions that pose a substantial hazard to residents, communities, infrastructure, aquatic habitats, and water supply. The location, extent, and severity of wildfire and the subsequent rainfall intensity and duration cannot be known in advance; however, hypothetical scenarios based on empirical debris-flow models are useful planning tools for conceptualizing potential postwildfire debris flows. A prewildfire study to determine the potential for postwildfire debris flows in the Pikes Peak area in El Paso and Teller Counties, Colorado, was initiated in 2010 by the U.S. Geological Survey, in cooperation with the City of Colorado Springs, Colorado Springs Utilities. The study was conducted to provide a relative measure of which subwatersheds might constitute the most serious potential debris-flow hazards in the event of a large-scale wildfire and subsequent rainfall.

The Rovibronic Spectra of the Cyclopentadienyl Radical

NASA Astrophysics Data System (ADS)

Sharma, Ketan; Miller, Terry A.; Stanton, John F.; Nesbitt, David

2017-06-01

Cyclopentadienyl (Cp) radical has been subject to numerous studies for the greater part of half a century. Experimental work has involved photo-electron spectroscopy, laser induced fluorescence excitation and emission, infrared absorption spectroscopy, and recently rotationally resolved spectra in the CH stretch region taken at JILA. Even more theoretical works appear in the literature, but substantial advances in computation have occurred since their completion. Cp's highly symmetric (D_{5h}) structure and doubly degenerate electronic ground (˜{X}^2E_1^{''}), which is subject to linear Jahn-Teller distortion, have been a great motivation for work on it. We have commenced new computational work to obtain a broad understanding of the electronic, vibrational, and rotational, i.e. rovibronic, structure of the Cp radical as revealed by its spectra, with particular emphasis on the new infrared spectra. The goal is to guide experiments and their analyses and reconcile results from spectroscopy and quantum chemistry calculations. T. Ichino, et al. J. Chem. Phys. 129, 084310 (2008) L. Yu, S. C. Foster, J. M. Williamson, M. C. Heaven and T. A. Miller J. Phys. Chem. 92, 4263 (1988) B. E. Applegate, A. J. Bezant and T. A. Miller J. Chem. Phys 114, 4869 (2001) D. Leicht, M. Kaufmann, G. Schwaab, and M. Havenith J. Chem. Phys. 145, 7 (2016), 074304.

Crystal and magnetic structure of the La1-xCaxMnO3 compound (0.11⩽x⩽0.175)

NASA Astrophysics Data System (ADS)

Pissas, M.; Margiolaki, I.; Papavassiliou, G.; Stamopoulos, D.; Argyriou, D.

2005-08-01

We studied the crystal and magnetic structure of the La1-xCaxMnO3 compound for (0.11⩽x⩽0.175) using stoichiometric samples. For x<0.13 the system’s ground state is insulating canted antiferromagnetic. For 0.13⩽x⩽0.175 below the Jahn-Teller transition temperature (TJT) the crystal structure undergoes a monoclinic distortion. The crystal structure can be described with P21/c space group which permits two Mn sites. The unit-cell strain parameter s=2(a-c)/(a+c) increases for Ta>b/2) structure.

Nanoscale orbital excitations and the infrared spectrum of a molecular Mott insulator: A15-Cs3C60.

PubMed

Naghavi, S S; Fabrizio, M; Qin, T; Tosatti, E

2016-10-14

The quantum physics of ions and electrons behind low-energy spectra of strongly correlated molecular conductors, superconductors and Mott insulators is poorly known, yet fascinating especially in orbitally degenerate cases. The fulleride insulator Cs 3 C 60 (A15), one such system, exhibits infrared (IR) spectra with low temperature peak features and splittings suggestive of static Jahn-Teller distortions with a breakdown of orbital symmetry in the molecular site. That is puzzling, since there is no detectable static distortion, and because the features and splittings disappear upon modest heating, which they should not. Taking advantage of the Mott-induced collapse of electronic wavefunctions from lattice-extended to nanoscale localized inside a caged molecular site, we show that the unbroken spin and orbital symmetry of the ion multiplets explains the IR spectrum without adjustable parameters. This demonstrates the importance of a fully quantum treatment of nuclear positions and orbital momenta in the Mott insulator sites, dynamically but not statically distorted. The observed demise of these features with temperature is explained by the thermal population of a multiplet term whose nuclear positions are essentially undistorted, but whose energy is very low-lying. That term is in fact a scaled-down orbital excitation analogous to that of other Mott insulators, with the same spin 1/2 as the ground state, but with a larger orbital momentum of two instead of one.

Spin orbital singlet system FeSc2S4 under pressure

NASA Astrophysics Data System (ADS)

Biffin, Alun; Chernyshov, Dmitry; Canevet, Emmanuel; Fennell, Tom; White, Jonathan S.; Khasanov, Rustem; Luetkens, Hubertus; Loidl, Alois; Tsurkan, Vladimir; Rüegg, Christian

The role of orbital degrees of freedom in quantum magnets is receiving intense focus recently, with the understanding that spin-orbit coupled systems can display physics qualitatively different from their spin only counter parts. An example is the spin-orbital singlet (SOS) state, which can provide an alternative to the conventional spin and orbitally ordered groundstates of quantum magnets. In such a scenario, the relative strengths of the exchange interaction and spin orbit coupling parameters determine the low temperature structure, with the former preferring ordered moments and the latter a non-magnetic singlet. Moreover the quantum critical point separating these two phases is rather unique in that it marks the onset of criticality in both the spin and orbital sectors. This SOS picture has recently been applied to FeSc2S4, where despite strong antiferromagnetic exchange between Jahn-Teller active Fe2+ ions no experimental signature of spin or orbital order has been detected. Building on our previous neutron scattering measurements, we have used hydrostatic pressure in neutron scattering, muon spin rotation and x-ray diffraction measurements to probe the unique phase diagram of FeSc2S4. My talk will focus on the results and interpretation of these experiments SNF SCOPES project IZ73Z0_152734/1, the Marie Curie FP7 COFUND PSI Fellowship program, Swiss National Science Foundation.

Tailoring of magnetic orderings in Fe substituted GdMnO3 bulk samples towards room temperature

NASA Astrophysics Data System (ADS)

Pal, A.; Dhana Sekhar, C.; Venimadhav, A.; Murugavel, P.

2017-10-01

The evolution of various magnetic ordering has been studied for the orthorhombic perovskite GdMn1-x Fe x O3 (0  ⩽  x  ⩽  0.7) system to obtain its comprehensive magnetic phase diagram. We observed that the substitution of Fe in GdMnO3 increases the antiferromagnetic Neel temperature (T N) from 40 K to above 400 K and importantly induces a spin-reorientation transition (T SR) for x  ⩾  0.4. These transitions are close to room temperature at x  =  0.5 and then gradually separated at a higher x value. The static orbital ordering induced by the Jahn-Teller distortion seems to play an important role in changing the T N. The variations of spin-reorientation ordering along with the competition between the magnetic orderings as a function of the composition were discussed with respect to antisymmetric exchange interactions and Mn3+ single-ion anisotropy in detail. In addition, the correlation between structural and magnetic properties suggests that the subtle structural change at composition x  =  0.4 may affect the magnetic ordering. The observed tunable T SR and T N in GdMn1-x Fe x O3 could add a practical value for these compositions in fields like spintronics and sensors.

Charge versus orbital-occupancy ordering in manganites

NASA Astrophysics Data System (ADS)

Luo, Weidong; Varela, Maria; Tao, Jing; Pennycook, Stephen J.; Pantelides, Sokrates T.

2006-03-01

It is generally assumed that density-functional theory (DFT) in the local-spin-density approximation (LSDA) or the generalized- gradient approximation (GGA) is not adequate to describe mixed- valence manganites. Here we report benchmark DFT/GGA calculations for the ground-state structural, electronic and magnetic properties for both undoped and doped CaMnO3 and find the results to be in excellent agreement with available data, including new atomic-resolution Z-contrast imaging and electron-energy loss spectra. More specifically, we found that the DFT results predict two inequivalent Mn atoms in both 0.33 and 0.5 electron-doped CaMnO3, in agreement with experimental evidence of Mn^+3/Mn^+4 oxidation state ordering. The inequivalent Mn atoms are marked by their distinctive orbital occupancies, dissimilar local Jahn-Teller distortion and different magnetic moments from DFT calculations. We also show that the spherically integrated charges associated with the two inequivalent Mn atoms are the same, and they are actually the same as in the Mn metal. This charge neutrality with different orbital occupancies is the result of self-consistency and atomic relaxations in the crystal. We conclude that DFT without additional correlations can account for the observed properties of oxidation-state ordering in this system. The impact of the results on other mixed-valence systems will be discussed.

Characterization of oxygen defects in diamond by means of density functional theory calculations

NASA Astrophysics Data System (ADS)

Thiering, Gergő; Gali, Adam

2016-09-01

Point defects in diamond are of high interest as candidates for realizing solid state quantum bits, bioimaging agents, or ultrasensitive electric or magnetic field sensors. Various artificial diamond synthesis methods should introduce oxygen contamination in diamond, however, the incorporation of oxygen into diamond crystal and the nature of oxygen-related point defects are largely unknown. Oxygen may be potentially interesting as a source of quantum bits or it may interact with other point defects which are well established solid state qubits. Here we employ plane-wave supercell calculations within density functional theory, in order to characterize the electronic and magneto-optical properties of various oxygen-related defects. Besides the trivial single interstitial and substitutional oxygen defects we also consider their complexes with vacancies and hydrogen atoms. We find that oxygen defects are mostly electrically active and introduce highly correlated orbitals that pose a challenge for density functional theory modeling. Nevertheless, we are able to identify the fingerprints of substitutional oxygen defect, the oxygen-vacancy and oxygen-vacancy-hydrogen complexes in the electron paramagnetic resonance spectrum. We demonstrate that first principles calculations can predict the motional averaging of the electron paramagnetic resonance spectrum of defects that are subject to Jahn-Teller distortion. We show that the high-spin neutral oxygen-vacancy defect exhibits very fast nonradiative decay from its optical excited state that might hinder applying it as a qubit.

Global earthquake casualties due to secondary effects: A quantitative analysis for improving rapid loss analyses

USGS Publications Warehouse

Marano, K.D.; Wald, D.J.; Allen, T.I.

2010-01-01

This study presents a quantitative and geospatial description of global losses due to earthquake-induced secondary effects, including landslide, liquefaction, tsunami, and fire for events during the past 40 years. These processes are of great importance to the US Geological Survey's (USGS) Prompt Assessment of Global Earthquakes for Response (PAGER) system, which is currently being developed to deliver rapid earthquake impact and loss assessments following large/significant global earthquakes. An important question is how dominant are losses due to secondary effects (and under what conditions, and in which regions)? Thus, which of these effects should receive higher priority research efforts in order to enhance PAGER's overall assessment of earthquakes losses and alerting for the likelihood of secondary impacts? We find that while 21.5% of fatal earthquakes have deaths due to secondary (non-shaking) causes, only rarely are secondary effects the main cause of fatalities. The recent 2004 Great Sumatra-Andaman Islands earthquake is a notable exception, with extraordinary losses due to tsunami. The potential for secondary hazards varies greatly, and systematically, due to regional geologic and geomorphic conditions. Based on our findings, we have built country-specific disclaimers for PAGER that address potential for each hazard (Earle et al., Proceedings of the 14th World Conference of the Earthquake Engineering, Beijing, China, 2008). We will now focus on ways to model casualties from secondary effects based on their relative importance as well as their general predictability. ?? Springer Science+Business Media B.V. 2009.

