title: Ozonolysis and photolysis of alkene-terminated self-assembled monolayers on quartz nanoparticles: implications for photochemical aging of organic aerosol particles.
abstract: Photolysis of alkene-terminated self assembled monolayers (SAM) deposited on Degussa SiO(2) nanoparticles is studied following oxidation of SAM with a gaseous ozone/oxygen mixture. Infrared cavity ring-down spectroscopy is used to observe gas-phase products generated during ozonolysis and subsequent photolysis of SAM in real time. Reactions taking place during ozonolysis transform alkene-terminated SAM into a photochemically active state capable of photolysis in the tropospheric actinic window (lambda > 295 nm). Formaldehyde and formic acid are the observed photolysis products. Photodissociation action spectra of oxidized SAM and the observed pattern of gas-phase products are consistent with the well-established Criegee mechanism of ozonolysis of terminal alkenes. There is strong evidence for the presence of secondary ozonides (1,3,4-trioxalones) and other peroxides on the oxidized SAM surface. The data imply that photolysis plays a role in atmospheric aging of primary and secondary organic aerosol particles.
authors.affiliation: Department of Chemistry, University of California, Irvine, 92697-2025, USA.
authors.forename: Jiho
authors.initials: J
authors.lastname: Park
authors.forename: Anthony L
authors.initials: AL
authors.lastname: Gomez
authors.forename: Maggie L
authors.initials: ML
authors.lastname: Walser
authors.forename: Ao
authors.initials: A
authors.lastname: Lin
authors.forename: Sergey A
authors.initials: SA
authors.lastname: Nizkorodov