Thermodynamic behavior of a water model with a liquid-liquid critical point

In this paper we calculate the constant pressure specific heat response of a water model with a liquid-liquid critical point. We show how, due to the existence of the critical point, there is a secondary maximum in the specific heat at some temperature T_*>T_h for any pressure P>P_c, being T_h the first order transition temperature between the high and the low density liquid phases and P_c the pressure of the critical point. This secondary maximum does not correspond to any long range correlated phase transition and does not show up in the temperature dependence of the isothermal compressibility.     

Ab initio study of phase transition and thermodynamic properties of PtN

The transition phase of PtN from zincblende (ZB) structure to rocksalt (RS) structure is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures under high pressure and temperature are obtained through the quasi-harmonic Debye model. The transition phase from the ZB structure to the RS structure occurs at the pressure of 18.2 GPa, which agrees well with other calculated values. Moreover, the dependences of the relative volume V/V₀ on the pressure P, the Debye temperature Θ and heat capacity C_V on the pressure P, together with the heat capacity C_V on the temperature T are also successfully obtained.     

Precision improvements in the geo-fit retrieval of pressure and temperature from MIPAS limb observations by modeling CO2 line-mixing

In this paper, we present an improvement of the retrieval of pressure and temperature from the observations of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board of the environmental satellite (ENVISAT). The improvement has been obtained by integrating a state-of-the-art CO₂ line-mixing model in a two-dimensional inversion system (Geo-fit). We describe the implementation of this model in the Geo-fit system and we show its capability to reproduce the CO₂ spectral features affected by line-mixing. The upgraded analysis algorithm provides a better fit of the set of MIPAS observations analyzed by the European Space Agency (ESA) ground segment although these observations have been selected with criteria that should avoid line-mixing effects. Moreover, we show that this set of observations can be extended improving the precision of the retrieved pressure and temperature fields without increasing the computing demands. Since the CO₂Q branches are very sensitive to pressure and temperature, the capability to model accurately the line-mixing effects opens the possibility to exploit at best these spectral regions to infer pressure and temperature distributions. According to this idea, we propose a new set of spectral intervals, including the most intense CO₂Q branches. It is shown that the analysis of these intervals provides a significant improvement (up to 70%) in the precision of the retrieved pressure and temperature profiles, while using a smaller number of observations with respect to the ESA ground segment analysis. Since the knowledge of pressure and temperature is necessary for the retrieval of the altitude distribution of all the atmospheric constituents, the benefits of more precise pressure and temperature fields obtained in this work propagate into the quality of all the MIPAS products.     

First-principles study of structural and thermodynamic properties of osmium

We employ the first-principles plane wave pseudopotential density functional theory method to calculate the equilibrium lattice parameters of osmium and the thermodynamic properties of hcp structure osmium. The obtained lattice parameters are in good agreement with the experimental data investigated up to 58.2 GPa using radial X-ray diffraction (RXRD) together with lattice strain theory in a diamond-anvil cell and the available theoretical data of others. Through the quasi-harmonic Debye model, the dependencies of the normalized lattice parameters a/a₀ and c/c₀ on pressure P, the normalized primitive volume V/V₀ on pressure P, the Debye temperature Θ_D and the heat capacity C_V on pressure P and temperature T, as well as the variation of the thermal expansion α with temperature and pressure are obtained successfully.     

Elastic and thermodynamic properties of CaB6 under pressure from first principles

The elastic and thermodynamic properties of CsCl-type structure CaB₆ under high pressure are investigated by first-principles calculations based on plane-wave pseudopotential density functional theory method within the generalized gradient approximation (GGA). The calculated lattice parameters of CaB₆ under zero pressure and zero temperature are in good agreement with the existing experimental data and other theoretical data. The pressure dependences of the elastic constants, bulk modulus B (GPa), and its pressure derivative B′, shear modulus G, Young's modulus E, elastic Debye temperature Θ_B, Zener's anisotropy parameter A, Poisson ratios σ, and Kleinmann parameter ζ are also presented. An analysis for the calculated elastic constants has been made to reveal the mechanical stability of CaB₆ up to 100 GPa. The thermodynamic properties of the CsCl-type structure CaB₆ are predicted using the quasi-harmonic Debye model. The pressure-volume-temperature (P-V-T) relationship, the variations of the heat capacity C_V, Debye temperature Θ_D, and the thermal expansion α with pressure P and temperature T, as well as the Grüneisen parameters γ are obtained systematically in the ranges of 0-100 GPa and 0-2000 K.     

