It is shown how certain thermodynamic functions, and also the radial distribution function, can be expressed in terms of the potential energy distribution in a fluid. A miscellany of results is derived from this unified point of view. (i) With g(r) the radial distribution function and Φ(r) the pair potential, it is shown that g exp (Φ/kT) may be written as a Fourier integral, or as a power series in r2 the terms of which alternate in sign. (ii) A potential‐energy distribution which is independent of the temperature implies an equation of state which is a generalization of a number of well‐known approximations. (iii) The grand partition function of the one‐dimensional lattice gas is obtained from thermodynamic arguments without evaluating a sum over states. (iv) If in a two‐dimensional honeycomb (three‐coordinates) lattice gas fr(r=0, 1, 2, 3) is the fraction of all the empty sites which at equilibrium are neighbored by exactly r filled sites, then at the critical density the values of all four of the f's as functions of temperature follow from previously known properties of this system; in particular, at the critical point, f0 = 3/8+5√3/24, f1 = 1/8+√3/24, f2 = 1/8—√3/24, f3 = 3/8–5√3/24.
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1 December 1963
Research Article|
December 01 1963
Some Topics in the Theory of Fluids
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JCP 90 for 90 Anniversary Collection
B. Widom
B. Widom
Department of Chemistry, Cornell University, Ithaca, New York
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J. Chem. Phys. 39, 2808–2812 (1963)
Article history
Received:
August 06 1963
Citation
B. Widom; Some Topics in the Theory of Fluids. J. Chem. Phys. 1 December 1963; 39 (11): 2808–2812. https://doi.org/10.1063/1.1734110
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