The rotational spectrum and structure of the HOOO radical

The adduct of the hydroxyl radical with oxygen has been studied theoretically, in connection with atmospheric reactions, but its stability and structure remained an open question. Pure rotational spectra of the HOOO and DOOO radicals have now been observed in a supersonic jet by using a Fourier-transform microwave spectrometer with a pulsed discharge nozzle. The molecular constants extracted from 12 rotational transitions with fine and hyperfine splittings support a trans planar molecular structure, in contrast to the cis planar structure predicted by most ab initio calculations. The bond linking the HO and O-2 moieties is fairly long (1.688 angstroms) and comparable to the F-O bond in the isoelectronic FOO radical.