Quantum-chemical study of the singlet potential energy surface of the nitrene-dioxygen system

The potential energy surfaces of the HN—O2 and PhN—O2 systems were calculated by the MP2 and B3LYP methods. The mechanism of photooxidation of azides was refined. Photooxidation produces the nitrene—O2 adducts with dioxaziridine and non-cyclic structures. The parameters of IR spectra of the adducts were calculated. The rearrangement of dioxaziridine to a nitro compound is likely a reason for chemiluminescence accompanying the photooxidation of azides.