title: Femtosecond pump-probe studies of actinic-wavelength dependence in aqueous chlorine dioxide photochemistry.
abstract: The actinic or photolysis-wavelength dependence of aqueous chlorine dioxide (OClO) photochemistry is investigated using femtosecond pump-probe spectroscopy. Following photoexcitation at 310, 335, and 410 nm the photoinduced evolution in optical density is measured from the UV to the near IR. Analysis of the optical-density evolution illustrates that the quantum yield for atomic chlorine production (Phi(Cl)) increases with actinic energy, with Phi(Cl)=0.16+/-0.02 for 410 nm excitation and increasing to 0.25+/-0.01 and 0.54+/-0.10 for 335 and 310 nm excitations, respectively. Consistent with previous studies, the production of Cl occurs through two channels, with one channel corresponding to prompt (<5 ps) Cl formation and the other corresponding to the thermal decomposition of ClOO formed by OClO photoisomerization. The partitioning between Cl production channels is dependent on actinic energy, with prompt Cl production enhanced with an increase in actinic energy. Limited evidence is found for enhanced ClO production with an increase in actinic energy. Stimulated emission and excited-state absorption features associated with OClO populating the optically prepared (2)A(2) surface decrease with an increase in actinic energy suggesting that the excited-state decay dynamics are also actinic energy dependent. The studies presented here provide detailed information on the actinic-wavelength dependence of OClO photochemistry in aqueous solution.
authors.affiliation: Department of Chemistry, University of Washington, P.O. Box 351700, Seattle, Washington 98195, USA.
authors.forename: Teresa J
authors.initials: TJ
authors.lastname: Bixby
authors.forename: Joshua C
authors.initials: JC
authors.lastname: Bolinger
authors.forename: Joshua D
authors.initials: JD
authors.lastname: Patterson
authors.forename: Philip J
authors.initials: PJ
authors.lastname: Reid