Configurational entropy-induced phase transition in spinel LiMn2O4

The spinel-type LiMn$_{2}$O$_{4}$ is a promising candidate as cathode material for rechargeable Li-ion batteries due to its good thermal stability and safety. Experimentally, it is observed that in this compound there occur the structural phase transitions from cubic ($Fd\bar{3}m)$ to tetragonal ($I4_{1}/{amd}$) phase at slightly below room temperature. To understand the phase transition mechanism, we compare the Gibbs free energy between cubic phase and tetragonal phase by including the configurational entropy. Our results show that the configurational entropy contributes substantially to the stability of the cubic phase at room temperature due to the disordered Mn$^{3+}$/Mn$^{4+}$ distribution as well as the orientation of the Jahn-Teller elongation of the Mn$^{3+}$O$_{6}$ octahedron in the the spinel phase. Meanwhile, the phase transition temperature is predicted to be 267.8 K, which is comparable to the experimentally observed temperature. These results serve as a good complement to the experimental study, and are beneficial to the improving of the electrochemical performance of LiMn$_{2}$O$_{4}$ cathode.     

Measuring the configurational heat capacity of liquids

A high electric field impedance experiment on supercooled molecular liquids is employed to transfer energy to the slow modes by absorption from the field and detect the increase of their "configurational temperature", T(cfg), via the change of the relaxation times. This allows us to determine the configurational heat capacity, which accounts for most of the excess heat capacity for stronger liquids, but for only half of the heat capacity step in the case of more fragile systems. It is also observed that T(cfg) gradually approaches the phonon temperature on the structural relaxation time scale.     

Low-temperature heat capacities and standard molar enthalpy of formation of 4-（2-aminoethyl）-phenol （C8H11NO）

This paper reports that low-temperature heat capacities of 4-（2-aminoethyl）-phenol （C8H11NO） are measured by a precision automated adiabatic calorimeter over the temperature range from 78 to 400 K. A polynomial equation of heat capacities as a function of the temperature was fitted by the least square method. Based on the fitted polynomial, the smoothed heat capacities and thermodynamic functions of the compound relative to the standard reference temperature 298.15K were calculated and tabulated at the interval of 5K. The energy equivalent, εcalor, of the oxygen-bomb combustion calorimeter has been determined from 0.68g of NIST 39i benzoic acid to be εcalor=（14674.69±17.49）J·K^-1. The constant-volume energy of combustion of the compound at T=298.15 K was measured by a precision oxygen-bomb combustion calorimeter to be ΔcU=-（32374.25±12.93）J·g^-1. The standard molar enthalpy of combustion for the compound was calculated to be ΔcHm = -（4445.47 ± 1.77） kJ·mol^-1 according to the definition of enthalpy of combustion and other thermodynamic principles. Finally, the standard molar enthalpy of formation of the compound was derived to be ΔfHm（C8H11NO, s）=-（274.68 ±2.06） kJ·mol^-1, in accordance with Hess law.     

Irreversible Brownian Heat Engine

We model a Brownian heat engine as a Brownian particle that hops in a periodic ratchet potential where the ratchet potential is coupled with a linearly decreasing background temperature. We show that the efficiency of such Brownian heat engine approaches the efficiency of endoreversible engine \(\eta =1-\sqrt{{T_{c}/T_{h}}}\) [23]. On the other hand, the maximum power efficiency of the engine approaches \(\eta ^{MAX}=1-({T_{c}/T_{h}})^{1\over 4}\). It is shown that the optimized efficiency always lies between the efficiency at quasistatic limit and the efficiency at maximum power while the efficiency at maximum power is always less than the optimized efficiency since the fast motion of the particle comes at the expense of the energy cost. If the heat exchange at the boundary of the heat baths is included, we show that such a Brownian heat engine has a higher performance when acting as a refrigerator than when operating as a device subjected to a piecewise constant temperature. The role of time on the performance of the motor is also explored via numerical simulations. Our numerical results depict that the time t and the external load dictate the direction of the particle velocity. Moreover, the performance of the heat engine improves with time. At large t (steady state), the velocity, the efficiency and the coefficient of performance of the refrigerator attain their maximum value. Furthermore, we study the effect of temperature by considering a viscous friction that decreases exponentially as the background temperature increases. Our result depicts that the Brownian particle exhibits a fast unidirectional motion when the viscous friction is temperature dependent than that of constant viscous friction. Moreover, the efficiency of this motor is considerably enhanced when the viscous friction is temperature dependent. On the hand, the motor exhibits a higher performance of the refrigerator when the viscous friction is taken to be constant.     

