title: Physical properties and spectra of IO, IO- and HOI studied by ab initio methods.
abstract: Structure and properties of the IO, IO- and HOI species, which are of potential importance for the ozone destruction catalytic cycle in the troposphere, have been calculated together with the EPR, NMR and UV-visible spectra by ab initio methodology with account of spin-orbit coupling (SOC) effects. Multi-configuration self-consistent field calculations with linear and quadratic response techniques and the multi-reference configuration interaction method have been employed. Photodissociation of these species, crucial for the catalytic ozone-destruction cycle, is critically reviewed and analyzed. Calculations predict that the singlet-triplet (S-T) transition to the lowest triplet state (X1 A' --> 3A'') should be responsible for the weak long-wavelength tail absorption (approximately 450-560 nm) and photodissociation of the HOI molecule. The second, more intense, band around 400 nm is produced by two overlapping S-S and S-T transitions. In order to check this assignment of the HOI photodissociation the isoelectronic IO- anion and IO radical have been studied by the same methods. Comparison with the EPR spectrum of the IO radical indicates that the methods are reliable which gives credit to the accuracy of the HOI spectral interpretation. NMR spectra of HOI and IO- molecules and some other properties are calculated for the first time.
authors.affiliation: Laboratory of Theoretical Chemistry, Royal Institute of Technology, Stockholm, Sweden.
authors.forename: Boris
authors.initials: B
authors.lastname: Minaev
authors.forename: Oleksandr
authors.initials: O
authors.lastname: Loboda
authors.forename: Olav
authors.initials: O
authors.lastname: Vahtras
authors.forename: Hans
authors.initials: H
authors.lastname: Agren
authors.forename: Elena
authors.initials: E
authors.lastname: Bilan
mesh_terms: D001703:Biophysics / Q000379:methods*; D002384:Catalysis; D004578:Electron Spin Resonance Spectroscopy; D005609:Free Radicals; D006219:Halogens / Q000737:chemistry; D007454:Iodides / Q000032:analysis*; D017613:Iodine Compounds / Q000032:analysis*; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D014466:Ultraviolet Rays
chemical_list: D005609:Free Radicals; D006219:Halogens; D007454:Iodides; D017613:Iodine Compounds; C081961:hypoiodous acid