Reference Hypernetted Chain Closure Research Articles

Predicting the structure of fluids with piecewise constant interactions: Comparing the accuracy of five efficient integral equation theories.

We use molecular dynamics simulations to test integral equation theory predictions for the structure of fluids of spherical particles with eight different piecewise-constant pair-interaction forms comprising a hard core and a combination of two shoulders and/or wells. Since model pair potentials like these are of interest for discretized or coarse-grained representations of effective interactions in complex fluids (e.g., for computationally intensive inverse optimization problems), we focus here on assessing how accurately their properties can be predicted by analytical or simple numerical closures including Percus-Yevick, hypernetted-chain, and reference hypernetted-chain closures and first-order mean spherical and modified first-order mean spherical approximations. To make quantitative comparisons between the predicted and simulated radial distribution functions, we introduce a cumulative structural error metric. For equilibrium fluid state points of these models, we find that the reference hypernetted-chain closure is the most accurate of the tested approximations as characterized by this metric or related thermodynamic quantities.

Reference hypernetted chain theory for ferrofluid bilayer: distribution functions compared with Monte Carlo.

Properties of ferrofluid bilayer (modeled as a system of two planar layers separated by a distance h and each layer carrying a soft sphere dipolar liquid) are calculated in the framework of inhomogeneous Ornstein-Zernike equations with reference hypernetted chain closure (RHNC). The bridge functions are taken from a soft sphere (1/r(12)) reference system in the pressure-consistent closure approximation. In order to make the RHNC problem tractable, the angular dependence of the correlation functions is expanded into special orthogonal polynomials according to Lado. The resulting equations are solved using the Newton-GRMES algorithm as implemented in the public-domain solver NITSOL. Orientational densities and pair distribution functions of dipoles are compared with Monte Carlo simulation results. A numerical algorithm for the Fourier-Hankel transform of any positive integer order on a uniform grid is presented.

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.

Integral equation and simulation studies of the Heisenberg spin fluid in an external magnetic field

We develop a general method to study inhomogeneous liquids in an external field using orthogonal polynomials tailored to the one-body density. The procedure makes integral equation calculations of these systems no more difficult than those of ordinary homogeneous molecular fluids. We apply this method to the ferromagnetic Heisenberg spin fluid in an external magnetic field using both the reference-hypernetted chain closure and a reference version of the Zerah-Hansen closure, with no further approximations. The calculation includes a mapping of the two-phase region for several values of the external magnetic field. Comparison with Monte Carlo simulation data shows the integral equation procedure yielding nearly exact results, in particular for nonzero external fields.