Infrared chemiluminescence from the O + CF2 reaction: part 2.—Analysis of the emission near 2000 cm–1

Abstract

Emission from vibrationally excited CO₂, formed in the reaction sequence O + CF₂→ FCO + F (1), O + FCO → CO₂+ F (2) has been observed under conditions such that, although rotational relaxation was complete, the nascent vibrational distribution was essentially preserved. Although emission occurred in the Δv₃=–1 bands, the vibrational excitation was shown not to be confined to the ν₃ mode. The data were found to fit a prior distribution only if the energy available for partitioning in the products was some 15% higher than that expected from reaction (2). The energy could come from an uncertainty in the recommended value of the heat of formation of FCO, or if this radical carried some 40% of the energy released in process (1). Alternatively, specific vibrational excitation of CO₂ is consistent both with the data and with the reaction pathways expected from calculations on the FCO₂ system.