Pair correlations in magnetic nanodispersed fluids

The pair distribution function of a monodisperse magnetic fluid simulated by a liquid made of dipolar hard spheres with constant magnetic moments is calculated. The anisotropy of the pair distribution function and the related structure factor of scattering in a dc uniform magnetic field are studied. The calculation is performed by diagrammatic expansion in the volume concentration of particles and the interparticle magnetic-dipole interaction intensity using a thermodynamic perturbation theory. Limitation by three-particle diagrams makes it possible to apply the results obtained to magnetic fluids with a moderate concentration. Even for low-concentration and weakly nonideal magnetic fluids, the anisotropic interparticle magnetic-dipole correlations in a magnetic field lead to the repulsion of particles in the direction normal to the field and to the formation of particle dimers along the field.     

Structural and response functions at equilibrium in path-integral quantum simple fluids

A discussion on the physical meaning of the r-space structures that can be defined in path-integral quantum simple fluids far from exchange is presented by making the connection with their associated experimentally measurable properties in k-space (response functions). The role played in this issue by weak external fields acting on the fluid is examined by considering both the standard quantum treatment of neutron scattering and the path-integral functional analysis approach. For the sake of completeness, the same discussion is presented for the approximate Gaussian Feynman-Hibbs effective potential picture that can be derived from the path-integral, and also the structural interrelations between both formalisms are stated. To illustrate the points addressed in this paper results for liquid helium-4 at 4.2 K (SVP), obtained with the use of the Aziz-Slaman and the ab initio SAPT2 pair potentials, are reported.     

Analytical model of equation of state for polydisperse fluid of adhesive spherical particles

An analytical model of the equation of state is presented for the polydisperse fluid of adhesive colloidal particles. The model is based on the mean-spherical approximation solution of the Ornstein-Zernike equation for a multicomponent hard sphere Yukawa fluid in which the Yukawa tails are sufficiently short range and strong. In particular, assuming that distributions of diameters and ‘charges’ of particles are described by the Schulz function, the analytical expressions for the compressibility and the pressure for the intrinsically polydisperse fluid are given in terms of simple functions of the packing fraction, the adhesion parameter and the Schulz distribution parameter.     

Perturbation theory for equilibrium properties of molecular fluids

Perturbation theory for the angular pair correlation function g(r₁₂ ω ₁ ω ₂), using a fluid with isotropic intermolecular forces as the reference system, is applied to the calculation of a variety of macroscopic properties. Comparisons with experiment are made for methane, oxygen and nitrogen (and carbon monoxide for infra-red and Raman band moments) in the dense fluid and liquid states. Theoretical expressions are given and calculations made for thermodynamic properties (isothermal compressibility, pressure, configurational energy, entropy and specific heat) both along and away from the vapour-liquid co-existence curve, for infra-red and Raman band moments, and for neutron scattering cross sections. Excellent agreement with experiment is obtained for all properties, except for the infra-red and Raman band moments; this latter comparison is inconclusive because of large experimental uncertainties. The anisotropic intermolecular forces are found to have very little effect on the liquid isothermal compressibility, in agreement with the first-order theory. Molecular anisotropy has a relatively small effect on the configurational energy and on the Helmholtz free energy, but the effect is large for pressure and specific heat. The pressure is more sensitive to short-range anisotropic forces than the other properties, whereas the specific heat is particularly sensitive to the long-range anisotropic forces. Mean squared torques (derived from infra-red and Raman band moments) are very sensitive to the strengths of the anisotropic forces, and are more sensitive to higher terms in the multipole series than are the other properties. The structure factors for oxygen and nitrogen are found to be little affected by the anisotropic forces.     

Calculation of static correlations in a fluid of linear molecules

Recently, both X-ray and neutron diffraction data have been obtained for liquid crystalline materials. While these results contain information about the instantaneous correlations of molecular positions and orientations in such fluids, no relevant calculations are available to aid the interpretation of the data. In this paper a formalism which may be used to describe static, molecular correlations in isotropic or anisotropic fluids of linear molecules is developed. To obtain the theory, the direct and total correlation functions of two molecules are expanded as series of spherical harmonics the arguments of which describe the molecular orientations. A relation between the expansion coefficients of these series is obtained by making use of the Ornstein-Zernike equation. It is shown that this equation may be solved in the Percus-Yevick or Optimized-Random-Phase approximations by a variational technique. This technique is used to find the total correlation function in the Percus-Yevick approximation of hard, linear molecules of various length-breadth ratios at several fluid densities.     

