Experimental determination of the absolute infrared absorption intensities of formyl radical HCO.

ABSTRACT

Formyl radical HCO is an important reactive intermediate in combustion, atmospheric and extraterrestrial chemistry. Like in the case of other transients, the lack of knowledge of the absolute IR intensities limits the quantitative spectroscopic studies on this species. We report the first experimental determination of the absorption intensities for the fundamental vibrational bands of HCO. The measurements have been performed using matrix-isolation FTIR spectroscopy. Determination of the values was based on the repeated photodissociation and thermal recovery of the HCO radical using the known value of the absorption coefficient of CO. The experimentally determined values (93.2±6.0, 67.2±4.5, and 109.2±6.6kmmol-1 for the ν1, ν2, and ν3 modes, respectively) have been compared to the calculated IR intensities obtained by DFT and UCCSD(T) computations.