Quantum chemical study on UV-vis spectra of microhydrated iodine dimer radical anion.
UV-vis spectral properties of I(2)(*-).nH(2)O systems are reported based on ab initio quantum chemical calculations. Second order Moller-Plesset perturbation theory is applied for geometry search and time dependent density functional theory is applied to study excited state properties. Relativistic corrections are considered for all the calculations. Geometry search is carried out applying simulated annealing combined with Monte Carlo sampling method. Strong optical absorption band of these hydrated clusters, I(2)(*-).nH(2)O in the UV-vis region is assigned to sigma(g) --> sigma(u)* type valence electron transition in contrast to charge transfer to solvent spectra in I(-).nH(2)O systems. Simulated optical absorption profile of I(2)(*-).8H(2)O system is in excellent agreement with the reported aqueous phase spectrum of iodine dimer radical anion.
Pathak
A K
AK
Radiation and Photochemistry Division, Chemistry Group, Bhabha Atomic Research Centre, Mumbai-400085, India.
Mukherjee
T
T
Maity
D K
DK