Nuclear structure properties and stellar weak rates for 76Se: Unblocking of the Gamow Teller strength

NASA Astrophysics Data System (ADS)

Nabi, Jameel-Un; Ishfaq, Mavra; Böyükata, Mahmut; Riaz, Muhammad

2017-10-01

At finite temperatures (≥ 107K), 76Se is abundant in the core of massive stars and electron capture on 76Se has a consequential role to play in the dynamics of core-collapse. The present work may be classified into two main categories. In the first phase we study the nuclear structure properties of 76Se using the interacting boson model-1 (IBM-1). The IBM-1 investigations include the energy levels, B (E 2) values and the prediction of the geometry. We performed the extended consistent-Q formalism (ECQF) calculation and later the triaxial formalism calculation (constructed by adding the cubic term to the ECQF). The geometry of 76Se can be envisioned within the formalism of the potential energy surface based on the classical limit of IBM-1 model. In the second phase, we reconfirm the unblocking of the Gamow-Teller (GT) strength in 76Se (a test case for nuclei having N > 40 and Z < 40). Using the deformed pn-QRPA model we calculate GT transitions, stellar electron capture cross section (within the limit of low momentum transfer) and stellar weak rates for 76Se. The distinguishing feature of our calculation is a state-by-state evaluation of stellar weak rates in a fully microscopic fashion. Results are compared with experimental data and previous calculations. The calculated GT distribution fulfills the Ikeda sum rule. Rates for β-delayed neutrons and emission probabilities are also calculated. Our study suggests that at high stellar temperatures and low densities, the β+-decay on 76Se should not be neglected and needs to be taken into consideration along with electron capture rates for simulation of presupernova evolution of massive stars.

Tritium β decay in chiral effective field theory

DOE PAGES

Baroni, A.; Girlanda, L.; Kievsky, A.; ...

2016-08-18

We evaluate the Fermi and Gamow-Teller (GT) matrix elements in tritiummore » $$\\beta$$-decay by including in the charge-changing weak current the corrections up to one loop recently derived in nuclear chiral effective field theory ($$\\chi$$ EFT). The trinucleon wave functions are obtained from hyperspherical-harmonics solutions of the Schroedinger equation with two- and three-nucleon potentials corresponding to either $$\\chi$$ EFT (the N3LO/N2LO combination) or meson-exchange phenomenology (the AV18/UIX combination). We find that contributions due to loop corrections in the axial current are, in relative terms, as large as (and in some cases, dominate) those from one-pion exchange, which nominally occur at lower order in the power counting. Furthermore, we also provide values for the low-energy constants multiplying the contact axial current and three-nucleon potential, required to reproduce the experimental GT matrix element and trinucleon binding energies in the N3LO/N2LO and AV18/UIX calculations.« less

An investigation of the sites occupied by atomic barium in solid xenon—A 2D-EE luminescence spectroscopy and molecular dynamics study

NASA Astrophysics Data System (ADS)

Davis, Barry M.; Gervais, Benoit; McCaffrey, John G.

2018-03-01

A detailed characterisation of the luminescence recorded for the 6p 1P1-6s 1S0 transition of atomic barium isolated in annealed solid xenon has been undertaken using two-dimensional excitation-emission (2D-EE) spectroscopy. In the excitation spectra extracted from the 2D-EE scans, two dominant thermally stable sites were identified, consisting of a classic, three-fold split Jahn-Teller band, labeled the blue site, and an unusual asymmetric 2 + 1 split band, the violet site. A much weaker band has also been identified, whose emission is strongly overlapped by the violet site. The temperature dependence of the luminescence for these sites was monitored revealing that the blue site has a non-radiative channel competing effectively with the fluorescence even at 9.8 K. By contrast, the fluorescence decay time of the violet site was recorded to be 4.3 ns and independent of temperature up to 24 K. The nature of the dominant thermally stable trapping sites was investigated theoretically with Diatomics-in-Molecule (DIM) molecular dynamics simulations. The DIM model was parameterized with ab initio multi-reference configuration interaction calculations for the lowest energy excited states of the BaṡXe pair. The simulated absorption spectra are compared with the experimental results obtained from site-resolved excitation spectroscopy. The simulations allow us to assign the experimental blue feature spectrum to a tetra-vacancy trapping site in the bulk xenon fcc crystal—a site often observed when trapping other metal atoms in rare gas matrices. By contrast, the violet site is assigned to a specific 5-atom vacancy trapping site located at a grain boundary.

A facile approach to nanoarchitectured three-dimensional graphene-based Li-Mn-O composite as high-power cathodes for Li-ion batteries.

PubMed

Zhang, Wenyu; Zeng, Yi; Xu, Chen; Xiao, Ni; Gao, Yiben; Li, Lain-Jong; Chen, Xiaodong; Hng, Huey Hoon; Yan, Qingyu

2012-01-01

We report a facile method to prepare a nanoarchitectured lithium manganate/graphene (LMO/G) hybrid as a positive electrode for Li-ion batteries. The Mn(2)O(3)/graphene hybrid is synthesized by exfoliation of graphene sheets and deposition of Mn(2)O(3) in a one-step electrochemical process, which is followed by lithiation in a molten salt reaction. There are several advantages of using the LMO/G as cathodes in Li-ion batteries: (1) the LMO/G electrode shows high specific capacities at high gravimetric current densities with excellent cycling stability, e.g., 84 mAh·g(-1) during the 500th cycle at a discharge current density of 5625 mA·g(-1) (~38.01 C capacity rating) in the voltage window of 3-4.5 V; (2) the LMO/G hybrid can buffer the Jahn-Teller effect, which depicts excellent Li storage properties at high current densities within a wider voltage window of 2-4.5 V, e.g., 93 mAh·g(-1) during the 300th cycle at a discharge current density of 5625 mA·g(-1) (~38.01 C). The wider operation voltage window can lead to increased theoretical capacity, e.g., 148 mAh·g(-1) between 3 and 4.5 V and 296 mAh·g(-1) between 2 and 4.5 V; (3) more importantly, it is found that the attachment of LMO onto graphene can help to reduce the dissolution of Mn(2+) into the electrolyte, as indicated by the inductively coupled plasma (ICP) measurements, and which is mainly attributed to the large specific surface area of the graphene sheets.

Dianionic Titanyl and Vanadyl (Cation+ )2 [MIV O(Pc4- )]2- Phthalocyanine Salts Containing Pc4- Macrocycles.

PubMed

Konarev, Dmitri V; Kuzmin, Alexey V; Khasanov, Salavat S; Litvinov, Alexey L; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Lyubovskaya, Rimma N

2018-06-18

In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu 4 N + ) 2 [M IV O(Pc 4- )] 2- (M=Ti, V) and (Bu 3 MeP + ) 2 [M IV O(Pc 4- )] 2- (M=Ti, V) with [M IV O(Pc 4- )] 2- dianions were synthesized and characterized. Reduction of M IV O(Pc 2- ) carried out with an excess of sodium fluorenone ketyl in the presence of Bu 4 N + or Bu 3 MeP + is exclusive to the phthalocyanine centers, forming Pc 4- species. During reduction, the metal +4 charge did not change, implying that Pc is an non-innocent ligand. The Pc negative charge increase caused the C-N(pyr) bonds to elongate and the C-N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn-Teller effects are significant in the [eg(π*)] 2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q-bands were observed in the UV/Vis/NIR when M IV O(Pc 2- ) was reduced to [M IV O(Pc . 3- )] . - and [M IV O(Pc 4- )] 2- . From magnetic measurements, [Ti IV O(Pc 4- )] 2- was found to be diamagnetic and (Bu 4 N + ) 2 [V IV O(Pc 4- )] 2- and (Bu 3 MeP + ) 2 [V IV O(Pc 4- )] 2- were found to have magnetic moments of 1.72-1.78 μ B corresponding to an S=1/2 spin state owing to V IV electron spin. As a result, two latter salts show EPR signals with V IV hyperfine coupling. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Local distortion and EPR parameters of copper(II) in borate glasses

NASA Astrophysics Data System (ADS)

Kuang, Min-Quan; Wang, Li-Dan; Duan, Shu-Kai

2017-12-01

The EPR parameters (g and A tensors) of the paramagnetic Cu2+ sites in CaB4O7, LiCaBO3, Li2B4O7, KLiB4O7 glasses are well explained by utilizing the fourth-order perturbation formulas for 3 d9 ions in the tetragonally elongated octahedral [CuO6]10- clusters. The magnitude of the local distortion for the [CuO6]10- clusters suffering the Jahn-Teller effect is denoted by the relative elongation ratio ρ which is proportional to the ratio Δg///Δg⊥ (Δg//= g//-gs and Δg⊥ = g⊥-gs). The g isotropies giso (=(g//+2g⊥)/3) undergo an linear increase with the decline of the covalecny of the glass systems (i.e., the augment of the orbital reduction factor k). The signs of the hyperfine structure constants are determined by computing the quantitative contributions arising from the isotropic and anisotropic copper 3d-3s (4s) orbital admixtures indicated by the core polarization constant κ and the reduction factor H, respectively. The above correlations are proved to be available for analogous borate glasses doping with copper ions, e.g., MRbB4O7 (M = Li, Na and K), 90M2B4O7·9PbO·CuO (M = Li, Na and K), 10MO·30ZnO·60B2O3 (M = Mg, Ca and Sr) and xLi2O·(30-x)Na2O·69.5B2O3 (5 ≤ x ≤ 25 mol%), and all the results are discussed.

Dinuclear metallacycles with single M-O(H)-M bridges [M = Fe(II), Co(II), Ni(II), Cu(II)]: effects of large bridging angles on structure and antiferromagnetic superexchange interactions.

PubMed

Reger, Daniel L; Pascui, Andrea E; Foley, Elizabeth A; Smith, Mark D; Jezierska, Julia; Ozarowski, Andrew

2014-02-17

The reactions of M(ClO4)2·xH2O and the ditopic ligands m-bis[bis(1-pyrazolyl)methyl]benzene (Lm) or m-bis[bis(3,5-dimethyl-1-pyrazolyl)methyl]benzene (Lm*) in the presence of triethylamine lead to the formation of monohydroxide-bridged, dinuclear metallacycles of the formula [M2(μ-OH)(μ-Lm)2](ClO4)3 (M = Fe(II), Co(II), Cu(II)) or [M2(μ-OH)(μ-Lm*)2](ClO4)3 (M = Co(II), Ni(II), Cu(II)). With the exception of the complexes where the ligand is Lm and the metal is copper(II), all of these complexes have distorted trigonal bipyramidal geometry around the metal centers and unusual linear (Lm*) or nearly linear (Lm) M-O-M angles. For the two solvates of [Cu2(μ-OH)(μ-Lm)2](ClO4)3, the Cu-O-Cu angles are significantly bent and the geometry about the metal is distorted square pyramidal. All of the copper(II) complexes have structural distortions expected for the pseudo-Jahn-Teller effect. The two cobalt(II) complexes show moderate antiferromagnetic coupling, -J = 48-56 cm(-1), whereas the copper(II) complexes show very strong antiferromagnetic coupling, -J = 555-808 cm(-1). The largest coupling is observed for [Cu2(μ-OH)(μ-Lm*)2](ClO4)3, the complex with a Cu-O-Cu angle of 180°, such that the exchange interaction is transmitted through the dz(2) and the oxygen s and px orbitals. The interaction decreases, but it is still significant, as the Cu-O-Cu angle decreases and the character of the metal orbital becomes increasingly d(x(2)-y(2)). These intermediate geometries and magnetic interactions lead to spin Hamiltonian parameters for the copper(II) complexes in the EPR spectra that have large E/D ratios and one g matrix component very close to 2. Density functional theory calculations were performed using the hybrid B3LYP functional in association with the TZVPP basis set, resulting in reasonable agreement with the experiments.

High-resolution study of Gamow-Teller transitions in the 47Ti(3He,t)47V reaction

NASA Astrophysics Data System (ADS)

Ganioǧlu, E.; Fujita, H.; Fujita, Y.; Adachi, T.; Algora, A.; Csatlós, M.; Deaven, J. M.; Estevez-Aguado, E.; Guess, C. J.; Gulyás, J.; Hatanaka, K.; Hirota, K.; Honma, M.; Ishikawa, D.; Krasznahorkay, A.; Matsubara, H.; Meharchand, R.; Molina, F.; Okamura, H.; Ong, H. J.; Otsuka, T.; Perdikakis, G.; Rubio, B.; Scholl, C.; Shimbara, Y.; Susoy, G.; Suzuki, T.; Tamii, A.; Thies, J. H.; Zegers, R. G. T.; Zenihiro, J.

