The production of electronically excited ozone by flash irradiation

Rotational structure in the absorption spectra of O318 and O316 near 1 μm: A comparative study of the A23 and B23 states

“…6. The derived rotational constants for the 2 ϭ1 level of the 3 That the upper state A-values respond predictably to isotopic substitution suggests that the upper state potential energy surface is sufficiently harmonic to justify extraction of adiabatic electronic energies via isotope shifts. In this case transition energies for fully substituted molecules can be found from those of the unsubstituted ones by incorporating the theoretically expected variations of v and r with atomic mass into Eq.…”

“…This interest derives in part from the possibility that one or more of these states was thought to be bound relative to the energy of thermal O( 3 P)ϩO 2 ( 3 ⌺g Ϫ ) collisions and also from the expected triplet nature of the lowest states, which would make them metastable with respect to single-photon optical transitions to the 1 A 1 ground state. Such states have been thought to be responsible for a number of anomalies in O-O 2 photochemistry, including kinetics, [1][2][3] isotopic enrichment experiments, 4-6 as well as playing a role in atmospheric chemistry as a yet unrecognized reservoir of ozone 7 or a participant in a new class of photochemical reactions 8 similar to, but distinct from those recently proposed for O 2 (vу26). 9 Early ab initio theoretical calculations 10 indicated an adiabatic electronic energy of 0.6 eV for the 3 B 2 state, well below the 1.1 eV dissociation energy of the 1 A 1 ground state inferred from calorimetry experiments.…”

“…Pack 33 has shown that if the upper state of a triatomic molecule is unbound along 3 , the variation of the dissociative upper state wave function with transition energy yields optimum overlap with the ground state wave function for 3 energies slightly above the saddle point. Vibronic peaks, as occur in the Chappuis bands of ozone, 34 are the result.…”

“…The transition energy of the 0-0 band, written as 00 ϭ e ϩE zp Ј ϪE zp Љ , can be combined with the vibrational zero point energy (( 1 ϩ 2 ϩ 3 )/2) to yield 3 Ј , 3 Јϭ2͑ 00 Ϫ e ϩE zp Љ ͒Ϫ͑ 1 Јϩ 2 Ј͒. …”

“…In contrast to photoabsorption, electron photodetachment transitions to the triplet states of O 3 from O 3 Ϫ are allowed.…”