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Zeitschrift für Physikalische Chemie

International journal of research in physical chemistry and chemical physics

Editor-in-Chief: Rademann, Klaus


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2196-7156
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Volume 227, Issue 9-11

Issues

A Theoretical Study of the X-Abstraction Reactions (X = H, Br, or I) from CH2IBr by OH Radicals: Implications for Atmospheric Chemistry

Martin Šulka
  • Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina CH1, 84215 Bratislava, Slovakia
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Katarína Šulková
  • Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina CH1, 84215 Bratislava, Slovakia
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Florent Louis
  • Corresponding author
  • PhysicoChimie des Processus de Combustion et de l'Atmosphère (PC2A), UMR 8522 CNRS/Lille1, Université Lille 1 Sciences et Technologies, Cité Scientifique, Bât. C11/C5, 59655 Villeneuve d'Ascq Cedex, France
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  • De Gruyter OnlineGoogle Scholar
/ Pavel Neogrády
  • Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina CH1, 84215 Bratislava, Slovakia
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  • De Gruyter OnlineGoogle Scholar
/ Ivan Černušák
  • Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina CH1, 84215 Bratislava, Slovakia
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  • De Gruyter OnlineGoogle Scholar
Published Online: 2013-06-10 | DOI: https://doi.org/10.1524/zpch.2013.0391

Abstract

We report the calculation of the H-, Br-, and I-abstraction channels in the reaction of OH radicals with bromoiodomethane CH2IBr. The resulting energy profiles at 0 K were obtained by high-level all-electron ab initio methods including valence and core-valence electron correlation, scalar relativistic effects, spin-orbit coupling, spin-adaptation, vibration contributions, and tunneling corrections. In terms of activation enthalpy at 0 K, the energy profile for the Br-abstraction showed that this reaction pathway is not energetically favorable in contrast to the two other channels (H- and I-abstractions), which are competitive. The H-abstraction was strongly exothermic (−84.4 kJ mol1), while the I-abstraction was modestly endothermic (16.5 kJ mol1). On the basis of our calculations, we predicted the rate constants using canonical transition state theory over the temperature range 250–500K for each abstraction pathway. The overall rate constant at 298 K was estimated to be 3.40 × 10−14 and 4.22 × 10−14 cm3 molecule1 s1 for complex and direct abstraction mechanisms, respectively. In addition, the overall rate constant computed at 277 K was used in the estimation of the atmospheric lifetime for CH2IBr. On the basis of our theoretical calculations, the atmospheric lifetime for the OH removal process is predicted to be close to 1 year. In terms of atmospheric lifetime, the OH reaction is not competitive with the Cl reaction and photolysis processes.

Keywords: Bromoiodomethane; Hydroxyl Radicals; Potential Energy Profile; Kinetic Parameters; Atmospheric Lifetime

About the article

Received: 2013-02-13

Published Online: 2013-06-10

Published in Print: 2013-11-01


Citation Information: Zeitschrift für Physikalische Chemie, Volume 227, Issue 9-11, Pages 1337–1359, ISSN (Online) 2196-7156, ISSN (Print) 0942-9352, DOI: https://doi.org/10.1524/zpch.2013.0391.

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© 2013 by Walter de Gruyter Berlin Boston. This article is distributed under the terms of the Creative Commons Attribution Non-Commercial License, which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited. BY-NC-ND 4.0

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