AN ABINITIO STUDY ON THE CORRELATION BETWEEN THE ABSOLUTE-CONFIGURATION AND CIRCULAR-DICHROISM SPECTRA OF ORGANIC PEROXIDES

The correlation between the absolute configuration and the circular dichroism spectra of organic peroxides was studied by an ab initio method and a model molecule (CH3-O-O-CH3). The absorption peaks of singlet-singlet transitions in the 200-400 nm region and the corresponding rotational strengths were calculated for the model molecule in the P conformation. The results suggest that for the P form, when 0 less-than-or-equal-to theta < 90-degrees where theta is the dihedral angle C-O-O-C, there is a positive Cotton effect; when 90-degrees < theta less-than-or-equal-to 180-degrees, there is a negative Cotton effect; there is a turning point at theta = 90-degrees.