A quantum theory of higher virial coefficients

Recently a theory of time-delay phenomena in few particle scattering has been developed. The results of this theory are used to investigate the quantum virial coefficient problem in the case of Boltzmann statistics. Working within the frame work of Faddeev's time-dependent scattering theory we find explicit formulas for the higher virial coefficients. One aim of statistical mechanics is to derive all the equilibrium properties of a macroscopic system from the dynamical laws of the constituent particles. Our solutions for the higher virial coefficients prove that the macroscopic properties of a quantum gas are sensitive only to the time-delay aspect of the collision process. The analysis does not restrict the type of interactions between the constituents with the one exception of long-range Coulomb forces. In particular, the interaction may be attractive and strong enough to form stable few-particle clusters. Thus our solution describes the equilibrium in a quantum gas where the interactions are responsible for creating different species types.     

The kinetics of adsorption to a one-dimensional lattice with nearest-neighbor exclusion: A series expansion study

Exact 15-term series expansions are given for the cooperative kinetics of adsorption of particles to a one-dimensional lattice with nearest-neighbor exclusion. Padé approximants to various forms of the series accurately describe the relaxation process, which is found to be well-approximated by assuming instantaneous internal equilibrium on the lattice. The series do not describe the very last stages of decay to equilibrium well and it has not been possible to extract from them the limiting relaxation parameters. The series show that the rate of change of the particle density on the lattice is not analytic in the density when expanded about the equilibrium state.     

Analytical representation of the higher virial coefficients of binary mixtures of additive hard spheres

Approximate expressions for the fourth and fifth virial coefficients of binary hard-sphere fluid mixtures are derived. The procedure used to obtain these expressions is based on that previously proposed by Wheatley [J. chem. Phys., 111, 5455 (1999)], but slightly modified. Wheatley's procedure starts from a prescribed general analytical form of the virial coefficients, from which the particular expression for each virial coefficient is obtained by imposing to the general form a number of limiting conditions. Here, we propose an alternative general expression of the virial coefficients and derive one more condition. This condition is satisfied when the fourth and fifth virial coefficients are expressed in the form we propose, but not when they are expressed in Wheatley's form. The agreement of the proposed analytical expressions with exact numerical data is excellent. The procedure can be extended to higher virial coefficients, although the lack of exact numerical data prevents any comparison.     

Evaluating virial coefficients for multicomponent mixtures: hard sphere mixtures and flexible chains

A new algorithm to compute the virial coefficients of multicomponent mixtures is proposed. The number of graphs that must be evaluated increases dramatically in a multicomponent mixture so that it becomes difficult to enumerate and compute all possible graphs. However, once all of them are known and evaluated, the virial coefficient of the mixture can be evaluated for any composition. If one is interested in the virial coefficient of a mixture of a certain composition, then a simpler approach can be followed. Starting from the graphs of a pure fluid, we assign a random chemical identity to each of the molecules of the graph. The probability of assigning a given chemical identity is taken from the composition of the mixture. In this way composition is treated as a random variable within the Monte Carlo procedure which determines the virial coefficient. The algorithm is checked by comparison with the virial coefficients of binary hard spheres mixtures which are well known. Good agreement is found. The procedure is then extended to multicomponent mixtures of hard spheres. Finally the procedure is applied to the determination of the virial coefficients of a flexible molecule. For flexible molecules the possible configurations of the molecules are treated as different components of the mixture. In this way we present what appears to be the first determination of the third and fourth virial coefficients of polymers in the continuum.     

Density expansion of the magnetic susceptibility

The pressure of a system may be expanded as a power series in the density, whose coefficients are the virial coefficients. In this paper, the magnetic susceptibility of a $\text{spin}\text{-}\text{1}\text{2}$ fermion system is also expanded in powers of density. This process explicitly separates the temperature and density dependence of the magnetic susceptibility. The coefficients of this series are shown to be related to certain virial coefficients. The first (previously established) and second corrections to Curie's law are explicitly expressed in terms of second and third virial coefficients. These corrections to Curie's law are small for temperatures above 4K, but become important below that temperature. The first correction has been previously measured. Given a set of second and third virial coefficients, the importance of the second correction can be calculated immediately at any density of interest.     

