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Theoretical Chemistry Accounts

, Volume 127, Issue 4, pp 355–367 | Cite as

Predicting rate constants of OH radical reactions with organic substances: advances for oxygenated organics through a molecular orbital HF/6-31G** approach

  • Anna Böhnhardt
  • Ralph Kühne
  • Ralf-Uwe Ebert
  • Gerrit SchüürmannEmail author
Regular Article

Abstract

The molecular orbital OH (MOOH) approach is a perturbational quantum chemical method to predict rate constants of OH radical reactions with organic compounds. Going beyond previous AM1 parameterizations, a first ab initio implementation employing the HF/6-31G** level of calculation has been developed. For a set of 799 organic compounds with experimental rate constants, k OH, varying over more than six orders of magnitude, the new MOOH-HF method is superior to both MOOH-AM1 and Atkinson’s increment scheme, yielding a predictive squared correlation coefficient (q 2) of 0.95 and a root-mean-square error of 0.29 log units. For oxygenated compounds, MOOH-HF shows significant improvements over MOOH-AM1, which holds in particular for aldehydes and ketones. The discussion includes detailed comparative analyses of the model performances for individual compound classes.

Keywords

Atmospheric degradation Hydroxyl radical Rate constant Molecular orbital model MOOH method Atkinson increment scheme Consensus modelling 

Notes

Acknowledgments

The authors thank Dr. Andreas Klamt for making available the original MOOH source code. This research was financially supported by the European Commission through the projects NOMIRACLE (FP6 contract no. 003956) and OSIRIS (contract no. 037017).

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Copyright information

© Springer-Verlag 2010

Authors and Affiliations

  • Anna Böhnhardt
    • 1
    • 2
  • Ralph Kühne
    • 1
  • Ralf-Uwe Ebert
    • 1
  • Gerrit Schüürmann
    • 1
    • 2
    Email author
  1. 1.UFZ Department of Ecological ChemistryHelmholtz Centre for Environmental ResearchLeipzigGermany
  2. 2.Institute for Organic ChemistryTechnical University Bergakademie FreibergFreibergGermany

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