The plastic state of C2Cl6

A model structure of the plastic phase of C₂Cl₆ generated by a Monte Carlo method is compared with single crystal neutron data. The model simulates the bcc-structure by an (8 + 1) molecular cluster with a gaussian a priori molecular centre of mass distribution and hard core Cl-Cl interaction. The effective closest Cl-Cl approach is about 10 per cent smaller than the van der Waals radius observed in the low temperature normal crystalline phase of C₂Cl₆. The effect of the hard core interaction on the distribution of the molecular axes, the density of Cl, and the centre of mass distribution is clearly demonstrated.     

Dissociation and dissociative phase transition in dense hydrogen

A simple physical model is proposed for dissociating dense fluid hydrogen. We propose that free dissociated atoms interact via quantum electron-electron exchange analogously to the interaction in the liquid-metal phase of alkali metals. The density dependence of a hydrogen atom’s binding energy in such a quasi-liquid is calculated. It is shown that the transition from the molecular fluid to liquid hydrogen is a first-order phase transition. The critical parameters of the transition are determined: P _c = 72 GPa, T _c = 10500 K, and ρ _c = 0.5 g/cm³. The possibility of the metastable existence of atomic liquid hydrogen in a dissociated molecular fluid under decreased pressure is established.     

Fullerene glasses

We present the phase diagram of (C₆₀)_1-x(C₇₀)._x alloys, obtained from low frequency (1Hz) elastic and thermal expansion measurements. Whereas thermal expansion measurements show only a. fcc to sc phase transition in C₆₀-rich and a hcp to a distorted hcp phase transition in C₇₀-rich samples, low-frequency (1 Hz) elastic compliance measurements show an additional dynamic anomaly for all the samples (except for the pure C₇₀) due to freezing of the molecular motion. This anomaly is centered around T_g≈ 120 K for the pure C₆₀ and rises with rising concentration of C₇₀, reaching T_g ≈ 150 K for mixtures with 95mol% C₇₀. For C₇₀-rich samples with more than 10mol% C₆₀ no orientational phase transition was found. The phase diagram can be described in terms of the orientational glass model.     

A simple molecular theory for photo-induced smectic phase

The response of liquid crystals to light is very important for applications of liquid crystals in display and memory devices. Recently experiments have been carried out on liquid crystals doped with photoactive azo compounds. It is seen that UV rays incident on such systems can lower the nematic isotropic transition temperature T _NI . Also, in some mixtures, a photo-induced smectic phase is observed. This is attributed to the change in the trans (longer) isomer to cis (shorter) isomer of the photoactive dopant. We have earlier developed a molecular mean-field model assuming the medium to consist of inter-converting anti-parallel and parallel pairs to explain the molecular origin of “two lengths”. The model was used to explain double re-entrance, the effect of electric field on T _NI , etc. This model is modified to include the change of trans to cis isomer which is equivalent to an increase of fraction of parallel (shorter) pairs. The calculated phase diagram with respect to incident UV radiation energy shows an induced smectic phase. This is in qualitative agreement with experimental trends.     

Phase transition,structural, mechanical and thermal properties of erbium pnictides under pressure

In this article, we have investigated the high-pressure structural phase transition of erbium pnictides (ErX; X?=?N, P and As). An extended interaction potential model has been developed (including the zero-point energy effect in three-body interaction potential model). Phase transition pressures are associated with a sudden collapse in volume. The phase transition pressures and associated volume collapses have been predicted successfully. The elastic constants, their combinations and pressure derivatives are also reported. The pressure behaviour of elastic constants, bulk modulus and shear modulus have been presented and discussed. Moreover, the thermophysical properties such as molecular force constant (f), infrared absorption frequency (υ ₀), Debye temperature (θ _D) and Grunneisen parameter (γ) have also been predicted.     

