Surface and bulk order-disorder transitions

Interrelation of surface an bulk order-disorder transitions in binary alloys A_xB_1−x is discussed within the framework of the Bragg-Williams approximation, using the fcc (100) and bcc (110) surfaces as an example. In an fcc alloy with a (100) surface, layers parallel to the surface undergo alternately second-order transitions. On the other hand, the bulk fee alloy reveals a first-order transition from the disordered phase to a mixture of the disordered and the AB₃- (or A₃B-) type ordered phases except for X = 0.5. The origin of the bulk first-order transition is discussed by taking into account order-disorder transitions in the surface region. For comparison, the bulk second-order transition in a bcc alloy is also discussed.     

Line strengths in the v2 band of H2S

A comparison is made between recent measurements of line intensities in the v₂ band of H₂S and the theory for first-order intensity perturbations in an asymmetric rotor.     

Control of the temperature hysteresis and diffuse dielectric anomaly in the temperature range of the ferroelectric-antiferroelectric phase transition in PbZr1 − x TixO3 (0.03 ≤ x ≤ 0.05) ceramics

The magnitudes of the temperature hysteresis and diffuse dielectric anomaly corresponding to the transition from the antiferroelectric phase to the ferroelectric phase in PbZr_{1 ? x} Ti_xO₃ (0.03 ≤ x ≤ 0.05) ceramics can be reversibly changed by varying the temperatures of heating and cooling in the course of thermocycling. The results obtained indicate that the antiferroelectric-ferroelectric transition in the PbZr_{1 ? x} Ti_xO₃ ceramics materials is a smeared first-order phase transition.     

First-order transition features of the triangular Ising model with nearest- and next-nearest-neighbor antiferromagnetic interactions

We implement a new and accurate numerical entropic scheme to investigate the first-order transition features of the triangular Ising model with nearest-neighbor (J_nn) and next-nearest-neighbor (J_nnn) antiferromagnetic interactions in ratio R=J_nn/J_nnn=1. Important aspects of the existing theories of first-order transitions are briefly reviewed, tested on this model, and compared with previous work on the Potts model. Using lattices with linear sizes L=30,40,…,100,120,140,160,200,240,360 and 480 we estimate the thermal characteristics of the present weak first-order transition. Our results improve the original estimates of Rastelli et al. and verify all the generally accepted predictions of the finite-size scaling theory of first-order transitions, including transition point shifts, thermal, and magnetic anomalies. However, two of our findings are not compatible with current phenomenological expectations. The behavior of transition points, derived from the number-of-phases parameter, is not in accordance with the theoretically conjectured exponentially small shift behavior and the well-known double Gaussian approximation does not correctly describe higher correction terms of the energy cumulants. It is argued that this discrepancy has its origin in the commonly neglected contributions from domain wall corrections.     

Effects of interstitial H and/or C atoms on the magnetic and magnetocaloric properties of La(Fe, Si)13-based compounds

La(Fe, Si)₁₃-based compounds have been considered as promising candidates for magnetic refrigerants particularly near room temperature. Herein we review recent progress particularly in the study of the effects of interstitial H and/or C atoms on the magnetic and magnetocaloric properties of La(Fe, Si)₁₃ compounds. By introducing H and/or C atoms, the Curie temperature T _C increases notably with the increase of lattice expansion which makes the Fe 3d band narrow and reduces the overlap of the Fe 3d wave functions. The first-order itinerant-electron metamagnetic transition is conserved and the MCE still remains high after hydrogen absorption. In contrast, the characteristic of magnetic transition varies from first-order to second-order with the increase of C concentration, which leads to remarkable reduction of thermal and magnetic hysteresis. In addition, the introduction of interstitial C atoms promotes the formation of NaZn₁₃-type (1:13) phase in La(Fe, Si)₁₃ compounds, and thus reducing the annealing time significantly from 40 days for LaFe_11.7Si_1.3 to a week for LaFe_11.7Si_1.3C_0.2. The pre-occupied interstitial C atoms may depress the rate of hydrogen absorption and release, which is favorable to the accurate control of hydrogen content. It is found that the reduction of particle size would greatly depress the hysteresis loss and improve the hydrogenation process. By the incorporation of both H and C atoms, large MCE without hysteresis loss can be obtained in La(Fe, Si)₁₃ compounds around room temperature, for instance, La_0.7Pr_0.3Fe_11.5Si_1.5C_0.2H_1.2 exhibits a large |ΔS _M| of 22.1 J/(kg·K) at T _C = 321 K without hysteresis loss for a field change of 0–5 T.     

