Phase diagrams from spin probe studies for binary mixtures of non-mesomorphic solutes in 5CB

The effect of low concentrations of a non-mesomorphic solute impurity on the nematicto-isotropic transition of 4-cyano-4′-n-pentylbiphenyl (5CB), has been investigated by ESR spectroscopy, using predeuterated-2,2,6,6-tetramethyl-4-piperidone-N-oxide (PD-Tempone), at mole fractions of the order of 10^?5, as a probe. It has been found that at such low mole fractions PD-Tempone simply probes the nematic-to-isotropic transition without observably perturbing it. This fast approach relies on the fact that a smaller coupling constant is obtained for the spin probe in the orientationally ordered nematic phase relative to the isotropic phase. The method has been further refined in this study by the use of an especially designed sample holder which, in conjunction with a temperature control and monitoring system, allowed control of the temperature of the sample to within ±0.02°C. Additionally measurements were made, for each solute, at several solute mole fractions within the range from 0.01 to 0.07. The results were used to obtainβ _N andβ ₁, the moduli of the slopes of the nematic and isotropic boundary lines respectively in the reduced nematic-to-isotropic transition temperature (T ^*) versus solute mole fraction (x ₂) diagrams. The non-mesomorphic solutes used in this study are n-nonane, 3,3-diethylpentane, tetrapropyltin and tetrabutyltin.     

Magnetic field effects on the hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol as studied by a picosecond laser flash photolysis technique

The hydrogen abstraction reaction of triplet 4-methoxybenzophenone with thiophenol at 265 K has been studied with a newly developed picosecond laser flash photolysis apparatus under magnetic fields of 0–1.7 T. The decay rate constant of the radical pair generated was found to increase from 3.42 × 10⁹ s^?1 to 4.15 × 10⁹ s^?1 with increasing the magnetic field from 0 to 1.7 T. The observed magnetic field effects can be explained by the Δg mechanism. Using the simple kinetics model with the Δg mechanism, the rate constant of the escape process from the pair (k _esc) and two rate constants for the T-S spin conversion process (k _T-S) at 0 and 1.7 T were found to be 1.97 × 10⁹ s^?1, 1.45 × 10⁹ s^?1, and 2.12 × 10⁹ s^?1, respectively. From the magnetic field dependence on k _T-S, the difference in the g values of the 4-methoxybenzophenone ketyl and phenylthiyl radicals was estimated to be 0.0087.     

Magnetic orientation of carbon nanotubes at temperatures of 231 K and 314 K

Carbon nanotubes were placed in magnetic fields of  80.0 kOe at temperatures of 231 K and 314 K. Scanning electron microscopy showed that nanotubes were oriented with the tube axis parallel to the fields. It was also observed that the probability of the orientation became higher, when the temperature was raised from 231 K to 314 K. The anisotropy in the susceptibilities parallel X∥ and perpendicular X _⊥ to the tube axis is suggested to increase with rise in temperature: X∥ ? X⊥ = (4 ± 2) × 10^?6 emu mol^?1 (per mol of carbon atoms) at 231 K and X∥ ? X⊥ = (45 ± 27) × 10^?6 emu mol^?1 at 314 K.     

Equation of state and thermal expansivity of LiF and NaF

The high-pressure and high-temperature behaviors of LiF and NaF have been studied up to 37 GPa and 1000 K. No phase transformations have been observed for LiF up to the maximum pressure reached. The B1 to B2 transition of NaF at room temperature was observed at ～28 GPa, this transition pressure decreases with temperature. Unit-cell volumes of LiF and NaF B1 phase measured at various pressures and temperatures were fitted using a P–V–T Birch–Murnaghan equation of state. For LiF, the determined parameters are: α₀ = 1.05 (3)×10^?4 K^?1, dK/dT = ?0.025 (2) GPa/K, V ₀ = 65.7 (1) Å³, K ₀ = 73 (2) GPa, and K′ = 3.9 (2). For NaF, α₀ = 1.34 (4)×10^?4 K^?1, dK/dT = ?0.020 (1) GPa/K, V ₀ = 100.2 (2) Å³, K ₀ = 46 (1) GPa, and K′ = 4.5 (1).     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

