Direct angle resolved photoemission spectroscopy and superconductivity of strained high-T c films

Since 1997 we systematically perform direct angle resolved photoemission spectroscopy (ARPES) on in-situ grown thin (<30 nm) cuprate films. Specifically, we probe low-energy electronic structure and properties of high-T _c superconductors (HTSC) under different degrees of epitaxial (compressive vs. tensile) strain. In overdoped and underdoped in-plane compressed (the strain is induced by the choice of substrate) ≈15 nm thin La_{2 − x} Sr _x CuO₄ (LSCO) films we almost double T _c to 40 K, from 20 K and 24 K, respectively. Yet the Fermi surface (FS) remains essentially two-dimensional. In contrast, ARPES data under tensile strain exhibit the dispersion that is three-dimensional, yet T _c drastically decreases. It seems that the in-plane compressive strain tends to push the apical oxygen far away from the CuO₂ plane, enhances the two-dimensional character of the dispersion and increases T _c, while the tensile strain acts in the opposite direction and the resulting dispersion is three-dimensional. We have established the shape of the FS for both cases, and all our data are consistent with other ongoing studies, like EXAFS. As the actual lattice of cuprates is like a ‘Napoleon-cake’, i.e. rigid CuO₂ planes alternating with softer ‘reservoir’, that distort differently under strain, our data rule out all oversimplified two-dimensional (rigid lattice) mean field models. The work is still in progress on optimized La-doped Bi-2201 films with enhanced T _c.      

Silver ionic conductivity enhancement by network former mixed in oxide-based glasses

Glasses in the binary system xAg₂P₂O₆ − (1 − x)Ag₂Te₂O₅ have been prepared for 0 x 1. For each composition only one glass transition temperature is observed in the temperature range of 180–220 °C. All glasses appear homogeneous considering their optical and electrical properties. Nevertheless, in SEM observations, some glass compositions appear to be heterogeneous after decoration following short nitric acid etching. For each composition, conductivity data obtained in the temperature range of 25–200 °C using impedance techniques obey an Arrhenius relationship with a composition independent pre-exponential term. Variation of the conductivity activation energy with x induces correlative variations of isothermal conductivity curves leading to an increase of the ionic conductivity of about one order of magnitude compared with linearity at 25 °C. This behaviour is discussed with respect to the thermodynamic properties of the glassy solutions.     

A Runge-Kutta method for index 1 stochastic differential-algebraic equations with scalar noise

The paper deals with the numerical treatment of stochastic differential-algebraic equations of index one with a scalar driving Wiener process. Therefore, a particularly customized stochastic Runge-Kutta method is introduced. Order conditions for convergence with order 1.0 in the mean-square sense are calculated and coefficients for some schemes are presented. The proposed schemes are stiffly accurate and applicable to nonlinear stochastic differential-algebraic equations. As an advantage they do not require the calculation of any pseudo-inverses or projectors. Further, the mean-square stability of the proposed schemes is analyzed and simulation results are presented bringing out their good performance.     

Adductor spasmodic dysphonia: case reports withacoustic analysis following botulinum toxin injection and acupuncture

We analyzed frequency and duration parameters of voice and speech in two men with adductor spasmodic dysphonia (SD). One was treated with botulinum toxin injection; the other received acupuncture therapy. Im provement after acupuncture therapy in terms of standard deviation of fundamental frequency, acoustic perturbation measurements, durational measurements of voice and speech, and spectrographic analysis was comparable to the results achieved with botulinum toxin injection. Voice and speech parameters were stable I year after acupuncture therapy.     

