Phase transitions and modulated structure of the incommensurate phase in Mg[H2O]6SiF6 crystal

The temperature and angular dependences of the EPR spectra of Mg[H₂O]₆SiF₆:Mn²⁺ crystal were investigated in order to clarify the successive phase transitions and existence of the incommensurate phase. Five successive phase transitions were found to occur, and phase II was found to be incommensurately modulated. The modulated structure is caused mainly by the vibrational displacement of the Mg[H₂O]²⁺ ₆ ion along the c-axis. The soliton density of this phase is almost independent of temperature and remains equal to unity.     

39K quadrupole coupling and spin-lattice relaxation in the high temperature phases in KLiSO4

³⁹K quadrupole perturbed nuclear magnetic resonance spectra show that in KLiSO₄ atT _c =743 K a phase transition from a room temperature hexagonal to a high temperature orthorhombic phase takes place. The high temperature phase is definitely not incommensurately modulated. The huge shortening of the³⁹K spin-lattice relaxation time on approachingT _c from below demonstrates that KLiSO₄ becomes a superionic conductor above 743 K. The self-diffusion coefficient of the Li-ions is estimated asD=10^–6 cm²/s at 780 K.     

Structure and SHG of the high pressure phase IV of HgBr2

Angle dispersive X-ray diffraction experiments on mercuric bromide (HgBr₂) under high pressure up to 11.0 GPa were carried out at room temperature using synchrotron radiation. In addition to the already known four different phases of HgBr₂ in the pressure-temperature range of p<4.5 GPa, 90<T<600 K our observations show the existence of a new phase (V) above 9.0 GPa and, together with published material, support the phase transition sequence: (I) orthorhombic-(II) orthorhombic-(III) monoclinic-(IV) trigonal-(V) trigonal/hexagonal. The structure of phase IV with space group symmetry P3 has been determined from powder diffraction data. The observation of second-harmonic-generation signals confirms the absence of an inversion center. The structure of phase IV is a commensurately modulated variant of the CdI₂ type layer structure, where part of the Hg atoms are displaced from the centers of the HgBr₆ octahedra by a much as 0.76 Å in the direction perpendicular to the layers.     

Phase transition of [(C6H5)3PCH3]+(TCNQ)-2 and electrical transport properties

The electrical conductivity at 10GHz, the dielectric constant, and the thermoelectric power (TEP) of [(C₆H₅)₃PCH₃]⁺(TCNQ)^-₂, from 230 up to 400 K, have been measured. This organic quasi-one-dimensional solid undergoes a first order phase transition at 314 K. At the transition the conductivity increases by a factor of 2.2 and the activation energy drops to 0.26 from 0.31 eV. At 314 K TEP decreases abruptly from -75 to -60μVK^-1 and remains almost constant for T > 314 K. The dielectric permeability ?₀ is constant and equal to 5 in the low temperature phase, increases abruptly by 7% at the transition, and then depends strongly on temperature in the high temperature phase. Results of the high temperature phase are interpreted in terms of a strongly correlated salt.     

Influence of hydrostatic pressure on the phase transition in the complex antifluorites and hexammines: Rigid-sphere model interpretation

Abstract

The pressure coefficient of the phase transition temperature T_c, dT_c/dp = -(11⁺-1) K/GPa, has been determined for Ni (NH₃)₆Cl₂ using a new high pressure and low temperature probe. The relations between T_c and dT_c/dp were determined for antifluorite K₂MCl₆ compounds and hexammines applying the rigid-sphere model.     

LiNaSO4-MgSO4赝二元系中离子导体的研究

本文用差热分析和X射线衍射方法,对LiNaSO₄-MgSO₄赝二元系相图进行了研究。在此体系中存在三个化合物,它们分别为(LiNa)_0.8Mg(0.2)SO₄,(LiNa)_0.67Mg_0.33SO₄和(LiNa)_0.4Mg_0.6SO₄。研究了三种化合物的离子导电性,在490℃时上述三个化合 关键词：     

Static and dynamic effects in the EPR spectra of [A(H2O)6]BF6 systems

EPR studies of [Mg(H₂O)₆]BF₆ (B=Si, Ge) crystals are performed by using Mn²⁺ paramagnetic probes. The temperature dependence of the EPR spectra shows that the crystals undergo a ferroelastic phase transition to a monoclinic phase. In both systems the ferroelastic phase transition is preceded by intermediate states. The spin Hamiltonian parameters determined in the low and high temperature phases of the systems are useful to precise some aspects of the local atomic displacements involved in the intermediate states. The nature of this state is analyzed in the framework of different models as well.     

Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies

The group-theoretical study of the structural phase transition to incommensurate state of MgSiF₆·6H₂O crystals, revealed by the electron paramagnetic resonance (EPR) method, as well as analysis of the EPR results, are presented. The consideration of temperature dependences of Mn²⁺ admixture ion EPR spectrum symmetry and parameters leads to the conclusion that at T _i1 = 370 ± 0.3 K they undergo second-order structural phase transition to incommensurately modulated state, the order parameter of this transition may be the angle of [Mg(H₂O)₆]²⁺ octahedra rotation around crystal C ₃ axis. At temperature decreasing below T _i1 the gradual transformation of plane-wave modulation of lattice displacements into soliton mode occurs, which is interrupted by the first-order phase transition at T _i2 = 343 ± 0.3 K accompanied by abrupt decrease in modulation amplitude. At T _c = 298.5 ± 0.3 K the first-order improper ferroelastic phase transition into monoclinic phase occurs. The group-theoretical analysis of the phase transition at T _i1 in the investigated crystals, carried out for the first time, has shown that the existence of the incommensurately modulated phase is conditioned by the fundamental reasons (presence of Lifshitz invariant). The conclusions of this analysis on the nature of order parameter, the structural motifs of incommensurate phase and the possible character of temperature evolution of the structure are in agreement with the EPR investigation data.     

Methods of reference signal and phase shifts in the multipass laser schemes for the detection of trace gas impurities

The application of the methods using the phase shift of modulated radiation and ICOS for the measurement of relatively low concentrations of gas impurities is considered. The measurement sensitivities of 0.01 ppbv and 6 × 10⁻¹¹ cm⁻¹ with respect to concentration and absorption coefficient, respectively, are obtained for the NO₂ molecules.     

LiKSO4的无公度相

本文用多晶X射线衍射配合差热分析的方法研究了LiKSO₄室温以上的相变。发现当温度在熔点以下到675℃之间,晶体结沟与α-K₂SO₄的高温相同构,α相最可能的空间群为P6₃/mmc.在T_i=675℃以下出现调制结构,类似K₂WO₄,K₂MoO₄等的无公度相;参数κ的值由0.492(640℃)而随温度变化。在470℃出现整合相变κ=0.500,整合后的结构为室温相的超点阵。然后在439℃转变为室温相(空间群为P6₃)。 关键词：     

Monte Carlo studies of wilson loops in four-dimensional U(2) gauge theory

Wilson loops are calculated using Monte Carlo simulations for pure U(2) gauge theory on a 6⁴ lattice. The loops appear to contain an area law piece in both the high and low temperature regions. The string tension is discontinuous at β = β_c, where β_c is the critical inverse temperature. This suggests that the first-order phase transition in U(2) gauge theory is not a deconfining phase transition. The determinant of the Wilson loop, however, extracts the U(1) part of the theory and appears to lose the area law at low temperature.     

A Streak Camera System for Time Resolved Fluorimetry

Presently, there are several techniques for measurement of fluorescence lifetimes of organic molecules. These techniques, reviewed by Ware,¹ can be divided into two basic groups, those based upon pulsed sources and those based on modulated sources and phase shift measurement. In the pulsed methods, repetitive, short pulse width, intense excitation pulses excite the fluorophor and the fluorescence decay is measured; the source temporal response must be deconvoluced from the fluorescence decay in order to evaluate the fluorescence signal and lifetime. Typical sources of excitation include nanosecond flashlamps and more recently nanosecond N₂-laser (with or without a dye laser) and mode-locked lasers with picosecond pulse widths^2-6. The modulated source phase shift methods,¹ involve sinusoidal excitation of the fluorophor and measurement of the phase shift between the modulated excitation source and the modulated flourescence. Because modulation frequencies are limited to approximately 20 MHz, fluorescence lifetimes are limited to ～.1 ns and above. In addition, in the phase shift methods, only “one point” lifetimes are obtained, i.e., the entire fluorescence decay curve is not obtained.     

High field magnetic susceptibility of individual single crystals of the organic conductor (fluoranthene)2PF6

Using single crystals of a sufficient size (4–7 mg) and a high quality (about 5 × 10^-4 paramagnetic defects per formula unit) we measured the anisotropic static magnetic properties of the quasi-1d organic conductor (FA)₂PF₆ in external fields of up to 70 kOe. Thus the strong anisotropy of the molecular diamagnetism was determined for the first time. The contribution of the conduction electrons to the static susceptibility of (FA)₂PF₆ was separated. We analysed the influence of fluctuations (pseudogaps) in the metallic high temperature phase and we derived the temperature dependence of the energy gap in the low-temperature (T < 185 K) semiconducting phase of (FA)₂PF₆.     

On the ordering in [(C2H5)4N]2CuCl4 crystal: an X-ray study and theoretical considerations

The crystal structure [(C₂H₅)₄N]₂CuCl₄ has been determined by X-ray diffraction at 243K. The room temperature phase (phase I) belongs to the space group P4₂/nm [1] whereas the low temperature phase (phase II) is orthorhombic and belongs to the space group Pnna. The phase transition at T_c=258K is of improper ferroelastic type and it is associated with the ordering of the CuCl₄ ^2? and a partial ordering of the [(C₂H₅)₄N]⁺ ions which are disordered in the high temperature tetragonal phase. At lower temperature, there occurs another instability which could correspond to a complete ordering in the crystal.     

