CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute

VDE w
(eV)
6.0
5.5
5.0
4.5
I 2 .- .nH 2
O (n=1-8)
E w
(ev)
4
3
2
1
I 2 .- .nH 2
O (n=1-8)
b
a
E w
solv
E w
int
0 2 4 6 8
n
0
4.4 4.8 5.2 5.6 6.0
VDE w
(eV)
I
II
Fig. 2.6. (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
solv 2 O (n ≤ 8) showing a linear relationship and (b) solvation energy, E w
in eV vs. weighted average
vertical detachment energy (VDE w ) in eV for the hydrated cluster, I 2•¯.nH 2 O (n ≤ 8).
Plot of the weighted average stabilzation energy, E w
solv
in eV vs. the weighted
average vertical detachment energy (VDE w ) in eV for the hydrated cluster, I 2•¯.nH 2 O (n ≤
solv
8) is displayed in Fig. 2.6-II(b). No simple relation is observed between calculated E w
and VDE w . It is worthwhile to mention that VDE is a measurable quantity following
photoelectron spectroscopy and based on the above simple linear relation, E int for a
hydrated cluster can be extracted. I 2•¯.(CO 2 ) n and I 2•¯.(OCS) n systems are well studied
following photoelectron spectroscopy and measured VDE values for different cluster size
are reported in the literature. 48-49
54