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Wolfe GM, Crounse JD, Parrish JD, et al. Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs). Phys Chem Chem Phys. 2012;14(20):7276-86doi: 10.1039/c2cp40388a.
Wolfe, G. M., Crounse, J. D., Parrish, J. D., St Clair, J. M., Beaver, M. R., Paulot, F., Yoon, T. P., Wennberg, P. O., & Keutsch, F. N. (2012). Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs). Physical chemistry chemical physics : PCCP, 14(20), 7276-86. https://doi.org/10.1039/c2cp40388a
Wolfe, Glenn M, et al. "Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs)." Physical chemistry chemical physics : PCCP vol. 14,20 (2012): 7276-86. doi: https://doi.org/10.1039/c2cp40388a
Wolfe GM, Crounse JD, Parrish JD, St Clair JM, Beaver MR, Paulot F, Yoon TP, Wennberg PO, Keutsch FN. Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs). Phys Chem Chem Phys. 2012 May 28;14(20):7276-86. doi: 10.1039/c2cp40388a. Epub 2012 Apr 19. PMID: 22517221.
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Phys Chem Chem Phys. 2012 May 28;14(20):7276-86. doi: 10.1039/c2cp40388a. Epub 2012 Apr 19.

Photolysis, OH reactivity and ozone reactivity of a proxy for isoprene-derived hydroperoxyenals (HPALDs).

Physical chemistry chemical physics : PCCP

Glenn M Wolfe, John D Crounse, Jonathan D Parrish, Jason M St Clair, Melinda R Beaver, Fabien Paulot, Tehshik P Yoon, Paul O Wennberg, Frank N Keutsch

Affiliations

  1. Department of Chemistry, University of Wisconsin, Madison, WI, USA. [email protected]

PMID: 22517221 DOI: 10.1039/c2cp40388a

Abstract

The C(5)-hydroperoxyenals (C(5)-HPALDs) are a newly-recognized class of multi-functional hydrocarbons produced during the hydroxyl radical (OH)-initiated oxidation of isoprene. Recent theoretical calculations suggest that fast photolysis of these compounds may be an important OH source in high-isoprene, low-NO regions. We report experimental constraints for key parameters of photolysis, OH reaction and ozone reaction of these compounds as derived from a closely-related, custom-synthesized C(6)-HPALD. The photolysis quantum yield is 1.0 ± 0.4 over the range 300-400 nm, assuming an absorption cross section equal to the average of those measured for several analogous enals. The yield of OH from photolysis was determined as 1.0 ± 0.8. The OH reaction rate constant is (5.1 ± 1.8) × 10(-11) cm(3) molecule(-1) s(-1) at 296 K. The ozone reaction rate constant is (1.2 ± 0.2) × 10(-18) cm(3) molecule(-1) s(-1) at 296 K. These results are consistent with previous first-principles estimates, though the nature and fate of secondary oxidation products remains uncertain. Incorporation of C(5)-HPALD chemistry with the above parameters in a 0-D box model, along with experimentally-constrained rates for C(5)-HPALD production from isomerization of first-generation isoprene hydroxyperoxy radicals, is found to enhance modeled OH concentrations by 5-16% relative to the traditional isoprene oxidation mechanism for the chemical regimes of recent observational studies in rural and remote regions. This enhancement in OH will increase if C(5)-HPALD photo-oxidation products also photolyze to yield additional OH or if the C(5)-HPALD production rate is faster than has been observed.

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