A GAUSSIAN-2 AB-INITIO STUDY OF ISOMERIC CH3O2 AND CH3O2+

By means of a geometry optimization at the MP2/6-31G(d) level, the CH3O2 radicals have been found to exist in five isomeric forms. In order of decreasing stabilities, they are: HO-CH-OH (1)>O-CH2-OH (2)>CH3-O-O (3)>CH2-O-OH (4)>CH2-OH-O (5). On the other hand, there are six CH3O2+ isomers: HO-CH-OH+ (1+)>CH2-O-OH+ (4+)>cyclic-O-CH2-OH+ (2+)>CH3-O-O+ (3+)>CH2-OH-O+(5+)>cyclic-HO-CH-OH+ (6+). The Gaussian-2 predictions for the heats of formation at 298 K are in agreement with available experimental values.