ISSN 1017-2548(Print)
ISSN 2234-8530(Online)
Volume 55, Number 3
JKCSEZ 55(3)
June 20, 2011 

The ab initio calculations for fluoromethyl fluoroperoxides have been carried out using MP2/6-311G(d,p) and B3LYP/6-311++G(d,p) method. The structural optimizations were performed for several isomers and conformers of methyl fluoroperoxide, CH3OOF and the vibrational frequencies were calculated. The most stable conformer of CH3OOF is skew form and has fairly short O-O bond distance. The trans and cis conformers have 8-12 kcal/mol higher energies than skew form and the other isomers are very unstable. The structures of CH2FOOF, CHF2OOF and CF3OOF are also optimized and vibrational frequencies were calculated. These molecules also have skew forms as the lowest energy conformers. The O-O bond distances are longer and C-O bond distances are shorter than CH3OOF, but the structural parameters are almost independent of the number of fluorine atoms in methyl group.