Ornstein-Zernike equation with core condition and direct correlation function of Yukawa form

A detailed explication of the analytic structure of the Ornstein-Zernike equation with a core condition and a direct correlation function of Yukawa form is given. The solution found by Waisman [4] is simplified. The resulting analytic expressions are the basis of the generalized mean spherical results of Stell and Sun [7] for charged spheres and are fundamental to the approximation scheme of Høye and Stell [8] for polar fluids. Our study of the case of a two-Yukawa c(r) [following article] is also based upon the development given here.     

Analytic solution of the RISM equation for symmetric diatomics with Yukawa closure

We present the site-site direct correlation function c(r) for a fluid of hard diatomic symmetric molecules obtained from Monte Carlo simulation data via the RISM integral equation. This c(r) ensures that the site-site correlation function given by the RISM equation is exact, and thus provides a basis for critically examining the usual closure for the RISM equation. As an example of an improved closure we present the analytic solution of the RISM integral equation with a Yukawa closure for c(r).     

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.     

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.     

Solution of Ornstein-Zernike equation for wall-particle distribution function

The Ornstein-Zernike (OZ) equation is considered for the wall-particle distribution functiong ₀(x) in the case of a flat, impenetrable wall atx = 0 and a fluid of hard-core particles whose centers are constrained by the wall to occupy the semiinfinite spacex >/2, where is the particle diameter. A solution is given in terms of the wall-particle direct correlation function c₀(x) forx >/2, the bulk-fluid direct correlation function c_B (t), and p_B, the average bulk density. Explicit formulas for the contact surface density, total excess surface density, and the Laplace transform of the fluid density near the wall are given. For mean spherical type approximations, c₀ (x) forx >/2 and c_B (t) are both prescribed functions; for this case, a closed-form solution is obtained. An example is discussed and additional equations that enable one to go beyond the approximations considered above are introduced.Report #270, February 1976.The observation of this paper that the wall-particle problem can be treated using standard Wiener-Hopf techniques was independently made by Percus in his work, which came to our attention too late to be compared to, or incorporated into, our own results here.     

Convergence to SPDEs in Stratonovich Form

We consider the perturbation of parabolic operators of the form ∂ _t  + P(x, D) by large-amplitude highly oscillatory spatially dependent potentials modeled as Gaussian random fields. The amplitude of the potential is chosen so that the solution to the random equation is affected by the randomness at the leading order. We show that, when the dimension is smaller than the order of the elliptic pseudo-differential operator P(x, D), the perturbed parabolic equation admits a solution given by a Duhamel expansion. Moreover, as the correlation length of the potential vanishes, we show that the latter solution converges in distribution to the solution of a stochastic parabolic equation with multiplicative noise that should be interpreted in the Stratonovich sense. The theory of mild solutions for such stochastic partial differential equations is developed. The behavior described above should be contrasted to the case of dimensions larger than or equal to the order of the elliptic pseudo-differential operator P(x, D). In the latter case, the solution to the random equation converges strongly to the solution of a homogenized (deterministic) parabolic equation as is shown in [2]. A stochastic limit is obtained only for sufficiently small space dimensions in this class of parabolic problems.     

A hard sphere fluid model for superionic conductors

We develop a theory for the mobile constituent of a superionic conductor using the Ornstein-Zernike integral equation for the pair correlation function of an inhomogeneous fluid. We solve this equation in the Percus-Yevick approximation using a simple decoupling procedure and hard core potentials. Comparison is made with molecular dynamics calculations on α-AgI.     

Second-Order Corrections to Mean Field Evolution of Weakly Interacting Bosons. I.

