Photodissociation dynamics of the methyl perthiyl radical at 248 and 193 nm using fast-beam photofragment translational spectroscopy

Journal Article · Thu Jul 14 04:00:00 EDT 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4955195· OSTI ID:22675968

Harrison, Aaron W.; Ryazanov, Mikhail; Sullivan, Erin N.

The photodissociation dynamics of the methyl perthiyl radical (CH{sub 3}SS) have been investigated using fast-beam coincidence translational spectroscopy. Methyl perthiyl radicals were produced by photodetachment of the CH{sub 3}SS{sup −} anion followed by photodissociation at 248 nm (5.0 eV) and 193 nm (6.4 eV). Photofragment mass distributions and translational energy distributions were measured at each dissociation wavelength. Experimental results show S atom loss as the dominant (96%) dissociation channel at 248 nm with a near parallel, anisotropic angular distribution and translational energy peaking near the maximal energy available to ground state CH{sub 3}S and S fragments, indicating that the dissociation occurs along a repulsive excited state. At 193 nm, S atom loss remains the major fragmentation channel, although S{sub 2} loss becomes more competitive and constitutes 32% of the fragmentation. The translational energy distributions for both channels are very broad at this wavelength, suggesting the formation of the S{sub 2} and S atom products in several excited electronic states.

• OSTI ID: 22675968
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 145; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ANGULAR DISTRIBUTION
DISSOCIATION
ENERGY SPECTRA
EXCITED STATES
EXPERIMENTAL DATA
FRAGMENTATION
GROUND STATES
MASS DISTRIBUTION
PHOTOLYSIS
SPECTROSCOPY