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Sample records for jahn-teller glass formation

  1. 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. PMID:26575745

  2. Theory of the Jahn-Teller Soliton

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis

    2006-03-01

    It is demonstrated that under common conditions a molecular solid subject to Jahn-Teller interactions supports stable Q- ball-like non-topological solitons. Such solitons represent a localized lump of excess electric charge in periodic motion accompanied by a time-dependent shape distortion of a set of adjacent molecules. The motion of the distortion can correspond to a true rotation or to a pseudo-rotation about the symmetric shape configuration. These solitons are stable for Jahn-Teller coupling strengths below a critical value; however, as the Jahn- Teller coupling approaches this critical value, the size of the soliton diverges signaling an incipient structural phase transition. The soliton phase mimics features commonly attributed to phase separation in complex solids.

  3. Jahn-Teller effect: its history and applicability

    SciTech Connect

    Teller, E.

    1981-08-31

    The interactions between Teller, Renner, Jahn and Landau which led to the formulation of the Jahn-Teller effect are discussed. The applicability of Jahn-Teller type of theory to superconductivity and the explanation proposed by the use of Goldstone particles are assessed.

  4. Jahn-Teller Effect: Its History and Applicability

    DOE R&D Accomplishments Database

    Teller, E.

    1981-08-31

    The interactions between Teller, Renner, Jahn and Landau which led to the formulation of the Jahn-Teller effect are discussed. The applicability of Jahn-Teller type of theory to superconductivity and the explanation proposed by the use of Goldstone particles are assessed.

  5. Jahn-Teller and pseudo-Jahn-Teller effects in trifluoromethane radical cation

    NASA Astrophysics Data System (ADS)

    Ghanta, Susanta

    2016-08-01

    Jahn-Teller (JT) and pseudo-Jahn-Teller (PJT) effects in the ground, first and second excited electronic states of the trifluoromethane radical cation are theoretically examined here. Extensive ab initio computation of electronic potential energy surfaces and their coupling surfaces are performed. Full quantum dynamics are obtained by both time-independent and time-dependent quantum mechanical methods. This system belongs to (E+A)⊗e JT-PJT family. Our results compare well with the experimental data. JT interactions are fairly strong in the second excited B˜2 E electronic state and the PJT interaction between A˜2A2 - B˜2 E electronic states is stronger which cause an increase of the spectral line density of the vibronic spectrum.

  6. Polarons and solitons in Jahn Teller systems

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis P.

    2007-07-01

    Using a semiclassical continuum model of an electron in a deformable molecular crystal, some properties of multicomponent generalizations of the polaron - "vector polarons" - are elucidated. Analytical solutions for the case of two electronic bands coupled to two vibrational modes are given in detail. Within the model considered, the vector polaron can be classified by its wavefunction into several types and can have features that include: (1) a spatial variation in the electronic and vibrational character, and (2) low-energy internal degrees of freedom. For the case of electronic and vibrational degeneracy, local Jahn-Teller interactions can also lead to a novel spatiotemporal soliton, a long-lived excited state of the many-electron system stabilized by the conservation law resulting from degeneracy.

  7. Photophysics of barrelene: The Jahn-Teller and pseudo-Jahn-Teller effects

    NASA Astrophysics Data System (ADS)

    Ghanta, Susanta

    2016-04-01

    The static and dynamic aspects of Jahn-Teller(JT) and pseudo-Jahn-Teller(PJT) interactions between ground (X˜2A2‧) and first three excited electronic states (A˜2E‧ , B˜2E″ and C˜2A‧1) of bicyclo- [2,2,2]-octa-2,5,7-triene (barrelene) radical cation (Bl+) are theoretically investigated here. This belongs to the (E + E) ⊗ e and (E + A) ⊗ e JT-PJT class of compounds as described by the symmetry of the electronic states and the molecular point group. The complex vibronic dynamics on the coupled electronic states of the cation is simulated by both time-independent and time-dependent wave packet propagation method using multi configuration time-dependent Hartree scheme. The JT effects in the A˜ and B˜ electronic states and the PJT coupling between the B˜ and C˜ electronic states of Bl+ are found very strong. The final theoretical results are compared with the experimental results.

  8. Jahn-Teller solitons, structural phase transitions, and phase separation.

    PubMed

    Clougherty, Dennis P

    2006-02-01

    It is demonstrated that under common conditions a molecular solid subject to Jahn-Teller interactions supports stable Q-ball-like nontopological solitons. Such solitons represent a localized lump of excess electric charge in periodic motion accompanied by a time-dependent shape distortion of a set of adjacent molecules. The motion of the distortion can correspond to a true rotation or to a pseudorotation about the symmetric shape configuration. These solitons are stable for Jahn-Teller coupling strengths below a critical value; however, as the Jahn-Teller coupling approaches this critical value, the size of the soliton diverges signaling an incipient structural phase transition. The soliton phase mimics features commonly attributed to phase separation in complex solids. PMID:16486846

  9. Jahn-Teller Solitons, Structural Phase Transitions, and Phase Separation

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis P.

    2006-02-01

    It is demonstrated that under common conditions a molecular solid subject to Jahn-Teller interactions supports stable Q-ball-like nontopological solitons. Such solitons represent a localized lump of excess electric charge in periodic motion accompanied by a time-dependent shape distortion of a set of adjacent molecules. The motion of the distortion can correspond to a true rotation or to a pseudorotation about the symmetric shape configuration. These solitons are stable for Jahn-Teller coupling strengths below a critical value; however, as the Jahn-Teller coupling approaches this critical value, the size of the soliton diverges signaling an incipient structural phase transition. The soliton phase mimics features commonly attributed to phase separation in complex solids.

  10. Optimized unconventional superconductivity in a molecular Jahn-Teller metal.

    PubMed

    Zadik, Ruth H; Takabayashi, Yasuhiro; Klupp, Gyöngyi; Colman, Ross H; Ganin, Alexey Y; Potočnik, Anton; Jeglič, Peter; Arčon, Denis; Matus, Péter; Kamarás, Katalin; Kasahara, Yuichi; Iwasa, Yoshihiro; Fitch, Andrew N; Ohishi, Yasuo; Garbarino, Gaston; Kato, Kenichi; Rosseinsky, Matthew J; Prassides, Kosmas

    2015-04-01

    Understanding the relationship between the superconducting, the neighboring insulating, and the normal metallic state above T c is a major challenge for all unconventional superconductors. The molecular A3C60 fulleride superconductors have a parent antiferromagnetic insulator in common with the atom-based cuprates, but here, the C60 (3-) electronic structure controls the geometry and spin state of the structural building unit via the on-molecule Jahn-Teller effect. We identify the Jahn-Teller metal as a fluctuating microscopically heterogeneous coexistence of both localized Jahn-Teller-active and itinerant electrons that connects the insulating and superconducting states of fullerides. The balance between these molecular and extended lattice features of the electrons at the Fermi level gives a dome-shaped variation of T c with interfulleride separation, demonstrating molecular electronic structure control of superconductivity. PMID:26601168

  11. Dynamic Jahn-Teller coupling and high T c superconductivity

    NASA Astrophysics Data System (ADS)

    Clougherty, Dennis P.; Johnson, Keith H.; McHenry, Michael E.

    1989-12-01

    Based on the cooperative dynamic Jahn-Teller effect, a universal model of superconductivity is sketched which accounts for many aspects of conventional BCS and high T c superconductors. Within the quasi-molecular approximation, a real space vibronic coupling of degenerate (or nearly degenerate) electronic states to anharmonically mixed nuclear distortions is shown to lead to electron pairing. The crossover from electron-phonon behavior to electronic behavior as a function of Jahn-Teller coupling and anharmonic mixing is illustrated for the case of a CuO 4 cluster having D 4 h symmetry.

  12. Optimized unconventional superconductivity in a molecular Jahn-Teller metal

    PubMed Central

    Zadik, Ruth H.; Takabayashi, Yasuhiro; Klupp, Gyöngyi; Colman, Ross H.; Ganin, Alexey Y.; Potočnik, Anton; Jeglič, Peter; Arčon, Denis; Matus, Péter; Kamarás, Katalin; Kasahara, Yuichi; Iwasa, Yoshihiro; Fitch, Andrew N.; Ohishi, Yasuo; Garbarino, Gaston; Kato, Kenichi; Rosseinsky, Matthew J.; Prassides, Kosmas

    2015-01-01

    Understanding the relationship between the superconducting, the neighboring insulating, and the normal metallic state above Tc is a major challenge for all unconventional superconductors. The molecular A3C60 fulleride superconductors have a parent antiferromagnetic insulator in common with the atom-based cuprates, but here, the C603– electronic structure controls the geometry and spin state of the structural building unit via the on-molecule Jahn-Teller effect. We identify the Jahn-Teller metal as a fluctuating microscopically heterogeneous coexistence of both localized Jahn-Teller–active and itinerant electrons that connects the insulating and superconducting states of fullerides. The balance between these molecular and extended lattice features of the electrons at the Fermi level gives a dome-shaped variation of Tc with interfulleride separation, demonstrating molecular electronic structure control of superconductivity. PMID:26601168

  13. Jahn-Teller driven perpendicular magnetocrystalline anisotropy in metastable ruthenium

    NASA Astrophysics Data System (ADS)

    Odkhuu, Dorj; Rhim, S. H.; Park, Noejung; Nakamura, Kohji; Hong, Soon Cheol

    2015-01-01

    A metastable phase of body-centered-tetragonal ruthenium (bct Ru) is identified to exhibit a large perpendicular magnetocrystalline anisotropy (PMCA), whose energy EMCA is as large as 150 μ eV /atom , which is two orders of magnitude greater than those of 3 d magnetic metals. Further investigation over the range of tetragonal distortion suggests that the appearance of magnetism in the bct Ru is governed by the Jahn-Teller spit eg orbitals. Moreover, from band analysis, MCA is mainly determined by an interplay between two eg states, dx2-y2 and dz2 states, as a result of level reversal associated with tetragonal distortion.

  14. Electric Field Control of Jahn-Teller Distortions in Bulk Perovskites

    NASA Astrophysics Data System (ADS)

    Varignon, Julien; Bristowe, Nicholas C.; Ghosez, Philippe

    2016-02-01

    The Jahn-Teller distortion, by its very nature, is often at the heart of the various electronic properties displayed by perovskites and related materials. Despite the Jahn-Teller mode being nonpolar, we devise and demonstrate, in the present Letter, an electric field control of Jahn-Teller distortions in bulk perovskites. The electric field control is enabled through an anharmonic lattice mode coupling between the Jahn-Teller distortion and a polar mode. We confirm this coupling and quantify it through first-principles calculations. The coupling will always exist within the P b 21m space group, which is found to be the favored ground state for various perovskites under sufficient tensile epitaxial strain. Intriguingly, the calculations reveal that this mechanism is not only restricted to Jahn-Teller active systems, promising a general route to tune or induce novel electronic functionality in perovskites as a whole.

  15. The Jahn-Teller plus pseudo-Jahn-Teller vibronic problem in the C3 radical and its topological implications.

    PubMed

    Rocha, C M R; Varandas, A J C

    2016-02-14

    The combined Jahn-Teller plus pseudo-Jahn-Teller [(E'+A1')⊗e'] problem is discussed for the tricarbon radical (C3) by means of ab initio calculations at the multireference configuration interaction level of theory. For the (1)E' electronic state arising from a e'(2) valence configuration, three additional symmetry-equivalent C2v seams are found to lie in close proximity to the D3h symmetry-required seam over the entire range of the breathing coordinate here considered. As the perimeter of the molecule increases, the C2v disjoint seams approach the D3h one almost linearly and ultimately coalesce with it at Q1 = 5.005 a0, thence forming an intersection node or confluence. By further increasing the size of the molecular triangle, the C2v seams get rotated by ±π in the g-h plane. A three-state vibronic Hamiltonian is also proposed to model locally the title system and shown to accurately mimic the calculated data over the region close to the minimum energy crossing point. No net geometric phase effect is observed when the associated electronic wave functions are adiabatically transported along closed paths encircling the four singularity points. For all paths enclosing the intersection node, the sign reversal criterion is shown to be not fulfilled, even for infinitesimal loops. The results so obtained are expected to be valid for other ring systems experiencing similar topological attributes. PMID:26874490

  16. The Jahn-Teller plus pseudo-Jahn-Teller vibronic problem in the C3 radical and its topological implications

    NASA Astrophysics Data System (ADS)

    Rocha, C. M. R.; Varandas, A. J. C.

    2016-02-01

    The combined Jahn-Teller plus pseudo-Jahn-Teller [ ( E ' + A1 ' ) ⊗ e ' ] problem is discussed for the tricarbon radical (C3) by means of ab initio calculations at the multireference configuration interaction level of theory. For the 1E' electronic state arising from a e'2 valence configuration, three additional symmetry-equivalent C2v seams are found to lie in close proximity to the D3h symmetry-required seam over the entire range of the breathing coordinate here considered. As the perimeter of the molecule increases, the C2v disjoint seams approach the D3h one almost linearly and ultimately coalesce with it at Q1 = 5.005 a0, thence forming an intersection node or confluence. By further increasing the size of the molecular triangle, the C2v seams get rotated by ±π in the g-h plane. A three-state vibronic Hamiltonian is also proposed to model locally the title system and shown to accurately mimic the calculated data over the region close to the minimum energy crossing point. No net geometric phase effect is observed when the associated electronic wave functions are adiabatically transported along closed paths encircling the four singularity points. For all paths enclosing the intersection node, the sign reversal criterion is shown to be not fulfilled, even for infinitesimal loops. The results so obtained are expected to be valid for other ring systems experiencing similar topological attributes.

  17. Jahn-Teller instability in dissipative quantum systems

    SciTech Connect

    Meaney, Charles P.; Duty, Tim; McKenzie, Ross H.; Milburn, G. J.

    2010-04-15

    We consider the steady states of a harmonic oscillator coupled so strongly to a two-level system (a qubit) that the rotating wave approximation cannot be made. The Hamiltonian version of this model is known as the E x {beta} Jahn-Teller model. The semiclassical version of this system exhibits a fixed-point bifurcation, which in the quantum model leads to a ground state with substantial entanglement between the oscillator and the qubit. We show that the dynamical bifurcation survives in a dissipative quantum description of the system, amidst an even richer bifurcation structure. We propose an experimental implementation of this model based on a superconducting cavity: a superconducting junction in the central conductor of a coplanar waveguide.

  18. Synchronization of networked Jahn-Teller systems in SQUIDs

    NASA Astrophysics Data System (ADS)

    Gül, Yusuf

    2016-06-01

    We consider the nonlinear effects in a Jahn-Teller (JT) system of two coupled resonators interacting simultaneously with a flux qubit using coupled SQUIDs. A two-frequency description of JT system that inherits the networked structure of both nonlinear Josephson junctions and harmonic oscillators is employed to describe the synchronous structures in a multifrequency scheme. Eigenvalue spectrum is used to show the switch between the effective single mode and two mode configuration in terms of frequency difference. The Rabi supersplitting is investigated by the spectral response of JT systems in different coupling regimes. Second-order coherence functions are employed to investigate antibunching effects in resonator mode. Synchronous structure between correlations of privileged mode and qubit is obtained in localization-delocalization and photon blockade regime controlled by the population imbalance.

  19. Persistence of Jahn Teller distortion in high pressure metallic phase of LaMnO3

    SciTech Connect

    Baldini, Maria; Struzhkin, Viktor V.; Goncharov, Alexander F.; Postorino, P.; Mao, Wendy L.

    2011-02-11

    High pressure, low temperature Raman measurements performed on LaMnO{sub 3} up to 34 GPa provide the first experimental evidence for the persistence of the Jahn-Teller distortion over the entire stability range of the insulating phase. This result resolves the ongoing debate about the nature of the pressure driven insulator to metal transition (IMT), demonstrating that LaMnO{sub 3} is not a classical Mott insulator. The formation of domains of distorted and regular octahedra, observed from 3 to 34 GPa, sheds new light on the mechanism behind the IMT suggesting that LaMnO{sub 3} becomes metallic when the fraction of undistorted octahedra domains increases beyond a critical threshold.

  20. Jet-Cooled Laser Spectroscopy of a Jahn-Teller and Pseudo Jahn-Teller Active Molecule: the Nitrate Radical

    NASA Astrophysics Data System (ADS)

    Chen, Ming-Wei; Takematsu, Kana; Okumura, Mitchio; Miller, Terry A.

    2009-06-01

    Well-known as an important intermediate in atmospheric chemistry, the nitrate radical (NO_3) has been extensively studied both experimentally and theoretically. The three energetically lowest electronic states (tilde{X} ^{2}A_{2}^', tilde{A} ^{2}E^'', and tilde{B} ^{2}E^') are strongly coupled by vibronic interactions and hence it is a textbook molecule for understanding the coupling between nearby potential energy surfaces. Such coupling has been treated in considerable detail theoretically. However, corresponding experimental characterization of the interaction is much less detailed. The experimental results primarily consist of IR measurements of vibrational transitions in the ground state. In addition, the electronically forbidden tilde{A}-tilde{X} transition has been observed in ambient temperature CRDS studies. To understand both the Jahn-Teller and pseudo Jahn-Teller coupling in the molecule, further measurements are required with different selection rules and/or higher resolution to resolve the rotational structures of different transitions. In our group, a high-resolution (source Δν≈ 100 MHz in NIR region), jet-cooled CRDS system can be applied to rotationally resolve the electronically forbidden tilde{A}-tilde{X} transition. Furthermore, our high-resolution LIF/SEP system (source Δν≈ 100 MHz) can provide the direct, rotationally resolved measurements of the tilde{B}-tilde{X} and tilde{B}-tilde{A} transitions by operating in the LIF and SEP modes respectively. Such data can provide unambiguous spectral assignments in the tilde{X}, tilde{A} and tilde{B} states. J. F. Stanton, J. Chem. Phys., 126, 134309 (2007) K. Kawaguchi, E. Hirota, T. Ishiwata, and I. Tanaka, J. Chem. Phys., 93, 951 (1990) K. Kawaguchi, T. Ishiwata, E. Hirota, and I. Tanaka, Chem. Phys., 231, 193 (1998) A. Deev, J. Sommar, and M. Okumura, J. Chem. Phys., 122, 224305 (2005) S. Wu, P. Dupré, and T. A. Miller, Phys. Chem. Chem. Phys., 8, 1682, (2006)

  1. Unusual ferroelectricity induced by the Jahn-Teller effect: A case study on lacunar spinel compounds

    NASA Astrophysics Data System (ADS)

    Xu, Ke; Xiang, Hongjun

    The Jahn-Teller effect refers to the symmetry-lowering geometrical distortion in a crystal (or nonlinear molecule) due to the presence of a degenerate electronic state. Usually, the Jahn-Teller distortion is not polar. Recently, GaV4S8 with a lacunar spinel structure was found to undergo a Jahn-Teller distortion from a cubic to ferroelectric rhombohedral structure at TJT = 38 K. Here, we carry out a general group theory analysis to show how and when the Jahn-Teller effect gives rise to ferroelectricity. On the basis of this theory, we ?nd that the ferroelectric Jahn-Teller distortion in GaV4S8 is due to the noncentrosymmetric nature of the parent phase and a strong electron-phonon interaction related to two low-energy T2 phonon modes. Interestingly, GaV4S8 is not only ferroelectric, but also ferromagnetic with a magnetic easy axis along the ferroelectric direction. This suggests that GaV4S8 is a multiferroic material in which an external electric ?eld may control its magnetization direction. Our study not only explains the Jahn-Teller physics in GaV4S8, but also paves a way for searching and designing different ferroelectrics and multiferroics.

  2. Jahn-Teller Transitions in the Bimetallic Oxalates

    SciTech Connect

    Fishman, Randy Scott

    2011-01-01

    Bimetallic oxalates are a class of layered molecule-based magnets with transition-metal ions M(II) and M'(III) coupled by oxalate molecules (C2O4)-2 in an open honeycomb structure. Magnetic compensation (MC) has been observed in ferrimagnetic Fe(II)Fe(III) compounds with certain cations between the bimetallic layers. This behavior can be explained [1] by considering the C3-symmetric crystal field produced by the six oxygen atoms surrounding each Fe ion, which splits the L = 2, 3d6 multiplet on the Fe(II) sites into two doublets and one singlet. MC occurs when the doublet lies lowest in energy and carries an orbital angular momentum Lz between about 0.25 and 1.0. Because the low-energy doublet is half-filled, a Jahn-Teller (JT) distortion may break the C3 symmetry near the ferrimagnetic transition temperature. In the absence of spin-orbit coupling on the Fe(II) sites, the JT distortion would always occur at T = 0. However, due to the competition between the spin-orbit coupling and JT energies, the JT distortion disappears at low temperatures in compounds that display MC [2]. Comparison is made with recent experiments and predictions are made for controlling the MC and JT critical temperatures.

  3. Chemically-induced Jahn-Teller ordering on manganite surfaces

    NASA Astrophysics Data System (ADS)

    Gai, Zheng; Lin, Wenzhi; Burton, J. D.; Tsymbal, Evgeny Y.; Fuchigami, K.; Shen, Jian; Snijders, P. C.; Ward, T. Z.; Jesse, Stephen; Kalinin, Sergei V.; Baddorf, A. P.

    2014-03-01

    Physical and electrochemical phenomena at the surfaces of transition metal oxides and their coupling to local functionality remains one of the enigmas of condensed matter physics. Understanding the emergent physical phenomena at surfaces requires the capability to probe the local composition, map order parameter fields, and establish their coupling to electronic properties. Here we demonstrate that measuring the sub 30 pm displacements of atoms from high-symmetry positions in the atomically resolved scanning tunneling microscopy (STM) allows the physical order parameter fields to be visualized in real space on the single atom level. Here, this local crystallographic analysis is applied to the in-situ grown manganite surfaces. In particular, using direct bond-angle mapping we report direct observation of structural domains on manganite surfaces, and trace their origin to surface-chemistry-induced stabilization of ordered Jahn-Teller displacements. Density functional calculations provide insight into the intriguing interplay between the various degrees of freedom now resolved on the atomic level. Research was supported by MSED and CNMS, which are sponsored at Oak Ridge National Laboratory by the Office of Basic Energy Sciences, U.S. Department of Energy.

  4. Pseudo-Jahn-Teller origin of the low barrier hydrogen bond in N2H7+

    NASA Astrophysics Data System (ADS)

    García-Fernández, P.; García-Canales, L.; García-Lastra, J. M.; Junquera, J.; Moreno, M.; Aramburu, J. A.

    2008-09-01

    The microscopic origin and quantum effects of the low barrier hydrogen bond (LBHB) in the proton-bound ammonia dimer cation N2H7+ were studied by means of ab initio and density-functional theory (DFT) methods. These results were analyzed in the framework of vibronic theory and compared to those obtained for the Zundel cation H5O2+. All geometry optimizations carried out using wavefunction-based methods [Hartree-Fock, second and fourth order Möller-Plesset theory (MP2 and MP4), and quadratic configuration interaction with singles and doubles excitations (QCISD)] lead to an asymmetrical H3N-H+⋯NH3 conformation (C3v symmetry) with a small energy barrier (1.26kcal/mol in MP4 and QCISD calculations) between both equivalent minima. The value of this barrier is underestimated in DFT calculations particularly at the local density approximation level where geometry optimization leads to a symmetric H3N⋯H+⋯NH3 structure (D3d point group). The instability of the symmetric D3d structure is shown to originate from the pseudo-Jahn-Teller mixing of the electronic A1g1 ground state with five low lying excited states of A2u symmetry through the asymmetric α2u vibrational mode. A molecular orbital study of the pseudo-Jahn-Teller coupling has allowed us to discuss the origin of the proton displacement and the LBHB formation in terms of the polarization of the NH3 molecules and the transfer of electronic charge between the proton and the NH3 units (rebonding). The parallel study of the H5O2+ cation, which presents a symmetric single-well structure, allows us to analyze why these similar molecules behave differently with respect to proton transfer. From the vibronic analysis, a unified view of the Rudle-Pimentel three-center four-electron and charge transfer models of LBHBs is given. Finally, the large difference in the N-N distance in the D3d and C3v configurations of N2H7+ indicates a large anharmonic coupling between α2u-α1g modes along the proton

  5. Photoluminescence properties of Jahn-Teller transition-metal ions

    NASA Astrophysics Data System (ADS)

    Sanz-Ortiz, Marta N.; Rodríguez, Fernando

    2009-09-01

    This work investigates the influence of electron-phonon coupling associated with E ⊗e and T ⊗e Jahn-Teller (JT) effect in different transition-metal (TM) ions on de-excitation phenomena through nonradiative multiphonon relaxation, i.e., photoluminescence (PL) quenching. We developed a configurational curve model which is able to predict from the absorption spectrum whether a given JT-TM ion is PL or quenched. The prediction is made on the basis of an adapted Dexter-Klick-Russell parameter for JT systems, defined in terms of spectroscopic parameters through ΛJT=αΔeabs/Eabs, where Δeabs refers to the splitting of the parent octahedral Eg states by the JT distortion in E ⊗e (α =3/4) or T ⊗e (α =1/4), and Eabs is the energy of the first absorption band involving electronic transition between Eg and T2g. We show that PL in any JT-TM ion occurs whenever ΛJT<0.1 or is quenched if ΛJT>0.2. This result is noteworthy since it allows us to establish structural requirements for the JT-TM ion and the host crystal to be PL. Although PL properties of materials containing TM ions depend on a variety of structural factors such as the electronic configuration, the site symmetry, and the crystal field produced by neighboring atoms, the present model achieves this goal through a simple spectroscopic parameter: ΛJT. In this work we correlated the PL properties of different sixfold-coordinated JT systems such as Ti3+, Cu2+, Mn3+, Cr2+, Fe2+, Co3+, and Ni3+ in halides and oxides with ΛJT obtained from their respective absorption spectra. From this analysis we conclude that depending on the nature of the JT coupling and its strength, PL is either strongly favored or quenched in T ⊗e while it is mostly quenched in E ⊗e systems due to the larger JT distortion.

  6. Angular-overlap calculation of the Jahn-Teller stabilization energie for f-orbital degeneracies

    SciTech Connect

    Warren, K.D.

    1980-03-01

    The angular-overlap model is applied to the calculation of the linear Jahn-Teller coupling constants for f-orbital degeneracies. The MX/sub 6/, O/sub h/, chromophore is treated as representative of the highest symmetry commonly occurring in the lanthanide and actinide series, and it is shown that, even when spin-orbit effects are taken into account, 5f orbital degeneracies may lead to significant Jahn-Teller stabilization energies. The operation of this effect for F/sup 1/ GAMMA/sub 8/ states is considered. 2 tables.

  7. The Phenalenyl Free Radical - a Jahn-Teller D3H PAH

    NASA Astrophysics Data System (ADS)

    O'Connor, G. D.; Troy, T. P.; Roberts, D. A.; Chalyavi, N.; Fückel, B.; Crossley, M. J.; Nauta, K.; Schmidt, T. W.; Stanton, J. F.

    2012-06-01

    After benzene and naphthalene, the smallest polycyclic aromatic hydrocarbon bearing six-membered rings is the threefold-symmetric phenalenyl radical. Despite the fact that it is so fundamental, its electronic spectroscopy has not been rigorously scrutinized, in spite of growing interest in graphene fragments for molecular electronic applications. Here we used complementary laser spectroscopic techniques to probe the jet-cooled phenalenyl radical in vacuo. Its spectrum reveals the interplay between four electronic states that exhibit Jahn-Teller and pseudo-Jahn-Teller (Herzberg-Teller) vibronic coupling. The coupling mechanism has been elucidated by the application of various ab initio quantum-chemical techniques.

  8. Jahn Teller effect and superparamagnetism in zn substituted copper-gallate ferrite

    NASA Astrophysics Data System (ADS)

    Ata-Allah, S. S.; Hashhash, A.

    2006-12-01

    Spinel ferrite CuFe 2O 4 and solid solution of Cu 1-xZn xFe 2-yGa yO 4 with 0.0⩽ x⩽0.5 are synthesized through the usual ceramic method. X-ray diffraction measurements confirm the presence of single-phase tetragonal structure with c/ a>1for CuFe 2O 4 and compositions with x⩽0.1. The formation of the tetragonal phase in these samples is attributed to the presence of the cooperative Jahn-Teller Cu ion at the octahedral B-site in the spinel lattice. At the compositional parameter x⩾0.2, tetragonal-to-cubic transformation occurred and the lattice parameter a for the cubic unit cell is found to decrease with increasing Zn content x. 57Fe Mössbauer measurements at 293 K for these compounds reveal superparamagnetic phase for samples with 0.0⩽ x⩽0.2. In contrast, Mössbauer spectra at 12 K for these materials show well ordered spectra where, the cation distribution and the hyperfine parameters are determined.

  9. Flattening a puckered cyclohexasilane ring by suppression of the pseudo-Jahn-Teller effect.

    PubMed

    Pokhodnya, Konstantin; Olson, Christopher; Dai, Xuliang; Schulz, Douglas L; Boudjouk, Philip; Sergeeva, Alina P; Boldyrev, Alexander I

    2011-01-01

    We report the experimental and theoretical characterization of neutral Si(6)X(12) (X = Cl, Br) molecules that contain D(3d) distorted six-member silicon rings due to a pseudo-Jahn-Teller (PJT) effect. Calculations show that filling the intervenient molecular orbitals with electron pairs of adduct suppresses the PJT effect in Si(6)X(12), with the Si(6) ring becoming planar (D(6h)) upon complex formation. The stabilizing role of electrostatic and covalent interactions between positively charged silicon atoms and chlorine atoms of the subject [Si(6)Cl(14)](2-) dianionic complexes is discussed. The reaction of Si(6)Cl(12) with a Lewis base (e.g., Cl(-)) to give planar [Si(6)Cl(14)](2-) dianionic complexes presents an experimental proof that suppression of the PJT effect is an effective strategy in restoring high Si(6) ring symmetry. Additionally, the proposed pathway for the PJT suppression has been proved by the synthesis and characterization of novel compounds containing planar Si(6) ring, namely, [(n)Bu(4)N](2)[Si(6)Cl(12)I(2)], [(n)Bu(4)N](2)[Si(6)Br(14)], and [(n)Bu(4)N](2)[Si(6)Br(12)I(2)]. This work represents the first demonstration that PJT effect suppression is useful in the rational design of materials with novel properties. PMID:21218995

  10. The vibrational Jahn-Teller effect in E⊗e systems

    NASA Astrophysics Data System (ADS)

    Thapaliya, Bishnu P.; Dawadi, Mahesh B.; Ziegler, Christopher; Perry, David S.

    2015-10-01

    The Jahn-Teller theorem is applied in the vibrational context where degenerate high-frequency vibrational states (E) are considered as adiabatic functions of low-frequency vibrational coordinates (e). For CH3CN and Cr(C6H6)(CO)3, the global minimum of the non-degenerate electronic potential energy surface occurs at the C3v geometry, but in CH3OH, the equilibrium geometry is far from the C3v reference geometry. In the former cases, the computed spontaneous Jahn-Teller distortion is exceptionally small. In methanol, the vibrational Jahn-Teller interaction results in the splitting of the degenerate E-type CH stretch into what have been traditionally assigned as the distinct ν2 and ν9 vibrational bands. The ab initio vibrational frequencies are fit precisely by a two-state high-order Jahn-Teller Hamiltonian (Viel and Eisfeld, 2004). The presence of vibrational conical intersections, including 7 for CH3OH, has implications for spectroscopy, for geometric phase, and for ultrafast localized non-adiabatic energy transfer.

  11. Interplay Between Structural, Jahn-Teller, and Magnetic States of Slightly Doped Lanthanum Manganites

    NASA Astrophysics Data System (ADS)

    Golenishchev-Kutuzov, V. A.; Golenishchev-Kutuzov, A. V.; Kalimullin, R. I.; Semennikov, A. V.

    2016-03-01

    By combining the results of elastic moduli, electrical resistivity, and magnetization measurements for La_{1-x} Srx MnO3 (x = 0.125, x = 0.15, and x = 0.175), we have constructed a phase diagram that describes the structural, magnetic, transport properties and the relationships among them as a function of the composition and temperature (140-340 K). The local, intermediate, and cooperative Jahn-Teller distortions of the octahedral structural units MnO6 have been studied. It is common for these distortions to be observed using probes of intermediate structures (domains or super-cells), but they are absent in the averaged crystallographic structure. In the cooperative Jahn-Teller distorted phase, the macroscopic sample length is temperature dependent. We presume that the structural transitions from the cooperative Jahn-Teller phase to the charge ordering phase at low temperatures (150 and 180 K at x = 0.125 and x = 0.15) are due to the increase in the spontaneous magnetization with the conservation of the local deformations of separate octahedra. The agreement between the types of the orbital ordering and the local, intermediate, and Jahn-Teller cooperative distortions of octahedra was established.

  12. Jahn-Teller Effect in Systems with Strong On-Site Spin-Orbit Coupling

    NASA Astrophysics Data System (ADS)

    Plotnikova, Ekaterina M.; Daghofer, Maria; van den Brink, Jeroen; Wohlfeld, Krzysztof

    2016-03-01

    When strong spin-orbit coupling removes orbital degeneracy, it would at the same time appear to render the Jahn-Teller mechanism ineffective. We discuss such a situation, the t2 g manifold of iridates, and show that, while the Jahn-Teller effect does indeed not affect the jeff=1 /2 antiferromagnetically ordered ground state, it leads to distinctive signatures in the jeff=3 /2 spin-orbit exciton. It allows for a hopping of the spin-orbit exciton between the nearest-neighbor sites without producing defects in the jeff=1 /2 antiferromagnet. This arises because the lattice-driven Jahn-Teller mechanism only couples to the orbital degree of freedom but is not sensitive to the phase of the wave function that defines isospin jz. This contrasts sharply with purely electronic propagation, which conserves isospin, and the presence of Jahn-Teller coupling can explain some of the peculiar features of measured resonant inelastic x-ray scattering spectra of Sr2 IrO4 .

  13. Jahn Teller effect of cations in water: The cupric ion in water

    SciTech Connect

    Halley, J.W.; Wang, X.R.; Curtiss, L.A.

    1993-02-01

    We report a molecular dynamics model for the Jahn Teller effect in the solvation shell of a cation in solution in an aqueous liquid. We apply the model to the cupric ion and compare results with results of neutron scattering experiments on copper chlorate solutions. We conclude that the original interpretation of the experiments in terms of a Jan Teller effect may require modification.

  14. Theory of Jahn Teller signatures in the infrared absorption of C603-

    NASA Astrophysics Data System (ADS)

    Naghavi, S. Shahab; Fabrizio, Michele; Tosatti, Erio; Condensed Matter Physics Team

    2014-03-01

    Among the molecular superconductors, trivalent fullerides such as Cs3C60, with three folded degenerate HOMO and a fully ordered pressure induced superconductor-insulator are still intriguing. The orbital degeneracy of the fulleride ion C60-3 implies that besides a Jahn-Teller distorted state with S=1/2 and high-lying spin (S=3/2) excitation known from NMR, another undetected orbital excitation with S=1/2 should exist. Building upon accurate density hybrid functional theory calculations where properties such as the infrared (IR) spectrum and its Jahn-Teller features are well described, we extracted the ab-initio orbital and spin spectrum of a C60-3 ion in different spin and orbital states including a new low lying L=2 S=1/2 excitation. Despite a Jahn-Teller distortion so small to be observable in its IR spectrum, this state is found to gain a large zero-point energy, placing it just above the L=1, S=1/2 ion ground state, and way below the L=0, S=3/2 high lying excitation. We can now elegantly explain the surprising early thermal disappearance of the low-temperature Jahn-Teller IR spectral features and splitting without a concurrent rise of spin susceptibility that would instead be required by population of the high spin S=3/2 excitation. Sponsored by EU LEMSUPER Grant 283214.

