187 research outputs found

    Pulsed Laval nozzle study of the kinetics of OH with unsaturated hydrocarbons at very low temperatures

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    The kinetics of reactions of the OH radical with ethene, ethyne (acetylene), propyne (methyl acetylene) and t-butyl-hydroperoxide were studied at temperatures of 69 and 86 K using laser flash-photolysis combined with laser-induced fluorescence spectroscopy. A new pulsed Laval nozzle apparatus is used to provide the low-temperature thermalised environment at a single density of similar to 4 x 10(16) molecule cm(-3) in N-2. The density and temperature within the flow are determined using measurements of impact pressure and rotational populations from laser-induced fluorescence spectroscopy of NO and OH. For ethene, rate coefficients were determined to be k(2) = (3.22 +/- 0.46) x 10(-11) and (2.12 +/- 0.12) x 10(-11) cm(3) molecule(-1) s(-1) at T = 69 and 86 K, respectively, in good agreement with a master-equation calculation utilising an ab initio surface recently calculated for this reaction by Cleary et al. (P. A. Cleary, M. T. Baeza Romero, M. A. Blitz, D. E. Heard, M. J. Pilling, P. W. Seakins and L. Wang, Phys. Chem. Chem. Phys., 2006, 8, 5633-5642) For ethyne, no previous data exist below 210 K and a single measurement at 69 K was only able to provide an approximate upper limit for the rate coefficient of k(3) < 1 x 10(-12) cm(3) molecule(-1) s (-1), consistent with the presence of a small activation barrier of similar to 5 kJ mol (-1) between the reagents and the OH-C2H2 adduct. For propyne, there are no previous measurements below 253 K, and rate coefficients of k(4) = (5.08 +/- 0.65), (5.02 +/- 1.11) and (3.11 +/- 0.09) x 10(-12) cm(3) molecule(-1) s(-1) were obtained at T = 69, 86 and 299 K, indicating a much weaker temperature dependence than for ethene. The rate coefficient k(1) = (7.8 +/- 2.5) x 10(-11) cm(3) molecule(-1) s (-1) was obtained for the reaction of OH with t-butyl-hydroperoxide at T = 86 K. Studies of the reaction of OH with benzene and toluene yielded complex kinetic profiles of OH which did not allow the extraction of rate coefficients. Uncertainties are quoted at the 95% confidence limit and include systematic errors

    Recent high-magnetic-field studies of unusual groundstates in quasi-two-dimensional crystalline organic metals and superconductors

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    After a brief introduction to crystalline organic superconductors and metals, we shall describe two recently-observed exotic phases that occur only in high magnetic fields. The first involves measurements of the non-linear electrical resistance of single crystals of the charge-density-wave (CDW) system (Per)2_2Au(mnt)2_2 in static magnetic fields of up to 45 T and temperatures as low as 25 mK. The presence of a fully gapped CDW state with typical CDW electrodynamics at fields higher that the Pauli paramagnetic limit of 34 T suggests the existence of a modulated CDW phase analogous to the Fulde-Ferrell-Larkin-Ovchinnikov state. Secondly, measurements of the Hall potential of single crystals of α\alpha-(BEDT-TTF)2_2KHg(SCN)4_4, made using a variant of the Corbino geometry in quasistatic magnetic fields, show persistent current effects that are similar to those observed in conventional superconductors. The longevity of the currents, large Hall angle, flux quantization and confinement of the reactive component of the Hall potential to the edge of the sample are all consistent with the realization of a new state of matter in CDW systems with significant orbital quantization effects in strong magnetic fields.Comment: SNS 2004 Conference presentatio

    Magnetic order and ballistic spin transport in a sine-Gordon spin chain

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    We report the results of muon-spin spectroscopy (μ+SR) measurements on the staggered molecular spin chain [pym-Cu(NO3 )2(H2O)2] (pym = pyrimidine), a material previously described using sine-Gordon field theory. Zero-field μ+SR reveals a long range magnetically ordered ground state below a transition temperature TN = 0.23(1) K. Using longitudinal-field (LF) μ+SR we investigate the dynamic response in applied magnetic fields 0 < B < 500 mT and find evidence for ballistic spin transport. Our LF μ+SR measurements on the chiral spin chain [Cu(pym)(H2O)4]SiF6 · H2O instead demonstrate one-dimensional spin diffusion, and the distinct spin transport in these two systems suggests that additional anisotropic interactions play an important role in determining the nature of spin transport in S = 1/2 antiferromagnetic chains