Strain hardening and fracture of heat-set fractal globular protein gels

Non-linear mechanical behavior at large shear deformation was been investigated for heat-set beta-lactoglobulin gels at pH 7 and 0.1 M NaCl using both oscillatory shear and shear flow. These gels have a self-similar structure at length scales smaller than the correlation length of the gel with fractal dimension d(f)=2. Strain hardening is observed that can be well described using the model proposed by Gisler et al. [T.C. Gisler, R.C. Ball, D.A. Weitz, Phys. Rev. Let. 82 (1999) 1064] for fractal colloidal gels. The increase of the shear modulus normalized by the low strain value (G(0)) is independent of G(0). For weak gels the elasticity increases up to a factor of ten, while for strong gels the increase is very small. At higher deformation irreversible fracture occurs, which leads eventually to macroscopic failure of the gel. For weak gels formed at low concentrations the deformation at failure is about 2, independent of the shear modulus. For strong gels fracture occurs at approximately constant stress (2 x 10(3) Pa).     

Photomagnetic properties of an iron(II) low-spin complex with an unusually long-lived metastable LIESST state

A comprehensive study of the photomagnetic behavior of the [Fe(L222N5)(CN)2].H2O complex has been carried out. This complex is characterized by a low-spin (LS) iron(II)-metal center up to 400 K and exhibits at 10 K the well-known Light-Induced Excited Spin State Trapping (LIESST) effect. The critical LIESST temperature (T(LIESST)) has been measured to be 105 K. The kinetics of the transition from the metastable high-spin (HS) state to the low-spin state have been determined and used for reproducing the experimental T(LIESST) curve. This study represents a second example of a fully low-spin iron(II)-metal complex up to 400 K, which can be photoexcited at low temperature with an atypical long-lived metastable HS state. This underlines the preponderant role of the inner coordination sphere for stabilizing the lifetime of the photoinduced HS state.     

1H and 19F ultra-fast MAS double-quantum single-quantum NMR correlation experiments using three-spin terms of the dipolar homonuclear Hamiltonian

Measuring internuclear distances through dipolar interaction is a major challenge for solid-state nuclear magnetic resonance (NMR) spectroscopy. Obtaining reliable interatomic distances provides an access to the local structure in ordered or disordered solids. We show that at magic angle spinning (MAS) frequencies larger than ca. 50 kHz, some of the three-spin terms of the homogeneous homonuclear dipolar Hamiltonian can be used to promote the creation of double-quantum coherences between neighbouring (1)H or (19)F spins without using dipolar recoupling pulse sequences in the Dipolar Homonuclear Homogeneous Hamiltonian (DH(3)) double-quantum/single-quantum correlation experiment. This makes it possible to probe inter-nuclear spatial proximity with limited risk of probe or sample damage from radio-frequency (RF) irradiation, and is fully appropriate for fast repetition rate offering sensitivity gains in favourable cases. Experimental demonstrations are supported by multi-spin numerical simulations, which points to new possibilities for the characterization of spin-system geometries.     

Effects of substituted ligands on the mobility of complexed anions

From conductance and viscosities measurements on Pr₄NCl, Et₄NBr, and AgNO₃ in acetonitrile and Et₃NBr in nitrobenzene, the Walden products of the anion at infinite dilution were determined in presence of various concentrations of substituted benzoic acids. From these data it was possible to compute the values of the Walden products of the once complexed anions and to estimate the order of magnitude of the Walden products of twice complexed anions. Stokes' law is not obeyed, and the Walden products are not proportional to the third root of the molar volume of the complexed ions, as a consequence of their lack of sphericity. The assumption that the drag force which acts on the ions is proportional to the volume of the substituents results in a linear expression between the reciprocals of the Walden products and the molar volume of the ligands. The experimental results fit this expression within the limits of the experimental errors, and the slopes of the lines are nearly the same for all the anions and for the two solvents studied here, namely, 2.5×10^–4 ohm-cm^–5 mole-cP^–1.     

Tetrathiafulvalene hydrazone: efficient synthon for the synthesis of novel bidentate redox active ligands

The synthesis and the ability of TTF-hydrazone to act as a versatile precursor for the design of electroactive ligands are reported together with the chelating ability of these ligands through their M(CO)₄ complexes, (M = Mo, W).