Effect of heat treatment procedure on magnetic and magnetocaloric properties of Ni43Mn46In11 melt spun ribbons

The effect of heat treatment on the structural, magnetic and magnetocaloric properties of Ni₄₃Mn₄₆In₁₁ melt-spun ribbons was systematically investigated using X-ray powder diffraction (XRD), scanning electron microscope (SEM), atomic force microscope (AFM), magnetic force microscope (MFM) and magnetic measurements. From the XRD studies, tetragonal and cubic phases were detected at room temperature for as-spun, quenched and slow-cooled ribbons. Furthermore, it was observed, upon annealing martensite transition temperatures increased when compared to the as-spun ribbon. To avoid magnetic hysteresis losses in the vicinity of the structural transition region, the magnetic entropy changes-ΔS _m of the investigated ribbons were evaluated from temperature-dependent magnetisation-M(T) curves on cooling for different applied magnetic fields. The maximum ΔS _m value was found to be 6.79 J kg^?1 K^?1 for the quenched ribbon in the vicinity of structural transition region for a magnetic field change of 50 kOe.     

Thermal diffusivity of MORB-composition rocks to 15 GPa: implications for triggering of deep seismicity

We have measured the thermal diffusivity of eclogite and majorite with a model MORB composition at pressures of 3 and 15 GPa, respectively. Both phase assemblages show inverse dependences of their thermal diffusivities on temperature: D _eclogite=9(10)×10^?10+7(1)×10^?4/T(K) m ²/s and D _majorite=6.2(5)×10^?7+3.0(5)×10^?4/T(K) m ²/s. The values for majorite are in good agreement with previous measurements for other garnets and are considerably lower than thermal diffusivities of wadsleyite and ringwoodite, which are the main components of the mantle transition zone. We discuss the implications of the low thermal conductivity of subducted oceanic crust in the transition zone for the triggering of deep seismicity.     

Magnetization behaviour of DyAl2 single crystals

We report the theoretical interpretation of the magnetization and the magnetocrystalline anisotropy of ferromagnetic DyAl₂ single crystals between 4.2 and 60 K and magnetic fields up to 15 T. Good agreement between theory and experiment is obtained by using three temperature independent parameters: the two crystal field parameters B₄ = (?0.50 ± 0.05) × 10^?4 meV, B₆ = ? (0.51 ± 0.05) × 10^?6 meV and the Curie temperature T_c = (62 ± 2) K.     

Effects of linking chain length and magnetic field on the kinetics of photoprocesses in covalently bonded porphyrin—viologen dyads

The formation and decay kinetics of chain linked triplet radical pairs derived from photo-induced electron transfer reactions in a series of 21 zinc porphyrin-flexible spacer-viologen (ZnP-Sp _n -Vi²⁺) dyads containing 2–138 atoms (n) in the spacer, have been examined by nanosecond laser flash photolysis techniques in an external magnetic field. In non-viscous polar solvents (acetone and CHCl₃ plus CH₃OH = 1:1 v/v), the effect of the spacer length on the rate constant of forward electron transfer can be described by the equation: k _et = k ⁰ _et(n + 6)^?1.5, with k ⁰ _et = 3 × 10¹⁰ s^?1 and 1.2 × 10¹⁰ s^?1 for electron transfer from the singlet and triplet states of ZnP, respectively. In zero magnetic field, the value of the triplet radical pair recombination rate constant, k _r(0) = 0.7 × 10⁶-8 × 10⁶ s^?1, is significantly smaller than k _et. The dependence of k _r(0) on n has an extremum with the maximum near n = 20. In a strong magnetic field (B = 0.21 T), significant retardation of triplet radical pair recombination is observed. In strong magnetic fields the effect of the chain length on triplet radical pair recombination rates is rather small and k _r(B) may vary in the range 0.3 × 10⁶-1 × 10⁷ s^?1. The phenomena observed are discussed in terms of the interplay of molecular and spin dynamics in the limits of slow and fast encounters, taking into account the exchange-interaction.     

