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Multiscale Ice Fluidity in NO_x Photodesorption from Frozen Nitrate Solutions

Boxe, C. S. and Colussi, A. J. and Hoffmann, M. R. and Tan, D. and Mastromarino, J. and Case, A. T. and Sandholm, S. T. and Davis, D. D. (2003) Multiscale Ice Fluidity in NO_x Photodesorption from Frozen Nitrate Solutions. Journal of Physical Chemistry A, 107 (51). pp. 11409-11413. ISSN 1089-5639. doi:10.1021/jp0349536.

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The temperature-programmed desorption of nitric oxide, NO, and nitrogen dioxide, NO_2, during the 302 nm photolysis of KNO_3-doped, spray-frozen ice layers was investigated using two-photon laser-induced NO_x fluorescence detection in the range −35 ≤ T/°C ≤ 0. Upon applying steady illumination and a 0.67 °C min^(-1) heating ramp, frozen KNO_3 solutions begin to evolve NO_2 at increasing rates, while NO emissions plateau soon after until, at ∼ −8 ° C, both species surge abruptly. Although the primary photoproduct NO_2 avoids geminate recombination by escaping from a permeable molecular cage throughout, NO_2(g) levels are controlled by desorption from the outermost ice layers rather than by NO_3^- photolysis rates. The NO_x accumulated in the deeper layers bursts when the solid undergoes a sintering transition following the onset of surface melting at −10 °C. Since elementary photochemical events occur in a communal fluid phase of molecular dimensions at temperatures far below the KNO_3/H_2O eutectic (T_(eutectic) = − 2.88 °C), we infer that doped polycrystalline ice contains operationally distinguishable fluid phases of low dimensionality over various length scales and temperature ranges.

Item Type:Article
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Colussi, A. J.0000-0002-3400-4101
Hoffmann, M. R.0000-0001-6495-1946
Additional Information:© 2003 American Chemical Society. Received: April 9, 2003; In Final Form: October 3, 2003.
Issue or Number:51
Record Number:CaltechAUTHORS:20150623-154756299
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Official Citation:Multiscale Ice Fluidity in NOx Photodesorption from Frozen Nitrate Solutions C. S. Boxe, A. J. Colussi, M. R. Hoffmann, D. Tan, J. Mastromarino, A. T. Case, S. T. Sandholm, and D. D. Davis The Journal of Physical Chemistry A 2003 107 (51), 11409-11413 DOI: 10.1021/jp0349536
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:58478
Deposited By: George Porter
Deposited On:28 Jul 2015 21:00
Last Modified:10 Nov 2021 22:05

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