Inspired by the works of Rodnianski and Schlein [31] and Wu [34,35], we derive a new nonlinear Schrödinger equation that describes a second-order correction to the usual tensor product (mean-field) approximation for the Hamiltonian evolution of a many-particle system in Bose-Einstein condensation. We show that our new equation, if it has solutions with appropriate smoothness and decay properties, implies a new Fock space estimate. We also show that for an interaction potential ${v(x)= \epsilon \chi(x) |x|^{-1}}Inspired by the works of Rodnianski and Schlein [31] and Wu [34,35], we derive a new nonlinear Schr?dinger equation that describes a second-order correction to the usual tensor product (mean-field) approximation for the Hamiltonian evolution of a many-particle system in Bose-Einstein condensation. We show that our new equation, if it has solutions with appropriate smoothness and decay properties, implies a new Fock space estimate. We also show that for an interaction potential v(x) = ec(x) |x|^-1{v(x)= \epsilon \chi(x) |x|^{-1}}, where e{\epsilon} is sufficiently small and c ? C₀^￥{\chi \in C_0^{\infty}} even, our program can be easily implemented locally in time. We leave global in time issues, more singular potentials and sophisticated estimates for a subsequent part (Part II) of this paper.     

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.     

Network Forming Fluids: Yukawa Square-Well <Emphasis Type="Italic">m</Emphasis>-Point Model

Thermal and connectivity properties of the Yukawa square-well m-point (YSWmP) model of the network forming fluid are studied using solution of the multidensity Ornstein-Zernike and connectedness Ornstein-Zernike equations supplemented by the associative mean spherical approximation (AMSA). The model is represented by the multicomponent mixture of Yukawa hard spheres with m_s^am_{s}^{a} square-well sites, located on the surface of each hard sphere. To validate the accuracy of the theory, computer simulation is used to calculate the structure, thermodynamic and connectivity properties of the one-component YSW4P version of the model which is compared against corresponding theoretical data. In addition, connectivity properties of the model were studied using Flory-Stockmayer (FS) theory. Predictions of the AMSA for the thermal properties of the model (radial distribution functions (RDF), internal energy, pressure, fractions of the particles in different bonding states) are in good agreement with computer simulation predictions. Similarly, good agreement was found for the connectedness RDF (CRDF), except for the statepoints located close to the percolation threshold, where the theory fails to reproduce the long-range behavior of the CRDF. Results of both theories (AMSA and FS) for the mean cluster size are reasonably accurate only at low degrees of association. Predictions of the FS theory for the percolation lines are in a good agreement with computer simulation predictions. AMSA predictions of percolation are much less accurate, where corresponding percolation lines are located at a temperatures approximately 25% lower then those calculated using computer simulation.     

The bridge function of hard spheres by direct inversion of computer simulation data

The bridge function of the hard sphere fluid has been calculated from our new highly accurate Monte Carlo and molecular dynamics simulation data on the radial distribution function using the (inverted) Ornstein-Zernike equation. Both the systematic errors (finite size, grid size, tail) and statistical errors are analysed in detail and ways to suppress them are proposed. Uncertainties in the resulting values of B(r) are about 0.001. In contrast with many previous findings the bridge function is both positive and negative.     

Analytic calculation of scaling dimensions: Tricritical hard squares and critical hard hexagons

The finite-size corrections, central chargesc, and scaling dimensionsx of tricritical hard squares and critical hard hexagons are calculated analytically. This is achieved by solving the special functional equation or inversion identity satisfied by the commuting row transfer matrices of these lattice models at criticality. The results are expressed in terms of Rogers dilogarithms. For tricritical hard squares we obtainc=7/10,x=3/40, 1/5, 7/8, 6/5 and for hard hexagons we obtainc=4/5,x=2/15, 4/5, 17/15, 4/3, 9/5, in accord with the predictions of conformal and modular invariance.     

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.     

Determining Liquid Structure from the Tail of the Direct Correlation Function

In important early work, Stell showed that one can determine the pair correlation function h(r) of the hard-sphere fluid for all distances r by specifying only the tail of the direct correlation function c(r) at separations greater than the hard-core diameter. We extend this idea in a very natural way to potentials with a soft repulsive core of finite extent and a weaker and longer ranged tail. We introduce a new continuous function T(r) which reduces exactly to the tail of c(r) outside the (soft) core region and show that both h(r) and c(r) depend only on the out projection of T(r): i.e., the product of the Boltzmann factor of the repulsive core potential times T(r). Standard integral equation closures can thus be reinterpreted and assessed in terms of their predictions for the tail of c(r) and simple approximations for its form suggest new closures. A new and very efficient variational method is proposed for solving the Ornstein–Zernike equation given an approximation for the tail of c. Initial applications of these ideas to the Lennard-Jones and the hard-core Yukawa fluid are discussed.     

