Thermodynamic properties of a two-dimensional square-well fluid

Analytic expressions for the thermodynamic properties of a classical two-dimensional square-well fluid and the first quantum correction to them are derived using the Barker-Henderson perturbation theory. Numerical results are reported. It is found that the quantum effect, which increases with increase of density, is largely determined by the hard-core and the attractive tail has a minor effect at high density.     

Thermodynamic properties of molecular fluid mixtures of hard ellipsoids

Thermodynamic properties of molecular fluid mixtures of hard ellipsoids are calculated. Numerical results are given for equation of state and excess-free energy of the binary mixture of both additive and non-additive hard ellipsoids. It is found that the equation of state and free energy of mixtures increase with increase of anisotropy parameterx ₀.     

Perturbation theory for thermodynamic properties of a ν-dimensional square-well fluid

The Barker-Henderson perturbation theory is used for a ν-dimensional fluid with square-well potential. Analytic expressions are given for the equation of state, excess free energy per particle and internal energy. The numerical results are discussed. A significant feature is the increase of the thermodynamic properties with increasing dimensionality.     

Equilibrium properties of hard non-sphere fluids

Derivation of the thermodynamic properties of fluids of hard non-spherical molecules of arbitrary symmetry is based on the decoupling approximation. Theoretical expressions are given and calculations made for the equation of state and virial coefficients for hard ellipsoids. These results are compared with Monte Carlo values and show fair agreement in all cases. The theoretical predictions for the equation of state for binary mixtures are compared with the Monte Carlo results for hard spheres and hard prolate spherocylinders. Theoretical expressions for the first order quantum correction to the free energy, pressure and virial coefficients are also given. The quantum effects increase with increase of density and with increase of anisotropy parameter.     

Perturbation theory of polar hard Gaussian overlap fluid mixtures

A perturbation theory of polar hard Gaussian overlap fluid mixture is discussed. Explicit analytic expressions for the second and third varial coefficients are given. Numerical results are estimated for the thermodynamic properties of quadrupolar hard Gaussian overlap fluid and fluid mixture. It is found that the excess free energy and internal energy depend on concentrationsc ₁,c ₂, molecular diameter ratioR, shape parameterK and the quadrupole momentsQ*₁,Q*₂.     

The effect of steepness of soft-core square-well potential model on some fluid properties

The effect of repulsive steepness of the soft-core square well (SCSW) potential model on the second virial coefficient, critical behaviour (two- phase region and the position of critical point), and coordination number are investigated. The soft-core thermodynamic perturbation theory (TPT) presented by Weeks-Chandler-Anderson (WCA) recently developed by Ben-Amotz and Stell (BAS) has been used for the reference system, and the Barker-Henderson TPT for the perturbed system. The Barker-Henderson macroscopic compressibility approximation has been used for all order perturbation terms in which the second-order one is improved by assuming that the molecules in every two neighbouring shells are correlated upon the original assumption. By using the hard-sphere isothermal compressibility consistency for the radial distribution function (RDF), an analytical closed expression has been derived for the Helmholtz free energy function contained effective hard-sphere diameter. The accuracy of the model has been examined for the hard-core system, and an appropriate range found for the attractive width of the potential well (R), then the effect of steepness parameter on the critical quantities, coordination number, and the inversion temperature of the second virial coefficient, has been investigated qualitatively. The predicted results are in good agreement with the computer simulation data for the critical constants, and coordination number at the limit of the hard-core square-well potential model at least qualitatively, and for the attractive range 1.55 ≤ R ≤ 1.7, quantitatively. It was found that the steepness of the potential model has a marginal effect on the critical behaviour, and also every thermodynamic quantity at low and medium temperatures for which the molecular penetration is negligible, but since the penetration at high temperatures is significant, the role of the steepness of potential on the inversion temperature of the second virial coefficient and coordination number is highlighted.     

