Chemical lasers produced from O(¹D) atom reactions. IV. Competitive eliminations of HCl and HF from the vibrationally excited CIFHCOH, Cl₂FCOH, and ClF₂COH molecules

Chemical HCl and HF laser emissions were observed from the competitive, four-centered unimolecular elimination reactions of chemically activated ClFHCOH, Cl₂FCOH, and ClF₂COH molecules in an optical cavity. The HF emission was found to be significantly stronger and was observed in all three reactions; the HCl emission, however, was detected only in the Cl₂FCOH system. This is attributable to a larger stimulated emission coefficient as well as a preferentially faster rate of elimination of HF than HCl. The vibrationally excited methanol molecule, which possesses at least 130 kcal/mol of internal energy, was generated by insertion of an O(¹D) atom into a C-H bond of a chlorofluoromethane molecule. The O(¹D) atom was produced from the flash-photolytic decomposition of O₃. The initial population ratios of the highest gain transitions have been estimated and compared with the values obtained from other O(¹D) atom insertion-elimination reactions reported previously.