CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

6.8
6
ΔE VDE (n) in eV
6.6
6.4
6.2
6.0
5.8
R=0.98
0.02 0.03 0.04 0.05
n -1
ΔE ADE
(n) in eV
5
4
3
2
1
R=0.99
0.02 0.04 0.06 0.08
(n+σ) -1
A
B
Fig. 8.1. (A) Plot of ΔΕ VDE (n) vs. (n) -1 for I − . nH 2 O systems. The result based on new relation are shown by
solid line, and the solid squares (■ ) represent the experimental values taken from ref. 86. (B) Plot of
ΔΕ ADE (n) vs (n+σ) -1 (σ=8) for SO −2 4 .nH 2 O. The result based on new relation are shown by solid line, and
the open circle (○ ) represent the experimental values taken from ref. 31
based on Eqs (27) and (28) and the results are tabulated in Table 8.1. Here also, the
calculated results of ∆E DE ∞ and ∆E DE ∞ based on Eq.(27) are found to show much
better agreement than the same calculated values based on Eq(1). The
value of these
systems is taken as 8, which is large in comparison to the size of the clusters and thus
justifies the use of Eq.(27) rather than Eq.(16). The results of ∆E VDE (n) and ∆E ADE (n) are
calculated for the system . using the value of σ8 and the optimized values
of , , and . The calculated results are plotted along with available
experimental results in Fig.8.2(B). The ∆E DE ∞ value is also calculated for the
. system based on Eq. (28) and shown in Table 8.1. The correlation
coefficient for all the plots (R) is greater than 0.99, indicating that there is very good
correspondence between the theory and the experiment. It is clear from the Table 8.1 that
the maximum error in bulk values based on present theoretical calculation is 7% with
134