Photodissociation dynamics of ozone in the Hartley and Huggins bands studied by dissociative resonance Raman spectroscopy

[摘要] Two experimental approaches to dissociative resonance Raman spectroscopy, Raman emission spectra and Raman excitation profiles, have been applied to investigate the photodissociation dynamics of ozone in the Hartley and Huggins absorption bands. Resonance Raman spectra of ozone at 266 and 270 nm excitation wavelengths have been measured up to 11000 cm$sp{-1}$ with improved accuracy. Several bands beyond the dissociation limit have been observed. All prominent bands observed are well fit by an analytical Darling-Dennison model. A new analytical two-dimensional potential energy surface for the electronic ground state of ozone has been constructed based on the new experimental data. Resonance Raman spectra with excitation in the Huggins band were also measured. The symmetry issue of the electronic state responsible for Huggins band is addressed. A novel continuously-scanned Raman excitation profile technique has been applied to the red wing (276-297 nm) of the Hartley band. Several Raman excitation profiles for the lowest three vibrational bands have been determined. These spectra show characteristic oscillatory structures. We also report the discovery of the chemiluminescence of O$sb2$ and OH following the photodissociation of ozone.

[发布机构] Rice University