We have produced and directly detected a metastable state of tetraoxyg
en in a molecular beam, both by means of a de discharge and by photodi
ssociation of ozone in the collision region. The O-4 produces a compl
ex spectrum from which general conclusions may be made about its energ
etics and structure. The detection proceeds through a (1 + 1) resonant
photoionization process in the vicinity of 300 nm, implying an energy
for this species about 4 eV above that of two isolated O-2 molecules.
A predominance of peak frequency differences in the range 411-419 cm(
-1) supports a cyclic D-2d geometry as predicted by ab initio calculat
ions, although a definitive judgment on the structure of O-4 awaits f
urther study.