Critical temperature of infinitely long chains from Wertheim's perturbation theory

Wertheim's theory is used to determine the critical properties of chains formed by m tangent spheres interacting through the pair potential u(r). It is shown that within Wertheim's theory the critical temperature and compressibility factor reach a finite non-zero value for infinitely long chains, whereas the critical density and pressure vanish as m ^-1.5. Analysing the zero density limit of Wertheim's equation or state for chains it is found that the critical temperature of the infinitely long chain can be obtained by solving a simple equation which involves the second virial coefficient of the reference monomer fluid and the second virial coefficient between a monomer and a dimer. According to Wertheim's theory, the critical temperature of an infinitely long chain (i.e. the Θ temperature) corresponds to the temperature where the second virial coefficient of the monomer is equal to 2/3 of the second virial coefficient between a monomer and dimer. This is a simple and useful result. By computing the second virial coefficient of the monomer and that between a monomer and a dimer, we have determined the Θ temperature that follows from Wertheim's theory for several kinds of chains. In particular, we have evaluated Θ for chains made up of monomer units interacting through the Lennard-Jones potential, the square well potential and the Yukawa potential. For the square well potential, the Θ temperature that follows from Wertheim's theory is given by a simple analytical expression. It is found that the ratio of Θ to the Boyle and critical temperatures of the monomer decreases with the range of the potential.     

Special points on the phase diagrams of langbeinites. The case of (x,T)-phase diagram of mixed K2xRb2(1−x)Cd2(SO4)3 crystals

We have studied special points that appear on the (x, T)-phase diagram of mixed K_2xRb_2(1?x)Cd₂(SO₄)₃ crystals. This phase diagram has been constructed issuing from the changes in domain structure occurring in the course of phase transitions. We have found that two triple points on the (x, T)-phase diagram of the above solid solutions are very close to each other in the phase space and can change their places or transform into a quadruple point. These special points are associated with disappearance of ferroelectric phases with the symmetries P1 and P2₁ taking place when Rb₂⁺ are substituted with K₂⁺ ions.     

Effect of the “negative chemical” pressure on the temperatures of phase transitions in the TlInS<Subscript>2</Subscript> layered crystal

The temperature dependences of the permittivity of TlInS_{2(1 −x)}Se_2x solid solutions have been experimentally investigated in the temperature range including the points of structural phase transitions in the solid solutions. It has been established that the isovalent substitution of selenium for sulfur in the anion sublattice of the TlInS_{2(1 − x)}Se_2x solid solutions shifts the phase transition temperatures T _i and T _c toward the low-temperature range with a simultaneous decrease in the temperature interval of the existence of the incommensurate phase. The T-x phase diagram is constructed for the solid solutions under study and the coordinates are determined for a critical point (of the Lifshitz type) at which the lines T _i (x) and T _c (x) converge in the phase diagram. The pattern of the T-x phase diagram for the TlInS_{2(1 − x)}Se_2x solid solutions has been analyzed within the phenomenological model of a virtual crystal.     

Ternary oil—water—amphiphile systems: self-assembly and phase equilibria

The micellization properties and phase behaviour of model ternary surfactant—oil—water systems were studied by grand canonical Monte Carlo simulations assisted by histogram reweighting techniques. Larson's lattice model was used for a symmetrical H₄T₄ surfactant, where H represents hydrophilic and T hydrophobic groups. In contrast to earlier studies, oil chains of variable length, from T to T₄, were studied and the effect of added oil on the critical micelle concentration (cmc) was determined quantitatively. It was found that the cmc decreases as the volume fraction of oil in the aqueous phase is increased. Longer oil chains have a stronger effect than shorter chains for the same volume fraction. The oil, tail and head density profiles were obtained for typical micelles. Simulation results for the density profiles indicate that long chain oils are almost exclusively located within the micellar aggregates, in agreement with single-chain mean-field theory predictions. Ternary phase diagrams were obtained both by simulations and by quasichemical theory. The results suggest that the critical micelle concentration line is directed towards the oil-lean corner of the three-phase triangle, if there is one present in the system. It was also found that the amount of oil that can be dissolved in the ternary system increases sharply at the surfactant critical micelle concentration, indicating that micellization greatly enhances oil solubility.     