Conservative Solutions to a Nonlinear Variational Wave Equation

We establish the existence of a conservative weak solution to the Cauchy problem for the nonlinear variational wave equation u _tt − c(u)(c(u)u _x ) _x =0, for initial data of finite energy. Here c(·) is any smooth function with uniformly positive bounded values.     

The compressibility theorem for quantum simple fluids at equilibrium

An extension of the compressibility theorem for quantum simple fluids within the pathintegral approach is presented. First, it is demonstrated that in the absence of quantum exchange, the isothermal compressibility can be formulated in an exact manner with the use of the pair radial correlation function of the path-integral centroids corresponding to the particles of the fluid. This adds up to the two known formulations based on the pair correlations between true quantum particles, namely the instantaneous and the pair linear response correlations. To complement this extension, an exact Ornstein-Zernike equation for pair centroid correlations is derived, which permits accurate estimates for the isothermal compressibility to be obtained. Several fluids are studied, new numerical results for the latter quantity are reported to support the theoretical points, and some difficulties present in this sort of calculation are discussed. The systems studied are the following: the quantum hard sphere fluid with and without attractive Yukawa interaction, liquid helium-4 and liquid para-hydrogen. Finally, the possibilities of extending the theorem to deal with quantum exchange are considered, and it is shown that the extension and its computational Ornstein-Zernike scheme also hold for a Bose fluid.     

Stability for the Korteweg-de Vries equation by inverse scattering theory

The stability problems for the Korteweg-de Vries equation, where linear stability fails, are investigated by the inverse scattering method. A rather general solution u(t, x) of the K-dV equation is shown to depend, for fixed time t, continuously on the initial condition u(0, x). For a continuum solution u_c(t, x), this continuity holds uniformly in t (stability), but for a soliton solution this is not true. A soliton solution can be uniquely decomposed into a continuum and discrete (soliton) part: u(t, x) = u_e(t, x) + u_d(t, x). Then the perturbed solution u is close to u after a suitable t-dependent “shift” of the soliton part (form stability).     

Structural and thermodynamic properties of a multicomponent freely jointed hard sphere multi-Yukawa chain fluid

The product-reactant Ornstein-Zernike approach, represented by the polymer mean-spherical approximation (PMSA), is utilized to describe the structure and thermodynamic properties of the fluid of Yukawa hard sphere chain molecules. An analytical solution of the PMSA for the most general case of the multicomponent freely jointed hard sphere multi-Yukawa chain fluid is presented. As in the case of the regular MSA for the hard sphere Yukawa fluid, the problem is reduced to the solution of a set of nonlinear algebraic equations in the general case, and to a single equation in the case of the factorizable Yukawa potential coefficients. Closed form analytical expressions are presented for the contact values of the monomer-monomer radial distribution function, structure factors, internal energy, Helmholtz free energy, chemical potentials and pressure in terms of the quantities, which follows directly from the PMSA solution. By way of illustration, several different versions of the hard sphere Yukawa chain model are considered, represented by one-Yukawa chains of length m, where m = 2, 4, 8, 16. To validate the accuracy of the present theory, Monte Carlo simulations were carried out and the results are compared systematically with the theoretical results for the structure and thermodynamic properties of the system at hand. In general it is found that the theory performs very well, thus providing an analytical route to the equilibrium properties of a well defined model for chain fluids.     

Approximate solution of the Percus-Yevick equation for a binary mixture of hard spheres with non-additive diameters

We present an approximate solution of the Percus-Yevick integral equation for a binary mixture of hard spheres with non-additive diameters. Defining R_ij the distance of closest approach between particles of species i and j by R ₁₂ = ½(R ₁₁ + R ₂₂) + α, we obtain a closed set of equations for the direct correlation functions c_ij (r) when 0 < α ? min [½(R ₂₂ - R ₁₁), ½R ₁₁]. Our expressions for c_ii (r), and for c ₁₂(r) in the range 0 < r ? ½[R ₂₂ - R ₁₁] - α, agree with those previously obtained by Lebowitz and Zomick.