Quantum corrections to the thermodynamic properties of a two-dimensional fluid with hard-core potential

A simple theory, based on the physical interpretation of the reciprocal of activity, is developed to evaluate the thermodynamic properties of a two-dimensional fluid in the semi-classical limit. The theory is applied to calculate the quantum corrections to the equation of state and excess free energy of two-dimensional fluids, whose molecules interactvia hard-disc and square-well potential. It is found that the quantum effect increases with the increase of density and decrease of temperature.     

Thermodynamic properties of the Lennard-Jones FCC solid: perturbation theory parameterisation and Monte Carlo simulation

This work is concerned with a valid representation of the solid-phase equation of state (EOS), the validity of which is evaluated by comparing to Monte Carlo (MC) simulation results. The proposed EOS has been developed by employing an optimal division of the Lannard-Jones (LJ) potential and an effective temperature- and density-dependent diameter into the framework of the simplified perturbation theory. Then, with the aim of extending to the chain systems, the conventional chain contribution (i.e. TPT1) is added to the proposed model (i.e. the atomic LJ system). Finally, the solid-state EOS based on Helmholtz free energy will be introduced for low temperature and high density conditions. To verify the accuracy of the proposed model, its performance is compared with the results of MC simulation. The comparison between the obtained results from the proposed model and the MC simulations shows that the EOS can satisfactorily predict the properties of the solid LJ system, both for the atomic system and for the chains.     

Equilibrium properties of a semiclassical fluid with square-well plus hard core potential

A cluster expansion theory, in which the quantum hard sphere system is taken as a reference system and the attractive interactions as a perturbation, is applied to calculate the equilibrium properties of the square-well fluid in the semiclassical limit. The radial distribution function and direct correlation function are obtained using the exponential approximation. The isothermal compressibility is also evaluated.     

Thermodynamic properties for the triangular-well fluid

The thermodynamic properties of the triangular-well fluid with a well range of up to twice the hard sphere diameter were studied by means of a new developed equation of state and molecular simulation. This EoS is based on the perturbation theory of Barker and Henderson with the first and second-order perturbation terms evaluated by molecular simulation and then a fit with a simple function based on the radial distribution function of the reference fluid. The thermodynamic properties for the triangular-well fluid were also obtained directly by Gibbs ensemble and NPT Monte Carlo simulations. Good agreement is observed between the proposed EoS and the molecular simulation results. A model for the triangular-well solid is also presented; this has been used to calculate the solid–liquid transition line. Very good agreement is obtained with previously report values for this line and for the triple point temperature and pressure.     

Perturbation theory for equilibrium properties of a binary mixture of hard discs

The radial distribution function (RDF) and thermodynamic properties of a two-dimensional hard-disc mixture are calculated by using the perturbation theory. Numerical results are given for theRDF, pressure and excess-free energy of the binary mixture of both additive and non-additive hard discs. It is found that the thermodynamic properties of the binary mixture of non-additive hard discs increase with Δ, the non-additive parameter.     

Quantum corrections to thermodynamics of polar hard sphere fluids

The quantum corrections to the thermodynamic properties of polar hard sphere fluids and fluid mixtures are estimated taking into account the influence of dipole and quadrupole moments. Expressions are given for the second virial coefficient, free energy and pressure and results are given for different values ofμ* andϑ*. The first order quantum correction arises due to the translational contribution only. The quantum effect increases with density,μ* andϑ*. Numerical results are also estimated for binary mixtures of (i) hard spheres and dipole hard spheres and (ii) hard spheres and quadrupole hard spheres. The ‘excess’ free energy for dipole hard sphere binary mixture is also reported. It is found that the ‘excess’ quantum effect depends on the concentration and the particle diameter ratio and increases with increase ofμ* andϑ*.     

