bending and rotational energies, A^x is the excess free energy of the reference atomic
fluid, p(r) is the total segment density at r and D∣,2'' is defined as
D?....."(г”) = ⅛2(r∞, r<12>)⅛3(r<2>, r<3>)... r<->), (3.6)
where ⅛β2(r∣1∖ rɪ2^) is the cavity correlation function of the inhomogeneous reference
fluid and rɪ^ is the position of the segment i on chain 1. Л}’2’’'∙,to(γm) takes into
consideration the volume exclusion effects of a m-mer. The volume exclusion due to a
m-mer is less than m times the excluded volume of a single atom due to the overlap of
excluded volumes of the neighboring atoms. However, approximating it as a product
of pair cavity correlation functions treats the excluded volume effect at the pair level
only (deficiency in TPTl). uɪʃ(rʌʃ) takes care of the chain connectivity.
The theory has been applied to study the structure of linear chains of freely joined
hard spheres [102] and hard semi-flexible triatomic fluid [106] in slit-like pores. The
results are in good agreement with the simulation results. The theory does satisfy
the wall contact theorem, but the Gibbs adsorption equation was not verified [102].
However, the multi-point-based density formalism of the theory result in mth order
implicit integral equations making the computations extremely demanding.
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