    Robustness of superconductivity to structural disorder in Sr0.3(NH2)y(NH3)1−yFe2Se2

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    The superconducting properties of a recently discovered high-Tc superconductor, Sr/ammonia-intercalated FeSe, have been measured using pulsed magnetic fields down to 4.2 K and muon spin spectroscopy down to 1.5 K. This compound exhibits intrinsic disorder resulting from random stacking of the FeSe layers along the c axis that is not present in other intercalates of the same family. This arises because the coordination requirements of the intercalated Sr and ammonia moieties imply that the interlayer stacking (along c) involves a translation of either a/2 or b/2 that locally breaks tetragonal symmetry. The result of this stacking arrangement is that the Fe ions in this compound describe a body-centered-tetragonal lattice in contrast to the primitive arrangement of Fe ions described in all other Fe-based superconductors. In pulsed magnetic fields, the upper critical field Hc2 was found to increase on cooling with an upward curvature that is commonly seen in type-II superconductors of a multiband nature. Fitting the data to a two-band model and extrapolation to absolute zero gave a maximum upper critical field μ0Hc2(0) of 33(2)T. A clear superconducting transition with a diamagnetic shift was also observed in transverse-field muon measurements at Tc≈36.3(2)K. These results demonstrate that robust superconductivity in these intercalated FeSe systems does not rely on perfect structural coherence along the c axis

    Adiabatic physics of an exchange-coupled spin-dimer system: Magnetocaloric effect, zero-point fluctuations, and possible two-dimensional universal behavior

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    We present the magnetic and thermal properties of the bosonic-superfluid phase in a spin-dimer network using both quasistatic and rapidly changing pulsed magnetic fields. The entropy derived from a heat-capacity study reveals that the pulsed-field measurements are strongly adiabatic in nature and are responsible for the onset of a significant magnetocaloric effect (MCE). In contrast to previous predictions we show that the MCE is not just confined to the critical regions, but occurs for all fields greater than zero at sufficiently low temperatures. We explain the MCE using a model of the thermal occupation of exchange-coupled dimer spin states and highlight that failure to take this effect into account inevitably leads to incorrect interpretations of experimental results. In addition, the heat capacity in our material is suggestive of an extraordinary contribution from zero-point fluctuations and appears to indicate universal behavior with different critical exponents at the two field-induced critical points. The data at the upper critical point, combined with the layered structure of the system, are consistent with a two-dimensional nature of spin excitations in the system

    Evolution of magnetic interactions in a pressure-induced Jahn-Teller driven magnetic dimensionality switch

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    We present the results of high-field magnetization and muon-spin relaxation measurements on the coordination polymer CuF 2 (H 2 O) 2 (pyrazine) in pressures up to 22.5 kbar. We observe a transition from a quasi-two-dimensional to a quasi-one-dimensional antiferromagnetic phase at 9.1 kbar, driven by a rotation of the Jahn-Teller axis. Long-range antiferromagnetic ordering is seen in both regimes, as well as a phase separation in the critical pressure region. The magnetic dimensionality switching as pressure is increased is accompanied by a halving of the primary magnetic exchange energy J and a fivefold decrease in the ordering temperature T N . J decreases gradually with pressure in the two-dimensional phase, and then increases in the one-dimensional regime. We relate both effects to the changes in the crystal structure with applied pressure

    Magnetic ground state of the one-dimensional ferromagnetic chain compounds M(NCS)2(thiourea)2 (M=Ni,Co)