About the existence of a Lifshitz point on the phase diagram of Sn2P2(Se x S1– x )6 solid solutions: acoustic and optical studies

On the basis of combined studies of the acoustic and optical properties of Sn₂P₂(Se _x S_{1– x} )₆ solid solutions with x?=?0 and 0.28 it is shown that two special points exist on the x,T-phase diagram of these ferroelectric crystals, a tricritical point and a triple one. With increasing Se concentration, the phase transition changes its character at x?≈?0.28 from second-order to first-order. The phase transition becomes split at x?≈?0.4, with the appearance of an intermediate incommensurate phase.     

The spin-S Blume-Capel RG flow diagram

Using the finite-size scaling renormalization group, we obtain the two-dimensional flow diagram of the Blume-Capel model forS=1 andS=3/2. In the first case our results are similar to those of mean-field theory, which predicts the existence of first- and second-order transitions with a tricritical point. In the second case, however, our results are different. While we obtain in theS=1 case a phase diagram presenting a multicritical point, the mean-field approach predicts only a second-order transition and a critical endpoint.     

Quantum fluctuation driven first-order phase transition in weak ferromagnetic metals

In a local Fermi liquid (LFL), we show that there is a line of weak first-order phase transitions between the ferromagnetic and paramagnetic phases due to purely quantum fluctuations. We predict that an instability towards superconductivity is only possible in the ferromagnetic state. At T?=?0 we find a point on the phase diagram where all three phases meet and we call this a quantum triple point (QTP). A simple application of the Gibbs phase rule shows that only these three phases can meet at the QTP. This provides a natural explanation of the absence of superconductivity at this point coming from the paramagnetic side of the phase diagram, as observed in the recently discovered ferromagnetic superconductor, UGe ₂.     

The effect of a surface on the dynamic and thermodynamic properties of S=1 Heisenberg ferromagnet with biquadratic exchange

Properties of semi-infinite (S=1) Heisenberg ferromagnet with biquadratic exchange were studied in terms of surface exchange (=I_S/I) and biquadratic coupling (a). It was shown that a strict correlation exists, depending on , between the type of surface spin waves (acoustic or optical) and the mean-field (MF) critical temperature, bulk (T_c) and surface T_c^S>T_c (for ). Within the framework of the Landau–Ginsburg theory for semi-infinite simple cubic ferromagnet, a detailed study is presented of the critical behaviour of the system, in particular in the vicinity of the tricritical point which is the consequence of the biquadratic interaction. It is shown that tricritical exponents satisfy exactly the scaling relations for d=3. The analysis of the spin–spin correlation function within the framework of the same theory, shows that there occurs the critical magnetic scattering of low-energy electrons (LEED) from the surface in the case , when the ordering temperature T_c^S is approached from above (from paramagnetic phase). In the opposite case, , there occurs no surface critical scattering. It was also shown that in the vicinity of the tricritical point, the biquadratic interaction increases the range of validity of the MF approximation.     

Critical properties of homopolymer fluids studied by a Lennard-Jones statistical associating fluid theory

A Lennard-Jones statistical associating fluid theory, the soft-SAFT equation of state, is used to study the dependence of the critical properties on chain length for pure polymers. The critical constants of chains up to 10⁶ monomer units are predicted. The main advantage of these calculations, versus others found in the literature, is the fact that the equation is able to accurately predict experimental data available only for short chain lengths and, at the same time, it is able to predict the critical properties in the infinite chain length scaling regime, without any further assumptions. The equation gives quantitative agreement with experimental and Monte Carlo simulation data for normal alkanes. For very long chains, the equation predicts mean-field scaling behaviour, as expected. Moreover, taking advantage of the linearity of the molecular volumes and dispersive energies with the chain molecular weight, a value of 1/5 is found for the critical compressibility factor of an infinitely long n-alkane chain. It is demonstrated that this is not contradictory to Wertheim's theory.     

