TY - JOUR
T1 - Infrared absorption spectrum of the simplest deuterated Criegee intermediate CD2OO
AU - Huang, Yu Hsuan
AU - Nishimura, Yoshifumi
AU - Witek, Henryk Arnold
AU - Lee, Yuan-Pern
N1 - Publisher Copyright:
© 2016 Author(s).
PY - 2016/7/28
Y1 - 2016/7/28
N2 - We report a transient infrared (IR) absorption spectrum of the simplest deuterated Criegee intermediate CD2OO recorded using a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. CD2OO was produced from photolysis of flowing mixtures of CD2I2, N2, and O2 (13 or 87 Torr) with laser light at 308 nm. The recorded spectrum shows close structural similarity with the spectrum of CH2OO reported previously [Y.-T. Su et al., Science 340, 174 (2013)]. The four bands observed at 852, 1017, 1054, and 1318 cm-1 are assigned to the OO stretching mode, two distinct in-plane OCD bending modes, and the CO stretching mode of CD2OO, respectively, according to vibrational wavenumbers, IR intensities, rotational contours, and deuterium-isotopic shifts predicted with extensive quantum-chemical calculations. The CO-stretching mode of CD2OO at 1318 cm-1 is blue shifted from the corresponding band of CH2OO at 1286 cm-1; this can be explained by a mechanism based on mode mixing and isotope substitution. A band near 936 cm-1, observed only at higher pressure (87 Torr), is tentatively assigned to the CD2 wagging mode of CD2IOO.
AB - We report a transient infrared (IR) absorption spectrum of the simplest deuterated Criegee intermediate CD2OO recorded using a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. CD2OO was produced from photolysis of flowing mixtures of CD2I2, N2, and O2 (13 or 87 Torr) with laser light at 308 nm. The recorded spectrum shows close structural similarity with the spectrum of CH2OO reported previously [Y.-T. Su et al., Science 340, 174 (2013)]. The four bands observed at 852, 1017, 1054, and 1318 cm-1 are assigned to the OO stretching mode, two distinct in-plane OCD bending modes, and the CO stretching mode of CD2OO, respectively, according to vibrational wavenumbers, IR intensities, rotational contours, and deuterium-isotopic shifts predicted with extensive quantum-chemical calculations. The CO-stretching mode of CD2OO at 1318 cm-1 is blue shifted from the corresponding band of CH2OO at 1286 cm-1; this can be explained by a mechanism based on mode mixing and isotope substitution. A band near 936 cm-1, observed only at higher pressure (87 Torr), is tentatively assigned to the CD2 wagging mode of CD2IOO.
UR - http://www.scopus.com/inward/record.url?scp=84980047698&partnerID=8YFLogxK
U2 - 10.1063/1.4958932
DO - 10.1063/1.4958932
M3 - Article
AN - SCOPUS:84980047698
SN - 0021-9606
VL - 145
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 4
M1 - 044305
ER -