Various high levels of theory have been applied to the characterization of two higher lying biradicaloid metastable singlet states of peroxynitrous acid. A singlet minimum (cis-2) was located that had an elongated O-O distance (2.17 Angstrom) and was only 12.2 kcal/mol [UB3LYP/6-31 1 + G(3df,2p) + ZPVE] higher in energy than its ground-state precursor. A trans-metastable singlet (trans-2) was 10.9 kcal/mol higher in energy than ground-state HO-ONO. CASSCF(12,10)/6-311+G(d,p) calculations predict the optimized geometries of these cis- and trans-metastable singlets to be close to those obtained with DFT. Optimization of cis- and trans-2 within the COSMO solvent model suggests that both exist as energy minima in polar media. Both Cis- and trans-2 exist as hydrogen bonded complexes with several water molecules. These collective data suggest that solvated forms of cis-2.3H(2)O and trans-2.3H(2)O represent the elusive higher lying biradicaloid minima that were recently (J. Am. Chem. Soc. 2003, 125, 16204) advocated as the metastable forms of peroxynitrous acid (HOONO*). The involvement of metastable trans-2 in the gas phase oxidation of methane and isobutane is firmly established to take place on the unrestricted [UB3LYP/6-311+G(d,p)] potential energy surface (PES) with classical activations barriers for the hydrogen abstraction step that are 15.7 and 5.9 kcal/mol lower than the corresponding activation energies for producing products methanol and tert-butyl alcohol formed on the restricted PES. The oxidation of dimethyl sulfide and dimethyl selenide, two-electron oxidations, proceeds by an S(N)2-like attack of the heteroatom lone pair on the O-O bond of ground-state peroxynitrous acid. No involvement of metastable forms of HO-ONO was discernible.