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

Pei Ling Luo*, Yasuki Endo, Yuan-Pern Lee*

*Corresponding author for this work

Research output: Contribution to journalArticle

10 Scopus citations

Abstract

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.

Original languageEnglish
Pages (from-to)4391-4395
Number of pages5
JournalJournal of Physical Chemistry Letters
Volume9
Issue number15
DOIs
StatePublished - 2 Aug 2018

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