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Title: Ab initio study of the reaction of NO{sub 3} with the OH radical

Abstract

The geometries of transition states and adducts have been optimized in MP2/6-311++G** calculations on both the singlet and triplet potential energy surfaces for the reaction of NO{sub 3} with OH. Single point calculations have been made at the G2MP2 level. Reaction is shown to be most likely to occur on the singlet surface via an adduct whose structure is very similar to that of pernitric acid, HO{sub 2}NO{sub 2}. The formation of the adduct is exothermic, and the calculated enthalpy of activation is {minus}8 kJ mol{sup {minus}1}. This adduct can dissociate to HO{sub 2} + NO{sub 2} directly or via rotational isomers. Reaction on the triplet surface is unlikely to be important because the formation of a triplet adduct has a large enthalpy of activation.

Authors:
;
Publication Date:
Research Org.:
Univ. of Warwick, Coventry (GB)
OSTI Identifier:
20003186
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory
Additional Journal Information:
Journal Volume: 103; Journal Issue: 33; Other Information: PBD: 19 Aug 1999
Country of Publication:
United States
Language:
English
Subject:
54 ENVIRONMENTAL SCIENCES; MATHEMATICAL MODELS; HYDROXYL RADICALS; NITROGEN OXIDES; RADICALS; ENTHALPY; ATMOSPHERIC CHEMISTRY; TROPOSPHERE

Citation Formats

Jitariu, L.C., and Hirst, D.M. Ab initio study of the reaction of NO{sub 3} with the OH radical. United States: N. p., 1999. Web. doi:10.1021/jp991709z.
Jitariu, L.C., & Hirst, D.M. Ab initio study of the reaction of NO{sub 3} with the OH radical. United States. doi:10.1021/jp991709z.
Jitariu, L.C., and Hirst, D.M. Thu . "Ab initio study of the reaction of NO{sub 3} with the OH radical". United States. doi:10.1021/jp991709z.
@article{osti_20003186,
title = {Ab initio study of the reaction of NO{sub 3} with the OH radical},
author = {Jitariu, L.C. and Hirst, D.M.},
abstractNote = {The geometries of transition states and adducts have been optimized in MP2/6-311++G** calculations on both the singlet and triplet potential energy surfaces for the reaction of NO{sub 3} with OH. Single point calculations have been made at the G2MP2 level. Reaction is shown to be most likely to occur on the singlet surface via an adduct whose structure is very similar to that of pernitric acid, HO{sub 2}NO{sub 2}. The formation of the adduct is exothermic, and the calculated enthalpy of activation is {minus}8 kJ mol{sup {minus}1}. This adduct can dissociate to HO{sub 2} + NO{sub 2} directly or via rotational isomers. Reaction on the triplet surface is unlikely to be important because the formation of a triplet adduct has a large enthalpy of activation.},
doi = {10.1021/jp991709z},
journal = {Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory},
number = 33,
volume = 103,
place = {United States},
year = {1999},
month = {8}
}