Characterization of two photon excited fragment spectroscopy (TPEFS) for HNO₃ detection in gas-phase kinetic experiments

We have developed and tested two-photon excited fragment spectroscopy (TPEFS) for detecting HNO₃ in pulsed laser photolysis kinetic experiments. Dispersed (220-330 nm) and time-dependent emission at (310 ± 5) nm following the 193 nm excitation of HNO₃ in N₂, air and He was recorded and analysed to characterise the OH(A²Σ) and NO(A²Σ⁺) electronic excited states involved. The limit of detection for HNO₃ using TPEFS was ∼5 × 10⁹ molecule cm^-3 (at 60 torr N₂ and 180 μs integration time). Detection of HNO₃ using the emission at (310 ± 5 nm) was orders of magnitude more sensitive than detection of NO and NO₂, especially in the presence of O₂ which quenches NO(A²Σ⁺) more efficiently than OH(A²Σ). While H₂O₂ (and possibly HO₂) could also be detected by 193 nm TPEFS, the relative sensitivity (compared to HNO₃) was very low. The viability of real-time TPEFS detection of HNO₃ using emission at (310 ± 5) nm was demonstrated by monitoring HNO₃ formation in the reaction of OH + NO₂ and deriving the rate coefficient, k₂. The value of k₂ obtained at 293 K and pressures of 50-200 torr is entirely consistent with that obtained by simultaneously measuring the OH decay and is in very good agreement with the most recent literature values.