  15. The Cyclopentadienyl Radical Revisited: the Effects of Asymmetric Deuteration of Jahn-Teller Molecules

    NASA Astrophysics Data System (ADS)

    Strom, Samantha; Liu, Jinjun

    2012-06-01

    Asymmetric deuteration of Jahn-Teller active molecules partially lifts the vibronic degeneracy and hence provides a unique approach to understanding the Jahn-Teller effect. Previously, a spectroscopic model was proposed and used to simulate the spectra of the asymmetrically deuterated isotopomers of the methoxy radical. The same model has been implemented and successfully simulated the previously reported high-resolution laser-induced fluorescence (LIF) spectra of the asymmetrically deuterated cyclopentadienyl radical (C_5H_4D and C_5HD_4). A joint fitting of the transitions from both of the zero-point levels of the tilde X ^2E''_1 ground electronic state, split by the asymmetric deuteration, to the tilde A ^2A''_2 state yields one set of molecular constants for both levels, which, when combined with molecular constants of C_5H_5 and C_5D_5, can be used to determine the molecular geometry and magnitude of the Jahn-Teller distortion. The main goal of this new investigation is to resolve the discrepancy between the experimentally determined and the ab initio calculated Jahn-Teller distortion. In addition, a theoretic model is proposed to quantitatively reproduce the splitting of the zero-point level due to the asymmetric deuteration and zero-point energies for the Jahn-Teller distorted structures around the conical intersection. D. G. Melnik, J. Liu, R. F. Curl, and T. A. Miller, Mol. Phys. 105, 529 (2007). D. G. Melnik, J. Liu, M.-W. Chen, T. A. Miller, and R. F. Curl, J. Chem. Phys. 135, 094310 (2011) L. Yu, D.W. Cullin, J.M. Williamson, and T.A. Miller, J. Chem. Phys. 98, 2682 (1993). M. J. Bearpark, M. A. Robb, and N. Yamamoto, Spectrochim. Acta Part A 55, 639 (1999).

  16. Persistence of Jahn-Teller Distortion up to the Insulator to Metal Transition in LaMnO3

    NASA Astrophysics Data System (ADS)

    Baldini, M.; Struzhkin, V. V.; Goncharov, A. F.; Postorino, P.; Mao, W. L.

    2011-02-01

    High pressure, low temperature Raman measurements performed on LaMnO3 up to 34 GPa provide the first experimental evidence for the persistence of the Jahn-Teller distortion over the entire stability range of the insulating phase. This result resolves the ongoing debate about the nature of the pressure driven insulator to metal transition (IMT), demonstrating that LaMnO3 is not a classical Mott insulator. The formation of domains of distorted and regular octahedra, observed from 3 to 34 GPa, sheds new light on the mechanism behind the IMT suggesting that LaMnO3 becomes metallic when the fraction of undistorted octahedra domains increases beyond a critical threshold.

  17. Persistence of Jahn-Teller distortion up to the insulator to metal transition in LaMnO3.

    PubMed

    Baldini, M; Struzhkin, V V; Goncharov, A F; Postorino, P; Mao, W L

    2011-02-11

    High pressure, low temperature Raman measurements performed on LaMnO3 up to 34 GPa provide the first experimental evidence for the persistence of the Jahn-Teller distortion over the entire stability range of the insulating phase. This result resolves the ongoing debate about the nature of the pressure driven insulator to metal transition (IMT), demonstrating that LaMnO3 is not a classical Mott insulator. The formation of domains of distorted and regular octahedra, observed from 3 to 34 GPa, sheds new light on the mechanism behind the IMT suggesting that LaMnO3 becomes metallic when the fraction of undistorted octahedra domains increases beyond a critical threshold. PMID:21405481

  18. Time-dependent Jahn-Teller problem: Phonon-induced relaxation through conical intersection

    SciTech Connect

    Pae, Kaja Hizhnyakov, Vladimir

    2014-12-21

    A theoretical study of time-dependent dynamical Jahn-Teller effect in an impurity center in a solid is presented. We are considering the relaxation of excited states in the E⊗e-problem through the conical intersection of the potential energy. A strict quantum-mechanical treatment of vibronic interactions with both the main Jahn-Teller active vibration and the nontotally symmetric phonons causing the energy loss is given. The applied method enables us to calculate the time-dependence of the distribution function of the basic configurational coordinate. We have performed a series of numerical calculations allowing us, among other relaxation features, to visualise the details of the relaxation through the conical intersection. In particular, we elucidate how the Slonczewski quantization of the states in the conical intersection affects the relaxation.

  19. Experimental evidence of a dynamic Jahn-Teller effect in C-60(+)

    SciTech Connect

    Canton, S.E.; Yencha, A.J.; Kukk, E.; Bozek, J.D.; Lopes, M.C.A.; Snell, G.; Berrah, N.

    2002-05-20

    Detailed analysis of the HOMO bandshape in the photoelectron spectrum of gaseous C60 reveals a dynamic Jahn-Teller effect in the ground state of C60+. The direct observation of three tunneling states asserts a D3d geometry for the isolated cation, originating from a strong vibronic coupling. These results show that the ionic motion of the ions plays an important role in the electron-phonon interaction.

  20. An exploration of operator methods in the E⊗e Jahn Teller problem

    NASA Astrophysics Data System (ADS)

    Bosnick, K. A.

    2000-02-01

    A new treatment of the E⊗e Jahn-Teller problem, which uses operator methods, is presented. An analytical expression for the energy spectrum in the weak coupling limit is found by analogy with Russell-Saunders coupling. The matrix elements for general linear and quadratic coupling follow from simple coupling Hamiltonians given in this Letter. The formalism presented is conceptually simple and easily extended to other systems.

  1. Jahn-Teller effects in transition-metal compounds with small charge-transfer energy

    NASA Astrophysics Data System (ADS)

    Mizokawa, Takashi

    2013-04-01

    We have studied Jahn-Teller effects in Cs2Au2Br6, ACu3Co4O12(A=Ca or Y), and IrTe2 in which the ligand p-to-transition-metal d charge-transfer energy is small or negative. The Au+/Au3+ charge disproportionation of Cs2Au2Br6 manifests in Au 4f photoemission spectra. In Cs2Au2Br6 with negative Δ and intermediate U, the charge disproportionation can be described using effective d orbitals constructed from the Au 5d and Br 4p orbitals and is stabilized by the Jahn-Teller distortion of the Au3+ site with low-spin d8 configuration. In ACu3Co4O12, Δs for Cu3+ and Co4+ are negative and Us are very large. The Zhang-Rice picture is valid to describe the electronic state, and the valence change from Cu2+/Co4+ to Cu3+/Co3+ can be viewed as the O 2p hole transfer from Co to Cu or d9 + d6L → d9L + d6. In IrTe2, both Δ and U are small and the Ir 5d and Te 5p electrons are itinerant to form the multi-band Fermi surfaces. The ideas of band Jahn-Teller transition and Peierls transition are useful to describe the structural instabilities.

  2. PREFACE: XXIst International Symposium on the Jahn-Teller Effect 2012

    NASA Astrophysics Data System (ADS)

    Koizumi, Hiroyasu

    2013-04-01

    (The PDF contains the full conference program, the list of sponsors and the conference poster.) The 21st International Symposium on the Jahn-Teller effect was held at the University of Tsukuba, Japan, from 26-31 August 2012. People from 23 different countries participated and the number of registered participants was 118. In this symposium, the phrase 'Jahn-Teller effect' was taken to have a rather broad meaning. We discussed the Jahn-Teller and pseudo Jahn-Teller distortions. We also discussed general vibronic problems, and the problems associated with the conical intersections of the potential energy surfaces. As is indicated in the subtitle of the present symposium, 'Physics and Chemistry of Symmetry Breaking', a number of different topics concerning symmetry breaking were also extensively discussed. In particular, we had many discussions on magnetism, ferroelectricity, and superconductivity. A subtle but important problem that was dealt with was the appearance of multi-valuedness in the use of multi-component wave functions. In the Jahn-Teller problems, we almost always use the multi-component wave functions, thus, the knowledge of the proper handling of multi-valuedness is very important. Digital computers are not good at dealing with multi-valuedness, but we need to somehow handle it in our calculations. A very well known example of successful handling is found in the problem of the molecular system with the conical intersection: we cannot obtain the solution that satisfies the single-valuedness of wave functions (SVWF) just using the potential energy surface generated by a package program, and solving the Schrödinger equation with the quantum Hamiltonian constructed from the classical counterpart by replacing the classical variables with the corresponding operators; however, if a gauge potential is included and the double-valuedness of the electronic wave functions around the conical intersections is taken into account, the solution that satisfies the SVWF

  3. A Genuine Jahn-Teller System with Compressed Geometry and Quantum Effects Originating from Zero-Point Motion.

    PubMed

    Aramburu, José Antonio; García-Fernández, Pablo; García-Lastra, Juan María; Moreno, Miguel

    2016-07-18

    First-principle calculations together with analysis of the experimental data found for 3d(9) and 3d(7) ions in cubic oxides proved that the center found in irradiated CaO:Ni(2+) corresponds to Ni(+) under a static Jahn-Teller effect displaying a compressed equilibrium geometry. It was also shown that the anomalous positive g∥ shift (g∥ -g0 =0.065) measured at T=20 K obeys the superposition of the |3 z(2) -r(2) ⟩ and |x(2) -y(2) ⟩ states driven by quantum effects associated with the zero-point motion, a mechanism first put forward by O'Brien for static Jahn-Teller systems and later extended by Ham to the dynamic Jahn-Teller case. To our knowledge, this is the first genuine Jahn-Teller system (i.e. in which exact degeneracy exists at the high-symmetry configuration) exhibiting a compressed equilibrium geometry for which large quantum effects allow experimental observation of the effect predicted by O'Brien. Analysis of the calculated energy barriers for different Jahn-Teller systems allowed us to explain the origin of the compressed geometry observed for CaO:Ni(+) . PMID:27028895

  4. Jahn-Teller distortion of neutral divacancy in Si studied by positron annihilation spectroscopy

    NASA Astrophysics Data System (ADS)

    Nagai, Y.; Inoue, K.; Tang, Z.; Yonenaga, I.; Chiba, T.; Saito, M.; Hasegawa, M.

    2003-12-01

    Jahn-Teller (JT) distortion of the diamagnetic neutral divacancy (V20) in Si is studied by positron annihilation spectroscopy. Based on the anisotropy of electron momentum distribution around the divacancies obtained by two-dimensional angular correlation of positron annihilation radiation (2D-ACAR) technique, the preferred alignment of the divacancy in a specimen by compressing uniaxial stress along the [0 1 1] axis is detected. The direction of the alignment evidences the pairing JT distortion rather than the resonant bonding distortion, which is similar to the distortion in the singly negative divacancy (V2-).

  5. Jahn-Teller stabilization energies for ZnS:Mn and ZnSe:Mn excited states obtained by the angular overlap model

    NASA Astrophysics Data System (ADS)

    Stavrev, K. K.; Kynev, K. D.; Nikolov, G. St.

    1988-06-01

    Linear Jahn-Teller coupling constants are obtained by the angular overlap model. A comparison with the data published recently [Parrot et al., J. Chem. Phys. 87, 1463 (1987)] is made in order to demonstrate the considerable improvement in the calculated Jahn-Teller coefficients when the parameters of the angular overlap model are extracted from a spectral analysis of the systems under consideration.

  6. Spin-Orbit Interaction and Jahn-Teller Transition in Bimetallic Oxalates

    SciTech Connect

    Fishman, Randy Scott; Okamoto, Satoshi; Reboredo, Fernando A

    2009-01-01

    The C3-symmetric crystal-field potential in the Fe(II)Fe(III) bimetallic oxalates splits the L = 2 Fe(II) multiplet into two doublets and one singlet. In compounds that exhibit magnetic compensation, one of the doublets lies lowest in energy and carries an average orbital angular momentum Lcf z that exceeds a threshold value of roughly 0.25. In a range of Lcf z , a Jahn-Teller (JT) distortion increases the energy splitting of the low-lying doublet and breaks the C3 symmetry of the bimetallic planes around the ferrimagnetic transition temperature. Due to the competition with the spin-orbit coupling, the JT distortion disappears at low temperatures in compounds that display magnetic compensation. A comparison with recent measurements provides strong evidence for this inverse, low-temperature JT transition. The size of the JT distortion is estimated using first-principles calculations, which suggest that the long-range ordering of smaller, non-C3-symmetric organic cations can eliminate magnetic compensation. Keywords: Jahn-Teller distortion; Spin-orbit interaction; Crystal fields; Bimetallic oxalates

  7. Persistence of Jahn-Teller Distortion up to the Insulator to Metal Transition in LaMnO3

    NASA Astrophysics Data System (ADS)

    Baldini, Maria; Struzhkin, Viktor; Goncharov, Alex; Postorino, Paolo; Mao, Wendy

    2012-02-01

    High pressure, low temperature Raman measurements performed on LaMnO3 up to 34 GPa provide the first evidence for the persistence of the Jahn-Teller distortion over the entire stability range of the insulating phase. This result resolves the ongoing debate about the nature of the pressure driveninsulator to metal transition (IMT), demonstrating that LaMnO3 is not a classical Mott insulator. The formation of domains of distorted and regular octahedra, observed from 3 to 34 GPa, suggests that LaMnO3 becomes metallic when the fraction of undistorted octahedra domains increases beyond a critical threshold. In this scenario, it is interesting to consider whether or not the CMR effect may be induced in LaMnO3 by applying pressure. Preliminary results obtained performing high pressure resistivity measurements in a magnetic field will be reported. [4pt] [1] I. Loa, et al., Phys. Rev. Lett. 87, 125501 (2001). [0pt] [2] A.Y. Ramos et al., Phys. Rev. B 75, 052103(2007). [0pt] [3] A.Y. Ramos et al., J. Phys. Conf. Ser. 190, 012096 (2009). [0pt] [4] A. Yamasaki et al., Phys. Rev. Lett. 96, 166401 (2006). [0pt] [5]J. D. Fuhr et al., Phys. Rev. Lett. 100, 216402 (2008). [0pt] [6] M. Baldini et al., Phys. Rev. Letter 106, 066402 (2011).

  8. Jahn-Teller inactivity and magnetic frustration in GeCo2O4 probed by ultrasound velocity measurements

    NASA Astrophysics Data System (ADS)

    Watanabe, Tadataka; Hara, Shigeo; Ikeda, Shin-Ichi

    2008-09-01

    Ultrasound velocity measurements of cubic spinel GeCo2O4 in single crystal were performed for the investigation of shear and compression moduli. The shear moduli in the paramagnetic state reveal the absence of Jahn-Teller activity despite the presence of orbital degeneracy in the Co2+ ions. Such a Jahn-Teller inactivity indicates that the intersite orbital-orbital interaction is much stronger than the Jahn-Teller coupling. The compression moduli in the paramagnetic state near the Néel temperature TN reveal that the most relevant exchange path for the antiferromagnetic transition lies in the [111] direction. This exchange-path anisotropy is consistent with the antiferromagnetic structure with the wave vector q∥[111] , suggesting the presence of bond frustration due to competition among a direct ferromagnetic interaction and several distant-neighbor antiferromagnetic interactions. In the Jahn-Teller-inactive condition, the bond frustration can be induced by geometrical orbital frustration of t2g-t2g interaction between the Co2+ ions, which can be realized in the pyrochlore lattice of the high-spin Co2+ with t2g -orbital degeneracy. In GeCo2O4 , the tetragonal elongation below TN releases the orbital frustration by quenching the orbital degeneracy.

  9. Jahn-Teller Coupling in the Methoxy Radical: Insights Into the Infrared Spectrum of Molecules with Vibronic Coupling

    NASA Astrophysics Data System (ADS)

    Johnson, Britta; Sibert, Edwin

    2015-06-01

    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 coupling which leads to large amplitude vibrations and extensive mixing of the two lowest electronic states. The spectrum is further complicated due to spin-orbit and Fermi couplings. The standard diabatic normal mode quantum numbers are poor labels due to this vibronic mixing. Using the potential energy force field and calculated spectra of the methoxy radical by Nagesh and Sibert^1 as a starting point, we look to develop a method for assigning states to a spectrum with vibronic coupling. We simplify the analysis by considering only the lowest two e modes of methoxy (the rock and the bend). When we include first-order Jahn-Teller coupling between these two modes in a new zero-order Hamiltonian, we are able to use an expanded version of the linear Jahn-Teller quantum numbers to assign the states.^2 This zeroth order representation is nontrivial; therefore, we study the properties of its eigenstates using correlation diagrams with respect to the strength of the Jahn-Teller coupling constant. [^1] Nagesh, J.; Sibert, E. L. J. Phys. Chem. A 2012, 116, 3846-3855. [^2] Barckholtz, T. A.; Miller, T. A. Int. Revs. in Phys. Chem. 1998, 17, 435-524.

  10. DFT-based studies on the Jahn-Teller effect in 3d hexacyanometalates with orbitally degenerate ground states.

    PubMed

    Atanasov, Mihial; Comba, Peter; Daul, Claude A; Hauser, Andreas

    2007-09-20

    The topology of the ground-state potential energy surface of M(CN)(6) with orbitally degenerate (2)T(2g) (M = Ti(III) (t(2g)(1)), Fe(III) and Mn(II) (both low-spin t(2g)(5))) and (3)T(1g) ground states (M = V(III) (t(2g)(2)), Mn(III) and Cr(II) (both low-spin t(2g)(4))) has been studied with linear and quadratic Jahn-Teller coupling models in the five-dimensional space of the epsilon(g) and tau(2g) octahedral vibrations (Tg[symbol: see text](epsilon(g)+tau(2g)) Jahn-Teller coupling problem (T(g) = (2)T(2g), (3)T(1g))). A procedure is proposed to give access to all vibronic coupling parameters from geometry optimization with density functional theory (DFT) and the energies of a restricted number of Slater determinants, derived from electron replacements within the t(2g)(1,5) or t(2g)(2,4) ground-state electronic configurations. The results show that coupling to the tau(2g) bending mode is dominant and leads to a stabilization of D(3d) structures (absolute minima on the ground-state potential energy surface) for all complexes considered, except for [Ti(CN)(6)](3-), where the minimum is of D(4h) symmetry. The Jahn-Teller stabilization energies for the D3d minima are found to increase in the order of increasing CN-M pi back-donation (Ti(III) < V(III) < Mn(III) < Fe(III) < Mn(II) < Cr(II)). With the angular overlap model and bonding parameters derived from angular distortions, which correspond to the stable D(3d) minima, the effect of configuration interaction and spin-orbit coupling on the ground-state potential energy surface is explored. This approach is used to correlate Jahn-Teller distortion parameters with structures from X-ray diffraction data. Jahn-Teller coupling to trigonal modes is also used to reinterpret the anisotropy of magnetic susceptibilities and g tensors of [Fe(CN)(6)](3-), and the (3)T(1g) ground-state splitting of [Mn(CN)(6)](3-), deduced from near-IR spectra. The implications of the pseudo Jahn-Teller coupling due to t(2g)-e(g) orbital mixing via

  11. (Bis(terpyridine))copper(II) Tetraphenylborate: A Complex Example for the Jahn-Teller Effect.

    PubMed

    Meyer, Andreas; Schnakenburg, Gregor; Glaum, Robert; Schiemann, Olav

    2015-09-01

    The surprisingly complicated crystal structure of (bis(terpyridine))copper(II) tetraphenylborate [Cu(tpy)2](BPh4)2 (tpy = 2,2':6',2″-terpyridine) consists of six crystallographically independent [Cu(tpy)2](2+) complexes. At ambient temperature, five out of six [Cu(II)N6] chromophores appear to be compressed octahedra, while at 100 K, four exhibit elongated and only two compressed octahedral geometry. Temperature dependent single crystal UV/vis (100, 298 K) and EPR measurements (20, 100, 298 K) as well as AOM calculations suggest that the octahedra which show apparently compressed octahedral geometry (XRD) result from dynamic Jahn-Teller behavior of elongated octahedra [Cu(II)N6]. The detailed correlation of structural and spectroscopic data allows an understanding of the strongly solvent-dependent structures of the [Cu(tpy)2](2+) complex in solution. PMID:26275138

  12. Jahn-Teller versus quantum effects in the spin-orbital material LuVO3

    DOE PAGESBeta

    Skoulatos, M.; Toth, S.; Roessli, B.; Enderle, M.; Habicht, K.; Sheptyakov, D.; Cervellino, A.; Freeman, P. G.; Reehuis, M.; Stunault, A.; et al

    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 LuVO3 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 study enabledmore » 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 LuVO3 and similar systems.« less

  13. Dynamic Jahn-Teller Effect in Negatively Charged Nitrogen-Vacancy Center in Diamond

    NASA Astrophysics Data System (ADS)

    Abtew, Tesfaye; Zhang, Peihong

    2011-03-01

    The negatively charged nitrogen-vacancy (NV) center in diamond has attracted much research interest recently owing to its desirable optical properties and long spin coherent lifetime. The ground state of NV- center has a 3 A2 symmetry, which can be optically excited, to a 3 E state. The excited state is orbitally degenerate therefore should experience either static or dynamic Jahn-Teller (JT) effects. We use accurate first-principles methods to study structural and electronic properties of the NV- center in diamond both in the ground and excited states. Our results indicate that the excited state of the NV- center is indeed a dynamic JT system. We acknowledge the Center for Computational Research at the University at Buffalo, SUNY. This work is supported by the National Science Foundation under Grant No. DMR-0946404 and by the Department of Energy under GrantNo. DE-SC0002623.

  14. Dynamical Jahn-Teller effect in spin-orbital coupled system

    NASA Astrophysics Data System (ADS)

    Nasu, Joji; Ishihara, Sumio

    2012-02-01

    Orbital degree of freedom is one of the most attractive themes in strongly correlated electron system. A coupling between the orbital and the lattice vibration is known as a Jahn-Teller effect (JTE). The dynamical aspect of the Jahn-Teller interaction is often neglected in solid, because it is strongly suppressed by the cooperative JTE. Recently, Ba3CuSb2O9 has been reported as a candidate of the spin liquid. A Cu^2+ has the eg orbital degree of freedom and is surrounded by the O^2- octahedron. The octahedra on the neighboring sites do not have the common O ions. This fact implies that the cooperative JTE is weak, and the dynamical JTE is expected to play some key roles on orbital and magnetic properties. The purpose of this research is to study the dynamical JTE in a spin-orbital coupled system. In particular, we focus on the competitive or cooperative phenomena between the superexchange interaction and the dynamical JTE. The superexchange interactions are derived from the d-p model on a honeycomb lattice. We have confirmed this interaction stabilizes the antiferro-spin and ferro-orbital configurations for the realistic parameters. The dynamical JTE described as the orbital-lattice coupling is obtained by extracting the low energy states of the vibronic Hamiltonian. We analyze the model including the two kinds of interactions by using the Bethe approximation. We find that the magnetic order is unstable in wide parameter region and the spin-dimer state with the orbital order is realized. Furthermore the orbital order is strongly suppressed by the dynamical JTE.

  15. Assigning States in the Jahn-Teller Coupled Infrared Spectra of CH_3O and CD_3O

    NASA Astrophysics Data System (ADS)

    Johnson, Britta; Sibert, Edwin

    2014-06-01

    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 coupling, this leading 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. In this talk we describe our efforts to assign the states of both CH_3O and CD_3O. Using the potential energy force field and calculated spectra of Nagesh and Sibert^1 as a starting point, vibrational mixing is considered using various zero-order representations. When the zero-order states are the diabatic normal mode states, there is sufficient mode mixing that the normal mode quantum numbers are no longer good labels. The mixing of the zero-order states can be reduced by including additional terms in the zero-order Hamiltonian, H^o. We consider the choice of including the first order Jahn-Teller coupling between one of the three degenerate normal modes. As the rocking motion has the largest Jahn-Teller coupling, this is the coupling that is included in H^o. Although the normal mode quantum numbers of the rocking basis functions are no longer good quantum numbers, due to the Jahn-Teller induced vibronic mixing, the zero-order states can be labeled with the linear Jahn-Teller quantum numbers.^2 This work extends these ideas by considering an H^o that includes linear Jahn-Teller coupling between two sets of degenerate vibrations. Plots of the resulting zero-order states are presented, and the spectral transitions recently observed3 for both CH_3O and CD_3O in a p-H_2 matrix are assigned using these basis functions. The extent of state-mixing found for the full Hamiltonian H for various choices of H^o is illustrated via the use of correlation diagrams obtained by

  16. E × e Jahn-Teller effect in the P4+ cation and its signatures in the photoelectron spectrum of P4

    NASA Astrophysics Data System (ADS)

    Bhattacharyya, Swarnendu; Opalka, Daniel; Domcke, Wolfgang

    2015-10-01

    The Jahn-Teller effect in the electronic ground state of the P4+ radical cation, which is one of the strongest E × e Jahn-Teller effects known in nature, has been revisited in this work with computational methods. The relevance of the Jahn-Teller coupling terms beyond second order in normal-mode displacements has been investigated. An elegant and efficient scheme based on polynomial invariant theory has been employed to expand the E × e potential energy matrix up to arbitrarily high orders in normal mode displacements. Using the state-averaged complete-active-space self-consistent-field method and a correlation consistent double- ζ basis set, an accurate ab initio adiabatic E × e Jahn-Teller potential-energy surface was obtained. It is shown that a polynomial expansion of least up to sixth order is necessary to account for the pronounced anharmonicity of the ab initio potential-energy surface for large amplitude displacements of the Jahn-Teller active vibrational mode. The vibronic structure of the X ˜ 2 E band of the photoelectron spectrum of P4 has been computed using a time-dependent wave-packet propagation method. The results reveal the significance of the higher-order Jahn-Teller coupling terms for the high-resolution vibronic spectrum as well as for the low-resolution band shape.

  17. The role of the Jahn-Teller coupling in dissociative recombination of H3O+ and H ions

    NASA Astrophysics Data System (ADS)

    Douguet, N.; Orel, A.; Mikhailov, I.; Schneider, I. F.; Greene, C. H.; Kokoouline, V.

    2011-07-01

    We discuss the importance of the non Born-Oppenheimer Jahn-Teller coupling in the dissociative recombination of H3O+ and H ions with low energy electrons. The coupling is known to be important for dissociative recombination of H, for which detailed and simplified theoretical models have been previously developed. In this study we discuss how the detailed theoretical model reproduces individual resonances in the experimental spectrum of H. We present a simplified theoretical model of the dissociative recombination of H3O+. Similarly to H, we consider the Jahn-Teller coupling as a key factor responsible for the capture of the electron into a Rydberg state associated with excited vibrational levels of the ion. We use a simplified Jahn-Teller model for highly symmetrical ions (not only for H3O+ and H) and adopt the normal mode approximation for the vibrational states of H3O+. Using the multi-channel quantum defect formalism and accurate ab initio calculations, we derive the cross sections for electron capture by the ion that is initially in the ground vibrational level. In our approximation, once the electron is captured by the ion, the autoionization probability is neglected compared to the predissociation probability. This allows us to evaluate the cross section for the dissociative recombination of H3O+ using just a few parameters obtained from ab initio calculation. The total cross section obtained is in good agreement with data from storage ring experiments.

  18. Collective versus local Jahn-Teller distortion in Ba3CuSb2O9 : Raman scattering study

    NASA Astrophysics Data System (ADS)

    Drichko, Natalia; Broholm, Collin; Kimura, K.; Ishii, R.; Nakasutji, Satoru

    2016-05-01

    We present temperature dependent Raman spectra of single crystals of two different samples of the spin-orbital liquid candidate Ba3CuSb2O9 . The "hexagonal" sample is known to show no magnetic order down to low temperatures, while the "orthorhombic" sample undergoes a crossover into an orthorhombic crystal structure below TJT of approximately 200 K and shows spin freezing at 110 μ K . Our Raman scattering results demonstrate a strong influence of disorder in both samples. The frequencies of stretching vibrations of oxygens associated with CuSbO9 octahedra indicate a difference in the crystal structure between the hexagonal and orthorhombic samples even at room temperature. On cooling below TJT we observe new bands in the spectra of the orthorhombic sample due to a lowering of symmetry of the unit cell and a collective Jahn-Teller distortion. The spectra of the hexagonal sample show that average hexagonal symmetry is maintained at least down to 20 K. An analysis of the band shape of stretching oxygen vibrations suggests a weak disordered local Jahn-Teller distortion in the hexagonal sample of Ba3CuSb2O9 which increases slightly on cooling. This Jahn-Teller distortion is either static or dynamic with a frequency below 1.5 THz.

  19. A Jahn-Teller analysis of K3 and Rb3 in the electronic states 12E‧ and 12E″

    NASA Astrophysics Data System (ADS)

    Hauser, Andreas W.; Callegari, Carlo; Soldán, Pavel; Ernst, Wolfgang E.

    2010-09-01

    The potential energy surfaces (PES) of the Jahn-Teller distorted doublet 1 2E' (1B 2/1A 1) ground state and 1 2E″ (2B 1/1A 2) excited state of alkali metal trimers (K 3, Rb 3) are studied with three high-level computational chemistry methods whose results are compared: single-reference coupled cluster, equation-of-motion coupled cluster and multi-reference second-order Rayleigh-Schrödinger perturbation theory. The doubly degenerate E electronic state interacts with the twofold degenerate vibrational e mode. We use the E ⊗ e Jahn-Teller effect theory to analyze in detail one- and two-dimensional cuts of the PES as a function of the symmetry-adapted internal coordinates Qs, Qx and Qy and we extract the associated Jahn-Teller parameters. Spin-orbit coupling is accounted for by means of the Effective-Core-Potential-LS technique and spin-orbit splitting constants are extracted. We also provide the geometries, the binding energies and tentative vibronic spectra for the 1 2E″ ← 1 2E' transitions.

  20. Microscopic Insight into the Isosymmetric Jahn-Teller Bond Axis Reorientation in Na3MnF6

    NASA Astrophysics Data System (ADS)

    Charles, Nenian; Rondinelli, James

    2014-03-01

    Using first-principles density functional theory calculations, we investigate the hydrostatic pressure-induced spontaneous reorientation of the Jahn-Teller bond axis in the fluoride cryolite Na3MnF6. We find a first-order isosymmetric transition occurs between crystallographically equivalent monoclinic structures at approximately 2.15 GPa, consistent with earlier experimental studies. Analogous calculations for Na3ScF6 show no evidence of a transition up to 6.82 GPa. Mode crystallography analysis of the pressure-dependent structures in the vicinity of the transition reveals a clear evolution of the Jahn-Teller bond distortions in cooperation with an asymmetrical stretching of the equatorial fluorine atoms in the MnF6 octahedral units. We identify a change in orbital occupancy of the eg manifold in the d4 Jahn-Teller active Mn(III) to be responsible for the transition, which stabilizes one monoclinic P21/n variant over the other. From our results, we conjecture that the same transition may be accessible in epitaxially grown thin films of Na3MnF6 with a modest biaxial tensile strain.

  1. Pseudo-Jahn-Teller instability in the axial Fe+ center in KTaO3

    NASA Astrophysics Data System (ADS)

    Trueba, A.; García-Fernández, P.; Barriuso, M. T.; Moreno, M.; Aramburu, J. A.

    2009-07-01

    The nature of the axial Fe4/2 center in KTaO3 , detected by electron-paramagnetic resonance experiments, has been a source of conflict until recently. Density-functional-theory calculations strongly support the model that ascribes such center to a Fe+ impurity ( 3d7 configuration) which enters the K+ site and spontaneously moves off-center along a ⟨100⟩ -type direction. This work is aimed at clarifying what are the main mechanisms responsible for such off-center instability using pseudo-Jahn-Teller theory. We find that the mixing of 3dx2-y2 and 3dxy orbitals of iron ion with odd oxygen orbitals favored by the off-center displacement plays a significant role in the stabilization. Other important effects include the mixing with unoccupied 4s and 4p orbitals of iron and 5d orbitals of the Ta5+ second-shell neighbors. As an important conclusion, the present analysis shows that the distortion in KTaO3:Fe+ is unrelated to steric effects often considered to be the origin of off-center movements in impurities. The detailed approach followed in this work for exploring a complex system can be useful for gaining a better insight into the origin of structural instabilities in pure and doped insulating materials.

  2. Reentrant-Like Band Jahn-Teller Effect and its Field Dependence

    NASA Astrophysics Data System (ADS)

    Gangadhar Reddy, G.; Venkatappa Rao, T.; Ramakanth, A.; Ghatak, S. K.; Behera, S. N.

    In the presence of the electron-lattice interaction where the lattice strain is coupled to the difference in orbital occupancy, the metallic system whose Fermi level lies in an orbitally degenerate eg band undergoes a structural transition to a lower symmetric state with distortion. The distortion is the consequence of the band Jahn-Teller (J-T) effect, and results from the gain of the electronic energy against the increase in the elastic energy. The extent of distortion depends on the nature of the density of states (DOS) and carrier concentration. These effects are examined for a system described by a different model DOS, and an orbitally degenerate eg band with the J-T interaction. In a certain region of parameter space, the temperature dependence of distortion exhibits a reentrant-like behavior, and the magnetic field augments the distortion in this region. In the parameter space where there is no reentrant-like behavior, the field suppresses the distortion, and the normalized distortion becomes a universal function of the normalized field. A phase diagram is obtained in the magnetic field-temperature plane.

  3. Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues.

    PubMed

    Liu, Yang; Wang, Ya; Bersuker, Isaac B

    2016-01-01

    We revealed the origin of the structural features of a series of tetrasilacyclobutadiene analogues based on a detailed study of their electronic structure and the pseudo Jahn-Teller effect (PJTE). Starting with the D4h symmetry of the Si4R4 system with a square four-membered silicon ring as a reference geometry, and employing ab initio calculations of energy profiles along lower-symmetry nuclear displacements in the ground and several excited states, we show that the ground-state boat-like and chair-like equilibrium configurations are produced by the PJT interaction with appropriate excited sates. For Si4F4 a full two-mode b1g-b2g adiabatic potential energy surface is calculated showing explicitly the way of transformation from the unstable D4h geometry to the two equilibrium C2h configurations via the D2h saddle point. The PJTE origin of these structural features is confirmed also by estimates of the vibronic coupling parameters. For Si4R4 with large substituents the origin of their structure is revealed by analyzing the PJT interaction between the frontier molecular orbitals. The preferred chair-like structures of Si4R4 analogues with amido substituents, and heavier germanium-containing systems Ge4R4 (potential precursors for semiconducting materials) are predicted. PMID:26996445

  4. A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections

    NASA Astrophysics Data System (ADS)

    Csehi, A.; Bende, A.; Halász, G. J.; Vibók, Á.; Das, A.; Mukhopadhyay, D.; Baer, M.

