Molecular dynamics simulations of phase transition of n-nonadecane under high pressure

The phase transition behavior of n-nonadecane under high pressure was investigated with molecular dynamics (MD) simulations method. A simplified model with amorphous structure and periodic boundary conditions in constant-temperature, constant-pressure ensemble was used in this study. The results showed that the whirling and molecules motion of n-nonadecane chains were restrained by the high pressure. The simulated phase transition temperature of n-nonadecane under high pressure is higher than that under atmospheric pressure. The order parameter of n-nonadecane decreases with the increase in temperature. The simulations reveal that MD is an effective method to understand the phase transition of alkane-based phase change materials on molecular and atomic scale.     

Non-polytropic effect on shock-induced phase transitions in a hard-sphere system

By adopting a simplified model of a non-polytropic hard-sphere system where heat capacity depends on the temperature, we demonstrate the importance of non-polytropic effect on the shock-induced phase transitions. We show explicitly that with the increase of the shock strength the perturbed temperature (the temperature after a shock) increases and the vibrational modes are gradually excited, and as a result, shock-induced phase transitions are qualitatively and quantitatively different from the phase transitions observed in a simple polytropic model. The effect on the admissibility (stability) of a shock wave is also analyzed.     

高压作用下相分离液体玻璃转变的分子动力学研究

采用分子动力学模拟方法,研究了二元混合液体在不同外压作用下的相分离与玻璃转变过程,计算了相分离液体在玻璃转变过程中的结构和动力学特征.研究发现,外压会促进相分离的产生,并提高玻璃转变温度,会使β弛豫出现的温度更高、存在的时间更长,导致系统扩散性降低.同时还发现,相分离液体的玻璃转变过程存在微观不均匀现象. 关键词： 相分离 玻璃转变 分子动力学模拟 外压影响     

Molecular dynamics simulation of the pressure-induced phase transition in BaFCl

The structural phase transition in BaFCl under high-pressure up to 30 v GPa has been studied using molecular dynamics (MD) method. It was found that BaFCl transforms from a tetragonal structure to a monoclinic structure in the upstroke process and then the tetragonal structure is recovered upon releasing the pressure. The atomistic mechanisms of the transformation have been examined using the pair-correlation functions and the coordination numbers for the lattices with or without vacancies in the MD cell. It was also demonstrated that the Cl atoms between the adjacent weakly bonded Cl layers shift in the compressed direction and move to positions with a 2-fold coordination number at a nearest-neighbour site after the transition.     

First-principles study of the high pressure phase transition and lattice dynamics of cerium

We present a first-principles study of the phase transition and lattice dynamics of Ce within the framework of the density functional theory using the GGA+U method. Our calculated results denote that under pressure the transition path is α-Ce (fcc)→α″-Ce (monoclinic, with two atoms per unit cell)→bct-Ce (body centered tetragonal), and the transition pressures are located at 5.36 and 14.37 GPa, respectively. The equation of state in a wide range of pressure is consistent with the experimental data. During the γ-α phase transition, the magnetic moment disappears gradually, which is mainly due to the strong interaction between the 4f and 5d electrons. By calculating the free energies from phonon dispersions including electronic contribution, the obtained γ-α transition temperature at zero pressure is 148 K. From the Blackman diagram of dimensionless elastic constant ratios, we can find that both γ- and α-Ce show negative Cauchy pressure—C₄₄>C₁₂.     

On the definition of phase transition

It is shown that there exists a phase transition associated with a singularity of the free energy for a model such that for all temperatures the equilibrium state is unique and thus stable with respect to boundary perturbations. It is also shown on this model that there exist phase transitions without symmetry breakdown, which can be related to a phase transition with symmetry breakdown on an equivalent model.     

A first-order level-2 phase transition in thermodynamic formalism

We show the existence of a phase transition at the level of measures for the generalized dimension of the maximal entropy measure in a model that was considered by F. Hofbauer and which is related to a model of M. Fisher. The model presented here is related to the one-dimensional Ising model in which a wall effect is assumed. In this situation, the problem has to be considered in the one-dimensional lattice . In general there is no first-order transition for the Ising model in the lattice , but under our assumptions such transitions can occur. The Ising model has the purpose of explaining the magnetization of ferromagnetic systems at low temperatures. The main difference of our result from a previous result of F. Hofbauer is that the transition is analyzed in the setting of the generalized dimension. This setting is more closely related to the observables. The main purpose of this paper is to explain another mathematical model for phase transition using the mathematical results obtained by F. Hofbauer. We also use results of the thermodynamic formalism in an essential way.     

Pressure controllable phase transition in MoTe2 by the interlayer band occupancy

High pressure can effectively control the phase transition of MoTe₂ in experiment, but the mechanism is still unclear. In this work, we show by first-principles calculations that the phase transition is suppressed and $1T^{\prime }$ phase becomes more stable under high pressure, which originates from the pressure-induced change of the interlayer band occupancies near the Fermi energy. Specifically, the interlayer states of $1T^{\prime }$ phase tend to be fully occupied under high pressure, while they keep partially occupied for the $T_d$ phase. The increase of the band occupancies makes the $1T^{\prime }$ phase more favorable in energy and prevents the structure changing from $1T^{\prime }$ to $T_d$ phase. Moreover, we also analyze the superconductivity under high pressure based on BCS theory by calculating the density of states and phonon spectra. Our results may shed some light on understanding the relationship between the interlayer band occupancy and crystal stability of MoTe₂ under high pressures.     

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.     

