Photodissociation of HNO3 at 193, 222, and 248 nm: Products and quantum yields

Abstract

The quantum yields for OH, O(3P), O(1D), and H(2S) from the photolysis of HNO3 have been determined at 248, 222, and 193 nm at 298 K. The quantum yield for OH was observed to be near unity at 248 [Φ(OH)=0.95±0.09] and 222 nm [Φ(OH)=0.90±0.11]. However, at 193 nm the quantum yield for OH was found to be 0.33±0.06. The quantum yield for O atoms [O(3P)+O(1D)], Φ(O), was observed to be 0.031±0.010, 0.20±0.03, 0.81±0.13, at 248, 222, and 193 nm, respectively. Both O(3P) and O(1D) were observed at 222 and 193 nm, but only O(3P) was detected at 248 nm. It was observed that 40% of the O atoms formed at both 193 and 222 nm were O(1D) atoms. The upper limits for H(2S) quantum yields: Φ(H)≤0.002 at 248 nm, ≤0.01 at 222 nm, and ≤0.012 at 193 nm were also determined. This present work quantifies the photolysis channel producing HONO+O and show that it accounts for a large fraction at HNO3 photolysis at 193 nm.