Transport properties of n-type ferromagnetic semiconductor HgCr2−xInxSe4(x = 0.100)

Measurements of the electrical conductivity, magnetoresistance, and Hall effect were performed on a n-type ferromagnetic semiconductor HgCr_2?xIn_xSe₄(x = 0.100) single crystal from 6.3 to 296 K in magnetic fields up to 1.19×l0⁶A/m. The conductivity decreases rapidly near the Curie temperatureT_c (≈120 K) as the temperature is raised. A large peak in the magnetoresistance is observed near T_c. The Hall effect measurements indicate that the temperature dependence of the conductivity and the magnetoresistance are due mostly to a change in electron mobility. The electron mobility is 1.2 × 10^?2 m²/V · s at 6.3 K, and decreases rapidly near T_c with the rise in temperature. Then it increases slowly from 5.5 × 10^?4 m²/V · s at 160 K to 7.5 × 10^?4 m²/V · s at 241 K. This temperature dependence of the electron mobility can be explained in terms of the spin-disorder scattering which takes into account the exchange interaction between charge carriers and localized magnetic moments.     

Structure,thermal behavior,and dielectric properties of new cesium hydrogen sulfate arsenate: Cs<Subscript>2</Subscript>(HSO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>AsO<Subscript>4</Subscript>)

Synthesis and structural characterization by single-crystal X-ray diffraction method, thermal behavior, and electrical proprieties are given for a new compound with a superprotonic phase transition Cs₂(HSO₄)(H₂AsO₄). The title compound crystallizes in the monoclinic system with the P2₁/n space group. The structure contains zigzag chains of hydrogen-bonded anion tetrahedra that extend in the [010] direction. Each tetrahedron is additionally linked to a tetrahedron neighboring chain to give a planar structure with hydrogen-bonded sheets lying parallel to (10ī). The existence of O–H and (S/As)–O bonds in the structure at room temperature has been confirmed by IR and Raman spectroscopy in the frequency ranges 4000–400 cm^?1and 1200–50 cm^?1, respectively. Differential scanning calorimetry analysis of the superprotonic transition in Cs₂(HSO₄)(H₂AsO₄) showed that the transformation to high temperature phase occurs at 417 K by one-step process. Thermal decomposition of the product takes place at much higher temperatures, with an onset of approximately 534 K. The superprotonic transition was also studied by impedance and modulus spectroscopy techniques. The conductivity in the high temperature phase at 423 K is 1.58 × 10^?4 Ω^?1 cm^?1, and the activation energy for the proton transport is 0.28 eV. The conductivity relaxation parameters associated with the high disorder protonic conduction have been examined from analysis of the M”/M”_max spectrum measured in a wide temperature range. Transport properties of this material appear to be due to the proton hopping mechanism.     

The B 2Σ+–X 2Σ+ Transition of 12C17O+: The 2‐υ″ Progression

Abstract

Three new bands of the B ²Σ⁺–X ²Σ⁺ system of ¹²C¹⁷O⁺ have been investigated using conventional spectroscopic techniques. The spectra were observed in a graphite hollow‐cathode lamp by discharging molecular oxygen (enriched in about 45% of the ¹⁷O₂ isotope) under 1.0 Torr pressure. The rotational analysis of the 2–4, 2–5, and 2–6 bands was performed with the effective Hamiltonian of Brown (Brown et al., J. Mol. Spectrosc. 1979; 74: 294–318). Molecular constants were derived from a merge calculation, including both the current wavenumbers and the spectroscopic data published by the authors previously. The principal equilibrium constants for the ground state of ¹²C¹⁷O⁺ are ω_e=2185.9658(84), ω_e x _e = 14.7674(11), B _e=1.927001(38), α_e=1.8236(22)×10^?2, γ_e=?0.331(28)×10^?4, D _e=6.041(12)×10^?6, β_e=0.100(31)×10^?7 cm^?1, and the equilibrium constants for the excited state are σ_e=45876.499(15), ω_e=1712.201(12), ω_e x _e=27.3528(39), B _e=1.754109(35), α_e=2.8706(57)×10^?2, γ_e = ?1.15(19)×10^?4, D _e=7.491(20)×10^?6, β_e=2.13(12)×10^?7, γ_e = 2.0953(97)×10^?2, and α_γe=?9.46(59)×10^?4 cm^?1, respectively. Rydberg–Klein–Rees potential energy curves were constructed for the B ²Σ⁺ and X ²Σ⁺ states of this molecule, and Franck–Condon factors were calculated for the vibrational bands of the B–X system.     

