Prototype for in situ detection of atmospheric NO3 and N2O5 via laser-induced fluorescence

We describe a prototype designed for in situ detection of the nitrate radical (NO3) by laser-induced fluorescence (LIF) and of N2O5 by thermal dissociation followed by LIF detection of NO3. An inexpensive 36 mW continuous wave multi-mode diode laser at 662 nm is used to excite NO3 in the (B) over tilde E-2'(0000) <-- (X) over tilde (2)A'(2)(0000) band. Fluorescence is collected from 700 to 750 nm. The prototype has a sensitivity to NO3 of 76 ppt for a 60 s integration with an accuracy of 8%. Although this sensitivity is adequate for studies of N2O5 in many environments, it is much less sensitive (about 300 times) than expected based on a comparison of previously measured photophysical properties of NO2 and NO3. This implies much stronger nonradiative coupling of electronic states in NO3 than in NO2.