High-resolution spectroscopy of HoFe<Subscript>3</Subscript>(BO<Subscript>3</Subscript>)<Subscript>4</Subscript> crystal: a study of phase transitions

The transmission spectra of HoFe₃(BO₃) multiferroic single crystals are studied by optical Fourier-transform spectroscopy at temperatures of 1.7–423 K in polarized light in the spectral range 500–10 000 cm^–1 with a resolution up to 0.1 cm^–1. A new first-order structural phase transition close to the second-order transition is recorded at T_c = 360 K by the appearance of a new phonon mode at 976 cm^–1. The reasons for considerable differences in T_c for different samples of holmium ferroborate are discussed. By temperature variations in the spectra of the f–f transitions in the Ho³⁺ ion, we studied two magnetic phase transitions, namely, magnetic ordering into an easy-plane structure as a second-order phase transition at T_N = 39 K and spin reorientation from the ab plane to the c axis as a first-order phase transition at T_SR = 4.7 ± 0.2 K. It is shown that erbium impurity in a concentration of 1 at % decreases the spin-reorientation transition temperature to T_SR = 4.0 K.     

Superionic behavior in the xAgI–(1−x)CsAg2I3 polycrystalline system

A superionic phase behavior (with DC ionic conductivities higher than 0.01 S/cm) has been observed in xAgI–(1−x)CsAg₂I₃ (x≈0.67) polycrystalline system grown by slow evaporation using AgI and CsI powders (molar ratio Cs/Ag=0.25) as starting salts and an aqueous solution of HI as solvent. The transition from the normal-to- the superionic state is first-order with a hysteretic behavior in temperature centered at about 116 °C as reflected by thermal (DSC) and electrical conductivity measurements. This mixture is composed of CsAg₂I₃ and AgI crystalline phases and an additional amorphous AgI phase that explains the glassy-type behavior observed in the superionic phase transition.     

Magnetic ordering in uranium monophosphide

The magnetic ordering in uranium monophosphide (UP) has been studied by neutron diffraction from a single crystal in a magnetic field. UP orders at T_N ? 122 ± 0.1 K with the type-I antiferromagnetic structure (+-+-), the ordering taking place in a first-order transition. At T₀ = 22.5 K the ordered magnetic moment jumps from 1.7 μ_B to 1.9 μ_B. With a magnetic field H = 25 kOe applied along the [11&#x0304;10] direction, it is found that UP has the collinear single-$\text{K}$ type-I structure above T₀ and undergoes a first-order transition to the planar double-$\text{K}$ type-I structure, accompanied by a “moment jump” due to the change in the moment direction from <001> to <110>.     

The gas phase Raman band contours of 1,3,5-trifluorobenzene and the infrared and Raman band contours of 1,3,5-trifluorobenzene-d3

The gas phase infrared and Raman spectra of 1,3,5-trifluorobenzene-d₃ has been recorded. The gas phase Raman spectrum of 1,3,5-trifluorobenzene-h₃ has also been recorded. Computer simulations of the band contours of the degenerate vibrational modes have been used to determine the first-order Coriolis coupling constants for both molecules. The ζ^z values were then compared with those evaluated from force field calculations.     

The vapor phase Raman spectra,Raman band contour analyses,Coriolis coupling constants,and e-species force constants of the molecules SPF3, FCCl3, and BrCCl3

The vapor phase Raman spectra of the molecules SPF₃, FCCl₃, and BrCCl₃ have been recorded at pressures of up to 1 atm over the fundamental frequency regions. The Raman band contours of the e-species fundamentals have been analyzed to yield first-order Coriolis coupling constants from which, together with the fundamental frequencies, e-species force constants of the general harmonic potential function have been evaluated. The results for thiophosphoryltrifluoride are compared with those deduced previously on the basis of infrared band contour analyses.     

Ising models with two- and three-spin interactions: Mean field equation of state

The Ising model with pair and triplet interactions on the triangular lattice is solved in the mean-field approximation. With a sufficiently strong triplet interaction two first-order transitions take place at low temperature, and at intermediate temperatures one transition, terminating in a critical point. For J₂ > 0.75J₃ only the latter transition remains.     