    2013-01-01

    The present study concentrates on a situation where a Renner-Teller (RT) system is entangled with Jahn-Teller (JT) conical intersections. Studies of this type were performed in the past for contours that surround the RT seam located along the collinear axis [see, for instance, G. J. Halász, Á. Vibók, R. Baer, and M. Baer, J. Chem. Phys. 125, 094102 (2006)]. The present study is characterized by planar contours that intersect the collinear axis, thus, forming a unique type of RT-non-adiabatic coupling terms (NACT) expressed in terms of Dirac-δ functions. Consequently, to calculate the required adiabatic-to-diabatic (mixing) angles, a new approach is developed. During this study we revealed the existence of a novel molecular parameter, η, which yields the coupling between the RT and the JT NACTs. This parameter was found to be a pure number η = 2√ 2 /π (and therefore independent of any particular molecular system) and is designated as Renner-Jahn coupling parameter. The present study also reveals an unexpected result of the following kind: It is well known that each (complete) group of states, responsible for either the JT-effect or the RT-effect, forms a Hilbert space of its own. However, the entanglement between these two effects forms a third effect, namely, the RT/JT effect and the states that take part in it form a different Hilbert space.

  5. Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

    NASA Astrophysics Data System (ADS)

    Liu, Yang; Wang, Ya; Bersuker, Isaac B.

    2016-03-01

    We revealed the origin of the structural features of a series of tetrasilacyclobutadiene analogues based on a detailed study of their electronic structure and the pseudo Jahn-Teller effect (PJTE). Starting with the D4h symmetry of the Si4R4 system with a square four-membered silicon ring as a reference geometry, and employing ab initio calculations of energy profiles along lower-symmetry nuclear displacements in the ground and several excited states, we show that the ground-state boat-like and chair-like equilibrium configurations are produced by the PJT interaction with appropriate excited sates. For Si4F4 a full two-mode b1g‑b2g adiabatic potential energy surface is calculated showing explicitly the way of transformation from the unstable D4h geometry to the two equilibrium C2h configurations via the D2h saddle point. The PJTE origin of these structural features is confirmed also by estimates of the vibronic coupling parameters. For Si4R4 with large substituents the origin of their structure is revealed by analyzing the PJT interaction between the frontier molecular orbitals. The preferred chair-like structures of Si4R4 analogues with amido substituents, and heavier germanium-containing systems Ge4R4 (potential precursors for semiconducting materials) are predicted.

  6. Dynamic Jahn-Teller Coupling, Anharmonic Oxygen Vibrations and HIGH-Tc Superconductivity in Oxides

    NASA Astrophysics Data System (ADS)

    Johnson, K. H.; Clougherty, D. P.; McHenry, M. E.

    A universal dynamic Jahn-Teller (DJT) mechanism for superconductivity and its applications to CuO and BaBiO3 high-Tc oxides are reviewed. Dynamical interconversion between the shallow "double-well" potentials of degenerate delocalized oxygen-oxygen "pπ-bonds" at the Fermi energy (EF) induces anharmonic oxygen vibrations, lattice-electron coupling, and Cooper pairing. This mechanism yields high Tc's and small-to-vanishing isotope shifts for cuprates, where O(pπ)-O(pπ) bond overlap at EF is promoted by Cu(dπ*)-O(pπ) hybridization. It yields lower Tc's and larger isotope shifts for BaBiO3's, where O(pπ)-O(pπ) overlap is small. For vanishing bond overlap at EF, DJT coupling reduces to harmonic phonon coupling in BCS theory. Simple formulae for calculating Tc and isotope shifts for any superconductor from the "real-space" chemical bonding at EF are presented, yielding (Tc)max ≈ 230 K.

  7. Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

    PubMed Central

    Liu, Yang; Wang, Ya; Bersuker, Isaac B.

    2016-01-01

    We revealed the origin of the structural features of a series of tetrasilacyclobutadiene analogues based on a detailed study of their electronic structure and the pseudo Jahn-Teller effect (PJTE). Starting with the D4h symmetry of the Si4R4 system with a square four-membered silicon ring as a reference geometry, and employing ab initio calculations of energy profiles along lower-symmetry nuclear displacements in the ground and several excited states, we show that the ground-state boat-like and chair-like equilibrium configurations are produced by the PJT interaction with appropriate excited sates. For Si4F4 a full two-mode b1g−b2g adiabatic potential energy surface is calculated showing explicitly the way of transformation from the unstable D4h geometry to the two equilibrium C2h configurations via the D2h saddle point. The PJTE origin of these structural features is confirmed also by estimates of the vibronic coupling parameters. For Si4R4 with large substituents the origin of their structure is revealed by analyzing the PJT interaction between the frontier molecular orbitals. The preferred chair-like structures of Si4R4 analogues with amido substituents, and heavier germanium-containing systems Ge4R4 (potential precursors for semiconducting materials) are predicted. PMID:26996445

  8. Pressure-driven suppression of the Jahn-Teller effects and structural changes in cupric oxide.

    PubMed

    Greschner, Michael J; Chen, Ning; Yao, Yansun

    2016-01-20

    Multiferroics have been of interest as materials for use in data storage due to their coexisting ferroelectric and ferromagnetic properties. The properties of cupric oxide have been studied at pressures below 70 GPa, and it has even been suggested that it may be a room temperature multiferroic at pressures of 20 to 40 GPa. However, the properties of cupric oxide above these pressures have yet to be thoroughly examined. Here, we investigate changes in the crystal structure of cupric oxide via first principles methods. We find that the crystal structure transforms from a monoclinic structure at low pressure to a face-centred cubic and body-centred cubic structure at high pressure. We also find that the magnetic ordering switches from antiferromagnetic in the monoclinic phase to net zero magnetic moment in the face-centred cubic phase and ferromagnetic in the body-centred cubic phase. This shift in magnetic ordering is due to the superexchange interactions and Jahn-Teller instabilities, or the lack of thereof, arising from the d-orbital electrons of the cupric ions, which disrupt the mechanical stability of other possible magnetic orderings. PMID:26678699

  9. Pressure-driven suppression of the Jahn-Teller effects and structural changes in cupric oxide

    NASA Astrophysics Data System (ADS)

    Greschner, Michael J.; Chen, Ning; Yao, Yansun

    2016-01-01

    Multiferroics have been of interest as materials for use in data storage due to their coexisting ferroelectric and ferromagnetic properties. The properties of cupric oxide have been studied at pressures below 70 GPa, and it has even been suggested that it may be a room temperature multiferroic at pressures of 20 to 40 GPa. However, the properties of cupric oxide above these pressures have yet to be thoroughly examined. Here, we investigate changes in the crystal structure of cupric oxide via first principles methods. We find that the crystal structure transforms from a monoclinic structure at low pressure to a face-centred cubic and body-centred cubic structure at high pressure. We also find that the magnetic ordering switches from antiferromagnetic in the monoclinic phase to net zero magnetic moment in the face-centred cubic phase and ferromagnetic in the body-centred cubic phase. This shift in magnetic ordering is due to the superexchange interactions and Jahn-Teller instabilities, or the lack of thereof, arising from the d-orbital electrons of the cupric ions, which disrupt the mechanical stability of other possible magnetic orderings.

  10. Symmetry-adapted excited states for the T1u⊗hg Jahn-Teller system

    NASA Astrophysics Data System (ADS)

    Qiu, Q. C.; Dunn, J. L.; Bates, C. A.

    2001-08-01

    Jahn-Teller (JT) systems typically contain a set of equivalent-energy wells in the lowest adiabatic potential-energy surface (APES). Quantum-mechanical tunneling between these wells (the dynamic JT effect) must be allowed for by taking appropriate symmetrized combinations of oscillator-type states associated with the wells. It is important to be able to describe the excited states of such systems for a number of reasons. One particular reason is that they are required for the calculation of second-order vibronic reduction factors, which in turn are useful for modeling experimental data using effective Hamiltonians. In this paper, projection-operator techniques are used to obtain general expressions for the symmetry-adapted excited states of the icosahedral T1u⊗hg JT system for the case of D5d minima in the APES. Analytical expressions for the states and their energies for one-phonon excitation are given explicitly. The energies of a selection of states with two-phonon excitations are also obtained and plotted. The results obtained in this paper are applicable to the C-60 molecule.

  11. Jahn-Teller splitting and Zeeman effect of acceptors in diamond.

    SciTech Connect

    Anthony, T. R.; Grimsditch, M.; Kim, H.; Ramdas, A. K.; Rodriguez, S.

    1999-09-11

    Employing the high resolution of a 5+4 tandem Fabry-Perot interferometer, we discovered that {Delta}{prime}, the Raman active electronic transition between the spin-orbit split 1s(p{sub 3/2}): {Lambda}{sub 8} and 1s(P{sub 1/2}) {Lambda}{sub 7} acceptor ground states, is a doublet for a boron impurity in diamond with a clearly resolved spacing of 0.81 {+-} 0.15 cm{sup {minus}1}. The direct observation of a Stokes/anti-Stokes pair with 0.80 {+-} 0.04 cm{sup {minus}1} shift provides a striking confirmation that the lower 1s(p{sub 3/2}): {Lambda}{sub 8} ground state has experienced a splitting due to a static Jahn-Teller distortion. The Zeeman effect of {Delta}{prime} has been investigated with a magnetic field along several crystallographic directions. Theory of the Zeeman effect, formulated in terms of the symmetry of the substitutional acceptor and the Luttinger parameters of the valence band, allows quantitative predictions of the relative intensities of the Zeeman components in full agreement with experiments. The observation of transitions within the {Lambda}{sub 8} Zeeman multiplet, i.e., the Raman-electron-paramagnetic-resonances, is yet another novel feature to emerge from the present study. The investigation has also yielded g-factors characterizing the Zeeman multiplets.

  12. Pseudo Jahn-Teller origin of bending instability of triatomic molecules

    NASA Astrophysics Data System (ADS)

    Kayi, Hakan; Bersuker, Isaac B.; Boggs, James E.

    2012-09-01

    For several decades the bending of linear molecules in degenerate states has been assumed to be due to the Renner-Teller effect (RTE), whereas the pseudo Jahn-Teller effect (PJTE) has been completely ignored. But in a recent publication of ab initio calculations performed on a series of triatomics it was shown that the contribution of the PJTE to their bending instability is much larger than that of the RTE. This raised the question of whether the finding of the essential role of the PJTE in the instability is a particular case for the molecules studied or a general trend. The problem is important not only for rationalizing the experimental observations and ab initio calculations of such systems, but also for a correct interpretation of their spectra, as the PJTE, by admixing excited states of different symmetry (opposite parity) to the ground one, influences significantly their spectroscopic properties. To contribute to the solution of this problem we performed ab initio calculations of electronic structure and energy profiles of a group of triatomic systems including CH2+,HO,SiH2+,PH, and HNF which have a Π twofold degenerate state in the linear configuration, but are bent in the equilibrium geometry. For them we formulated the combined RTE and PJTE problem and, by calculating ab initio the Renner-Teller vibronic coupling constant g and estimating the other parameters by fitting the PJTE equations to the ab initio calculated energy profiles, we show that in all the cases under consideration the PJTE contribution is significantly larger than that of the RTE. The parameters of the equilibrium geometry and electronic structure of these systems obtained in our calculations are in good agreement with those reported in other publications.

  13. Novel Effect Induced by Pseudo-Jahn-Teller Interactions: Broken Cylindrical Symmetry in Linear Molecules.

    PubMed

    Hermoso, Willian; Liu, Yang; Bersuker, Isaac B

    2014-10-14

    It is shown that in linear molecules the pseudo-Jahn-Teller (PJT) interaction of a Σ or Π term with a Δ term induces a bending instability that is angular dependent, reducing the symmetry of the adiabatic potential energy surface from expected D∞h to D4h and C∞v to C2v or C4v. This spontaneously broken cylindrical symmetry (BCS) emerges from the solution of the vibronic coupling equations of the PJT effect (PJTE) problems (Σ+Δ)⊗w, (Π+Δ)⊗w, (Π+Σ+Δ)⊗w, and (Δ+Δ)⊗w, where w includes linear, quadratic, and fourth order vibronic coupling terms, and it is confirmed by ab initio calculations for a series of triatomic molecules with ground or excited Δ terms. The BCS is due to the angular symmetry of the electronic wave functions of the Δ term, ∼cos 2φ, and ∼sin 2φ, split by the fourth order vibronic coupling, which in overlap with the other symmetry wave functions of the Σ or Π term provides for the periodical symmetry of the added covalency that facilitates the bending. The mechanism of this PJT-induced BCS effect is discussed in detail; the numerical values of the vibronic coupling parameters for the molecules under consideration were estimated by means of combining separate ab initio calculations of some of them with a procedure fitting the analytical expressions to ab initio calculated energy profiles. It is also shown that the bending of linear molecules in Δ states, similar to Π states, is exclusively a PJT (not Renner-Teller) effect. The BCS revealed in this paper illustrates again the predicting power of the PJTE. PMID:26588135

  14. Percolation features of cooperative Jahn-Teller systems: Ising EFT framework

    NASA Astrophysics Data System (ADS)

    Moujaes, Elie A.; Abou Ghantous, Michel

    2014-08-01

    Elastic exchange between two nearest Jahn-Teller (JT) centers in two or three dimensional dense crystals, can give an ordered macroscopic distortion known as cooperative JT effect (CJTE). A very diluted JT crystal does not show this effect. In the dynamic JT effect (DJTE), tunneling between different equivalent distorted wells has a pronounced influence on the CJTE. We investigate this phenomenon using a progressive increase in the concentration of these centers in the JT crystals, based on a bond percolation vector spin analogy technique within the framework of effective field theory (EFT). Mean field theory (MFT) was extensively used in previous studies of CJTE; however it neither includes correlation between JT centers in the lattice due to the complexity of the distortion field in the crystal nor the effect of tunneling between wells. We resort to an alternative procedure, by describing a JT center as a pseudo-spin vector , induced to represent the degenerate JT-distorted states, where two nearest JT centers interact via an elastic exchange described by an Ising type spin interaction. The DJTE is considered to be similar to an elastic transverse field term in the Hamiltonian portraying the effect of tunneling between equivalent wells in the adiabatic potential energy surface (APES). We will be particularly discussing S = 1, S = 3/2 and S = 5/2 spin cases, where 2 S + 1 wells in the APES are present and what JT systems they actually represent, with a percolative mechanism applied to the interactions between different JT centers. The different lattices are distinguished by their coordination numbers. Strong tunneling effects can suppress the CJTE and lead to a new state of criticality. Generalizations to higher spin systems will be obtained using a scaling technique. For the relevant distortions, we determine single site correlations, the macroscopic average distortion describing a structural phase transition and the elastic isothermal susceptibility as a

  15. A Local Approach to Solid State Problems: Pseudo Jahn-Teller origin of Ferroelectricity and Multiferroicity

    NASA Astrophysics Data System (ADS)

    Bersuker, I. B.

    2013-04-01

    This is a partially review paper in which, in continuation of previous work, it is shown that in perovskite crystals of ABO3 type the spontaneous polarization is triggered by local vibronic interactions, the pseudo Jahn-Teller effect (PJTE). The driving force of the latter is added covalency by distortion, which is essentially of local (chemical) origin. The local origin of polar instability in crystals is confirmed by the theorem of structural instability proved earlier. For crystals of BaTiO3 type local PJT interactions of the metal ion with the oxygen environment results in a peculiar adiabatic potential energy surface (APES) which has eight trigonal [111] type minima, twelve [110] type saddle points between them, six higher in energy [100] type saddle points at the top of the barrier connecting four minima, and a maximum at the cubic symmetry. The temperature dependence of the free energy with this potential explains the origin of all the four phases in such crystals; only the lowest rhombohedral phase is fully ordered, the other two ones at higher temperatures are partially disordered, and the paraelectric phase is fully (three-dimensionally) disordered. For BaTiO3 this picture is confirmed by numerical estimates and ab initio DFT calculations. An important further development of this theory was reached recently by showing that not only B ions with electronic d0 configurations are subject to the PJTE instability to produce ferroelectricity in perovskite crystals ("the d0 mystery"), but some other specific dn configurations with unpaired electrons may be dipolar active too, the crystal being thus both magnetic and ferroelectric (multiferroic), and the necessary conditions for such multiferroicity are formulated for the whole d0-dn variety of perovskites. Moreover, the condition of multiferroicity was shown to depend also on the spin state, high-spin or low-spin, which in conditions of spin crossover leads to a magnetic-ferroelectric crossover that can be

  16. Further studies of anisotropy in the T1u⊗hg Jahn-Teller system

    NASA Astrophysics Data System (ADS)

    Qiu, Q. C.; Dunn, J. L.; Bates, C. A.; Liu, Y. M.

    1998-08-01

    In the linear T1u⊗hg Jahn-Teller system, the adiabatic potential energy surface (APES) is a trough. However, in real systems, quadratic coupling will be present, which warps the APES to give wells of either D3d or D5d symmetry. The degeneracy of the vibrations within the wells is also lifted. This anisotropy has recently been investigated in the T1u⊗hg system, and expressions for the frequencies in both types of wells obtained in the strong coupling limit using the method of Öpik and Pryce. A scale transformation procedure was then used to incorporate these results into expressions for the states in the wells and their associated energies. However, this calculation did not allow for second-order perturbation effects and is only valid in the strong coupling limit. In this paper, a revised scale transformation procedure is developed for the D5d wells, which allows expressions for the anisotropic frequencies to be obtained without employing the Öpik and Pryce procedure. An expression is obtained for the phonon overlap that is correct to second-order and is not restricted to the strong coupling limit. Results are then obtained for the ground-state energies and inversion splitting. For D3d wells, the previous results are improved by application of a modified scale transformation procedure and overlaps correct to second order obtained. The results obtained in this paper are of interest in studies of the C-60 anion state of the C60 molecule, which is known to occupy a T1u orbital ground state.

  17. Jahn-Teller coupling and fragmentation after core-shell excitation in CF{sub 4} investigated by partial-ion-yield spectroscopy

    SciTech Connect

    Guillemin, Renaud; Stolte, Wayne C.; Lindle, Dennis W.; Piancastelli, Maria Novella

    2010-10-15

    We investigate fragmentation processes induced by core-level photoexcitation in CF{sub 4} at both the carbon and fluorine K edges by means of partial-ion-yield spectroscopy. The molecule CF{sub 4} is a textbook example of systems in which Jahn-Teller coupling strongly manifests itself in the photoabsorption spectrum. Spectral features related to Jahn-Teller and quasi-Jahn-Teller splitting are observed, and important differences in the fragmentation pathways are revealed depending on the symmetries of the core-excited states. We interpret these experimental observations on the grounds of symmetry lowering from the T{sub d} to the C{sub 3v} point group as well as preferential orientation with respect to the polarization vector of the incident radiation.

  18. Ultrasonic evaluation of the Jahn-Teller effect parameters. Application to ZnSe:Cr2 +

    NASA Astrophysics Data System (ADS)

    Gudkov, V. V.; Bersuker, I. B.; Zhevstovskikh, I. V.; Korostelin, Yu V.; Landman, A. I.

    2011-03-01

    A method is constructed that uses ultrasonic experiments to evaluate the parameters of the Jahn-Teller (JT) effect in impurity centers in crystals. The method is based on measurements of temperature dependent attenuation and phase velocity and does not require assumptions about mechanisms of relaxation. The results are illustrated by measurements performed on the impurity system ZnSe:Cr2 + , in which the Cr2 + ion has a threefold degenerate T term in the ground state, subject to the T\\otimes (e+t_2) JT problem. Ultrasound propagation anomalies show that the main JT distortions of the tetrahedral environment of the Cr2 + ion are of tetragonal E type and hence the lowest branch of the adiabatic potential energy surface (APES) is formed in accordance with the T\\otimes e problem. With dopant concentration 3.8 × 1018 cm - 3 the modulus of the constant of linear vibronic coupling to tetragonal E type vibrations is determined by two independent experiments: |FE| = 5.49 × 10 - 5 dyn revealed from attenuation measurements, while a slightly different value |FE| = 5.57 × 10 - 5 dyn emerges from phase velocity measurements. Contributions of other active vibronic modes to the elastic modulus Cl = (C11 + C12 + 2C44)/2 are analyzed and it is shown that the influence of the totally symmetric mode is negligible. Using additional information about this system obtained from independent sources, we also estimated the primary force constant in the E direction (KE≈(1.4-4.2) × 104 dyn cm - 1) and orthorhombic and trigonal saddle points of the APES in the five-dimensional space of the tetragonal and trigonal coordinates, their stabilization energies being EJTO≈81-450 cm - 1 and EJTT≈48-417 cm - 1, respectively (the variations of the KE, EJTO and EJTT values are due to different literature data for EJTE). With these data the APES of the JT linear T\\otimes (e+t_2) problem for the Cr2 + ion in the ZnSe:Cr2 + system is revealed.

  19. 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…

  20. 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…

  1. Jahn-Teller versus quantum effects in the spin-orbital material LuVO3

    SciTech Connect

    Skoulatos, M.; Toth, S.; Roessli, B.; Enderle, M.; Habicht, K.; Sheptyakov, D.; Cervellino, A.; Freeman, P. G.; Reehuis, M.; Stunault, A.; McIntyre, G. J.; Tung, L. D.; Marjerrison, C.; Pomjakushina, E.; Brown, P. J.; Khomskii, D. I.; Rüegg, Ch.; Kreyssig, A.; Goldman, A. I.; Goff, J. P.

    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 LuVO3 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 study 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 LuVO3 and similar systems.

  2. N-terminal peptide sequence repetition influences the kinetics of backbone fragmentation: a manifestation of the Jahn-Teller effect?

    PubMed

    Good, David M; Yang, Hongqian; Zubarev, Roman A

    2013-11-01

    Analysis of large (>10,000 entries) databases consisting of high-resolution tandem mass spectra of peptide dications revealed with high statistical significance (P < 1[Symbol: see text]10(-3)) that peptides with non-identical first two N-terminal amino acids undergo cleavages of the second peptide bond at higher rates than repetitive sequences composed of the same amino acids (i.e., in general AB- and BA- bonds cleave more often than AA- and BB- bonds). This effect seems to depend upon the collisional energy, being stronger at lower energies. The phenomenon is likely to indicate the presence of the diketopiperazine structure for at least some b2 (+) ions. When consisting of two identical amino acids, these species should form through intermediates that have a symmetric geometry and, thus, must be subject to the Jahn-Teller effect that reduces the stability of such systems. PMID:23633015

  3. Absence of Jahn-Teller transition in the hexagonal Ba3CuSb2O9 single crystal.

    PubMed

    Katayama, Naoyuki; Kimura, Kenta; Han, Yibo; Nasu, Joji; Drichko, Natalia; Nakanishi, Yoshiki; Halim, Mario; Ishiguro, Yuki; Satake, Ryuta; Nishibori, Eiji; Yoshizawa, Masahito; Nakano, Takehito; Nozue, Yasuo; Wakabayashi, Yusuke; Ishihara, Sumio; Hagiwara, Masayuki; Sawa, Hiroshi; Nakatsuji, Satoru

    2015-07-28

    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. Moreover, 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, experiments 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. 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. PMID:26170280

  4. EPR, ENDOR, and electronic structure studies of the Jahn-Teller distortion in an Fe(V) nitride.

    PubMed

    Cutsail, George E; Stein, Benjamin W; Subedi, Deepak; Smith, Jeremy M; Kirk, Martin L; Hoffman, Brian M

    2014-09-01

    The recently synthesized and isolated low-coordinate Fe(V) nitride complex has numerous implications as a model for high-oxidation states in biological and industrial systems. The trigonal [PhB((t)BuIm)3Fe(V)≡N](+) (where (PhB((t)BuIm)3(-) = phenyltris(3-tert-butylimidazol-2-ylidene)), (1) low-spin d(3) (S = 1/2) coordination compound is subject to a Jahn-Teller (JT) distortion of its doubly degenerate (2)E ground state. The electronic structure of this complex is analyzed by a combination of extended versions of the formal two-orbital pseudo Jahn-Teller (PJT) treatment and of quantum chemical computations of the PJT effect. The formal treatment is extended to incorporate mixing of the two e orbital doublets (30%) that results from a lowering of the idealized molecular symmetry from D3h to C3v through strong "doming" of the Fe-C3 core. Correspondingly we introduce novel DFT/CASSCF computational methods in the computation of electronic structure, which reveal a quadratic JT distortion and significant e-e mixing, thus reaching a new level of synergism between computational and formal treatments. Hyperfine and quadrupole tensors are obtained by pulsed 35 GHz ENDOR measurements for the (14/15)N-nitride and the (11)B axial ligands, and spectra are obtained from the imidazole-2-ylidene (13)C atoms that are not bound to Fe. Analysis of the nitride ENDOR tensors surprisingly reveals an essentially spherical nitride trianion bound to Fe, with negative spin density and minimal charge density anisotropy. The four-coordinate (11)B, as expected, exhibits negligible bonding to Fe. A detailed analysis of the frontier orbitals provided by the electronic structure calculations provides insight into the reactivity of 1: JT-induced symmetry lowering provides an orbital selection mechanism for proton or H atom transfer reactivity. PMID:25137531

  5. Stability of Jahn-Teller distortion in LaMnO{sub 3} under pressure: An x-ray absorption study

    SciTech Connect

    Ramos, Aline Y.; Tolentino, Helio C. N.; Souza-Neto, Narcizo M.; Itie, Jean-Paul; Morales, Liliana; Caneiro, Alberto

    2007-02-01

    The local environment of manganese atoms in LaMnO{sub 3} under pressure up to 15.3 GPa has been studied by x-ray absorption spectroscopy. For pressures below 8 GPa, no change is detected within the MnO{sub 6} octahedra. Above this pressure a continuous reduction of the long Mn-O distance takes place, however, the octahedral distortion persists over the whole pressure range. At 15.3 GPa the average Jahn-Teller splitting of the distances is reduced by about one-third, indicating that a total removal of the local Jahn-Teller distortion would occur only for pressures around 30 GPa, where metallization is reported to take place. A hysteresis in the long distance reduction is observed down to ambient pressure, suggesting the coexistence of MnO{sub 6} distorted and undistorted units.

  6. Remarks on the Phase Change of the Electronic Wave Function upon Going Once around a Jahn-Teller Conical Intersection in Vibrational Coordinate Space

    NASA Astrophysics Data System (ADS)

    Hougen, Jon T.

    2012-06-01

    In this talk we revisit, with pedagogical emphasis for high-resolution spectroscopists, some presently existing discussions of phase factors for fixed-nuclei electronic wavefunctions in the Jahn-Teller problem. We give explicit examples, for a symmetric pyramidal NH_3-like molecular shape, of perfectly reasonable variants of such electronic wavefunctions that do not transform into their negatives upon going once around the conical intersection (i.e., that do not exhibit a Berry phase change of -1), as well as an example calculation for the pseudo-rotational energy levels and wavefunctions near the bottom of a deep Jahn-Teller moat that does not make use of half-integral quantum numbers and that does not require abandoning ordinary C3v point group theory. Some cautionary remarks on drawing inappropriate conclusions from overly hasty Berry phase arguments will also be presented.

  7. Jahn-Teller effects and surface interactions in multiply-charged fullerene anions and the effect on scanning tunneling microscopy images

    NASA Astrophysics Data System (ADS)

    Dunn, Janette L.; Alqannas, Haifa S.; Lakin, Andrew J.

    2015-10-01

    We investigate the combined effects of Jahn-Teller (JT) coupling and interactions with a surface substrate on fullerene anions C602- to C604-. JT coupling alone causes the C60 ions to instantaneously distort from the icosahedral symmetry of the neutral molecule to a lower symmetry, with the molecule moving dynamically between a set of equivalent distortions. When adsorbed on a surface, the number of equivalent minimum-energy distortions is reduced. The implications of this on observed scanning tunneling microscopy (STM) images will be discussed, and comparisons made with existing experimental data. We show that a consistent interpretation of the images from all of the charge states of C60 can only be obtained using a JT model in which the symmetry is further reduced by surface interactions. The comparison with experimental data also allows us to determine relationships between the quadratic Jahn-Teller coupling and surface interaction parameters.

  8. Dependence of the Jahn-Teller distortion in LaMn 1-x ScxO3 on the isovalent Mn-site substitution

    NASA Astrophysics Data System (ADS)

    Subías, G.; Cuartero, V.; Blasco, J.; García, J.; Meneghini, C.; Aquilanti, G.

    2016-05-01

    We investigated the relative importance of removing the Mn3+ Jahn-Teller distortion in driving ferromagnetism in LaMn1-xScxO3 combining x-ray powder diffraction and x-ray absorption spectroscopy at the Mn and Sc K-edges. By increasing the Sc content, the orthorhombic distortion of the Pbnm cell in LaMnO3 decreases but the unit-cell remains slightly distorted in LaScO3. Besides, the nearly tetragonal-distorted MO6 in LaMnO3 continuously evolves into a nearly regular one in LaScO3. On the other hand, x-ray absorption spectra show that the MnO6 octahedron remains Jahn-Teller distorted and the ScO6 octahedron is nearly regular along the whole series. Moreover, the ordering of the Mn3+ Jahn-Teller distortion is not disrupted in the ab plane for any Sc concentration. This contrasts with the Ga- substituted compounds, where a regular MnO6 is found for x>0.5. However, both LaMn0.5Sc0.5O3 and LaMn0.5Ga0.5O3 show ferromagnetic behavior independently of the presence (or not) of Jahn-Teller distorted Mn3+. Thus, our results point to the Mn-sublattice dilution as the main effect in driving ferromagnetism in these manganites over local structure effects previously proposed by the spin flipping or the vibronic superexchange models.

  9. Is the pseudogap in the high T{sub c} cuprates evidence for dynamic van Hove Jahn-Teller effects?

    SciTech Connect

    Markiewicz, R.S.

    1995-10-01

    Angle-resolved photoemission has demonstrated that in optimally doped YBa{sub 2}Cu{sub 3}O{sub 7} (YBCO) and Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8}, the van Hove singularity (vHs) is pinned close to the Fermi level. Such a pinning was predicted by the vHs scenario, due to strong electron-phonon coupling. This coupling arises for a novel Jahn-Teller (JT) effect, in which a structural distortion splits the degeneracy of the two vHs`s. In the lanthanum cuprates, there appears to be a sequence of dynamic JT phases, possibly terminating in a low-temperature static JT phase. The highest-temperature JT phase corresponds to the onset of octahedral tilts in the La cuprates (pyramidal tilts in YBCO), can can be identified with the experimentally observed pseudogap phase. Here the author summarizes recent experimental evidence for such a dynamic JT effect in the cuprates.

  10. Density functional theory study of the multimode Jahn-Teller problem in the open-shell corannulenes and coronenes

    NASA Astrophysics Data System (ADS)

    Andjelković, Ljubica; Gruden-Pavlović, Maja; Zlatar, Matija

    2015-10-01

    Analysis of the multimode Jahn-Teller (JT) distortion in anions and cations of corannulene and coronene is presented, combining multideterminantal-DFT (MD-DFT) and Intrinsic Distortion Path (IDP) methods. The JT distortion is derived from the sum of contributions of all possible JT active normal modes. The Csbnd C stretching modes play the most important role in the stabilization of the systems, in all investigated species, pushing the nuclei toward the minima on the potential energy surface. The further inspection of the IDP revealed that the relaxation of the geometry arrives in the final part of the path and is encountered by the softest vibrational modes. The same trend was observed in cyclopentadienyl radical, benzene anion, benzene cation and fullerene ions. This gives microscopic origin into the mechanism of the distortion and provides general behavior of the JT effect in these similar molecules. Moreover, MD-DFT and IDP, as fast and fully non-empirical approaches, can be considered as a reliable tool for better understanding of the JT effect.

  11. Effect of lattice constant on pseudo Jahn-Teller polar distortion: Application to search for new multiferroic compounds

    NASA Astrophysics Data System (ADS)

    Song, Guang; Zhang, Weiyi

    2016-08-01

    By analog to Maxwell construction for the first-order phase transition, the pseudo Jahn-Teller polar distortion arises naturally once the local bond length of transition-metal oxygen octahedra is enhanced beyond the inflexion point of pair potential into the concave-down dominated region. This concept is applied to search for the new multiferroic compounds for which we specifically choose the (BaMnO3)1/(BaFeO3)1 superlattice as a candidate. The large Ba radius favors the polar distortion in a BaMnO3 layer, while the orbital-ordering-induced superexchange ferromagnetic coupling among Fe-Fe and double-exchange mediated ferromagnetic coupling among Fe-Mn ions stabilize the overall ferromagnetic insulator. A large magnetic moment of 7 μB per unit cell and electric polarization of 14.4 μ Ccm -2 are obtained. Our study offers an important insight for designing robust multiferroic compounds in the future.

  12. Suppression of Jahn-Teller Distortions and Origin of Piezochromism and Thermochromism in Cu-Cl Hybrid Perovskite.

    PubMed

    Gupta, Sunny; Pandey, Tribhuwan; Singh, Abhishek Kumar

    2016-07-01

    While pressure-induced changes in the electronic, magnetic, and optical properties of Cu-Cl hybrid perovskites have been studied intensively, the correlation between these properties and pressure-induced structural changes is still vaguely understood. Here, by first-principles calculations on a model system (EDBE)[CuCl4] (EDBE = 2,2'-(ethylenedioxy)bis(ethylammonium)) (a Cu-Cl hybrid perovskite), we correlate the evolution of a series of exciting physical properties with pressure while resolving some of the long-standing debates on the fundamental electronic nature of this important class of material. The material shows two structural phase transitions and an anisotropy in compressibility with increasing pressure. After a critical pressure of 17 GPa, the structure becomes highly symmetric, thereby suppressing the Jahn-Teller distortions. At zero pressure, mapping the optical transitions with the Laporte selection rules, lower and higher energy excitations are found to be of Mott-Hubbard (MH) and charge transfer (CT) type, respectively, signifying the material to be a Mott insulator. The material shows a red shift in the charge transfer band edge with increasing pressure and temperature, demonstrating the piezochromism and the thermochromism, respectively. Piezochromism originates from the changes in mixing of Cl-Cu p-d states, while thermochromism is due to broadening of conduction band states, thereby showing different electronic and structural evolution with pressure and temperature. Furthermore, the magnetic ordering in the material was found to be stable up to higher pressures, making pressure a tool to tune the electronic property without perturbing the magnetic property. PMID:27337489

  13. Control of magnetic ordering by Jahn--Teller distortions in Nd(2)GaMnO(6) and La(2)GaMnO(6).

    PubMed

    Cussen, E J; Rosseinsky, M J; Battle, P D; Burley, J C; Spring, L E; Vente, J F; Blundell, S J; Coldea, A I; Singleton, J

    2001-02-14

    The substitution of Ga(3+) into the Jahn--Teller distorted, antiferromagnetic perovskites LaMnO(3) and NdMnO(3) strongly affects both the crystal structures and resulting magnetic ordering. In both compounds the Ga(3+) and Mn(3+) cations are disordered over the six coordinate sites. La(2)GaMnO(6) is a ferromagnetic insulator (T(c) = 70 K); a moment per Mn cation of 2.08(5) mu(B) has been determined by neutron powder diffraction at 5 K. Bond length and displacement parameter data suggest Jahn--Teller distortions which are both coherent and incoherent with the Pnma space group symmetry of the perovskite structure (a = 5.51122(4) A, b = 7.80515(6) A, c = 5.52947(4) A) at room temperature. The coherent distortion is strongly suppressed in comparison with the parent LaMnO(3) phase, but the displacement ellipsoids suggest that incoherent distortions are significant and arise from local Jahn--Teller distortions. The preparation of the new phase Nd(2)GaMnO(6) has been found to depend on sample cooling rates, with detailed characterization necessary to ensure phase separation has been avoided. This compound also adopts the GdFeO(3)-type orthorhombically distorted perovskite structure (space group Pnma, a = 5.64876(1) A, b = 7.65212(2) A, c = 5.41943(1) A at room temperature). However, the B site substitution has a totally different effect on the Jahn--Teller distortion at the Mn(3+) centers. This phase exhibits a Q(2) mode Jahn--Teller distortion similar to that observed in LaMnO(3), although reduced in magnitude as a result of the introduction of Ga(3+) onto the B site. There is no evidence of a dynamic Jahn-Teller distortion. At 5 K a ferromagnetically ordered Nd(3+) moment of 1.06(6) mu(B) is aligned along the y-axis and a moment of 2.8(1) mu(B) per Mn(3+) is ordered in the xy plane making an angle of 29(2) degrees with the y-axis. The Mn(3+) moments couple ferromagnetically in the xz plane. However, along the y-axis the moments couple ferromagnetically while the x

  14. Influence of Fe substitution on the Jahn-Teller distortion and orbital anisotropy in orthorhombic Y(Mn1-xFex)O3 epitaxial films.

