An ab initio transition state theory based procedure for accurately predicting the combination kinetics of two alkyl radicals is described. This procedure employs direct evaluations of the orientation dependent interaction energies at the CASPT2/cc-pvdz level within variable reaction coordinate transition state theory (VRC-TST). One-dimensional corrections to these energies are obtained from CASþ1þ2/aug-cc-pvtz calculations for CH3 þ CH3 along its combination reaction path. Direct CASþ1þ2/aug-cc-pvtz calculations demonstrate that, at least for the purpose of predicting the kinetics, the corrected CASPT2/cc-pvdz potential energy surface is an accurate approximation to the CASþ1þ2/aug-cc-pvtz surface. Furthermore, direct trajectory simulations, performed at the B3LYP/6-31G * level, indicate that there is little local recrossing of the optimal VRC transition state dividing surface. The corrected CASPT2/cc-pvdz potential is employed in obtaining direct VRC-TST kinetic predictions for the self and cross combinations of methyl, ethyl, iso-propyl, and tert-butyl radicals. Comparisons with experiment suggest that the present dynamically corrected VRC-TST approach provides quantitatively accurate predictions for the capture rate. Each additional methyl substituent adjacent to a radical site is found to reduce the rate coefficient by about a factor of two. In each instance, the rate coefficients are predicted to decrease quite substantially with increasing temperature, with the more sterically hindered reactants having a more rapid decrease. The simple geometric mean rule, relating the capture rate for the cross reaction to those for the self-reactions, is in remarkably good agreement with the more detailed predictions. With suitable generalizations the present approach should be applicable to a wide array of radical–radical combination reactions. 1.