极端条件下6Li2O的热力学性能与电子结构

 采用密度泛函理论与准谐振德拜模型研究了面心立方相的⁶Li₂O在极端条件下的热力学性质与电子结构。结果表明: ⁶Li₂O的热膨胀系数在任何温度下都随压强增加明显降低,但仅当压强较低(低于40 GPa)时,温度对6Li2O的热膨胀系数的影响才明显;O原子半径随压强增大而迅速降低,而随温度的变化并不明显;在低压条件下(低于40 GPa),带隙随温度的升高缓慢降低;而在高压条件下(高于40 GPa),温度对带隙宽度的影响几乎可以忽略;无论在什么温度条件下,带隙宽度均随压强的增大而迅速增加。     

四方、单斜和正交Ge3N4的结构、电子结构和热力学性质

数值计算了四方、单斜和正交结构Ge₃N₄的点阵常数、晶胞体积、弹性模量、维氏硬度和态密度.计算结果与已有的实验数据和理论值符合得很好.形成焓为负、晶格形变和晶胞体积随压强呈线性变化,表明三种相在0~20 GPa压强范围内可以保持结构稳定.态密度研究表明三种氮化锗内部存在强烈的s-p杂化.三种相都属于脆性半导体材料,具备各向异性且硬度适中.采用包含原子振动和非谐效应的准谐波近似方案,研究材料的热力学性质,发现压强对赫姆霍兹自由能和内能有显著影响.结果为进一步理解氮化锗三种新结构的电子结构和热力学性质提供初步的物理图像.     

极端条件下6Li2O的热力学性能与电子结构

采用密度泛函理论与准谐振德拜模型研究了面心立方相的6Li2O在极端条件下的热力学性质与电子结构。结果表明: 6Li2O的热膨胀系数在任何温度下都随压强增加明显降低,但仅当压强较低(低于40 GPa)时,温度对6Li2O的热膨胀系数的影响才明显;O原子半径随压强增大而迅速降低,而随温度的变化并不明显;在低压条件下(低于40 GPa),带隙随温度的升高缓慢降低;而在高压条件下(高于40 GPa),温度对带隙宽度的影响几乎可以忽略;无论在什么温度条件下,带隙宽度均随压强的增大而迅速增加。     

Semiclassical statistical mechanics ofv-dimensional fluid mixture of hardv-spheres

The problem of calculating the equilibrium properties ofv-dimensional fluid mixture of hardv-spheres is studied. High temperature expansion for the density independent radial distribution function is derived for a hardv-sphere mixture. The ‘excess’ quantum corrections to the second virial coefficient and the excess free energy are also studied. Significant features are the large increase in ‘excess’ quantum correction with increasing dimensionality.     

Berthelot流体的热力学性质和参数解

研究了Berthelot流体的热力学性质.导出了单原子Berthelot流体Helmholtz自由能、熵、吉布斯函数、内能和焓;求得了Berthelot流体两相共存的的参数解,并用参数解讨论了Berthelot流体的相图和热力学量在临界点的行为及其相关性质.本文的研究为符合Berthelot流体的物质提供了热力学及其相变的解析理论.     

高压下AuCu3热动力学性质的第一性原理研究

利用平面波赝势密度泛函理论研究了AuCu3的结构性质,得到了晶格常数a、体弹模量 、体弹模量对压强的一阶导数 ,计算结果与实验值相吻合。通过准谐德拜模型成功地获得了高温高压下AuCu3的状态方程、热膨胀系数、热容及德拜温度。     

An equation of state contribution for dipolar and quadrupolar square-well fluids

A dipolar–quadrupolar contribution to the residual Helmholtz energy for a polar square well (a square well plus either a point dipole or a point quadrupole) fluid is developed based on the Padé approximation. Taking the square well system as reference, the contribution is formulated using an expansion for radial distribution function of the reference system. In addition to square well potential parameters the contribution depends only on dipole and quadrupole moments. This term is added as perturbation to a generalized equation of state for square well fluids. The results are then compared with the available simulation data in the literature. With the new equation obtained, it was possible to predict liquid–vapour equilibrium properties and critical properties of polar square well fluids more accurately than with available perturbation theories for multipolar square well systems. Application of the equation of state to a real dipolar (water) and a real quadrupolar (carbon dioxide) fluid indicated that the polar contribution greatly improved the predictions of saturation properties. Accurate prediction of critical properties for polar square well fluids remains as a challenge. This work can be useful in the development of better equations of state.