范德瓦耳斯气液状态方程纵横谈

首先强调了范氏方程是气液系统的状态方程,范氏方程可以很好地说明物质气态和液态的相互转变．分析了焦-汤效应,简述了气体的液化与低温的获得．     

范德瓦耳斯和他的状态方程

在物理学发展史上，范德瓦耳斯对气—液流体系统做了开创性的研究工作，建立了人类历史上第一个既能反映气、液各相性质，又能描述相交和临界现象的状态方程。范德瓦耳斯的理论成就和研究方法对热力学、统计力学和低温物理学的发展产生了重要而深远的影响。文章系统探讨了范德瓦耳斯方程产生的历史背景、科学意义和局限性，讨论了范德瓦耳斯的理论和方法对当代物理学的启发意义。     

论范德瓦尔斯a和b参数与温度的关系

范德瓦尔斯方程中a、b参数是否与温度相关,不但不同文献中的说法互不相同,而且有同一文献前后的结论相互矛盾.本文分析了这个令人迷惑的问题.在热力学中a和b参量被处理为与温度无关,它仅仅在临界点附近有效并可以把范德瓦尔斯方程表述为对应态定律;在更加广泛的温度区间a、b参量和温度有关,但是范德瓦尔斯方程却丧失了其独特性.统计物理文献把a和b参量处理成为位力展开的一种拟合方程,发现一般情况下两个参数都依赖于温度,仅仅在特殊情况下和温度无关,以说明对应态定律成立的条件.热力学和统计物理关于a和b参量是否依赖于温度相互矛盾的表述,源于这两个理论中范德瓦尔斯状态方程适用范围不同.     

Two-dimensional Rydberg gases and the quantum hard-squares model

We study a two-dimensional lattice gas of atoms that are photoexcited to Rydberg states in which they interact via the van?der?Waals interaction. We explore the regime of dominant nearest-neighbor interaction where this system is intimately connected with a quantum version of Baxter's hard-squares model. We show that the strongly correlated ground state of the Rydberg gas can be analytically described by a projected entangled pair state that constitutes the ground state of the quantum hard-squares model. This correspondence allows us to identify a phase boundary where the Rydberg gas undergoes a transition from a disordered (liquid) phase to an ordered (solid) phase.     

A Simple Kinetic Model for the Phase Transition of the van der Waals Fluid

A simple kinetic model, which is presumably minimum, for the phase transition of the van der Waals fluid is presented. In the model, intermolecular collisions for a dense gas has not been treated faithfully. Instead, the expected interactions as the non-ideal gas effect are confined in a self-consistent force term. Collision term plays just a role of thermal bath. Accordingly, it conserves neither momentum nor energy, even globally. It is demonstrated that (i) by a natural separation of the mean-field self-consistent potential, the potential for the non-ideal gas effect is determined from the equation of state for the van der Waals fluid, with the aid of the balance equation of momentum, (ii) a functional which monotonically decreases in time is identified by the H theorem and is found to have a close relation to the Helmholtz free energy in thermodynamics, and (iii) the Cahn–Hilliard type equation is obtained in the continuum limit of the present kinetic model. Numerical simulations based on the Cahn–Hilliard type equation are also performed.     

Wetting of Alkanes on Water from a Cahn-Type Theory: Effects of Long-Range Forces

We apply the phenomenological wetting theory of Cahn to fluids with van der Waals forces, and in particular to the wetting of pentane on water. Taking into account explicitly the long-range substrate–adsorbate interaction allows us to reproduce the experimentally observed critical wetting transition, which arises from the vanishing of the Hamaker constant at T53°C. This transition is preceded by a first-order transition between a thin and a thick film at a (much) lower temperature. If long-range forces are neglected, this thin–thick transition is the only wetting transition and critical wetting is missed. Our study focuses on the development of useful theoretical tools, such as phase portraits and interface potentials adapted to systems with van der Waals forces.     

A self-consistent approach for modelling the interfacial properties and phase diagrams of Yukawa,Lennard-Jones and square-well fluids

A self-consistent density-functional approach is presented for describing the phase behaviour and interfacial tensions of van der Waals fluids represented by the hard-core Yukawa (HCY), Lennard-Jones (LJ) and square-well (SW) potentials. The excess Helmholtz energy functional is formulated in terms of a modified fundamental measure theory (MFMT) for the short-ranged repulsion and a density-gradient expansion for the van der Waals attractions. Analytical expressions for the direct correlation functions of uniform fluids are utilized to take into account the effect of van der Waals’ attraction on intermolecular correlations. For bulk phases, the density functional theory is reduced to an equation of state (EOS) that provides accurate saturation pressures and vapour–liquid phase diagrams. Near the critical region, the long-range fluctuations can be corrected by using the renormalization group (RG) theory. With the same set of molecular parameters, the theory also yields satisfactory surface tensions and interfacial density profiles at all relevant temperatures.     

Coulombic Phase Transitions in Dense Plasmas

We give a survey on the predictions of Coulombic phase transitions in dense plasmas (PPT) and derive several new results on the properties of these transitions. In particular we discuss several types of the critical point and the spinodal curves of quantum Coulombic systems. We construct a simple theoretical model which shows (in dependence on the parameter values) either one alkali-type transition (Coulombic and van der Waals forces determine the critical point) or one Coulombic transition and another van der Waals transition. We investigate the conditions to find separate Van der Waals and Coulomb transitions in one system (typical for hydrogen and noble gas-type plasmas). The separated Coulombic transitions which are strongly influenced by quantum effects are the hypothetical PPT, they are in full analogy to the known Coulombic transitions in classical ionic systems. Finally we give a discussion of several numerical and experimental results referring to the PPT in high pressure plasmas.     

