TY - JOUR
T1 - 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
AU - Lee, Yu Fang
AU - Kong, Lin Jun
AU - Lee, Yuan-Pern
PY - 2012/3/28
Y1 - 2012/3/28
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84859528012&partnerID=8YFLogxK
U2 - 10.1063/1.3696894
DO - 10.1063/1.3696894
M3 - Article
C2 - 22462877
AN - SCOPUS:84859528012
SN - 0021-9606
VL - 136
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 12
M1 - 124510
ER -