Publication Details

Category Text Publication
Reference Category Journals
DOI 10.1007/s00214-009-0724-8
Document Shareable Link
Title (Primary) Predicting rate constants of OH-mediated indirect photolysis - advances for oxygenated compounds through a molecular orbital HF/6-31G** approach
Author Böhnhardt, A.; Kühne, R. ORCID logo ; Ebert, R.-U.; Schüürmann, G.
Source Titel Theoretical Chemistry Accounts
Year 2010
Department OEC
Volume 127
Issue 4
Page From 355
Page To 367
Language englisch
Keywords Atmospheric degradation; Hydroxyl radical; Rate constant; Molecular orbital model; MOOH method; Atkinson increment scheme; Consensus modelling
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.
Persistent UFZ Identifier https://www.ufz.de/index.php?en=20939&ufzPublicationIdentifier=9825
Böhnhardt, A., Kühne, R., Ebert, R.-U., Schüürmann, G. (2010):
Predicting rate constants of OH-mediated indirect photolysis - advances for oxygenated compounds through a molecular orbital HF/6-31G** approach
Theor. Chem. Acc. 127 (4), 355 - 367 10.1007/s00214-009-0724-8