Kirkwood superposition approximation

John G. Kirkwood 1935 (Eq. 40 Ref. 1, Eq. 5.6 Ref. 2)

$g_{N}^{(3)}(r_{1},r_{2},r_{3})=g_{N}^{(2)}(r_{1},r_{2})g_{N}^{(2)}(r_{2},r_{3})g_{N}^{(2)}(r_{3},r_{1})$

It appears that this was used as a basis of a closure for the Kirkwood integral equation (Ref. 1) and the Yvon, and Born-Green (Ref. 2) until the work of Morita and Hiroike (Ref. 3). It was pointed out in Ref.s 4 and 5, that there is an inconsistency between the pressure and the compressibility equation if this superposition approximation is used to generate $g(r)$.

References

1. John G. Kirkwood, "Statistical Mechanics of Fluid Mixtures", Journal of Chemical Physics 3 pp. 300-313 (1935)
2. M. Born and H. S. Green "A General Kinetic Theory of Liquids. I. The Molecular Distribution Functions" Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences 188 pp. 10-18 (1946)
3. Tohru Morita and Kazuo Hiroike "A New Approach to the Theory of Classical Fluids. I" Progress of Theoretical Physics 23 pp. 1003-1027 (1960)
4. B. R. A. Nijboer and L. Van Hove "Radial Distribution Function of a Gas of Hard Spheres and the Superposition Approximation", Physical Review 85 pp. 777 - 783 (1952)
5. [PRSA_1953_216_0203]