Negative heat capacity of Ar55 cluster

The solid–liquid phase transitions of Ar₅₅ cluster was simulated by the microcanonical molecular dynamics and microcanonical parallel tempering methods using Lennard–Jones potential, and thermodynamic quantities were calculated. The caloric curve of cluster has S-bend. To understand this behaviour, configurational and total entropies were evaluated, and the dents on the entropy curves were noticed as the sign of negative heat capacity. The heat capacities were evaluated by using configurational entropy data. The potential energy distributions have bimodal behaviour in the given range at the melting temperature. At the same time by using configurational entropy canonical caloric curve and canonical heat capacity were calculated. To obtain entropy change upon melting, total entropy were calculated from the caloric curve. The microcanonical results melting temperature, latent heat and entropy change upon melting values were reported and compared with the values reported in the literature and the values calculated from the thermodynamic relations offered for bulk matter, consistent values were found.     

‘Monte Carlo’ computer simulation of chain molecules III. Simulation of n-alkane molecules

Considering a realistic model for isolated n-alkane molecules, their configurational behaviour has been explored employing a ‘Monte Carlo’ method. The present study shows that the behaviour of the short molecules is unlike that of the longer molecules in regard to the variation with temperature of the mean-square end-to-end distance and radius of gyration. For the short molecules the mean-square end-to-end distance and the radius of gyration are decreasing functions of temperature, but they increase with temperature in the case of the longer molecules. The macromolecules assume random-walk behaviour at approximately 600 K. The computed heat capacity versus temperature curves disclose configurational transitions in the chains.     

Magnetic properties and coercivity mechanism of precipitation-hardened Gd－Co based ribbons

Gd(Co_{0.88-x}Cu_xFe_{0.09}Zr_{0.03})_z ribbons with x=0.075-0.200 and z=6.4－7.7 have been prepared by a melt-spinning technique. A cellular microstructure consisting of 2:17 cells surrounded by the 1:5 cell boundary phase is obtained after precipitation hardening. The dependence of room temperature coercivity on the heat treatment process suggests that the long-time isothermal aging is not helpful for the development of magnetic properties. Positive temperature coefficient of remanence from room temperature to about 673K is typical for all samples, while positive temperature coefficient of coercivity is obtained only in ribbons with low Cu content. The coercivity mechanism of the precipitation-hardened ribbons at different temperatures is also discussed.     

Heat capacity of isolated clusters

The character of interaction between thermal (vibrational) and configurational cluster excitations is considered under adiabatic conditions when a cluster is a member of a microcanonical ensemble. The hierarchy of equilibration times determines the character of atomic equilibrium in the cluster. The behavior of atoms in the cluster can be characterized by two effective (mean) temperatures, corresponding to the solid and liquid aggregate states, because the typical time for equilibration of atomic motion is less than the transition time between aggregate states. If the cluster is considered for a time much longer than the typical dwell time in either phase, then it is convenient to characterize the system by only one temperature, which is determined from the statistical-thermodynamic long-time average. These three temperatures are not far apart, nor are the cluster heat capacities evaluated on the basis of these definitions of temperature. The heat capacity of a microcanonical ensemble may be negative for two coexisting phases if the mean temperature is defined in terms of the mean kinetic energy, rather than as the derivative of energy with respect to microcanonical entropy. However, if the configurational excitation energy is smaller than the total excitation energy separating the phases, then the two-state model predicts a positive heat capacity under either definition of temperature. Moreover, if the cluster is sufficiently large, then the maximum values of the microcanonical and canonical heat capacities are equal.     

Phase coherence of conduction electrons below the Kondo temperature

We have measured the phase decoherence rate tau_{varphi};{-1} of conduction electrons in disordered Ag wires implanted with 2 and 10 ppm Fe impurities, by means of the weak-localization magnetoresistance. The Kondo temperature of Fe in Ag, T_{K} approximately 4 K, is in the ideal temperature range to study the progressive screening of the Fe spins as the temperature T falls below T_{K}. The contribution to tau_{varphi};{-1} from the Fe impurities is clearly visible over the temperature range 40 mK-10 K. Below T_{K}, tau_{varphi};{-1} falls rapidly until T/T_{K} approximately 0.1, in agreement with recent theoretical calculations. At lower T tau_{varphi};{-1} deviates from theory with a flatter T-dependence. Understanding this anomalous dephasing for T/T_{K}<0.1 may require theoretical models with larger spin and number of channels.     

