CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

espect to experimentally measured values compared to 57% based on the previous
model.
8.4. Conclusions
A new general relation connecting the finite size dependent vertical detachment
energy and adiabatic detachment energy of the solvated anionic clusters of finite size is
derived based on a microscopic theory. The n-dependence of the detachment energy is
independent of the solute solvent interaction energy. The derived expressions are valid
for system containing large number of solvent molecules. This relation is tested for
cluster of medium size viz. . and the calculated ∆E DE ∞ value is found to be in
very good agreement with the experimental ∆E DE ∞ value. However, the experimental
results are available mainly for small finite size clusters. To obtain the bulk values of
∆E DE ∞ and ∆E DE ∞ from the knowledge of ∆E VDE (n) and ∆E ADE (n) for small finite
size cluster, general expressions given by Eqs. (27) and (28) have been proposed. It is
worthwhile to mention that Eqs. (27) and (28) converge to Eqs. (16) and (17),
respectively in large n limit. Using these expressions, (Eqs. (27) and (28)),
∆E DE ∞ and ∆E DE ∞ values are obtained from the knowledge of clusters of small
size and are found to be in very good agreement with the available experimental results.
The n-dependent expressions for ∆E VDE (n) and ∆E ADE (n) do not change from system to
system in contrast to the expression proposed by Dixon and coworkers (Eq.2) where the
exponent p varies from system to system. The calculated results based on the microscopic
expressions (Eqs. (16) and (17) for cluster of large size and Eqs (27) and (28) for cluster
of small size are found to be in very good agreement with the experimental results in
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