Using Variable and Fixed Topological Indices for the Prediction of Reaction Rate Constants of Volatile Unsaturated Hydrocarbons with OH Radicals 英文参考文献.docVIP

Molecules 2004, 9, 1160-1176 molecules ISSN 1420-3049 Using Variable and Fixed Topological Indices for the Prediction of Reaction Rate Constants of Volatile Unsaturated Hydrocarbons with OH Radicals 1, Matev? Pompe *, Marjan Veber 1 , Milan Randi? and Alexandru T. Balaban 2 3 1 Faculty of Chemistry and Chemical Technology, University of Ljubljana, A?ker?eva 5, 1000 Ljubljana, Slovenia; Tel. ++386-1-2419-172, Fax ++386-1-2419-220 National Institute of Chemistry, Hajdrihova 19, 1000 Ljubljana, Slovenia Texas AM University at Galveston, 5007 Avenue U, Galveston, TX 77551, USA 2 3 * Author to whom correspondence should be addressed; e-mail: matevz.pompe@uni-lj.si Received: 5 August 2004; in revised form: 1 December 2004 / Accepted: 1 December 2004 / Published: 31 December 2004 Abstract: Volatile organic compounds (VOCs) play an important role in different photochemical processes in the troposphere. In order to predict their impact on ozone formation processes a detailed knowledge about their abundance in the atmosphere as well as their reaction rate constants is required. The QSPR models were developed for the prediction of reaction rate constants of volatile unsaturated hydrocarbons. The chemical structure was encoded by constitutional and topological indices. Multiple linear regression models using CODESSA software was developed with the RMSCV error of 0.119 log units. The chemical structure was encoded by six topological indices. Additionally, a regression model using a variable connectivity index was developed. It provided worse cross- validation results with an RMSCV error of 0.16 log units, but enabled a structural interpretation of the obtained model. We differentiated between three classes of carbon atoms: sp -hybridized, non-allylic sp -hybridized and allylic sp -hy