Reaction class transition state theory: Hydrogen abstraction reactions by hydrogen atoms as test cases

We present a new method called Reaction Class Transition State Theory (RC-T ST) for estimating thermal rate constants of a large number of reactions in a class. This method is based on the transition state theory framework wit hin the reaction class approach. Thermal rate constants of a given reaction in a class relative to those of its principal reaction can be efficiently predicted from only its differential barrier height and reaction energy. Su ch requirements are much less than what is needed by the conventional TST m ethod. Furthermore, we have shown that the differential energetic informati on can be calculated at a relatively low level of theory. No frequency calc ulation beyond those of the principal reaction is required for this theory. The new theory was applied to a number of hydrogen abstraction reactions. Excellent agreement with experimental data shows that the RC-TST method can be very useful in design of fundamental kinetic models of complex reaction s. (C) 2000 American Institute of Physics. [S0021-9606(00)01133-8].