Optical Studies of the Photolysis of CO2 at 1470 Å

Experiments have failed to detect radiation from O(1D) at 6300 Å in the photolysis of CO2 and O2 using 1470-Å radiation. From the observed rate of CO formation [which had been expected to equal the rate of O(1D) formation] and the sensitivity of the optical detection, it is concluded that insignificant amounts of O(1D) exist in photolyzed CO2 under these conditions. Measurements on O2 irradiated with 1470-Å light imply that O2 deactivated O(1D) with a rate coefficient greater than 10−12 cm3/sec. From an analysis of the photolysis of mixtures of CO+CO2, CO+O2, and CO+O2+CO2, it is determined that O(1D) complexes with CO2 (probably from CO3) with a rate coefficient greater than 10−12 cm3/sec, that CO3+CO is less than 20% as efficient as O(3P) in producing chemiluminescent radiation, and that O(1D) forms CO3 at least five times more rapidly that it is deactivated to O(3P) by CO2.