Giant volume magnetostriction and colossal magnetoresistance in La0.7Ba0.3MnO3 at room temperature

In single-crystal La_0.7Ba_0.3MnO₃, giant volume magnetostriction was observed for the first time to reach 2.54 × 10^?4 at room temperature and a still larger level of 4 × 10^?4 at the Curie point T _C = 310 K in a magnetic field of 8.2 kOe. At the same temperatures and magnetic field, this effect is complemented by a colossal magnetoresistance of 15.2 and 22.7%, respectively. The volume magnetostriction ω and magnetoresistance Δρ/ρ follow similar patterns in the proximity of T _C; namely, ω and Δρ/ρ are negative, maxima are observed in the |ω|(T) and |Δρ/ρ|(T) curves, and the ω and Δρ/ρ isotherms do not saturate in the highest fields applied. These phenomena are assigned to the fact that, in the above composition, there exists a two-phase magnetic (ferromagnetic-antiferromagnetic) state induced by strong s–d exchange.     

Temperature dependence of Bi2O3 structural parameters close to the α–δ phase transition

This article presents the results of in situ X-ray powder diffraction, Raman spectroscopy, and electrical impedance spectroscopy of the α-phase of Bi₂O₃, at 0.1 MPa in the temperature range below and above the α–δ-phase transition. This work demonstrated subtle nonlinear temperature variations of the cell parameters, of the hard-mode Raman shift, and of the activation energy of electrical conductivity in the temperature range about 100–120°C below the α–δ phase transition temperature T _Tr ≈ 725°C in Bi₂O₃. At T < 600°C, the linear variation of the inverse dielectric susceptibility (χ ^?1) correlates well with the hard mode frequency shift Δ(ω ²) of Raman A_1g mode as Δ(χ ^?1)/Δ(ω ²) ≈ 5.5 × 10^?7 cm². A structural model describing the mechanism of O^2? anion distribution and electric dipole disordering in the vicinity of T _Tr is discussed.     

Effect of proton irradiation on the physical properties of PC/PBT blends

Samples from polycarbonate/poly (butylene terephthalate) (PC/PBT) blends film have been irradiated using different fluences (1?×?10¹⁵– 5?×?10¹⁷ H⁺/cm²) of 1?MeV protons at the University of Surrey Ion Beam Center, UK. The structural modi?cations in the proton irradiated samples have been studied as a function of fluence using different characterization techniques such as X-ray diffraction and UV spectroscopy. The results indicate that the proton irradiation reduces the optical energy gap that could be attributed to the increase in structural disorder of the irradiated samples due to crosslinking. Furthermore, the color intensity ΔE, which is the color difference between the non-irradiated sample and those irradiated with different proton fluences, increased with increasing the proton fluence up to 5?×?10¹⁷ H^+/cm², convoyed by an increase in the red and yellow color components. In addition, the resultant effect of proton irradiation on the thermal properties of the PC/PBT samples has been investigated using thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It is found that the PC/PBT decomposes in one weight loss stage. Also, the variation of transition temperatures with proton fluence has been determined using DSC. The PC/PBT thermograms were characterized by the appearance of two endothermic peaks due to the glass transition and melting temperatures. The melting temperature of the polymer, T_m, was investigated to probe the crystalline domains of the polymer, since the proton irradiation destroys the crystalline structure so reducing the melting temperature.     

Preparation and thermoelectric power of SnBi4Se7

Polycrystalline samples of Bi₂Se₃ and a stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ have been prepared and characterized by X-ray powder diffraction analysis. At room temperature the carrier concentration values are n?=?1.1?×?10¹⁹?cm^?3 for Bi₂Se₃ and n?=?0.53?×?10¹⁹?cm^?3 for SnBi₄Se₇. The thermoelectric power has been measured over the temperature range 90–420?K. The thermoelectric power of Bi₂Se₃ is higher than that for SnBi₄Se₇, which shows that the Sn impurity has an acceptor character. Therefore, doping Bi₂Se₃ with tin atoms does not improve thermoelectric properties of this material, due to decrease the value of the power factor σS ². Transport properties of the studied polycrystalline samples are characterized by a mixed transport mechanism of free carriers. It is necessary to add more than one Sn atom to the Bi₂Se₃ compound in order to suppress the electron concentration by one electron. Such behaviour of the dopant is explained by the formation of various structural defects. Besides the dominant substitutional defect, Sn_Bi, tin atoms also form uncharged defects, corresponding to seven-layer lamellae of the composition Se–Bi–Se–Sn–Se–Bi–Se which corresponds to the structure of the SnBi₂Se₄.     

