Strain-induced ferroelectric phase transitions in incipient ferroelectric rutile TiO2

Uniaxial strain induced ferroelectric phase transitions in rutile TiO₂ are investigated by first-principles calculations. The calculated results show that the in-plane tensile strain induces rutile TiO₂, paraelectric phase with P_4-2/mnm (D_4h) space group, to a ferroelectric phase with P_m (C_s) space group,driven by the softening behaviour of the E_u1 mode. In addition, the out-of-plane tensile strain, vertical to the ab plane, leads to a ferroelectric phase with P_42nm (C_4v) space group, driven by the softening behaviour of the A_2u mode. The critical tensile strains are 3.7% in-plane and 4.0% out-of-plane, respectively. In addition, the in-plane compression strain, which has the same structure variation as out-of-plane tensile strain due to Poisson effect, leads the paraelectric rutile TiO₂ to a paraelectric phase with P_nnm (D_2h) space group driven by the softening behaviour of the B_1g mode. These results indicate that the sequence ferroelectric (or paraelectric) phase depends on the strain applied. The origin of ferroelectric stabilization in rutile TiO₂ is also discussed briefly in terms of strain induced Born effective charge transfer.     

Elastic constants of single crystals of the three phases of In---Pb alloys

In a study of the elastic behaviour of the InPb alloys, the elastic stiffness tensor components of crystals of each of the three phases (fct, $\text{c}\text{a}\text{> 1}$; fct, $\text{c}\text{a}\text{> 1}$; fcc) have been obtained as a function of temperature from pulse superposition measurements of ultrasonic wave velocities. Comparison of the elastic stiffness constants obtained for a fct ($\text{c}\text{a}\text{> 1}$) 5 atm.% Pb alloy with those of In itself and those of InTl and InCd alloys, establishes for this phase that alloying with Pb, as with TI and Cd, enhances the softening of the acoustic [110] phonon mode, polarization [1$\text{1}$0] near the Brillouin zone centre. The elastic properties of a 17 atm.% Pb crystal, which is in the fct ($\text{c}\text{a}\text{> 1}$) phase, are quite different from those shown by In alloys in the fct ($\text{c}\text{a}\text{> 1}$ phase; in particular the response to a shear stress is remarkably isotropie: there is no phonon mode softening in this alloy. Neither is there softening of this mode (which corresponds at the zone centre to the shear stiffness $\text{1}\text{2}$(C₁₁;C₁₂)) in crystals of the fee phase — in complete contrast to the dominating influence of the softening of $\text{1}\text{2}$(C₁₁;C₁₂) in the InTl and InCd fee alloys. In fact for a fcc In-75 atm.% Pb alloy the anistropy ratio for shear $\text{2C}{}_{44}\text{(C}{}_{11}\text{C}{}_{12}\text{)}$ is close to unity. The transitions between the three phases of the InPb alloys are markedly first order and acoustic mode softening has a much smaller influence on the elastic behaviour of the fct ($\text{c}\text{a}\text{< 1}$) and fcc InPb alloys than it has on the fct ($\text{c}\text{a}\text{< 1}$) InPb, InCd and InTl alloys.     

Glassy phase and thermodynamics for random field Ising model on spherical lattice in magnetic field

Phase diagram and thermodynamic parameters of the random field Ising model (RFIM) on spherical lattice are studied by using mean field theory. This lattice is placed in an external magnetic field (B). The random field (hi) is assumed to be Gaussian distributed with zero mean and a variance     

