References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-7-713-2007

Near-UV photolysis cross sections of CH3OOH and HOCH2OOH determined via action spectroscopy

Roehl

C. M.

¹ Marka

¹ ⁴ Fry

J. L.

² ⁵ Wennberg

P. O.

¹ ³

Division of Geological and Planetary Sciences, California Institute of Technology, Pasadena, CA 91125, USA

Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, CA 91125, USA

Division of Engineering and Applied Science, California Institute of Technology, Pasadena, CA 91125, USA

now at: Columbia Astrophysics Laboratory, Columbia University, New York, NY 10027, USA

now at: Department of Chemistry, University of California, Berkeley, Berkeley, CA 94720-1460, USA

14 02 2007

7 3 713 720

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

This article is available from http://www.atmos-chem-phys.net/7/713/2007/acp-7-713-2007.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/7/713/2007/acp-7-713-2007.pdf

Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10−23 cm2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections.

References 1

Barnes, R. J., Lock, M., Coleman, J., and Sinha, A.: Observation of a new absorption band of HOBr and its atmospheric implications, J. Phys. Chem. 100, 453–457, 1996.

Bauerle, S. and Moortgat, G. K.: Absorption cross-sections of HOCH2OOH vapor between 205 and 360 nm at 298 K, Chem. Phys. Lett., 309, 43–48, 1999.

Finlayson-Pitts, B. J. and Pitts Jr., J. N.: Atmospheric Chemistry: Fundamentals and Experimental Techniques, Wiley, New York, 1986.

Jaegle, L., Webster, C. R., May, R. D., Scott, D. C., Stimpfle, R. M., Kohn, D. W., Wennberg, P. O., Hanisco, T. F., Cohen, R. C., Proffitt, M. H., Kelly, K. K., Elkins, J., Baumgardner, D., Dye, J. E., Wilson, J. C., Pueschel, R. F., Chan, K. R., Salawitch, R. J., Tuck, A. F., Hovde, S. J., and Yung, Y. L.: Evolution and stoichiometry of heterogeneous processing in the Antarctic stratosphere, J. Geophys. Res. – Atmos., 102, 13 235–13 253, 1997.

Knight, G., Ravishankara, A. R., and Burkholder, J. B.: UV absorption cross sections of HO2NO2 between 343 and 273 K, Phys. Chem. Chem. Phys., 4, 1432–1437, 2002.

Matthews, J., Sinha, A., and Francisco, J. S.: The importance of weak absorption features in promoting tropospheric radical production, Proceedings of the National Academy of Sciences of the USA, 102, 7449–7452, 2005.

Molina, L. T. and Molina, M. J.: UV absorption cross-sections of HO2NO2 vapor, J. Photochem., 15, 97–108, 1981.

Neeb, P., Sauer, F., Horie, O., and Moortgat, G. K.: Formation of hydroxymethyl hydroperoxide and formic acid in alkene ozonolysis in the presence of water vapour, Atmos. Environ., 31, 1417–1423, 1997.

Nicovich, J. M. and Wine, P. H.: Temperature-dependent absorption cross-sections for hydrogen-peroxide vapor, J. Geophys. Res., 93, 2417–2421, 1988.

Niki, H., Maker, P. D., Savage, C. M., and Breitenbach, L. P.: A Fourier-transform infrared study of the kinetics and mechanism for the reaction HO+CH3OOH, J. Phys. Chem., 87, 2190–2193, 1983.

Ondrey, G., van Veen, N., and Bersohn, R.: The state distribution of OH radicals photodissociated from H2O2 at 193 and 248 nm, J. Chem. Phys., 78(6), 3732–3737, 1983.

Orlando, J. J. and Burkholder, J. B.: Gas-phase UV visible absorption-spectra of HOBr and Br2O, J. Phys. Chem., 99, 1143–1150, 1995.

Rothman, L. S., Barbe, A., Benner, D. C., Brown, L. R., Camy-Peyret, C., Carleer, M. R., Chance, K., Clerbaux, C., Dana, V., Devi, V. M., Fayt, A., Flaud, J. M., Gamache, R. R., Goldman, A., Jacquemart, D., Jucks, K. W., Lafferty, W. J., Mandin, J. Y., Massie, S. T., Nemtchinov, V., Newnham, D. A., Perrin, A., Rinsland, C. P., Schroeder, J., Smith, K. M., Smith, M. A. H., Tang, K., Toth, R. A., Vander Auwera, J., Varanasi, P., and Yoshino, K.: The HITRAN molecular spectroscopic database: edition of 2000 including updates through 2001, J. Quant. Spect. & Rad. Trans., 82, 5–44, 2003.

Sander, S. P., Friedl, R. R., Golden, D. M., Kurylo, M. J., Moortgat, G. K., Wine, P. H., Ravishankara, A. R., Kolb, C. E., Molina, M. J., Finlayson-Pitts, B. J., Huie, R. E., and Orkin, V. L.,: Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Eval. 15, National Aeronautics and Space Administration, Jet Propulsion Laboratory, and California Institute of Technology, Pasadena, CA, 2006.

Vaghjiani, G. L. and Ravishankara, A. R.: Absorption cross-sections of CH3OOH, H2O2, and D2O2 vapors between 210 nm and 365 nm at 297 K, J. Geophys. Res., 94, 3487–3492, 1989a.

Vaghjiani, G. L. and Ravishankara, A. R.: Kinetics and mechanism of OH reaction with CH3OOH, J. Phys. Chem., 93, 1948–1959, 1989b.

Vaghjiani, G. L. and Ravishankara, A. R.: Photodissociation of H2O2 and CH3OOH at 248 nm and 298 K: Quantum yields for OH, O($^3$\textitP) and H(2\textitS), J. Chem. Phys., 92, 996–1003, 1990.

Wennberg, P. O., Cohen, R. C., Hazen, N. L., Lapson, L. B., Allen, N. T., Hanisco, T. F., Oliver, J. F., Lanham, N. W., Demusz, J. N., and Anderson, J. G.: Aircraft-borne, laser-induced fluorescence instrument for the in-situ detection of hydroxyl and hydroperoxyl radicals, Rev. Sci. Instrum., 65, 1858–1876, 1994.

Wu, S., Blake, G. A., Sun, Z. Y., and Ling, J. W.: Simple, high-performance type II beta-BaB2O4 optical parametric oscillator, Appl. Opt., 36, 5898–5901, 1997.