Stabilities and properties of complexes pairing hydroperoxyl radical with monohalomethanes.
UMP2/aug-cc-pvdz calculations are used to analyze the interaction between hydroperoxyl radical (HOO) and CH(3)X (X = F, Cl, Br). Two minima are located on the potential energy surface of each complex. The more strongly bound contains a OH...X bond, along with CH...O; only CH...O bonds occur in the less stable minimum. Binding energies of the dominant minimum lie in the range of 20-24 kJ/mol, with X = F the most strongly bound. Analysis of the perturbations of the covalent bond lengths within each subunit caused by complexation, coupled with vibrational frequencies and charge transfers, opens a window into the nature of the interactions.
Solimannejad
Mohammad
M
Quantum Chemistry Group, Department of Chemistry, Arak University, Iran. m-solimannejad@araku.ac.ir
Scheiner
Steve
S