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    The magnetic properties of the two isostructural molecule-based magnets—Ni(NCS)2(thiourea)2, S = 1 [thiourea = SC(NH2 )2] and Co(NCS)2 (thiourea)2, S = 3/2—are characterized using several techniques in order to rationalize their relationship with structural parameters and to ascertain magnetic changes caused by substitution of the spin. Zero-field heat capacity and muon-spin relaxation measurements reveal low-temperature long-range ordering in both compounds, in addition to Ising-like (D < 0) single-ion anisotropy (DCo ∼ −100 K, DNi ∼ −10 K). Crystal and electronic structure, combined with dc-field magnetometry, affirm highly quasi-onedimensional behavior, with ferromagnetic intrachain exchange interactions JCo ≈ +4 K and JNi ∼ +100 K and weak antiferromagnetic interchain exchange, on the order of J ∼ −0.1 K. Electron charge- and spin-density mapping reveals through-space exchange as a mechanism to explain the large discrepancy in J-values despite, from a structural perspective, the highly similar exchange pathways in both materials. Both species can be compared to the similar compounds MCl2(thiourea)4, M = Ni(II) (DTN) and Co(II) (DTC), where DTN is known to harbor two magnetic-field-induced quantum critical points. Direct comparison of DTN and DTC with the compounds studied here shows that substituting the halide Cl− ion for the NCS− ion results in a dramatic change in both the structural and magnetic properties

    Magnetic order and disorder in a quasi-two-dimensional quantum Heisenberg antiferromagnet with randomized exchange

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    We present an investigation of the effect of randomizing exchange coupling strengths in the S = 1/2 square lattice quasi-two-dimensional quantum Heisenberg antiferromagnet (QHAF) (QuinH)2Cu(ClxBr1−x )4 · 2H2O (QuinH = Quinolinium, C9H8N+), with 0 x 1. Pulsed-field magnetization measurements allow us to estimate an effective in-plane exchange strength J in a regime where exchange fosters short-range order, while the temperature TN at which long-range order (LRO) occurs is found using muon-spin relaxation, allowing us to construct a phase diagram for the series. We evaluate the effectiveness of disorder in suppressing TN and the ordered moment size, and we find an extended disordered phase in the region 0.4 x 0.8 where no magnetic order occurs. The observed critical substitution levels are accounted for by an energetics-based competition between different local magnetic orders. Furthermore, we demonstrate experimentally that the ground-state disorder is driven by quantum effects of the exchange randomness, which is a feature that has been predicted theoretically and has implications for other disordered quasi-two-dimensional QHAFs

    The BRST quantization and the no-ghost theorem for AdS_3

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    In our previous papers, we prove the no-ghost theorem without light-cone directions (hep-th/0005002, hep-th/0303051). We point out that our results are valid for more general backgrounds. In particular, we prove the no-ghost theorem for AdS_3 in the context of the BRST quantization (with the standard restriction on the spin). We compare our BRST proof with the OCQ proof and establish the BRST-OCQ equivalence for AdS_3. The key in both approaches lies in the certain structure of the matter Hilbert space as a product of two Verma modules. We also present the no-ghost theorem in the most general form.Comment: 22 pages, JHEP and AMS-LaTeX; v2 & 3: minor improvement

    Conformal Field Theory Approach to the 2-Impurity Kondo Problem: Comparison with Numerical Renormalization Group Results

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    Numerical renormalization group and conformal field theory work indicate that the two impurity Kondo Hamiltonian has a non-Fermi liquid critical point separating the Kondo-screening phase from the inter-impurity singlet phase when particle-hole (P-H) symmetry is maintained. We clarify the circumstances under which this critical point occurs, pointing out that there are two types of P-H symmetry. Only one of them guarantees the occurance of the critical point. Much of the previous numerical work was done on models with the other type of P-H symmetry. We analyse this critical point using the boundary conformal field theory technique. The finite-size spectrum is presented in detail and compared with about 50 energy levels obtained using the numerical renormalization group. Various Green's functions, general renormalization group behaviour, and a hidden SO(7)SO(7) are analysed.Comment: 38 pages, RevTex. 2 new sections clarify the circumstances under which a model will exhibit the non-trivial critical point (hence potentially resolving disagreements with other Authors) and explain the hidden SO(7) symmetry of the model, relating it to an alternative approach of Sire et al. and Ga
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