Magnetocaloric effect in Y-doped La0.6Ca0.4MnO3 enhanced by Griffiths phase and re-entrance of first-order phase transition

It has been known that bulk La_0.6Ca_0.4MnO₃ is an intermediate material of the first- and second-order characters with the tricritical-point exponents, and the doping of a metal ion in it usually causes a continuous second-order transition. The present work reports the re-entrance of a discontinuous first-order transition in orthorhombic La_0.6-xY_xCa_0.4MnO₃ (x = 0.03–0.09) compounds. This enhances the magnetocaloric effect. For the field H = 30 kOe, the maximum magnetic-entropy change (|ΔS_max|) and relative cooling power (RCP) have been evaluated being about 5.45–6.3 J/kg·K and 130–185 J/kg, respectively. If combining these compounds as refrigerant blocks in a rotary ring model, a magnetic cooling device can operate at temperatures T = 85–280 K, with |ΔS_max| ≈ 5.5 J/kg⋅K and RCP ≈ 1073 J/kg. Aside from the re-entranced first-order phase transition, the magnetization and structural analyses have proved the enhanced magnetocaloric effect in La_0.6-xY_xCa_0.4MnO₃ related to a Griffiths singularity, and local Jahn-Teller distortions of the perovskite structure (since the Mn³⁺/Mn⁴⁺ ratio and orthorhombic structural phase are unchanged vs. x).     

Effects of divalent impurities on the fluctuation conductivity of YBa2Cu3O7 single crystals

We have studied experimentally the in-plane fluctuation conductivity near the superconducting transition in single crystal samples of YBa₂Cu₃O₇, Y_0.98Ca_0.02Ba₂Cu₃O₇, YBa_1.9Sr_0.1Cu₃O₇ and YBa₂Cu_2.97Zn_0.03O₇. In order to test the stability of the observed fluctuation regimes, low magnetic fields were applied perpendicular to the Cu-O₂ atomic planes. When the transition is approached from above we first observe a three-dimensional (3D) Gaussian regime then a crossover to a genuine critical region where the exponent is consistent with the predictions of the 3D-XY-E universality class. Decreasing further the temperature towards T_c, our results systematically reveal the occurrence of a regime beyond 3D-XY characterized by a very small critical exponent. We propose that this regime is precursory to a weak first-order superconducting transition driven by antiferromagnetic excitations related to the pseudogap phenomenon. The dilution of divalent impurities in YBa₂Cu₃O₇ does not affect the stability of the fluctuation regime beyond 3D-XY and in the case of Ca doping a further approach towards the first-order behaviour is observed.     

First-order transitions from singly peaked distributions

Suppose that, in the thermodynamic limit, a single-component particle system exhibits a standard first-order transition marked by a jump in the density, ρ, at a chemical potential μ_σ(T). In grand canonical simulations of model fluids that realize such a transition when L→∞ (where L is the linear dimension of the simulation volume) the presence of the transition is typically signaled by the appearance of a double-peaked structure in the distribution function, P_N(T,μ_σ;L), of the particle number, N. A simple, explicit counterexample is presented, however, that proves, contrary to popular beliefs, that the converse proposition is false: i.e., a single-peaked distribution, P_N(T,μ_σ;L), may, when L→∞, give rise to a first-order transition. Alternatively, the existence of a first-order transition does not imply a double-peaked distribution. Systems that may exhibit such single-peaked, first-order behavior are discussed and a possible route to constructing explicit models exhibiting the phenomenon is described. Strategies to use in simulating such systems are briefly considered in the light of related studies.     

Three-dimensional 3-state Potts model revisited with new techniques

We report a fairly detailed finite-size scaling analysis of the first-order phase transition in the three-dimensional 3-state Potts model on cubic lattices with emphasis on recently introduced quantities whose infinite-volume extrapolations are governed only by exponentially small terms. In these quantities no asymptotic power series in the inverse volume are involved which complicate the finite-size scaling behaviour of standard observables related to the specific-heat maxima or Binder-parameter minima. Introduced initially for strong first-order phase transitions in q-state Potts models with “large enough” q, the new techniques prove to be surprisingly accurate for a q value as small as 3. On the basis of the high-precision Monte Carlo data of Alves et al. [Phys. Rev. B 43 (1991) 5846], this leads to a refined estimate of β_t = 0.550 565(10) for the infinite-volume transition point.     

