Absolute Infrared Absorption Cross Section of the Simplest Criegee Intermediate Near 1285.7 cm.

The ν fundamental of the simplest Criegee intermediate, CHOO, has been monitored with high-resolution infrared (IR) transient absorption spectroscopy under total pressures of 4-94 Torr. This IR spectrum provides an unambiguous identification of CHOO and is potentially useful to determine the number density of CHOO in various laboratory studies. Here we utilized an ultraviolet (UV) and IR coupled spectrometer to measure the UV and IR absorption spectra of CHOO simultaneously; the absolute IR cross section can then be determined by using a known UV cross section. Due to significant pressure broadening in the studied pressure range, we integrated the IR absorption spectra between 1285.2 and 1286.4 cm (covering the Q branch), and then we converted this integrated absorbance to the absolute integral IR cross section of CHOO (for the Q branch); its absolute value is (3.7 ± 0.6) × 10 cm·molecule or 2.2 ± 0.4 km·mol. The whole rotational band (P, Q, and R branches) can be adequately simulated by using the precise spectroscopic parameters from the literature, yielding the absolute integral IR cross section (full ν band) to be 19.2 ± 3.5 km·mol. For a practical detection of CHOO, this work also reports the peak cross section as a function of total pressure (4-94 Torr O). At low pressure (≤4 Torr), where the pressure broadening is insignificant, the absorption cross section of the highest peak is (6.2 ± 0.9) × 10 cm·molecule (at the system line width of 0.004 cm fwhm).