CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

M
DE
= (r, ω)C DE , (r, ω) C DE , ] + (22)
M
DE
= (r, ω)C DE , (r, ω) C DE , ] + (23)
C DE , = S(0) ρg, ; , = S(0) ρg
, (24)
C DE , S0
C DE , S0
ρ
ρ
ρg ,
ρg ,
0
ρg , (25)
0
ρg , (26)
Equations (16) and (17) are derived based on some approximations including
truncation of higher order terms, and the accuracy of these expressions can be tested if
experimental results are available for the systems with large and wide range of values of
n. However, the results are available for the systems clusters of small size, since
experimentally, it is difficult to prepare the clusters of desired size. Therefore, to obtain
the bulk values of ∆E DE ∞ and ∆E DE ∞ from the knowledge of experimental results
of ∆E VDE (n) and ∆E ADE (n) for few clusters of finite size is problematic. So what is
needed are expressions for ∆E VDE (n) and ∆E ADE (n) valid for small size clusters that
converge to the respective equations (16) and (17) valid for large size clusters. Motivated
by the derived Eqs.(16) and (17), the more general expressions similar to those equations
defined as is proposed
∆E VDE (n) = ∆E DE ∞ + M DE
+ M DE
(27)
∆E ADE (n) = ∆E DE ∞ M DE
+ M DE
, (28)
by introducing a parameter
representing the contribution from the solute volume as
well as the charge on the solute ion. It is assumed here that the parameter
to be given by
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