Electron temperature fluctuation in the HT-7 Tokamak plasma observed by electron cyclotron emission imaging

The fluctuation of the electron temperature has been measured by using the electron cyclotron emission imaging in the Hefei Tokamak-7 (HT-7) plasma. The electron temperature fluctuation with a broadband spectrum shows that it propagates in the electron diamagnetic drift direction, and the mean poloidal wave-number $\bar{k}_{\theta}$is calculated to be about 1.58 cm^-1, or \bar{k}_θ ρ_s≈ 0.34. It indicates that the fluctuation should come from the electron drift wave turbulence. The linear global scaling of the electron temperature fluctuation with the gradient of electron temperature is consistent with the mixing length scale qualitatively. Evolution of spectrum of the fluctuation during the sawtooth oscillation phases is investigated, and the fluctuation is found to increase with the gradient of electron temperature increasing during most phases of the sawtooth oscillation. The results indicate that the electron temperature gradient is probably the driver of the fluctuation enhancement. The steady heat flux driven by electron temperature fluctuation is estimated and compared with the results from power balance estimation.     

Thermodynamic aspects of the glass transition of silicates

The marked increase in second-order thermodynamic properties observed at the glass-transition signals the onset of configurational changes in viscous liquids. Experimental determinations in the glass-transition range will illustrate this point for thermal expansivity and demonstrate that the kinetics of volume, enthalpy and structural relaxation are identical for silicate liquids. Within the framework of the Adam–Gibbs theory, heat capacity and viscosity data may be combined to calculate configurational entropies and gain insights into the potential energy barrier to viscous flow. Finally, the considerable effect of water on the glass transition temperature of geologically relevant silicates is presented.     

Electric Conductivity of Poly(3-dodecylthiophene) and Its Dependence on the Conformational Changes of Polymer Chains

The influence of the heat-induced conformational changes in side alkyls and in the backbone of poly(3-dodecylthiophene) (PDDT) with a higher content of configurational head-to-head defects (39 studied. It has been found that conformational changes affect the electric conductivity values of PDDT doped with FeCl₃ which attain at 0.021 mol of Fe/mol dodecylthiophene more than 10⁸ S m^-1 within the whole temperature range (from 78 up to 320 K). For the analysis of conformational changes the entropy temperature dependence was calculated from the experimental data on the specific heat capacity. In this paper dependences between the resistance and the conformational changes of PDDT were discussed.     

Expression for the stationary distribution in nonequilibrium steady states

We study the nonequilibrium steady state realized in a general stochastic system attached to multiple heat baths. Starting from the detailed fluctuation theorem, we derive concise and suggestive expressions for the corresponding stationary distribution which are correct up to the second order in thermodynamic forces. The probability of a microstate eta is proportional to exp[Phi(eta)] where Phi(eta)=-[under summation operator]kbeta_{k}E_{k}(eta) is the excess entropy change. Here, E_{k}(eta) is the difference between two kinds of conditioned path ensemble averages of excess heat transfer from the kth heat bath whose inverse temperature is beta_{k}. This result can be easily extended to steady states maintained with other sources, e.g., particle current driven by an external force. Our expression may be verified experimentally in nonequilibrium states realized, for example, in mesoscopic systems.     

High-resolution calorimetric study of pb(mg_{1/3}nb_{2/3})o_{3} single crystal

Motivated by the long-standing unresolved enigma of the relaxor ferroelectric ground state, we performed a high-resolution heat capacity and polarization study of the field-induced phase transition in the relaxor ferroelectric single crystal Pb(Mg_{1/3}Nb_{2/3})O_{3} (PMN) oriented along the [110] direction. We show that the discontinuous evolution of polarization as a function of the electric field or temperature is a consequence of a true first order transition from a glassy to ferroelectric state, which is accompanied by an excess heat capacity anomaly and released latent heat. We also find that in a zero field there is no ferroelectric phase transition in bulk PMN at any temperature, indicating that the nonergodic dipolar glass phase persists down to the lowest temperatures.     

Quantum diffusion in solid H2?Ne solutions

Quantum diffusion in solid hydrogen containing 0.02–0.25 mol.% neon has been investigated by the calorimetric method in temperature range 1–3 K. The concentrations of orthohydrogen were 0.23; 0.5 and 1 mol. %. The parameter studied was characteristic configurational relaxation time τ. Heat capacity is very sensitive to space distribution of orthohydrogen molecules. Therefore, the determination of configuration relaxation rate has been performed by observing the time dependence of heat capacity. A neon impurity in the indicated concentration is observed to accelerate quantum diffusion in hydrogen. The magnitude of the effect diminishes as the temperature increases.     

Experimental realization of a spin-1/2 triangular-lattice Heisenberg antiferromagnet

We report the results of magnetization and specific heat measurements on Ba{3}CoSb{2}O{9}, in which the magnetic Co{2+} ion has a fictitious spin 1/2, and provide evidence that a spin-1/2 Heisenberg antiferromagnet on a regular triangular lattice is actually realized in Ba{3}CoSb{2}O{9}. We found that the entire magnetization curve including the one-third quantum magnetization plateau is in excellent quantitative agreement with the results of theoretical calculations. We also found that Ba{3}CoSb{2}O{9} undergoes a three-step transition within a narrow temperature range.     

