Photodissociation of ozone in the Hartley band: Potential energy surfaces, nonadiabatic couplings, and singlet/triplet branching ratio

Abstract

The lowest five A1′ states of ozone, involved in the photodissociation with UV light, are analyzed on the basis of multireference configuration interaction electronic structure calculations with emphasis on the various avoided crossings in different regions of coordinate space. Global diabatic potential energy surfaces are constructed for the lowest four states termed X, A, B, and R. In addition, the off-diagonal potentials that couple the initially excited state B with states R and A are constructed to reflect results from additional electronic structure calculations, including the calculation of nonadiabatic coupling matrix elements. The A/X and A/R couplings are also considered, although in a less ambitious manner. The photodissociation dynamics are studied by means of trajectory surface hopping (TSH) calculations with the branching ratio between the singlet, O(D1)+O2(Δ1g), and triplet, O(P3)+O2(Σ3g−), channels being the main focus. The semiclassical branching ratio agrees well with quantum mechanical results except for wavelengths close to the threshold of the singlet channel. The calculated O(D1) quantum yield is approximately 0.90–0.95 across the main part of the Hartley band, in good agreement with experimental data. TSH calculations including all four states show that transitions B→A are relatively unimportant and subsequent transitions A→X/R to the triplet channel are negligible.