Toluene photooxidation is chosen as an example to examine how simulations of smog-chamber experiments can be used to unravel shortcomings in detailed mechanisms and to provide information on complex reaction systems that will be crucial for the design of future validation experiments. The mechanism used in this study is extracted from the Master Chemical Mechanism Version 3 (MCM v3) and has bee...

We report artifactual degradation of pharmaceutical compounds containing primary and secondary amines during peroxy radical-mediated oxidative stress carried out using azoalkane initiators. Two degradation products were detected when model drug compounds dissolved in methanol/water were heated to 40°C with radical initiators such as 2,2'-azobis(2-methylpropionitrile) (AIBN). The primary artifac...

We have recorded high resolution, partially rotationally resolved, jet-cooled cavity ringdown spectra of the origin band of the A-X electronic transition of both the G and T conformers of the perproteo and perdeutero isotopologues of the ethyl peroxy radical, C(2)H(5)O(2). This transition, located in the near infrared, was studied using a narrow band laser source (< or approximately 250 MHz) an...

Ion irradiation is known to generate well-localized cylindrical ionization and excitation tracks in materials. The resulting radiation chemistry organic material thus initiated by a strongly heterogeneous source of radicals. We present comparison homogeneous radio-oxidation kinetics polymer. Our analysis based on kinetic Monte Carlo simulation the diffusion-reaction process radicals material. c...

We estimate the CIMS sensitivity for the hydroxyhydroperoxides (ISOPOOH) and hydroperoxyaldehydes (HPALD) from the ion-molecule collision rate, calculated using the parameterization of Su and Chesnavich [1]. This requires knowledge of the average dipole moment and polarizibility of the neutral species. We obtain these parameters for the species of interest from ab initio calulations. For accura...

Recent experiments have prompted a theoretical investigation of the effect of methyl rotation on the A-X electronic spectrum of the CH3O2 and CD3O2 radicals. Quantum chemistry calculations have mapped the potential for the methyl rotation. Using these results, we calculate the torsional eigenvalues for both the A and X states and simulate the A-X spectrum. We find that the simulation captures t...

We describe measurements of total peroxy nitrates (6PNs), NO2, O3 and several aldehydes at Granite Bay, California, during the Chemistry and Transport of the Sacramento Urban Plume-2001 (CATSUP 2001) campaign, from 19 July–16 September 2001. We observed a strong photochemically driven variation of 6PNs during the day with the median of 1.2 ppb at noon. Acetaldehyde, pentanal, hexanal and methac...