The kinetic spin-1 Blume-Capel model with Glauber dynamic

We study the dynamic phase transitions (DPT), within a mean-field approach, in the kinetic spin-1 Blume-Capel model by using the Glauber-type stochastic dynamics. The nature of the transition is characterized by investigating the behavior of the thermal variation of the dynamic order parameter and the Lyapunov exponent. The phase diagram is constructed in the temperatures (T) and single-ion anisotropy amplitude (D) plane. Our results predict first-order transitions at low temperature and large anisotropy strengths, which correspond in the phase diagram to the existence of a nonequilibrium tricritical point (TCP). We compare our results with the equilibrium phase diagram.     

Application of low field NMR T2 measurements to clathrate hydrates

Low field (2 MHz) Nuclear Magnetic Resonance (NMR) proton spin–spin relaxation time (T₂) distribution measurements were employed to investigate tetrahydrofuran (THF)—deuterium oxide (D₂O) clathrate hydrate formation and dissociation processes. In particular, T₂ distributions were obtained at the point of hydrate phase transition as a function of the co-existing solid/liquid ratios. Because T₂ of the target molecules reflect the structural arrangements of the molecules surrounding them, T₂ changes of THF in D₂O during hydrate formation and dissociation should yield insights into the hydrate mechanisms on a molecular level. This work demonstrated that such T₂ measurements could easily distinguish THF in the solid hydrate phase from THF in the coexisting liquid phase. To our knowledge, this is the first time that T₂ of guest molecules in hydrate cages has been measured using this low frequency NMR T₂ distribution technique. At this low frequency, results also proved that the technique can accurately capture the percentages of THF molecules residing in the solid and liquid phases and quantify the hydrate conversion progress. Therefore, an extension of this technique can be applied to measure hydrate kinetics. It was found that T₂ of THF in the liquid phase changed as hydrate formation/dissociation progressed, implying that the presence of solid hydrate influenced the coexisting fluid structure. The rotational activation measured from the proton response of THF in the hydrate phase was 31 KJ/mole, which agreed with values reported in the literature.     

Anisotropic compressible Ising model for quasi-one-dimensional hydrogen-bonded ferroelectrics

A compressible pseudo-spin Ising model hamiltonian is used to calculate the pressure-temperature phase diagram of quasi-one-dimensional hydrogen-bonded ferroelectric crystals such as CsD₂PO₄. We assume strong effective interactions, which are treated exactly, along chains, and weak volume dependent interactions, which are treated in the mean field approximation, between chains. In agreement with the experimental findings, the phase diagram exhibits a triple point and transition lines between ferroelectric, antiferroelectric, and paraelectric phases. However, the results suggest that the Ising model may be too simple to account for the detailed form of the phase diagram of CsD₂PO₄.     

Compensation point (or points) of nanoscaled transverse Ising thin films: effects of surface dilution

The phase diagram (critical temperature and compensation temperature) and the total magnetizations in a nanoscaled transverse Ising thin film with thickness L and a negative interlayer coupling at the surfaces are investigated by the use of both the effective-field theory with correlations and the mean-field theory. Particular emphasis is given to the effects of the surface and its dilution on them. We have found that, for appropriate values of the system parameters, compensation point (or points) may be obtained in the present system with L?=?5 (or L?=?10).     