Ultrasonic investigation of phase transitions in K2SnCl6

The velocities and the attenuation of ultrasonic waves have been investigated as a function of temperature (255KT350K) for the cubic phase of K₂SnCl₆ which undergoes a structural transition atT _c1263K. An anomalous decrease of the shear stiffness constantc=1/2(c ₁₁ –c ₁₂) of about 30% between room temperature andT _c1 is found in this cubic high temperature phase whenT _c1 is approached from above. Whereas the softening ofc extends over a substantial temperature range (about 50 K), the other shear constantc ₄₄ shows only a weak decrease, which is an order of magnitude smaller and restricted toT–T _c110 K. NearT _c1, a strong increase occurs in the attenuation of the shear acoustic wave propagated along the [111] direction, while such an anomalous attenuation is not observed for the transverse acoustic wave propagated along [100]. Furthermore, atT _c1 a hysteresis is detected for the longitudinal sound wave velocityv _L[100], which is restricted to the temperature region 262KT263.5 K. In addition, the room-temperature elastic constants of (NH₄)₂SiF₆ and the hydrostatic pressure derivatives of the elastic constants of K₂SnCl₆ and (NH₄)₂SiF₆ at room-temperature are presented and discussed in terms of mode softening behaviour.     

对关联对于Pb208附近α衰变的影响——α约化宽度的绝对值的计算

本文利用BCS波函数及投影波函数计算了₈₄Po的偶-偶同位素及₈₅At的奇-偶同位素的α约化宽度γ_α²的绝对值。文中仔细研究γ_α²的绝对值及相对趋势和参数b,R₀,G的关系;b为谐振子势阱参数,R₀为道半径,G为对关联相互作用常数。计算结果的分析表明:(1)对关联有利于α的形成,它可以使α约化宽度的绝对值增加一个数量级,且可以使相对趋势与实验符合得更好。(2)BCS波函数的粒子数不守恒的缺点,对于满壳外粒子数不多的核的α衰变来说相当严重。用了粒子数守恒的投影波函数,绝对值可以增加1—2倍,且可以使相对趋势变好。(3)考虑了阻塞效应后,宽度约减小10％,使奇A核的阻碍因子的理论值和实验值一致。(4)绝对值对参数的选择很敏感,而相对趋势对参数则不太敏感,要使理论的绝对值接近实验值,必须取R₀在8f以内。     

Nanomechanics of single silkworm and spider fibres: a Raman and micro‐mechanical in situ study of the conformation change with stress

The combination of micro‐Raman spectroscopy and an advanced universal fibre tester (UFT) made it possible to probe at the nanoscale (through monitoring the modification of chemical bonds) the change in conformation (α‐helix, β‐sheet, etc.), macromolecular fibroin chain orientation and coupling during the application of stress, quantitatively. Different single fibres of silkworms (Bombyx mori, Gonometa rufobrunea, Gonometa postica) and a spider (Nephila madagascariensis) were tested in a dry environment and compared with the behaviour of keratin fibre. As observed previously for single keratin fibres, a direct relationship is observed between nano‐ and micro‐mechanical tensile behaviour. The phase transition plateau, well defined for some pristine B. mori fibres, disappears in degummed fibres, which indicates a structural modification and increasing disorder with chemical treatments. Stress‐controlled micro‐Raman analysis shows that a few modes involving CH₂ and/or amide groups of β‐conformation chains undergo a wavenumber softening during the elastic behaviour (∼0–3%), although most of the modes are not affected. A different behaviour is observed for modes associated with ‘ordered’ and ‘disordered’ β‐sheets and helical chains. Larger softening is observed for lattice modes with increasing stress/strain, as expected. Structural changes and relationships with mechanical behaviour are discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Neutron scattering study of the phase transition in s-triazine at high pressure

The elastic transition in s-triazine (C₃N₃H₃) from a trigonal ($\text{R}\text{3}\text{c}$) high temperature (low pressure) structure to a monoclinic (C2/c) low temperature (high pressure) phase has been investigated at pressures up to 5 kbar using neutron scattering techniques. Neutron diffraction was used to measure the pressure dependence of the order parameter and inelastic scattering to study the softening of the transverse acoustic phonon modes on three isotherms. In both cases the effect of pressure on the transition is found to be described primarily by that on the temperature of the transition.     

Dynamics in molecular crystals: An application of proton NMR to selectively protonated biphenyl. Do the rings flip together or independently?