Free energy and structural phase transitions in mixed crystals: A microscopic derivation

We consider mixed crystals of the form(MY) _x (MX) _1–x , whereY is an active component which drives a structural phase transition, while the componentX has no active internal degree of freedom. We describe this system by a compressible Ising model, including the dilution of the spinsY and the elastic strain fields caused by the componentX. We derive a Landau expansion of the free energy for this system, within molecular field theory. The coefficients of this expansion depend on temperature, pressure, spin concentrationx and the strain fields. This simple model exhibits a rich phase diagram. At sufficiently high concentrationsx, the phase transition is first order. Decreasingx, the transition passes through a tricritical point and eventually becomes second order. For lowx or high strain fields, no transition occurs.     

Molecular dynamics investigation of the size effect upon the β → α transformation in Zr nanocrystals

The stability of the β phase in cubic zirconium nanoparticles has been calculated as a function of the size r (r varies in the range from 2.5 to 11.5 nm) by the molecular dynamics method with the many-body interatomic interaction potential obtained within the embedded-atom model. It has been demonstrated that the temperature T _k at which the cubic cluster of body-centered cubic zirconium becomes structurally unstable depends nonlinearly on the particle size. The curve T _k (r) exhibits a pronounced maximum in the range r ≈ 4.3−4.7 nm. It has been established that the mechanism of the structural transition from the body-centered cubic phase to the hexagonal close-packed phase depends substantially on the particle size. For particles with sizes in the range from 2.5 to 5.0 nm, there exists a temperature range in which the transition from the body-centered cubic phase to the hexagonal close-packed phase remains incomplete for a long time. In this case, two phases coexist and the initial particle undergoes a strong deformation along the habit plane.     

Biased motion about the long molecular axis in ‘ordered’ smectic phases as studied by deuterium NMR relaxation

Spectral densities of motion were determined by deuteron NMR relaxation measurements in the ‘ordered’ smectic-B and -G phases of 4-n-pentyloxybenzylidene-d ₁-4′-heptylaniline and 4-n-pentyloxybenzylidene-4′-heptylaniline-2,3,5,6-d ₄ at two different Larmor frequencies. Different forms of motional behaviour are involved in these phases in comparison with those in the high temperature ‘disordered’ phases. Specifically, internal ring rotation and direction fluctuation are not effective in the ordered smectic phases. In addition, the fast rotation of the molecule about its long molecular axis is now strongly hindered to give a libration motion of angular amplitudes of about 100°. The third-rate model is again used to describe the molecular reorientation, taking the restricted γ motion into account. The effects of phase biaxiality on spin relaxation in the smectic-G phase are also discussed.     

Zero and finite temperature phase diagram of the spinless fermion model in infinite dimensions

The phase diagram of the model of spinless fermions with repulsive nearest neighbour interaction is calculated analytically on a hypercubic lattice in infinite dimensions (d → ∞). In spite of its simplicity the model displays a rich phase diagram depending on the doping δ, the interaction U and the temperature T. The system can be in the homogeneous phase (HOM), the nonsegregated AB charge density wave (AB-CDW), the AB phase separation region (PS-AB/HOM; coexistence of AB-CDW and HOM), the incommensurate phase (IP) or the IP phase separation region (PS-AB/IP; coexistence of AB-CDW and IP). We identify three important values of the interaction U_IPL = 0.572 < U_IPH = 1.914 < U_IP/PS = 4.212 which distinguish four intervals of U. These imply four different types of phase diagrams. In all the three phase diagrams with U below U_IP/PS the IP appears. We propose a new general ansatz for the order parameter of this phase. A competition between the IP, the PS-AB/IP and the PS-AB/HOM is found. The relevance of our findings for the phase scenario of the Hubbard model is shown.     