Acoustic beam interaction with a rigid sphere: The case of a first-order non-diffracting Bessel trigonometric beam

Mathematical expressions for the acoustic scattering, instantaneous (linear), and time-averaged (nonlinear) forces resulting from the interaction of a new type of Bessel beam, termed here a first-order non-diffracting Bessel trigonometric beam (FOBTB) with a sphere, are derived. The beam is termed “trigonometric” because of the dependence of its phase on the cosine function. The FOBTB is regarded as a superposition of two equi-amplitude first-order Bessel vortex (helicoidal) beams having a unit positive and negative order (known also as topological charge), respectively. The FOBTB is non-diffracting, possesses an axial null, a geometric phase, and has an azimuthal phase that depends on cos(?±?₀), where ?₀ is an initial arbitrary phase angle. Beam rotation around its wave propagation axis can be achieved by varying ?₀. The 3D directivity patterns are computed, and the resulting modifications of the scattering are illustrated for a rigid sphere centered on the beam's axis and immersed in water. Moreover, the backward and forward acoustic scattering by a sphere vanish for all frequencies. The present paper will shed light on the novel scattering properties of an acoustical FOBTB by a sphere that may be useful in particle manipulation and entrapment, non-destructive/medical imaging, and may be extended to other potentially useful applications in optics and electromagnetism.     

Redundancy coefficients for vibrations involving atoms with four bonds

Simple expressions for the first-order redundancy coefficients in vibrational problems involving atoms with four bonds are given. The general case of no local symmetry is treated as well as the specialization to O_h, C_3v, and C_s symmetry. The elements of the U matrix resulting from the orthogonalization of the local symmetry coordinates with respect to the redundancy condition are given for two suitable sets of symmetry coordinates. The theoretical results are illustrated with the numerical values for ethylsilane.     

Electronic thermal conduction in suspended graphene

The electronic thermal conductivity (ETC), κ_e, of suspended graphene (SG) is studied for 15<T<400 K, following the Boltzmann transport formalism. The electrons are considered to be scattered from defects along with the intrinsic in-plane acoustic phonons, out-of-plane flexural phonons (FPs) and optical phonons. The ETC is evaluated by computing the first-order perturbation distribution function by directly solving the linearized Boltzmann equation by an iterative method. Numerical calculations of the temperature and concentration dependences of κ_e show the dominance of charged impurity scattering at lower temperatures (T<75 K) and of FPs at higher temperatures. The results are compared with the commonly used low-temperature and high-energy relaxation time approximations. Our calculations are in good agreement with recent κ_e data extracted for high-mobility SG samples. The validity of Wiedemann–Franz law is also discussed.     

An effective atomic charge model for infrared intensities

Infrared intensities, in particular the dipole derivatives with respect to internal (symmetry) coordinates derived from the intensities, can be explained in terms of an effective atomic charge model which includes both the equilibrium charges and their first-order fluxes. For diatomic molecules it is found that most of the intensity arises from the equilibrium charges in the case of the hydrogen halides, but conversely, in CO, most of the intensity is due to the charge flux. The parameters found can be nicely related to elementary bonding theory.In small symmetrical polyatomic molecules the number of parameters is sufficiently restricted by symmetry and charge conservation that the parameters would be uniquely determinate except for the ambiguity in sign of the experimental dipole derivatives. The examples of AB₂ (D_∞h and C_2v), AB₃ (D_3h and C_3v), and AB₄ (Td) are discussed in detail; a simple generalization for molecular ions is included.For nonpolar molecules, the effective equilibrium charges are determined by the motion (not the equilibrium value) of the electronic centroid.     

An i.r. study of heavy phosphine in the solid state

The near i.r. spectra of PD₃ and of PHD₂; isolated as a point defect in PD₃ have been obtained. Analysis of these spectra indicates that PD₃ exists in at least two crystalline forms. In the low-temperature form the molecules probably occupy two sets of sites of C_s. symmetry. A first-order phase transition accompanied by hysteresis occurs at 50 K and 60 K. This is most probably an order-disorder transition, because the spectrum of the high-temperature phase is that of a disordered crystal.