    PubMed

    Haw, Shu-Chih; Lee, Jenn-Min; Chen, Shin-Ann; Lu, Kueih-Tzu; Lee, Ming-Tao; Pi, Tun-Wen; Lee, Chih-Hao; Hu, Zhiwei; Chen, Jin-Ming

    2016-08-01

    Multiferroic YMn1-xFexO3(020) (x = 0.125, 0.25, 0.50) epitaxial thin films with an orthorhombic structure (space group Pbnm) were prepared on a YAlO3(010) substrate by pulsed-laser deposition. Upon Fe substitution, the b-axis was clearly shortened, whereas the a- and c-axes were slightly lengthened based on XRD analysis. To understand the influence of orbital polarization and the Jahn-Teller effect of Mn(3+) on Fe substitution and also the local octahedral-site distortion of Fe(3+) in an environment of Jahn-Teller-active Mn(3+) ions in YMn1-xFexO3 films, we measured the polarization-dependent X-ray absorption spectra at the Mn-L2,3 and Fe-L2,3 edges, and also simulated the experimental spectra using configuration-interaction multiplet calculations. Although Δeg for the Mn(3+) ion decreased from 0.9 eV in pure YMnO3 to 0.6 eV in the half-Fe-substituted sample, a single eg electron was still strongly constrained to the d3y(2)-r(2) orbital for all the Fe concentrations tested. The largest Δeg, 0.5 eV, for the Fe(3+) ion was derived for a sample with 12.5% Fe substitution, and gradually decreased to 0.15 eV for the half-Fe-substituted sample. The local octahedral-site distortion of the Fe(3+) ion inside the YMnO3 lattice was similar to that of the Mn(3+) ion, whereas the Jahn-Teller distortion and GdFeO3-type distortion of the Mn(3+) ion were decreased by the spherical high-spin Fe(3+) ions. The combination of the experimental and theoretical data provides both profound insight into the variation of the Jahn-Teller distortion and orbital anisotropy and instructive information about the magnetic structures in these orthorhombic YMn1-xFexO3 thin films. PMID:27430045

  15. Jahn-Teller distortion in tris[4,4,4-trifluoro-1-(2-thienyl)-1,3-butanedionato]manganese(III) isomers: An X-ray and computational study

    NASA Astrophysics Data System (ADS)

    Gostynski, Roxanne; van Rooyen, Petrus H.; Conradie, Jeanet

    2016-09-01

    The solid state crystal data of a mer isomer of the [Mn(CF3COCHCOC4H3S)3] complex, [Mn(tfth)3], exhibits elongation Jahn-Teller distortion (elongation of the metal-ligand bonds along the z-axis and shortening of the metal-ligand bonds along both the x and y-axes). Density functional theory calculations (DFT) show that one fac and three mer isomers of [Mn(tfth)3] can exist. The difference between the three mer isomers of [Mn(tfth)3] is that the Jahn-Teller elongation of the two trans axial Mn-O bonds along the z-axis occur along three different Otfth-Mn-Otfth bonds. DFT calculations further show that the ground state geometry of all the [Mn(tfth)3] isomers exhibits elongation Jahn-Teller distortion.

  16. 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

  17. Lattice Distortion, Polaron Conduction, and Jahn-Teller Effect on teh Magnetoresistance of La(sub 0.7)Ca(sub 0.5)CoO(sub 3) Epitaxial Films

    NASA Technical Reports Server (NTRS)

    Yeh, N. C.; Vasquez, R. P.; Beam, D. A.; Fu, C. C.; Huynh, H.; Beach, G.

    1996-01-01

    In summary, we have investigated the role of lattice distortion, polaron conduction and Jahn-Teller coupling in the occurrence of the colossal negative magnetoresistance in perovskite oxides. We conclude that larger lattice distortion gives rise to larger zero-field resistivity and larger magnitude of negative magnetoresistance.

  18. Spin-lattice coupling, Jahn-Teller effect and the influence of the measurement rate in La0.7Ca0.3-xSrxMnO3 manganites

    NASA Astrophysics Data System (ADS)

    Burrola-Gándara, L. A.; Sáenz-Hernández, R. J.; Santillán-Rodríguez, C. R.; Lardizabal-Gutiérrez, D.; Pizá-Ruiz, P.; Elizalde Galindo, J. T.; Matutes-Aquino, J. A.

    2016-05-01

    This work presents a study of how the magnetic and temperature variables, as well as the measurement rate, affect magnetic and structural phase transitions for La0.7Ca0.3-xSrxMnO3 (x=0.15, 0.08, 0.07 and 0.06) manganites. A single phase rhombohedral crystal structure for Sr0.15 compound and a single phase orthorhombic crystal structure for Sr0.08, Sr0.07, and Sr0.06 compounds were identified by X ray diffraction. The Curie temperature adjustment to room temperature was reached for Sr0.07 sample, in which a Jahn-Teller transition was observed. This Jahn-Teller transition showed a susceptible response to 0.5, 1, 2, 3, 5 and 7 K/min measurement rates, and was revealed without measurement sequence at 234, 257, 196, 233, 245 and 238 K respectively in thermomagnetic curves (10mT). Also, Curie temperature increases sequentially around 2 K for the same measurement rates. To avoid magnetic field effect, a differential scanning calorimetry for Sr0.07 sample was obtained in the same temperature region, for 2, 3, 5, 7 K/min showing the Jahn-Teller phase transition at 225 K and a vibrational like behavior in the heat flux below 225 K, for all the temperature rates. The latter, is related to the static to dynamic Jahn-Teller transition. Furthermore, Curie temperature appears around 284 K.

  19. The 2A1-2E electronic spectrum of methoxy, CH3O - Vibrational progressions, and spin-orbit and Jahn-Teller couplings

    NASA Astrophysics Data System (ADS)

    Brossard, S. D.; Carrick, P. G.; Chappell, E. L.; Hulegaard, S. C.; Engelking, P. C.

    1986-03-01

    Although the methoxy radical has been studied in a great number of investigations, some very basic questions have not yet been answered. The methoxy radical is of practical importance in studies related to astronomy, the atmosphere, and combustion. The present paper is concerned with the generation of the emission spectrum of CH3O in a corona excited supersonic expansion. Dimethylperoxide was prepared for the experiments by the method reported by Hanst and Calvert (1959), taking into account a modification of the collection and purification procedure. A mixture of a few percent dimethylperoxide in helium was supplied to a corona excited supersonic expansion at about four atmospheres pressure. Attention is given to band positions and assignments, and aspects of spin-orbit and Jahn-Teller coupling.

  20. LETTER TO THE EDITOR: A distortion of pseudotetramers coupled with the Jahn Teller effect in the geometrically frustrated spinel system CdV2O4

    NASA Astrophysics Data System (ADS)

    Onoda, Masashige; Hasegawa, Junichi

    2003-01-01

    For the geometrically frustrated spinel system CdV2O4 with V3+ (S = 1) that undergoes structural and magnetic transitions at Tc1 = 97 K, and may exhibit a transition to the antiferromagnetic state at Tc2 = 35 K, the crystal structures at 299 and 85 K have been determined with space groups Fdbar 3m and I41 /amd, respectively, by means of x-ray four-circle diffraction. At 85 K, the VO6 octahedron is distorted due to the Jahn-Teller effect with contraction of the V-O bond along the tetragonal c axis, and the network of V ions is achieved by the linkage of a distorted V4-tetrahedron block with two kinds of V-V bonds. On the basis of these structural properties, magnetic susceptibilities at temperatures between Tc1 and Tc2 are explained in terms of the tetragonally distorted pseudotetramer model.

  1. Temperature-dependent XRD, IR, magnetic, SEM and TEM studies of Jahn-Teller distorted NiCr2O4 powders

    NASA Astrophysics Data System (ADS)

    Ptak, M.; Maczka, M.; Gągor, A.; Pikul, A.; Macalik, L.; Hanuza, J.

    2013-05-01

    In the present work we report detailed structural, magnetic and phonon properties of NiCr2O4 powders synthesized via a simple coprecipitation method. Temperature-dependent XRD as well as temperature-dependent IR studies reveal that cubic to tetragonal phase transition is lowered due to size effects. Observed changes in the IR spectra indicate that the paramagnetic-ferrimagnetic phase transition taking place at 74 K is related to further lowering of symmetry to orthorhombic system. Assignment of modes was proposed and factor group analyses in three possible symmetries were carried out. Our results show strong anomalies due to the Jahn-Teller tetragonal distortion and weak due to the orthorhombic distortion and onset of collinear ferrimagnetic order. Shifts of wavenumbers observed below 31 K, where the onset of antiferromagnetic ordering occurs, were attributed to spin-phonon interactions.

  2. EPR Study of the Low-Spin [d3; S =1/2], Jahn-Teller-Active, Dinitrogen Complex of a Molybdenum Trisamidoamine

    PubMed Central

    McNaughton, Rebecca L.; Chin, Jia Min; Weare, Walter W.; Schrock, Richard R.; Hoffman, Brian M.

    2008-01-01

    The first EPR study of the trisamidoamine complex, [Mo]N2, where [Mo] = [Mo(III)[HIPTN3N]3- = [3,5-(2,4,6-i-Pr3-C6H2)2C6H3NCH2CH2]3N3-], reveals that this low-spin (S = ½) [d3] complex exhibits a 2E state that undergoes a pseudo Jahn-Teller distortion in the adiabatic limit, modified by interactions with the solvent, and gives approximate values of interaction energies. The experiments establish that [Mo]N2 exhibits the low-spin [e3] electronic configuration, not [a2e1], with the a(z2) antibonding orbital substantially higher in energy than the e[xz, yz] orbitals. PMID:17341079

  3. The Jahn-Teller effect in the 3pe' Rydberg state of H3: review of experimental and ab initio determinations.

    PubMed

    Jungen, Ch; Jungen, M; Pratt, S T

    2012-11-13

    The dissociative recombination (DR) of H(3)(+) ions with electrons, producing neutral atomic and molecular fragments, is driven primarily by the vibronic Jahn-Teller (JT) interaction between the electronic components of the pe' e(-)-H(3)(+) collision (Rydberg) channel. The JT parameters characterizing this interaction are therefore of great interest as they are required for the theoretical predictions of the DR cross section. In this contribution, we review various determinations of these quantities that have been made previously, based both on spectroscopic studies of 3pe' Rydberg-excited H(3) states, and on the analysis of the corresponding ab initio H(3) Rydberg potential surfaces near the conical intersection (D(3h) symmetry) for n=3-5. The highly correlated theoretical 3pe' potential surfaces of Mistrík et al. are used for a new determination of both the linear and quadratic JT terms. PMID:23028155

  4. Unexpected Spin-Crossover and a Low-Pressure Phase Change in an Iron(II)/Dipyrazolylpyridine Complex Exhibiting a High-Spin Jahn-Teller Distortion.

    PubMed

    Kershaw Cook, Laurence J; Thorp-Greenwood, Flora L; Comyn, Tim P; Cespedes, Oscar; Chastanet, Guillaume; Halcrow, Malcolm A

    2015-07-01

    The synthesis of 4-methyl-2,6-di(pyrazol-1-yl)pyridine (L) and four salts of [FeL2]X2 (X(-) = BF4(-), 1; X(-) = ClO4(-), 2; X(-) = PF6(-), 3; X(-) = CF3SO3(-), 4) are reported. Powder samples of 1 and 2 both exhibit abrupt, hysteretic spin-state transitions on cooling, with T1/2↓ = 204 and T1/2↑ = 209 K (1), and T1/2↓ = 175 and T1/2↑ = 193 K (2). The 18 K thermal hysteresis loop for 2 is unusually wide for a complex of this type. Single crystal structures of 2 show it to exhibit a Jahn-Teller-distorted six-coordinate geometry in its high-spin state, which would normally inhibit spin-crossover. Bulk samples of 1 and 2 are isostructural by X-ray powder diffraction, and undergo a crystallographic phase change during their spin-transitions. At temperatures below T1/2, exposing both compounds to 10(-5) Torr pressure inside the powder diffractometer causes a reversible transformation back to the high-temperature crystal phase. Consideration of thermodynamic data implies this cannot be accompanied by a low → high spin-state change, however. Both compounds also exhibit the LIESST effect, with 2 exhibiting an unusually high T(LIESST) of 112 K. The salts 3 and 4 are respectively high-spin and low-spin between 3 and 300 K, with crystalline 3 exhibiting a more pronounced version of the same Jahn-Teller distortion. PMID:26052980

  5. The Jahn-Teller effect in CH3Cl+(X̃2E): a combined high-resolution experimental measurement and ab initio theoretical study.

    PubMed

    Shao, Zhuo; Li, Hua; Zhang, Shiyang; Li, Juan; Dai, Zuyang; Mo, Yuxiang; Bae, Yong Jin; Kim, Myung Soo

    2012-02-14

    The energy levels of CH(3)Cl(+)X̃(2)E showing strong spin-vibronic coupling effect (Jahn-Teller effect) have been measured up to 3500 cm(-1) above the ground vibrational state using one-photon zero-kinetic energy photoelectron and mass-analyzed threshold ionization spectroscopic method. Theoretical calculations have been also performed to calculate the spin-vibronic energy levels using a diabatic model and ab initio adiabatic potential energy surfaces (PESs). In the theoretical calculations the diabatic potential energy surfaces are expanded by the Taylor expansions up to the fourth-order including the multimode vibronic interactions. The calculated spin-orbit energy splitting (224.6 cm(-1)) for the ground vibrational state is in good agreement with the experimental data (219 ± 3 cm(-1)), which indicates that the Jahn-Teller and the spin-orbit coupling have been properly described in the theoretical model near the zero-point energy level. Based on the assignments predicted by the theoretical calculations, the experimentally measured energy levels were fitted to those from the diabatic model by optimizing the main spectroscopic parameters. The PESs from the ab initio calculations at the level of CASPT2/vq(t)z were thus compared with those calculated from the experimentally determined spectroscopic parameters. The theoretical diagonal elements in the diabatic potential matrix are in good agreement with those determined using the experimental data, however, the theoretical off-diagonal elements appreciably deviate from those determined using the experimental data for geometric points far away from the conical intersections. It is also concluded that the JT effect in CH(3)Cl(+) mainly arises from the linear coupling and the mode coupling between the CH(3) deform (υ(5)) and CH(3) rock (υ(6)) vibrations. The mode couplings between the symmetric C-Cl stretching vibration υ(3) with υ(5) and υ(6) are also important to understand the spin-vibronic structure of the

  6. Jahn-Teller phase transition in Cu 0.50TiO(PO 4): Powder structural characterization of the β-variety and thermal study

    NASA Astrophysics Data System (ADS)

    Gravereau, Pierre; Benmokhtar, Saïd; Chaminade, Jean-Pierre; El Jazouli, Abdelaziz; Lebraud, Eric; Denux, Dominique

    2007-03-01

    The thermal study of Cu 0.50TiO(PO 4), by X-ray diffraction and DSC, shows a phase transition α → β with a hysteresis (˜600 °C during heating; ˜300 °C during cooling). Single crystals have been obtained for the α-phase but the β-phase can only be stabilised at room temperature as a powder mixture with α. Structural characterization of the β-variety has been done with diffraction data (X-ray Cu Kα 1 and neutrons) using a powder rich in β-phase (α(20%) + β(80%)). A monoclinic cell ( a = 7.1134(7) Å; b = 7.7282(7) Å; c = 7.3028(7) Å; β=119.30(1)°; V = 350.1(1) Å 3) has been found for β-phase, space group P2 1/ c. An " ab initio" structure determination has been done, and the Rietveld refinement leads to cRwp = 0.150 and RB = 0.041. The results from the X-ray data were confirmed by refinements from neutron data. Similarly to the α-phase, the structure of β-Cu 0.50TiO(PO 4) can be described as a TiOPO 4 framework constituted of chains of tilted corner-sharing [TiO 6] octahedra running parallel to the c axis and cross linked by [PO 4] tetrahedra. Ti atoms are displaced from the centres of the octahedral units, leading to long (2.27 Å) and short (1.73 Å) Ti-O(1) bonds. The [CuO 6] octahedra exhibit a typical Jahn-Teller distorted coordination with four short equatorial Cu-O bonds (2 × 1.93 Å and 2 × 2.06 Å), and two longer apical Cu-O bonds (2 × 2.33 Å). The two longer Cu-O bonds are almost parallel to the b axis. The transition from the α to the β-phase is characterized by a "rocking" of the Jahn-Teller elongation from the ( a, c) plane to the b direction accompanied by a relatively strong expansion of the cell volume.

  7. Local Jahn-Teller distortions and orbital ordering in Ba3Cu1+xSb2-xO9 investigated by neutron scattering

    SciTech Connect

    Li, Bing; Feygenson, Mikhail; Brown, Craig; Copley, John R. D.; Iida, Kazuki

    2016-01-01

    A spin-orbital quantum liquid state is theoretically proposed in the honeycomb lattice of Ba3CuSb2O9, enabled by dynamic short-range correlations between the spin and orbital degrees of freedom. Using neutron diffraction, the local atomic structure of Ba3Cu1+xSb2-xO9 at x = 0 and 0.1 is obtained via the pair density function analysis. The results indicate that both compositions exhibit local Jahn-Teller (JT) distortions with the elongated CuO3 octahedral configuration. In Ba3Cu1.1Sb1.9O9, JT ordering of the distorted CuO3 octahedra gives rise to the orthorhombic symmetry with ferro-orbital order. On the other hand, in Ba3CuSb2O9, even though the CuO3 octahedra are JT distorted, there is no long-range ordering hence the symmetry is hexagonal. Furthermore, the local singlet excitation at 5.8 meV observed in Ba3CuSb2O9 below 50 K is absent in Ba3Cu1.1Sb1.9O9. Instead, an excitation at 2.5 meV is observed in the latter, which is likely associated with short-range spin order.

  8. Synthetic, structural, spectroscopic and theoretical study of a Mn(III)-Cu(II) dimer containing a Jahn-Teller compressed Mn ion.

    PubMed

    Berg, Nelly; Hooper, Thomas N; Liu, Junjie; Beedle, Christopher C; Singh, Saurabh Kumar; Rajaraman, Gopalan; Piligkos, Stergios; Hill, Stephen; Brechin, Euan K; Jones, Leigh F

    2013-01-01

    The heterobimetallic complex [Cu(II)Mn(III)(L)(2)(py)(4)](ClO(4))·EtOH (1) built using the pro-ligand 2,2'-biphenol (LH(2)), contains a rare example of a Jahn-Teller compressed Mn(III) centre. Dc magnetic susceptibility measurements on 1 reveal a strong antiferromagnetic exchange between the Cu(II) and Mn(III) ions mediated through the phenolate O-atoms (J = -33.4 cm(-1)), with magnetisation measurements at low temperatures and high fields suggesting significant anisotropy. Simulations of high-field and high frequency powder EPR data suggest a single-ion anisotropy D(Mn(III)) = +4.45 cm(-1). DFT calculations also yield an antiferromagnetic exchange for 1, though the magnitude is overestimated (J(DFT) = -71 cm(-1)). Calculations reveal that the antiferromagnetic interaction essentially stems from the Mn(d(x(2)-y(2)))-Cu(d(x(2)-y(2))) interaction. The computed single-ion anisotropy and cluster anisotropy also correlates well with experiment. A larger cluster anisotropy for the S = 3/2 state compared to the single-ion anisotropy of Mn(III) is rationalised on the basis of orbital mixing and various contributions that arise due to the spin-orbit interaction. PMID:23108057

  9. Evidence for Jahn-Teller Coupling and Fano Resonance of Lower Hg Modes in K3C60 and Rb3C60 Films from Raman Scattering

    NASA Astrophysics Data System (ADS)

    Denisov, V. N.; Zakhidov, A. A.; Danieli, R.; Ruani, G.; Zamboni, R.; Taliani, C.; Imaeda, K.; Yakushi, K.; Inokuchi, H.; Achiba, Y.

    The Raman scattering study of superconducting thin films of A3C60 (A=K,Rb) carried out upon laser excitations at 1.16 and 2.41 eV have revealed the significant broadening and Fano-lineshapes of several low energy Hg intramolecular modes with relative intensities and widths depending on excitation energies. The most interesting feature of the 1.16 eV excited spectrum is the wide asymmetric band at 400 cm-1 which can be assigned by Fano-shape fitting to enormously broadened Hg(2) mode red shifted compared to its bare frequency of 408 cm-1. The narrowing of all lower Hg modes in insulating A6C60 phase indicates strong electron-phonon coupling of this Jahn-Teller modes in x=3 phase and suggests that this low energy vibrations are contributing to superconducting pairing. However the possibility to interpret the wide band at 400 cm-1 as the maximum of electronic background can not be ruled out yet and is supported by our preliminary observations of its disappearance at low temperature below Tc.

  10. 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.

  11. Polar and Magneto-Electric Properties of Anti-Ferrodistortive Ordered Jahn-Teller Distortions in a multiferroic metal-organic framework

    NASA Astrophysics Data System (ADS)

    Stroppa, Alessandro

    2013-04-01

    There is great interest in hybrid organic-inorganic materials such as metal-organic frameworks (MOFs). Here, we focus on [C(NH2)3]Cu(HCOO)3, a MOF with perovskite topology which crystallizes in polar space group Pna21. In inorganic compounds, octahedral tilting and Jahn-Teller structural distortions are usually non-polar distortions. However, in this MOF cooperative interactions between the antiferro-distortive distortions of the framework and the C(NH2)3 organic cation via hydrogen bonding breaks the inversion symmetry and induces a ferroelectric polarization. Our ab-initio study supports the picture of an orbital-order-induced ferroelectricity, a rare example of dipolar ordering caused by electronic degrees of freedom. Moreover, we show that the switching of polarization direction implies the reversal of the weak ferromagnetic component. These results therefore offer an important starting point for tailoring multiferroic properties in this emerging class of materials for various technological applications.

  12. Local Jahn-Teller distortions and orbital ordering in Ba3Cu1+xSb2-xO9 investigated by neutron scattering

    DOE PAGESBeta

    Li, Bing; Feygenson, Mikhail; Brown, Craig M.; Copley, John R. D.; Iida, Kazuki

    2016-01-15

    In this study, a spin-orbital quantum liquid state is theoretically proposed in the honeycomb lattice of Ba3CuSb2O9, enabled by dynamic short-range correlations between the spin and orbital degrees of freedom. Using neutron diffraction, the local atomic structure of Ba3Cu1+xSb2-xO9 at x = 0 and 0.1 is obtained via the pair density function analysis. The results indicate that both compositions exhibit local Jahn-Teller (JT) distortions with the elongated CuO3 octahedral configuration. In Ba3Cu1.1Sb1.9O9, JT ordering of the distorted CuO3 octahedra gives rise to the orthorhombic symmetry with ferro-orbital order. On the other hand, in Ba3CuSb2O9, even though the CuO3 octahedra aremore » JT distorted, there is no long-range ordering hence the symmetry is hexagonal. Furthermore, the local singlet excitation at 5.8 meV observed in Ba3CuSb2O9 below 50 K is absent in Ba3Cu1.1Sb1.9O9. Instead, an excitation at 2.5 meV is observed in the latter, which is likely associated with short-range spin order.« less

  13. Local Jahn-Teller distortions and orbital ordering in Ba3Cu1 +xSb2 -xO9 investigated by neutron scattering

    NASA Astrophysics Data System (ADS)

    Li, Bing; Louca, Despina; Feygenson, Mikhail; Brown, Craig M.; Copley, John R. D.; Iida, Kazuki

    2016-01-01

    A spin-orbital quantum liquid state is theoretically proposed in the honeycomb lattice of Ba3CuSb2O9 , enabled by dynamic short-range correlations between the spin and orbital degrees of freedom. Using neutron diffraction, the local atomic structure of Ba3Cu1 +xSb2 -xO9 at x =0 and 0.1 is obtained via the pair density function analysis. The results indicate that both compositions exhibit local Jahn-Teller (JT) distortions with the elongated CuO3 octahedral configuration. In Ba3Cu1.1Sb1.9O9 , JT ordering of the distorted CuO3 octahedra gives rise to the orthorhombic symmetry with ferro-orbital order. On the other hand, in Ba3CuSb2O9 , even though the CuO3 octahedra are JT distorted, there is no long-range ordering hence the symmetry is hexagonal. Furthermore, the local singlet excitation at 5.8 meV observed in Ba3CuSb2O9 below 50 K is absent in Ba3Cu1.1Sb1.9O9 . Instead, an excitation at 2.5 meV is observed in the latter, which is likely associated with short-range spin order.

  14. 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

    2016-04-01

    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. PMID:26987273

  15. Origin of warping in the E⊗e Jahn-Teller problem: Quadratic vibronic coupling versus anharmonicity and application to NaCl: Rh2+ and triangular molecules

    NASA Astrophysics Data System (ADS)

    García-Fernández, P.; Bersuker, I. B.; Aramburu, J. A.; Barriuso, M. T.; Moreno, M.

    2005-05-01

    A general method is suggested which allows one to separate the quadratic, cubic, and pseudo Jahn-Teller contributions to the warping of the adiabatic potential energy surface (APES) of the E⊗e problem employing ab initio calculations. Numerical results were obtained for NaCl:Rh2+ in a cluster approximation and triangular molecules (Na3,K3,Cu3,Ag3) using density functional theory (DFT) and multireference second-order perturbation theory (CASPT2) methods. A largely unexpected result is that the contribution of cubic anharmonicity to the energy barrier between the minima of the lower and upper branches of the APES is dominant in all the systems and amounts for not less than 60% of the total. Another feature is that the three different contributions mentioned above may have different signs, thus either enhancing or diminishing each other, affecting in different ways the lower and upper branches of the APES. Other details of the numerical results are also analyzed.

  16. Symmetry-adapted excited states for the T{sub 1u}(direct-product)h{sub g} Jahn-Teller system

    SciTech Connect

    Qiu, Q. C.; Dunn, J. L.; Bates, C. A.

    2001-08-15

    Jahn-Teller (JT) systems typically contain a set of equivalent-energy wells in the lowest adiabatic potential-energy surface (APES). Quantum-mechanical tunneling between these wells (the dynamic JT effect) must be allowed for by taking appropriate symmetrized combinations of oscillator-type states associated with the wells. It is important to be able to describe the excited states of such systems for a number of reasons. One particular reason is that they are required for the calculation of second-order vibronic reduction factors, which in turn are useful for modeling experimental data using effective Hamiltonians. In this paper, projection-operator techniques are used to obtain general expressions for the symmetry-adapted excited states of the icosahedral T{sub 1u}(direct-product)h{sub g} JT system for the case of D{sub 5d} minima in the APES. Analytical expressions for the states and their energies for one-phonon excitation are given explicitly. The energies of a selection of states with two-phonon excitations are also obtained and plotted. The results obtained in this paper are applicable to the C{sub 60}{sup -} molecule.

  17. Crystal structure and EPR studies of (cinchonineH 2) 2(CdCl 4)(Cd/CuCl 4) crystals with thermochromic and Jahn-Teller effect

    NASA Astrophysics Data System (ADS)

    Wesełucha-Birczyńska, A.; Oleksyn, B. J.; Śliwiński, J.; Goslar, J.; Hilczer, W.; Hoffmann, S. K.

    2005-09-01

    colour from green to yellow which is characteristic for thermochromic transitions observed in tetrachlorocuprates. The dynamics is related to the Jahn-Teller effect operating in the triplet ground state T 2 of Cu 2+in weakly deformed tetrahedra. It is described as reorientations of the CuCl 4 between two Jahn-Teller distorted configurations, across the energy barrier of about 80 cm -1, resulting in dynamically averaged geometry of the CuCl 4-tetrahedra observed at room temperature.

  18. Jahn-Teller effect in van der Waals complexes; Ar-C6H6+ and Ar-C6D6+

    NASA Astrophysics Data System (ADS)

    van der Avoird, Ad; Lotrich, Victor F.

    2004-06-01

    The two asymptotically degenerate potential energy surfaces of argon interacting with the X˜ 2E1g ground state benzene+ cation were calculated ab initio from the interaction energy of the neutral Ar-benzene complex given by Koch et al. [J. Chem. Phys. 111, 198 (1999)] and the difference of the geometry-dependent ionization energies of the complex and the benzene monomer computed by the outer valence Green's function method. Coinciding minima in the two potential surfaces of the ionic complex occur for Ar on the C6v symmetry axis of benzene+ (the z axis) at ze=3.506 Å. The binding energy De of 520 cm-1 is only 34% larger than the value for the neutral Ar-benzene complex. The higher one of the two surfaces is similar in shape to the neutral Ar-benzene potential, the lower potential is much flatter in the (x,y) bend direction. Nonadiabatic (Jahn-Teller) coupling was taken into account by transformation of the two adiabatic potentials to a two-by-two matrix of diabatic potentials. This transformation is based on the assumption that the adiabatic states of the Ar-benzene+ complex geometrically follow the Ar atom. Ab initio calculations of the nonadiabatic coupling matrix element between the adiabatic states with the two-state-averaged CAS-SCF(5,6) method confirmed the validity of this assumption. The bound vibronic states of both Ar-C6H6+ and Ar-C6D6+ were computed with this two-state diabatic model in a basis of three-dimensional harmonic oscillator functions for the van der Waals modes. The binding energy D0=480 cm-1 of the perdeuterated complex agrees well with the experimental upper bound of 485 cm-1. The ground and excited vibronic levels and wave functions were used, with a simple model dipole function, to generate a theoretical far-infrared spectrum. Strong absorption lines were found at 10.1 cm-1 (bend) and 47.9 cm-1 (stretch) that agree well with measurements. The unusually low bend frequency is related to the flatness of the lower adiabatic potential in the

  19. Pseudo Jahn-Teller origin of ferroelectric instability in BaTiO3 type perovskites: The Green's function approach and beyond

    NASA Astrophysics Data System (ADS)

    Polinger, V.; Garcia-Fernandez, P.; Bersuker, I. B.

    2015-01-01

    The local origin of dipolar distortions in ABO3 perovskite crystals is reexamined by means of a novel approach, the Green's function method augmented by DFT computations. The ferroelectric distortions are shown to be induced by the pseudo Jahn-Teller effect (PJTE). The latter involves vibronic hybridization (admixture) of the ground state to same-spin opposite-parity excited electronic bands. Similar to numerous molecular calculations, the PJT approach provides a deeper insight into the nature of chemical bonding in the octahedral cluster [BO6] and, in particular, reveals the local origin of its polar instability. This allows predicting directly which transition ions can create ferroelectricity. In particular, the necessary conditions are established when an ABO3 perovskite crystal with an electronic dn configuration of the complex ion [BO6] can possess both proper ferroelectric and magnetic properties. Distinguished from the variety of cluster approaches to local properties, the Green's function method includes the influence of the local vibronic-coupling perturbation on the whole crystal via the inter-cell interaction responsible for creation of electronic and vibrational bands. Calculated Green's functions combined with the corresponding numeric estimates for the nine electronic bands, their density of states, and the local adiabatic potential energy surface (APES) confirm the eight-minimum form of this surface and feasibility of the PJT origin of the polar instability in BaTiO3. We show also that multicenter long-range dipole-dipole interactions critically depend on the PJTE largely determining the magnitude of the local dipoles. DFT calculations for the bulk crystal and its clusters confirm that the dipolar distortions are of local origin, but become possible only when their influence on (relaxation of) the whole lattice is taken into account. The results are shown to be in full qualitative and semiquantitative agreement with the experimental data for this

  20. Pseudo Jahn-Teller origin of puckering in cyclohexahomoatomic molecules E6 (E = S, Se, Te) and restoring S6 planar ring configuration

    NASA Astrophysics Data System (ADS)

    Ilkhani, Ali Reza

    2015-10-01

    The pseudo Jahn-Teller effect (PJTE) is employed to explore the origin of the puckering structure of cyclohexasulfur (S6), cyclohexaselenium (Se6) and cyclohexatellurium (Te6) and their nondegenerate and degenerate vibronic excited states and their planar structure instabilities have investigated. The ab initio geometry optimization and frequency calculations show that all these cyclohexahomoatomic molecules chose D6h symmetry in the planar configuration, and according the S6 and Se6 experimental structure, the chair form of the molecules is stable structure. The vibronic coupling between the ground state 1A1g and excited state 1B2g is the cause of chair puckering in all these series compounds and the numerical solutions of the PJTE (1A1g+1B2g)⊗b2g problems describe their instability. The adiabatic potential energy surfaces (APES) cross sections of low-lying electronic states along the b2g puckering normal coordinates have calculated by the state-average complete active space self-consistent field (SA-CASSCF) method. The calculation results show that, the chair puckering instability in the S6 from unstable planar configuration with D6h symmetry to a stable D3d distorted geometry, is stronger than others, whereas it is weaker in Te6. Additionally, coordination two canions (X = H+, He2+) to the S6 chair structure restore the planarity of S6 puckered ring in the S6X2 systems, although the D6h symmetry in S6 planar ring configuration changes to the Cs symmetry in the systems.

  1. High-T c superconductivity in potassium-doped fullerene, K xC 60, via coupled C 60 (pπ) cluster molecular orbitals and dynamic Jahn-Teller coupling

    NASA Astrophysics Data System (ADS)

    Johnson, K. H.; McHenry, M. E.; Clougherty, D. P.

    1991-11-01

    Recently observed superconductivity at 18 K in potassium-doped fullerene, K xC 60, may be due to Cooper pairing of partially occupied icosahedral C 60 cluster t 1u (pπ) molecular orbitals, induced by cooperative dynamic Jahn-Teller coupling of these orbitals to “soft-mode” vibrations of the C 60 molecules, leading to a BCS-like mechanism. Predicted are a nonvanishing isotope effect and Tc increasing to 30 K or more with optimization of doping, and significant effects with pressure.

  2. Nd, Ce(fπ)-O(pπ) Hybridization in Nd2-xCexCuO4 and Dynamic Jahn-Teller Pairing in HIGH-Tc Superconductors

    NASA Astrophysics Data System (ADS)

    Johnson, K. H.; Clougherty, D. P.; McHenry, M. E.

