We review recent theoretical studies of the photodissociation of ozone in the wavelength region from 200 nm to 1100 nm comprising four major absorption bands: Hartley and Huggins (near ultraviolet), Chappuis (visible), and Wulf (near infrared). The quantum mechanical dynamics calculations use global potential energy surfaces obtained from new high-level electronic structure calculations. Altogether nine electronic states are taken into account in the theoretical descriptions: four 1A', two 1A'', one 3A' and two 3A'' states. Of particular interest is the analysis of diffuse vibrational structures, which are prominent in all absorption bands, and their dynamical origin and assignment. Another focus is the effect of non-adiabatic coupling on lifetimes in the excited states and on the population of the specific electronic product channels.

Articles you may be interested inCommunication: Rigorous quantum dynamics of O + O2 exchange reactions on an ab initio potential energy surface substantiate the negative temperature dependence of rate coefficients Erratum: "Theoretical study of the non-Arrhenius temperature dependence of thermal rate constants for the H+H 2 S → H 2 + SH reaction" [J.

Dynamical studies of the recombination of O and O2 to form ozone are reviewed. The focus is the intriguing isotope dependence of the recombination rate coefficient as observed by Mauersberger and coworkers in the last decade. The key quantity for understanding of this dependence appears to be the difference of zero-point energies of the two fragmentation channels to which excited ozone can dissociate, i.e., X + YZ <-- XYZ* --> XY + Z, where X, Y, and Z stand for the three isotopes of oxygen. Besides the isotope dependence, the variation of the recombination rate coefficient with pressure and temperature is also addressed. Despite the numerous approaches of recent years, the recombination of ozone is far from being satisfactorily explained; there are still several essential questions to be solved by detailed theoretical analysis. We mainly discuss--and critically assess--the results of our own investigations of the ozone kinetics. The work of other research groups is also evaluated.

An intramolecular theory of the mass-independent isotope effect for ozone. New analytical model for the ozone electronic ground state potential surface and accurate ab initio vibrational predictions at high energy range