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.
; 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 |
|