Physics
Scientific paper
Jun 2011
adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2011mss..conferb09l&link_type=abstract
"International Symposium On Molecular Spectroscopy, 66th Meeting, Held 20-24 June, 2011 at Ohio State University. http://molspec
Physics
Atmospheric Species
Scientific paper
A step-scan Fourier-transform spectrometer coupled with a 6.4-m multipass absorption cell was employed to detect time-resolved infrared absorption spectra of reaction intermediates produced upon UV irradiation of a flowing mixture of CH3SSCH3 and NO2 in CO2. Irradiation of CH3SSCH3 at 248 nm produces CH3S radicals that subsequently react with NO2. Under a total pressure of 100 Torr, we observed bands near 1560 Cm-1, assignable to mainly the N=O stretching mode of CH3SONO, with a small contribution from CH3SNO2. Calculations with density-functional theory (B3LYP/aug-cc-pVTZ and B3P86/aug-cc-pVTZ) predicted the geometry, vibrational wavenumbers, and rotational parameters of CH3SONO and CH3SNO2. Based on these predicted rotational parameters, the simulated absorption band agrees satisfactorily with experimental results. Under a total pressure of 16 Torr, bands near 1560 and 1260 Cm-1 are assigned to NO2 asymmetric and symmetric stretching modes of CH3SNO2, respectively; the former is overlapped with the N=O stretching mode of CH3SONO. An additional band near 1070 Cm-1 is assigned to the S=O stretching mode of CH3SO, reported previously as a secondary product in the reaction of CH3S + O2. Reaction of CH3S + NO2 at high pressure clearly yields CH3SONO, rather than CH3SNO2, as a major product.
L.-K. Chu and Y.-P. Lee, J. Chem. Phys. 133, 184303 (2010).
Chen Jin-Dah
Lee Yuan-Pern
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