Abstract
The radicals obtained from the additions of alkenes with the hydroxyl radical (•OH) and from the H-atom abstraction of aromatics initiated by the OH radical were, respectively, used to calculate quantum chemical descriptors for quantitative structure-activity relationship (QSAR) models for the rate constants (k OH) of the reactions of alkenes and aromatics with the OH radical in the troposphere. Quantum chemical descriptors used as the inputs for the support vector machine (SVM) models were calculated with the unrestricted hybrid density functional theory (DFT), at the UB3LYP level of theory with 6-31G(d) basis set. The average root-mean-square errors (RMSE) for 70 alkenes and 80 aromatics are 0.101 and 0.236 log units, respectively, which show the SVM models in this paper are accuracy and acceptable. To develop QSAR models for k OH, calculating quantum chemical descriptors from the reaction radicals of alkenes and from aromatic radicals formed by the H-atom abstraction is feasible.
Similar content being viewed by others
References
Atkinson, R.: Gas-phase tropospheric chemistry of organic compounds: A review. Atmos. Environ. 41, S200–S240 (2007)
Böhnhardt, A., Kühne, R., Ebert, R.-U., Schüürmann, G.: Indirect photolysis of organic compounds: prediction of OH reaction rate constants through molecular orbital calculations. J. Phys. Chem. A 112, 11391–11399 (2008)
Cortes, C., Vapnik, V.: Support-vector networks. Mach. Learn. 20, 273–297 (1995)
de Oliveira, D.B., Gaudio, A.C.: BuildQSAR: a new computer program for QSAR analysis. Quant. Struct.-Act. Relat. 19, 599–601 (2000)
Fatemi, M.H., Baher, E.: Quantitative structure–property relationship modelling of the degradability rate constant of alkenes by OH radicals in atmosphere. SAR QSAR Environ. Res. 20, 77–90 (2009)
Gramatica, P., Pilutti, P., Papa, E.: A tool for the assessment of VOC degradability by tropospheric oxidants starting from chemical structure. Atmos. Environ. 38, 6167–6175 (2004a)
Gramatica, P., Pilutti, P., Papa, E.: Validated QSAR prediction of OH tropospheric degradation of VOCs: splitting into training-test sets and consensus modeling. J. Chem. Inf. Comput. Sci. 44, 1794–1802 (2004b)
Huang, X.W., Yu, X.L., Yi, B., Zhang, S.H.: Prediction of rate constants for the reactions of alkanes with the hydroxyl radicals. J. Atmos. Chem. 69, 201–213 (2012)
Karelson, M., Lobanov, V.S., Katritzky, A.R.: Quantum-chemical descriptors in QSAR/QSPR studies. Chem. Rev. 96, 1027–1043 (1996)
Klotz, B., Sørensen, S., Barnes, I., Becker, K.H., Etzkorn, T., Volkamer, R., Platt, U., Wirtz, K., Martín-Reviejo, M.: Atmospheric oxidation of toluene in a large-volume outdoor photoreactor: In situ determination of ring-retaining product yields. J. Phys. Chem. A 102, 10289–10299 (1998)
Lei, W., Derecskei-Kovacs, A., Zhang, R.: Ab initio study of OH addition reaction to isoprene. J. Chem. Phys. 113, 5354–5360 (2000a)
Lei, W., Zhang, R., McGivern, W.S., Derecskei-Kovacs, A., North, S.W.: Theoretical study of isomeric branching in the isoprene–OH reaction: implications to final product yields in isoprene oxidation. Chem. Phys. Lett. 326, 109–114 (2000b)
Lei, W., Zhang, R., McGivern, W.S., Derecskei-Kovacs, A., North, S.W.: Theoretical study of OH − O2 − isoprene peroxy radicals. J. Phys. Chem. A 105, 471–477 (2001)
Luan, F., Zhang, R.S., Yao, X.J., Liu, M.C., Hu, Z.D., Fan, B.T.: Support vector machine-based QSPR for the prediction of van der waals constants. QSAR Comb. Sci. 24, 227–239 (2005)
Öberg, T.: A QSAR for the hydroxyl radical reaction rate constant: validation, domain of application, and prediction. Atmos. Environ. 39, 2189–2200 (2005)
Roy, P.P., Kovarich, S., Gramatica, P.: QSAR model reproducibility and applicability: a case study of rate constants of hHydroxyl radical reaction models applied to polybrominated diphenyl ethers and (benzo-)triazoles. J. Comput. Chem. 32, 2386–2396 (2011)
Sabljic, A., Peijnenburg, W.: Modeling lifetime and degradability of organic compounds in air, soil, and water systems (IUPAC Technical Report). Pure Appl. Chem. 73, 1331–1348 (2001)
Seinfeld, J. H., Pandis, S. N.: Atmospheric Chemistry and Physics–From Air Pollution to Climate Change, 2nd edn. Wiley (2006)
Sewell, M.: WinSVM software. Retrieved from http://www.cs.ucl.ac.uk/staff/M.Sewell/winsvm (2005)
Wang, Y.N., Chen, J.W., Li, X.H., Wang, B., Cai, X.Y., Huang, L.P.: Predicting rate constants of hydroxyl radical reactions with organic pollutants: algorithm, validation, applicability domain, and mechanistic interpretation. Atmos. Environ. 43, 1131–1135 (2009)
Xu, Y.Y., Yu, X.L., Zhang, S.H.: QSAR models of reaction rate constants of alkenes with ozone and hydroxyl radical. J. Braz. Chem. Soc. 24, 1781–1788 (2013)
Yu, X.L., Yi, B., Wang, X.Y., Chen, J.F.: Predicting reaction rate constants of ozone with organic compounds from radical structures. Atmos. Environ. 51, 124–130 (2012)
Acknowledgments
The project was supported by the National Natural Science Foundation of China (No. 21472040), Hunan province science and technology plan project in 2015 for Xinliang Yu, and the Scientific Research Fund of Hunan Provincial Education Department (Nos. 13A133; 13C302).
Author information
Authors and Affiliations
Corresponding authors
Rights and permissions
About this article
Cite this article
Yu, X., Deng, J., Yi, B. et al. Predicting rate constants of hydroxyl radical reactions with alkenes and aromatics. J Atmos Chem 72, 129–141 (2015). https://doi.org/10.1007/s10874-015-9310-8
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10874-015-9310-8