First principles studies of elastic and thermodynamic properties of fcc-VH2 with pressure and temperature

In this work, we study elastic and thermodynamic properties of VH₂ at different pressures and temperatures. Elastic constants and bulk modulus of VH₂ decrease with increase in temperature, and hence increase with pressure. Thermal expansion of the crystal lattice will be suppressed by high pressure. When the temperature is 1500 K, 15.99 GPa of pressure can completely restrain the volume expansion caused by temperature. At a given pressure, the lower the temperature, the easier the cell compression. At low temperatures, C_v is proportional to T³, and C_v tends to the Dulong-Petit limit at higher temperatures. The Debye temperature increases with pressure, but decreases with temperature. At low temperature and low pressure, thermal expansion coefficient increases sharply with temperature. At high temperature and high pressure, the increasing trend slows down.     

Transition phase and thermodynamic properties of GaN via first-principles calculations

The transition phase of GaN from zincblende (ZB) structure to rocksalt structure (RS) is investigated by ab initio plane-wave pseudopotential density functional theory method, and the thermodynamic properties of the ZB and RS structures are obtained through the quasi-harmonic Debye model. We find that the transition phase from the ZB structure to the RS structure occurs at the pressure of 42.2 GPa, which is in good agreement with other calculated values. Moreover, the dependences of the relative volume V/V₀ on the pressure P, the Debye temperature Θ and heat capacity C_V on the pressure P, as well as the heat capacity C_V on the temperature T are also successfully obtained.     

Relaxation of the normal electrical resistivity induced by high-pressure in strongly underdoped YBa2Cu3O7–δ single crystals

We investigate the relaxation of the normal electrical resistivity, induced by high-pressure in YBa₂Cu₃O_6.45 single crystals. It is determined that the pressure affects to the phase composition of the sample. Under pressure phases with different (but similar) critical temperatures form. It is determined that the application-removal pressure process is completely reversible. Above T_c the temperature dependence of the resistivity in the layers' plane at different hydrostatic pressures can be approximated with high accuracy with the scattering of electrons by phonons model. With increasing pressure, the residual resistance is reduced and the contribution of intraband s–s scattering increases. Additionally, the role of the interband s–d scattering and the Debye temperature is enhanced.     

Elasticity and thermodynamic properties of RuB2 under pressure

First-principles calculations of the crystal structure and the elastic properties of RuB₂ have been carried out with the plane-wave pseudopotential density functional theory method. The calculated values are in very good agreement with experimental data as well as with some of the existing model calculations. The elastic constants c_ij, the aggregate elastic moduli (B, G, E), Poisson's ratio, and the elastic anisotropy with pressure have been investigated. Through the quasi-harmonic Debye model considering the phonon effects, the isothermal bulk modulus, the thermal expansions, Grüneisen parameters, and Debye temperatures depending on the temperature and pressure are obtained in the whole pressure range from 0 to 60 GPa and temperature range from 0 to 1100 K as well as compared to available data.     

Decoupling of the order-disorder and displacive contributions to the phase transition in NH4H(ClH2CCOO)2

The effects of hydrostatic pressure and substitution of Rb⁺for the ammonium cations on the ferroelectric phase transition temperature in NH₄H(ClH₂CCOO)₂ have been studied by electric permittivity measurements. The transition temperature (T_c) decreases with increasing pressure up to 800 MPa and the pressure coefficient dT_c/dp=−1.4×10⁻² [K/MPa] has been experimentally determined. The substitution of Rb⁺ for the ammonium cations has been shown to considerably lower the ferroelectric phase transition temperature T_c. In mixed crystals, additional electric permittivity anomaly has been clearly evidenced. The results are discussed assuming a model, which combines polarizability effects, related to the heavy ion units, with the pseudo-spin tunnelling.     

