Mean spherical approximation

The Lebowitz and Percus mean spherical approximation (MSA) (1966) (Ref. 1) closure is given by

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle c(r) = -\beta \omega(r), ~~~~ r>\sigma.}

The Blum and Høye mean spherical approximation (MSA) (1978-1980) (Refs 2 and 3) closure is given by

${\rm {g}}_{ij}(r)\equiv h_{ij}(r)+1=0~~~~~~~~r<\sigma _{ij}=(\sigma _{i}+\sigma _{j})/2$

and

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle c_{ij}(r)= \sum_{n=1} \frac{K_{ij}^{(n)}}{r}e^{-z_nr} ~~~~~~ \sigma_{ij} < r}

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle h_{ij}(r)} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle c_{ij}(r)} are the total and the direct correlation functions for two spherical molecules of i and j species, Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \sigma_i} is the diameter of 'i species of molecule. Duh and Haymet (Eq. 9 Ref. 4) write the MSA approximation as

$g(r)={\frac {c(r)+\beta \Phi _{2}(r)}{1-e^{\beta \Phi _{1}(r)}}}$

where Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Phi_1} and Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Phi_2} comes from the WCA division of the Lennard-Jones potential. By introducing the definition (Eq. 10 Ref. 4)

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \left.s(r)\right. = h(r) -c(r) -\beta \Phi_2 (r)}

one can arrive at (Eq. 11 in Ref. 4)

Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle B(r) \approx B^{\rm MSA}(s) = \ln (1+s)-s}

The Percus Yevick approximation may be recovered from the above equation by setting Failed to parse (SVG (MathML can be enabled via browser plugin): Invalid response ("Math extension cannot connect to Restbase.") from server "https://wikimedia.org/api/rest_v1/":): {\displaystyle \Phi_2=0} .

References

1. J. L. Lebowitz and J. K. Percus "Mean Spherical Model for Lattice Gases with Extended Hard Cores and Continuum Fluids", Physical Review 144 pp. 251 - 258 (1966)
2. L. Blum and J. S. Høye "Solution of the Ornstein-Zernike equation with Yukawa closure for a mixture", Journal of Statistical Physics, 19 pp. 317-324 (1978)
3. Lesser Blum "Solution of the Ornstein-Zernike equation for a mixture of hard ions and Yukawa closure" Journal of Statistical Physics, 22 pp. 661-672 (1980)
4. Der-Ming Duh and A. D. J. Haymet "Integral equation theory for uncharged liquids: The Lennard-Jones fluid and the bridge function", Journal of Chemical Physics 103 pp. 2625-2633 (1995)