2013-01-01

Given the importance of Gamow-Teller (GT) transitions in nuclear structure and astrophysical nuclear processes, we have studied Tz=+3/2→+1/2, GT transitions starting from the 47Ti nucleus in the (3He,t) charge-exchange reaction at 0∘ and at an intermediate incident energy of 140 MeV/nucleon. The experiments were carried out at the Research Center for Nuclear Physics (RCNP), Osaka, using the high-resolution facility with a high-dispersion beam line and the Grand-Raiden spectrometer. With an energy resolution of 20 keV, individual GT transitions were observed and GT strength was derived for each state populated up to an excitation energy (Ex) of 12.5 MeV. The GT strength was widely distributed from low excitation energy up to 12.5 MeV, where we had to stop the analysis because of the high level density. The distribution of the GT strengths was compared with the results of shell model calculations using the GXPF1 interaction. The calculations could reproduce the experimental GT distributions well. The GT transitions from the ground state of 47Ti and the M1 transitions from the isobaric analog state in 47V to the same low-lying states in 47V are analogous. It was found that the ratios of GT transition strengths to the ground state, the 0.088-MeV state, and the 0.146-MeV state are similar to the ratios of the strengths of the analogous M1 transitions from the isobaric analog state (IAS) to these states. The measured distribution of the GT strengths was also compared with those starting from the Tz=+3/2 nucleus 41K to the Tz=+1/2 nucleus 41Ca.

Walén test and de Hoffmann-Teller frame of interplanetary large-amplitude Alfvén waves

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

Chao, J. K.; Hsieh, Wen-Chieh; Lee, L. C.

2014-05-10

In this study, three methods of analysis are compared to test the Walén relation. Method 1 requires a good de Hoffmann-Teller (HT) frame. Method 2 uses three components separately to find the frame that is slightly modified from Method 1. This method is intended to improve the accuracy of the HT frame and able to demonstrate the anisotropic property of the fluctuations. The better the relation is, the closer the slope of a regression fitting the data of plasma versus Alfvén velocities is to 1. However, this criterion is based on an average HT frame, and the fitted slope doesmore » not always work for the Walén test because the HT frame can change so fast in the high-speed streams. We propose Method 3 to check the Walén relation using a sequence of data generated by taking the difference of two consecutive values of plasma and Alfvén velocities, respectively. The difference data are independent of the HT frame. We suggest that the ratio of the variances between plasma and Alfvén velocities is a better parameter to qualify the Walén relation. Four cases in two solar wind streams are studied using these three methods. Our results show that when the solar wind HT frame remains stable, all three methods can predict Alfvénic fluctuations well, but Method 3 can better predict the Walén relation when solar wind contains structures with several small streams. A simulated case also demonstrates that Method 3 is better and more robust than Methods 1 and 2. These results are important for a better understanding of Alfvénic fluctuations and turbulence in the solar wind.« less

Gamow-Teller Strength Distributions in {sup 48}Sc by the {sup 48}Ca(p,n) and {sup 48}Ti(n,p) Reactions and Two-Neutrino Double-beta Decay Nuclear Matrix Elements

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

Yako, K.; Sasano, M.; Miki, K.

2009-07-03

The double-differential cross sections for the {sup 48}Ca(p,n) and {sup 48}Ti(n,p) reactions were measured at 300 MeV. A multipole decomposition technique was applied to the spectra to extract the Gamow-Teller (GT) components. The integrated GT strengths up to an excitation energy of 30 MeV in {sup 48}Sc are 15.3+-2.2 and 2.8+-0.3 in the (p,n) and (n,p) spectra, respectively. In the (n,p) spectra additional GT strengths were found above 8 MeV where shell models within the fp shell-model space predict almost no GT strengths, suggesting that the present shell-model description of the nuclear matrix element of the two-neutrino double-beta decay ismore » incomplete.« less

COMPARATIVE STUDY ON THE LEVEL OF BACTERIOLOGICAL CONTAMINATION OF AUTOMATIC TELLER MACHINES, PUBLIC TOILETS AND PUBLIC TRANSPORT COMMERCIAL MOTORCYCLE CRASH HELMETS IN KIGALI CITY, RWANDA.

PubMed

Nigatu, W; Fabiola, N S; Flora, I J; Mukahirwa, M A; Omar, M; Nsengimana, J; Nsabimana, A

2014-12-01

The environments can be contaminated by infectious agents that constitute a major health hazards as sources of community and hospital-acquired infections due to various activities. A comparative study on the level of bacteriological contamination of automatic teller machines (ATMs), public toilets and commercial motorcycle crash helmets were conducted in Kigali city during the period of January to March, 2013. Samples were collected from selected ATMs, public toilets and commercial motorcycle crash helmets surfaces. Micro-organisms identified from these samples were associated to infecting organisms recovered from unwashed hands surfaces and recorded results in the nearby hospital. Samples from each device and subject were transported to the laboratory where they were analysed for the presence of coliforms and other airborne, human skin and intestinal disease causing microorganisms. Microbiological methods including spread plate techniques and some biochemical tests were used to partially identify the microorganisms. Subjects involved in this study were consented students from University of Rwanda and Kigali motorcyclists for collections of samples from hands and crash helmets respectively. The following pathogenic bacteria have been found on the devices, Staphylococcus aureus, Staphylococcus epidermis, Streptococcus species, Escherichia coli, Salmonella, Klebsiella, Enterobacter aerogenes, Pseudomonas. The commercial motorcycle crash helmets had the highest level of bacteriological contamination compared to ATMs and public toilets. There was no growth observed on samples collected after treatment from ATMs, public toilets, and commercial motorcycle crash helmets. Attempt to correlate this finding with infecting organisms recovered from unwashed hands surfaces and recorded results in the nearby hospital show that the presences of some of these infectious pathogens. This study has revealed the ability of these public devices to serve as vehicle of transmission of

Measurements of the {sup 116}Cd(p,n) and {sup 116}Sn(n,p) reactions at 300 MeV for studying Gamow-Teller transition strengths in the intermediate nucleus of the {sup 116}Cd double-{beta} decay

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

Sasano, M.; Kuboki, H.; Sekiguchi, K.

2009-11-09

The double differential cross sections for the {sup 116}Cd(p,n) and {sup 116}Sn(n,p) reactions at 300 MeV have been measured over a wide excitation-energy region including Gamow-Teller (GT) giant resonance (GTGR) for studying GT transition strengths in the intermediate nucleus of the {sup 116}Cd double-{beta} decay, namely {sup 116}In. A large amount of the strengths in the {beta}{sup +} direction has been newly found in the energy region up to 30 MeV, which may imply that the GT strengths in the GTGR region contribute to the nuclear matrix element of the two-neutrino double-{beta} decay.

Striking changes in tea metabolites due to elevational effects.

PubMed

Kfoury, Nicole; Morimoto, Joshua; Kern, Amanda; Scott, Eric R; Orians, Colin M; Ahmed, Selena; Griffin, Timothy; Cash, Sean B; Stepp, John Richard; Xue, Dayuan; Long, Chunlin; Robbat, Albert

2018-10-30

Climate effects on crop quality at the molecular level are not well-understood. Gas and liquid chromatography-mass spectrometry were used to measure changes of hundreds of compounds in tea at different elevations in Yunnan Province, China. Some increased in concentration while others decreased by 100's of percent. Orthogonal projection to latent structures-discriminant analysis revealed compounds exhibiting analgesic, antianxiety, antibacterial, anticancer, antidepressant, antifungal, anti-inflammatory, antioxidant, anti-stress, and cardioprotective properties statistically (p = 0.003) differentiated high from low elevation tea. Also, sweet, floral, honey-like notes were higher in concentration in the former while the latter displayed grassy, hay-like aroma. In addition, multivariate analysis of variance showed low elevation tea had statistically (p = 0.0062) higher concentrations of caffeine, epicatechin gallate, gallocatechin, and catechin; all bitter compounds. Although volatiles represent a small fraction of the total mass, this is the first comprehensive report illustrating how normal variations in temperature, 5 °C, due to elevational effects impact tea quality. Copyright © 2018 Elsevier Ltd. All rights reserved.

Super-reduced polyoxometalates: excellent molecular cluster battery components and semipermeable molecular capacitors.

PubMed

Nishimoto, Yoshio; Yokogawa, Daisuke; Yoshikawa, Hirofumi; Awaga, Kunio; Irle, Stephan

2014-06-25

Theoretical investigations are presented on the molecular and electronic structure changes that occur as α-Keggin-type polyoxometalate (POM(3-)) clusters [PM12O40](3-) (M = Mo, W) are converted toward their super-reduced POM(27-) state during the discharging process in lithium-based molecular cluster batteries. Density functional theory was employed in geometry optimization, and first-principles molecular dynamics simulations were used to explore local minima on the potential energy surface of neutral POM clusters adorned with randomly placed Li atoms as electron donors around the cluster surface. On the basis of structural, electron density, and molecular orbital studies, we present evidence that the super-reduction is accompanied by metal-metal bond formation, beginning from the 12th to 14th excess electron transferred to the cluster. Afterward, the number of metal-metal bonds increases nearly linearly with the number of additionally transferred excess electrons. In α-Keggin-type POMs, metal triangles are a prominently emerging structural feature. The origin of the metal triangle formation during super-reduction stems from the formation of characteristic three-center two-electron bonds in triangular metal atom sites, created under preservation of the POM skeleton via "squeezing out" of oxygen atoms bridging two metal atoms when the underlying metal atoms form covalent bonds. The driving force for this unusual geometrical and electronic structure change is a local Jahn-Teller distortion at individual transition-metal octahedral sites, where the triply degenerate t2 d orbitals become partially filled during reduction and gain energy by distortion of the octahedron in such a way that metal-metal bonds are formed. The bonding orbitals show strong contributions from mixing with metal-oxygen antibonding orbitals, thereby "shuffling away" excess electrons from the cluster center to the outside of the cage. The high density of negatively charged yet largely separated

On the Study of Statistical Intuitions.

DTIC Science & Technology

1981-05-15

teller; 3. Linda is a bank teller who is PAGE 10 active in the feminist movement. In a large sample of statistically naive undergraduates, 86% judged...Linda is both a bank teller and an active feminist must be smaller than the probability that she is a bank teller. (ii) B is more probable than A...because Linda resembles a bank teller who is active in the feminist movement more than she resembles a bank teller. Argument (i) favoring the conjunction

Spin-orbit coupling, strong correlation, and insulator-metal transitions: The J eff = 3 2 ferromagnetic Dirac-Mott insulator Ba 2 NaOsO 6

DOE PAGES

Gangopadhyay, Shruba; Pickett, Warren E.

2015-01-15

The double perovskite Ba 2NaOsO 6 (BNOO), an exotic example of a very high oxidation state (heptavalent) osmium d1 compound and also uncommon by being a ferromagnetic open d-shell (Mott) insulator without Jahn-Teller (JT) distortion, is modeled using a density functional theory based hybrid functional incorporating exact exchange for correlated electronic orbitals and including the large spin-orbit coupling (SOC). The experimentally observed narrow-gap ferromagnetic insulating ground state is obtained, but only when including spin-orbit coupling, making this a Dirac-Mott insulator. The calculated easy axis along [110] is in accord with experiment, providing additional support that this approach provides a realisticmore » method for studying this system. The predicted spin density for [110] spin orientation is nearly cubic (unlike for other directions), providing an explanation for the absence of JT distortion. An orbital moment of –0.4μ B strongly compensates the +0.5μ B spin moment on Os, leaving a strongly compensated moment more in line with experiment. Remarkably, the net moment lies primarily on the oxygen ions. An insulator-metal transition, by rotating the magnetization direction with an external field under moderate pressure, is predicted as one consequence of strong SOC, and metallization under moderate pressure is predicted. In conclusion, a comparison is made with the isostructural, isovalent insulator Ba 2LiOsO 6, which, however, orders antiferromagnetically.« less

Charge and orbital orders and structural instability in high-pressure quadruple perovskite CeCuMn6O12

NASA Astrophysics Data System (ADS)

Zhang, Lei; Matsushita, Yoshitaka; Katsuya, Yoshio; Tanaka, Masahiko; Yamaura, Kazunari; Belik, Alexei A.

