TY - JOUR
T1 - Infrared absorption of 3-propenonyl (ṡCH 2 CHCO) radical generated upon photolysis of acryloyl chloride [cH 2 CHC(O)Cl] in solid para-H 2
AU - Das, Prasanta
AU - Lee, Yuan-Pern
PY - 2013/8/28
Y1 - 2013/8/28
N2 -
Irradiation at 193 nm of a p-H
2
matrix containing acryloyl chloride CH
2
CHC(O)Cl at 3.2 K yielded infrared absorption lines at 3143.6 (ν
1
), 3057.0 (ν
2
), 3048.0 (ν
3
), 2103.1 (ν
4
), 1461.0 (ν
5
), 1349.8 (ν
6
), 1223.7 (ν
11
+ν
12
or 2ν
12
), 1092.8 (ν
8
), 918.1 (ν
9
), 691.0 (ν
10
), 624.3 (ν
11
), and 597.1 (ν
12
) cm
-1
that are assigned to the 3-propenonyl (ṡCH
2
CHCO) radical. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers and infrared intensities with those predicted with the B3PW91/aug-cc-pVDZ method. The observation is consistent with a major radical formation channel CH
2
CHCO + Cl followed by escape of the Cl atom from the original p-H
2
cage. The observation of 3-propenonyl (ṡCH
2
CHCO) radical but not 3-propenalyl (s-cis- or s-trans-CH
2
CHĊO) radical indicates that the former is the most stable isomer and that the barrier heights for conversion from s-cis- or s-trans-CH
2
CHĊO to ṡCH
2
CHCO are small.
AB -
Irradiation at 193 nm of a p-H
2
matrix containing acryloyl chloride CH
2
CHC(O)Cl at 3.2 K yielded infrared absorption lines at 3143.6 (ν
1
), 3057.0 (ν
2
), 3048.0 (ν
3
), 2103.1 (ν
4
), 1461.0 (ν
5
), 1349.8 (ν
6
), 1223.7 (ν
11
+ν
12
or 2ν
12
), 1092.8 (ν
8
), 918.1 (ν
9
), 691.0 (ν
10
), 624.3 (ν
11
), and 597.1 (ν
12
) cm
-1
that are assigned to the 3-propenonyl (ṡCH
2
CHCO) radical. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers and infrared intensities with those predicted with the B3PW91/aug-cc-pVDZ method. The observation is consistent with a major radical formation channel CH
2
CHCO + Cl followed by escape of the Cl atom from the original p-H
2
cage. The observation of 3-propenonyl (ṡCH
2
CHCO) radical but not 3-propenalyl (s-cis- or s-trans-CH
2
CHĊO) radical indicates that the former is the most stable isomer and that the barrier heights for conversion from s-cis- or s-trans-CH
2
CHĊO to ṡCH
2
CHCO are small.
UR - http://www.scopus.com/inward/record.url?scp=84903362612&partnerID=8YFLogxK
U2 - 10.1063/1.4818880
DO - 10.1063/1.4818880
M3 - Article
AN - SCOPUS:84903362612
SN - 0021-9606
VL - 139
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 8
M1 - 084320
ER -