CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

number of solvent molecules. In this approximation, one may relate these quantities to
the compressibility defined along the lines of Salacuse et. al. 84 as
= S(0),
=S0 S
µ
12
where S(0) = 1+ 4
1 and g , , where the latter
represents the angular average of the pair distribution function g , , β = 1/kT (k and
T represent Boltzmann constant and absolute temperature, respectively) and μ is the
chemical potential of the solvent molecules. Now substituting Eq.(11) in Eq.(10) and for
simplicity relabeling by n and retaining the terms up to 1/n 2
g , , g , ,
,
(13)
is obtained, where, C r, ω and C r, ω are respectively defined as
C r, ω S(0) (g ,
14
C r, ω S0
4
ρ
g , 0
0
6
g , 15
Now substituting Eq.(13) in Eqs.(5a) and (5b)
∆E VDE (n) = ∆E DE ∞
∆E ADE (n) = ∆E DE ∞
+
16
+
17
is obtained, where
∆E DE ∞ = (, ) (, g ,
18
M
DE
= (r, ω) (r, ω) ] (, (19)
M
DE
= (r, ω) (r, ω) ] (, (20)
∆E DE ∞ = (, ) g 2 (, ) (, ) g 1 (, ) ] (21)
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