title: Kinetic modeling of hydrogen abstractions involving sulfur radicals.
abstract: One of the requisites for the development of detailed reaction networks is the availability of accurate kinetic data. Group additivity based models linking the Arrhenius parameters to structural characteristics of the transition state have proven to be a valuable tool to obtain those data. In this work, group additivity values are presented to allow a broad range of CH and SH hydrogen abstraction reactions by S radicals to be modeled. Rate coefficients in the temperature range from 300 to 1500 K are obtained by using the CBS-QB3 method in the high-pressure limit and are corrected for tunneling and anharmonicity of rotation about the transitional bond. A total of 149 reactions are studied. From these reactions, a total of 52 group additivity values and 35 resonance corrections are derived. The general applicability of the group additivity method is demonstrated for a test set containing 25 reactions. At 300 K, rate coefficients are on average reproduced within a factor of 2.8. The mean absolute deviations on the Arrhenius parameters are 2 kJ mol(-1) for the activation energy and 0.38 for log A in which A is the pre-exponential factor.
authors.affiliation: ANL Chemical Sciences and Engineering Division, 9700 South Cass Avenue, Argonne, IL, 60439 (USA).
authors.forename: Aäron G
authors.initials: AG
authors.lastname: Vandeputte
authors.forename: Marie-Françoise
authors.initials: MF
authors.lastname: Reyniers
authors.forename: Guy B
authors.initials: GB
authors.lastname: Marin
mesh_terms: D003198:Computer Simulation; D005609:Free Radicals / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D013455:Sulfur / Q000737:chemistry*
chemical_list: D005609:Free Radicals; D013455:Sulfur; D006859:Hydrogen
keywords: ab initio calculations; group additivity; hydrogen abstraction reactions; kinetic modeling; sulfur