Photolysis of nitric acid at 308 nm in the absence and in the presence of water vapor.

Abstract

We have re-examined the NOx channels from the 308 nm gas-phase photolysis of nitric acid (HNO3) by using excimer laser photolysis combined with cavity ring-down spectroscopy. The photolysis products were monitored in the 552-560 and 640-648 nm regions. Direct comparison of the photolysis product spectrum in the 640-648 nm region with literature vibronic band origins and line intensities in electronically excited NO2 (NO2*) suggests that NO2* is not formed from HNO3 photolysis at 308 nm. A comparison of the photolysis product spectrum in the 552-560 nm region with a standard NO2 spectrum indicates that ground-state NO2 is a photolysis product. We have determined the NO2 quantum yield from the 308 nm HNO3 photolysis. We also investigated HNO3 photolysis in the presence of water vapor. For equilibrated HNO3/H2O mixtures, we did not observe significant variation of product absorption around 552 nm with delay times between the firing of the photolysis and the probe lasers. Transient product absorption measurements at 342.0 and 343.5 nm (respective wavelengths where the peak and valley of HONO absorptions are located) are consistent with ground-state NO2 being the predominant NOx product from the 308 nm photolysis of a HNO3/H2O mixture. Atmospheric implications are also discussed.