Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions
 Author
 Maarten Sabbe (UGent) , Aäron Vandeputte (UGent) , MarieFrançoise Reyniers (UGent) , Michel Waroquier (UGent) and Guy Marin (UGent)
 Organization
 Abstract
 Resonance stabilization of the transition state is one of the key factors in modeling the kinetics of hydrogen abstraction reactions between hydrocarbons. A group additive model is developed which allows the prediction of rate coefficients for bimolecular hydrogen abstraction reactions over a broad range of hydrocarbons and hydrocarbon radicals between 300 and 1300 K. Group additive values for 50 groups are determined from rate coefficients determined using the high level CBSQB3 ab initio method, corrected for tunneling and the hindered internal rotation around the transitional bond. Resonance and hyperconjugative stabilization of the transition state is accounted for by introducing 4 corrections based on the structure of the reactive moiety of the transition state. The corrections, fitted to a set of 28 reactions, are temperatureindependent and reduce the mean absolute deviation on Ea to 0.7 kJ mol(1) and to 0.05 for log A. Tunneling contributions are accounted for by using a fourth order polynomial in the activation energy. Final validation for 19 reactions yields a mean factor of deviation between group additive prediction and ab initio calculation of 2.4 at 300 K and 1.8 at 1000 K. In comparison with 6 experimental rate coefficients (600719 K), the mean factor of deviation is less than 3.
 Keywords
 CENTERED RADICALADDITION, TRANSITIONSTATE THEORY, THEORETICAL PROCEDURES, REACTIONRATE PREDICTION, BETASCISSION REACTIONS, ABINITIO, STATISTICAL FACTORS, THERMALREACTION, ACTIVATIONENERGIES, THERMOCHEMICAL PROPERTIES
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Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU869755
 Chicago
 Sabbe, Maarten, Aäron Vandeputte, MarieFrançoise Reyniers, Michel Waroquier, and Guy Marin. 2010. “Modeling the Influence of Resonance Stabilization on the Kinetics of Hydrogen Abstractions.” Physical Chemistry Chemical Physics 12 (6): 1278–1298.
 APA
 Sabbe, Maarten, Vandeputte, A., Reyniers, M.F., Waroquier, M., & Marin, G. (2010). Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 12(6), 1278–1298.
 Vancouver
 1.Sabbe M, Vandeputte A, Reyniers MF, Waroquier M, Marin G. Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2010;12(6):1278–98.
 MLA
 Sabbe, Maarten, Aäron Vandeputte, MarieFrançoise Reyniers, et al. “Modeling the Influence of Resonance Stabilization on the Kinetics of Hydrogen Abstractions.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 12.6 (2010): 1278–1298. Print.
@article{869755, abstract = {Resonance stabilization of the transition state is one of the key factors in modeling the kinetics of hydrogen abstraction reactions between hydrocarbons. A group additive model is developed which allows the prediction of rate coefficients for bimolecular hydrogen abstraction reactions over a broad range of hydrocarbons and hydrocarbon radicals between 300 and 1300 K. Group additive values for 50 groups are determined from rate coefficients determined using the high level CBSQB3 ab initio method, corrected for tunneling and the hindered internal rotation around the transitional bond. Resonance and hyperconjugative stabilization of the transition state is accounted for by introducing 4 corrections based on the structure of the reactive moiety of the transition state. The corrections, fitted to a set of 28 reactions, are temperatureindependent and reduce the mean absolute deviation on Ea to 0.7 kJ mol(1) and to 0.05 for log A. Tunneling contributions are accounted for by using a fourth order polynomial in the activation energy. Final validation for 19 reactions yields a mean factor of deviation between group additive prediction and ab initio calculation of 2.4 at 300 K and 1.8 at 1000 K. In comparison with 6 experimental rate coefficients (600719 K), the mean factor of deviation is less than 3.}, author = {Sabbe, Maarten and Vandeputte, A{\"a}ron and Reyniers, MarieFran\c{c}oise and Waroquier, Michel and Marin, Guy}, issn = {14639076}, journal = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS}, keyword = {CENTERED RADICALADDITION,TRANSITIONSTATE THEORY,THEORETICAL PROCEDURES,REACTIONRATE PREDICTION,BETASCISSION REACTIONS,ABINITIO,STATISTICAL FACTORS,THERMALREACTION,ACTIVATIONENERGIES,THERMOCHEMICAL PROPERTIES}, language = {eng}, number = {6}, pages = {12781298}, title = {Modeling the influence of resonance stabilization on the kinetics of hydrogen abstractions}, url = {http://dx.doi.org/10.1039/b919479g}, volume = {12}, year = {2010}, }
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