Photochemical production of odd nitrogen directly from O₂, N₂ principals: Atmospheric implications and related open issues

Abstract

[1] The present study examines the effects of atmospheric production of NO X directly from the O 2 and N 2 principals via the reaction of O 2 (B 3 S) with N 2 and a second process provisionally theorized as absorption of a photon with 190 l 204 nm by O 2 .N 2 collision complex. The NO X production from O 2 (B 3 S) is $12% of the production from the ''classical'' O( 1 D) + N 2 O reaction in the region of their maxima in altitude. The diurnally averaged vmr (volume mixing ratios) of both NO X and NO Y are enhanced similarly by 10 to 15% at the most. The NO X /NO Y ratio is therefore unaffected. The production of NO X from O 2 (B 3 S) compensates for the decrease in the classical production due to the recently discovered faster quenching of O( 1 D) by N 2 . In the O 2 -poor ancient atmosphere, when the solar UV in the Schumann-Runge bands penetrated much deeper into the denser lower atmosphere, the contribution of the NO X production from O 2 (B 3 S) may have been more pronounced than in the O 2 -rich present atmosphere. Below 22 km, NO X production from the second process far exceeds the classical production. Such a production would almost certainly lead to NO X and NO Y vmr exceeding their observed values and would call for an extensive rethinking of the atmospheric NO X budget. Because these implications of the two new NO X sources are quite serious, attention has been drawn to many, equally serious, open issues at the levels of both laboratory experiments and basic quantal processes that require further studies.

Resonant Inelastic Scattering Spectra of Free Molecules with Vibrational Resolution

“…These results may therefore be of importance in atmospheric photochemistry [23,24], concerning greenhouse gases and atmospheric thermal balance considerations. In particular, there are uncertainties in atmospheric modeling concerning the sources and sinks of NO and NO 2 [25,26], which play an important role, e.g., as catalysts in destruction of ozone.…”

Vibrational spectra of N2: An advanced undergraduate laboratory in atomic and molecular spectroscopy

“…For instance, the experiment described here uses molecular nitrogen, a predominant constituent of Earth's atmosphere, which plays a central role in auroras and airglows, 1 as well as in physical phenomena of environmental concern, 2 such as the photochemical formation of nitrogen oxides which catalyse the destruction of stratospheric ozone. 3 Also, the fact that the collisional properties of nitrogen are employed in glow discharge plasma nitriding-a technique used to improve the mechanical properties of materials, especially iron-based alloys 4 -is likely to raise the attention of students planning for careers in applied science and engineering. Hence, the importance of atomic, molecular, and optical physics in science education cannot be overemphasized.…”

Atmospheric production of nitrous oxide from excited ozone and its potentially important implications for global change studies

“…The generic model and the list of species and their reactions distributed with the model can be accessed at NCAR's Community Data Portal (Data are available at http://www.acd.ucar.edu/Models (click on the download link in SOCRATES row in the table)) after a simple registration. The generic model has been expanded to include advances in atmospheric chemistry since the time the SOCRATES development was frozen, as described in some detail by Prasad and Zipf [2004]. The expanded model has 192 reactions involving 53 species.…”

“…The expanded model has 192 reactions involving 53 species. For the present study, Prasad and Zipf 's [2004] implementation of SOCRATES was further elaborated by including atmospheric production of N 2 O from excited O 3 as discussed in section 2. Furthermore, the original scheme of calculating the O( 1 D) yield was replaced by the scheme recommended by Sander et al [2002] The “native” O 3 absorption cross sections and their temperature dependence have been updated on the basis of Malicet et al 's [1995] measurements as recommended by Sander et al [2002].…”