Temporal correlations and persistence in the kinetic Ising model: the role of temperature

We study the statistical properties of the sum S _t = dt'σ _t', that is the difference of time spent positive or negative by the spin σ _t, located at a given site of a D-dimensional Ising model evolving under Glauber dynamics from a random initial configuration. We investigate the distribution of S_t and the first-passage statistics (persistence) of this quantity. We discuss successively the three regimes of high temperature ( T > T _c), criticality ( T = T _c), and low temperature ( T < T _c). We discuss in particular the question of the temperature dependence of the persistence exponent , as well as that of the spectrum of exponents (x), in the low temperature phase. The probability that the temporal mean S _t/t was always larger than the equilibrium magnetization is found to decay as t ^{- - ?}. This yields a numerical determination of the persistence exponent in the whole low temperature phase, in two dimensions, and above the roughening transition, in the low-temperature phase of the three-dimensional Ising model. Received 4 December 2000     

Low-energy scattering of muonic hydrogen on hydrogen molecules: a semi-classical approach

We present results of PAC measurements in heavy-fermion compound Yb₄As₃. The quadrupole hyperfine interaction has been investigated over the temperature range 78–850 K. The interpretation of the experimental data yields a microscopic proof of the existence of a charge-ordered state with periodic arrangement of Yb²⁺ and Yb³⁺ ions in the low temperature phase. In the high temperature phase all Yb ions are in a valence fluctuating state.     

Bi luminescence in ABiO2Cl (A=Sr, Ba) and BaBiO2Br

Trivalent bismuth luminescence is reported in three Sillen bismuth oxyhalide phases, SrBiO₂Cl, BaBiO₂Cl, and BaBiO₂Br. These compounds exhibit Bi 6s6p→6s² emission under UV and X-ray radiations. At room temperature, BaBiO₂Cl shows the most intense light emission, with spectral and decay properties similar to those found in Bi₄Ge₃O₁₂ (BGO). At low temperatures, each phase show an increase in the photoluminescence intensities and a narrowing of the emission peaks. In contrast to the temperature dependence of BGO, X-ray excited luminescence intensities of all three phases remain relatively constant throughout the temperature range 10-295 K, though much lower than BGO at low temperatures. This result indicates that the Sillen phases undergo less thermal quenching than BGO. The low temperature and room temperature radio-luminescence decay times were determined from pulsed X-ray measurements. At room temperature, SrBiO₂Cl exhibits faster decays than BGO, while BaBiO₂Cl and BaBiO₂Br have decay times similar to BGO.     

反应扩散法制备的PbMo6S8超导带的超导特性

本文报道反应扩散法制备Chevrel相PbMo₆S₈超导带材的过程以及带材的超导特性。Mo带与H₂S气体反应生成单相的Mo-S化合物(MoS₂或Mo₂S₃,根据反应温度而定),再与Pb的蒸汽反应生成单相的PbMo₆S₈薄层。PbMo₆S₈超导层的临界温度T_c=13.0 关键词：     

Low frequency dielectric permittivity of quasi-one-dimensional conductor (TMTTF)2Br

Conductivity and permittivity of the organic transfer salt (TMTTF)₂Br have been measured at low frequencies (10²-10⁷ Hz) between room temperature down to 4 K. The real part of the permittivity, , is shown to grow below the temperature at which the conductivity is maximum due to charge localization of Mott-Hubbard type. reaches a maximum of 10⁵-10⁶ at 35 K-50 K depending on the samples. Decreasing temperature below , sharply decreases down to helium temperature through the antiferromagnetic phase transition at T _N = 15 K. We explain the magnitude, the temperature and frequency dependence of as resulting from short range charge density wave states in the temperature range where charge localization occurs. This interpretation is supported by recent X-ray scattering measurements. Received: 10 October 1997 / Revised: 28 February 1998 / Accepted: 3 March 1998     

Pressure and temperature induced modification of luminescence from tetracene single crystals

Fluorescence spectra of crystalline tetracene have been recorded in the temperature range 120 to 300 K under hydrostatic pressure up to 600 MPa. From discontinuities in both emission spectra and spectral intensities it is concluded that two phase transitions occur. The room temperature phase is transformed to a low temperature phase/high pressure phase I at T^I_t (p = 0) = 182 K, the temperature coefficient being dT^I_t/dp = 0.395 K/MPa. The phase transition is induced by a decrease of the specific volume under pressure and/or upon cooling. Lack of a significant shift of the origin of the fluorescence band near T^I_t at constant pressure is an artifact resulting from the neglect of reabsorption effects. The Stokes shift is 260 cm^-1, independent of temperature and crystal modification. In accord with previous Raman data a second phase transition occurs at T^II_t (p) = 143 K, the pressure shift being dT^II_t/dp = 0.088 K/MPa.In addition, the shift of the triplet energy as a function of pressure as well as the pressure-dependence of the rate constants governing fission of a singlet exciton into a pair of triplets is discussed utilizing their magnetic field dependences.