CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

Fig. 2.6 54
(I) Plot of calculated weighted average vertical detachment energy (VDE w ) in eV vs.
number of water molecules (n) in I 2•¯.nH 2 O (n=1-8) cluster at BHHLYP/6-311++G(d,p)
level of theory (II) Plot of calculated weighted average (a) interaction,
int Ew in eV vs.
weighted in eV for the hydrated cluster, I 2•¯.nH 2 O (n ≤ 8) showing a linear relationship
and (b) solvation energy, E w
solv
in eV vs. weighted average vertical detachment energy
(VDE w ) in eV for the hydrated cluster, I 2•¯.nH 2 O (n ≤ 8).
Fig. 3.1 60
Calculated scaled IR spectra at BHHLYP/6-311++G(d,p) level free H 2 O molecule. The
scaling factor is taken as 0.92 to account for the anharmonic nature of stretching
vibrations. Lorentzian line shape has been applied with peak half-width of 10 cm -1 .
Fig. 3.2 61-62
Fully optimized minimum energy structures at BHHLYP/6-311++G(d,p) level of theory
for (I) Cl 2•¯.H 2 O, (II) Cl 2•¯.2H 2 O, (III) Cl 2•¯.3H 2 O, (IV) Cl 2•¯.4H 2 O and (V) Cl 2•¯.5H 2 O
clusters. Marked alphabets in the upper case are used to refer different minimum energy
conformers for each size of the hydrated cluster arranged in order of stability showing
‘A’ as the most stable one. Cl atoms are shown by the largest green colour spheres, the
smallest spheres refer to H atoms and the rest (red in colour) corresponds to O atoms in
each structure shown in the figure. In each case, the distance between the two Cl atoms is
~ 2.6 Å, the distance between Cl and H-bonded H atoms is 2.3-2.8 Å and the distance
between O and H atoms in inter water network is ~ 2.0 Å.
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