Raman scattering study of temperature and hydrostatic pressure phase transitions in Rb2KTiOF5 crystal

Raman spectra of Rb₂KTiOF₅ crystal were obtained and analyzed in the temperature range from 77 to 297 K and under hydrostatic pressure up to 4.2 GPa (at T = 295 K). The experimental results were compared with quantum‐chemical simulation of TiOF₅ pseudo‐octahedron. To interpret effects of lattice ordering, phonon spectra of several ordered phases of Rb₂KTiOF₅ were calculated within ab initio generalized Gordon–Kim model, and ordering of TiOF₅ molecular groups were simulated within Monte Carlo approach. The spectra exhibited orientation disordering in the cubic phase under ambient conditions. Cooling below the phase transition temperature (215 K) leads to partial ordering of the structure. The isotropic perovskite‐like phase was found to undergo first‐order transition into a low‐symmetry anisotropic phase at about 1 GPa. Further compression up to 4.1 GPa did not show any effects associated with phase transitions. Copyright © 2011 John Wiley & Sons, Ltd.     

Effect of the dimension of the phonon spectrum on the stability of condensed media states

The effect of dimension index d _f of the phonon spectrum, which is a structural characteristic in continual models, on the stability of states of condensed media is considered in the Einstein and Debye approximations. The estimate of the phase state stability is based on the Lindemann criterion generalized to arbitrary values of 0 ≤ d _f ≤ ∞. The problem of variation of physical characteristic of a substance by controlling the structure of its phonon spectrum is considered by analyzing the possibility of obtaining molecular hydrogen in the superfluid state. The Einstein and Debye models as applied to the problem on the dynamics of atomic oscillations are compared, and the divergence of the latter model for fractal dimensions d _f < 2 of the phonon spectrum is demonstrated, as well as the incompatibility of the Debye model at high temperatures and the model of a classical oscillator for all dimensions except d _f → ∞.     

Effect of the ferroelastic order parameter on the formation of lead titanate-zirconate phases

A phase diagram identical to the x-T diagram for lead zirconate-titanate (PZT) solid solutions (PbZr_{1 − x} Ti _x O₃) was obtained on the basis of a statistical 12-minima model in the vicinity of the cubic phase boundary. The applicability of this model to the phase transitions in PZT is discussed.     

Orientational order and distribution function in nematic 1-(4-trans hexylcyclohexyl)-4-[(2-4-isothiocyanato phenyl)ethyl] benzene

The refractive indices (n _e,?n _o) and density have been measured as a function of temperature in the liquid-crystalline and liquid phases of nematic 1-(4-trans hexylcyclohexyl)-4-[(2-4-isothiocyanato phenyl)ethyl] benzene. The molecular polarizability and orientational order parameter have been computed using the Neugebauer anisotropic local field model. The distribution function f(β), and hence the higher order parameter ?P ₄?, and nematic pair-potential have been computed at different temperatures in the nematic phase.     

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.     

Molecular-dynamics simulation of methane adsorbed on MgO: Evidence for a Kosterlitz-Thouless transition

A realistic model of a monolayer molecular crystal of methane adsorbed on the (100) surface of MgO has been studied by means of molecular dynamics. The model treates the atomicity of the MgO substrate explicitly. Large corrugations in energy are found for both the translational and rotational motion of methane across the substrate. The preferred configurations of adsorption is over an Mg²⁺ ion in a tripod-down orientation. The orientationally ordered low-energy states of the monolayer have been found. Finite-size-scaling calculations on systems of different sizes indicate, however, that the ordered state exhibits only quasi-long-range order. The disclinations in the ordered phase exist in low concentrations and in bound pairs. Evidence is presented for a Kosterlitz-Thouless-type unbinding transition occurring at T _c ≈ 27 K. No evidence is found for a first-order transition. The specific heat exhibits an anomaly at T ≈ 32 K. The disclination density in the region of the transition is reported; below T _c, this density can be fitted to an Arrhenius-type law, yielding an estimate of the core enegy for a bound vortex-antivortex pair.     