On the formal equivalence of the Frisch-Berne and Watts perturbation theories to evaluate transport coefficients

A system of hard spheres in contact with a structureless wall is considered. The potential between the wall and the particles is of Lennard-Jones type. The second, the third and the fourth three-dimensional virial coefficient of the adsorption isotherm are calculated. The result being that over an extremely large temperature range the two-dimensional virial treatment is a rather good approximation. Conclusions are drawn about the deviations from Henry's law and the coverage, which can be described by virial expansions. It is doubted whether, from experimentally determined virial coefficients, information about the potential between the adatoms can be extracted.     

Monte-Carlo integration for virial coefficients re-visited: hard convex bodies,spheres with a square-well potential and mixtures of hard spheres

Techniques to adapt the hit-and-miss Monte-Carlo numerical integration are proposed with the aim to determine virial coefficients up to eighth order in fluids of hard convex bodies, hard spheres with an attractive square-well potential and a two-component mixture of hard spheres. These algorithms make use of look-up tables of all the blocks contributing to the coefficients. Each type of block is represented in the tables by several entries. These correspond to all possible topologically equivalent graphs that can be generated by the Monte-Carlo process. This rendered the Monte-Carlo method statistically more efficient. In the case of a two-component system the look-up tables had to have representations of blocks having two sorts of vertices. The reported data are: improved values of the seventh and eighth virial coefficients for hard spheres, the sixth, seventh and eighth coefficients of spheroids, spherocylinders and cutspheres, fifth virial coefficient of spheres with a square-well potential of relative range 1.25; 1.5; 1.75 and 2.0 and the partial contributions of the sixth virial coefficient for a mixture of hard spheres with the size ratio 0.1.     

Measurements on polar liquids at a microwave frequency — evaluation of molecular parameters — a new method

A simple method of estimating the dipole moment (μ) and relaxation time (τ) of polar molecules in liquid state, from a single set of dielectric measurements at high frequency, is proposed by using the concept of dielectric virial coefficients and employing Onsager model. The proposed method is tested in a number of polar liquids and the results are discussed.     

Virial Coefficients from Unified Statistical Thermodynamics of Quantum Gases Trapped under Generic Power Law Potential in d Dimension and Equivalence of Quantum Gases

From the unified statistical thermodynamics of quantum gases, the virial coefficients of ideal Bose and Fermi gases, trapped under generic power law potential are derived systematically. From the general result of virial coefficients, one can produce the known results in d=3 and d=2. But more importantly we found that, the virial coefficients of Bose and Fermi gases become identical (except the second virial coefficient, where the sign is different) when the gases are trapped under harmonic potential in d=1. This result suggests the equivalence between Bose and Fermi gases established in d=1 (J. Stat. Phys. DOI 10.1007/s10955-015-1344-4). Also, it is found that the virial coefficients of two-dimensional free Bose (Fermi) gas are equal to the virial coefficients of one-dimensional harmonically trapped Bose (Fermi) gas.     

A new method to obtain the Carnahan–Starling equation and its generalization

We obtain the Carnahan–Starling equation for a system of hard spheres using the Euler method of accelerated series convergence. For this purpose, the virial series is transformed into a new series with coefficients that differ slightly from each other, even when considering the eleven currently known virial coefficients. The method of accelerated convergence was applied to this series; it allowed us to obtain the Carnahan–Starling equation. In this work, this equation is derived for the first time using the method of accelerated convergence. It is generalized to accurately reproduce all of the known virial coefficients and the asymptotic behavior of the free energy at high densities. This also makes it possible to describe a metastable region with a high degree of accuracy and to obtain the equation of state for a homogeneous system of hard spheres with the accuracy of a computer experiment.     

Transport Coefficients in Some Stochastic Models of the Revised Enskog Equation

A stochastic model of the revised Enskog equation is considered. A choice of the smearing function suggested by the work of Leegwater is used to apply the model to the repulsive part of the Lennard-Jones potential and the inverse-power soft-sphere potential. The virial coefficients obtained from the equilibrium properties of the models are in excellent agreement with the known exact coefficients for these models. The transport coefficients for the repulsive Lennard-Jones (RLP) model are also computed and appear to be of comparable accuracy to the Enskog-theory coefficients applied directly to a hard-sphere system, although exact results for the RLP with which to make an extensive comparison are not yet available. The pressure and the transport coefficients obtained from the model (shear viscosity, thermal conductivity, and self-diffusion) are compared with the pressure and the corresponding transport coefficients predicted by the Enskog and square-well kinetic theories.     