    Hybridization of Nd(fπ) and Ce(fπ) orbitals with composite O(pπ)-O(pπ) bonding/ Cu(dπ*)-O(pπ) antibonding orbitals at the Fermi energy (EF) is shown to promote high-Tc superconductivity in Nd2-xCexCuO4. Dynamic Jahn-Teller coupling of these hybrid molecular orbitals to the lattice leads to Cooper pairing as it does in other high-Tc superconductors, such as La2-xSrxCuO4, where O(pπ) character at EF is dominant.

  3. Charge delocalization and structural response in layered La{sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7}: Enhanced Jahn-Teller distortion in the metallic regime

    SciTech Connect

    Mitchell, J.F.; Argyriou, D.N.; Jorgensen, J.D.

    1996-11-01

    Temperature dependent neutron diffraction studies on melt-grown crystals of the layered compound La{sub 1.2}Sr{sub 1.8}Mn{sub 2}O{sub 7} reveal a dramatic structural response to the onset of ferromagnetism and the coincident insulator-metal transition. Unlike the related manganite perovskites, whose Jahn-Teller distorted octahedra become more regular at temperatures below the metal-insulator transition, the MnO{sub 6} octahedra of this layered material are more severely distorted when the charge is itinerant than when it is localized.

  4. Pseudo Jahn-Teller effect and natural bond orbital analysis of structural properties of tetrahydridodimetallenes M2H4, (M = Si, Ge, and Sn).

    PubMed

    Nori-Shargh, Davood; Mousavi, Seiedeh Negar; Boggs, James E

    2013-02-21

    The structural properties of ethene (1) and tetrahydridodimetallenes M(2)H(4) [M = Si (2), Ge (3), and Sn (4)] have been examined by means of CCSD(T)/Def2-TZVPP, MP4(SDTQ)/Def2-TZVPP, and B3LYP/Def2-TZVPP levels of theory and natural bond orbital analysis (NBO) interpretations. The results obtained showed the expected planar ground state structure for compound 1 (D(2h) symmetry) but trans-bent ground state structures for compounds 2-4 (C(2h) symmetry). The distortions of the high-symmetry configurations of compounds 2-4 are due to the pseudo Jahn-Teller effect (PJTE), which is the only source of instability of high-symmetry configurations in nondegenerate states. The distortions are due to the mixing of the ground A(g) and excited B(2g) states [i.e., HOMO(B(3u)) → LUMO + 3(B(1u)) for compound 1, HOMO(B(3u)) → LUMO + 2(B(1u)) for compound 2, and HOMO(B(3u)) → LUMO + 1(B(1u)) for compounds 3 and 4]. Importantly, the higher-lying B(1g), B(2u), and B(2g) states are not involved in the PJT interactions. The energy gaps between reference states (Δ) in the undistorted configurations decrease from compound 1 to compound 4, and the PJT stabilization energies increase. Therefore, the primary force constant of the ground state in the Q((b2g)) direction (K(0)) decreases from compound 1 to compound 4. This fact can be justified by the valence isoelectronic systems of these compounds (having similar vibronic coupling constants, F). For the purpose of more chemical transparency, the NBO results were analyzed, and their relation to the PJT interactions has been revealed. The NBO analysis showed that stabilization energy associated with π(M-H) (b(u)) → σ*(M═M) (b(u)) electron delocalization (i.e., the mixing of the distorted b(u) molecular orbitals along the b(2g) bending distortions) increases from compound 1 to compound 4. Also, by using the hybridized orbitals obtained, an n parameter is defined. The NBO results revealed that the n values in the mean hybrid orbitals

  5. Numerical adiabatic potentials of orthorhombic Jahn-Teller effects retrieved from ultrasound attenuation experiments. Application to the SrF2:Cr crystal

    NASA Astrophysics Data System (ADS)

    Zhevstovskikh, I. V.; Bersuker, I. B.; Gudkov, V. V.; Averkiev, N. S.; Sarychev, M. N.; Zherlitsyn, S.; Yasin, S.; Shakurov, G. S.; Ulanov, V. A.; Surikov, V. T.

    2016-06-01

    A methodology is worked out to retrieve the numerical values of all the main parameters of the six-dimensional adiabatic potential energy surface (APES) of a polyatomic system with a quadratic T-term Jahn-Teller effect (JTE) from the ultrasound experiments. The method is based on a verified assumption that ultrasound attenuation and speed encounter anomalies when the direction of propagation and polarization of its wave of strain coincides with the characteristic directions of symmetry breaking in the JTE. For the SrF2:Cr crystal, employed as a basic example, we observed anomaly peaks in the temperature dependence of attenuation of ultrasound at frequencies of 50-160 MHz in the temperature interval of 40-60 K for the wave propagating along the [110] direction, for both the longitudinal and the shear modes, the latter with two polarizations along the [001] and [1 1 ¯ 0 ] axes, respectively. We show that these anomalies are due to the ultrasound relaxation by the system of non-interacting Cr2+ JT centers with orthorhombic local distortions. The interpretation of the experimental findings is based on the T2 g⊗(eg+t2 g) JTE problem including the linear and the quadratic terms of vibronic interactions in the Hamiltonian and the same-symmetry modes reduced to one interaction mode. Combining the experimental results with a theoretical analysis, we show that on the complicated six-dimensional APES of this system with three tetragonal, four trigonal, and six orthorhombic extrema points, the latter are global minima, while the former are saddle points, and we estimate numerically all the main parameters of this surface, including the linear and quadratic vibronic coupling constants, the primary force constants, the coordinates of all the extrema points and their energies, the energy barrier between the orthorhombic minima, and the tunneling splitting of the ground vibrational states. To our knowledge, such a based-on-experimental-data numerical reconstruction of the APES

  6. Double Exchange via t2g Orbitals and the Jahn-Teller Effect in Ferromagnetic La0.7Sr0.3CoO3 Probed by Epitaxial Strain

    NASA Astrophysics Data System (ADS)

    Fuchs, D.; Merz, M.; Nagel, P.; Schneider, R.; Schuppler, S.; von Löhneysen, H.

    2013-12-01

    The magnetic exchange in hole-doped ferromagnetic cobaltates is investigated by studying the magnetic and electronic properties of La0.7Sr0.3CoO3 films as a function of epitaxial strain. We found a strong-coupling double exchange mechanism between Co3+(4t2g2eg) and Co4+(3t2g2eg) high-spin states mediated by t2g electrons—in contrast to the moderate coupling provided by the eg exchange in manganites. The strong sensitivity of the Curie temperature TC to the bulk compression can be explained by the small bandwidth of the t2g-derived states. A strain-induced Jahn-Teller effect is likewise observed. The experimental results clarify the magnetic exchange mechanism in the cobaltates.

  7. Investigation of dielectric relaxation, Jahn-Teller distortion, and magnetic ordering in Y substituted Pr1-xYxMnO3 (0.1 ≤ x ≤ 0.4)

    NASA Astrophysics Data System (ADS)

    Yadav, Ruchika; Nair, Harikrishnan S.; Kumar, Amit; Adiga, Shilpa; Bhat, H. L.; Yusuf, S. M.; Elizabeth, Suja

    2015-03-01

    We report structural, magnetic, and dielectric properties of the perovskite compound Pr1-xYxMnO3 (0.1 ≤ x ≤ 0.4) studied using dc magnetization, ac susceptibility, neutron powder diffraction, and dielectric techniques. These compounds crystallize in orthorhombic space group (Pnma) in the temperature range 5-300 K. The Mn-O-Mn bond angle decreases with the Y substitution along with an increase in the Jahn-Teller distortion. The Jahn-Teller distortion for Pr0.9Y0.1MnO3 shows an anomalous change near 50 K, below which it falls sharply. Neutron powder diffraction patterns of all reported compositions at low temperature constitute additional magnetic Bragg peaks that suggest magnetic ordering. Magnetic reflections were indexed in the nuclear lattice with the propagation vector k = (0, 0, 0). Rietveld refinement of powder patterns conform to A type antiferromagnetic ordering where moments are aligned ferromagnetically in a-c plane and coupled nearly antiferromagnetically along b-axis resulting in a net ferromagnetic component along the b-direction. The antiferromagnetic transition temperature was deduced from dc magnetization and ac susceptibility data. The transition temperature decreases by nearly 22 K (from 81 K to 59 K) as yttrium content (x) increases from 0.1 to 0.4. Measurements reveal strong frequency dispersion in dielectric constant and dielectric loss. Activation energy and relaxation time are estimated from the Arrhenius plot. It is further shown that relaxation behaviour is altered with yttrium doping concentration.

  8. Evolution of Jahn-Teller distortion, transport and dielectric properties with doping in perovskite NdFe1-xMnxO3 (0 ≤ x ≤ 1) compounds.

    PubMed

    Chakraborty, Tirthankar; Yadav, Ruchika; Elizabeth, Suja; Bhat, H L

    2016-02-21

    We have carried out dielectric and transport measurements in NdFe1-xMnxO3 (0 ≤ x ≤ 1) series of compounds and studied the variation of activation energy due to a change in Mn concentration. Despite similar ionic radii in Mn(3+) and Fe(3+), large variation is observed in the lattice parameters and a crossover from dynamic to static Jahn-Teller distortion is discernible. The Fe/Mn-O-Fe/Mn bond angle on the ab plane shows an anomalous change with doping. With an increase in the Mn content, the bond angle decreases until x = 0.6; beyond this, it starts rising until x = 0.8 and again falls after that. A similar trend is observed in activation energies estimated from both transport and dielectric relaxation by assuming a small polaron hopping (SPH) model. Impedance spectroscopy measurements delineate grain and grain boundary contributions separately both of which follow the SPH model. Frequency variation of the dielectric constant is in agreement with the modified Debye law from which relaxation dispersion is estimated. PMID:26817614

  9. Jahn-Teller distortion around Fe{sup 4+} in Sr(Fe{sub x}Ti{sub 1-x})O{sub 3-{delta}} from x-ray absorption spectroscopy, x-ray diffraction, and vibrational spectroscopy

    SciTech Connect

    Vracar, M.; Merkle, R.; Kotomin, E. A.; Maier, J.; Kuzmin, A.; Purans, J.; Mathon, O.

    2007-11-01

    Sr(Fe{sub x}Ti{sub 1-x})O{sub 3-{delta}} perovskites (strontium titanate ferrite solid solution) with well-defined oxygen stoichiometry have been studied as a function of iron concentration by x-ray diffraction, Fe and Ti K-edge x-ray absorption spectroscopy (XAS), and vibrational (Raman and infrared) spectroscopy. In reduced Sr(Fe{sub x}Ti{sub 1-x})O{sub 3-x/2} samples, the analysis of the Fe K-edge extended x-ray absorption fine structure indicates the expected presence of oxygen vacancies V{sub O}{sup {center_dot}}{sup {center_dot}} in the first coordination shell of Fe{sup 3+} ions. In oxidized Sr(Fe{sub x}Ti{sub 1-x})O{sub 3} samples, the combination of XAS and vibrational spectroscopy results yields strong indications for the presence of a Jahn-Teller distortion around Fe{sup 4+} ions, which is most pronounced for x{approx_equal}0.03 and decreases for higher iron concentrations.

  10. Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba2M(VO4)2(OH), M = V(3+), Mn(3+), and Fe(3+), with Interesting Jahn-Teller and Spin-Liquid Behavior.

    PubMed

    Sanjeewa, Liurukara D; McGuire, Michael A; Garlea, Vasile O; Hu, Longyu; Chumanov, George; McMillen, Colin D; Kolis, Joseph W

    2015-07-20

    A new series of transition metal vanadates, namely, Ba2M(VO4)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 Ba2V(VO4)2(OH) is monoclinic in space group P21/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). The other structures are similar and consist of one-dimensional trans edge-shared distorted octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba2Mn(VO4)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. Single-crystal temperature-dependent magnetic studies on Ba2V(VO4)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. PMID:26154989

  11. Pseudo Jahn-Teller origin of instability of planar configurations of hexa-heterocycles. Application to compounds with 1,2- and 1,4-C4X2 skeletons (X = O, S, Se, Te)

    NASA Astrophysics Data System (ADS)

    Ilkhani, Ali R.; Hermoso, Willian; Bersuker, Isaac B.

    2015-10-01

    The driving force of symmetry breaking in planar molecular-ring systems in nondegenerate states is the pseudo Jahn-Teller effect (PJTE), and the knowledge of the mechanism of the latter allows one to manipulate the molecular properties, in particular, by restoring the planar configuration. We explore the PJTE induced structural nonplanarity in a series of 12 hexa-heterocycles with a C4X2 skeleton, 1,2- and 1,4-dichalcogenins with X = O, S, Se, Te, and a variety of ligands (H, F, Cl, Br). All the structures are optimized in both distorted equilibrium and unstable planar configurations, and the vibrational frequencies of the latter are evaluated. Then the energy profiles of the ground and several excited states in the planar configuration along the coordinate of instability are calculated, the excited states producing the instability of the ground state via the PJTE are revealed, and the vibronic coupling constants are estimated by means of fitting the solutions of the secular equations to the corresponding energy profiles.

  12. Relaxation Phenomenon in the Formation of the C-Type Orbital-Ordered State in the Simple Perovskite Manganite Sr1-xNdxMnO3

    NASA Astrophysics Data System (ADS)

    Inoue, Yasuhide; Sato, Hiroki; Koyama, Yasumasa

    2016-02-01

    The formation of the C-type orbital-ordered (COO) state from the disordered cubic (DC) state in Sr1-xNdxMnO3 (SNMO) with the simple perovskite structure has been examined mainly by transmission electron microscopy. As the COO state has tetragonal I4/mcm symmetry, its formation is associated with the cubic-to-tetragonal structural transition. It was found that, when SNMO samples were cooled down from the DC state, the R25-type rotational displacement of MnO6 octahedra was first induced, together with the symmetry change into the tetragonal I4/mcm structure. The C-type orbital ordering then appeared due to the induction of the Jahn-Teller distortion as a response of a lattice system to this orbital ordering. Because no symmetry change occurred in the latter case, the Jahn-Teller distortion can be regarded as a dilatational distortion. One interesting feature is that the appearance of the dilatational Jahn-Teller distortion led to a nanometer-scale banded structure, characterized by an alternating array of two tetragonal variants with different c/a values. In addition, the formation of the COO state from the DC state exhibited a time-relaxation phenomenon. The origin of this relaxation phenomenon is also discussed here in terms of the competition between the tetragonal spontaneous strain for the rotational displacement and the dilatational Jahn-Teller distortion for orbital ordering.

  13. Glass formation in microgravity

    NASA Technical Reports Server (NTRS)

    Ray, C. S.; Day, D. E.

    1987-01-01

    An account is given of containerless glass-forming experiments conducted aboard the Space Shuttle in 1985, using a single-axis acoustic levitator furnace apparatus. An attempt was made to obtain quantitative evidence for the suppression of heterogeneous nucleation/crystallization in containerless melts under microgravity conditions, as well as to study melt homogenization in the absence of gravity-driven convection and assess the feasibility of laser fusion target glass microsphere preparation with a microgravity apparatus of the present type. A ternary calcia-gallia-silica glass thus obtained indicated a 2-3-fold increase in glass-formation tendency for this material composition in microgravity, by comparison with 1g.

  14. Nonpercolative nature of the metal-insulator transition and persistence of local Jahn-Teller distortions in the rhombohedral regime of La1 -xCaxMnO3

    NASA Astrophysics Data System (ADS)

    Shatnawi, Mouath; Bozin, Emil S.; Mitchell, J. F.; Billinge, Simon J. L.

    2016-04-01

    Evolution of the average and local crystal structure of Ca-doped LaMnO3 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 MnO6 octahedra across the OR transition at TS˜720 K. The study utilized explicit two-phase PDF structural modeling, revealing that away from TMI 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 CaMnO3. The results hence do not support the percolative scenario for the MI transition in La1 -xCaxMnO3 based on PS, and question its ubiquity in the manganites. In contrast to LaMnO3 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. Their magnitude and subnanometer spatial extent remain unchanged.

  15. Non percolative nature of the metal-insulator transition and persistence of local Jahn-Teller distortions in the rhombohedral regime of La1-xCaxMnO3

    DOE PAGESBeta

    Shatnawi, Mouath; Bozin, Emil S.; Mitchell, J. F.; Billinge, Simon J. L.

    2016-04-25

    Evolution of the average and local crystal structure of Ca-doped LaMnO3 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 MnO6 octahedra across the OR transition at TS~720 K. The study utilizedmore » explicit two-phase PDF structural modeling, revealing that away from TMI 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 CaMnO3. The results hence do not support the percolative scenario for the MI transition in La1–xCaxMnO3 based on PS, and question its ubiquity in the manganites. In contrast to LaMnO3 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

  16. Photoelectron spectroscopic study of the E ⊗ e Jahn-Teller effect in the presence of a tunable spin-orbit interaction. III. Two-state excitonic model accounting for observed trends in the X~ 2E ground state of CH3X+ (X=F, Cl, Br, I) and CH3Y (Y=O, S)

    NASA Astrophysics Data System (ADS)

    Grütter, M.; Qian, X.; Merkt, F.

    2012-08-01

    Open-shell molecules in doubly degenerate 2E electronic states are subject to the E ⊗ e Jahn-Teller effect and spin-orbit interactions. The rotational structure of the ground vibrational level of the tildeX^+ 2E ground state of CH3F+ has been observed by high-resolution photoelectron spectroscopy. In contrast to what is observed in other members of the isoelectronic families {CH}_3{X}^+ ({X}={Cl, Br, I}) and {CH}_3{Y} ({Y}={O, S}), the spin-orbit interaction does not lead to a splitting of the ground state of CH3F+. Observed trends in the spectra of the tildeX 2E ground states of these molecules are summarized. Whereas certain trends, such as the reduction of the observable effects of the Jahn-Teller interactions and the increase of the spin-orbit splitting with increasing nuclear charge of X and Y are easily understood, other trends are more difficult to explain, such as the much reduced spin-orbit splitting in {CH}_3{F}^+ compared to {CH}_3{O}. A simple two-state excitonic model is used to account for the trends observed within the series of the methyl-halide radical cations and also the similarities and differences between {CH}_3{F}^+ and the isoelectronic {CH}_3{O} radical. Within this model, the electron hole in the 2E ground states of {CH}_3{X}^+ and {CH}_3{Y} is described in terms of contributions from the halogenic (or chalcogenic) px, y orbitals and the pyramidal-methylic (e) orbitals. This model enables a global, semi-quantitative description of the combined effects of the Jahn-Teller and spin-orbit interactions in these molecules and also a simple interpretation of the spin-orbit-coupling reduction factor ζe.

  17. Pseudo Jahn-Teller distortion for a tricyclic carbon sulfide (C6S8) and its suppression in S-oxygenated dithiine (C4H4(SO2)2)

    NASA Astrophysics Data System (ADS)

    Pratik, Saied Md.; Chowdhury, Chandra; Bhattacharjee, Rameswar; Jahiruddin, Sk.; Datta, Ayan

    2015-10-01

    The tricyclic carbon-sulfide, C6S8 molecule containing two S-atoms in the 1,4-position of the central six-membered ring and one disulfide (Ssbnd S) and one thione (Cdbnd S) bond on the five membered rings on its either side (1) possesses a "butterfly flapping" type distorted ground state in the gas-phase and also in β-phase of the crystal. For the isolated molecule, better consideration of the S…S non-bonding interactions in the dithiine ring in the bent form at the M06-2X/6-31+G(d,p) level leads to a significant barrier for inversion of 2.4 kcal/mol which is 2-3 times more than that previously obtained by Weber and Dolg at the B3LYP/cc-pVTZ level due to underestimation of dispersion interactions at the B3LYP level. The origin of the distortion leading to lowering of symmetry for 1 (C2h → C2) is traced to vibronic mixing between the ground state (Ag) and the low lying excited states of Au symmetry through the au normal mode, a (1Ag + 1Au + 2Au + 3Au) × au pseudo Jahn-Teller effect (PJTE) problem. Based on fitting of the ground state APES to the lowest root of the 4 × 4 secular determinant, we calculate the linear vibronic coupling constants (F0i) between the relevant states. Similar in class to 1, the S-oxygenated derivative of dithiine, C4H4(SO2)2 (2) unlike most other dithiines, remains planar. The absence of the butterfly-type puckered structure in 2 is traced to the enhanced gap (Δ0) and very small vibronic coupling (F01) between the ground and PJT active state along the au distortion which suppress the PJT instability. Considering the separation of the occupied molecular orbital (OMO) and unoccupied molecular orbitals (UMO) energy levels provide a qualitative understanding for the contrasting behavior of 1 and 2. In effect, the PJT effect is shown to be a fruitful and general tool to describe the presence or lack of molecular distortion.

  18. Coupling of Jahn-Teller and tilting distortions in high temperature structural phase transition of the Ca0.2Sr0.6Nd0.2Mn1-xCrxO3; 0 ≤ x ≤ 0.2 perovskites

    NASA Astrophysics Data System (ADS)

    Tan, Teck-Yee; Zhou, Qingdi; Kennedy, Brendan J.; Gu, Qinfen; Kimpton, Justin A.

    2012-04-01

    The manganite perovskites Ca0.2Sr0.6Nd0.2Mn1-xCrxO3, 0 ≤ x ≤ 0.2, have been synthesized by solid state methods, and their room temperature structures determined using synchrotron X-ray powder diffraction. At room temperature, the oxides have a tetragonal structure in space group I4/mcm. Whereas the BO6 groups in the x = 0 sample are noticeably distorted those in the x = 0.2 sample are more regular as a consequence of the progressive removal of the Jahn-Teller type distortion. High temperature diffraction measurements of the x = 0, 0.1 and 0.2 samples reveal that Cr doping has little effect on the transition to the cubic Pm3¯m structure that occurs around 450 °C. Cr doping does however significantly alter the spontaneous strains in the oxides as a consequence of the cooperative Jahn-Teller distortion.

  19. The Jahn-Teller effect in the excitation and emission spectra of Ba/sub 6/Y/sub 2/Al/sub 4/O/sub 15/:Sn/sup 2+/ and Ba/sub 2/YAlO/sub 5/:Sn/sup 2+/

    SciTech Connect

    Smets, B.M.J.; Verlijsdonk, J.G.; Rutten, J. )

    1989-04-01

    Luminescence measurements are presented for Sn/sup 2+/ doped Ba/sub 6/Y/sub 2/Al/sub 4/O/sub 15/ and Ba/sub 2/YAlO/sub 5/. In these compounds several crystallographic sites are available for Sn/sup 2+/. The luminescence properties of Sn/sup 2+/ in one of these sites can be accounted for by assuming that the Jahn-Teller effect is acting on the /sup 3/P/sub 1/ excited state of the Sn/sup 2+/ ion. The vibronic interaction results in the occurrence of two emission bands in the case of Ba/sub 6/Y/sub 2/Al/sub 4/O/sub 15/:Sn/sup 2+/.

  20. Investigation of dielectric relaxation, Jahn-Teller distortion, and magnetic ordering in Y substituted Pr{sub 1−x}Y{sub x}MnO{sub 3} (0.1 ≤ x ≤ 0.4)

    SciTech Connect

    Yadav, Ruchika Elizabeth, Suja; Nair, Harikrishnan S.; Kumar, Amit; Yusuf, S. M.; Adiga, Shilpa

    2015-03-07

    We report structural, magnetic, and dielectric properties of the perovskite compound Pr{sub 1−x}Y{sub x}MnO{sub 3} (0.1 ≤ x ≤ 0.4) studied using dc magnetization, ac susceptibility, neutron powder diffraction, and dielectric techniques. These compounds crystallize in orthorhombic space group (Pnma) in the temperature range 5–300 K. The Mn-O-Mn bond angle decreases with the Y substitution along with an increase in the Jahn-Teller distortion. The Jahn-Teller distortion for Pr{sub 0.9}Y{sub 0.1}MnO{sub 3} shows an anomalous change near 50 K, below which it falls sharply. Neutron powder diffraction patterns of all reported compositions at low temperature constitute additional magnetic Bragg peaks that suggest magnetic ordering. Magnetic reflections were indexed in the nuclear lattice with the propagation vector k = (0, 0, 0). Rietveld refinement of powder patterns conform to A type antiferromagnetic ordering where moments are aligned ferromagnetically in a–c plane and coupled nearly antiferromagnetically along b-axis resulting in a net ferromagnetic component along the b-direction. The antiferromagnetic transition temperature was deduced from dc magnetization and ac susceptibility data. The transition temperature decreases by nearly 22 K (from 81 K to 59 K) as yttrium content (x) increases from 0.1 to 0.4. Measurements reveal strong frequency dispersion in dielectric constant and dielectric loss. Activation energy and relaxation time are estimated from the Arrhenius plot. It is further shown that relaxation behaviour is altered with yttrium doping concentration.

  1. Formation of Nanoporous Glass Layer

    NASA Astrophysics Data System (ADS)

    Grigoras, Kestutis; Franssila, Sami

    2004-01-01

    Porous layers have been formed in Pyrex glass by reactive ion etching (RIE). Chromium is used as an etch mask. Different etch gases (SF6, CF4/Ar) have been used, and depending on flow ratio, etch time and applied power, a dense array of high aspect ratio glass pillars with submicrometer dimensions was obtained instead of a smooth channel bottom. The pillars were about 500nm tall and 50 100nm in cross-section. The formation of porous layers is explained by the effect of mask material re-deposition during the plasma etching. Porous glass layers could have applications in chromatographic separations or microchemicalsample concentrators.

  2. Competitive formation of glasses and glass-matrix composites

    SciTech Connect

    Lu, Zhao Ping; Ma, D.; Liu, Chain T; Chang, Y. Austin

    2007-01-01

    By systematically investigating the effect of chemical composition on the competitive formation of glasses in various systems, we attempt to address two long-standing scientific puzzles upon metallic glasses, i.e., (i) which composition is the best for forming glasses and glass-matrix composites and (ii) what determines the easy glass-forming composition range in a given alloy system. Our findings have led to the construction of a qualitative microstructure selection map, which is useful for guiding the design of bulkier metallic glasses and glass-matrix composites. In addition, our analysis demonstrates that the classical kinetic treatment of glass formation is insufficient; to analyze glass formation properly, it is necessary to go beyond simple assumptions of single polymorphic solidification during crystallization.

  3. From spin induced ferroelectricity to dipolar glasses: Spinel chromites and mixed delafossites

    SciTech Connect

    Maignan, A.

    2012-11-15

    Magnetoelectric multiferroics showing coupling between polarization and magnetic order are attracting much attention. For instance, they could be used in memory devices. Metal-transition oxides are provided several examples of inorganic magnetoelectric multiferroics. In the present short review, spinel and delafossite chromites are described. For the former, an electric polarization is evidenced in the ferrimagnetic state for ACr{sub 2}O{sub 4} polycrystalline samples (A=Ni, Fe, Co). The presence of a Jahn-Teller cation such as Ni{sup 2+} at the A site is shown to yield larger polarization values. In the delafossites, substitution by V{sup 3+} at the Cr or Fe site in CuCrO{sub 2} (CuFeO{sub 2}) suppresses the complex antiferromagnetic structure at the benefit of a spin glass state. The presence of cation disorder, probed by transmission electron microscopy, favors relaxor-like ferroelectricity. The results on the ferroelectricity of ferrimagnets and insulating spin glasses demonstrate that, in this research field, transition-metal oxides are worth to be studied. - Graphical abstract: Electric polarization as a function of temperature is measured up to T{sub C} in three chromite ferrimagnetic spinels. Largest values are reached for spinels with Jahn-Teller cations at the A site (Ni or Fe). Highlights: Black-Right-Pointing-Pointer Electric polarization is evidenced in the ferrimagnetic state of the chromite spinels. Black-Right-Pointing-Pointer Jahn-Teller cations at the A site of these spinels lead to larger polarization values. Black-Right-Pointing-Pointer Vanadium substituted at the Cr (or Fe) site of delafossites changes the antiferromagnetic state to spin glass. Black-Right-Pointing-Pointer Electric polarization is not the result of magnetic ordering but magnetic disordering in Cr or Fe delafossites. Black-Right-Pointing-Pointer Relaxor-type ferroelectricity or spin induced ferroelectricity can be observed in the delafossites.

  4. Glass transition and stable glass formation of tetrachloromethane

    NASA Astrophysics Data System (ADS)

    Chua, Y. Z.; Tylinski, M.; Tatsumi, S.; Ediger, M. D.; Schick, C.

    2016-06-01

    Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 Tg. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 103. The glass transition temperature of liquid-cooled tetrachloromethane is determined as Tg ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation.

  5. Glass transition and stable glass formation of tetrachloromethane.

    PubMed

    Chua, Y Z; Tylinski, M; Tatsumi, S; Ediger, M D; Schick, C

    2016-06-28

    Physical vapor deposition (PVD) has been used to prepare organic glasses with very high kinetic stability and it has been suggested that molecular anisotropy is a prerequisite for stable glass formation. Here we use PVD to prepare glasses of tetrachloromethane, a simple organic molecule with a nearly isotropic molecular structure. In situ AC nanocalorimetry was used to characterize the vapor-deposited glasses. Glasses of high kinetic stability were produced by deposition near 0.8 Tg. The isothermal transformation of the vapor-deposited glasses into the supercooled liquid state gave further evidence that tetrachloromethane forms glasses with high kinetic stability, with the transformation time exceeding the structural relaxation time of the supercooled liquid by a factor of 10(3). The glass transition temperature of liquid-cooled tetrachloromethane is determined as Tg ≈ 78 K, which is different from previously reported values. The frequency dependence of the glass transition was also determined and the fragility was estimated as m ≈ 118. The successful formation of PVD glasses of tetrachloromethane which have high kinetic stability argues that molecular asymmetry is not a prerequisite for stable glass formation. PMID:27369523

  6. Theories of glass formation and glass transition

    SciTech Connect

    Langer, James S.

    2014-03-19

    This key-issues review is a plea for a new focus on simpler and more realistic models of glass-forming fluids. It seems to me that we have too often been led astray by sophisticated mathematical models that beautifully capture some of the most intriguing features of glassy behavior, but are too unrealistic to provide bases for predictive theories. As illustrations of what I mean, the first part of this article is devoted to brief summaries of imaginative, sensible, but disparate and often contradictory ideas for solving glass problems. Almost all of these ideas remain alive today, with their own enthusiastic advocates. I then describe numerical simulations, mostly by H Tanaka and coworkers, in which it appears that very simple, polydisperse systems of hard disks and spheres develop long range, Ising-like, bond-orientational order as they approach glass transitions. Finally, a summary of my recent proposal that topologically ordered clusters of particles, in disordered environments, tend to become aligned with each other as if they were two-state systems, and thus produce the observed Ising-like behavior. Neither Tanaka’s results nor my proposed interpretation of them fit comfortably within any of the currently popular glass theories.

  7. Effects of dynamic Jahn-Teller distortions by Raman spectroscopy in the layered CMR manganite La{sub 2{minus}2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7}, x = 0.36

    SciTech Connect

    Bordallo, H.N.; Argyriou, D.N.; Mitchell, J.F.; Strouse, G.F.

    1998-12-01

    The close interplay among charge, spin, and lattice degrees of freedom in the colossal magnetoresistive (CMR) manganite oxides is believed to play an important role in the transport mechanism in these itinerant ferromagnets. While the work on CMR materials has concentrated on the 3D perovskite manganites, the discovery of the layered compounds La{sub 2{minus}2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7} as another class of CMR oxides provides a rich opportunity to explore the relationship between structure and transport properties on varying length and time scales in reduced dimensions. The crystal structure of the layered CMR compounds La{sub 2{minus}2x}Sr{sub 1+2x}Mn{sub 2}O{sub 7} is comprised of perovskite bilayers of corner-linked MnO{sub 6} octahedra forming infinite sheets. Doping of divalent cations such as Sr{sup 2+} gives rise to a mixed valent system were Jahn-Teller (JT) active Mn{sup 3+} and JT-inactive Mn{sup 4+} co-exist on the lattice. Among the current theoretical models of transport in the three-dimensional perovskite materials is the role of JT. This transport mechanism plays a fundamental role above the Curie temperature (T{sub c}). Indeed, localized lattice distortions have been observed experimentally above T{sub c} in the (La,Ca)MnO{sub 3} perovskite system. In this communication, the authors report resonant Raman spectroscopic measurements on a micro-crystalline sample of La{sub 1.28}Sr{sub 1.72}Mn{sub 2}O{sub 7} (x = 0.36). The measurements suggest discrete phonon modes for the Mn{sup 3+} and Mn{sup 4+} lattice sites, which may arise from either dynamic or static localization and the presence of Mn{sup 2+} defects in the lattice.

  8. Bubble formation in additive manufacturing of glass

    NASA Astrophysics Data System (ADS)

    Luo, Junjie; Gilbert, Luke J.; Peters, Daniel C.; Bristow, Douglas A.; Landers, Robert G.; Goldstein, Jonathan T.; Urbas, Augustine M.; Kinzel, Edward C.

    2016-05-01

    Bubble formation is a common problem in glass manufacturing. The spatial density of bubbles in a piece of glass is a key limiting factor to the optical quality of the glass. Bubble formation is also a common problem in additive manufacturing, leading to anisotropic material properties. In glass Additive Manufacturing (AM) two separate types of bubbles have been observed: a foam layer caused by the reboil of the glass melt and a periodic pattern of bubbles which appears to be unique to glass additive manufacturing. This paper presents a series of studies to relate the periodicity of bubble formation to part scan speed, laser power, and filament feed rate. These experiments suggest that bubbles are formed by the reboil phenomena why periodic bubbles result from air being trapped between the glass filament and the substrate. Reboil can be detected using spectroscopy and avoided by minimizing the laser power while periodic bubbles can be avoided by a two-step laser melting process to first establish good contact between the filament and substrate before reflowing the track with higher laser power.

  9. Spin-singlet state formation in the cluster Mott insulator GaNb4S8 studied by μSR and NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Waki, T.; Kajinami, Y.; Tabata, Y.; Nakamura, H.; Yoshida, M.; Takigawa, M.; Watanabe, I.

    2010-01-01

    Muon spin relaxation (μSR) and nuclear magnetic resonance experiments revealed that the spin-singlet state with an excitation gap of ˜200K is realized from S=1/2Nb4 tetrahedral clusters in a cluster Mott insulator GaNb4S8 . The intercluster cooperative phenomenon to the singlet state at TS=32k is triggered by intracluster Jahn-Teller type structural instability developed from ˜3TS . Referring to the lattice symmetry, the formation of Nb8 octamer ( Nb4-Nb4 bond) is suggested.

  10. A simplified model for glass formation

    NASA Technical Reports Server (NTRS)

    Uhlmann, D. R.; Onorato, P. I. K.; Scherer, G. W.

    1979-01-01

    A simplified model of glass formation based on the formal theory of transformation kinetics is presented, which describes the critical cooling rates implied by the occurrence of glassy or partly crystalline bodies. In addition, an approach based on the nose of the time-temperature-transformation (TTT) curve as an extremum in temperature and time has provided a relatively simple relation between the activation energy for viscous flow in the undercooled region and the temperature of the nose of the TTT curve. Using this relation together with the simplified model, it now seems possible to predict cooling rates using only the liquidus temperature, glass transition temperature, and heat of fusion.

