Infrared absorption of CH 3OSO and CD 3OSO radicals produced upon photolysis of CH 3OS(O)Cl and CD 3OS(O)Cl in p-H 2 matrices

Yu Fang Lee, Lin Jun Kong, Yuan-Pern Lee*

*Corresponding author for this work

Research output: Contribution to journalArticle

11 Scopus citations

Abstract

Irradiation at 239 ± 20 nm of a p-H 2 matrix containing methoxysulfinyl chloride, CH 3OS(O)Cl, at 3.2 K with filtered light from a medium-pressure mercury lamp produced infrared (IR) absorption lines at 3028.4 (attributable to 1, CH 2 antisymmetric stretching), 2999.5 ( 2, CH 3 antisymmetric stretching), 2950.4 ( 3, CH 3 symmetric stretching), 1465.2 ( 4, CH 2 scissoring), 1452.0 ( 5, CH 3 deformation), 1417.8 ( 6, CH 3 umbrella), 1165.2 ( 7, CH 3 wagging), 1152.1 ( 8, SO stretching mixed with CH 3 rocking), 1147.8 ( 9, SO stretching mixed with CH 3 wagging), 989.7 ( 10, C-O stretching), and 714.5 cm -1 ( 11, S-O stretching) modes of syn-CH 3OSO. When CD 3OS(O)Cl in a p-H 2 matrix was used, lines at 2275.9 ( 1), 2251.9 ( 2), 2083.3 ( 3), 1070.3 ( 4), 1056.0 ( 5), 1085.5 ( 6), 1159.7 ( 7), 920.1 ( 8), 889.0 ( 9), 976.9 ( 10), and 688.9 ( 11) cm -1 appeared and are assigned to syn-CD 3OSO; the mode numbers correspond to those used for syn-CH 3OSO. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers, infrared intensities, and deuterium isotopic shifts with those predicted with the B3P86aug-cc-pVTZ method. Our results extend the previously reported four transient IR absorption bands of gaseous syn-CH 3OSO near 2991, 2956, 1152, and 994 cm -1 to 11 lines, including those associated with C-O, O-S, and SO stretching modes. Vibrational wavenumbers of syn-CD 3OSO are new. These results demonstrate the advantage of a diminished cage effect of solid p-H 2 such that the Cl atom, produced via UV photodissociation of CH 3OS(O)Cl in situ, might escape from the original cage to yield isolated CH 3OSO radicals.

Original languageEnglish
Article number124510
JournalJournal of Chemical Physics
Volume136
Issue number12
DOIs
StatePublished - 28 Mar 2012

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