Absolute Ultraviolet Absorption Spectrum of a Criegee Intermediate CH₂OO

Abstract

We present the time-resolved UV absorption spectrum of the B̃ ((1)A') ← X̃ ((1)A') electronic transition of formaldehyde oxide, CH2OO, produced by the reaction of CH2I radicals with O2. In contrast to its UV photodissociation action spectrum, the absorption spectrum of formaldehyde oxide extends to longer wavelengths and exhibits resolved vibrational structure on its low-energy side. Chemical kinetics measurements of its reactivity establish the identity of the absorbing species as CH2OO. Separate measurements of the initial CH2I radical concentration allow a determination of the absolute absorption cross section of CH2OO, with the value at the peak of the absorption band, 355 nm, of σabs = (3.6 ± 0.9) × 10(-17) cm(2). The difference between the absorption and action spectra likely arises from excitation to long-lived B̃ ((1)A') vibrational states that relax to lower electronic states by fluorescence or nonradiative processes, rather than by photodissociation.