Sulfur-catalyzed phase transition in MoS2 under high pressure and temperature

We report phase transition and stability of MoS₂ with and without the presence of sulfur melt under high-pressure and high-temperature conditions. Rhombohedral (3R) phase is found to be a high-temperature phase of MoS₂ at high pressures. Excess sulfur melt catalyzes the hexagonal (2H) to rhombohedral (3R) phase transformation and lowers the conversion temperature by more than 280 K. Boundary between 2H and 3R phases has been delineated with a negative slope. Based on experimental observations, sulfur-catalyzed 2H→3R transformation mechanisms are proposed involving atomic exchange between MoS₂ and sulfur, which is different from the case of without excess sulfur that proceeds through rotation and translation of the S–Mo–S sandwich layers.     

Lattice dynamics and phase transition of NiTi alloy

We have performed detailed first-principles calculations to investigate the structural and lattice dynamical properties of NiTi alloy. The calculated static structures consist well with the experimental data and other theoretical results. With quasi harmonic approximation, the phase boundary between B19′ and BCO phases can be described as a five order polynomial $T=100?89.28P+296.75P^2?717.94P^3+734.62P^4?274.25P^5$. The change of vibrational entropy is $0.07k_B$/atom at the transition temperature 100 K under zero pressure.     

Pressure induced phase transition in rare earth mono-antimonides

Pressure induced structural phase transition of mono-antimonides of lanthanum, cerium, praseodymium and neodymium (LnSb, Ln=La, Ce, Pr and Nd) has been studied theoretically using an inter-ionic potential with modified ionic charge which parametrically includes the effect of Coulomb screening by the delocalized f electrons of rare earth (RE) ion. The anomalous structural properties of these compounds have been interpreted in terms of the hybridization of f electrons with the conduction band and strong mixing of f states of Ln ion with the p orbital of neighbouring antimonide ion. All the four compounds are found to undergo from their initial NaCl (B₁) phase to body centered tetragonal (BCT) phase at high pressure and agree well with the experimental results. The body centered tetragonal phase is viewed as distorted CsCl structure and is highly anisotropic with c/a=0.82. The transition pressure of LnSb compounds is observed to increase with decreasing lattice constant in NaCl phase. The nature of bonds between the ions is predicted by simulating the ion-ion (Ln-Ln and Ln-Sb) distances at high pressure. The calculated values of elastic constants are also reported.     

Pressure-induced phase transition of zinc-blende AlN: An ab initio molecular dynamics study

An ab initio constant pressure technique is carried out to study the pressure-induced phase transition of the zinc blende AlN (aluminum nitride). A first order phase transformation into a rock salt structure is observed in the constant pressure simulations. The transformation is accompanied by an initial tetragonal distortion and a subsequent shearing, similar to that found in the other zinc blende structured materials. This phase transition should occur around 6.2 GPa based upon the enthalpy calculations.     

Molecular dynamics simulation of phase transition in AgNO3

Structural phase transition in AgNO₃ at high temperature is simulated by molecular dynamics. The simulations are based on the potentials calculated from the Gordon-Kim modified electron-gas formalism extended to molecular ionic crystals. AgNO₃ transforms into rhombohedral structure at high temperature and the phase transition is associated with the rotations of the NO₃ ions and displacements of the NO₃ and Ag ions.     

Pressure effect on phase transition in ferroelectic polymers

Pressure effects of phase transition behaviour in two kinds of ferroelectric polymers of poly(vinylidene fluoride), PVDF, and copolymers of vinylidene fluoride and trifluoroethylene, (VDF/TrFE), are discussed. In the case of PVDF, several high-pressure treatments including a high-pressure annealing and a uniaxial compression were shown to induce a crystal transformation from a non-polar Form II crystal to a polar Form I crystal, which has ferroelectric characteristics and high piezoelectric activity. In addition, substantial pressure effects on ferroelectric phase transition points as well as crystal structures were observed for (VDF/TrFE) copolymers with different VDF contents. The most significant pressure effects were observed for copolymer samples with unstable ferroelectric structures at atmospheric pressure. From high-pressure X-ray and Raman scattering studies, these pressure effects were suggested to originate from the pressure-induced conformational transition from gauche to trans in the molecular chains.     

Self-consistent treatment of a phase transition

A self-consistent treatment of a phase transition with a scalar order parameter in the ordered and disordered state is described. The factorization of the correlation functions in the disordered phase leads to a shift of the transition temperature, a linear divergence (=1) for the correlation length, a quadratic divergence (=2) for the susceptibility, and a finite value (=–1) for the specific heat. In the ordered phase the factorization of the correlation functions leads to no divergences in the correlation length and susceptibility. A study of the free energy shows that order persists above the transition temperature found by assuming disorder. The requirement of thermodynamic stability induces a first-order transition at a temperature which lies between the bare transition temperature and the shifted one.Supported in part by NSF grant No-GP-17560.This work is in partial fulfillment of Ph.D. requirements at Brandeis University.     

Importance of annealing on the order-disorder phase transition in alkali cyanides

Abstract

Contrary to monocrystals powdered KCN displays, after grinding and without annealing, an intermediate monoclinic phase between the high-temperature pseudocubic and the low-temperature orthorhombic phases. The consequence of annealing is the total disappearance of this intermediate phase. A further effect of the annealing process is the reduction of the cubic distortion at the transition. In this paper, we analyse this effect on the intermediate rhombohedral phase observed in the (KCN) _x (KBr)_1?x mixed system.     

A first-order phase transition between crystal phases in the shift model

We describe rigorously a many-body model of interacting classical particles exhibiting the following behavior at zero temperature: as the pressure varies through a critical value, the system goes through a first-order phase transition between different crystal phases. Moreover, at the critical pressure the system is demonstrably a mixture of the two phases.Supported in part by NSF Grant No. MCS81-01596.