Integral equation theory for fluids ordered by an external field: separable interactions

The structural and thermodynamical properties of classical fluids orientationally ordered by an external field are investigated by means of integral equation theories. A general theoretical framework for handling these theories is developed and detailed for the particular case of separable interactions between fluid particles. This approach is then illustrated for the case of two (off lattice) models: the ferromagnetic Heisenberg model and a simple liquid crystal model, for which the numerical solution of integral equations such as the Percus-Yevick, the hypernetted chain, and the reference hypernetted chain closure equations are presented and compared with Monte Carlo simulation results and the analytical solution of the mean spherical approximation. The zero-field case is also examined, and the spontaneous ordering is analyzed in detail, mainly in what concerns the appearance of infinite wavelength singularity in the Ornstein-Zernike equation and the relation with the one-body closure equations and the long range orientational ordering that occurs. In particular, it is shown that the Wertheim one-body closure equation appears as a sum rule compatible with the Ornstein-Zernike equation. The relation between the elastic constant and the long range tail of the pair correlation function is made explicit. In particular, the long range behavior of the various terms in the expansion of the pair correlation function is depicted. The numerical investigation of the two models shows that it is not possible to discriminate between the four integral equations, as to which one would be the most accurate in all cases. The general trends in the thermodynamical and structural properties seem to indicate that the Percus-Yevick approximation is generally better in the strong ordering case, whereas the reference hypernetted chain approximation might be better suited to the study of the isotropic phase and the low ordering regimes.     

Theoretical calculation of the structure of a polarizable-ionic fluid

Much theory of the structures of fluids depends on the assumption of pair-additive forces between the particles. Simulations and experiments have shown that many molten salts, molecular fluids and other systems have structures that depend sensitively on polarization of their electron clouds, or on other internal distortions. In such cases, the forces are not pair additive and the theoretical calculation of structure, expressed as a radial distribution function, g(r), is not possible using the ordinary methods. Part of the problem is that the internal structure is quantum mechanical. A theoretical method for the calculation of the structure of a fluid of polarizable particles is presented here, in a form that may be applied to any one of many structure theories in common use. The method is inspired by work on the simulation of polarizable fluids. It is applied to a simple model of a molten salt with polarizable ions. The theory is applicable to particles carrying any combination of induced electrical multipole moments, along with charges and permanent moments.     

Liquid fluorine properties by the hardsphere model with attractive interactions

We test the validity of an approximate equation of state of real fluids and the expression for surface tension of hardsphere liquids with attractive interactions derived by Sharma and others by obtaining expressions for isothermal compressibility,C ₁-parameter and acoustical parameter and relate them to microscopic Grüneisen parameter. The calculated values for liquid fluorine show fair agreement with experimental values.     

Liquids in equilibrium: Beyond the hypernetted chain

Density functional techniques are used to derive a charging expression for the non-uniform density of a molecular liquid. In the atomic limit the equation reduces to an exact form due to Fixman. The theory is simplified greatly via a physical approximation that accounts for three-body correlations beyond those included in the hypernetted chain (HNC) closure of the Ornstein-Zernike (OZ) equation. The radial distribution function is obtained as a special case. The theory is tested by examining the phase behavior of two fundamental complex fluids: the homopolymer blend and diblock copolymer melts. For the former it is found, contrary to HNC theory and its molecular generalizations, that a critical temperature T_c is predicted from the structure route. This T_c scales linearly with degree of polymerization N in agreement with Flory theory. The simplest form of the theory can be considered as a way to incorporate attractive interactions within a formalism that is very similar to that of the OZ or reference interaction site model (RISM). The relevance of the theory to charged liquids is also discussed.     

A density-corrected quantum Boltzmann equation

Binary correlations are a recognized part of the pair density operator, but the influence of binary correlations on the singlet density operator is usually not emphasized. Here free motion and binary correlations are taken as independent building blocks for the structure of the nonequilibrium singlet and pair density operators. Binary correlations are assumed to arise from the collision of twofree particles. Together with the first BBGKY equation and a retention of all terms that are second order in gas density, a generalization of the Boltzmann equation is obtained. This is an equation for thefree particle density operator rather than for the (full) singlet density operator. The form for the pressure tensor calculated from this equation reduces at equilibrium to give the correct (Beth-Uhlenbeck) second virial coefficient, in contrast to a previous quantum Boltzmann equation, which gave only part of the quantum second virial coefficient. Generalizations to include higher-order correlations and collision types are indicated.     

The Fisher-Widom line for systems with low melting temperature

We present Monte Carlo results for the pair distribution function of three simple fluid models, with pairwise interactions, which have low triple point temperatures and mimic some aspects of Na and Hg liquid metals. The results are then used to get the direct correlation function, by numerical solution of the Ornstein-Zernike equation, and to characterize the decay modes of any density distribution towards the bulk fluid. The Fisher-Widom line is obtained from the crossing of the two lowest inverse decay lengths, associated to monotonic and to oscillatory decay modes. For the pair potential models with a soft repulsive core, the Fisher-Widom line appears well below the critical temperature and has positive slope of the temperature with respect to the density, contrary to previous results for the Lennard-Jones and square-well potentials which had located that line quite close to T _c and with negative slope.     

