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Near-IR photodissociation of peroxy acetyl nitrate

  • Author(s): Nizkorodov, S. A.
  • Crounse, J. D.
  • Fry, J. L.
  • Roehl, C. M.
  • Wennberg, P. O.
  • et al.
Creative Commons 'BY' version 4.0 license
Abstract

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 (J(near-IR) approximate to 3 x 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 J(near-IR) approximate to 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 freedom in PAN, which make 4 nu(CH) the lowest overtone excitation with a high photodissociation yield (as opposed to 2 nu(OH) in PNA).

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