Physical Chemistry


We report rotational distributions for the O2 (a 1Δg) fragment from photodissociation of jet‐cooled O3 at 248, 266, and 282 nm. The rotational distributions show a population alternation that favors the even states, as previously reported for a 300 K sample by Valentini et al. (J. Chem. Phys. 86, 6745 (1987)). The alternation from the jet‐cooled precursor is much stronger than that observed by Valentini et al., and in contrast to their observations does not depend strongly on O2 (a 1Δg) vibrational state or photolysis wavelength. The odd/even alternation diminishes substantially when the ozone beam temperature is increased from 60 to 200 K, confirming its dependence on parent internal energy. The magnitude of the even/odd alternation in product rotational states from the cold ozone sample, its temperature dependence, and other experimental and theoretical evidence reported since 1987 suggest that the alternation originates from a Λ‐doublet propensity, and not from a mass independent curve crossing effect as previously proposed.

Original Citation

Michelle L. Warter, Carolyn E. Gunthardt, Wei Wei, George C. McBane, and Simon W. North. Nascent O2 ( a 1g ,v = 0,1 ) rotational distributions from the photodissociation of jet-cooled O3 in the Hartley band. J. Chem. Phys. 149(13), 134309 (2018). DOI: 10.1063/1.5051540