2018-02-01

We prepared a quadruple perovskite CeCuMn6O12 under high-pressure and high-temperature conditions at 6 GPa and about 1670 K and investigated its structural, magnetic and transport properties. CeCuMn6O12 crystallizes in space group Im-3 above T CO  =  297 K below this temperature, it adopts space group R-3 with the 1:3 (Mn4+:Mn3+) charge and orbital orders. Unusual compressed Mn3+O6 octahedra are realized in CeCuMn6O12 similar to CaMn7O12 with the  -Q 3 Jahn-Teller distortion mode. Below about 90 K, structural instability takes place with phase separation and the appearance of competing phases; and below 70 K, two R-3 phases coexist. CeCuMn6O12 exhibits a ferromagnetic-like transition below T C  =  140 K, and it is a semiconductor with the magnetoresistance reaching about  -40% at 140 K and 70 kOe. We argued that the valence of Ce is  +3 in CeCuMn6O12 with the Ce3+(C{{u}2+}Mn23+ )(Mn33+M{{n}4+} )O12 charge distribution in the charge-ordered R-3 phase and Ce3+(C{{u}2+}Mn23+ )(Mn43.25+ )O12 in the charge-disordered Im-3 phase.

Neutron and X-ray studies in suppressing orbital order in FeV2 O4 with Cr doping

NASA Astrophysics Data System (ADS)

Reig-I-Plessis, Dalmau; Wen, Zhangsu; Thaler, Alexander; Garlea, Vasile O.; Zhou, Haidong; Ruff, Jacob; MacDougall, Gregory

2015-03-01

FeV2O4 is a spinel compound with an orbitally active V3+ cation on a frustrated pyrochlore sublattice and Jahn-Teller active Fe3+ on a diamond sublattice. Previous studies show that this material has three structural and two magnetic transitions, and that orbital order leads to coupling between the spin and lattice degrees-of-freedom. The opposite end of the doping series is the multiferroic, FeCr2O4, which has spin, but no orbital degree of freedom on the Cr3+ and only two structural transitions. Although both materials show a higher temperature collinear ferrimagnetic state and a non-collinear phase at lower temperature, the physics must be different since the canting transition in FeV2O4 is associated with the orbital order at the lowest structural transition. In this talk, I will present the results of synchrotron X-ray and neutron powder diffraction studies of the structural and magnetic transitions in the doping series FeV2-xCrxO4. Specifically, I will comment on the doping-temperature phase diagram we extract from these measurements, and the region of co-existence between distinct non-collinear spin orders which exist at finite doping. This material is based upon work supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number DE-FG02-07ER46453.

Experimental access to elastic and thermodynamic properties of RbMnFe(CN)6

NASA Astrophysics Data System (ADS)

Boukheddaden, K.; Loutete-Dangui, E. D.; Codjovi, E.; Castro, M.; Rodriguéz-Velamazán, J. A.; Ohkoshi, S.; Tokoro, H.; Koubaa, M.; Abid, Y.; Varret, F.

2011-01-01

We use spectroscopic ellipsometry to study the elastic and thermodynamic properties of the structural first-order transition of the cooperative Jahn-Teller solid, RbMn[Fe(CN)6]. While the analysis of the thermal dependence of the dielectric constant revealed a remarkable energy shift in the metal-to-ligand charge transfer band, that of the refractive index allowed to evaluate the volumetric thermal expansion coefficient in the two phases through the Gladstone-Dale relation. The access to the elastic properties of the solid is obtained with the reflectivity under pressure measurements, from which we estimated the bulk modulus values in the low- and high-temperature phases as BLT=30(±3) GPa and BHT=23(±2) GPa, respectively. Assuming the system is isotropic, the corresponding Debye temperature values have been found to be θDLT(SE)≃360(±25) K and θDHT(SE)≃290(±20) K, in good agreement with those derived from independent Mössbauer spectrometry investigations which led to θDLT(Moss)≃332(±7) K and θDHT(Moss)≃280(±11) K. Moreover, we have been able to extract from the SE data, the entropy change at the transition, ΔS ≈64 J K-1 mol-1, which has been also found in good agreement with the value, ΔS ≈60±5 J K-1 mol-1, derived from calorimetric experiments performed in this work.

In situ XAFS and micro-XAFS studies on LiNi 0.8Co 0.15Al 0.05O 2 cathode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Nonaka, T.; Okuda, C.; Seno, Y.; Nakano, H.; Koumoto, K.; Ukyo, Y.

We have applied in situ X-ray absorption fine structure (XAFS) and in situ micro-XAFS techniques to study LiNi 0.8Co 0.15Al 0.05O 2 cathode materials in Li-ion coin cells that show various levels of capacity fading: fresh cell, cycle tested cell and aging tested cell. The change in the oxidation state and local structure of Ni and Co during charge has been investigated. Ni and Co K-edge X-ray absorption near edge structure (XANES) show that the Ni oxidation state is converted from Ni 3+ to Ni 4+ upon charging, whereas the Co oxidation state hardly changes. Ni K-edge extended X-ray absorption fine structure (EXAFS) reveals that the Jahn-Teller distorted NiO 6 octahedron turns into the symmetric octahedron upon charging, which is consistent with the change in the Ni oxidation state. Ni K-edge micro-XANES show that the oxidation of Ni proceeds homogeneously in a grain of LiNi 0.8Co 0.15Al 0.05O 2 within the special resolution of ∼2 μm, and proceeds independently of the grain size. All the behaviors of Ni and Co observed in these experiments for the fresh cell remain unchanged after the capacity fade is induced by cycle tests or aging tests, which demonstrates the considerable stability of the LiNi 0.8Co 0.15Al 0.05O 2 cathode material.

Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

NASA Astrophysics Data System (ADS)

Webb, S. M.; Bargar, J. R.; Tebo, B. M.

2003-12-01

Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.

Biomimetic Mn-Catalases Based on Dimeric Manganese Complexes in Mesoporous Silica for Potential Antioxidant Agent.

PubMed

Escriche-Tur, Luis; Corbella, Montserrat; Font-Bardia, Mercè; Castro, Isabel; Bonneviot, Laurent; Albela, Belén

2015-11-02

Two new structural and functional models of the Mn-catalase with formula [{Mn(III)(bpy)(H2O)}(μ-2-MeOC6H4CO2)2(μ-O){Mn(III)(bpy)(X)}]X, where X = NO3 (1) and ClO4 (2) and bpy = 2,2'-bipyridine, were synthesized and characterized by X-ray diffraction. In both cases, a water molecule and an X ion occupy the monodentate positions. The magnetic properties of these compounds reveal a weak antiferromagnetic behavior (2J = -2.2 cm(-1) for 1 and -0.7 cm(-1) for 2, using the spin Hamiltonian H = -2J S1·S2) and negative zero-field splitting parameter DMn (-4.6 cm(-1) and -3.0 cm(-1) for 1 and 2, respectively). This fact, together with the nearly orthogonal orientation of the Jahn-Teller axes of the Mn(III) ions explain the unusual shape of χMT versus T plot at low temperature. Compound 1 presents a better catalase activity than 2 in CH3CN-H2O media, probably due to a beneficial interaction of the NO3(-) ion with the Mn complex in solution. These compounds were successfully inserted inside two-dimensional hexagonal mesoporous silica (MCM-41 type) leading to the same hybrid material ([Mn2O]@SiO2), without the X group. The manganese complex occupies approximately half of the available pore volume, keeping the silica's hexagonal array intact. Magnetic measurements of [Mn2O]@SiO2 suggest that most of the dinuclear unit is preserved, as a non-negligible interaction between Mn ions is still observed. The X-ray photoelectron spectroscopy analysis of the Mn 3s peak confirms that Mn remains as Mn(III) inside the silica. The catalase activity study of material [Mn2O]@SiO2 reveals that the complex is more active inside the porous silica, probably due to the surface silanolate groups of the pore wall. Moreover, the new material shows catalase activity in water media, while the coordination compounds are not active.

Infrared spectroscopy of ionized corannulene in the gas phase.

PubMed

Alvaro Galué, Héctor; Rice, Corey A; Steill, Jeffrey D; Oomens, Jos

2011-02-07

The gas-phase infrared spectra of radical cationic and protonated corannulene were recorded by infrared multiple-photon dissociation (IRMPD) spectroscopy using the IR free electron laser for infrared experiments. Electrospray ionization was used to generate protonated corannulene and an IRMPD spectrum was recorded in a Fourier-transform ion cyclotron resonance mass spectrometer monitoring H-loss as a function of IR frequency. The radical cation was produced by 193-nm UV photoionization of the vapor of corannulene in a 3D quadrupole trap and IR irradiation produces H, H(2), and C(2)H(x) losses. Summing the spectral response of the three fragmentation channels yields the IRMPD spectrum of the radical cation. The spectra were analyzed with the aid of quantum-chemical calculations carried out at various levels of theory. The good agreement of theoretical and experimental spectra for protonated corannulene indicates that protonation occurs on one of the peripheral C-atoms, forming an sp(3) hybridized carbon. The spectrum of the radical cation was examined taking into account distortions of the C(5v) geometry induced by the Jahn-Teller effect as a consequence of the degenerate (2)E(1) ground electronic state. As indicated by the calculations, the five equivalent C(s) minima are separated by marginal barriers, giving rise to a dynamically distorted system. Although in general the character of the various computed vibrational bands appears to be in order, only a qualitative match to the experimental spectrum is found. Along with a general redshift of the calculated frequencies, the IR intensities of modes in the 1000-1250 cm(-1) region show the largest discrepancy with the harmonic predictions. In addition to CH "in-plane" bending vibrations, these modes also exhibit substantial deformation of the pentagonal inner ring, which may relate directly to the vibronic interaction in the radical cation.

Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries.

PubMed

Wang, Qin-Chao; Hu, Enyuan; Pan, Yang; Xiao, Na; Hong, Fan; Fu, Zheng-Wen; Wu, Xiao-Jing; Bak, Seong-Min; Yang, Xiao-Qing; Zhou, Yong-Ning

2017-11-01

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na + and vacancy ordering. An interesting structure change of Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 , effectively suppressing the Mn 3+ -induced Jahn-Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 during charge/discharge is contributed by Co 2.2+ /Co 3+ and Mn 3.3+ /Mn 4+ redox couples. This is the first time that the highly reversible Co 2+ /Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

Pseudopotential SCF-MO studies of hypervalent compounds. II. XeF+5 and XeF6

NASA Astrophysics Data System (ADS)

Rothman, Michael J.; Bartell, Lawrence S.; Ewig, Carl S.; Van Wazer, John R.

1980-07-01

New evidence bearing upon the anomalous properties of xenon hexafluoride has been obtained via the ab initio molecular orbital approach applied successfully to the di- and tetrafluorides in paper I. Structures of both XeF+5 and XeF6 are governed by a stereochemically active lone pair. In the case of the square-pyramidal cation the Fax-Xe-Feq angle calculated for the bare ion is within 2° of the value observed in the crystalline complex. For the hexafluoride, however, the calculated deformation from Oh symmetry is appreciably greater than that deduced from electron diffraction intensities. Nevertheless, the results of calculations are in sufficient conformity with the Bartell-Gavin, Pitzer-Bernstein interpretation and at variance with the ''electronic-isomers'' interpretation to leave little doubt about the answer. With increasing fluorination in the XeFn series the HOMO-LUMO energy difference decreases and the second-order Jahn-Teller effect is enhanced. Increasing fluorination (and increased positive charge on Xe) also shortens bond lengths; calculated shortenings parallel observed shortenings. The deformation of XeF6 from Oh is along t1u bend and stretch coordinates to a C3v structure with long bonds adjacent to the lone pair, as expected according to the valence-shell-electron-pair-repulsion model. Pure t2g deformations are destabilizing but anharmonic t1u-t2g coupling significantly stabilizes the deformation. Steric aspects of the structure and force field are diagnosed and found to be minor. Values for the force constants f44, f55, f¯4444, f¯444'4', and f¯445 are derived and found to be of the magnitude forecast in the Bartell-Gavin and Pitzer-Bernstein treatments except that the calculations do not reproduce the delicate balances believed to lead to almost free pseudorotation in XeF6.

