Hypemetted chain integral equation

We will describe integral equation approximations for the two-particle correlation fiinctions. There is no single approximation that is equally good for all interatomic potentials in the 3D world, but the solutions for a few important models can be obtained analytically. These include the Percus-Yevick (PY) approximation [27, 28] for hard spheres and the mean spherical (MS) approximation for charged hard spheres, for hard spheres with point dipoles and for atoms interacting with a Yukawa potential. Numerical solutions for other approximations, such as the hypemetted chain (EfNC) approximation for charged systems, are readily obtained by fast Fourier transfonn methods... 

D — and D oo the smooth and generic dimension-dependence of the integrals enables one to interpolate reasonably accurate D = 3 values (rms error 1%) from the dimensional limit results. The interpolated integrals can be used either on their ovm, or in conjunction with an integral equation approximation which sums some subset of the required integrals exactly (such as the hypemetted-chain or Percus-Yevick methods) the combination methods are invariably better than either dimensional interpolation or integral equations alone. Interpolation-corrected Percus-Yevick values can be computed quite easily at arbitrary order however, errors in higher-order values are... 

Once potential parameters have been determined, we can start calculation downward following arrow in the figure. The first key quantity is radial distribution function g(r) which can be calculated by the use of theoretical relation such as Percus-Yevick (PY) or Hypemetted chain (HNC) integral equation. However, these equations are an approximations. Exact values can be obtained by molecular simulation. Ifg(r) is obtained accurately as functions of temperature and pressure, then all the equilibrium properties of fluids and fluid mixtures can be calculated. Moreover, information on fluid structure is contained in g(r) itself. 

A fundamental approach to liquids is provided by the integral equation methods (sometimes called distribution function methods), initiated by Kirkwood and Yvon in the 1930s. As we shall show below, one starts by writing down an exact equation for the molecular distribution function of interest, usually the pair function, and then introduces one or more approximations to solve the problem. These approximations are often motivated by considerations of mathematical simplicity, so that their validity depends on a posteriori agreement with computer simulation or experiment. The theories in question, called YBG (Yvon-Bom-Green), PY (Percus-Yevick), and the HNC (hypemetted chain) approximation, provide the distribution functions directly, and are thus applicable to a wide variety of properties. 

Two of the classic integral equation approximations for atomic liquids are the PY (Percus-Yevick) and the HNC (hypemetted chain) approximations that use the following closures... 

Computer simulations are not the only methods which can be used to calculate the dielectric constant of pure liquids. Other approaches are given by the use of integral equations, in particular, the hypemetted chain (HNC) molecular integral equation and the molecular Omstein-Zemike (OZ) theory (see Section 8.7.1 for details on such methodologies). 

There have been other attempts to apply integral equations methods derived from Equation 3.51 or other similar expressions. One of them is the hypemetted chain (Henderson 1983), which is a generalization of the MSA theory, applicable to higher charge/potential values. It gives results comparable to the MPB ones but requires more extensive numerical evaluations. Another proposal is so-called dressed-ion theory of Kjellander and Mitchell (1994, 1997). 

The function n,(l) is a member of the family of direct correlation functions (1,2,..), which is the sum of all irreducible graphs with density factors pi(l) for every field point (For a detailed discussion of correlation functions see for example Hansen and McDonald [66]). The integral equations can be obtained by differentiation of this magnitude. Functional series differentiation[67, 68] produces approximations, such as the Hypemetted Chain (HNC) and its modifications, and... 

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