  11. Dimethylammonium copper formate [(CH3)2NH2]Cu(HCOO)3: A metal-organic framework with quasi-one-dimensional antiferromagnetism and magnetostriction

    NASA Astrophysics Data System (ADS)

    Wang, Zhenxing; Jain, Prashant; Choi, Kwang-Yong; van Tol, Johan; Cheetham, Anthony K.; Kroto, Harold W.; Koo, Hyun-Joo; Zhou, Haidong; Hwang, Jungmin; Choi, Eun Sang; Whangbo, Myung-Hwan; Dalal, Naresh S.

    2013-06-01

    Metal-organic frameworks (MOFs) can exhibit many interesting properties such as multiferroic behavior, dipolar glass, gas storage, and protonic conductivity. Here we report that dimethylammonium copper formate (DMACuF) [(CH3)2NH2]Cu(HCOO)3, a cation templated nonporous MOF with perovskite topology, exhibits strong one-dimensional (1D) antiferromagnetism with a Néel temperature, TN, of 5.2 K. These conclusions are derived from detailed magnetic susceptibility, heat capacity, dielectric constant, and high-frequency electron paramagnetic resonance measurements as well as density functional theory (DFT) calculations. The magnetic susceptibility exhibits a broad maximum at ˜50 K, suggesting low-dimensional magnetism; heat capacity measurements show a Néel temperature of 5.2 K. The magnetization versus field data at 1.8 K shows a spin-flop transition at Hsf ˜ 1.7 T. The ratio TN/J=6.5×10-2, where J is the near-neighbor exchange constant (77.4 K), and the small value (2 K) of the interchain coupling suggests that DMACuF is close to an ideal 1D magnet. In this three-dimensional crystal lattice, the 1D magnetic behavior is made possible by the Jahn-Teller distortion of the 3d9 Cu2+ ions. Temperature dependence of the electron paramagnetic resonance field and the linewidth exhibits critical broadening for temperatures below 50 K, following a behavior quite characteristic of 1D spin systems. DFT calculations show that [(CH3)2NH2]Cu(HCOO)3 has a magnetic structure in which 1D antiferromagnetic chains parallel to the c direction are weakly coupled ferromagnetically, supporting the thermomagnetic and EPR results. Dielectric measurements under applied magnetic fields of 0-7 T reveal a kink at the TN, a clear indication of magnetostriction behavior.

  12. The formation kinetics of lunar glasses

    NASA Technical Reports Server (NTRS)

    Uhlmann, D. R.; Handwerker, C. A.; Onorato, P. I. K.; Salomaa, R.; Goncz, D.

    1978-01-01

    The kinetic treatment of crystallization and glass formation, involving the construction of time-temperature-transformation curves (TTT) corresponding to a given degree of crystallinity, is extended to permit the description of crystallization of a body initially cooled to a glassy state. The key assumption is that if at any time and temperature a crystallite is smaller than the critical size corresponding to that temperature, it will melt completely and can be ignored in any further calculations of the crystal distribution. This approach is used to predict the temperature of maximum crystallization rate for the matrix composition of lunar breccia 67975; results are shown to be in excellent agreement with experiment. Theoretical results obtained for anorthite indicate a barrier to nucleation in the range of 75 kT when the ratio of the undercooling to the liquidus temperature is 0.2. Measured nucleation barriers for the 67975 matrix composition are in the range of 42 to 45 kT.

  13. Glass formation and local topological instability of atomic structure

    SciTech Connect

    Egami, T.

    1997-12-31

    A direct connection between the local topology of the atomic structure of liquids and glasses and thermodynamic quantities through the atomic level stresses is suggested for metallic alloys. In particular the role of local topological instability in the phase transformation involving liquid and glass will be discussed. It is pointed out that a single local geometrical criterion can explain various phase transformations, such as melting, glass transition, and glass formation by solid state reaction and liquid quenching.

  14. Theories of glass formation and the glass transition

    NASA Astrophysics Data System (ADS)

    Langer, J. S.

    2014-04-01

    This key-issues review is a plea for a new focus on simpler and more realistic models of glass-forming fluids. It seems to me that we have too often been led astray by sophisticated mathematical models that beautifully capture some of the most intriguing features of glassy behavior, but are too unrealistic to provide bases for predictive theories. As illustrations of what I mean, the first part of this article is devoted to brief summaries of imaginative, sensible, but disparate and often contradictory ideas for solving glass problems. Almost all of these ideas remain alive today, with their own enthusiastic advocates. I then describe numerical simulations, mostly by H Tanaka and coworkers, in which it appears that very simple, polydisperse systems of hard disks and spheres develop long range, Ising-like, bond-orientational order as they approach glass transitions. Finally, I summarize my recent proposal that topologically ordered clusters of particles, in disordered environments, tend to become aligned with each other as if they were two-state systems, and thus produce the observed Ising-like behavior. Neither Tanaka's results nor my proposed interpretation of them fit comfortably within any of the currently popular glass theories.

  15. Crystal nucleation and glass formation in metallic alloy melts

    NASA Technical Reports Server (NTRS)

    Spaepen, F.

    1984-01-01

    Homogeneous nucleation, containerless solidification, and bulk formation of metallic glasses are discussed. Homogeneous nucleation is not a limiting factor for metallic glass formation at slow cooling rates if the reduced glass transition temperature is high enough. Such glasses can be made in bulk if heterogeneous nucleants are removed. Containerless processing eleminates potential sources of nucleants, but as drop tube experiments on the Pd-Si alloys show, the free surface may still be a very effective heterogeneous nucleant. Combination of etching and heating in vacuum or fluxing can be effective for cleaning fairly large ingots of nucleants. Reduced gravity processing has a potentially useful role in the fluxing technique, for example to keep large metallic ingots surrounded by a low density, low fluidity flux if this proved difficult under ground conditions. For systems where heterogeneous nucleants in the bulk of the ingot need gravity to segregate to the flux-metal interface, reduced gravity processing may not be appropriate for bulk glass formation.

  16. Glass formation and physical properties of chalcogenide glasses in Ge-S-Pb system

    NASA Astrophysics Data System (ADS)

    Qu, Guoshun; Lin, Changgui; Li, Zhuobin; Zhai, Sumin; Gu, Shaoxuan; Tao, Haizheng; Xu, Tiefeng

    2014-03-01

    Chalcogenide glasses based on Ge-S-Pb system were prepared, and the compositional dependence of their physic-chemical properties and glass structure were investigated. Up to 23 mol% Pb can be dissolved in this glass system and the glass-formation region like a small isolated island was found. The effect of the introduction of Pb on the glass structure is discussed by employing Raman spectra. It is shown that the substitution of Pb for Ge decreases the number of [GeS4] and [S3Ge-GeS3] units, leading to the variation of properties, such as Tg, H‧, and Hv. The knowledge of this structure-properties relationship of Ge-S-Pb glasses would be of significance to select or to design suitable host glass for optoelectronic applications.

  17. Glass Formation Ability and Kinetics of the Gd55Al20Ni25 Bulk Metallic Glass

    NASA Astrophysics Data System (ADS)

    Jo, Chol-Lyong; Xia, Lei; Ding, Ding; Dong, Yuan-Da

    2006-03-01

    We report a new bulk glass-forming alloy Gd55Al20Ni25. The bulk sample of the alloy is prepared in the shape of rods in diameter 2 mm by suction casting. The rod exhibits typical amorphous characteristics in the x-ray diffraction pattern, paramagnetic property at 300 K, distinct glass transition and multi-step crystallization behaviour in differential scanning calorimetry traces. The glass formation ability of the alloy is investigated by using the reduced glass transition temperature Trg and the parameter γ. Kinetics of glass transition and primary crystallization is also studied. The fragility parameter m obtained from the Vogel-Fulcher-Tammann dependence of glass transition temperature Tg on ln phi (phi is the heating rate) classifies the bulk metallic glasses into the intermediate category according to Angell's classification.

  18. Formation of bulk metallic glass by fluxing

    NASA Technical Reports Server (NTRS)

    Kui, H. W.; Turnbull, D.; Greer, A. L.

    1984-01-01

    Bulk specimens (0.4-4 g mass) of the alloy Pd40Ni40P20 have been undercooled consistently to the glass state, with no detectable superficial crystallinity, in a molten flux of dehydrated boron oxide. The minimum dimension of the most massive glass specimen, so formed, was 1.0 cm. The absence of crystallinity in the specimens was confirmed by X-ray diffraction, scanning electron microscopy, and calorimetry.

  19. Tuning polymer glass formation with additives and ions

    NASA Astrophysics Data System (ADS)

    Simmons, David

    2015-03-01

    A polymer's glass transition and associated dynamic and mechanical properties are among the most important factors determining its performance in engineering applications. For this reason, decades of research have aimed to establish methods of tuning polymers' glass formation behavior. Here I describe molecular simulations providing new insight into two approaches to altering a polymer's glass formation behavior: introduction of small-molecule diluents; and introduction of charged moieties to form an ionomer. In the first case, we explore how diluent molecular properties control modifications to the host polymer's glass transition and mechanical response. Results indicate that diluents can induce a rich array of effects, necessitating development of an expanded classification beyond the usual plasticizer/antiplasticizer dichotomy. In the second case, simulations indicate that ionomer glass formation is indistinguishable from that in polymer nanocomposites, in contrast to the longstanding assumption that covalent grafting of chains to ionic aggregates in these systems leads to a qualitatively distinct effect. Taken together, these results provide new guidance towards the rational understanding and control of polymer glass-formation in a range of materials. In collaboration with Jayachandra Hari Mangalara and Dihui Ruan, The University of Akron. This material is based in part on work supported by the W.M. Keck Foundation.

  20. Formation of Apollo 15 green glass beads

    NASA Astrophysics Data System (ADS)

    Arndt, J.; Engelhardt, W. V.; Gonzalez-Cabeza, I.; Meier, B.

    1984-11-01

    The results of an analysis of the thermal history of green glass beads extracted from breccia 15427 in the north rim of Spur crater are reported. The vitrophyric beads were found to have lattice, fiber and polyhedral olivine morphologies. Cooling, heating, and crystallization experiments were performed with synthetically produced glass beads with the same compositions as the natural beads. The data indicated that the breccia samples cooled from 1000-1050 C at 1 C/sec, less than in free flight conditions. The homogeneity of the beads rules out solid rock impacts. The required cooling rate suggests that the process occurred in an atmosphere of volcanic gases. The suspension would have had to last at least 10 minutes.

  1. Formation and durability of hydrated layers for several oxide glasses

    SciTech Connect

    Nishii, Junji; Akai, Tomoko; Yamashita, Masaru; Yamanaka, Hiroshi; Wakabayashi, Hajimu

    1995-12-31

    Formations and durabilities of hydrated layers were compared between a soda-aluminosilicate (NAS), a soda-lime-aluminosilicate (NCAS) and a soda-lime-alumino-borosilicate (NCABS) glasses. The first step of the study was to prepare the optically transparent hydrated layers on the surface of specimens by an autoclave (400 C, 20 kgf/cm{sup 2}) treatment. Distributions of OH groups in hydrated layers were analyzed by an etch sectioning and FTIR measurement. The rates of hydration of the glasses were in the order NAS {much_gt} NCAS > NCABS. The hydration of the NCABS glass, which is a modified nuclear waste glass, required the treatment longer than those of the NAS and NCAS glasses. In the second step, the authors investigated the durabilities of hydrated layers by immersing the specimens into a distilled water at 100 C. The dissolutions of hydrated layers were confirmed for each glass. The dissolution rates of hydrated layers were in the order NCAS > NCABS {much_gt} NAS. It has become apparent by an XPS analysis that the highest durability of the hydrated NAS glass was due to the formation of a sodium free Al{sub 2}O{sub 3}-SiO{sub 2} layer on the surface. The hydrated layer of the NCAS glass, while the sodium ions were almost leached out during immersion, dissolved to water most quickly than those of other glasses. In the hydrated layer of the NCABS glass, a half amount of sodium and boron ions remained and inhibited the dissolution of hydrated layer.

  2. Study of the glass formation of high temperature superconductors

    NASA Technical Reports Server (NTRS)

    Ethridge, Edwin C.; Kaukler, William F.; Rolin, Terry

    1992-01-01

    A number of compositions of ceramic oxide high T(sub c) superconductors were elevated for their glass formation ability by means of rapid thermal analysis during quenching, optical, and electron microscopy of the quenched samples, and with subsequent DSC measurements. Correlations between experimental measurements and the methodical composition changes identified the formulations of superconductors that can easily form glass. The superconducting material was first formed as a glass; then, with subsequent devitrification, it was formed into a bulk crystalline superconductor by a series of processing methods.

  3. Glass formation, properties and structure of soda-yttria-silica glasses

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.

    1992-01-01

    The glass formation region of the soda yttria silicate system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cu cm, a refractive index of 1.50 to 1.60, a coefficient of thermal expansion of 7 x 10(exp -6)/C, softening temperatures between 500 and 780 C, and Vickers hardness values of 3.7 to 5.8 GPa. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to study the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.

  4. Glass formation, properties, and structure of soda-yttria-silicate glasses

    NASA Technical Reports Server (NTRS)

    Angel, Paul W.; Hann, Raiford E.

    1991-01-01

    The glass formation region of the soda yttria silicate system was determined. The glasses within this region were measured to have a density of 2.4 to 3.1 g/cu cm, a refractive index of 1.50 to 1.60, a coefficient of thermal expansion of 7 x 10(exp -6)/C, softening temperatures between 500 and 780 C, and Vickers hardness values of 3.7 to 5.8 GPa. Aqueous chemical durability measurements were made on select glass compositions while infrared transmission spectra were used to study the glass structure and its effect on glass properties. A compositional region was identified which exhibited high thermal expansion, high softening temperatures, and good chemical durability.

  5. Quantifying the origin of metallic glass formation

    NASA Astrophysics Data System (ADS)

    Johnson, W. L.; Na, J. H.; Demetriou, M. D.

    2016-01-01

    The waiting time to form a crystal in a unit volume of homogeneous undercooled liquid exhibits a pronounced minimum τX* at a `nose temperature' T* located between the glass transition temperature Tg, and the crystal melting temperature, TL. Turnbull argued that τX* should increase rapidly with the dimensionless ratio trg=Tg/TL. Angell introduced a dimensionless `fragility parameter', m, to characterize the fall of atomic mobility with temperature above Tg. Both trg and m are widely thought to play a significant role in determining τX*. Here we survey and assess reported data for TL, Tg, trg, m and τX* for a broad range of metallic glasses with widely varying τX*. By analysing this database, we derive a simple empirical expression for τX*(trg, m) that depends exponentially on trg and m, and two fitting parameters. A statistical analysis shows that knowledge of trg and m alone is therefore sufficient to predict τX* within estimated experimental errors. Surprisingly, the liquid/crystal interfacial free energy does not appear in this expression for τX*.

  6. Quantifying the origin of metallic glass formation

    PubMed Central

    Johnson, W. L.; Na, J. H.; Demetriou, M. D.

    2016-01-01

    The waiting time to form a crystal in a unit volume of homogeneous undercooled liquid exhibits a pronounced minimum τX* at a ‘nose temperature' T* located between the glass transition temperature Tg, and the crystal melting temperature, TL. Turnbull argued that τX* should increase rapidly with the dimensionless ratio trg=Tg/TL. Angell introduced a dimensionless ‘fragility parameter', m, to characterize the fall of atomic mobility with temperature above Tg. Both trg and m are widely thought to play a significant role in determining τX*. Here we survey and assess reported data for TL, Tg, trg, m and τX* for a broad range of metallic glasses with widely varying τX*. By analysing this database, we derive a simple empirical expression for τX*(trg, m) that depends exponentially on trg and m, and two fitting parameters. A statistical analysis shows that knowledge of trg and m alone is therefore sufficient to predict τX* within estimated experimental errors. Surprisingly, the liquid/crystal interfacial free energy does not appear in this expression for τX*. PMID:26786966

  7. Quantifying the origin of metallic glass formation.

    PubMed

    Johnson, W L; Na, J H; Demetriou, M D

    2016-01-01

    The waiting time to form a crystal in a unit volume of homogeneous undercooled liquid exhibits a pronounced minimum τX* at a 'nose temperature' T(*) located between the glass transition temperature Tg, and the crystal melting temperature, TL. Turnbull argued that τX* should increase rapidly with the dimensionless ratio trg=Tg/TL. Angell introduced a dimensionless 'fragility parameter', m, to characterize the fall of atomic mobility with temperature above Tg. Both trg and m are widely thought to play a significant role in determining τX*. Here we survey and assess reported data for TL, Tg, trg, m and τX* for a broad range of metallic glasses with widely varying τX*. By analysing this database, we derive a simple empirical expression for τX*(trg, m) that depends exponentially on trg and m, and two fitting parameters. A statistical analysis shows that knowledge of trg and m alone is therefore sufficient to predict τX* within estimated experimental errors. Surprisingly, the liquid/crystal interfacial free energy does not appear in this expression for τX*. PMID:26786966

  8. Potassium Chloride Nanowire Formation Inside a Microchannel Glass Array

    SciTech Connect

    Zhang, Daqing; Moore, Sam; Wei, Jiang; Alkhateeb, Abudullah I.; Gangadean, Dev; Mahmood, Hasan; Lantrips, Justin; McIlroy, David N.; LaLonde, Aaron D.; Norton, M G.; Young, James S.; Wang, Chong M.

    2005-06-27

    The synthesis of KCl nanowires has been achieved by atomic layer deposition inside high aspect ratio channels of microchannel glass. The average diameter of the KCl nanowires is 250 nm, with a minimum observed diameter of 50 nm, and lengths up to 5 {micro}m. The Cl precursor was TaCl5, while the source of K was determined to be impurities in the microchannel glass substrate. The process for KCl nanowire formation is a three-step chemical process that simultaneously etches K from the substrate concomitant with the formation of chlorine gas. It is postulated that the curvature of the channels may influence the diameters of the KCl nanowires.

  9. Formation of monatomic metallic glasses through ultrafast liquid quenching

    NASA Astrophysics Data System (ADS)

    Zhong, Li; Wang, Jiangwei; Sheng, Hongwei; Zhang, Ze; Mao, Scott X.

    2014-08-01

    It has long been conjectured that any metallic liquid can be vitrified into a glassy state provided that the cooling rate is sufficiently high. Experimentally, however, vitrification of single-element metallic liquids is notoriously difficult. True laboratory demonstration of the formation of monatomic metallic glass has been lacking. Here we report an experimental approach to the vitrification of monatomic metallic liquids by achieving an unprecedentedly high liquid-quenching rate of 1014 K s-1. Under such a high cooling rate, melts of pure refractory body-centred cubic (bcc) metals, such as liquid tantalum and vanadium, are successfully vitrified to form metallic glasses suitable for property interrogations. Combining in situ transmission electron microscopy observation and atoms-to-continuum modelling, we investigated the formation condition and thermal stability of the monatomic metallic glasses as obtained. The availability of monatomic metallic glasses, being the simplest glass formers, offers unique possibilities for studying the structure and property relationships of glasses. Our technique also shows great control over the reversible vitrification-crystallization processes, suggesting its potential in micro-electromechanical applications. The ultrahigh cooling rate, approaching the highest liquid-quenching rate attainable in the experiment, makes it possible to explore the fast kinetics and structural behaviour of supercooled metallic liquids within the nanosecond to picosecond regimes.

  10. Formation of monatomic metallic glasses through ultrafast liquid quenching.

    PubMed

    Zhong, Li; Wang, Jiangwei; Sheng, Hongwei; Zhang, Ze; Mao, Scott X

    2014-08-14

    It has long been conjectured that any metallic liquid can be vitrified into a glassy state provided that the cooling rate is sufficiently high. Experimentally, however, vitrification of single-element metallic liquids is notoriously difficult. True laboratory demonstration of the formation of monatomic metallic glass has been lacking. Here we report an experimental approach to the vitrification of monatomic metallic liquids by achieving an unprecedentedly high liquid-quenching rate of 10(14) K s(-1). Under such a high cooling rate, melts of pure refractory body-centred cubic (bcc) metals, such as liquid tantalum and vanadium, are successfully vitrified to form metallic glasses suitable for property interrogations. Combining in situ transmission electron microscopy observation and atoms-to-continuum modelling, we investigated the formation condition and thermal stability of the monatomic metallic glasses as obtained. The availability of monatomic metallic glasses, being the simplest glass formers, offers unique possibilities for studying the structure and property relationships of glasses. Our technique also shows great control over the reversible vitrification-crystallization processes, suggesting its potential in micro-electromechanical applications. The ultrahigh cooling rate, approaching the highest liquid-quenching rate attainable in the experiment, makes it possible to explore the fast kinetics and structural behaviour of supercooled metallic liquids within the nanosecond to picosecond regimes. PMID:25119235

  11. RADIATION EFFECTS ON TRANSPORT AND BUBBLE FORMATION IN SILICATE GLASSES

    EPA Science Inventory

    The objective of the research is to discover the molecular details of chemistry induced by -, γ-, and neutron-irradiation of silicate glasses. The ionization and ballistic effects of radiation will be studied from the viewpoint of defect formation and transport properties. D...

  12. The kinetics of lunar glass formation, revisited

    NASA Technical Reports Server (NTRS)

    Klein, L. C.; Uhlmann, D. R.

    1976-01-01

    The nucleation frequency of Lunar Composition 70019, a lithified soil breccia from the center of a small crater in the Taurus-Littrow Valley, is determined using a relation that describes nucleation throughout the volume of a liquid together with measurements of the time required at temperatures of 780 to 930 C to obtain sensibly crystalline bodies. Curves indicating the time required at a given temperature to reach a particular fraction crystallized are shown to have the general form predicted by kinetic analysis. Nucleation frequencies are evaluated by applying such analysis to a curve representing the transition between glassy material and material with a sensible degree of crystallinity. The results obtained are found to be in excellent agreement with the values expected from the classical theory of homogeneous nucleation, indicating that such nucleation represents the dominant contribution to crystal formation, at least over the range of undercoolings covered (250 to 400 C).

  13. The formation of crystals in glasses containing rare earth oxides

    NASA Astrophysics Data System (ADS)

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-01

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd2O3-22.7CeO2-11.7La2O3-10.9PrO2-1.3Eu2O3-1.3Gd2O3-8.1Sm2O3-4.8Y2O3 with a baseline glass of composition 60.2SiO2-16.0B2O3-12.6Na2O-3.8Al2O3-5.7CaO-1.7ZrO2. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La2O3 and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO5) and oxyapatite (Ca2La8Si6O26) were found in glasses containing La2O3, while oxyapatite (Ca2La8Si6O26 and NaNd9Si6O26) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (TL) of the glasses containing 5%, 10% and 15% La2O3 were 800°C, 959°C and 986°C, respectively; while TL was 825°C, 1059°C and 1267°C for glasses with 5%, 10% and 15% addition of mixed rare earth oxides. The component coefficients TB2O3, TSiO2, TCaO, and TRE2O3 were also evaluated using a recently published study.

  14. Radiation Effects on Transport and Bubble Formation in Silicate Glasses

    SciTech Connect

    Trifunac, A.D.; Shkrob, I.A.; Werst, D.W.

    2001-12-31

    Using advanced magnetic resonance spectroscopies and small-cluster modeling, atomic structure of radiation-induced point defects in alkali borate, silicate, and borosilicate glasses is fully characterized. It is shown that in boron-containing glasses, most of these point defects are electrons/holes trapped by cation/anion vacancies, such as O1 - - O3 + valence-alternation pairs. In microscopically phase-separated borosilicate glasses, radiation-induced defects are found to cluster at the interface between the borate and silicate phases. Reaction and diffusion dynamics of defect-annealing interstitial hydrogen atoms in boron and silica oxide glasses are studied. The yield of radiolytic O2 is estimated. This oxygen is shown to be the final product of triplet exciton decay. Plausible mechanisms for the oxygen bubble formation are put forward. Two practical conclusions relevant for the EMSP mission are made: First, the yield of radiolytic oxygen is shown to be too low to interfere with the storage of vitrified radioactive waste in the first 10 Kyr. Second, microscopic phase separation is demonstrated to increase both the chemical and radiation stability of borosilicate glass.

  15. Glass formation behavior of an isolated polymer chain

    NASA Astrophysics Data System (ADS)

    Merling, Weston; Mileski, Jack; Simmons, David

    2015-03-01

    A single polymer chain in isolation logically represents the extreme limit of nanoconfinement with respect to segmental dynamics and glass formation. Work in thin polymer films suggests that one should expect a large Tg suppression in such systems. However, recent dielectric relaxation measurements of isolated chains of P2VP on a silica substrate found bulk-like Tg in this system, apparently raising questions about the nature of observed nanoconfinement effects on the glass transition. Here we describe simulations of glass formation in an isolated polymer chain, both free-floating and deposited on a substrate. Results indicate that free-floating isolated polymer chains exhibit a depression in the dynamic glass transition temperature equivalent to more than 100K in polystyrene units. However, when a chain is deposited on a substrate with sufficiently favorable surface interactions, bulk-like dynamics can be recovered due to competition between the free-surface and adsorbed interface. When this compensation effect is taken account, these results indicate that the observation of bulk-like dynamics in isolated P2VP chains on a silica substrate is consistent with observations of large Tg suppressions in polymer films supported by less attractive substrates. This material is based upon work supported by the National Science Foundation under Grant No. DMR1310433.

  16. Glass formation and properties in the gallia-calcia system

    NASA Technical Reports Server (NTRS)

    Whichard, G.; Day, D. E.

    1984-01-01

    The critical cooling rate for glass formation was measured for five compositions in the Ga2O3-CaO system and varied from a low of (315 + or - 85) C/s for a eutectic melt containing 37.5 mol pct Ga2O3 to a high of (840 + or - 60) C/s for a melt containing 52 mol pct Ga2O3. The density and refractive index both increased with increasing Ga2O3 content, but the crystallization temperature and microhardness varied only slightly. The IR spectra of these glasses suggest that both GaO4 tetrahedra and GaO6 octahedra are present.

  17. 'Nose method' of calculating critical cooling rates for glass formation

    NASA Technical Reports Server (NTRS)

    Weinberg, Michael C.; Uhlmann, Donald R.; Zanotto, Edgar D.

    1989-01-01

    The use of the so-called 'nose method' for computing critical cooling rates for glass formation is examined and compared with other methods, presenting data for the glass-forming systems SiO2, GeO2, and P2O5. It is shown that, for homogeneous crystallization, the nose-method will give an overestimate of Rc, a conclusion which was drawn after assessing the enfluence of a range of values for the parameters which control crystal growth and nucleation. The paper also proposes an alternative simple procedure (termed the 'cutoff method') for computing critical cooling rates from T-T-T diagrams, which was shown in the SiO2 and GeO2 systems to be superior to the nose method.

  18. The formation of crystals in glasses containing rare earth oxides

    SciTech Connect

    Fadzil, Syazwani Mohd; Hrma, Pavel; Crum, Jarrod; Siong, Khoo Kok; Ngatiman, Mohammad Fadzlee; Said, Riduan Mt

    2014-02-12

    Korean spent nuclear fuel will reach the capacity of the available temporary storage by 2016. Pyroprocessing and direct disposal seems to be an alternative way to manage and reuse spent nuclear fuel while avoiding the wet reprocessing technology. Pyroprocessing produces several wastes streams, including metals, salts, and rare earths, which must be converted into stabilized form. A suitable form for rare earth immobilization is borosilicate glass. The borosilicate glass form exhibits excellent durability, allows a high waste loading, and is easy to process. In this work, we combined the rare earths waste of composition (in wt%) 39.2Nd{sub 2}O{sub 3}–22.7CeO{sub 2}–11.7La{sub 2}O{sub 3}–10.9PrO{sub 2}–1.3Eu{sub 2}O{sub 3}–1.3Gd{sub 2}O{sub 3}–8.1Sm{sub 2}O{sub 3}–4.8Y{sub 2}O{sub 3} with a baseline glass of composition 60.2SiO{sub 2}–16.0B{sub 2}O{sub 3}–12.6Na{sub 2}O–3.8Al{sub 2}O{sub 3}–5.7CaO–1.7ZrO{sub 2}. Crystallization in waste glasses occurs as the waste loading increases. It may produce complicate glass processing and affect the product quality. To study crystal formation, we initially made glasses containing 5%, 10% and 15% of La{sub 2}O{sub 3} and then glasses with 5%, 10% and 15% of the complete rare earth mix. Samples were heat-treated for 24 hours at temperatures 800°C to 1150°C in 50°C increments. Quenched samples were analyzed using an optical microscope, scanning electron microscope with energy dispersive spectroscopy, and x-ray diffraction. Stillwellite (LaBSiO{sub 5}) and oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26}) were found in glasses containing La{sub 2}O{sub 3}, while oxyapatite (Ca{sub 2}La{sub 8}Si{sub 6}O{sub 26} and NaNd{sub 9}Si{sub 6}O{sub 26}) precipitated in glasses with additions of mixed rare earths. The liquidus temperature (T{sub L}) of the glasses containing 5%, 10% and 15% La{sub 2}O{sub 3} were 800°C, 959°C and 986°C, respectively; while T{sub L} was 825°C, 1059°C and 1267°C for glasses

  19. Glass Formation, Chemical Properties and Surface Analysis of Cu-Based Bulk Metallic Glasses

    PubMed Central

    Qin, Chunling; Zhao, Weimin; Inoue, Akihisa

    2011-01-01

    This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu–Hf–Ti–(Mo, Nb, Ta, Ni) and Cu–Zr–Ag–Al–(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance. PMID:21731441

  20. New Model for Agglutinitic Glass Formation from LSCC Data

    NASA Technical Reports Server (NTRS)

    Pieters, C. M.; Taylor, L. A.

    2003-01-01

    Since the return of the first lunar samples it has been well known that glass-welded aggregates (agglutinates) accumulate in lunar soil as the result of multiple processes, many of which are driven by micrometeorite impacts. The proportion of agglutinates increases with increasing exposure to the space environment, and for an individual soil the proportion of agglutinates also increases with decreasing particle size. Detailed chemical and petrographic analyses of a suite of mare soils and their agglutinate constituents prepared by the Lunar Soil Characterization Consortium appeared to confirm the "Fusion of the Finest Fraction" model for agglutinate formation (or F3) proposed by Papike et al. However, recent LSCC data for highland soils are not consistent with the F3 model and alternate models for agglutinate formation must be revisited. Instead, we suggest differential melting of soil species may be more consistent with the full range of soil data to date.

  1. Smectite Formation from Basaltic Glass Under Acidic Conditions on Mars

    NASA Technical Reports Server (NTRS)

    Peretyazhko, T. S.; Sutter, B.; Morris, R. V.; Agresti, D. G.; Le, L.; Ming, D. W.

    2015-01-01

    Massive deposits of phyllosilicates of the smectite group, including Mg/Fe-smectite, have been identified in Mars's ancient Noachian terrain. The observed smectite is hypothesized to form through aqueous alteration of basaltic crust under neutral to alkaline pH conditions. These pH conditions and the presence of a CO2-rich atmosphere suggested for ancient Mars were favorable for the formation of large carbonate deposits. However, the detection of large-scale carbonate deposits is limited on Mars. We hypothesized that smectite deposits may have formed under acidic conditions that prevented carbonate precipitation. In this work we investigated formation of saponite at a pH of approximately 4 from Mars-analogue synthetic Adirondack basaltic glass of composition similar to Adirondack class rocks located at Gusev crater. Hydrothermal (200º Centigrade) 14 day experiments were performed with and without 10 millimoles Fe(II) or Mg under anoxic condition [hereafter denoted as anoxic_Fe, anoxic_Mg and anoxic (no addition of Fe(II) or Mg)] and under oxic condition [hereafter denoted as oxic (no addition of Fe(II) or Mg)]. Characterization and formation conditions of the synthesized saponite provided insight into the possible geochemical conditions required for saponite formation on Mars.

  2. Examining the role of canister cooling conditions on the formation of nepheline from nuclear waste glasses

    SciTech Connect

    Christian, J. H.

    2015-09-01

    Nepheline (NaAlSiO₄) crystals can form during slow cooling of high-level waste (HLW) glass after it has been poured into a waste canister. Formation of these crystals can adversely affect the chemical durability of the glass. The tendency for nepheline crystallization to form in a HLW glass increases with increasing concentrations of Al₂O₃ and Na₂O.

  3. Formation and segregation of copper, cadmium, and silver chlorides in photochromic glass

    SciTech Connect

    Mashir, Yu.I.

    1995-11-01

    The mechanism of formation and segregation of copper, cadmium, and silver chlorides in photochromic glass is considered. The possibility of obtaining photochromic glass with copper and cadmium halogenides with highly concentrated light-sensitive phases is established. The glass ensures substantial induced absorption in a thin layer (up to 0.3 mm).

  4. Apparatus and process to enhance the uniform formation of hollow glass microspheres

    DOEpatents

    Schumacher, Ray F

    2013-10-01

    A process and apparatus is provided for enhancing the formation of a uniform population of hollow glass microspheres. A burner head is used which directs incoming glass particles away from the cooler perimeter of the flame cone of the gas burner and distributes the glass particles in a uniform manner throughout the more evenly heated portions of the flame zone. As a result, as the glass particles are softened and expand by a released nucleating gas so as to form a hollow glass microsphere, the resulting hollow glass microspheres have a more uniform size and property distribution as a result of experiencing a more homogenous heat treatment process.

  5. 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≤Baglasses containing copper dopants.

  6. Universal non-Landau, self-organized, lattice disordering percolative dopant network sub-T(c) phase transition in ceramic superconductors.

    PubMed

    Phillips, J C

    2009-09-15

    Ceramic superconductors (cuprates, pnictides, etc.) exhibit universal features in both T(c)(max) and in their planar lattice disordering measured by EXAFS, as reflected by three phase transitions. The two highest temperature transitions are known to be associated with formation of Jahn-Teller pseudogaps and superconductive gaps, with corresponding Landau order parameters, but no new gap is associated with the third transition below T(c), and its origin is mysterious. It is argued that the third subT(c) transition is a dopant glass transition, which is remarkably similar to topological transitions previously observed in chalcogenide and oxide alloy network glasses (like window glass). PMID:19805211

  7. Probing Toluene and Ethylbenzene Stable Glass Formation using Inert Gas Permeation

    SciTech Connect

    Smith, R. Scott; May, Robert A.; Kay, Bruce D.

    2015-09-01

    Inert gas permeation is used to investigate the formation of stable glasses of toluene and ethylbenzene. The effect of deposition temperature (Tdep) on the kinetic stability of the vapor deposited glasses is determined using Kr desorption spectra from within sandwich layers of either toluene or ethylbenzene. The results for toluene show that the most stable glass is formed at Tdep = 0.92 Tg, although glasses with a kinetic stability within 50% of the most stable glass were found with deposition temperatures from 0.85 to 0.95 Tg. Similar results were found for ethylbenzene, which formed its most stable glass at 0.91 Tg and formed stable glasses from 0.81 to 0.96 Tg. These results are consistent with recent calorimetric studies and demonstrate that the inert gas permeation technique provides a direct method to observe the onset of molecular translation motion that accompanies the glass to supercooled liquid transition.

  8. Bulk Formation of Metallic Glasses and Amorphous Silicon from the Melt

    NASA Technical Reports Server (NTRS)

    Spaepen, F.