Relation between Tolman length and isothermal compressibility for simple liquids

The Tolman length δ 0 of a liquid with a plane surface has attracted increasing theoretical attention in recent years,but the expression of Tolman length in terms of observable quantities is still not very clear.In 2001,Bartell gave a simple expression of Tolman length δ 0 in terms of isothermal compressibility.However,this expression predicts that Tolman length is always negative,which is contrary to the results of molecular dynamics simulations(MDS) for simple liquids.In this paper,this contradiction is analyzed and the reason for the discrepancy in the sign is found.In addition,we introduce a new expression of Tolman length in terms of isothermal compressibility for simple fluids not near the critical points under some weak restrictions.The Tolman length of simple liquids calculated by using this formula is consistent with that obtained using MDS regarding the sign.     

Density-functional theory of inhomogeneous fluids in the canonical ensemble

We present a density-functional approach for dealing with inhomogeneous fluids in the canonical ensemble. A general relation is proposed between the free-energy functionals in the canonical and the grand canonical ensembles. The minimization of the canonical-ensemble free-energy functional gives rise to Euler-Lagrange equations which involve averaged Ornstein-Zernike equations of second and third order. The theory is especially appropriate for systems with a small, fixed number of particles. As an example of application we obtain accurate results for the density profile of a hard-sphere fluid in a closed spherical cavity that contains only a few particles.     

13C hyperfine splitting in the benzene negative ion

A method is developed to calculate the coefficients appearing in the Høye, Stell and Waisman analytic solution of the Ornstein-Zernike equation for a hard core potential with a direct correlation function of the two Yukawa form. The method is simple and makes the choice of a physical solution easy. The compressibility, energy and virial pressures are calculated in the vicinity of the liquid-gas transition region and their dependence on changing K ₂, the amplitude of the repulsive Yukawa part, is analysed. This method offers promising possibilities for the application of the hard core, two Yukawa (HCTY) system in the theory of fluids.     

The structure of two-dimensional dimerizing fluids from Wertheim’s Ornstein-Zernike equation

A dimerizing fluid of hard discs is studied using two-dimensional (2D) Wertheim’s Ornstein-Zernike (WOZ) equation and associative Percus-Yevick (APY) closure. Dimerization takes place due to site-site associative interactions. The dependences of the association constant on disc density at different association energies are obtained. We calculate the compressibility and the virial equations of state (EOS) using the solution of the WOZ equation. Theoretical structure and thermodynamics is compared with Monte Carlo computer simulation data. Extension of our solution for polymerizing models is of special interest for the development of EOS for 2D chain fluids. This work was supported in part by Cray Research of Mexico under University Research and Development grant program and by KBN of Poland under the Grant No. 3T09A06210.     

Statistical mechanics of linear molecules I: Percus-Yevick and convolution-hypernetted-chain approximations

It is shown how the Percus-Yevick and convolution-hypernetted-chain approximations for dense fluids of linear molecules can be brought into practically applicable forms by using cartesian tensor formalism and pertubation theory. The possibility of expanding the intermolecular potential and the correlation functions is discussed in detail. Also, exact reductions for the Ornstein-Zernike relation in real space and for the Percus-Yevick equation are given. Some other approaches to the statistical mechanics of linear molecules are critically discussed. It is shown in particular, that the mean spherical model is an inconsistent type of perturbation theory. The necessary cartesian tensor formulae are given in appendices as well as formally exact expressions for the second virial coefficient and for the Fourier-transformed Ornstein-Zernike relation.     

The O-H distance in ice

The thermodynamic properties of normal and para-hydrogen are computed from multiple time-step path integral hybrid Monte Carlo (PIHMC) simulations. Four different isotropic pair potentials are evaluated by comparing simulation results with experimental data. The Silvera–Goldman potential is found to be the most accurate of the potentials tested for computing the density and internal energy of fluid hydrogen. Using the Silvera–Goldman potential, simulation and experimental data are compared on isobars ranging from 0.1 to 100 MPa and for temperatures from 18 to 300 K. The Gibbs free energy is calculated from the PIHMC simulations by an adaptation of Widom's particle insertion technique to a path integral fluid. A new method is developed for computing phase equilibria for quantum fluids directly by combining PIHMC with the Gibbs ensemble technique. This Gibbs–PIHMC method is used to calculate the vapour–liquid phase diagram of hydrogen from simulations. Agreement with experimental data is good.     

Quantum-trajectory approach to time-dependent transport in mesoscopic systems with electron-electron interactions

It is proved that many-particle Bohm trajectories can be computed from single-particle time-dependent Schr?dinger equations. From this result, a practical algorithm for the computation of transport properties of many-electron systems with exchange and Coulomb correlations is derived. As a test, two-particle Bohm trajectories in a tunneling scenario are compared to exact results with an excellent agreement. The algorithm opens the path for implementing a many-particle quantum transport (Monte Carlo) simulator, beyond the Fermi liquid paradigm.     

Assignments and signs of 13C-31P coupling constants from off-resonance proton decoupled 13C spectra

The grand canonical ensemble is used to derive the first quantum correction (FQC) to the radial distribution function (RDF) for a fluid whose molecules interact with a potential which is an analytic function of distance. The low-order cluster integrals appearing in the density expansion of the RDF are evaluated on the Lennard-Jones (12-6) potential. The FQC to the isothermal compressibility and to the equation of state is discussed.