Molecular bonding in FO2 and ClO2

Non-empirical LCAO-MO-SCF calculations are reported for the ground state and some excited states of FO2 and ClO2 in both the symmetrical, C2v and unsymmetrical, Cs, geometries. In the case of FO2 the unsymmetric configuration, FOO, is found to be much more stable than the symmetric configuration, OFO. However, the ground state of the Cs configuration of ClO2 is found to be only slightly lower than the ground state of the C2v configuration. The possible existence of FO2 in the symmetric geometry is discussed.