Peculiar thermodynamic properties of LJ<Subscript> N</Subscript> (N = 39–55) clusters

The solid-liquid phase transitions of Lennard-Jones clusters LJ_N (N=39–55) were simulated by a microcanonical molecular dynamics method using Lennard-Jones potential, and their thermodynamic quantities were calculated. The caloric curves of clusters (except N=42) have S-bend. To understand this behaviour, configurational and total entropies were evaluated, and dents on the entropy curves were taken as a sign of negative heat capacity. The heat capacities were evaluated for N=39–55 clusters using configurational entropy data. The potential energy distributions have bimodal behaviour for all clusters in the given range at the melting temperature. The distinct melting behaviour of LJ₄₂ was explained by the topology of the potential energy surface by examining the isomer distributions at phase transitions for LJ₃₉-LJ₅₅. The isomer distributions were found to be a useful way to interpret this behaviour and melting dynamics in general. Melting temperature, latent heat and entropy change upon melting values were reported and are consistent with literature values and values calculated from bulk thermodynamic properties. The dependence of these quantities on the size of the clusters was examined and it is found that latent heat is the key quantity to determine the magic numbers.     

Magnetism and giant magnetocaloric effect in rare-earth-based compounds R_3BWO_9(R = Gd,Dy, Ho)

The magnetism and magnetocaloric effect(MCE) of rare-earth-based tungstate compounds R_3 BWO_9(R=Gd,Dy,Ho) have been studied by magnetic susceptibility,isothermal magnetization,and specific heat measurements.No obvious long-range magnetic ordering can be found down to 2 K.The Curie-Weiss fitting and magnetic susceptibilities under different applied fields reveal the existence of weak short-range antiferromagnetic couplings at low temperature in these systems.The calculations of isothermal magnetization exhibit a giant MCE with the maximum changes of magnetic entropy being 54.80 J/kg-K at 2 K for Gd_3 BWO_9,28.5 J/kg-K at 6 K for Dy_3 BWO_9,and 29.76 J/kg-K at 4 K for Ho_3 BWO_9,respectively,under a field change of 0-7 T.Especially for Gd_3 BWO_9,the maximum value of magnetic entropy change(-ΔS_M~(max)) and adiabatic temperature change(-ΔT_(ad)~(max)) are 36.75 J/kg·K and 5.56 K for a low field change of 0-3 T,indicating a promising application for low temperature magnetic refrigeration.     

Accurate Expansions of Internal Energy and Specific Heat of Critical Two-Dimensional Ising Model with Free Boundaries

The bond-propagation algorithm for the specific heat of the two dimensional Ising model is developed and that for the internal energy is completed. Using these algorithms, we study the critical internal energy and specific heat of the model on the square lattice and triangular lattice with free boundaries. Comparing with previous works (Phys Rev E 86:041149, 2012; Phys Rev E 87:022124, 2013), we reach much higher accuracy ( $10^{-28}$ ) of the internal energy and specific heat, compared to the accuracy $10^{-11}$ of the internal energy and $10^{-9}$ of the specific heat reached in the previous works. This leads to much more accurate estimations of the edge and corner terms. The exact values of all edge and corner terms are therefore conjectured. The accurate forms of finite-size scaling for the internal energy and specific heat are determined for the rectangle-shaped square lattice with various aspect ratios and various shaped triangular lattice. For the rectangle-shaped square and triangular lattices and the triangle-shaped triangular lattice, there is no logarithmic correction terms of order higher than $1/S$ , with $S$ the area of the system. For the triangular lattice in rhombus, trapezoid and hexagonal shapes, there exist logarithmic correction terms of order higher than $1/S$ for the internal energy, and logarithmic correction terms of all orders for the specific heat.     

Generalization of the Williams--Landel--Ferry equation

Based on the model of Gibbs-Di Marzio we write the logarithmic shift factor without explicit knowledge of the form for the entropy, an expression which enables us to write a generalization of the Williams--Landel--Ferry equation. Comparison with the empirical relation of Williams--Landel--Ferry and use of the fact that the model exhibits the existence of a isoentropic temperature T₀ for which the configurational entropy of the system vanishes, leads to a value of the isoentropic temperature for which the configurational entropy of the system vanishes. The form for the specific heat proposed by Dowell and Di Marzio based on the lattice model of Gibbs-Di Marzio for the glass transition of polymeric substances, has been used by García-Colín et al. to find the molar configurational entropy (MCE) of glass. Knowledge of the form of the MCE, allows us to find an expression for the critical configurational entropy (S^*_c) and a form for the potential energy hindering the cooperative rearrangement per monomer segment (Δμ).