The synthesis of a specific isotopomer, C₆D₄H(ortho)-H(ortho)D₄C₆ of biphenyl is reported. The intramolecular dipolar coupling of the protons leads to a well-resolved single-crystal proton nuclear magnetic resonance (NMR) spectrum and allows one to study the dynamics of the phenyl rings in a unique way. At room temperature and above, the most conspicuous dynamical mode consists of 180° ring flips. The present data together with previous measurements of the total flip rate allow us to conclude that the rings flip almost exclusively independently of each other. Between the incommensurate (IC) phase transition of biphenyl at 38 K andT=250 K, the prominent namical mode consists of oscillatory twists ϕ(t) of the two rings. The data allow us to infer the mean square, (φ²), of these twists. (φ²) is found to grow linearly withT for 50<T<200 K. From the slope of (φ²) vs.T the frequency (the wave number[(v)\tilde]\tilde v) is derived. The result is[(v)\tilde] = 20\tilde v = 20 cm⁻¹. ForT<38 K, the spectra give direct evidence of the IC phase transition and its nature (stripelike rather than quiltlike). The temperature dependence of the magnitude of the order parameter of the IC phase is obtained.     

Ultrasound studies of single crystal thulium in an applied magnetic field

The paper reports the first measurements of the single crystal elastic constants of the heavy rare earth metal thulium as a function of temperature and magnetic field. The constants were obtained from ultrasonic velocity measurements over a temperature range of 4.2–296 K and in applied magnetic fields of up to 5 T. The elastic constants; C₁₁, C₃₃, C₄₄ and C₆₆=(C₁₁–C₁₂)/2 were determined from the ultrasonic velocities. Anomalies in the elastic constants were observed at 58 K from the c-axis propagated shear wave measurements and at 55 K from the c-axis propagated longitudinal wave measurements. Significant softening of the elastic constants C₃₃ and C₄₄ was observed close to T_N. Application of a magnetic field (>2 T) along the c-axis direction induced further softening of the material. Electromagnetic acoustic transducers (EMATs) were also employed in addition to conventional piezoelectric quartz transducers. A marked increase in the EMATs acoustic coupling efficiency (generation and detection efficiency) occurred close to T_N.     

Frequency domain measurements on Na2B4O7−V2O5 semiconducting glass

Summary Dielectric measurements on Na₂B₄O₇(99.5%)−V₂O₅(0.5%) glass system, in the frequency range 10⁻³ to 10⁴ Hz and temperature range 300 to 500 K, have been carried out. The normalized plots of complex capacitance have shown a single mechanism responsible for conduction for both volume and surface measurements with their close values of activation energies (0.67±0.03) eV and (0.64±0.03) eV, respectively. The low-frequency dispersion (LFD) behaviour has been observed to be perturbed by the presence of more than one competing process. The impedance plots have shown a parallel combination of a capacitor (C) and a resistor (R), with some contribution of a dispersive element due to charge accumulation in the vicinity of the electrodes. The values ofR andC were found to be of the same order of magnitude, for both surface and volume measurements. The observedR has shown a decrease with an increase in temperature due to an increase in mobility of Na⁺ ions, whereasC remains practicaly constant. The complex capacitance surface behaviour is dominated by volume, due to hygroscopy of this glass system.     

Order parameter anisotropy of MgB2 using specific heat jump of layered superconductors

The recently obtained analytical result [1] for renormalization of the jump of the heat capacity (C _S–C _N)/C_N by anisotropy of the order parameter is applied to the layered superconductors. The graph of (C _S–C _N)/C _N vs. the anisotropy of the order parameter allows a direct determination of the gap anisotropy in MgB₂ using available experimental data     

One-dimensional Anderson model with dichotomic correlation in the presence of external electric field

A one-dimensional diagonal tight binding electronic system with dichotomic correlated disorder in the presence of external d.c field is investigated. It is found numerically that the conductance distribution obeys fairly well to log-normal distribution in weak disorder strength in localized regime, which indicates validity of single parameter scaling theory in this limit. Contrary to the universal cumulant relation C ₁ = 2C ₂ in the absence of d.c. field, we demonstrated numerically that C ₁ ≫ 2C ₂ in the presence of the field in localized regime. We interpret this result as suppression of the fluctuation effects by the external field. In addition, it is obtained that the quantity NF _c , here N is the system size and F _c is the crossover field, decreases as the as the system energy E increases. Moreover, we find numerically a simple linear relation between the average logarithm of the conductance 〈ln(g)〉 and the field strength as 〈ln(g)〉 = C(N, λ)F, here C(N, λ) is a constant for particular values of N and λ, which is the Poisson parameter of the dichotomic process.     