Letter to the Editors of Physics Today

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

Libby, S B; Weiss, M S

2004-11-11

Two points in our recent article on Edward Teller's scientific life (Physics Today, August 2004, page 45) require correction. In our description of Teller's students, we incorrectly stated that Arthur Kantrowitz's thesis was on the generation of hypersonic molecular beams. Actually, his thesis was on heat capacity lags in gas dynamics. Kantrowitz's invention of high intensity sources for molecular beams came later in his career. Maurice Goldhaber has emphasized that the situation with respect to possible nuclear resonances in ({gamma},n) or ({gamma},fission) reactions was quite unclear at the time of George C. Baldwin and G. Stanley Klaiber's papers on thesemore » reactions. This was because the rapid rise of their yield to a prominent peak with increasing energy, followed by a slower fall off was then thought to have been due to the competition between the rapidly rising density of nuclear states and the eventual domination of other reaction channels at higher energies. Goldhaber realized, however, that there could be an analogy between a possible collective nuclear resonance and the restrahl resonance (essentially the transverse optical phonon mode) in polar crystals. Goldhaber sought out Teller because of his paper with Russell Lyddane and Robert Sachs, relating the restrahl frequency to the asymptotic behavior of the crystal's dielectric function. Goldhaber and Teller, in their paper together, went on to predict universal, giant photo-nuclear resonances.« less

Unconventional high-Tc superconductivity in fullerides

PubMed Central

Takabayashi, Yasuhiro; Prassides, Kosmas

2016-01-01

A3C60 molecular superconductors share a common electronic phase diagram with unconventional high-temperature superconductors such as the cuprates: superconductivity emerges from an antiferromagnetic strongly correlated Mott-insulating state upon tuning a parameter such as pressure (bandwidth control) accompanied by a dome-shaped dependence of the critical temperature, Tc. However, unlike atom-based superconductors, the parent state from which superconductivity emerges solely by changing an electronic parameter—the overlap between the outer wave functions of the constituent molecules—is controlled by the C603− molecular electronic structure via the on-molecule Jahn–Teller effect influence of molecular geometry and spin state. Destruction of the parent Mott–Jahn–Teller state through chemical or physical pressurization yields an unconventional Jahn–Teller metal, where quasi-localized and itinerant electron behaviours coexist. Localized features gradually disappear with lattice contraction and conventional Fermi liquid behaviour is recovered. The nature of the underlying (correlated versus weak-coupling Bardeen–Cooper–Schrieffer theory) s-wave superconducting states mirrors the unconventional/conventional metal dichotomy: the highest superconducting critical temperature occurs at the crossover between Jahn–Teller and Fermi liquid metal when the Jahn–Teller distortion melts. This article is part of the themed issue ‘Fullerenes: past, present and future, celebrating the 30th anniversary of Buckminster Fullerene’. PMID:27501971

Exploring Renner-Teller induced quenching in the reaction H(2S)+NH(a 1Delta): a combined experimental and theoretical study.

PubMed

Adam, L; Hack, W; McBane, G C; Zhu, H; Qu, Z-W; Schinke, R

2007-01-21

Experimental rate coefficients for the removal of NH(a (1)Delta) and ND(a (1)Delta) in collisions with H and D atoms are presented; all four isotope combinations are considered: NH+H, NH+D, ND+H, and ND+D. The experiments were performed in a quasistatic laser-flash photolysis/laser-induced fluorescence system at low pressures. NH(a (1)Delta) and ND(a (1)Delta) were generated by photolysis of HN(3) and DN(3), respectively. The total removal rate coefficients at room temperature are in the range of (3-5)x10(13) cm(3) mol(-1) s(-1). For two isotope combinations, NH+H and NH+D, quenching rate coefficients for the production of NH(X (3)Sigma(-)) or ND(X (3)Sigma(-)) were also determined; they are in the range of 1 x 10(13) cm(3) mol(-1) s(-1). The quenching rate coefficients directly reflect the strength of the Renner-Teller coupling between the (2)A(") and (2)A(') electronic states near linearity and so can be used to test theoretical models for describing this nonadiabatic process. The title reaction was modeled with a simple surface-hopping approach including a single parameter, which was adjusted to reproduce the quenching rate for NH+H; the same parameter value was used for all isotope combinations. The agreement with the measured total removal rate is good for all but one isotope combination. However, the quenching rates for the NH+D combination are only in fair (factor of 2) agreement with the corresponding measured data.

Effectively selling astronomy to the public -- fusing lessons learned from education, entertainment, advertising and public relations

NASA Astrophysics Data System (ADS)

Pallone, Arthur; Day, Jacque

2010-03-01

A great celestial story is only as effective as the teller of the tale. With passion and knowledge at the helm, we must search for ways to pass on enthusiasm to others while conveying sound science. Based on our experiences, we present an integrated approach -- one that borrows elements from education, entertainment, advertising, and public relations -- to choose an event, hook and keep the public's attention while making them want more, and provide some tips for increasing media presence.

Nonadiabatic dynamics of O({sup 1}D) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}){yields}O({sup 3}P) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

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

Defazio, Paolo; Gamallo, Pablo; Petrongolo, Carlo

2012-02-07

We present the spin-orbit (SO) and Renner-Teller (RT) quantum dynamics of the spin-forbidden quenching O({sup 1}D) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}){yields}O({sup 3}P) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}) on the N{sub 2}O X-tilde{sup 1}A{sup '}, a-tilde{sup 3}A', and b-tilde{sup 3}A{sup '} coupled PESs. We use the permutation-inversion symmetry, propagate coupled-channel (CC) real wavepackets, and compute initial-state-resolved probabilities and cross sections {sigma}{sub j0} for the ground vibrational and the first two rotational states of N{sub 2}, j{sub 0}= 0 and 1. Labeling symmetry angular states by j and K, we report selection rules for j and for the minimum Kmore » value associated with any electronic state, showing that a-tilde{sup 3}A' is uncoupled in the centrifugal-sudden (CS) approximation at j{sub 0}= 0. The dynamics is resonance-dominated, the probabilities are larger at low K, {sigma}{sub j0} decrease with the collision energy and increase with j{sub 0}, and the CS {sigma}{sub 0} is lower than the CC one. The nonadiabatic interactions play different roles on the quenching dynamics, because the X-tilde{sup 1}A{sup '}-b-tilde{sup 3}A{sup '} SO effects are those most important while the a-tilde{sup 3}A'-b-tilde{sup 3}A{sup '} RT ones are negligible.« less

Effect of spanwise variations in gust intensity on the lift due to atmospheric turbulence

NASA Technical Reports Server (NTRS)

Diederich, Franklin W; Drischler, Joseph A

1957-01-01

The effect of spanwise variations in gust intensity on the power spectrum directly due to atmospheric turbulence is calculated for several analytic approximations to the correlation function or power spectra of atmospheric turbulence, for several spanwise weighing functions (span loadings), and for various angles of sweepback.

Adaptive memory: Is the animacy effect on memory due to emotional arousal?

PubMed

Meinhardt, Martin J; Bell, Raoul; Buchner, Axel; Röer, Jan P

2018-05-07

Animate entities are often better remembered than inanimate ones. The proximal mechanisms underlying this animacy effect on recall are unclear. In two experiments, we tested whether the animacy effect is due to emotional arousal. Experiment 1 revealed that translations of the animate words used in the pioneering study of Nairne et al. (Psychological science, 24, 2099-2105, 2013) were perceived as being more arousing than translations of the inanimate words, suggesting that animacy might have been confounded with arousal in previous studies. In Experiment 2, new word lists were created in which the animate and inanimate words were matched on arousal (amongst several other dimensions), and participants were required to reproduce the animate and inanimate words in a free recall task. There was a tendency towards better memory for arousing items, but robust animacy effects were obtained even though animate and inanimate words were matched on arousal. Thus, while arousal may contribute to the animacy effect when it is not carefully controlled for, it cannot explain the memory advantage of animate items.

Enhanced biennial variability in the Pacific due to Atlantic capacitor effect.

PubMed

Wang, Lei; Yu, Jin-Yi; Paek, Houk

2017-03-20

The El Niño-Southern Oscillation (ENSO) and the variability in the Pacific subtropical highs (PSHs) have major impacts on social and ecological systems. Here we present an Atlantic capacitor effect mechanism to suggest that the Atlantic is a key pacemaker of the biennial variability in the Pacific including that in ENSO and the PSHs during recent decades. The 'charging' (that is, ENSO imprinting the North Tropical Atlantic (NTA) sea surface temperature (SST) via an atmospheric bridge mechanism) and 'discharging' (that is, the NTA SST triggering the following ENSO via a subtropical teleconnection mechanism) processes alternate, generating the biennial rhythmic changes in the Pacific. Since the early 1990s, a warmer Atlantic due to the positive phase of Atlantic multidecadal oscillation and global warming trend has provided more favourable background state for the Atlantic capacitor effect, giving rise to enhanced biennial variability in the Pacific that may increase the occurrence frequency of severe natural hazard events.

Enhanced biennial variability in the Pacific due to Atlantic capacitor effect

PubMed Central

Wang, Lei; Yu, Jin-Yi; Paek, Houk

2017-01-01

The El Niño-Southern Oscillation (ENSO) and the variability in the Pacific subtropical highs (PSHs) have major impacts on social and ecological systems. Here we present an Atlantic capacitor effect mechanism to suggest that the Atlantic is a key pacemaker of the biennial variability in the Pacific including that in ENSO and the PSHs during recent decades. The ‘charging' (that is, ENSO imprinting the North Tropical Atlantic (NTA) sea surface temperature (SST) via an atmospheric bridge mechanism) and ‘discharging' (that is, the NTA SST triggering the following ENSO via a subtropical teleconnection mechanism) processes alternate, generating the biennial rhythmic changes in the Pacific. Since the early 1990s, a warmer Atlantic due to the positive phase of Atlantic multidecadal oscillation and global warming trend has provided more favourable background state for the Atlantic capacitor effect, giving rise to enhanced biennial variability in the Pacific that may increase the occurrence frequency of severe natural hazard events. PMID:28317857

Enhanced biennial variability in the Pacific due to Atlantic capacitor effect

NASA Astrophysics Data System (ADS)

Wang, Lei; Yu, Jin-Yi; Paek, Houk

2017-03-01

The El Niño-Southern Oscillation (ENSO) and the variability in the Pacific subtropical highs (PSHs) have major impacts on social and ecological systems. Here we present an Atlantic capacitor effect mechanism to suggest that the Atlantic is a key pacemaker of the biennial variability in the Pacific including that in ENSO and the PSHs during recent decades. The `charging' (that is, ENSO imprinting the North Tropical Atlantic (NTA) sea surface temperature (SST) via an atmospheric bridge mechanism) and `discharging' (that is, the NTA SST triggering the following ENSO via a subtropical teleconnection mechanism) processes alternate, generating the biennial rhythmic changes in the Pacific. Since the early 1990s, a warmer Atlantic due to the positive phase of Atlantic multidecadal oscillation and global warming trend has provided more favourable background state for the Atlantic capacitor effect, giving rise to enhanced biennial variability in the Pacific that may increase the occurrence frequency of severe natural hazard events.

Diabatic models with transferrable parameters for generalized chemical reactions

NASA Astrophysics Data System (ADS)

Reimers, Jeffrey R.; McKemmish, Laura K.; McKenzie, Ross H.; Hush, Noel S.

