Absolute Infrared Absorption Cross Section of the Simplest Criegee Intermediate Near 1285.7 cm-1

Abstract

The ν₄ fundamental of the simplest Criegee intermediate, CH₂OO, 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 CH₂OO and is potentially useful to determine the number density of CH₂OO in various laboratory studies. Here we utilized an ultraviolet (UV) and IR coupled spectrometer to measure the UV and IR absorption spectra of CH₂OO 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^-1 (covering the Q branch), and then we converted this integrated absorbance to the absolute integral IR cross section of CH₂OO (for the Q branch); its absolute value is (3.7 ± 0.6) × 10^-19 cm·molecule^-1 or 2.2 ± 0.4 km·mol^-1. 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 ν₄ band) to be 19.2 ± 3.5 km·mol^-1. For a practical detection of CH₂OO, this work also reports the peak cross section as a function of total pressure (4-94 Torr O₂). 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^-18 cm²·molecule^-1 (at the system line width of 0.004 cm^-1 fwhm).