%0 Journal Article %1 hlwoodcock:Rangel2004 %A Rangel, C. %A Navarrete, M. %A Corchado, J. C. %A Garcia, Espinosa J. %D 2004 %J JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM %K bibtex-import %N 3 %P 207--224 %T Mechanism and kinetics of the n-propyl bromide and OH reaction using integrated ab initio methods and variational transition-state theory %V 679 %X The reaction of the OH radical with n-propyl bromide, (CH3CH2CH2Br)-C-gamma-C-beta-C-alpha, was studied by integrated ab initio electronic 3 2 structure methods and variational transition-state theory with multidimensional tunneling. The mechanism of the reaction involves three channels, corresponding to hydrogen abstractions from three different carbon sites,alpha, beta, and gamma. While the attack on the alpha and beta carbons proceeds via hydrogen-bonded complexes in the entrance and exit channels, the reaction on the gamma carbon proceeds directly without intermediate complexes. For each hydrogen abstraction reaction, all the stationary points (reactants, products, saddle point, and complexes) were located and characterized. The respective intrinsic reaction paths were independently constructed using integrated ab initio methods, and the rate constants were independently calculated for the temperature range 200-2000 K using variational transition-state theory with multidimensional tunneling. The partial (alpha, beta, and gamma) and total rate constants show curvature of the Arrhenius plot in agreement with the experimental evidence, indicating the importance of the tunneling effect. Finally, the branching ratios were analysed, showing a change of the abstraction site from beta to gamma as temperature went up. (C) 2004 Elsevier B.V. All rights reserved.

@article{hlwoodcock:Rangel2004, abstract = {The reaction of the OH radical with n-propyl bromide, (CH3CH2CH2Br)-C-gamma-C-beta-C-alpha, was studied by integrated ab initio electronic 3 2 structure methods and variational transition-state theory with multidimensional tunneling. The mechanism of the reaction involves three channels, corresponding to hydrogen abstractions from three different carbon sites,alpha, beta, and gamma. While the attack on the alpha and beta carbons proceeds via hydrogen-bonded complexes in the entrance and exit channels, the reaction on the gamma carbon proceeds directly without intermediate complexes. For each hydrogen abstraction reaction, all the stationary points (reactants, products, saddle point, and complexes) were located and characterized. The respective intrinsic reaction paths were independently constructed using integrated ab initio methods, and the rate constants were independently calculated for the temperature range 200-2000 K using variational transition-state theory with multidimensional tunneling. The partial (alpha, beta, and gamma) and total rate constants show curvature of the Arrhenius plot in agreement with the experimental evidence, indicating the importance of the tunneling effect. Finally, the branching ratios were analysed, showing a change of the abstraction site from beta to gamma as temperature went up. (C) 2004 Elsevier B.V. All rights reserved.}, added-at = {2006-06-16T05:03:46.000+0200}, author = {Rangel, C. and Navarrete, M. and Corchado, J. C. and Garcia, Espinosa J.}, biburl = {https://www.bibsonomy.org/bibtex/24311fbcef0c581ec94c2cfd82eee4c60/hlwoodcock}, citeulike-article-id = {569950}, interhash = {8ce8d6ba20b6906c07108f3c529bb72e}, intrahash = {4311fbcef0c581ec94c2cfd82eee4c60}, journal = {JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM}, keywords = {bibtex-import}, number = 3, pages = {207--224}, priority = {2}, timestamp = {2006-06-16T05:03:46.000+0200}, title = {Mechanism and kinetics of the n-propyl bromide and OH reaction using integrated ab initio methods and variational transition-state theory}, volume = 679, year = 2004 }