Thermoelectric behaviour of SmS and Sm0.84Gd0.16S at high pressures and temperatures

The 4f→ 5d electronic phase transition in SmS has been studied using thermoelectric power as a probe. The variation of thermopower with pressure in Sm_0.84Gd_0.16S and in the high pressure phase of SmS is anomalous, characterized by a rather large pressure coefficient. The temperature coefficient of thermopower in Sm_0.84Gd_0.16S is large and negative at low pressures leading to a change of sign at higher temperatures. The anomalies can be understood on the basis of the ICF model.     

Effect of high pressure on the fluctuation paraconductivity in Y0.95Pr0.05Ba2Cu3O7−δ single crystals

The effect of high hydrostatic pressure up to 17 kbar on the fluctuation conductivity of lightly Pr-doped Y_1−xPr_xBa₂Cu₃O_7−δ (x ≈ 0.05) single crystals is investigated. We show that in contrast to non-doped YBa₂Cu₃O_7−δ samples, application of a high pressure leads to a substantial increase of the pressure derivative of the coherence length dξ_c/dP and a temperature shift of the 2D-3D crossover point. Possible mechanisms of the influence of high pressure on the critical temperature and the coherence length are discussed within the framework of a model assuming the presence of singularities in the charge carriers electron spectrum typical for lattices with strong coupling.     

Theoretical investigations of structural, elastic and thermodynamic properties for PtN2 under high pressure

We have investigated structural and elastic properties of PtN₂ under high pressures using norm-conserving pseudopotentials within the local density approximation (LDA) in the frame of density-functional theory. Calculated results of PtN₂ are in agreement with experimental and available theoretical values. The a/a₀, V/V₀, ductility/brittleness, elastic constants C_ij, shear modulus C′, bulk modulus B, shear modulus G, Young's modulus E, Poisson's ratio σ and anisotropy factor A as a function of applied pressure are presented. Through the quasi-harmonic Debye model, we also study thermodynamic properties of PtN₂. The thermal expansion versus temperature and pressure, thermodynamic parameters X (X=Debye temperature or specific heat) with varying pressure P, and heat capacity of PtN₂ at various pressures and temperatures are estimated.     

Effects of pressure and temperature on the isothermal bulk modulus of CaO

Molecular dynamics (MD) simulations have been performed to investigate the effects of pressure and temperature on the isothermal bulk modulus of CaO using pair-wise interactions that include polarization effects through the shell model (SM). The dependence of isothermal bulk modulus B_T of CaO on the compression ratio V/V₀ and pressure P have been obtained from MD runs at T=300 K, and compared with the available experimental data and other theoretical results. A good agreement between theory and experiment is obtained. Meanwhile, B_T dependence on temperature T at zero pressure is investigated. At extended pressure and temperature ranges, SM-MD method has also been carried out for predicting the P-V-T equation of state and isothermal bulk modulus at different temperatures along the isotherms 0, 1000, 2000, 3000, and 4000 K, and at different pressures along the isobars 5, 15, 30, 40, and 50 GPa for CaO, respectively.     

Lattice dynamics,third order elastic constants and thermal expansion of Cadmium

The lattice dynamics, second and third order elastic constants, pressure derivatives of the second order elastic constants and the temperature variation of the lattice thermal expansion of Cadmium have been worked out utilising Keating's approach. The ten TOE constants are calculated using four anharmonic parameters. The model used here reproduces the measured pressure derivatives of the SOE constants of Cadmium extremely well. The low temperature limit of the volume Gruneisen function γ_L is found to be nearer to the value of Andres. The high temperature limit γ_v(T) is in good agreement with the value calculated by Gschneidner Jr. from the Cv data for Cadmium. The lattice dynamics of Cadmium is found to be essentially similar to that of Zinc.     

