Dielectric relaxation near the antiferroelectric phase transition of squaric acid

The dielectric response of single crystals of squaric acid is studied around the antiferroelectric phase transition atT _c 100°C. The dielectric data between 64 and 400 GHz can be explained by a simple Debye-relaxation with a critical slowing-down of the relaxation frequency to about 55 Ghz on approachingT _c . The results in the paraelectric phase are discussed on the basis of weakly coupled one-dimensional Ising chains. Within the scope of this model we determine the intra and interchain coupling constants, the molecular dipolar moments and the noninteracting proton intrabond-jump time.     

13C-NMR study of the phase transition in the layered antiferroelectric squaric acid

The temperature dependence of the¹³C-NMR spectra of undoped crystals of the layered antiferroelectric squaric acid (C₄H₂O₄; H₂SQ was measured at a resonance frequency of about 75 MHz by means of the¹H–¹³C double resonance technique. The relation between the order parameter and the chemical shift tensors at the¹³C nuclei is discussed in detail. The line splitting in the ordered phase belowT _c100°C is shown to be proportional to the order parameter. The phase transition is of first order and can be well described by a Landau expansion of the free energy. The results are compared to previous determinations of the temperature dependence of the order parameter. The spin lattice relaxation time of the¹³C system is estimated to be 5000–7500 s at 5°C and the given magnetic field.     

Static and dynamical elastic behaviour of squaric acid around its phase transition

Ultrasonic velocity measurements could be performed on a good quality single crystal of squaric acid close to its transition temperature around 373 K. The behaviour of the stiffness componentsc ₃₃ andc ₄₄ clearly demonstrates a first-order transition. The temperature variation ofc ₁₁ andc ₆₆ can be fitted to a formula obtained from the Landau theory and assuming a strictive-type coupling between order parameter and strain. From attenuation measurements characteristic times for the order-parameter dynamics can be estimated, ranging from 10^?11 to several 10^?10s in a temperature range of about 12 K on either side of the transition.     

A structural phase transition in squaric acid

Squaric acid (3,4-dihydroxy-3-cyclobutene-1,2-dione) is found to undergo a second order antiferrodistortive tetragonal to monoclinic phase transition at 97.7°C. The transition temperature for the fully deuterated compound is 243°C. The crystals are optically biaxial negative at room temperature, and the partial birefringence decreases with temperature as (n_z ? n_y)α(T_C ? T)^β, where β_H = 0.34 ± 0.02 and β_D = 0.37 ± 0.04.     

Interacting one dimensional Ising spin chains as a model of the layered antiferroelectric squaric acid

Starting from the structure of the layered antiferroelectric squaric acid and assuming an ice rule type interaction mechanism of the protons it is shown that aboveT _c the molecular layers may be considered as a system of parallel and orthogonal nearly independent linear Ising spin chains with strong intrachain and comparatively weak interchain interactions. Whereas the former are treated exactly as nearest neighbour interactions the interchain interactions are taken into account either by the molecular field approximation or, in computer simulations, by nearest neighbour interactions. The parameters of the model are related to the unusually small transition entropy, to the high and nearly temperature independent dielectric constant aboveT _c ,and to neutron scattering data.     

Specific heat of the two dimensional antiferroelectric squaric acid

The heat capacity of a single crystal of the two dimensional antiferroelectric squaric acid was measured particularly near the phase transition. In a wide temperature range belowT _c a strong temperature dependence of the anomaleous specific heat is found which can be described by a critical exponent=0.5. The behaviour close toT _c is determined by a latent heat thus indicating the phase transition to be of the first order. Near the phase transition the thermal behaviour can be described by a Landau type theory. The smallness of the transition entropy detected may be ascribed possibly to proton tunneling.     

Dynamical studies of highly deuterated betaine phosphate near the antiferroelectric phase transition

The dielectric response and the Raman spectra of single crystals of deuterated betaine phosphate are studied around the antiferroelectric phase transition. The dielectric data between 10 MHz and 11 GHz can be explained on the basis of a simple Debye-relaxation with a critical slowing-down of the relaxation rate on approachingT _C . Using the Cole-Davidson form of the dielectric function we succeeded in fitting the data in the whole frequency range from 10 MHz to 11 GHz and from 64–400 GHz over a temperature range from 145–280 K. Raman spectra clearly indicate that the doubling of the unit cell does not take place at the antiferroelectric transition temperature, but some degrees below.     

Network traffic behaviour near phase transition point

We explore packet traffic dynamics in a data network model near phase transition point from free flow to congestion. The model of data network is an abstraction of the Network Layer of the OSI (Open Systems Interconnect) Reference Model of packet switching networks. The Network Layer is responsible for routing packets across the network from their sources to their destinations and for control of congestion in data networks. Using the model we investigate spatio-temporal packets traffic dynamics near the phase transition point for various network connection topologies, and static and adaptive routing algorithms. We present selected simulation results and analyze them.     

