A pulsed laser photolysis-pulsed laser induced fluorescence study of the kinetics of the gas-phase reaction of OH with NO2

The kinetics of the recombination reaction, OH+NO2+(M)--> HNO3 +(M) have been investigated by the pulsed laser photolysis-pulsed laser induced fluorescence (PLP-PLIF) technique in air, nitrogen, oxygen, and helium buffer gases at room temperature and as a function of pressure (30-700 Torr). Additional measurements in nitrogen at 273 K (100-700 Torr) are reported. The third-body efficiency of water vapor has also been investigated. Our values for the absolute rate coefficient in nitrogen at room temperature and at 273 K are in excellent agreement with the JPL 1994 recommendation but lie substantially above the current JPL 2000 recommendation. Our rate coefficients in helium agree with previous literature studies, suggesting that systematic errors are small. Oxygen is found to be about 20% less efficient than nitrogen, and we see no significant enhancement in recombination in the presence of water vapor. Our results suggest that formation of the pernitrous acid isomer cannot explain the discrepancies in the current experimental database.