Direct correlation function integrals

Thus, to the degree that the corresponding-states theory for the direct correlation function integrals is accurate, the results are applicable to any system. In practice, we have found that when the species are at... 

O Connell (1971a) also gave these formulas in terms of direct correlation function integrals with... 

The generalized Krichevskii parameter or its equivalent, the direct correlation function integral, Cu, is well behaved in the critical region, as shown in Figure 2.18, and on this is based Equation (2.85) (O Connell et al., 1996), which was used to fit the standard partial molar volume of nonelectrolytes all over the density range. 

Figure 2.18 Direct correlation function integral as a function of density for (O) CH4 ( ) CO2 ( ) H2S ( ) NH3. (Hn dkovsky, L. and Wood, R.H. (1997). J. Chem. Thermod., 29, 731-747 with permission of Elsevier).

The integrals are over the full two-dimensional volume F. For the classical contribution to the free energy /3/d([p]) the Ramakrishnan-Yussouff functional has been used in the form recently introduced by Ebner et al. [314] which is known to reproduce accurately the phase diagram of the Lennard-Jones system in three dimensions. In the classical part of the free energy functional, as an input the Ornstein-Zernike direct correlation function for the hard disc fluid is required. For the DFT calculations reported, the accurate and convenient analytic form due to Rosenfeld [315] has been used for this quantity. 

Most integral equations are based on the Ornstein-Zernike (OZ) equation [3-5]. The idea behind the OZ equation is to divide the total correlation function h ri2) iiito a direct correlation function (DCF) c r 12) that describes the fact that molecules 1 and 2 can be directly correlated, and an indirect correlation function 7( 12), that describes the correlation of molecule 1 with the other molecules that are also correlated with molecule 2. At low densities, when only direct correlations are possible, 7(r) = 0. At higher densities, where only triplet correlations are possible, we can write... 

From the many tools provided by statistical mechanics for determining the EOS [36, 173, 186-188] we consider first integral equation theories for the pair correlation function gxp(ra,rp) of spherical ions which relates the density of ion / at location rp to that of a at ra. In most theories gafi(ra,rp) enters in the form of the total correlation function hxp(rx,rp) = gxp(rx,rp) — 1. The Omstein-Zemike (OZ) equation splits up hap(rx,rp) into the direct correlation function cap(ra, rp) for pair interactions plus an indirect term that reflects these interactions mediated by all other particles y ... 

The first contribution to h(r) is the direct correlation function c(r) that represents the correlation between a particle of a pair with its closest neighbor separated by a distance r. The second contribution is the indirect correlation function y(r), which represents the correlation between the selected particle of the pair with the rest of the fluid constituents. The total and direct correlation functions are amenable to an analysis in terms of configurational integrals clusters of particles, known as diagrammatic expansions. Providing a brief resume of the diagrammatic approach of the liquid state theory is beyond the scope of this chapter. The reader is invited to refer to appropriate textbooks on this approach [7, 9, 18, 26]. 

Practically, the values of f c(r, p )r2dr are fitted in a wide range of densities by a polynomial of order 3 in density. Then, ppex is obtained by analytically integrating the resulting polynomial as a function of density. It should be stressed that this method involves only the direct correlation function c(r), but neither B (r) nor B r), which are known to be the keys of the IETs. It must be stressed that such a thermodynamic integration process is performed along an isotherm T. This method is only accurate for supercritical temperatures, but is not at all for lower temperatures. Furthermore, it is not adapted to a predictive scheme. 

Once the correlation functions have been solved, adsorption isotherms can be obtained from the Fourier transform of the direct correlation function Cc(r) [55]. The ROZ integral equation approach is noteworthy in that it yields model adsorption isotherms for disordered porous materials that have irregular pore geometries without resort to molecular simulation. In contrast, most other disordered structural models of porous solids implement GCMC or other simulation techniques to compute the adsorption isothem. However, no method has yet been demonstrated for determining the pore structure of model disordered or templated structures from experimental isotherm measurements using integral equation theory. 

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