Fast proton spin-lattice relaxation time in the rotating frame during the application of time averaged precession frequency

A relatively rapid phase alternation of the effective field in the time averaged precession frequency (TAPF) sequence results in averaging of the proton RF spin-lock field. The spin-locking of the proton magnetization becomes less efficient and thus shortens T(1rho)(H), the proton spin-lattice relaxation time in the rotating frame. The relaxation time also depends on the ratio of tau(1) and tau(2) intervals i.e. tau(1)/tau(2) and not only on the number of tau(c)=tau(1)+tau(2) blocks, i.e. the number of the phase transients. Experiments are performed on solid samples of ferrocene and glycine and for some time intervals, T(1rho)(H) is shortened by factors of 9-100 compared to the relaxation times obtained in the standard experiment.     

Critical behaviour near the incommensurate-commensurate phase transition in dysprosium

Neutron scattering measurements of the helical turnangle indicate that the incommensurate-commensurate transition in Dy obeys a logarithmic mean-field behaviour and not a β-exponent power law.     

Myocardial proton spin-lattice relaxation times in vitro: Effect of elapsed time after excision

An assumption made in using excised tissue for in vitro nuclear magnetic resonance (NMR) studies is that variables of interest, such as spin-lattice (T₁) relaxation times, remain stable for periods of time after excision sufficient to perform NMR spectroscopy. In this study, we evaluated the changes in T₁ of rat myocardium, measured at two NMR field strengths, at serial time intervals up to 72 hours postmortem. Left ventricular myocardium from six male Sprague-Dawley rats was excised and stored at room temperature in sealed NMR sample tubes. Spin-lattice relaxation times were determined with a modified inversion-recovery pulse sequence immediately postmortem and at intervals up to 72 hours post-excision; NMR studies were performed using 90 MHz and 360 MHz spectrometers. A gradual decrease in T₁ was noted with increasing time post-excision; T₁ was not significantly shorter than baseline until 72 hours postmortem at either field strength. The rate of change of T₁ was similar at the two field strengths. At any given time post-excision, T₁ was significantly higher (p < 0.001) at 360 MHz than at 90 MHz. We conclude that, with proper tissue handling and storage techniques, rat myocardial T₁ is stable postmortem sufficiently long to permit meaningful NMR studies of excised tissue.     

Vibronic model for antiferroelectric phase transition in squaric acid, H2C4O4

The antiferroelectric phase transition in H₂C₄O₄ crystals is analyzed using the neutron diffraction and high resolution ¹³C, ¹⁷O NMR data, Hartree-Fock, Moller-Plesset and DFT calculations. Is shown that AFE phase transition is of mixed order-disorder and of displacive type represented within of the unified vibronic interaction model.     

Anomalous behavior of the electrical resistivity of MnSi near the ferromagnetic phase transition

The results of measuring the electrical resistivity of a MnSi single crystal near the ferromagnetic phase transition at atmospheric and high pressures are reported. In contrast to the previous works, compressed helium is used as a pressure-transferring medium. It is shown that the temperature derivative of the electrical resistivity has the form of sharp maximum on the phase-transition line over the entire its length. Moreover, the observed maxima have a fine structure exhibiting a pronounced shoulder at temperatures slightly higher (by approximately 0.5 K) than the peak temperature, which indicates the existence of nontrivial fluctuations in the paramagnetic phase of MnSi. This feature disappears at a pressure of about 0.35 GPa, which corresponds to the tricritical-point coordinate.     

Proton spin-lattice relaxation time of hydrated gelatin

In this work we obtain a model to describe the relaxativity of water molecules, adsorbed on macromolecules, as a function of the concentration. Excellent agreement with experimental data was obtained. The model allows us to estimate the adsorption energy of water molecules on different sites of the macromolecules.     

Critical anomaly in the electron spin-lattice relaxation at the ferroelectric phase transition of X-irradiated KDA

The spin-lattice relaxation of X-irradiated ferroelectric KDA has been investigated by means of the electron spin-echo method in the range between 2 and 200 K. In the vicinity of the phase transition point an anomalous increase of T₁ has been observed. This effect could not be detected for KDA-KDP mixed crystals with a high concentration of KDP. The anomaly of the spin-lattice relaxation at the phase transition is explained by the increased damping of the “hard” optical mode which governs the relaxation behaviour at this temperature region.     

Selective and nonselective proton spin-lattice relaxation studies of enzyme-substrate interactions

The selective and nonselective longitudinal relaxation rates were measured for glycyl-l-tyrosine protons in the presence of Zn-carboxypeptidase A. Unlike the non-selective relaxation rates, the selective rate was found to be particularly sensitive to the presence of the enzyme. From the nonselective/selective ratio, the correlation times of the free and bound substrate were evaluated.     

Critical slowing down of fluctuations in squaric acid (H2C4O4) at the phase transition observed by 13C spin-lattice relaxation

Spin lattice relaxation T₁ of naturally abundant ¹³C nuclei in squaric acid was measured close to the antiferroelectric-paraelectric phase transition temperature T_c = 373 K. A rapid increase in $\text{1}\text{T}{}_1$ is observed close to T_c coming from above, which follows the power law $\text{1}\text{T}{}_1\text{～ ε}{}^{\mathrm{?1.4}}$ where $\text{ε =}\text{(T ? T}{}_{\mathrm{c}}\text{)}\text{T}{}_{\mathrm{c}}$. This behaviour is explained on the basis of the two-dimensional character of the fluctuations.