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perturbation from the reference hard-chain fluid.

2.2.1 Chain term

From eqn. 2.1, the Helmholtz free energy of a mixture of hard-chain fluids is given
by

y∣⅛c _ I дЬз ∣ chain

(2.2)

(2.3)

The ideal free energy of the segments is given by

j∖id ' ___v

= 22 m_ix_i(lnp_i -1) +C,

where the term ‘C’ includes the term involving the De Broglie wavelength. For re-
pulsive interactions, instead of using a purely repulsive hard sphere potential, softly-
repulsive potential suggested by Chen and Kreglewski [65] is used.

r <(σ_i- si)

^repulsion_ <

3e_i {σ_i - sɪ) ≤ r < σ_i ,

(2.4)

r ≥ σ_i

where e is the depth of the potential well that quantifies the square-well attractive
interactions between the segments of the chains (as will be discussed in the dispersion
term), and s_i = 0.12σ. Following Barker and Henderson perturbation theory [77], this
soft repulsion between spheres can be described using a purely repulsive hard-sphere

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