TY - JOUR
T1 - Reaction of CH2Cl radical with O2 in solid para-hydrogen
T2 - Infrared spectrum of gauche-CH2ClOO radical
AU - Haupa, Karolina A.
AU - Lee, Yuan Pern
PY - 2020/9/5
Y1 - 2020/9/5
N2 - Irradiation of a para-hydrogen (p-H2) matrix containing chloroiodomethane (CH2ClI) and O2 at 3.3 K with light at 290 nm yielded infrared absorption lines at 750.1/745.6, 891.7, 1004.6, 1090.7, 1241.3, 1315.6, 1427.8, and 2988.7 cm−1, which are assigned to the gauche-chloromethylperoxy radical (gauche-CH2ClOO). Further irradiation of the matrix at 240 nm selectively diminished these features. The assignments are based on the photolytic behavior and comparisons of the observed vibrational wavenumbers and IR intensities with those predicted with the B3LYP/aug-cc-pVTZ method. The irradiation of CH2ClOO at 240 nm was found to induce cleavage of the O–O bond to produce CH2ClO, but not cleavage of the C–Cl bond to produce the Criegee intermediate CH2OO.
AB - Irradiation of a para-hydrogen (p-H2) matrix containing chloroiodomethane (CH2ClI) and O2 at 3.3 K with light at 290 nm yielded infrared absorption lines at 750.1/745.6, 891.7, 1004.6, 1090.7, 1241.3, 1315.6, 1427.8, and 2988.7 cm−1, which are assigned to the gauche-chloromethylperoxy radical (gauche-CH2ClOO). Further irradiation of the matrix at 240 nm selectively diminished these features. The assignments are based on the photolytic behavior and comparisons of the observed vibrational wavenumbers and IR intensities with those predicted with the B3LYP/aug-cc-pVTZ method. The irradiation of CH2ClOO at 240 nm was found to induce cleavage of the O–O bond to produce CH2ClO, but not cleavage of the C–Cl bond to produce the Criegee intermediate CH2OO.
KW - Free radicals
KW - Infrared spectroscopy
KW - Matrix isolation
KW - Solid para-hydrogen
UR - http://www.scopus.com/inward/record.url?scp=85083801613&partnerID=8YFLogxK
U2 - 10.1016/j.molstruc.2020.128214
DO - 10.1016/j.molstruc.2020.128214
M3 - Article
AN - SCOPUS:85083801613
SN - 0022-2860
VL - 1215
JO - Journal of Molecular Structure
JF - Journal of Molecular Structure
M1 - 128214
ER -