Lc. Jitariu et al., Unimolecular decomposition of the n-C3H7 radical. Direct dynamics calculation of the thermal rate constant, PHYS CHEM P, 3(12), 2001, pp. 2459-2466
Rate constants for the unimolecular decomposition of the n-propyl radical h
ave been calculated over the temperature range 250-2600 K, using variationa
l transition state theory (VTST) with rectilinear coordinates and transmiss
ion coefficients calculated by the zero-curvature (ZCT) and small-curvature
(SCT) tunneling approximations. Single-level calculations, based upon AM1
potential energy surfaces using AM1 parameters optimized on the basis of hi
gh level ab initio calculations (UMP2/6-311++G**) for this reaction, yield
rate constants in good agreement with experiment. Dual-level direct dynamic
s calculations which explicitly include the results of the ab initio calcul
ations, yield rate constants within a factor of 2 of the experimental data.
Results of using the new AM1 parameters for the decomposition of n-C5H11 a
re encouraging.