TY - JOUR
T1 - Identification and Self-Reaction Kinetics of Criegee Intermediates syn-CH 3 CHOO and CH 2 OO via High-Resolution Infrared Spectra with a Quantum-Cascade Laser
AU - Luo, Pei Ling
AU - Endo, Yasuki
AU - Lee, Yuan-Pern
N1 - Publisher Copyright:
Copyright © 2018 American Chemical Society.
PY - 2018/7/19
Y1 - 2018/7/19
N2 - The Criegee intermediates, carbonyl oxides produced in ozonolysis of unsaturated hydrocarbons, play important roles in atmospheric chemistry. The two conformers of CH 3 CHOO exhibit distinct reactivity toward several atmospheric species, but a distinct conformer-specific probe is challenging because ultraviolet and infrared absorption bands of syn- and anti-CH 3 CHOO overlap at low-resolution. Employing a quantum-cascade laser and a Herriott cell, we recorded the O-O stretching bands of CH 2 OO and syn-CH 3 CHOO in region 880-932 cm -1 at resolution 0.0015 cm -1 . In addition to completely resolved vibration-rotational lines of CH 2 OO extending over 50 cm -1 , some spectral lines associated with hot bands were identified. Spectral lines solely due to syn-CH 3 CHOO were also identified. Probing these lines, we determined the rate coefficient for the self-reaction of syn-CH 3 CHOO to be k self = (1.6 ± 0.6 0.5 ) × 10 -10 cm 3 molecule -1 s -1 , about twice that of CH 2 OO.
AB - The Criegee intermediates, carbonyl oxides produced in ozonolysis of unsaturated hydrocarbons, play important roles in atmospheric chemistry. The two conformers of CH 3 CHOO exhibit distinct reactivity toward several atmospheric species, but a distinct conformer-specific probe is challenging because ultraviolet and infrared absorption bands of syn- and anti-CH 3 CHOO overlap at low-resolution. Employing a quantum-cascade laser and a Herriott cell, we recorded the O-O stretching bands of CH 2 OO and syn-CH 3 CHOO in region 880-932 cm -1 at resolution 0.0015 cm -1 . In addition to completely resolved vibration-rotational lines of CH 2 OO extending over 50 cm -1 , some spectral lines associated with hot bands were identified. Spectral lines solely due to syn-CH 3 CHOO were also identified. Probing these lines, we determined the rate coefficient for the self-reaction of syn-CH 3 CHOO to be k self = (1.6 ± 0.6 0.5 ) × 10 -10 cm 3 molecule -1 s -1 , about twice that of CH 2 OO.
UR - http://www.scopus.com/inward/record.url?scp=85050626905&partnerID=8YFLogxK
U2 - 10.1021/acs.jpclett.8b01824
DO - 10.1021/acs.jpclett.8b01824
M3 - Article
C2 - 30024766
AN - SCOPUS:85050626905
SN - 1948-7185
VL - 9
SP - 4391
EP - 4395
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 15
ER -