Mean spherical approximation

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

c(r)=-\beta \omega (r),~~~~r>\sigma .

In the Blum and Høye mean spherical approximation for mixtures (Refs 2 and 3) the closure is given by

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

and

c_{ij}(r)=\sum _{n=1}{\frac {K_{ij}^{(n)}}{r}}e^{-z_{n}r}~~~~~~\sigma _{ij}<r

where $h_{ij}(r)$ and $c_{ij}(r)$ are the total and the direct correlation functions for two spherical molecules of i and j species, $\sigma _{i}$ 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 $\Phi _{1}$ and $\Phi _{2}$ comes from the Weeks-Chandler-Anderson 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} .

Thermodynamic consistency

See Ref. 5.

References

Mean spherical approximation

Thermodynamic consistency

References

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