Group-theoretical analysis of possible structural phase transitions in the high-temperature superconductors

A group-theoretical analysis is performed for the complete condensation of order parameters at structural phase transitions (SPT's) in the high-temperature superconductors belonging to the D ¹⁷ _4h -14/mmm space group in the high-symmetry phase. As a rule, such transformations are due to a successive softening of phonons with wave vectors k ₁ = 1/2 b ₃ and k ₂ = 1/2 (b ₁ - b ₃) belonging to the K13(X) star of the Brillouin zone of a tetragonal body-centered Bravais cell. SPT's in system La_2-x Ba _x CuO₄ are considered in detail.     

Photopolymerization in the Fullerene Layers of the Molecular Donor–Acceptor Complex {Pt(nPr2dtc)2} · (C60)2

We measured Raman spectra in crystals of molecular donor–acceptor fullerene complexes {Me(nPr₂dtc)₂} · (C₆₀)₂ (Me = Ni, Cu, Pt). In the spectra of the {Pt(nPr₂dtc)₂} · (C₆₀)₂ complex under prolonged irradiation with a laser with λ = 532 nm, characteristic changes in the photopolymerization of fullerene are observed, associated with the splitting of degenerate phonon Hg modes and softening of Ag modes of the C₆₀ molecule. The kinetics of photopolymerization under conditions of weak irradiation at room temperature is studied. It was found that thermal destruction of the photopolymer with increasing temperature leads to a decrease in its concentration in the final photopolymerization product. The kinetics of thermal destruction is described by the Arrhenius equation, with the activation energy E_A of (0.68 ± 0.03) eV; the dimers are destructed to a concentration of 1% within 15 min at ~114°C.

     

Fluorescence Spectrometric Studies on the Binding of an Amino-Functionalized Ionic Liquid to Cytochrome c

The interaction of an amino-functionalized ionic liquid, 1-(2-aminoethyl)-3-butylimidazolium bromide ([NH₂C₂C₄im]Br), with cytochrome c (cyt c) at pH 7.4 was investigated using fluorescence and UV-Vis absorption spectroscopic techniques. From the experimental results, it is found that cyt c has a strong ability to quench the intrinsic fluorescence of [NH₂C₂C₄im]Br and the quenching mechanism is considered as a static quenching process. The binding constants and the number of binding sites (n) were calculated at different temperatures. The thermodynamic parameters such as free energy change (ΔG), enthalpy change (ΔH), and entropy change (ΔS) were calculated by thermodynamic equations. According to the results, the values of ΔG, ΔH, and ΔS are all negative, suggesting that interaction between [NH₂C₂C₄im]Br and cyt c is spontaneous and mainly driven by hydrogen bonding and van der Waals forces.     

Quadrupolar susceptibility and magnetic phase diagram of PrNi2Cd20 with non-Kramers doublet ground state

ABSTRACT

In this study, ultrasonic measurements were performed on a single crystal of cubic PrNi₂Cd₂₀, down to a temperature of 0.02?K, to investigate the crystalline electric field ground state and search for possible phase transitions at low temperatures. The elastic constant (C₁₁?C₁₂)/2, which is related to the Γ₃-symmetry quadrupolar response, exhibits the Curie-type softening at temperatures below ～30?K, which indicates that the present system has a Γ₃ non-Kramers doublet ground state. A leveling-off of the elastic response appears below ～0.1?K toward the lowest temperatures, which implies the presence of level splitting owing to a long-range order in a finite-volume fraction associated with Γ₃-symmetry multipoles. A magnetic field–temperature phase diagram of the present compound is constructed up to 28?T for H || [110]. A clear acoustic de Haas–van Alphen signal and a possible magnetic-field-induced phase transition at H ～26?T are also detected by high-magnetic-field measurements.     