Modulated Phase of a Potts Model with Competing Binary Interactions on a Cayley Tree

We study the phase diagram for Potts model on a Cayley tree with competing nearest-neighbor interactions J ₁, prolonged next-nearest-neighbor interactions J _p and one-level next-nearest-neighbor interactions J _o . Vannimenus proved that the phase diagram of Ising model with J _o =0 contains a modulated phase, as found for similar models on periodic lattices, but the multicritical Lifshitz point is at zero temperature. Later Mariz et al. generalized this result for Ising model with J _o ≠0 and recently Ganikhodjaev et al. proved similar result for the three-state Potts model with J _o =0. We consider Potts model with J _o ≠0 and show that for some values of J _o the multicritical Lifshitz point be at non-zero temperature. We also prove that as soon as the same-level interactionJ _o is nonzero, the paramagnetic phase found at high temperatures for J _o =0 disappears, while Ising model does not obtain such property. To perform this study, an iterative scheme similar to that appearing in real space renormalization group frameworks is established; it recovers, as particular case, previous work by Ganikhodjaev et al. for J _o =0. At vanishing temperature, the phase diagram is fully determined for all values and signs of J ₁,J _p and J _o . At finite temperatures several interesting features are exhibited for typical values of J _o /J ₁.     

T-X Br phase diagram for the NH4Br x Cl1−x system

In this study using a mean field model we calculate the phase line equations for the β-δ, β-γ and γ-δ phase transitions in the NH₄Br_xCl_{1 x} system. We then fit our phase line equations to the experimentally observed T-X _Br phase diagram for this system. Our calculated phase diagram agrees well with the observed one for the NH₄Br_xCl_{1 x} system.     

Absence of the partially ordered phase in theq-state models

We investigate theq-state models called (N ,N ) model using an infinitesimal Migdal-Kadanoff renormalization-group method. We distinguish two cases namely the isotropic model and the anisotropic model. The first one presents a critical value ofq,q _c such that forq _c we obtain an Ashkin-Teller phase diagrams while forq>q _c the partially ordered phase disappears then the model exhibits only phase transition between ferromagnetic phase and disordered one. The phase diagrams in the second case are qualitatively similar to one obtained forZ(6) model for all values ofq.     

X-ray Photoelectron Spectroscopy of Sb2S3 Crystals

The paper presents the X-ray photoelectron spectra (XPS) of the valence band and core levels of semiconductor ferroelectric Sb₂S₃ single crystals, which show weak phase transitions and anomalies of various physical properties. The XPS were measured with monochromatized Al K _α radiation in the energy range 0-1450 eV and the temperature range 160-450 K. The valence band is located 0.8-7.5 eV below the Fermi level. Experimental results of the valence band and core levels are compared with the results of theoretical ab initio calculations of the molecular model of Sb₂S₃ crystal. The chemical shifts in Sb₂S₃ crystal for the Sb and S states are obtained. Results revealed that the small structural rearrangements at the phase transition T _c1 = 300 K shift the Fermi level and all electronic spectrum. Also, temperature dependence of a spontaneous polarisation shifts the electronic spectra of the valence band and core levels. Specific temperature-dependent excitations in Sb 3d core levels are also revealed.     

Ab initio pair potential and phase equilibria predictions for the refrigerant methyl fluoride

Ab initio pair interaction energies for methyl fluoride (CH₃F) were calculated using symmetry adapted perturbation theory with the aug-cc-pVDZ basis set plus bond functions for a large number of configurations of a pair of methyl fluoride molecules in order to obtain a good representation of the two-body potential energy surface. These interaction energies were used to develop a site-site intermolecular potential that accurately reproduced the calculated energies and had the correct asymptotic behaviour at long range. This pair potential was used in Gibbs ensemble Monte Carlo simulations to predict the phase behaviour of methyl fluoride. The predicted equilibrium properties with the ab initio pair potential are in good agreement with the experimentally measured phase boundary, and give an estimated critical point in excellent agreement with measured values. Multi-body effects were then added to the pair potential using a polarizable model. The small changes to the phase behaviour that resulted established that pairwise interactions account for most of the molecular interactions in CH₃F.