Temperature dependence of nuclear magnetization and relaxation

The temperature dependences of nuclear magnetization and relaxation rates are reviewed theoretically and experimentally in order to quantify the effects of temperature on NMR signals acquired by common imaging techniques. Using common sequences, the temperature dependences of the equilibrium nuclear magnetization and relaxation times must each be considered to fully understand the effects of temperature on NMR images. The temperature dependence of the equilibrium nuclear magnetization is negative because of Boltzmann's distribution for all substances at all temperatures, but the combined temperature dependences of the equilibrium magnetization and relaxation can be negative, weak or positive depending on the temperature (T), echo time (T(E)), repetition time (T(R)), and the temperature dependences of the relaxation times T(1)(T) and T(2)(T) in a pulse sequence. As a result, the magnitude of the NMR signal from a given substance can decrease, increase or stay somewhat constant with increasing temperature. Nuclear thermal coefficients are defined and predictions for spin echo and other simple sequences are verified experimentally using a number of substances representing various thermal and NMR properties.     

A new graph expansion of virial coefficients

It is well known that the virial coefficients of the pressure of thermodynamic systems can be represented in terms of graphs. The existing graph expansions are compared with a new one, the overlap graph expansion. The merits of overlap graphs in general and especially for hard disks and spheres are discussed.     

Thermophysical properties and collision-induced light scattering as a probe for gaseous helium interatomic potentials

Isotropic and anisotropic collision-induced light scattering spectra of helium gas at room temperature 294.5?K and at 99.6?K with the second pressure virial coefficients, second acoustic virial coefficients, viscosity and thermal conductivity have been used for deriving the empirical models of the pair-polarizability trace and anisotropy and the interaction potential. Theoretical zeroth and second moments of the binary spectra using various models for the pair-polarizabilities and interatomic potential are compared with the experimental values performed by Le Duff's group. In addition, third pressure virial coefficients, isotopic thermal factors, self diffusion coefficients, second virial dielectric constants and second Kerr coefficients calculated for these models are compared with experimental ones. The results show that these models are the most accurate models reported to date for this system.     

Trace formulas for time delay and the second virial coefficient

A high-temperature expansion for the quantum-mechanical second virial coefficient is derived using newly developed trace formulas for time delay in scattering theory. The known cancellation between the bound state and continuum contributions is explained in this general framework. The method cam be extended to higher virial coefficients.     

An Ising model for the stress relaxation of solids

A kinetic theory of stress relaxation of solids as a cooperative process is proposed. The theory is based on a two-state model for the relaxation. It is shown that the conventional mean field approximation leads to an exponential dependence of the rate of stress relaxation on the stress while the multiplicative approximation of Vol'kenstein et al. leads to a power law. It is argued that the exponential law should be valid initially in the relaxation process while the power law is appropriate when the system is nearer equilibrium, which is in qualitative agreement with recent experimental findings.     

The calculation of singular points in the supercritical region for a system with a Lennard—Jones interaction potential

In this work the positions of the critical point, the supercritical point, and the maximum fluctuation point in a supercritical isotherm were found for a system with the Lennard—Jones interaction potential. Virial coefficients and methods based on accelerated convergence of the perturbation-theory series, which are well known for such systems, were used. The results were compared with computer-simulation data. As has been established, if one uses the positively defined Weeks—Chandler—Andersen potential as a reference system, the calculated parameters tend monotonically to exact values as a function of the number of virial coefficients. This decomposition is favorably different from the virial one, where the aspiration is not monotonic. These results indicate that this method makes it possible to determine the positions of the three vertices of the supercritical triangle with an accuracy that is comparable to that of a simulated experiment.     

Overlap graph representation of B6 and B7

The virial coefficients B_n of the pressure of a thermodynamic system can be represented in terms of graphs. The recently defined overlap graphs are studied in detail. Furthermore, the overlap graph representation of the sixth and seventh virial coefficientsB ₆ andB ₇) is determined.     

RESEARCH NOTE A method for predicting the virial coefficients of hard linear homonuclear molecules

This paper proposes a simple method for predicting the virial coefficients, up to the fifth, for hard linear homonuclear molecules. The method uses the virial coefficients for hard spherocylinders and hard linear tangent spheres to obtain the virial coefficients of linear fused hard spheres. The results are in very good agreement with the known values for the latter kind of molecules. Thus the method is suitable for predictive purposes when virial coefficients are not known, which makes it useful for the derivation of certain equations of state.     

Relaxation time of nonequilibrium nuclear system

In the framework of the exciton model an expression for the relaxation time of nonequilibrium nuclear system has been obtained. It was demonstrated that one can determine this time by the values of transition rates at equilibrium.