Distribution of Vibrational States of CO2 in the Reaction O(D-1) + CO2 from Time-Resolved Fourier Transform Infrared Emission Spectra

Abstract

A mixture Of O-3 and CO2 was irradiated with light from a KrF laser at 248 nm; time-resolved infrared emission Of CO2 in the region 2000-2400 cm(-1) was observed with a Fourier transform spectrometer. This emission involves one quantum in the asymmetric stretching mode (nu(3)) Of CO2 in highly vibrationally excited states. The band contour agrees satisfactorily with a band shape calculated based on a simplified polyad model of CO2 and a vibrational distribution estimated through a statistical partitioning of energy of similar to 13 000 cm(-1), similar to 3100 cm(-1) smaller than the available energy, into the vibrational modes Of CO2. From this model, approximately 44% and 5% of the available energy of O(D-1) + CO2 is converted into the vibrational and rotational energy of product CO2, respectively, consistent with previous reports of similar to 50% for the translational energy. An extent of rotational excitation Of CO2 much smaller than that expected from statistical calculations indicates a mechanism that causes a small torque to be given to CO2 when an O atom leaves the complex CO3 on the triplet exit surface of potential energy, consistent with quantum-chemical calculations.