Photoabsorption spectra of gaseous CH3SO2Cl, CCl3SCl, SO2ClF and (CH3O)2SO

Kozłowski, Roman; Fazekas, G.B.; Bloomer, K.; Sampson, Rebecca K; Allston, Thomas D; Takacs, G. A.

doi:10.1016/0047-2670(82)80014-2

Cited by 3 publications

(2 citation statements)

References 18 publications

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“…The spectra indicate that the MSC absorption starts around 250 nm and gradually increases to about 600 M -1 cm -1 at 195 nm. This agrees with the published spectrum in this region by Kozlowski et al MSE, on the other hand, exhibits a much sharper and somewhat shorter wavelength absorption onset at 195 nm. At 194 nm the extinction of MSC is about twice that of MSE.…”

Section: Resultssupporting

confidence: 93%

Methylsulfonyl Radical Unimolecular Dissociation Studied by Deep-UV Ultrafast Photoionization Spectroscopy

2000

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The secondary dissociation dynamics of the methylsulfonyl radical following the photodissociation near 193 nm of methylsulfonyl chloride and methylsulfonyl ethanol has been studied using femtosecond mass-resolved photoionization spectroscopy. The primary dissociation is instrument-limited (<200 fs) for both precursors. The methylsulfonyl unimolecular dissociation is measured to have a lifetime of 0.34 ps with complete secondary dissociation following methylsulfonyl chloride photolysis. For the case of methylsulfonyl ethanol, the measured lifetime is 1.1 ps and ∼40% of the radical remains undissociated for the 18 ps duration of the experiment. We have successfully modeled the experimental results assuming an impulsive dissociation process to yield the internal energy distributions in the primary photoproducts and RRKM calculations based on structures and energetics of the methylsulfonyl radical obtained from the literature.

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Section: Resultssupporting

confidence: 93%

Methylsulfonyl Radical Unimolecular Dissociation Studied by Deep-UV Ultrafast Photoionization Spectroscopy

2000

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“…CH3SC1 has apparently not been studied, but CH3SI has been recently investigated (47). CH3S02C1 photolyses readily (48) and should not accumulate as a reaction product under our conditions. Concentration-time profiles for a typical CH3SH-C12 irradiation experiment are shown in Figure 10.…”

Section: Additional Considerations Regarding Alkylthiylmentioning

confidence: 99%

Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol

Grosjean¹

1984

Environ. Sci. Technol.

103

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The dissociation of vibrationally excited CH3OSO radicals and their photolytic precursor, methoxysulfinyl chloride

Alligood

Womack

Straus

et al. 2011

The Journal of Chemical Physics

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The dissociation dynamics of methoxysulfinyl radicals generated from the photodissociation of CH(3)OS(O)Cl at 248 nm is investigated using both a crossed laser-molecular beam scattering apparatus and a velocity map imaging apparatus. There is evidence of only a single photodissociation channel of the precursor: S-Cl fission to produce Cl atoms and CH(3)OSO radicals. Some of the vibrationally excited CH(3)OSO radicals undergo subsequent dissociation to CH(3) + SO(2). The velocities of the detected CH(3) and SO(2) products show that the dissociation occurs via a transition state having a substantial barrier beyond the endoergicity; appropriately, the distribution of velocities imparted to these momentum-matched products is fit by a broad recoil kinetic energy distribution extending out to 24 kcal/mol in translational energy. Using 200 eV electron bombardment detection, we also detect the CH(3)OSO radicals that have too little internal energy to dissociate. These radicals are observed both at the parent CH(3)OSO(+) ion as well as at the CH(3)(+) and SO(2)(+) daughter ions; they are distinguished by virtue of the velocity imparted in the original photolytic step. The detected velocities of the stable radicals are roughly consistent with the calculated barriers (both at the CCSD(T) and G3B3 levels of theory) for the dissociation of CH(3)OSO to CH(3) + SO(2) when we account for the partitioning of internal energy between rotation and vibration as the CH(3)OSOCl precursor dissociates.

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Photoabsorption spectra of gaseous CH3SO2Cl, CCl3SCl, SO2ClF and (CH3O)2SO

Cited by 3 publications

References 18 publications

Methylsulfonyl Radical Unimolecular Dissociation Studied by Deep-UV Ultrafast Photoionization Spectroscopy

Methylsulfonyl Radical Unimolecular Dissociation Studied by Deep-UV Ultrafast Photoionization Spectroscopy

Photooxidation of methyl sulfide, ethyl sulfide, and methanethiol

The dissociation of vibrationally excited CH3OSO radicals and their photolytic precursor, methoxysulfinyl chloride

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