Carbon-centered radical addition and beta-scission reactions: modeling of activation energies and pre-exponential factors.
A consistent set of group additive values DeltaGAV degrees for 46 groups is derived, allowing the calculation of rate coefficients for hydrocarbon radical additions and beta-scission reactions. A database of 51 rate coefficients based on CBS-QB3 calculations with corrections for hindered internal rotation was used as training set. The results of this computational method agree well with experimentally observed rate coefficients with a mean factor of deviation of 3, as benchmarked on a set of nine reactions. The temperature dependence on the resulting DeltaGAV degrees s in the broad range of 300-1300 K is limited to +/-4.5 kJ mol(-1) on activation energies and to +/-0.4 on logA (A: pre-exponential factor) for 90 % of the groups. Validation of the DeltaGAV degrees s was performed for a test set of 13 reactions. In the absence of severe steric hindrance and resonance effects in the transition state, the rate coefficients predicted by group additivity are within a factor of 3 of the CBS-QB3 ab initio rate coefficients for more than 90 % of the reactions in the test set. It can thus be expected that in most cases the GA method performs even better than standard DFT calculations for which a deviation factor of 10 is generally considered to be acceptable.
Sabbe
Maarten K
MK
Laboratorium voor Chemische Technologie, Ghent University, Krijgslaan 281 S5, 9000 Gent, Belgium.
Reyniers
Marie-Françoise
MF
Van Speybroeck
Veronique
V
Waroquier
Michel
M
Marin
Guy B
GB
D002244:Carbon / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods*; D003198:Computer Simulation; D005609:Free Radicals; D007700:Kinetics; D008956:Models, Chemical; D008962:Models, Theoretical; D015394:Molecular Structure; D013696:Temperature; D013816:Thermodynamics
D005609:Free Radicals; D002244:Carbon