Low temperature magnetoresistance in La1.32Sr1.68Mn2O7 layered manganite under hydrostatic pressure

The La_1.32Sr_1.68Mn₂O₇ layered manganite system has been studied by the low temperature electrical resistance and magnetoresistance under hydrostatic pressure up to 25 kbar. We have observe both, a Curie temperature (T_C) and a metal-insulator transition (T_MI) at 118 K in the ambient pressure. The applied pressure shifts the T_MI to higher temperature values and induces a second metal-insulator transition (T²_MI) at 90 K, in the temperature dependence of resistivity measurements. Also, the pressure suppresses the peak resistance abruptly at T_C. When an external field of 5 T is applied, we have observed a large negative magnetoresistance of 300% at the transition temperature and a 128% at 4.5 K. However, the increased pressure decreases the magnetoresistance ratio gradually. When the pressure reaches its maximum available value of 25 kbar, the magnetoresistance ratio decreases at a rate of 1.3%/kbar. From our experimental results, the decrease of magnetoresistance ratio with pressure is explained by the pressure induced canted spin state which is not favor for the spin polarized intergrain tunneling in layered manganites.     

Pressure and temperature induced high spin–low spin phase transition: Macroscopic and microscopic consideration

The behavior under pressure of the high spin–low spin phase transition in the coordination compounds containing 3d ions is analyzed using thermodynamic and microscopic approaches. For thermodynamic approach the mean field model with interactions between spin-crossover molecules is considered. Microscopic model takes into account the interaction of d electrons of the transition metal ions with full symmetric distortions of the ligands. The relationship of the thermodynamic interaction parameters with microscopic ones is installed and shown how the quantum–mechanical interactions form the cooperativity of the system. Within the microscopic model the temperature and pressure dependences of the high spin fraction in 2-D compounds {Fe(3-Fpy)₂[M(CN)₄]} (M=Pd, Pt) are simulated and microscopic parameters are evaluated. It is concluded that different experimental behaviors of the temperature and pressure induced spin transitions are determined by different variations of the inelastic and elastic energies under pressure, and vibrational component of the free energy drives the ST equally with electronic part.     

Pressure effect on the anomalous electrical conductivity of magnetite

The temperature dependence of the electrical conductivity of magnetite was measured under hydrostatic pressure up to 18.4 kbar. It is found that the temperature of the conductivity maximum in the high temperature phase is more rapidly reduced by pressure (dT_m/dP = -4.1 K/kbar) than the Verwey temperature (dT_v/dP = -0.27 K/kbar). The discontinuous change of the conductivity at T_v appears to increase with applied pressure as a result of a lowering of T_m.     

Simple modeling of the temperature dependence of the first-order line-mixing coefficients Yl(T)

A simple approach is proposed in order to model the temperature dependence of the first-order line-mixing coefficients Y_l(T). It respects a sum rule whose breakdown leads to large errors in atmospheric spectra computations. Furthermore, only two parameters, which can be represented with no more than three significant figures, are required (for air-broadening) for each line. Contrary to previous ones, our model is thus particularly suitable for storage of line-mixing parameters in databases. Tests in the case of two CO₂ Q branches near 14 μm and of O₂ absorption in the centimeter wave region under various pressure and temperature conditions show the accuracy of our approach.     

The first-principle studies of the crystal phase transitions: Fd3m-MgAl2O4→F4-3m-MgAl2O4

Magnesium aluminum spinel (MgAl₂O₄) is a major constituent of the shallow upper mantle. It is of great geophysical importance to explore its physical properties under high pressure and temperature. The first-principle density functional theory (DFT) with the plane wave along with pseudopotential was employed to obtain the total energy for both Fd3m-MgAl₂O₄ and F4-3m-MgAl₂O₄, which was used to generate the Gibbs free energy as a function of temperature and pressure with the quasi-harmonic Debye model. It is found that the phase transition temperature from Fd3m-MgAl₂O₄ to F4-3m-MgAl₂O₄ is beyond 452.6 K in the pressure regime studied, which is consistent with the experiment. The phase transition temperature is related to pressure by a linear function, i.e. T=8.05P+452.6, which is the first equation of this kind to describe the phase transition Fd3m→F4-3m. The elastic constants, equation of states and thermodynamic properties of Fd3m-MgAl₂O₄ are also reported in this paper to make a complete study.