    1985-01-01

    By using metallic glass compositions with a high relative glass transition temperature, such as Pd40Ni40P20, homogeneous nucleation also becomes negligible. Large (5g) masses of this alloys were obtained using a molten B2O3 flux. Presently, bulk glass formation in iron based glasses is being investigated. It is expected that if an undercooling of about 250K can be achieved in a Ge or Si melt, formation of the amorphous semiconductor phase (rather than the crystal) may be kinetically favored. The volumetric behavior of undercooled liquid Ga droplet dispersion is investigated by dilatometry. A theoretical model (both analytical and numerical) was developed for transient nucleation in glass forming melts. The model, originally designed for isothermal conditions, was extended to continuous quenching. It is being applied to glass formation in various metallic and oxide systems. A further refinement will be the inclusion of diffusion controlled interfacial rearrangements governing the growth of the crystal embryos.

  9. Itinerant ferromagnetism to insulating spin glass in SrRu{sub 1-x}Cu{sub x}O{sub 3} (0 {<=} x {<=} 0.3)

    SciTech Connect

    Mangalam, R.V.K.; Sundaresan, A.

    2009-03-05

    The ferromagnetic metallic oxide, SrRuO{sub 3} (T{sub C} {approx} 165 K) undergoes structural, magnetic and metal-insulator transitions upon substitution of Cu at the Ru-site. For x = 0.2 in SrRu{sub 1-x}Cu{sub x}O{sub 3}, the structure becomes a tetragonal with the space group I4/mcm and there is a signature of both ferromagnetic (T{sub C} = 65 K) and antiferromagnetic (T{sub N} = 32 K) ordering due to possible magnetic phase separation. The antiferromagnetism arises due to short range ordering of Cu- and Ru-moments. Jahn-Teller distortion of (Ru,Cu)-O{sub 6} octahedra indicates that the copper ions are in 2+ oxidation state with t{sub 2g}{sup 6}e{sub g}{sup 3} electronic configuration. For x {>=} 0.1, narrowing of Ru-4d bandwidth by the substitution of Cu ions results in semiconducting behavior. For x = 0.3, the ac and dc susceptibility measurements indicate a spin glass behavior. The origin of spin glass behavior has been attributed to competing ferromagnetic and antiferromagnetic interactions.

  10. Effects of phosphate buffer in parenteral drugs on particle formation from glass vials.

    PubMed

    Ogawa, Toru; Miyajima, Makoto; Wakiyama, Naoki; Terada, Katsuhide

    2013-01-01

    The characteristics of inorganic particles generated in glass vials filled with phosphate buffer solutions were investigated. During storage, particles were visually detected in the phosphate buffer solution in particular glass vials which pass compendial tests of containers for injectable drugs. These particles were considered to be different from ordinal glass delamination, which has been reported in a number of papers because the particles were mainly composed of Al, P and O, but not Si. The formation of the particles accelerated at higher storage temperatures. Among the surface treatments tested for the glass vials, sulfur treatment showed a protective effect on the particle formation in the vials, whereas the SiO(2) coating did not have any protective effects. It was found that the elution ratio of Al and Si in the solution stored in the glass vials after the heating was similar to the ratio of Al and Si in borosilicate glass. However, the Al concentration decreased during storage (5°C, 6 months), and consequently, particle formation was observed in the solution. Adding citrate, which is a chelating agent for Al, effectively suppressed the particle formation in the heated solution. When 50 ppb and higher concentrations of Al ion were added to the phosphate buffer solution, the formation of white particles containing Al, P and O was detected. It is suggested that a phosphate buffer solution in a borosilicate glass vial has the ability to form particles due to interactions with the Al that is eluted from the glass during storage. PMID:23420583

  11. Pregrowth and Biofilm formation of Bacillus subtilis on Glass Studied via AFM, SEM and Optical Microsopy

    NASA Astrophysics Data System (ADS)

    Stutzman, Sydney; Otte, Michelle; Calabrese, Joseph; Senevirathne, Reshani; Senevirathne, Indrajith

    2014-03-01

    Lock Haven University of Pennsylvania - Research into surface adhesion properties and the selectivity of bacteria towards glass will provide a better understanding of biofilm formation and how this formation will in turn effect hospital and laboratory settings. Investigation was focused on quantifying the selectivity of non-pathogenic B. subtilis - on soda lime glass substrates. Standardized Corning 2947-75X25 microscope glass slides were used as the surface for bacterial attachment and facilitation of preliminary growth and formation of biofilms. Observations will be discussed both quantitatively and qualitatively. Structure morphology was investigated via Atomic Force Microscopy, Scanning Electron Microscopy and complemented with Optical Microscopy.

  12. Formation of metallic nanostructures on the surface of ion- exchange glass by focused electron beam

    NASA Astrophysics Data System (ADS)

    Komissarenko, F. E.; Zhukov, M. V.; Mukhin, I. S.; Golubok, A. O.; Sidorov, A. I.

    2015-11-01

    This paper presents a new method for formation of metallic nanostructures on the surface of ion-exchange glass. The method is based on the interaction of a focused electron beam with ions in ion-exchange glass. In experiments nanostructures with different shapes were obtained, depending on the electrons irradiation conditions.

  13. Colloid formation during the corrosion of SRL 200 glass

    SciTech Connect

    Buck, E.C.; Bates, J.K.; Feng, X.

    1994-05-01

    Nonradioactive SRL 200S glass and fully radioactive SRL 200R glass were reacted at glass surface areas to leachant volume (SA/V) ratios of 20,000, 2,000, and 340 m{sup {minus}1} for times varying from several days to a few years. The particles present in the leachates of these tests have been examined by analytical electron microscopy (AEM). The major colloidal clay phase was identified as a smectite clay from its characteristic electron diffraction pattern. The clay colloids eventually disappear from the solution and return to the glass; the time at which this occurs depends on the SA/V. Uranium silicate particles and calcium-bearing phases were also sometimes found in the leachates.

  14. THE IMPACT OF KINETICS ON NEPHELINE FORMATION IN NUCLEAR WASTE GLASSES

    SciTech Connect

    Amoroso, J.

    2011-03-07

    Sixteen glass compositions were selected to study the potential impacts of the kinetics of nepheline formation in high-level nuclear waste (HLW) glass. The chosen compositions encompassed a relatively large nepheline discriminator (ND) range, 0.40-0.66, and included a relatively broad range, and amount of, constituents including high aluminum and high boron concentrations. All glasses were fabricated in the laboratory and subsequently exposed to six different cooling treatments. The cooling treatments consisted of three 'stepped' profiles and their corresponding 'smooth' profiles. Included in the cooling treatment was the Defense Waste Processing Facility (DWPF) canister centerline cooling (CCC) profile in addition to a 'faster' and a 'slower' total cooling line. After quenching and heat treating, x-ray diffraction confirmed the type and amount of any resultant crystallization. The target compositions were shown to be consistent with the measured compositions. Two quenched glasses and several treated glasses exhibited minor amounts of spinel and spinel-like phases. Nepheline was not observed in any of the quenched glasses but was observed in many of the treated glasses. The amount of nepheline ranged from approximately 2wt% to 30wt% for samples cooled over shorter times and longer times respectively. Differences were observed in the amount of nepheline crystallization after smooth and stepped cooling and increased with total cooling time. In some glasses, nepheline crystallization appeared to be directly proportional to total cooling time while the total amount of nepheline crystallization varied, suggesting that the nepheline crystallization rate was independent of (or at least faster than) cooling rate but, varied depending on the glass composition. On the contrary, in another glass, nepheline crystallization appeared to be inversely proportional to cooling rate. The high alumina glasses, predicted to form nepheline according to the ND, did not precipitate

  15. Entropy Theory of Polymer Glass-Formation in Variable Spatial Dimension

    NASA Astrophysics Data System (ADS)

    Xu, Wen-Sheng; Douglas, Jack; Freed, Karl

    The importance of packing frustration is broadly appreciated to be an important aspect of glass-formation. Recently, great interest has focused on using spatial dimensionality () as a theoretical tool for exploring this and other aspects of glass-forming liquids. We explore glass-formation in variable based on the generalized entropy theory, a synthesis of the Adam-Gibbs model with direct computation of the configurational entropy of polymer fluids using an established analytical statistical thermodynamic model. We find that structural relaxation in the fluid state asymptotically becomes Arrhenius in the limit and that the fluid transforms upon sufficient cooling above a critical dimension near into a dense amorphous state with a finite positive residual configurational entropy. The GET also predicts the variation with of measures of fragility and of the characteristic temperatures of glass-formation demarking the onset , middle , and end , of the broad glass transition. Direct computations of the isothermal compressibility and thermal expansion coefficient, which are physical measures of packing frustration, demonstrate that these fluid properties strongly correlate with the fragility of glass-formation. Back to three dimensions, we deduce apparently universal relationships between , a measure of the breadth of the glass-formation and both the isothermal compressibility and thermal expansion coefficient of polymer melts at .

  16. Glass formation in a mixture of hard disks and hard ellipses.

    PubMed

    Xu, Wen-Sheng; Duan, Xiaozheng; Sun, Zhao-Yan; An, Li-Jia

    2015-06-14

    We present an event-driven molecular dynamics study of glass formation in two-dimensional binary mixtures composed of hard disks and hard ellipses, where both types of particles have the same area. We demonstrate that characteristic glass-formation behavior appears upon compression under appropriate conditions in such systems. In particular, while a rotational glass transition occurs only for the ellipses, both types of particles undergo a kinetic arrest in the translational degrees of freedom at a single density. The translational dynamics for the ellipses is found to be faster than that for the disks within the same system, indicating that shape anisotropy promotes the translational motion of particles. We further examine the influence of mixture's composition and aspect ratio on the glass formation. For the mixtures with an ellipse aspect ratio of k = 2, both translational and rotational glass transition densities decrease with increasing the disk concentration at a similar rate, and hence, the two glass transitions remain close to each other at all concentrations investigated. By elevating k, however, the rotational glass transition density diminishes at a faster rate than the translational one, leading to the formation of an orientational glass for the ellipses between the two transitions. Our simulations imply that mixtures of particles with different shapes emerge as a promising model for probing the role of particle shape in determining the properties of glass-forming liquids. Furthermore, our work illustrates the potential of using knowledge concerning the dependence of glass-formation properties on mixture's composition and particle shape to assist in the rational design of amorphous materials. PMID:26071719

  17. Anomalous structure-property relationships in metallic glasses through pressure-mediated glass formation

    NASA Astrophysics Data System (ADS)

    Ding, Jun; Asta, Mark; Ritchie, Robert O.

    2016-04-01

    Metallic glasses are commonly found to favor denser packing structures and icosahedral order in experiments, simulations, and theoretical models. Here we present a molecular dynamics simulation study of Cu-Zr metallic glasses, prepared through a pressure-mediated pathway. The resulting glasses exhibit anomalous structure-property relationships; these glasses are less energetically stable, concomitant with a denser atomic packing and a significant increase in icosahedral short-range order. The enhanced icosahedral order is shown to be accompanied by a pressure-mediated change in chemical short-range order. The results demonstrate that in amorphous alloys (nonmonatomic), theoretical frameworks of the two-order-parameter model must be generalized to account for chemical degrees of freedom.

  18. Glass formation, glass fragility, molecular mobility and longevity of germplasm stored at cryogenic temperatures.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Cryogenic storage of living specimens presupposes that viability can be maintained indefinitely when aqueous glasses are formed and maintained. Indeed, constrained mobility within glassy matrices is a thermodynamic barrier to many chemical and physical reactions. However, impeding molecular mobili...

  19. Computation assisted design of favored composition for ternary Mg-Cu-Y metallic glass formation.

    PubMed

    Wang, Q; Li, J H; Liu, B X

    2015-06-14

    With the aid of ab initio calculations, a realistic interatomic potential was constructed for the Mg-Cu-Y ternary system under the proposed formalism of smoothed and long-range second-moment approximation of tight-binding. Taking the potential as the starting base, an atomistic computation/simulation route was developed for designing favored and optimized compositions for Mg-Cu-Y metallic glass formation. Simulations revealed that the physical origin of metallic glass formation is the collapse of crystalline lattice when solute concentration exceeds a critical value, thus leading to predict a hexagonal region in the Mg-Cu-Y composition triangle, within which metallic glass formation is energetically favored. It is proposed that the hexagonal region can be defined as the intrinsic glass formation region, or quantitative glass formation ability of the system. Inside the hexagonal region, the driving force for formation of each specific glassy alloy was further calculated and correlated with its forming ability in practice. Calculations pinpointed the optimized stoichiometry in the Mg-Cu-Y system to be Mg64Cu16Y20, at which the formation driving force reaches its maximum, suggesting that metallic glasses designed to have compositions around Mg64Cu16Y20 are most stable or easiest to obtain. The predictions derived directly from the atomistic simulations are supported by experimental observations reported so far in the literature. Furthermore, Honeycutt-Anderson analysis indicated that pentagonal bipyramids (although not aggregating to form icosahedra) dominate in the local structure of the Mg-Cu-Y metallic glasses. A microscopic picture of the medium-range packing can then be described as an extended network of the pentagonal bipyramids, entangled with the fourfold and sixfold disclination lines, jointly fulfilling the space of the metallic glasses. PMID:25981154

  20. Quasi-containerless glass formation method and apparatus

    NASA Technical Reports Server (NTRS)

    Naumann, Robert J. (Inventor); Ethridge, Edwin C. (Inventor)

    1987-01-01

    Glass rods or fibers are prepared from a polycrystalline rod by heating a short section of the rod in a first furnace to form a molten zone of the rod, heating a second short section of the rod in a second furnace to form a second molten zone and gradually moving the furnaces apart from one another to form an elongated molten float zone, which is cooled in its midsection to produce a glass rod between the molten zones. In another embodiment a single moving furnace assembly and a precursor rod with compositional gradient sections, are used, and the moving furnace traverses the rod so that the molten portion is drawn out to a degree whereby a fiber of ultrapure glass is formed.

  1. A deep water turbidity origin for the Altuda Formation (Capitanian, Permian), Northwest Glass Mountains, Texas

    USGS Publications Warehouse

    Haneef, Mohammad; Rohr, D.M.; Wardlaw, B.R.

    2000-01-01

    The Altuda Formation (Capitanian) in the northwestern Glass Mountains is comprised of thin, even bedded limestones, dolostones, mixed clastic-carbonates, and silt/sandstones interbedded with basin-ward dipping wedge-shaped clinoforms of the Captian Limestone. The formation is characterized by graded bedding, planar laminations, flame structures, contorted/convolute bedding, horizontal branching burrows, and shelf-derived normal marine fauna. A detailed study of the Altuda Formation north of Old Blue Mountain, Glass Mountains, reveals that the formation in this area was deposited by turbidity currents in slope to basinal settings.

  2. Investigation of ruthenium dioxide formation mechanisms in containment glass synthesized by liquid feed

    SciTech Connect

    Sawada, K.; Shimada, T.; Sako, N.; Enokida, Y.; Schuller, S.; Angeli, F.; Charpentier, T.

    2013-07-01

    The presenting paper focuses on the structural configuration of ruthenium in vitreous matrices with the objective of obtaining more insight into ruthenium incorporation and solubilization mechanisms in borosilicate glasses. To determine the structural effect of an increasing RuO{sub 2} in a borosilicate glass, a series of glass samples were selected from a benchmark composition. {sup 11}B NMR shows that the borate network is influenced by the presence of RuO{sub 2} in the glass: the addition of 2% RuO{sub 2} in a borosilicate glass led to a significant rise of BO{sub 4}. RuO{sub 2} precipitated in the glass does not seem to be the cause of this modification because when RuO{sub 2} increase there is no further change of BO{sub 4} fraction. This effect can be therefore attributed to RuO{sub 2} dissolved in the glass. RuO{sub 2} is known to have a very low solubility in borosilicate glasses (50 to 2000 ppm depending on the temperature, sodium concentration and conditions of synthesis). The link between the ruthenium and the borated network is not yet clearly identified, however, assumptions can be made such as the formation of Ru-O-B when a sufficient quantity of Ru is add (> 400 ppm). Ruthenium could play the role of silicon in increasing the possibility of bridging bond formation with boron coordination number IV.

  3. A review of bioactive glasses: Their structure, properties, fabrication and apatite formation.

    PubMed

    Kaur, Gurbinder; Pandey, Om P; Singh, Kulvir; Homa, Dan; Scott, Brian; Pickrell, Gary

    2014-01-01

    Bioactive glass and glass-ceramics are used in bone repair applications and are being developed for tissue engineering applications. Bioactive glasses/Bioglass are very attractive materials for producing scaffolds devoted to bone regeneration due to their versatile properties, which can be properly designed depending on their composition. An important feature of bioactive glasses, which enables them to work for applications in bone tissue engineering, is their ability to enhance revascularization, osteoblast adhesion, enzyme activity and differentiation of mesenchymal stem cells as well as osteoprogenitor cells. An extensive amount of research work has been carried out to develop silicate, borate/borosilicate bioactive glasses and phosphate glasses. Along with this, some metallic glasses have also been investigated for biomedical and technological applications in tissue engineering. Many trace elements have also been incorporated in the glass network to obtain the desired properties, which have beneficial effects on bone remodeling and/or associated angiogenesis. The motivation of this review is to provide an overview of the general requirements, composition, structure-property relationship with hydroxyapatite formation and future perspectives of bioglasses.Attention has also been given to developments of metallic glasses and doped bioglasses along with the techniques used for their fabrication. PMID:23468256

  4. Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

    NASA Astrophysics Data System (ADS)

    Drummond, Charles H., III

    1991-08-01

    The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

  5. Glass formation and crystallization in high-temperature glass-ceramics and Si3N4

    NASA Technical Reports Server (NTRS)

    Drummond, Charles H., III

    1991-01-01

    The softening of glassy grain boundaries in ceramic matrix composites and Si3N4 at high temperatures reduces mechanical strength and the upper-use temperature. By crystallizing this glass to a more refractory crystalline phase, a material which performs at higher temperatures may result. Three systems were examined: a cordierite composition with ZrO2 as a nucleating agent; celsian compositions; and yttrium silicate glasses both in bulk and intergranular in Si3N4. For the cordierite compositions, a series of metastable phases was obtained. The crystallization of these compositions was summarized in terms of metastable ternary isothermal sections. Zircon formed at the expense of ZrO2 and spinel. In SiC composites, the transformations were slower. In celsian, two polymorphs were crystallized. One phase, hexacelsian, which always crystallized, even when metastable, had an undesirable volume change. The other phase, celsian, was very difficult to crystallize. In yttrium silicate bulk glasses, similar in composition to the intergranular glass in Si3N4, a number of polymorphs of Y2Si2O7 were crystallized. The conditions under which these polymorphs formed are compared with crystallization in Si3N4.

  6. Colloid formation in copper-implanted fused silica and silicate glasses

    SciTech Connect

    Mazzoldi, P.; Caccavale, F.; Cattaruzza, E.

    1993-12-31

    Copper implantations (90 keV, 5{times}10{sup 16} ions/cm{sup 2}) were made into fused silica, borosilicate glasses and soda-lime glass. The copper distribution has been found to vary according to glass type. The optical absorption band characteristic of the implanted metal optical properties was observed only for copper-implanted fused silica. Absorption for all the other samples was either not observable or was negligibly small, however very small metallic particles are present also in soda-lime glass. Subsequent nitrogen implantation (100 keV, 1.5{times}10{sup 17} ions/cm{sup 2}) completely eliminated the copper-colloid induced absorption in the copper-implanted fused silica, while it facilitated formation of copper-colloids in soda-lime glass.

  7. Formation of Si structure in glass with a femtosecond laser

    NASA Astrophysics Data System (ADS)

    Miura, Kiyotaka; Hirao, Kazuyuki; Shimotsuma, Yasuhiko; Sakakura, Masaaki; Kanehira, Shingo

    2008-10-01

    Mixing metallic Al into the starting material for silicate glass is proposed as a means of forming Si structures in glass. We confirmed that Si nanocrystals are space-selectively deposited in silicate glass via a thermite reaction triggered by femtosecond laser pulses. Small Si particles were transformed into larger, but still micrometer sized, Si particles by laser irradiation. These structures grew to micro-size particles due to the thermite reaction promoted by heat treatment. We discuss what effect the irradiation of the focused laser pulse had on the Si deposition process in the laser-irradiated region. Localized high temperatures and pressures and generation of shock waves appear to be very important in forming Si-rich structures that contribute to the growth of Si particles. The diffusion of calcium ions by the generation of shock waves and the presence of Al-rich structures is important for forming Si-rich structures such as Si clusters, which is achieved by continuously breaking Si-O bonds using localized high temperatures.

  8. Glass formation, magnetic properties and magnetocaloric effect of ternary Ho-Al-Co bulk metallic glass

    NASA Astrophysics Data System (ADS)

    Zhang, Huiyan; Li, Ran; Ji, Yunfei; Liu, Fanmao; Luo, Qiang; Zhang, Tao

    2012-11-01

    A ternary Ho-Al-Co system with high glass-forming ability (GFA) was developed and fully glassy rods with diameters up to 1 cm can be produced for the best glass former of Ho55Al27.5Co17.5 alloy. The thermal stability and low-temperature magnetic properties of the Ho55Al27.5Co17.5 bulk metallic glass (BMG) were studied. The magnetic transition temperature of this alloy is ˜14 K as determined by the thermomagnetic measurement. Two indicators, i.e. isothermal magnetic entropy change (ΔSM) and the relative cooling power (RCP), were adopted to evaluate the magnetocaloric effect (MCE) of the alloy under a low magnetic field up to 2 T, which can be generated by permanent magnets. The values of |ΔSM| and RCP are 7.98 J kg-1 K-1 and 191.5 J kg-1, respectively. The Ho55Al27.5Co17.5 BMG with good MCE and high GFA provides an attractive candidate for magnetic refrigeration applications, like hydrogen liquefaction and storage.

  9. Glass formation and the third harmonic generation of Cu2Se-GeSe2-As2Se3 glasses

    NASA Astrophysics Data System (ADS)

    Reshak, A. H.; Klymovych, O. S.; Myronchuk, G. L.; Zamuruyeva, O. V.; Zmiy, O. F.; Alahmed, Z. A.; Chyský, J.; Bila, Jiri; Kamarudin, H.

    2014-10-01

    We have performed the investigation of the nonlinear optical properties namely the third harmonic generation (THG) of the glass-formation region in the Cu2Se-GeSe2-As2Se3 system. The samples were synthesized by direct single-temperature method from high-purity elementary substances. We have found that the value of disorder parameter Δ depends on the composition of the glassy alloys. The measurements show that increasing the Cu2Se concentration leads to increased slope of the absorption edge, which may be explained by the decrease of the height of random potential relief for the electrons in the tails of the state density which border the band edges. A very sharp increase in the THG at low temperature was observed. Significant enhancement in THG was obtained with decreasing the energy gap, which agreed well with the nonlinear optical susceptibilities obtained from other glasses.

  10. Studies of the Local Distortions and the EPR Parameters for Cu2+ in xLi2O-(30-x)Na2O-69·5B2O Glasses

    NASA Astrophysics Data System (ADS)

    Ding, Chang-Chun; Wu, Shao-Yi; Kuang, Min-Quan; Hu, Xian-Fen; Li, Guo-Liang

    2016-03-01

    The local distortions and electron paramagnetic resonance (EPR) parameters for Cu2+ in lithium sodium borate (LNB) glasses xLi2O·(30-x)·Na2O·69.5B2O3 (5≤x≤25 mol%) are theoretically studied at various concentrations x in a consistent way. Owing to the Jahn-Teller effect, the [CuO6]10- clusters are found to experience the significant tetragonal elongations of 16% along C4 axis. Despite the nearly unchanging observed g factors, measured d-d transition band (or cubic field parameter Dq) shows remarkable linear increases with concentration x, whose influences on g‖ and g⊥ are actually cancelled by the linearly increasing covalency factor N and relative elongation ratio η with x. The almost unvarying hyperfine structure constants are attributed to the fact that the influences of the linearly increasing N and the linearly decreasing core polarisation constant κ largely cancel one another. The microscopic mechanisms of the above concentration dependences for these quantities are illustrated from mixed alkali effect (modification of B2O3 network by transforming some BO3 units into BO4 ones with variations in modifier Li2O concentration).

  11. Superexchange and spin-glass formation in semimagnetic semiconductors

    NASA Astrophysics Data System (ADS)

    Rusin, Tomasz M.

    1996-05-01

    The Mn-Mn superexchange interaction in semimagnetic semiconductors A1-xMnxB (where A=Zn, Cd and B=S, Se, Te) is studied within the three-level model of the band structure. We focus on the dependence of the interaction on the interion distance Jdd(r)=J0f(r). In the present work, the function f(r) is obtained analytically. This, only weakly material-dependent function is found to decrease with Mn-Mn distance much slower than its Gaussian approximation derived previously. The exact form of the decay of the superexchange can be approximated by a power law J0r-8.5. This is close to an experimental result, J0r-6.8, determined on the basis of the spin-glass transition temperature on the composition.

  12. Crystallization behavior and glass formation of selected lunar compositions.

    NASA Technical Reports Server (NTRS)

    Scherer, G.; Hopper, R. W.; Uhlmann, D. R.

    1972-01-01

    The kinetics of crystal growth have been determined over a wide range of temperature, from 800 to 1219 C, for lunar compositions 14259 and 14310. At all temperatures for both compositions the extent of crystal growth is found to be a linear function of time. For both materials, the growth rate versus temperature relations exhibit the form generally found with glass-forming materials. At all temperatures measured, the crystal growth rate of composition 14259 is smaller than that of composition 14310. The maximum growth rate for both compositions occurs at a temperature of about 1120 C. The growth rate data are combined with viscosity data obtained on the same compositions to construct the reduced growth rate versus undercooling relations.

  13. The formation of silver metal nanoparticles by ion implantation in silicate glasses

    NASA Astrophysics Data System (ADS)

    Vytykacova, S.; Svecova, B.; Nekvindova, P.; Spirkova, J.; Mackova, A.; Miksova, R.; Böttger, R.

    2016-03-01

    It has been shown that glasses containing silver metal nanoparticles are promising photonics materials for the fabrication of all-optical components. The resulting optical properties of the nanocomposite glasses depend on the composition and structure of the glass, as well as on the type of metal ion implanted and the experimental procedures involved. The main aim of this article was to study the influence of the conditions of the ion implantation and the composition of the glass on the formation of metal nanoparticles in such glasses. Four various types of silicate glasses were implanted with Ag+ ions with different energy (330 keV, 1.2 MeV and 1.7 MeV), with the fluence being kept constant (1 × 1016 ions cm-2). The as-implanted samples were annealed at 600 °C for 1 h. The samples were characterised in terms of: the nucleation of metal nanoparticles (linear optical absorption), the migration of silver through the glass matrix during the implantation and post-implantation annealing (Rutherford backscattering spectroscopy), and the oxidation state of silver (photoluminescence in the visible region).

  14. Heterogeneous-nucleation and glass-formation studies of 56Ga2O3-44CaO

    NASA Technical Reports Server (NTRS)

    Ethridge, Edwin C.; Curreri, Peter A.; Pline, David

    1987-01-01

    Glass formation and heterogeneous crystallization are described for the reluctant-glass-forming 56Ga2O3-44CaO eutectic composition. The times and temperatures for nucleation at various cooling rates and experimental conditions were measured and empirical continuous-cooling-crystallization boundaries were constructed for various heterogeneous nucleation processes. A definition for an empirical critical cooling rate to form a glass from reluctant borderline glass formers is proposed, i.e., the cooling rate that results in glass formation in 95 percent of the quenching experiments.

  15. Advances in the generalized entropy theory of glass-formation in polymer melts.

    PubMed

    Dudowicz, Jacek; Douglas, Jack F; Freed, Karl F

    2014-12-21

    The generalized entropy theory (GET) of polymeric glass-forming liquids is reformulated into a computationally simpler and more natural formalism than the original version of this theory. The new theoretical framework greatly facilitates establishing essential trends in the dependence of the segmental relaxation time τ, fragility, characteristic temperatures of glass-formation, etc., on the combined influences of monomer molecular structure, chain rigidity, and cohesive interaction strength. Special attention is placed on the estimating the parameters of the phenomenological Vogel-Fulcher-Tammann relations for describing segmental relaxation in diverse liquids in the low temperature range of glass-formation, Tg > T > Tc (or Tg < T < Tg + 100 K), where Tg and Tc are, respectively, the glass transition temperature and the crossover temperature separating the high and low temperature regimes of glass-formation. Finally, we discuss how the molecular energetic interaction parameters of the GET can be estimated from experimental data. Illustrative calculations are performed for the stiffness factor σ and the cohesive energy density u as a first step in this direction. PMID:25527959

  16. Advances in the generalized entropy theory of glass-formation in polymer melts

    NASA Astrophysics Data System (ADS)

    Dudowicz, Jacek; Douglas, Jack F.; Freed, Karl F.

    2014-12-01

    The generalized entropy theory (GET) of polymeric glass-forming liquids is reformulated into a computationally simpler and more natural formalism than the original version of this theory. The new theoretical framework greatly facilitates establishing essential trends in the dependence of the segmental relaxation time τ, fragility, characteristic temperatures of glass-formation, etc., on the combined influences of monomer molecular structure, chain rigidity, and cohesive interaction strength. Special attention is placed on the estimating the parameters of the phenomenological Vogel-Fulcher-Tammann relations for describing segmental relaxation in diverse liquids in the low temperature range of glass-formation, Tg > T > Tc (or Tg < T < Tg + 100 K), where Tg and Tc are, respectively, the glass transition temperature and the crossover temperature separating the high and low temperature regimes of glass-formation. Finally, we discuss how the molecular energetic interaction parameters of the GET can be estimated from experimental data. Illustrative calculations are performed for the stiffness factor σ and the cohesive energy density u as a first step in this direction.

  17. Formation of plasma induced surface damage in silica glass etching for optical waveguides

    NASA Astrophysics Data System (ADS)

    Choi, D. Y.; Lee, J. H.; Kim, D. S.; Jung, S. T.

    2004-06-01

    Ge, B, P-doped silica glass films are widely used as optical waveguides because of their low losses and inherent compatibility with silica optical fibers. These films were etched by ICP (inductively coupled plasma) with chrome etch masks, which were patterned by reactive ion etching (RIE) using chlorine-based gases. In some cases, the etched surfaces of silica glass were very rough (root-mean square roughness greater than 100 nm) and we call this phenomenon plasma induced surface damage (PISD). Rough surface cannot be used as a platform for hybrid integration because of difficulty in alignment and bonding of active devices. PISD reduces the etch rate of glass and it is very difficult to remove residues on a rough surface. The objective of this study is to elucidate the mechanism of PISD formation. To achieve this goal, PISD formation during different etching conditions of chrome etch mask and silica glass was investigated. In most cases, PISD sources are formed on a glass surface after chrome etching, and metal compounds are identified in theses sources. Water rinse after chrome etching reduces the PISD, due to the water solubility of metal chlorides. PISD is decreased or even disappeared at high power and/or low pressure in glass etching, even if PISD sources were present on the glass surface before etching. In conclusion, PISD sources come from the chrome etching process, and polymer deposition on these sources during the silica etching cause the PISD sources to grow. In the area close to the PISD source there is a higher ion flux, which causes an increase in the etch rate, and results in the formation of a pit.

  18. Formation of nanoscale dots on glass surface by microprobe ion manipulation

    NASA Astrophysics Data System (ADS)

    Yano, Tetsuji; Kubota, Shin-ichi; Kato, Hiroaki; Shibata, Shuichi

    2004-10-01

    Ion manipulation using micro-probe has been performed to fabricate the nano-scale dots on/or in the glass. Soda-lime-silica glass was subjected to the treatments. Two types of the manipulation treatments were carried out using various probes and electrical conditions. In the Na-extraction treatment, the thick needles and/or STM tips were used as a cathode. At 250°C, Na+ ions were extracted from the inside of the glass towards the cathode tip, and electrochemically reduced to Na-metal. Na-metal are held at the tip/glass interface as liquid state, and grew with the treatment time. After the treatment, they formed the micrometer-size dots of fodium compound on the glass surface, and their size was dependent on the total charge conducting through the tip. In the Ag-migration treatment, Ag-metal probes were prepared and used as an anode at 200°C. Ag atoms on the tip were oxidized to Ag+ ions and migrated into the glass. They could be optically recognized using the luminescence from Ag+ ions under the UV irradiation. a lot of Ag-metal dots with the size 100-300nm were also formed on the glass surface. They are considered to be transferred from the tip of Ag-metal probe onto the glass surface. The size of the Ag+ migrated region was dependent on the total charge of the treatment, and the available small size was found to be defined by the apex of the probe tip. The observed phenomena in these treatments were explained and the possibility of the formation of nano-scale dots on the glass by ion manipulation was discussed.

  19. Compositional landscape for glass formation in metal alloys

    PubMed Central

    Na, Jong Hyun; Demetriou, Marios D.; Floyd, Michael; Hoff, Andrew; Garrett, Glenn R.; Johnson, William L.

    2014-01-01

    A high-resolution compositional map of glass-forming ability (GFA) in the Ni–Cr–Nb–P–B system is experimentally determined along various compositional planes. GFA is shown to be a piecewise continuous function formed by intersecting compositional subsurfaces, each associated with a nucleation pathway for a specific crystalline phase. Within each subsurface, GFA varies exponentially with composition, wheres exponential cusps in GFA are observed when crossing from one crystallization pathway to another. The overall GFA is shown to peak at multiple exponential hypercusps that are interconnected by ridges. At these compositions, quenching from the high-temperature melt yields glassy rods with diameters exceeding 1 cm, whereas for compositions far from these cusps the critical rod diameter drops precipitously and levels off to 1 to 2 mm. The compositional landscape of GFA is shown to arise primarily from an interplay between the thermodynamics and kinetics of crystal nucleation, or more precisely, from a competition between driving force for crystallization and liquid fragility. PMID:24927600

  20. Nanosecond (ns) laser transfer of silver nanoparticles from silver-exchanged soda-lime glass to transparent soda-lime glass and shock waves formation

    NASA Astrophysics Data System (ADS)

    Sow, Mohamed Chérif; Blondeau, Jean-Philippe; Sagot, Nadine; Ollier, Nadège; Tite, Teddy

    2015-05-01

    In this contribution, we showed for the first time in our knowledge a single-step process for silver clusters and nanoparticles growth and transfer from silver-exchanged soda-lime glass to un-exchanged soda-lime glass (transparent glass in visible and NIR domain) by nanosecond (ns) laser irradiation. The transferred silver nanoparticles in transparent glass are strongly linked to the glass surface. In addition, we point out the formation of shock waves, with selective silver clustering on the top wave. This technique provides an alternative and simple way to obtain metallic nanoparticles in different media which can be traversed by laser wavelength used. Moreover, this experiment is made at room temperature and air environment. It is worth noting that our technique requires a glass previously doped with the corresponding silver ions.

  1. Influence of the Substrate on the Formation of Metallic Glass Coatings by Cold Gas Spraying

    NASA Astrophysics Data System (ADS)

    Henao, John; Concustell, Amadeu; Dosta, Sergi; Cinca, Núria; Cano, Irene G.; Guilemany, Josep M.