2017-05-01

Diabatic models applied to adiabatic electron-transfer theory yield many equations involving just a few parameters that connect ground-state geometries and vibration frequencies to excited-state transition energies and vibration frequencies to the rate constants for electron-transfer reactions, utilizing properties of the conical-intersection seam linking the ground and excited states through the Pseudo Jahn-Teller effect. We review how such simplicity in basic understanding can also be obtained for general chemical reactions. The key feature that must be recognized is that electron-transfer (or hole transfer) processes typically involve one electron (hole) moving between two orbitals, whereas general reactions typically involve two electrons or even four electrons for processes in aromatic molecules. Each additional moving electron leads to new high-energy but interrelated conical-intersection seams that distort the shape of the critical lowest-energy seam. Recognizing this feature shows how conical-intersection descriptors can be transferred between systems, and how general chemical reactions can be compared using the same set of simple parameters. Mathematical relationships are presented depicting how different conical-intersection seams relate to each other, showing that complex problems can be reduced into an effective interaction between the ground-state and a critical excited state to provide the first semi-quantitative implementation of Shaik’s “twin state” concept. Applications are made (i) demonstrating why the chemistry of the first-row elements is qualitatively so different to that of the second and later rows, (ii) deducing the bond-length alternation in hypothetical cyclohexatriene from the observed UV spectroscopy of benzene, (iii) demonstrating that commonly used procedures for modelling surface hopping based on inclusion of only the first-derivative correction to the Born-Oppenheimer approximation are valid in no region of the chemical

Effect of complex configurations on the description of properties of {sup 132}Sn beta decay

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

Severyukhin, A. P., E-mail: sever@theor.jinr.ru; Sushenok, E. O.

2015-07-15

Gamow–Teller transitions in the beta decay of the {sup 132}Sn neutron-rich nucleus was described microscopically. The coupling of one- and two-phonon components of the wave functions was taken into account on the basis of Skyrme interactions featuring various contributions of the tensor component. A separable approximation of the particle—hole interaction made it possible tohole interaction perform calculations in a large configuration space. It was shown that an increase in the strength of the neutron—proton tensor interaction led to an increase in the energy of Gamow—Teller transitions. In addition, a decrease in the {sup 132}Sn half-life with respect to beta decaymore » was obtained.« less

A variational theory of Hall effect of Anderson lattice model: Application to colossal magnetoresistance manganites (Re1-x Ax MnO3)

NASA Astrophysics Data System (ADS)

Panwar, Sunil; Kumar, Vijay; Singh, Ishwar

2017-10-01

An anomalous Hall constant RH has been observed in various rare earth manganites doped with alkaline earths namely Re1-xAxMnO3 (where Re = La, Pr, Nd etc., and A = Ca, Sr, Ba etc.) which exhibit colossal magnetoresistance (CMR), metal- insulator transition and many other poorly understood phenomena. We show that this phenomenon of anomalous Hall constant can be understood using two band (ℓ-b) Anderson lattice model Hamiltonian alongwith (ℓ-b) hybridization recently studied by us for manganites in the strong electron-lattice Jahn-Teller (JT) coupling regime an approach similar to the two - fluid models. We use a variational method in this work to study the temperature variation of Hall constant RH (T) in these compounds. We have already used this variational method to study the zero field electrical resistivity ρ (T) and magnetic susceptibility of doped CMR manganites. In the present study, we find that the Hall constant RH (T) reduces with increasing magnetic field parameters h&m and the metal-insulator transition temperature (Tρ) shifts towards higher temperature region. We have also observed the role of the model parameters e.g. local Coulomb repulsion U, Hund's rule coupling JH between eg spins and t2g spins, ferromagnetic nearest neighbor exchange coupling JF between t2g core spins and hybridization Vk between ℓ-polarons and d-electrons on Hall constant RH (T) of these materials at different magnetic fields. Here we find that RH (T) for a particular value of h and m shows a rapid initial increase, followed by a sharp peak at low temperature say 50 K in our case and a slow decrease at high temperatures, resembling with the key feature of many CMR compounds like La0.8Ba0.2 MnO3.The magnitude of RH (T) reduces and the anomaly (sharp peak) in RH becomes broader and shifts towards higher temperature region on increasing Vk or JH or doping x and even vanishes on further increasing these parameters. Our results of anomalous Hall constant (RH) have same

Effectiveness of a multifactorial handwashing program to reduce school absenteeism due to acute gastroenteritis.

PubMed

Azor-Martínez, Ernestina; Cobos-Carrascosa, Elena; Gimenez-Sanchez, Francisco; Martínez-López, Jose Miguel; Garrido-Fernández, Pablo; Santisteban-Martínez, Joaquin; Seijas-Vazquez, Maria Luisa; Campos-Fernandez, Maria Amparo; Bonillo-Perales, Antonio

2014-02-01

Acute gastroenteritis (AGE) is one of the most common diseases among children and an important cause of school absenteeism. The aim of this study was to assess the effectiveness of a handwashing program using hand sanitizers for the prevention of school absenteeism due to AGE. A randomized, controlled and open study of a sample of 1341 children between 4 and 12 years of age, attending 5 state schools in Almería (Spain), with an 8-month follow up (academic year). The experimental group (EG) washed their hands with soap and water, complementing this with the use of a hand sanitizer, and the control group (CG) followed the usual handwashing procedure. Absenteeism rates due GI were compared between the 2 groups through the multivariate Poisson regression analysis. Percent days absent in both groups were compared with a Z-test. 446 cases of school absenteeism due to AGE were registered. The school children from the EG had a 36% lower risk of absenteeism due to AGE (IRR: 0.64, 95% confidence interval: 0.52-0.78) and a decrease in absenteeism of 0.13 episodes/child/academic year (0.27 of EG vs 0.40 CG/episodes/child/academic year, P < 0.001). Pupils missed 725 school days due to AGE and absent days was significantly lower in the EG (EG: 0.31%, 95% confidence interval: 0.28-0.35 vs. CG: 0.44%, 95% confidence interval: 0.40-0.48, P < 0.001). The use of hand sanitizer as a complement to handwashing with soap is an efficient measure to reduce absent days and the number of school absenteeism cases due to AGE.

Occupational asthma due to formaldehyde.

PubMed Central

Burge, P S; Harries, M G; Lam, W K; O'Brien, I M; Patchett, P A

1985-01-01

Bronchial provocation studies on 15 workers occupationally exposed to formaldehyde are described. The results show that formaldehyde exposure can cause asthmatic reactions, and suggest that these are sometimes due to hypersensitivity and sometimes to a direct irritant effect. Three workers had classical occupational asthma caused by formaldehyde fumes, which was likely to be due to hypersensitivity, with late asthmatic reactions following formaldehyde exposure. Six workers developed immediate asthmatic reactions, which were likely to be due to a direct irritant effect as the reactions were shorter in duration than those seen after soluble allergen exposure and were closely related to histamine reactivity. The breathing zone concentrations of formaldehyde required to elicit these irritant reactions (mean 4.8 mg/m3) were higher than those encountered in buildings recently insulated with urea formaldehyde foam, but within levels sometimes found in industry. Images PMID:4023975

Jet-Cooled Laser-Induced Fluorescence Spectroscopy of T-Butoxy

NASA Astrophysics Data System (ADS)

Reilly, Neil J.; Cheng, Lan; Stanton, John F.; Miller, Terry A.; Liu, Jinjun

2015-06-01

The vibrational structures of the tilde A ^2A_1 and tilde X ^2E states of t-butoxy were obtained in jet-cooled laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectroscopic measurements. The observed transitions are assigned based on vibrational frequencies calculated using Complete Active Space Self-Consistent Field (CASSCF) method and the predicted Franck-Condon factors. The spin-orbit (SO) splitting was measured to be 35(5) cm-1 for the lowest vibrational level of the ground (tilde X ^2E) state and increases with increasing vibrational quantum number of the CO stretch mode. Vibronic analysis of the DF spectra suggests that Jahn-Teller (JT)-active modes of the ground-state t-butoxy radical are similar to those of methoxy and would be the same if methyl groups were replaced by hydrogen atoms. Coupled-cluster calculations show that electron delocalization, introduced by the substitution of hydrogens with methyl groups, reduces the electronic contribution of the SO splittings by only around ten percent, and a calculation on the vibronic levels based on quasidiabatic model Hamiltonian clearly attributes the relatively small SO splitting of the tilde X ^2E state of t-butoxy mainly to stronger reduction of orbital angular momentum by the JT-active modes when compared to methoxy. The rotational and fine structure of the LIF transition to the first CO stretch overtone level of the tilde A^2A_1 state has been simulated using a spectroscopic model first proposed for methoxy, yielding an accurate determination of the rotational constants of both tilde A and tilde X states.

Biological effects due to weak magnetic fields on plants

NASA Astrophysics Data System (ADS)

Belyavskaya, N.

In the evolution process, living organisms have experienced the action of the Earth's magnetic field (MF) that is a natural component of our environment. It is known that a galactic MF induction does not exceed 0.1 nT, since investigations of weak magnetic field (WMF) effects on biological systems have attracted attention of biologists due to planning long-term space flights to other planets where the magnetizing force is near 10-5 Oe. However, the role of WMF and its influence on organisms' functioning are still insufficiently investigated. A large number of experiments with seedlings of different plant species placed in WMF has found that the growth of their primary roots is inhibited during the early terms of germination in comparison with control. The proliferation activity and cell reproduction are reduced in meristem of plant roots under WMF application. The prolongation of total cell reproductive cycle is registered due to the expansion of G phase in1 different plant species as well as of G phase in flax and lentil roots along with2 relative stability of time parameters of other phases of cell cycle. In plant cells exposed to WMF, the decrease in functional activity of genome at early prereplicate period is shown. WMF causes the intensification in the processes of proteins' synthesis and break-up in plant roots. Qualitative and quantitative changes in protein spectrum in growing and differentiated cells of plant roots exposed to WMF are revealed. At ultrastructural level, there are observed such ultrastructural peculiarities as changes in distribution of condensed chromatin and nucleolus compactization in nuclei, noticeable accumulation of lipid bodies, development of a lytic compartment (vacuoles, cytosegresomes and paramural bodies), and reduction of phytoferritin in plastids in meristem cells of pea roots exposed to WMF. Mitochondria are the most sensitive organelle to WMF application: their size and relative volume in cells increase, matrix is electron

Effect of dewatering on seismic performance of multi-anchor wall due to high ground water level

NASA Astrophysics Data System (ADS)

Kobayashi, Makoto; Miura, Kinya; Konami, Takeharu; Hayashi, Taketo; Sato, Hiroki

2017-10-01

Previous research reported that the ground water in the backfill of reinforced soil wall made it deteriorate. According to the damage investigation of Great East Earthquake 2011, the reinforced soil structure due to high ground water level by seismic wave were deformed remarkably. Some of them classified ultimate limit state or restorability limit state. However, more than 90% of reinforced soil structure, which suffered from this earthquake, were classified into no damage condition. Therefore, it is necessary that the seismic behaviors of multi-anchor wall due to seepage flow should be clarified in order to adopt the performance-based design in such reinforced soil structure. In this study, a series of centrifugal shaking table tests were conducted to investigate the seismic behavior of multi-anchor wall due to high ground water level. The reinforced drainage pipes were installed into the backfill in order to verify the dewatering effect and additional reinforcement. Furthermore, to check only the dewatering effect, the model tests was carried out with several ground water table that was modeled the case reinforced drainage pipes installed. The test results show unique behavior of reinforced region that moved integrally. This implies that the reinforced region has been behaved as if it became one mass, and this behavior make this structure increase seismic performance. Thus, the effectiveness of dewatering was observed remarkably because of decreasing the inertial force during earthquake.

Uncertainties in global aerosols and climate effects due to biofuel emissions

NASA Astrophysics Data System (ADS)

Kodros, J. K.; Scott, C. E.; Farina, S. C.; Lee, Y. H.; L'Orange, C.; Volckens, J.; Pierce, J. R.