Characteristic features of the magnetic ordering of Dy3+ ions in a monoclinic RbDy(WO4)2 single crystal

The investigation of the specific heat of a RbDy(WO₄)₂ single crystal at temperatures 0.2–2.5 K and in magnetic fields up to 2 T are reported. The temperature dependence of the specific heat near T _N=0.818 K is compared with the predictions for different models. The 2D Ising model describes satisfactorily C(T) below T _N, while for T>T _N none of the theoretical models agree with the behavior of C(T) of RbDy(WO₄)₂. The H-T phase diagram for H∥c is complicated and possesses a triple point, where regions of existence of three magnetic phases converge. The magnetic ordering is analyzed from the standpoint of the Jahn-Teller nature of the structural phase transitions occurring in RbDy(WO₄)₂ at higher temperatures. It is shown that the form of the phase diagram depends on the direction of the vector H, for the general case of an arbitrary direction of H, two phase transitions can occur with increasing field. Fiz. Tverd. Tela (St. Petersburg) 41, 491–496 (March 1999)     

Interplay of metamagnetic and structural transitions in Ca2-xSrxRuO4

Metamagnetism in layered ruthenates has been interpreted as a novel kind of quantum critical behavior. In an external magnetic field, Ca_2-xSr_xRuO₄ undergoes a metamagnetic transition accompanied by a pronounced magnetostriction effect. In this paper we present a mean-field study for a microscopic model that naturally reproduces the key features of this system. The phase diagram calculated is equivalent to the experimental T-x phase diagram. The presented model also gives a good basis to discuss the critical metamagnetic behavior measured in the system.     

Coexistence of color superconductivity and chiral symmetry breaking within the NJL model

The phase diagram for quark matter is investigated within a simple Nambu-Jona-Lasinio model without vector correlations. It is found that the phase structure in the temperature-density plane depends sensitively on the parametrization of the model. We present two schemes of parametrization of the model where, within the first one, a first-order phase transition from a phase with broken chiral symmetry to a color superconducting phase for temperatures below the triple point at T _t = 55 MeV occurs, whereas for the second one a second-order phase transition for temperatures below T _t = 7 MeV is found. In the latter case, there is also a coexistence phase of broken chiral symmetry with color superconductivity, which is a new finding within this class of models. Possible consequences for the phenomenology of the QCD phase transition at high baryon densities are discussed. Received: 3 January 2003 / Accepted: 21 February 2003 / Published online: 24 April 2003     

Dielectric studies of phase transitions in the ferroelectric CdTiO3 and the Sr1−x CdxTiO3 solid solution

Temperature dependences of the permittivity and of the dielectric hysteresis loops in ceramic samples of nominally pure CdTiO₃ and a Sr_1?x Cd_xTiO₃ solid solution were studied. At 76.5±0.5 K, CdTiO₃ was established to undergo a ferroelectric phase transition close to the tricritical point. The temperature dependence of spontaneous polarization of CdTiO₃ is described within the Landau theory of phase transitions with the critical order parameter exponent ≈0.25. The phase diagram of the Sr_1?x Cd_xTiO₃ solid solution was drawn in (T, x) coordinates, and the critical concentration x _c =0.002, above which an induced polar state sets in the solid solution, was determined.     

Jordan-Wigner approach to the frustrated spin one-half XXZ chain

The Jordan-Wigner transformation is applied to study the ground state properties and dimerization transition in the J₁-J₂ XXZ chain. We consider different solutions of the mean-field approximation for the transformed Hamiltonian. Ground state energy and the static structure factor are compared with complementary exact diagonalization and good agreement is found near the limit of the Majumdar-Ghosh model. Furthermore, the ground state phase diagram is discussed within the mean-field theory. In particular, we show that an incommensurate ground state is absent for large J₂ in a fully self-consistent mean-field analysis.     

On the tricritical point on the (p,T)-phase diagram of Sn2P2S6 crystals

Using studies of the temperature dependence of the acoustic wave velocity at high hydrostatic pressures, a tricritical point where second-order phase transitions change to first-order ones was experimentally revealed on the pressure–temperature phase diagram of Sn₂P₂S₆ crystals. The behavior of the acoustic wave velocity is explained in the framework of mean-field theory.