    2016-06-01

    Cold gas spray technology has been used to build up coatings of Fe-base metallic glass onto different metallic substrates. In this work, the effect of the substrate properties on the viscoplastic response of metallic glass particles during their impact has been studied. Thick coatings with high deposition efficiencies have been built-up in conditions of homogeneous flow on substrates such as Mild Steel AISI 1040, Stainless Steel 316L, Inconel 625, Aluminum 7075-T6, and Copper (99.9%). Properties of the substrate have been identified to play an important role in the viscoplastic response of the metallic glass particles at impact. Depending on the process gas conditions, the impact morphologies show not only inhomogeneous deformation but also homogeneous plastic flow despite the high strain rates, 108 to 109 s-1, involved in the technique. Interestingly, homogenous deformation of metallic glass particles is promoted depending on the hardness and the thermal diffusivity of the substrate and it is not exclusively a function of the kinetic energy and the temperature of the particle at impact. Coating formation is discussed in terms of fundamentals of dynamics of undercooled liquids, viscoplastic flow mechanisms of metallic glasses, and substrate properties. The findings presented in this work have been used to build up a detailed scheme of the deposition mechanism of metallic glass coatings by the cold gas spraying technology.

  2. Exosomes in colorectal carcinoma formation: ALIX under the magnifying glass.

    PubMed

    Valcz, Gábor; Galamb, Orsolya; Krenács, Tibor; Spisák, Sándor; Kalmár, Alexandra; Patai, Árpád V; Wichmann, Barna; Dede, Kristóf; Tulassay, Zsolt; Molnár, Béla

    2016-08-01

    Exosomes are small membrane vesicles that have important roles in transporting a great variety of bioactive molecules between epithelial compartment and their microenvironment during tumor formation including colorectal adenoma-carcinoma sequence. We tested the mRNA expression of the top 25 exosome-related markers based on ExoCharta database in healthy (n=49), adenoma (n=49) and colorectal carcinoma (n=49) patients using Affymetrix HGU133 Plus2.0 microarrays. Most related genes showed significantly elevated expression including PGK1, PKM, ANXA5, ENO1, HSP90AB1 and MSN during adenoma-carcinoma sequence. Surprisingly, the expression of ALIX (ALG 2-interacting protein X), involved in multivesicular body (MVB) and exosome formation, was significantly reduced in normal vs adenoma (P=5.02 × 10(-13)) and in normal vs colorectal carcinoma comparisons (P=1.51 × 10(-10)). ALIX also showed significant reduction (P<0.05) at the in situ protein level in the epithelial compartment of adenoma (n=35) and colorectal carcinoma (n=37) patients compared with 27 healthy individuals. Furthermore, significantly reduced ALIX protein levels were accompanied by their gradual transition from diffuse cytoplasmic expression to granular signals, which fell into the 0.6-2 μm diameter size range of MVBs. These ALIX-positive particles were seen in the tumor nests, including tumor-stroma border, which suggest their exosome function. MVB-like structures were also detected in tumor microenvironment including α-smooth muscle actin-positive stromal cells, budding off cancer cells in the tumor front as well as in cancer cells entrapped within lymphoid vessels. In conclusion, we determined the top aberrantly expressed exosome-associated markers and revealed the transition of diffuse ALIX protein signals into a MVB-like pattern during adenoma-carcinoma sequence. These tumor-associated particles seen both in the carcinoma and the surrounding microenvironment can potentially mediate epithelial

  3. Thermochromic effects in a Jahn-Teller active CuCl(4-)6 layered hybrid system.

    PubMed

    Caretta, A; Miranti, R; Arkenbout, A H; Polyakov, A O; Meetsma, A; Hidayat, R; Tjia, M O; Palstra, T T M; van Loosdrecht, P H M

    2013-12-18

    The hybrid material copper (II) tetrachloro-bis(phenyl ethyl ammonium) (C6H5CH2CH2NH3)2CuCl4, or PEACuCl, has been investigated by temperature-dependent spectroscopic absorption experiments. The absorption bands observed in the near-infrared region (1.3-1.9 eV) generally exhibit redshifts with increasing temperature. The temperature-induced energy shifts of the spectral components are shown to be consistently related to temperature-induced Cu-Cl bond length changes. Additionally, the thermochromic color change is caused by a charge transfer band edge redshifting (in the visible region 2.0-2.8 eV) with increasing temperature. By comparison with similar Cu-based systems, it is suggested that this shift is caused by broadening and strengthening of the band. PMID:24220020

  4. Thermochromic effects in a Jahn-Teller active {{CuCl}}_{6}^{4-} layered hybrid system

    NASA Astrophysics Data System (ADS)

    Caretta, A.; Miranti, R.; Arkenbout, A. H.; Polyakov, A. O.; Meetsma, A.; Hidayat, R.; Tjia, M. O.; Palstra, T. T. M.; van Loosdrecht, P. H. M.

    2013-12-01

    The hybrid material copper (II) tetrachloro-bis(phenyl ethyl ammonium) (C6H5CH2CH2NH3)2CuCl4, or PEACuCl, has been investigated by temperature-dependent spectroscopic absorption experiments. The absorption bands observed in the near-infrared region (1.3-1.9 eV) generally exhibit redshifts with increasing temperature. The temperature-induced energy shifts of the spectral components are shown to be consistently related to temperature-induced Cu-Cl bond length changes. Additionally, the thermochromic color change is caused by a charge transfer band edge redshifting (in the visible region 2.0-2.8 eV) with increasing temperature. By comparison with similar Cu-based systems, it is suggested that this shift is caused by broadening and strengthening of the band.

  5. Vibrational states of the triplet electronic state of H3+. The role of non-adiabatic Jahn-Teller coupling

    NASA Astrophysics Data System (ADS)

    Alijah, Alexander; Kokoouline, Viatcheslav

    2015-10-01

    Vibrational energies and wave functions of the triplet state of the H3+ ion have been determined. In the calculations, the ground and first excited triplet electronic states are included as well as the most important part of the non-Born-Oppenheimer coupling between them. The diabatization procedure proposed by Longuet-Higgins is then applied to transform the two adiabatic ab initio potential energy surfaces of the triplet-H3+ state into a 2 × 2 diabatic matrix. The diabatization takes into account the effect of the geometrical phase due to the conical intersection between the two adiabatic potential surfaces. The results are compared to the calculation involving only the lowest adiabatic potential energy surface of the triplet-H3+ ion and neglecting the geometrical phase. The energy difference between results with and without the non-adiabatic coupling and the geometrical phase is about one wave number for the lowest vibrational levels.

  6. Effects of Oxygen Impurities on Glass-Formation Ability in Zr2Cu Alloy.

    PubMed

    Wang, Zhanyu; Huang, Li; Yue, G Q; Shen, B; Dong, F; Zhang, R J; Zheng, Y X; Wang, S Y; Wang, C Z; Kramer, M J; Ho, K M; Chen, L Y

    2016-09-01

    Using ab initio molecular dynamics simulations, we show that oxygen (O) impurities have a noticeable influence on the glass-formation ability (GFA) in Zr2Cu alloy. Cu-centered icosahedral clusters and Zr-centered Kasper polyhedra are the dominate short-range orders in undercooled Zr2Cu liquid which are most likely to be responsible for the glass formation in Zr2Cu systems. When O is introduced, a Zr octahedron is formed around the O impurity. Most of the Zr atoms in the octahedron also serve as the bridging atoms for cross-linked Kasper polyhedral network, resulting in an O-centered medium range order (MRO) structure. Meanwhile, Cu atoms are moved away from the first shell of O-centered octahedral clusters. With 1 at. % O impurities, the fractions of Zr-centered clusters are less affected, while the increase of ideal icosahedral order and decrease of distorted icosahedral order lead to a more stable atomic structure. This result suggests that a low concentration of O impurities would improve the GFA in Zr2Cu alloy. However, when ∼5 at. % O impurities are included, the ideal icosahedral clusters and Zr-centered Kasper polyhedra are seriously suppressed by the formation of O-centered MRO, which can lead to deterioration of GFA. Our analyses provide useful insight into glass formation behavior in O-doped metallic alloy systems. PMID:27509394

  7. Characterization and Glass Formation of JSC-1 Lunar and Martian Soil Simulants

    NASA Technical Reports Server (NTRS)

    Sen, Subhayu

    2008-01-01

    The space exploration mission of NASA requires long duration presence of human being beyond the low earth orbit (LEO), especially on Moon and Mars. Developing a human habitat or colony on these planets would require a diverse range of materials, whose applications would range from structural foundations, (human) life support, (electric) power generation to components for scientific instrumentation. A reasonable and cost-effective approach for fabricating the materials needed for establishing a self-sufficient human outpost would be to primarily use local (in situ) resources on these planets. Since ancient times, glass and ceramics have been playing a vital role on human civilization. A long term project on studying the feasibility of developing glass and ceramic materials using Lunar and Martian soil simulants (JSC-1) as developed by Johnson Space Center has been undertaken. The first step in this on-going project requires developing a data base on results that fully characterize the simulants to be used for further investigations. The present paper reports characterization data of both JSC-1 Lunar and JSC Mars-1 simulants obtained up to this time via x-ray diffraction analysis, scanning electron microscopy, thermal analysis (DTA, TGA) and chemical analysis. The critical cooling rate for glass formation for the melts of the simulants was also measured in order to quantitatively assess the glass forming tendency of these melts. The importance of the glasses and ceramics developed using in-situ resources for constructing human habitats on Moon or Mars is discussed.

  8. Characterization and Glass Formation of JSC-1 Lunar and Martian Soil Simulants

    NASA Astrophysics Data System (ADS)

    Ray, Chandra S.; Reis, Signo T.; Sen, Subhayu

    2008-01-01

    The space exploration mission of NASA requires human and robotic presence for long duration beyond the low earth orbit (LEO), especially on Moon and Mars. Developing a human habitat or colony on these planets would require a diverse range of materials, whose applications would range from structural foundations, (human) life support, (electric) power generation to components for scientific instrumentations. A reasonable and cost-effective approach for fabricating the materials needed for establishing a self-sufficient human outpost would be to primarily use local (in situ) resources on these planets. Since ancient times, glass and ceramics have been playing a vital role on human civilization. A long term project on studying the feasibility of developing glass and ceramic materials has been undertaken using Lunar and Martian soil simulants (JSC-1) as developed by Johnson Space Center. The first step in this on-going project requires developing a data base on results that fully characterize the simulants to be used for further investigations. The present paper reports characterization data of both JSC-1 Lunar and JSC Mars-1 simulants obtained up to this time via x-ray diffraction analysis, scanning electron microscopy, thermal analysis (DTA, TGA) and chemical analysis. The critical cooling rate for glass formation for the melts of the simulants was also measured in order to quantitatively assess the glass forming tendency of these melts. The importance of the glasses and ceramics developed using in-situ resources for constructing human habitats on Moon or Mars is discussed.

  9. Structural aspects of glass-formation in Ni-Nb melts

    SciTech Connect

    Holland-Moritz, D.; Yang, F.; Gegner, J.; Meyer, A.; Hansen, T.; Ruiz-Martín, M. D.

    2014-05-28

    We report on investigations of the static structure factors of glass-forming Ni{sub 59.5}Nb{sub 40.5} alloy melts by combination of the containerless processing technique of electrostatic levitation with neutron diffraction. By application of the isotopic substitution method, the full set of partial structure factors was determined. The short-range order in liquid Ni{sub 59.5}Nb{sub 40.5} is characterized by a large nearest neighbor coordination number of Z{sub NN} = 14.3 and a chemical short-range order with an affinity for the formation of heterogeneous Nb-Ni nearest neighbors. The structure factors observed here in the liquid state closely resemble those reported for amorphous Nb-Ni solids. The comparison with earlier results on the short-range structure in Zr-based glass-forming melts suggests that a large local density of packing, chemical order, and structural frustration are, amongst others, common structural properties of these metallic glass-forming systems, which favor glass-formation.

  10. Glass formation and cluster evolution in the rapidly solidified monatomic metallic liquid Ta under high pressure

    NASA Astrophysics Data System (ADS)

    Jiang, Dejun; Wen, Dadong; Tian, Zean; Liu, Rangsu

    2016-12-01

    Molecular dynamics (MD) simulations have been performed to examine the glass formation and cluster evolution during the rapid solidification of monatomic metallic liquid Ta under high pressure. The atomic structures in the systems are characterized by the radical distribution function (RDF), Honeycutt-Anderson (H-A) bond-type index method and cluster-type index method (CTIM). It is observed that the defective icosahedra play the critical role in the formation of Ta monatomic metallic glasses (MGs) rather than (12 0 12 0) perfect icosahedra, which have been identified as the basic local atomic units in many multi-component MGs. With the increase of pressure P, the fraction of icosahedral type clusters decreases remarkably in Ta MGs, while the fraction of bcc type clusters rises evidently. The evolution of vitrification degree (DSRO or DMRO) of the rapidly cooled metal Ta system further reveals that a higher pressure P is disadvantageous to the formation of Ta monatomic MGs. The weaker glass forming ability (GFA) of liquid metal Ta obtained under higher pressure P can be contributed to the decrease of DSRO or DMRO which is induced by increasing high pressure P to some extent.

  11. Recrystallized Impact Glasses of the Onaping Formation and the Sudbury Igneous Complex, Sudbury Structure, Ontario, Canada

    NASA Technical Reports Server (NTRS)

    Dressler, B. O.; Weiser, T.; Brockmeyer, P.

    1996-01-01

    The origin of the Sudbury Structure and of the associated heterolithic breccias of the Onaping Formation and the Sudbury Igneous Complex have been controversial. While an impact origin of the structure has gained wide acceptance over the last 15 years, the origin of the recrystallized Onaping Formation glasses and of the igneous complex is still being debated. Recently the interpretation of the breccias of the Onaping Formation as suevitic fall-back impact breccias has been challenged. The igneous complex is interpreted either as a differentiated impact melt sheet or as a combination of an upper impact melt represented by the granophyre, and a lower, impact-triggered magmatic body consisting of the norite-sublayer formations. The Onaping Formation contains glasses as fluidal and nonfluidal fragments of various shapes and sizes. They are recrystallized, and our research indicates that they are petrographically heterogeneous and span a wide range of chemical compositions. These characteristics are not known from glasses of volcanic deposits. This suggests an origin by shock vitrification, an interpretation consistent with their association with numerous and varied country rock clasts that exhibit microscopic shock metamorphic features. The recrystallized glass fragments represent individual solid-state and liquid-state vitrified rocks or relatively small melt pods. The basal member lies beneath the Gray and Black members of the Onaping Formation and, where not metamorphic, has an igneous matrix. Igneous-textured melt bodies occur in the upper two members and above the Basal Member. A comparison of the chemical compositions of recrystallized glasses and of the matrices of the Basal Member and the melt bodies with the components and the bulk composition of the igneous complex is inconclusive as to the origin of the igneous complex. Basal Member matrix and Melt Bodies, on average, are chemically similar to the granophyre of the Sudbury Igneous Complex, suggesting that

  12. Application of the entropy theory of glass formation to poly(α-olefins)

    NASA Astrophysics Data System (ADS)

    Stukalin, Evgeny B.; Douglas, Jack F.; Freed, Karl F.

    2009-09-01

    The entropy theory of glass formation, which has previously been developed to describe general classes of polymeric glass-forming liquids, is extended here to model the thermodynamic and dynamic properties of poly(α-olefins). By combining this thermodynamic theory with the Adam-Gibbs model (which relates the configurational entropy to the rate of structural relaxation), we provide systematic computations for all four characteristic temperatures (TA, Tc, Tg, T0), governing the position and breadth of the glass transition, and the fragility parameters (D,m) describing the strength of the temperature dependence of the structural relaxation time, where TA is the temperature below which the relaxation is non-Arrhenius, Tc is the crossover or empirical mode-coupling temperature, Tg is the glass transition temperature, and T0 is the temperature at which the extrapolated relaxation time diverges. These temperatures and fragility parameters are evaluated as a function of molar mass, pressure, and the length n of the α-olefin side chains. The nearest neighbor interaction energy and local chain rigidities are found to strongly influence the four characteristic temperatures and the low temperature fragility. We also observe an "internal plasticization" of the poly(α-olefins) wherein the fragility decreases as the number n of "flexible" side group units increases. Our computations provide solid support for a pressure counterpart of the Vogel-Fulcher-Tammann relation. The entropy theory of glass formation predicts systematic changes in fragility with chain stiffness, cohesive energy, polymerization index, and side chain length, and qualitative trends in these parameters are discussed.

  13. Nanometer-scale tunnel formation in metallic glass by helium ion irradiation

    SciTech Connect

    Shao Lin; Gorman, Brian P.; Aitkaliyeva, Assel; David Theodore, N.; Xie Guoqiang

    2012-07-23

    We have shown that upon high fluence helium ion irradiation, metallic glass Cu{sub 50}Zr{sub 45}Ti{sub 5} becomes highly porous at the depth of the helium projected range. The resulting porous region is characterized by the formation of a tunnel like structure and self-linkage of nanometer size gas bubbles. Furthermore, the irradiation leads to the formation of nanometer size Cu{sub x}Zr{sub y} crystals that are randomly distributed. The results of this study indicate that the He-filled bubbles have attractive interactions and experience considerable mobility. Movement of the bubbles is believed to be assisted by ballistic collisions.

  14. Porous wall hollow glass microspheres as a medium or substrate for storage and formation of novel materials

    DOEpatents

    Wicks, George G; Serkiz, Steven M.; Zidan, Ragaiy; Heung, Leung K.

    2014-06-24

    Porous wall hollow glass microspheres are provided as a template for formation of nanostructures such as carbon nanotubes, In addition, the carbon nanotubes in combination with the porous wall hollow glass microsphere provides an additional reaction template with respect to carbon nanotubes.

  15. Formation of nanostructures in Eu3+ doped glass-ceramics: an XAS study

    NASA Astrophysics Data System (ADS)

    Pellicer-Porres, J.; Segura, A.; Martínez-Criado, G.; Rodríguez-Mendoza, U. R.; Lavín, V.

    2013-01-01

    We describe the results of x-ray absorption experiments carried out to deduce structural and chemical information in Eu3+ doped, transparent, oxyfluoride glass and nanostructured glass-ceramic samples. The spectra were measured at the Pb and Eu-LIII edges. The Eu environment in the glass samples is observed to be similar to that of EuF3. Complementary x-ray diffraction experiments show that thermal annealing creates β-PbF2 type nanocrystals. X-ray absorption indicates that Eu ions act as seeds in the nanocrystal formation. There is evidence of interstitial fluorine atoms around Eu ions as well as Eu dimers. X-ray absorption at the Pb-LIII edge shows that after the thermal treatment most lead atoms form a PbO amorphous phase and that only 10% of the lead atoms remain available to form β-PbF2 type nanocrystals. Both x-ray diffraction and absorption point to a high Eu content in the nanocrystals. Our study suggests new approaches to the oxyfluoride glass-ceramic synthesis in order to further improve their properties.

  16. Formation and evolution of ultrashort pulse-induced nanogratings in Borosilicate glass

    NASA Astrophysics Data System (ADS)

    Zimmermann, F.; Plech, Anton; Richter, S.; Tünnermann, Andreas; Nolte, S.

    2014-05-01

    The versatility of ultrashort laser pulses as a tool for laser materials processing has augmented particular interest in the past decade. Especially birefringent modifications, so-called nanogratings, have found to exhibit tremendous potential for manifold photonic functionalities. These self-assembling structures, orienting always perpendicular to the laser polarization, have been up to now extensively studied in bulk fused silica. Commonly it is assumed that the formation of nanogratings is actually limited to anomalous glasses like silica or slightly doped silica. However, we recently found that even in glasses like borosilicate or BK7 nanogratings can be observed within certain parameter regimes. Here we present an extensive study of the fundamental constituents of nanogratings in bulk borosilicate glass using small angle X-ray scattering (SAXS) in combination with focused ion beam milling (FIB) and scanning electron microscopy (SEM). The irradiation produces void-like sheets (10-20 nm wide) as well as elongated cracks of up to 400 nm. In contrast to nanogratings in fused silica, borosilicate shows a significant smaller optical retardance. The cumulative action of several hundreds of laser pulses lead to the formation of individual grating planes with a period of about 60 nm (at an inscribing laser wavelength of 800 nm) while the well-known λ/2n (n-refractive index) period is prevented. This has never been observed for ultrashort pulse induced nanogratings so far.

  17. Recent advances with generalized entropy theory of glass-formation in polymers

    NASA Astrophysics Data System (ADS)

    Freed, Karl

    The generalized entropy theory (GET) of glass-formation in polymers is a combination of the lattice cluster theory (LCT) for the configurational entropy density with the Adam-Gibbs (AG) theory for the structural relaxation time. A greatly simplified form of the GET (whose expression for the free energy is roughly double that of Flory-Huggins theory) accurately reproduces the four characteristic temperatures of glass-formation (the onset, crossover, glass transition, and Kauzmann temperatures) of the full GET to within 4K for a series of models of polymers composed of semi-flexible chains having the structure of poly(n-alpha olefins). The theory is now simple enough to be used in courses in polymer physics. Although the successes of the GET provide a strong validation of the final form of the AG theory provided the configurational entropy is used, the physical basis of the AG theory has remained an enigma. Hence, we have developed a new, more general, statistical mechanical derivation of AG theory that explains the previously perplexing observations that the string-like elementary excitations have the mass and temperature dependence of systems undergoing equilibrium self-assembly. This work is supported by the (U.S.) Department of Energy (DOE), Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award No. DE- SC0008631.

  18. Thermodynamic calculation and interatomic potential to predict the favored composition region for the Cu-Zr-Al metallic glass formation.

    PubMed

    Cui, Y Y; Wang, T L; Li, J H; Dai, Y; Liu, B X

    2011-03-01

    For the Cu-Zr-Al system, the glass forming compositions were firstly calculated based on the extended Miedema's model, suggesting that the amorphous phase could be thermodynamically favored over a large composition region. An n-body potential was then constructed under the smoothed and long-range second-moment-approximation of tight-binding formulism. Applying the constructed Cu-Zr-Al potential, molecular dynamics simulations were conducted using solid solution models to compare relative stability of crystalline solid solution versus its disordered counterpart. Simulations reveal that the physical origin of metallic glass formation is crystalline lattice collapsing while solute concentration exceeding the critical value, thus predicting a hexagonal composition region, within which the Cu-Zr-Al ternary metallic glass formation is energetically favored. The molecular dynamics simulations predicted composition region is defined as the quantitative glass-forming-ability or glass-forming-region of the Cu-Zr-Al system. PMID:21229150

  19. Effect of variable valence impurities on the formation of bismuth-related optical centres in a silicate glass

    SciTech Connect

    Galagan, B I; Denker, B I; Lili Hu; Sverchkov, S E; Shulman, I L; Dianov, Evgenii M

    2012-10-31

    We have studied the effect of variable valence impurities (cerium and iron) on the formation of bismuth-related IR luminescence centres and the optical loss between 1000 and 1300 nm in a magnesium aluminosilicate glass. The results demonstrate that additional doping of the glass with ceria leads to effective bleaching in a wide spectral range, including the luminescence range of the bismuth centres. At the same time, ceria reduces the concentration of luminescence centres. Gamma irradiation of the glass bleached by cerium restores the luminescence centres but leads to a background loss in a wide spectral range. Iron is shown to be a very harmful impurity in bismuth-doped active media: even trace levels of iron prevent the formation of bismuth-related active centres in the glass and produce a strong, broad absorption band centred near 1 {mu}m. (luminescence of glasses)

  20. A New DTA Method for Measuring Critical Cooling Rate for Glass Formation

    NASA Technical Reports Server (NTRS)

    Ray, Chandra S.; Reis, Signo T.; Brow, Richard K.; Holand, Wolfram; Rheinberger, Volker

    2004-01-01

    A new differential thermal analysis (DTA) experimental method has been developed to determine the critical cooling rate for glass formation, R(sub c). The method, which is found especially suitable for melts that, upon cooling, have a small heat of crystallization or a very slow crystallization rate, has been verified using a 38Na2O-62SiO2 (mol%) melt with a known R(sub c) (-approx. 19 C/min), then used to determine R(sub c) for two complex lithium silicate glass forming melts. The new method is rapid, easy to conduct and yields values for R(sub c) that are in excellent agreement with the R(sub c)-values measured by standard DTA techniques.

  1. Effects of nanocrystal formation on the soft magnetic properties of Fe-based bulk metallic glasses

    NASA Astrophysics Data System (ADS)

    Gao, J. E.; Li, H. X.; Jiao, Z. B.; Wu, Y.; Chen, Y. H.; Yu, T.; Lu, Z. P.

    2011-08-01

    We developed several Fe-based bulk metallic glasses with a unique combination of large glass-forming ability and excellent soft magnetic properties by minor doping of Cu in the Fe76C7.0Si3.3B5.0P8.7 alloy. Proper additions of the non-magnetic copper element which has a positive heat of mixing with Fe, coupled with adequate annealing, can stimulate formation of ˜5 nm αFe ferromagnetic nanocrystals, which results in the increment in the saturation magnetization. Over-annealing which induced coarsening of the α-Fe nanocrystals reduces the ferromagnetic exchange interaction between the nanosized α-Fe crystals and increases the effective magneto-crystalline anisotropy, thereby deteriorating the soft magnetic properties.

  2. Mechanisms of microhole formation on glasses by an abrasive slurry jet

    SciTech Connect

    Wang, J.; Nguyen, T.; Pang, K. L.

    2009-02-15

    Abrasive jet micromachining is considered as a promising precision processing technology for brittle materials such as silicon substrates and glasses that are increasingly used in various applications. In this paper, the mechanisms of microhole formation on brittle glasses by an abrasive slurry jet are studied based on the viscous flow and erosion theories. It is shown that the hole cross section is characterized by a ''W'' shape and can be classified into three zones caused, respectively, by jet direct impact, viscous flow, and turbulent flow induced erosion. An analysis of the surface morphology shows that ductile-mode erosion is dominant. The effect of process parameters on material removal is studied which shows that increasing the pressure and erosion time increases the hole depth, but has little effect on the hole diameter.

  3. Communication: The simplified generalized entropy theory of glass-formation in polymer melts

    SciTech Connect

    Freed, Karl F.

    2015-08-07

    While a wide range of non-trivial predictions of the generalized entropy theory (GET) of glass-formation in polymer melts agree with a large number of observed universal and non-universal properties of these glass-formers and even for the dependence of these properties on monomer molecular structure, the huge mathematical complexity of the theory precludes its extension to describe, for instance, the perplexing, complex behavior observed for technologically important polymer films with thickness below ∼100 nm and for which a fundamental molecular theory is lacking for the structural relaxation. The present communication describes a hugely simplified version of the theory, called the simplified generalized entropy theory (SGET) that provides one component necessary for devising a theory for the structural relaxation of thin polymer films and thereby supplements the first required ingredient, the recently developed Flory-Huggins level theory for the thermodynamic properties of thin polymer films, before the concluding third step of combining all the components into the SGET for thin polymer films. Comparisons between the predictions of the SGET and the full GET for the four characteristic temperatures of glass-formation provide good agreement for a highly non-trivial model system of polymer melts with chains of the structure of poly(n-α olefins) systems where the GET has produced good agreement with experiment. The comparisons consider values of the relative backbone and side group stiffnesses such that the glass transition temperature decreases as the amount of excess free volume diminishes, contrary to general expectations but in accord with observations for poly(n-alkyl methacrylates). Moreover, the SGET is sufficiently concise to enable its discussion in a standard course on statistical mechanics or polymer physics.

  4. Communication: The simplified generalized entropy theory of glass-formation in polymer melts

    NASA Astrophysics Data System (ADS)

    Freed, Karl F.

    2015-08-01

    While a wide range of non-trivial predictions of the generalized entropy theory (GET) of glass-formation in polymer melts agree with a large number of observed universal and non-universal properties of these glass-formers and even for the dependence of these properties on monomer molecular structure, the huge mathematical complexity of the theory precludes its extension to describe, for instance, the perplexing, complex behavior observed for technologically important polymer films with thickness below ˜100 nm and for which a fundamental molecular theory is lacking for the structural relaxation. The present communication describes a hugely simplified version of the theory, called the simplified generalized entropy theory (SGET) that provides one component necessary for devising a theory for the structural relaxation of thin polymer films and thereby supplements the first required ingredient, the recently developed Flory-Huggins level theory for the thermodynamic properties of thin polymer films, before the concluding third step of combining all the components into the SGET for thin polymer films. Comparisons between the predictions of the SGET and the full GET for the four characteristic temperatures of glass-formation provide good agreement for a highly non-trivial model system of polymer melts with chains of the structure of poly(n-α olefins) systems where the GET has produced good agreement with experiment. The comparisons consider values of the relative backbone and side group stiffnesses such that the glass transition temperature decreases as the amount of excess free volume diminishes, contrary to general expectations but in accord with observations for poly(n-alkyl methacrylates). Moreover, the SGET is sufficiently concise to enable its discussion in a standard course on statistical mechanics or polymer physics.

  5. Real-time study of bulk damage formation in glass initiated by intense femtosecond pulses

    NASA Astrophysics Data System (ADS)

    Kudriašov, V.; Gaižauskas, E.; Sirutkaitis, V.

    2005-12-01

    Dynamics of damage formation by focusing intense femtosecond pulses inside the fused silica glass is studied in wide energy range. Damage usually is initiated in the zone near geometrical focus, which is preceded by the zone where beam propagates in the form of multiple filaments. For high repetition rate pulses damage appears as an extended narrow track along the beam path, which forms due to the propagation of the initial damage zone toward the laser source. For low repetition rate pulses extended damage tracks don't form.

  6. Glass formation and optical properties of Ge-Te-Ga-CuI far-IR transmitting chalcogenide glasses

    NASA Astrophysics Data System (ADS)

    He, Yuju; Wang, Xunsi; Nie, Qiuhua; Xu, Yinsheng; Xu, Tiefeng; Dai, Sixun

    2013-09-01

    To discover the signs of life on terrestrial planets, we must accurately detect the existence of CO2, which has two vibrational absorption bands at 4 μm and 16 μm. Therefore optical materials be able to transmit light far beyond 20 μm are essential for manufacturing these detectors. In this paper, a series of Ge-Te-Ga-CuI far-IR transmitting chalcogenide glasses were synthesized by conventional melt-quenching method and their glass-forming region was determined. Properties measurements including X-ray Diffraction (XRD), Differential Scanning Calorimetry (DSC), Vis-NIR and IR transmitting spectra were performed on glasses. The results of XRD measurements confirmed the amorphous state of studied glasses. With the help of Ga and CuI, these glasses have high glass transition temperature Tg (>175 °C), indicating their good thermal stability. The allowed indirect transition of samples was also calculated according to the Tauc equation. The infrared transmission spectra measured by Fourier transform infrared spectrometer (FTIR) show that these glasses all have wide optical transmitting window from 1.68 to 25 μm revealing that it may have great potential for application in far-IR material fields.

  7. Formation of metallic and metallic-glass hollow spheres and their solidification characteristics

    NASA Technical Reports Server (NTRS)

    Lee, M. C.

    1985-01-01

    Various metals and metallic glass systems have bene processed into hollow spheres with sizes ranging from 3 mm to 440 microns in diameter. The technique for the formation of the large hollow spheres, in general, is based on the fluid-dynamic instability of a hollow annular jet. A refined technique has also been developed for microshell formation, in which discrete bubbles are injected into the stream of the molten material and individually 'flushed' out at a frequency related to the Rayleigh jet instability. The surfaces of those spheres of all sizes exhibit a range of contrasting solidification behaviors and characteristics. Metal shells of varying materials, sizes, aspect ratios, sphericity and concentricity have many useful and novel applications.

  8. Study of hydroxyl carbonate apatite formation on bioactive glass coated dental ceramics by confocal laser scanning microscopy (CLSM)

    NASA Astrophysics Data System (ADS)

    Stanciu, G. A.; Savu, B.; Sandulescu, I.; Paraskevopoulos, K.; Koidis, P.

    2007-03-01

    Some dental ceramics were coated with a bioactive glass and resulted the formation of a stable and well bonded with the ceramic substrate thin layer. After immersion in a solution with ion concentrations similar to those of human blood plasma the development of hydroxy carbonate apatite layer on the surface of bioactive glass may be observed. The objective of this study was to investigate structural surface changes of bioactive glass, after exposure in a simulated body fluid for a different number of days. The roughness and topography of the hydroxyapatite surface were investigated by Confocal Scanning Laser Microscopy. The chemical composition was analyzed by Energy Dispersive Spectroscopy measurements.

  9. Effects of secondary electrons emitted from surroundings on defect formation in silica glass under γ-ray irradiation

    NASA Astrophysics Data System (ADS)

    Obata, S.; Yoshida, T.; Tanabe, T.; Allen, C.; Okada, M.; Xu, Qiu

    2006-09-01

    We have investigated the effects of secondary electrons and photons emitted from surrounding materials on defect formation in silica glass under γ-ray irradiation. SiO 2 (silica) glass plates and those sandwiched in a pair of various material disks (carbon, stainless steel or lead) were irradiated by γ-ray, and the optical absorption spectra (UV-vis spectra) of the silica glass plates before and after the irradiation were examined. UV-vis spectra of the glass plates after the irradiation showed three absorption bands peaked around 2 eV, 4 eV and 5.8 eV being assigned to color centers relate metal impurities (Al and Ge) and oxygen-deficient centers like E' center, respectively. All three bands were found to grow with γ-ray irradiation dose and saturated at higher doses, and absorbance of the bands at the saturation for the sandwiched glass plates was higher than that for the bare glass plate. Moreover, the saturated absorbance was higher for the glass plate sandwiched with heavier materials. Employing Monte Carlo N-Particle (MCNP) code for the simulation of the photon-electron transport process, enhanced energy deposition and numbers of secondary electrons and photons emitted from sandwiching material disks to a silica glass plate were calculated. The higher deposition energy correlates well to the higher saturated absorbance, indicating that the secondary electrons and photons emitted from the disks clearly enhanced the defect formation in the sandwiched silica glass plates. This suggests the existence of the dose effect above a critical does, i.e. the irradiation with higher dose will result in higher saturated absorbance.

  10. Radiation effects in moist-air systems and the influence of radiolytic product formation on nuclear waste glass corrosion

    SciTech Connect

    Wronkiewicz, D.J.; Bates, J.K.; Buck, E.C.; Hoh, J.C.; Emery, J.W.; Wang, L.M.

    1997-07-01

    Ionizing radiation may affect the performance of glass in an unsaturated repository site by interacting with air, water vapor, or liquid water to produce a variety of radiolytic products. Tests were conducted to examine the effects of radiolysis under high gas/liquid ratios. Results indicate that nitrate is the predominant radiolytic product produced following both gamma and alpha radiation exposure, with lesser amounts of nitrite and carboxylic acids. The formation of nitrogen acids during exposure to long-lived, alpha-particle-emitting transuranic elements indicates that these acids may play a role in influencing nuclear waste form reactions in a long-term unsaturated disposal scenario. Experiments were also conducted with samples that simulate the composition of Savannah River Plant nuclear waste glasses. Radiolytic product formation in batch tests (340 m{sup {minus}1}, 90 C) resulted in a small increase in the release rates of many glass components, such as alkali and alkaline earth elements, although silicon and uranium release rates were slightly reduced indicating an overall beneficial effect of radiation on waste form stability. The radiolytic acids increased the rate of ion exchange between the glass and the thin film of condensate, resulting in accelerated corrosion rates for the glass. The paragenetic sequence of alteration phases formed on both the irradiated and nonirradiated glass samples reacted in the vapor hydration tests matches closely with those developed during volcanic glass alteration in naturally occurring saline-alkaline lake systems. This correspondence suggests that the high temperatures used in these tests have not changed the underlying glass reaction mechanism relate to that which controls glass reactions under ambient surficial conditions.