2015-04-01

Aerosol emissions from biofuel combustion impact both health and climate; however, while reducing emissions through improvements to combustion technologies will improve health, the net effect on climate is largely unconstrained. In this study, we examine sensitivities in global aerosol concentration, direct radiative climate effect, and cloud-albedo aerosol indirect climate effect to uncertainties in biofuel emission factors, optical mixing-state, and model nucleation and background SOA. We use the Goddard Earth Observing System global chemical-transport model (GEOS-Chem) with TwO Moment Aerosol Sectional (TOMAS) microphysics. The emission factors include: amount, composition, size and hygroscopicity, as well as optical mixing-state properties. We also evaluate emissions from domestic coal use, which is not biofuel but is also frequently emitted from homes. We estimate the direct radiative effect assuming different mixing states (internal, core-shell, and external) with and without absorptive organic aerosol (brown carbon). We find the global-mean direct radiative effect of biofuel emissions ranges from -0.02 to +0.06 W m-2 across all simulation/mixing state combinations with regional effects in source regions ranging from -0.2 to +1.2 W m-2. The global-mean cloud-albedo aerosol indirect effect ranges from +0.01 to -0.02 W m-2 with regional effects in source regions ranging from -1.0 to -0.05 W m-2. The direct radiative effect is strongly dependent on uncertainties in emissions mass, composition, emissions aerosol size distributions and assumed optical mixing state, while the indirect effect is dependent on the emissions mass, emissions aerosol size distribution and the choice of model nucleation and secondary organic aerosol schemes. The sign and magnitude of these effects have a strong regional dependence. We conclude that the climate effects of biofuel aerosols are largely unconstrained, and the overall sign of the aerosol effects is unclear due to uncertainties

Magnetoelectric Andreev Effect due to Proximity-Induced Nonunitary Triplet Superconductivity in Helical Metals

NASA Astrophysics Data System (ADS)

Tkachov, G.

2017-01-01

Noncentrosymmetric superconductors exhibit the magnetoelectric effect, which manifests itself in the appearance of the magnetic spin polarization in response to a dissipationless electric current (supercurrent). While much attention has been dedicated to the thermodynamic version of this phenomenon (Edelstein effect), nonequilibrium transport magnetoelectric effects have not been explored yet. We propose the magnetoelectric Andreev effect (MAE), which consists in the generation of spin-polarized triplet Andreev conductance by an electric supercurrent. The MAE stems from the spin polarization of the Cooper-pair condensate due to a supercurrent-induced nonunitary triplet pairing. We propose the realization of such a nonunitary pairing and MAE in superconducting proximity structures based on two-dimensional helical metals—strongly spin-orbit-coupled electronic systems with the Dirac spectrum such as the topological surface states. Our results uncover an unexplored route towards electrically controlled superconducting spintronics and are a smoking gun for induced unconventional superconductivity in spin-orbit-coupled materials.

Teller, Edward (1908-)

NASA Astrophysics Data System (ADS)

Murdin, P.

2000-11-01

American physicist, born in Budapest, Hungary; at George Washington University collaborated with George Gamow in studying nuclear beta decay, and astrophysics. Worked on the atomic and hydrogen bombs....

Study of antioxidative effects and anti-inflammatory effects in mice due to low-dose X-irradiation or radon inhalation

PubMed Central

Kataoka, Takahiro

2013-01-01

Low-dose irradiation induces various stimulating effects, especially activation of the biological defense system including antioxidative and immune functions. Oxidative stress induced by reactive oxygen species (ROS) can cause cell damage and death and can induce many types of diseases. This paper reviews new insights into inhibition of ROS-related diseases with low-dose irradiation or radon inhalation. X-irradiation (0.5 Gy) before or after carbon tetrachloride (CCl4) treatment inhibits hepatopathy in mice. X-irradiation (0.5 Gy) before ischemia-reperfusion injury or cold-induced brain injury also inhibits edema. These findings suggest that low-dose X-irradiation has antioxidative effects due to blocking the damage induced by free radicals or ROS. Moreover, radon inhalation increases superoxide dismutase activity in many organs and inhibits CCl4-induced hepatic and renal damage and streptozotocin-induced type I diabetes. These findings suggest that radon inhalation also has antioxidative effects. This antioxidative effect against CCl4-induced hepatopathy is comparable to treatment with ascorbic acid (vitamin C) at a dose of 500 mg/kg weight, or α-tocopherol (vitamin E) treatment at a dose of 300 mg/kg weight, and is due to activation of antioxidative functions. In addition, radon inhalation inhibits carrageenan-induced inflammatory paw edema, suggesting that radon inhalation has anti-inflammatory effects. Furthermore, radon inhalation inhibits formalin-induced inflammatory pain and chronic constriction injury-induced neuropathic pain, suggesting that radon inhalation relieves pain. Thus, low-dose irradiation very likely activates the defense systems in the body, and therefore, contributes to preventing or reducing ROS-related injuries, which are thought to involve peroxidation. PMID:23420683

Study of antioxidative effects and anti-inflammatory effects in mice due to low-dose X-irradiation or radon inhalation.

PubMed

Kataoka, Takahiro

2013-07-01

Low-dose irradiation induces various stimulating effects, especially activation of the biological defense system including antioxidative and immune functions. Oxidative stress induced by reactive oxygen species (ROS) can cause cell damage and death and can induce many types of diseases. This paper reviews new insights into inhibition of ROS-related diseases with low-dose irradiation or radon inhalation. X-irradiation (0.5 Gy) before or after carbon tetrachloride (CCl4) treatment inhibits hepatopathy in mice. X-irradiation (0.5 Gy) before ischemia-reperfusion injury or cold-induced brain injury also inhibits edema. These findings suggest that low-dose X-irradiation has antioxidative effects due to blocking the damage induced by free radicals or ROS. Moreover, radon inhalation increases superoxide dismutase activity in many organs and inhibits CCl4-induced hepatic and renal damage and streptozotocin-induced type I diabetes. These findings suggest that radon inhalation also has antioxidative effects. This antioxidative effect against CCl4-induced hepatopathy is comparable to treatment with ascorbic acid (vitamin C) at a dose of 500 mg/kg weight, or α-tocopherol (vitamin E) treatment at a dose of 300 mg/kg weight, and is due to activation of antioxidative functions. In addition, radon inhalation inhibits carrageenan-induced inflammatory paw edema, suggesting that radon inhalation has anti-inflammatory effects. Furthermore, radon inhalation inhibits formalin-induced inflammatory pain and chronic constriction injury-induced neuropathic pain, suggesting that radon inhalation relieves pain. Thus, low-dose irradiation very likely activates the defense systems in the body, and therefore, contributes to preventing or reducing ROS-related injuries, which are thought to involve peroxidation.

EFFECT OF THE LESION DUE TO INFLUENZA VIRUS ON THE RESISTANCE OF MICE TO INHALED PNEUMOCOCCI

PubMed Central

Harford, Carl G.; Leidler, Virginia; Hara, Mary

1949-01-01

1. The normal lung of the mouse possesses the power of reducing markedly its content of Type I pneumococci within 3 hours after inhalation of the organisms in the form of fine droplets. 2. Lungs with fully developed influenza viral pneumonia not only fail to reduce the pulmonary content of pneumococci administered in this manner but, on the contrary, support their growth. 3. After intrabronchial inoculation into mice, influenza virus multiplies rapidly in the lung within 24 hours. 4. Criteria have been established for distinction between true viral lesions of the lung and changes due to the inoculation of diluents as vehicles for the virus. 5. 24 hours after inoculation of virus, there are no macroscopic lesions in the lung and the microscopic changes are due to the diluent. 6. Presence and multiplication of the virus in the lung 24 hours after inoculation have no apparent effect on the power of the lung to reduce rapidly its content of inhaled pneumococci. 7. The effect of the virus in lowering resistance to secondary bacterial infection appears to be due to the presence of the lesion produced by the virus. PMID:18099165

Giant Faraday effect due to Pauli exclusion principle in 3D topological insulators.

PubMed

Paudel, Hari P; Leuenberger, Michael N

2014-02-26

Experiments using ARPES, which is based on the photoelectric effect, show that the surface states in 3D topological insulators (TI) are helical. Here we consider Weyl interface fermions due to band inversion in narrow-bandgap semiconductors, such as Pb1-xSnxTe. The positive and negative energy solutions can be identified by means of opposite helicity in terms of the spin helicity operator in 3D TI as ĥ(TI) = (1/ |p|_ |) β (σ|_ x p|_ ) · z^, where β is a Dirac matrix and z^ points perpendicular to the interface. Using the 3D Dirac equation and bandstructure calculations we show that the transitions between positive and negative energy solutions, giving rise to electron-hole pairs, obey strict optical selection rules. In order to demonstrate the consequences of these selection rules, we consider the Faraday effect due to the Pauli exclusion principle in a pump-probe setup using a 3D TI double interface of a PbTe/Pb₀.₃₁Sn₀.₆₉Te/PbTe heterostructure. For that we calculate the optical conductivity tensor of this heterostructure, which we use to solve Maxwell's equations. The Faraday rotation angle exhibits oscillations as a function of probe wavelength and thickness of the heterostructure. The maxima in the Faraday rotation angle are of the order of mrds.

Theory of optical transitions in π-conjugated macrocycles

NASA Astrophysics Data System (ADS)

Marcus, Max; Coonjobeeharry, Jaymee; Barford, William

2016-04-01

We describe a theoretical and computational investigation of the optical properties of π-conjugated macrocycles. Since the low-energy excitations of these systems are Frenkel excitons that couple to high-frequency dispersionless phonons, we employ the quantized Frenkel-Holstein model and solve it via the density matrix renormalization group (DMRG) method. First we consider optical emission from perfectly circular systems. Owing to optical selection rules, such systems radiate via two mechanisms: (i) within the Condon approximation, by thermally induced emission from the optically allowed j = ± 1 states and (ii) beyond the Condon approximation, by emission from the j = 0 state via coupling with a totally non-symmetric phonon (namely, the Herzberg-Teller effect). Using perturbation theory, we derive an expression for the Herzberg-Teller correction and show via DMRG calculations that this expression soon fails as ħ ω/J and the size of the macrocycle increase. Next, we consider the role of broken symmetry caused by torsional disorder. In this case the quantum number j no longer labels eigenstates of angular momentum, but instead labels localized local exciton groundstates (LEGSs) or quasi-extended states (QEESs). As for linear polymers, LEGSs define chromophores, with the higher energy QEESs being extended over numerous LEGSs. Within the Condon approximation (i.e., neglecting the Herzberg-Teller correction) we show that increased disorder increases the emissive optical intensity, because all the LEGSs are optically active. We next consider the combined role of broken symmetry and curvature, by explicitly evaluating the Herzberg-Teller correction in disordered systems via the DMRG method. The Herzberg-Teller correction is most evident in the emission intensity ratio, I00/I01. In the Condon approximation I00/I01 is a constant function of curvature, whereas in practice it vanishes for closed rings and only approaches a constant in the limit of vanishing curvature. We

Stress Induced Charge-Ordering Process in LiMn 2O 4

DOE PAGES

Chen, Yan; Yu, Dunji; An, Ke

2016-07-25

In this letter we report the stress-induced Mn charge-ordering process in the LiMn 2O 4 spinel, evidenced by the lattice strain evolutions due to the Jahn–Teller effects. In situ neutron diffraction reveals the initial stage of this process at low stress, indicating the eg electron localization at the preferential Mn sites during the early phase transition as an underlying charge-ordering mechanism in the charge-frustrated LiMn 2O 4. The initial stage of this transition exhibits as a progressive lattice and charge evolution, without showing a first-order behavior.

Multi-State Vibronic Interactions in Fluorinated Benzene Radical Cations.

NASA Astrophysics Data System (ADS)

Faraji, S.; Köppel, H.