Cooperative phenomena of random electric dipoles in an amorphous matrix

A ferroelectric phase transition has been observed for the first time in a series of glasses containing WO₆-octahedra. The techniques of thermally stimulated depolarization currents were used to observe the transition from independent dipole behavior to cooperative behavior in this amorphous system as a function of concentration. These measurements yielded the activation energy ΔE=1.2eV, the pre-exponential τ₀=2 × 10^-22sec, and the dipole moment p?=1.3 × 10^?15 esu cm for WO₃ in Li₂B₄O₇. A dipole moment bearing species due to Li₂B₄O₇ was observed with ΔE=0.44eV and pre-exponential τ₀=5 × 10^?8 sec. The depolarization peaks of WO₃ occur in the temperature range 265–275 K depending upon WO₃ concentration and are pressure dependent with an initial slope of 2 × 10^?5K dyne^?1 cm². A model was developed for a possible phase transition associated with a random “pseudo-spin” system in an amorphous matrix.     

The transport properties of Dirac fermions in chemical vapour-deposited single-layer graphene

Abstract

The electronic transport properties of Dirac fermions in chemical vapour-deposited single-layer epitaxial graphene on anSiO₂/Si substrate have been investigated using the Shubnikov–de Haas (SdH) oscillations technique. The magnetoresistance measurements were performed in the temperature range between 1.8 and 43 K and at magnetic fields up to 11 T. The 2D carrier density and the Fermi energy have been determined from the period of the SdH oscillations. In addition, the in-plane effective mass as well as the quantum lifetime of 2D carriers have been calculated from the temperature and magnetic field dependences of the SdH oscillation amplitude. The sheet carrier density (1.42 × 10¹³ cm^?2 at 1.8 K), obtained from the low-field Hall Effect measurements, is larger than that of 2D carrier density (8.13 × 10¹² cm^?2). On the other hand, the magnetoresistance includes strong magnetic field dependent positive, non-oscillatory background magnetoresistance. The strong magnetic field dependence of the magnetoresistance and the differences between sheet carrier and 2D carrier density can be attributed to the 3D carriers between the graphene sheet and the SiO₂/Si substrate.     

Spectroscopy of YAl3(BO3)4:Cr3+ crystals following first principles and crystal field calculations

The CASTEP module of the Materials Studio package was used for calculations of the structural, electronic and optical properties of pure and Cr³⁺-doped YAl₃(BO₃)₄ (YAB). The exchange-correlation effects were treated within the generalized gradient approximation with the Perdew–Burke–Ernzerhof functional. The Monkhorst–Pack scheme k-points grid sampling was set at 3?×?3?×?4 for the Brillouin zone. The plane-wave basis set energy cutoff was set at 340?eV; ultrasoft pseudopotentials were used for all chemical elements. The convergence parameters were as follows: total energy tolerance 1?×?10^?5?eV/atom, maximum force tolerance 0.03?eV/nm, maximal stress component 0.05?GPa and maximal displacement 0.001?Å. The principal absorption peaks of the studied crystal were identified. The influence of 532?nm?cw, 300?mW laser radiation on the observed absorptions was studied.     

Electrooptical Kerr constant and third-order susceptibility measurements in nematic liquid crystals and their mixtures

We report for the first time the determination of the real part of the third order nonlinear susceptibilities ⁽³⁾ (–, , 0, 0) in the isotropic phase of two nematic liquid crystalsp-(ethoxybenzylidine)-p-butylaniline (EBBA) andp-(methoxybenzylidene)-p-butylaniline (MBBA) from electrooptic Kerr effect experiments. The highest value of ⁽³⁾ observed near nematic-to-isotropic transition temperature, at 632.8 nm is found to be 1.067×10^–20 m²V^–2 for EBBA and 6.602×10^–20 m²V^–2 for MBBA.