CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

The calculated bulk detachment energy ∆E DE ∞ is shown in Table 8.1 along
with the experimentally measured value. It is clear from Table1 that the results of
∆E DE ∞ obtained from the expression derived here based on microscopic theory are in
very good agreement with experimental results in comparison to the calculated results
obtained from the empirical law given by Eq(1). ∆E DE ∞ using Eq.(27) is also
calculated and obtained the same value ∆E DE ∞ based on Eq.(16). This happens
because
is 3 and is not large enough in comparison to the average sizes (n) of the
cluster. However, in the case of small size hydrated clusters 86,32 viz. . (n= 1 to
6), . (n=1 to 15), and . (n=1 to 5), it is found that the calculated
results of ∆E DE ∞ based on Eq.(27) are in much better agreement than the same
quantity calculated based on Eq.(16). The reason is very obvious, since
values of
. , . and . systems are 2, 2.5 and 2.5, respectively, and
these values are significant in comparison to the sizes of the clusters. The calculated
values of ∆E DE ∞ along with the same calculated values based on empirical relation
given by Eq.(1) for these three systems, are shown in Table 8.1. Here also, the calculated
results of ∆E DE ∞ based on Eq.(27) are found to be in much better agreement than the
same calculated values based on the empirical Eq(1) (see Table 8.1).
Now the doubly negatively charged ionic clusters viz. . and
. are considered. The size of the hydrated clusters for these systems for
which experimental data are available cover the range from n= 4 to 13 (for VDE) and
from n= 4 to 40 (for ADE) for . clusters 9,30-31
and n= 4 to 40 for
. clusters (ADE). 9 Since the sizes of the clusters are small here, ∆E VDE (n) is
calculated and ∆E ADE (n) for . system and ∆E ADE (n) for . system
133