A theoretical ab initio study on the H2NO + O3 reaction

✍ Scribed by Julio Peiró–García; Víctor M. Ramírez–Ramírez; Ignacio Nebot–Gil

• Publisher: John Wiley and Sons
• Year: 2003
• Tongue: English
• Weight: 202 KB
• Volume: 24
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.10287

✦ Synopsis

Abstract

The deviation of the NH~2~ pseudo‐first‐order decay Arrhenius plots of the NH~2~ + O~3~ reaction at high ozone pressures measured by experimentalists, has been attributed to the regeneration of NH~2~ radicals due to the subsequent reactions of the products of this reaction with ozone. Although these products have not yet been characterized experimentally, the radical H~2~NO has been postulated, because it can regenerate NH~2~ radicals through the reactions: H~2~NO + O~3~ → NH~2~ + O~2~ and H~2~NO + O~3~ → HNO + OH + O~2~. With the purpose of providing a reasonable explanation from a theoretical point of view to the kinetic observed behaviour of the NH~2~ + O~3~ system, we have carried ab initio electronic structure calculations on both H~2~NO + O~3~ possible reactions. The results obtained in this article, however, predict that of both reactions proposed, only the H~2~NO + O~3~ → NH~2~ + O~2~ reaction would regenerate indeed NH~2~ radicals, explaining thus the deviation of the NH~2~ pseudo‐first‐order decay observed experimentally. © 2003 Wiley Periodicals, Inc. J Comput Chem 24: 1321–1328, 2003