J. Phys. Chem. A, 110, 7247-7252 (2006)


Effect of Dimerization and Racemization Processes on the Electron Density and the Optical Rotatory Power of Hydrogen Peroxide Derivatives

The variation of the electron density properties and optical rotatory power of the monomers and dimers of seven monosubstituted hydrogen peroxide derivatives, HOOX (X = CCH, CH3, CF3, t-Bu, CN, F, Cl), upon racemization has been studied using DFT (B3LYP/6-31+G**) and MP2 (MP2/6-311+G**) methods. The geometrical results have been rationalized on the basis of natural bond orbital (NBO) analysis. The atomic partition of the electron density properties within the atoms in molecules (AIM) methodology has allowed investigating the energy and charge redistribution in the different structures considered. The calculated optical rotatory power (ORP) of the dimers are, in general, twice of the values obtained for the monomers.