CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute
CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute
CHEM01200604005 A. K. Pathak - Homi Bhabha National Institute
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molecules can be examined in such studies, which will also provide information on the<br />
evolution of hydration motifs of X 2 systems in water. It is also known that gaseous<br />
bromine is much more soluble than gaseous chlorine in water. But no information is<br />
available on the order of solubility of iodine in the gas phase. As these species have zero<br />
dipole moment, one has to apply an explicit solvation model to study the solvent effect<br />
rather than taking a continuum model like Onsager’s reaction field model. 4 At present,<br />
various possible minimum energy configurations of X 2 .nH 2 O cluster (X=Cl, Br and I;<br />
n=1-8), bonding characteristics and energy parameters (both solvent stabilization and<br />
interaction) are reported following first principle based electronic structure theory to<br />
predict the solubility order of halogen gases in water.<br />
4.2. Theoretical Approach<br />
To decide a suitable level of theoretical method for calculations, geometrical<br />
parameters of mono- and di- hydrated clusters of Cl 2 and Br 2 are calculated following<br />
correlated hybrid density functionals (B3LYP and BHHLYP) and second-order Moller-<br />
Plesset perturbation (MP2) theory adopting triple spit Gaussian type basis functions. It is<br />
observed that Becke’s half-and-half (BHH) non-local exchange and Lee-Yang-Parr<br />
(LYP) non-local correlation functionals (BHHLYP) perform well to describe these<br />
clusters producing geometrical parameters and polarizability close to MP2 values.<br />
Geometry optimization on all the hydrated clusters has been carried out at BHHLYP<br />
level of theory to locate minimum energy structures followed by single point energy<br />
calculation applying second order Moller-Plesset perturbation theory (MP2) for<br />
improvement in energy of the systems. Triple split valence basis function due to Pople<br />
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