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Near-IR photodissociation of peroxy acetyl nitrate

Nizkorodov, S. A. and Crounse, J. D. and Fry, J. L. and Roehl, C. M. and Wennberg, P. O. (2004) Near-IR photodissociation of peroxy acetyl nitrate. Atmospheric Chemistry and Physics Discussions, 4 (2). pp. 1269-1289. ISSN 1680-7367.

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Measurements of the C-H overtone transition strengths combined with estimates of the photodissociation cross sections for these transitions suggest that near-IR photodissociation of peroxy acetyl nitrate (PAN) is less significant (Jnear−IR ~3×10^−8 s^−1 at noon) in the lower atmosphere than competing sinks resulting from unimolecular decomposition and ultraviolet photolysis. This is in contrast to the photochemical behavior of a related peroxy nitrate, pernitric acid (PNA), that undergoes rapid near-IR photolysis in the atmosphere with Jnear−IR ~10^−5 s^−1 at noon (Roehl et al., 2002). This difference is attributed to the larger binding energy and larger number of vibrational degrees of 10 freedom in PAN, which make 4[Greek nu]CH the lowest overtone excitation with a high photodissociation yield (as opposed to 2[Greek nu]OH in PNA).

Item Type:Article
Additional Information:© European Geosciences Union 2004. Received: 4 February 2004 – Accepted: 22 February 2004 – Published: 1 March 2004. This work was funded in part by NASA’s Atmospheric Effects of Aviation Program and the Atmospheric Chemistry program of the National Science Foundation. SAN thanks the Camille and Henry Dreyfus Foundation for financial support during his postdoctoral research at Caltech. The authors thank R. Salawitch (JPL) for providing 24-averaged UV-photolysis rates of PAN used in Fig. 5 and A. Sinha (UCSD) for a preprint of Ref. (Matthews et al., 2004).
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Deposited On:18 May 2005
Last Modified:26 Dec 2012 08:39

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