Hydrogen embrittlement under load as a first-order phase transition

The stress-strain equation of state for a material with dissolved hydrogen is derived within a two-component continuum model. It is demonstrated that, for the parameters corresponding to conventional metals, it has the shape of a loop similar to the van der Waals loop. On this basis, it is concluded that hydrogen embrittlement of materials under load is a typical first-order phase transition and, therefore, occurs through nucleation of a new phase. Thermodynamic and kinetic theories of this transition are developed, and time dependences of all the main characteristics of this process are calculated.     

Letter: Brane Cosmology with a van der Waals Equation of State

The evolution of a Universe confined onto a 3-brane embedded in a five-dimensional space-time is investigated where the cosmological fluid on the brane is modeled by the van der Waals equation of state. It is shown that the Universe on the brane evolves in such a manner that three distinct periods concerning its acceleration field are attained: (a) an initial accelerated epoch where the van der Waals fluid behaves like a scalar field with a negative pressure; (b) a past decelerated period which has two contributions, one of them is related to the van der Waals fluid which behaves like a matter field with a positive pressure, whereas the other contribution comes from a term of the Friedmann equation on the brane which is inversely proportional to the scale factor to the fourth power and can be interpreted as a radiation field, and (c) a present accelerated phase due to a cosmological constant on the brane.     

Calculation of a one dimensional van der waals liquid-gas transition by means of a Ginzburg-Landau expansion

The grand canonical partition function written as a Feynman path integral over the order parameter is calculated numerically within the framework of a Ginzburg-Landau theory for a one dimensional van der Waals system. The equation of state is calculated. The results show that the transition is of quasi first order.     

Excited nucleon as a van der Waals system of partons

Saturation in deep inelastic scattering (DIS) and deeply virtual Compton scattering (DVCS) is associated with a phase transition between the partonic gas, typical of moderate x and Q ², and partonic fluid appearing at increasing Q ² and decreasing Bjorken x. We suggest the van der Waals equation of state to describe properly this phase transition.     

The van der Waals energy of an atom near a carbon nanotube

Using a unified macroscopic QED formalism, an integral equation for the van der Waals energy of a two-level atomic system near a carbon nanotube is derived. The equation is valid for both strong and weak atom-vacuum field coupling. By solving it numerically, the inapplicability of weak coupling-based van der Waals interaction models in the close vicinity of the nanotube surface is demonstrated. It is also shown that encapsulation of doped atoms into the nanotube is energetically more favorable than their outside adsorption by the nanotube surface.     

High pressure structural phase transition and elastic properties of Ga<Subscript>1-x</Subscript>In<Subscript>x</Subscript>As semiconducting compounds

The present paper addresses the high-pressure phase transformation and mechanical properties of Ga_1-xIn_xAs (x = 0.25, 0.5 and 0.75) by formulating an effective interionic interaction potential. This potential consists of the long-range Coulomb and charge transfer caused by the deformation of the electron shells of the overlapping ions and the Hafemeister and Flygare type short-range overlap repulsion extended upto the second neighbor ions and the van der Waals (vdW) interaction. The estimated values of phase transition pressure and the vast volume discontinuity in pressure-volume (PV) phase diagram indicate the structural phase transition from zinc blende (B3) to rock salt (B1). The equation of state curves plotted between V (P)/ V (0) and pressure are for both the zincblende (B3) and rocksalt (B1) structures. Further, the variations of the second and third order elastic constants with pressure have followed a systematic trend, which are almost identical to those exhibited by the observed data measured for other compounds of this family.     

Two disks in a box

Exact analytical expressions are derived for the thermodynamic properties of two discs in square and rhomboidal boxes with hard walls, and in a square cell with periodic boundaries. With periodic boundaries the equation of state has a van der Waals loop and a second order cusp. In a box with hard walls there is a third order “glass transition” which seems to capture the essence of the glass transition observed in systems of a few hundred hard spheres.     

Influence of the chain length of long molecules on the equation of state in binary gas-liquid mixtures

The simple Flory-Huggins model can be combined with the lattice gas as was done by Tompa and others. Here the same method is used to obtain the van der Waals equation of state for a binary gas-liquid system containing a solute consisting of segmented molecules. The simplified equation of state developed here is useful for the study of the critical properties of such systems, in particular, the dependence of the various parameters on the chain length of the molecules.     

Study of interaction between protein and main active components in Citrus aurantium L. by optical spectroscopy

The interaction between flavonoids and proteins was investigated by fluorescence and absorption spectroscopy. The binding parameters of drugs with proteins were obtained according to the corrected fluorescence data by an improved calculation method. The ΔH, ΔS and ΔG obtained indicate that the van der Waals or hydrogen bond, electrostatic force and hydrophobic forces all play a role in the interaction of drugs with proteins. Based on Förster's theory, the binding average distance r between the protein and drug was evaluated and found to be less than 3 nm. The interaction of drug-metal ion complexes and proteins was also investigated.