Phase transitions and temperature changes of the optical absorption edge in (NH2(C2H5)2)2CoCl4 layered crystal

This work was devoted to X-ray diffraction study and investigations of temperature changes of the optical absorption edge of (NH₂(C₂H₅)₂)₂CoCl₄ crystals in the region of possible phase transitions. The X-ray powder diffraction data revealed the monoclinic phase at room temperature – space group P2/n. The cobalt atom was found to be square-plane coordinated by four chlorine atoms resulting [CoCl₄]^2– anion, which is surrounded by two DEA⁺ cations. It was shown that the low-energy tail of the absorption edge in these materials possesses an exponential shape. In the temperature range above 255?K it follows the empirical Urbach’s rule. The obtained experimental data confirmed the existence of the ferroelastic phase in (NH₂(C₂H₅)₂)₂CoCl₄ in the temperature range between 255 and 326?K. The anomalous behaviour of the investigated parameters observed at the temperatures below 255?K would be related to earlier unknown phase transitions.     

Exchange interactions and spin dynamics in a [CuNd2(C4O4)4(H2O)16]·2H2O crystal

Crystalline [CuNd₂(C₄O₄)₄(H₂O)₁₆]·2H₂O constructed of complexes of trivalent neodymium and divalent copper, has been synthesized and studied by EPR. The square anion groups (C₄O₄) enter as bridge ligands, forming chains of neodymium ions interconnected by (C₄O₄)Cu(C₄O₄) fragments. It is found that the relaxation rate of the neodymium subsystem at room temperature significantly exceeds the exchange interaction rate between copper and neodymium ions. Under these conditions the magnetic properties of the crystal are determined by two magnetically nonequivalent chains of copper ions, which do not interact. The intrachain exchange interaction via hydrogen bonds is estimated to be ∼0.1 cm⁻¹. As one proceeds from the high-temperature (250<T<300 K) to the low-temperature region (T<40 K), a substantial change in the nature of the interaction is revealed. An unusual magnetic structure given in a crystal is observed at low temperatures, which is determined by the presence of two magnetically nonequivalent “ribbons,” formed by the interacting copper and neodymium ions: chains of copper ions are framed on two sides by chains of neodymium ions. The magnitude of the parameter of the exchange interaction between the copper and neodymium ions is estimated as J ^Cu-Nd⩾0.2 cm⁻¹. An exchange interaction between magnetically nonequivalent neodymium ions is not revealed in the EPR spectra. Fiz. Tverd. Tela (St. Petersburg) 39, 2057–2061 (November 1997)     

Critical behaviour in the shear elasticity of adamantane in the plastic phase

The elastic constants of the molecular crystal adamantane (C₁₀H₁₆) have been measured at 10 MHz as a function of temperature in the cubic plastic phase, with special attention given to the region just above the order-disorder transition into the tetragonal rigid phase. Both the velocity and attenuation of the C′ shear wave exhibit incipient critical behavior near this transition. The C′ stiffness also shows a pretransitional softening when this transition is approached by increasing the pressure along several isotherms.     

Isotopic effects on non-linearity, molecular radius and intermolecular free length

Computation of non-linearity parameter (B/A), molecular radius (r _m) and intermolecular free length (L _f) for H₂O, C₆H₆, C₆H₁₂, CH₃OH, C₂H₅OH and their deuterium-substituted compounds have been carried out at four different temperatures, viz., 293.15, 303.15, 313.15 and 323.15 K. The aim of the investigation is an attempt to study the isotopic effects on the non-linearity parameter and the physicochemical properties of the liquids, which in turn has been used to study their effect on the intermolecular interactions produced thereof.