Diminished cage effect in solid p-H{sub 2}: Infrared absorption of CH{sub 3}S observed from photolysis in situ of CH{sub 3}SH, CH{sub 3}SCH{sub 3}, or CH{sub 3}SSCH{sub 3} isolated in p-H{sub 2} matrices

Journal Article · Thu Oct 28 00:00:00 EDT 2010 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3502105· OSTI ID:21559939

Bahou, Mohammed ^[1]; Lee, Yuan-Pern ^[1]

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1. Department of Applied Chemistry, National Chiao Tung University, 1001 Ta-Hsueh Rd., Hsinchu 30010, Taiwan (China)

We report the infrared absorption spectrum of the methylthio (or thiomethoxy) radical, CH{sub 3}S (X {sup 2}E{sub 3/2}), produced via photodissociation in situ of three precursors CH{sub 3}SH, CH{sub 3}SCH{sub 3}, and CH{sub 3}SSCH{sub 3} isolated in solid p-H{sub 2}. The common absorption features observed with similar intensity ratios in each experiment are assigned to CH{sub 3}S. The wavenumbers of these features agree satisfactorily with those predicted with a spin-vibronic Hamiltonian accounting for the anharmonic effects and the Jahn-Teller effects to the quartic term [A. V. Marenich and J. E. Boggs, J. Chem. Theory Comput. 1, 1162 (2005)]. In addition to an absorption line at 724.2 cm{sup -1}, corresponding to a transition of 3{sup 1} previously determined to be 727 cm{sup -1} from fluorescence spectra of gaseous CH{sub 3}S, we identified fundamental transitions 6{sup 1}(a{sub 1}) at 771.1, 6{sup 1}(e) at 1056.6, 5{sup 1}(a{sub 1}) at 1400.0, 4{sup 1}(a{sub 1}) at 2898.4 cm{sup -1}, and several combination and overtone transitions. In contrast, photolysis of CH{sub 3}SSCH{sub 3} isolated in solid Ar produces mainly H{sub 2}CS, CH{sub 3}SH, and CS{sub 2}, but no CH{sub 3}S. These results demonstrate the feasibility of using photolysis in situ of precursors isolated in solid p-H{sub 2} to produce free radicals by taking advantage of the diminished cage effect of the matrix.

• OSTI ID: 21559939
• Journal Information: Journal of Chemical Physics, Vol. 133, Issue 16; Other Information: DOI: 10.1063/1.3502105; (c) 2010 American Institute of Physics; ISSN 0021-9606
• Country of Publication: United States
• Language: English

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37 INORGANIC
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PHYSICAL AND ANALYTICAL CHEMISTRY
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION
ABSORPTION SPECTRA
CARBON SULFIDES
CESIUM SULFIDES
DISSOCIATION
FLUORESCENCE
FLUORESCENCE SPECTROSCOPY
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PHOTON EMISSION
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