Ab initio quantum mechanical study of the O((1)D) formation in the photolysis of ozone between 300 and 330 nm.
Spin-allowed production of O((1)D) in the near-UV photolysis of ozone is studied using ab initio potential energy surfaces and quantum mechanics. The O((1)D) quantum yield, reconstructed from the absolute cross sections for eight initial vibrational states in the ground electronic state, is shown to agree with the measurements in a broad range of photolysis wavelengths and temperatures. Relative contributions of one- and two-quantum stretching and bending initial excitations are quantified, with the contribution of the antisymmetric stretch being dominant for lambda < 330 nm. Large scale structures in the low-resolution quantum yield are shown to reflect excitations in the high-frequency short bond stretch in the upper electronic state. Spin-forbidden contribution to the O((1)D) quantum yield at wavelengths lambda > 320 nm is estimated using ab initio energies of the triplet states and their spin-orbit couplings.
Grebenshchikov
Sergy Yu
SY
Department of Chemistry, Technische Universität München, Lichtenbergstrasse 4, 85747 Garching, Germany. Sergy.Grebenshchikov@ch.tum.de
Rosenwaks
Salman
S