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surfaces.

3.5 Yu and Wu

Yu and Wu [61] extended the idea of using a weighted density approximation for
associating fluids from Segura et. al. [62] to freely jointed hard chain fluids. However
the density independent weights for calculating the weighted densities are based on
the Fundamental Measure Theory (FMT) of Rosenfeld [110].

The free energy functional for chain fluids is expressed as the sum of an ideal gas
term Ald[pyv∕(r'w)] and an excess term
√1-ej-λc [pʌʃ(rʌʃ)] due to intra- and intermolecular
interactions.

A [pm (rʌʃ)] = A‰(γm)] + Aex[pm(tm)].            (3.14)

Yu and Wu used the same ideal free energy functional as used by Woodward [111].
All monomers in a ideal chain are non-interacting, i.e. the chain is made up of point
monomers, where successive monomers in a given chain are held at a fixed separation
given by the bond length,
σ , but otherwise are allowed full configurational freedom.
The free energy of such a random flight chain based on the molecular density
рм(гм')
is given as,

(3Ald[pM] = ʃ drMpM(rM)[lnpM(rM) - 1] +β j drMpmm)⅛(γm),    (3.15)

71



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