2009-06-01

Conical intersections of potential energy surfaces have emerged as paradigms for signalling strong nonadiabatic coupling effects. An important class of systems where some of these effects have been analyzed in the literature, are the benzene and benzenoid cations, where the electronic structure, spectroscopy, and dynamics have received great attention in the literature. In the present work a brief overview is given over our theoretical treatments of multi-mode and multi-state vibronic interactions in the benzene radical cation and some of its fluorinated derivatives. The fluorobenzene derivatives are of systematic interest for at least two different reasons. (1) The reduction of symmetry by incomplete fluorination leads to a disappearance of the Jahn-Teller effect present in the parent cation. (2) A specific, more chemical effect of fluorination consists in the energetic increase of the lowest σ-type electronic states of the radical cations. The multi-mode multi-state vibronic interactions between the five lowest electronic states of the fluorobenzene radical cations are investigated theoretically, based on ab initio electronic structure data, and employing the well-established linear vibronic coupling model, augmented by quadratic coupling terms for the totally symmetric vibrational modes. Low-energy conical intersections, and strong vibronic couplings are found to prevail within the set of tilde{X}-tilde{A} and tilde{B}-tilde{C}-tilde{D} cationic states, while the interactions between these two sets of states are found to be weaker and depend on the particular isomer. This is attributed to the different location of the minima of the various conical intersections occurring in these systems. Wave-packet dynamical simulations for these coupled potential energy surfaces, utilizing the powerful multi-configuration time-dependent Hartree method are performed. Ultrafast internal conversion processes and the analysis of the MATI and photo-electron spectra shed new light

Synthesis, X-ray structure, magnetic resonance, and DFT analysis of a soluble copper(II) phthalocyanine lacking C-H bonds.

PubMed

Moons, Hans; Łapok, Łukasz; Loas, Andrei; Van Doorslaer, Sabine; Gorun, Sergiu M

2010-10-04

The synthesis, crystal structure, and electronic properties of perfluoro-isopropyl-substituted perfluorophthalocyanine bearing a copper atom in the central cavity (F(64)PcCu) are reported. While most halogenated phthalocyanines do not exhibit long-term order sufficient to form large single crystals, this is not the case for F(64)PcCu. Its crystal structure was determined by X-ray analysis and linked to the electronic properties determined by electron paramagnetic resonance (EPR). The findings are corroborated by density functional theory (DFT) computations, which agree well with the experiment. X-band continuous-wave EPR spectra of undiluted F(64)PcCu powder, indicate the existence of isolated metal centers. The electron-withdrawing effect of the perfluoroalkyl (R(f)) groups significantly enhances the complexes solubility in organic solvents like alcohols, including via their axial coordination. This coordination is confirmed by X-band (1)H HYSCORE experiments and is also seen in the solid state via the X-ray structure. Detailed X-band CW-EPR, X-band Davies and Mims ENDOR, and W-band electron spin-echo-detected EPR studies of F(64)PcCu in ethanol allow the determination of the principal g values and the hyperfine couplings of the metal, nitrogen, and fluorine nuclei. Comparison of the g and metal hyperfine values of F(64)PcCu and other PcCu complexes in different matrices reveals a dominant effect of the matrix on these EPR parameters, while variations in the ring substituents have only a secondary effect. The relatively strong axial coordination occurs despite the diminished covalency of the C-N bonds and potentially weakening Jahn-Teller effects. Surprisingly, natural abundance (13)C HYSCORE signals could be observed for a frozen ethanol solution of F(64)PcCu. The (13)C nuclei contributing to the HYSCORE spectra could be identified as the pyrrole carbons by means of DFT. Finally, (19)F ENDOR and easily observable paramagnetic NMR were found to relate well to the

Geochemical reanalysis of historical U.S. Geological Survey sediment samples from the Kougarok area, Bendeleben and Teller quadrangles, Seward Peninsula, Alaska

USGS Publications Warehouse

Werdon, Melanie B.; Granitto, Matthew; Azain, Jaime S.

2015-01-01

The State of Alaska’s Strategic and Critical Minerals (SCM) Assessment project, a State-funded Capital Improvement Project (CIP), is designed to evaluate Alaska’s statewide potential for SCM resources. The SCM Assessment is being implemented by the Alaska Division of Geological & Geophysical Surveys (DGGS), and involves obtaining new airborne-geophysical, geological, and geochemical data. As part of the SCM Assessment, thousands of historical geochemical samples from DGGS, U.S. Geological Survey (USGS), and U.S. Bureau of Mines archives are being reanalyzed by DGGS using modern, quantitative, geochemical-analytical methods. The objective is to update the statewide geochemical database to more clearly identify areas in Alaska with SCM potential. The USGS is also undertaking SCM-related geologic studies in Alaska through the federally funded Alaska Critical Minerals cooperative project. DGGS and USGS share the goal of evaluating Alaska’s strategic and critical minerals potential and together created a Letter of Agreement (signed December 2012) and a supplementary Technical Assistance Agreement (#14CMTAA143458) to facilitate the two agencies’ cooperative work. Under these agreements, DGGS contracted the USGS in Denver to reanalyze historical USGS sediment samples from Alaska. For this report, DGGS funded reanalysis of 302 historical USGS sediment samples from the statewide Alaska Geochemical Database Version 2.0 (AGDB2; Granitto and others, 2013). Samples were chosen from the Kougarok River drainage as well as smaller adjacent drainages in the Bendeleben and Teller quadrangles, Seward Peninsula, Alaska (fig. 1). The USGS was responsible for sample retrieval from the National Geochemical Sample Archive (NGSA) in Denver, Colorado through the final quality assurance/quality control (QA/QC) of the geochemical analyses obtained through the USGS contract lab. The new geochemical data are published in this report as a coauthored DGGS report, and will be incorporated

Evaluation of World Population-Weighted Effective Dose due to Cosmic Ray Exposure

PubMed Central

Sato, Tatsuhiko

2016-01-01

After the release of the Report of the United Nations Scientific Committee of the Effects of Atomic Radiation in 2000 (UNSCEAR2000), it became commonly accepted that the world population-weighted effective dose due to cosmic-ray exposure is 0.38 mSv, with a range from 0.3 to 2 mSv. However, these values were derived from approximate projections of altitude and geographic dependences of the cosmic-ray dose rates as well as the world population. This study hence re-evaluated the population-weighted annual effective doses and their probability densities for the entire world as well as for 230 individual nations, using a sophisticated cosmic-ray flux calculation model in tandem with detailed grid population and elevation databases. The resulting world population-weighted annual effective dose was determined to be 0.32 mSv, which is smaller than the UNSCEAR’s evaluation by 16%, with a range from 0.23 to 0.70 mSv covering 99% of the world population. These values were noted to vary with the solar modulation condition within a range of approximately 15%. All assessed population-weighted annual effective doses as well as their statistical information for each nation are provided in the supplementary files annexed to this report. These data improve our understanding of cosmic-ray radiation exposures to populations globally. PMID:27650664

Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior

DOE PAGES

Sanjeewa, Liurukara D.; McGuire, Michael A.; Garlea, Vasile O.; ...

2015-07-08

In a new series of transition metal vanadates, namely, Ba 2M(VO 4) 2(OH) (M = V 3+, Mn 3+, and Fe 3+), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 °C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba 2V(VO 4) 2(OH) is monoclinic in space group P2 1/m, a = 7.8783(2) Å, b = 6.1369(1) Å, c = 9.1836(2) Å, β = 113.07(3)°, V = 408.51(2) Å 3. Moreover, the other structures are similar and consist of one-dimensional trans edge-shared distortedmore » octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba 2Mn(VO 4) 2(OH) analogue yielded a new understanding of the Jahn–Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Finally, single-crystal temperature-dependent magnetic studies on Ba 2V(VO 4) 2(OH) reveal a broad feature over a wide temperature range with maximum at ~100 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetism studies.« less

Effects of macroeconomic trends on social security spending due to sickness and disability.

PubMed

Khan, Jahangir; Gerdtham, Ulf-G; Jansson, Bjarne

2004-11-01

We analyzed the relationship between macroeconomic conditions, measured as unemployment rate and social security spending, from 4 social security schemes and total spending due to sickness and disability. We obtained aggregated panel data from 13 Organization for Economic Cooperation and Development member countries for 1980-1996. We used regression analysis and fixed effect models to examine spending on sickness benefits, disability pensions, occupational-injury benefits, survivor's pensions, and total spending. A decline in unemployment increased sickness benefits spending and reduced disability pension spending. These effects reversed direction after 4 years of unemployment. Inclusion of mortality rate as an additional variable in the analysis did not affect the findings. Macroeconomic conditions influence some reimbursements from social security schemes but not total spending.

Uncertainties in global aerosols and climate effects due to biofuel emissions

NASA Astrophysics Data System (ADS)

Kodros, J. K.; Scott, C. E.; Farina, S. C.; Lee, Y. H.; L'Orange, C.; Volckens, J.; Pierce, J. R.

2015-08-01

effects is unclear due to uncertainties in model inputs. This uncertainty limits our ability to introduce mitigation strategies aimed at reducing biofuel black carbon emissions in order to counter warming effects from greenhouse gases. To better understand the climate impact of particle emissions from biofuel combustion, we recommend field/laboratory measurements to narrow constraints on (1) emissions mass, (2) emission size distribution, (3) mixing state, and (4) ratio of black carbon to organic aerosol.

Effective dilution of surfactants due to thinning of the soap film

NASA Astrophysics Data System (ADS)

Sane, Aakash; Mandre, Shreyas; Kim, Ildoo

2017-11-01

A flowing soap film is a system whose hydrodynamic properties can be affected by its thickness. Despite abundant experiments performed using soap films, few have examined the dependence of its physical as well as chemical properties with respect to its thickness. We investigate one such property - surface tension of the flowing film and delineate its dependence on the concentration of the soap solution and flow rate per unit width i.e. thickness of the soap film. Using our proposed method to measure the average surface tension in-situ over the whole soap film, we show that the surface tension increases by reducing the thickness of the film and by reducing the concentration of the soap solution. Our data suggests that thinning of the soap film is effectively diluting the solution. Thinning increases the adsorption of surfactants to the surfaces, but it decreases the total number of molecules per unit area. Our work brings new insight into the physics of soap films and we believe that this effective dilution due to thinning is a signature of the flowing soap films, whose surface concentration of surfactants is affected by the thickness.

Saltwater Intrusion Through Submerged Caves due to the Venturi Effect

NASA Astrophysics Data System (ADS)

Khazmutdinova, K.; Nof, D.

2016-12-01

Saltwater intrusion into freshwater sources is a concern in coastal areas. In order to reduce the intrusion of seawater the physical mechanisms that allow this to occur must be understood. This study presents an approach to quantify saltwater intrusion in karstic coastal aquifers due to the presence of submerged caves. Many water-filled caves have variable tunnel cross-sections and often have narrow connections between two otherwise large tunnels. Generally, the diameter of these restrictions is 1 - 2 m and the flow speed within them is approximately 1 - 5 m/s. Main cave tunnels can be 10 - 20 times bigger than restrictions, and have flow speeds ranging anywhere between 0.5 cm/s and 20 cm/s. According to Bernoulli's theorem, in order to balance high velocities within a restriction, the pressure has to drop as the water flow passes through a narrow tunnel. This is expected to influence the height to which a deeper saline aquifer can penetrate in conduits connecting the narrow restriction and saltwater. For sufficiently small restrictions, saline water can invade the freshwater tunnel. The intrusion of saltwater from a deeper, saline aquifer into a fresh groundwater system due to the Venturi effect in submerged caves was computed, and an analytical and a qualitative model that captures saltwater intrusion into a fresh aquifer was developed. Using Bernoulli's theorem, we show that depths from which the saline water can be drawn into the freshwater tunnel reach up to 450 m depending on the difference in the density between fresh and saltwater. The velocity of the saline upward flow is estimated to be 1.4 m/s using the parameters for Wakulla Spring, a first order magnitude spring in Florida, with a saltwater interface 180 m below the spring cave system.