Journal of Chemical Physics, Vol.101, No.6, 4790-4802, 1994
Simplification of the Transition-State Concept in Reactive Island Theory - Application to the HCN-Reversible-Arrow-Cnh Isomerization
The reactive island (RI) theory of chemical reaction rates is modified so that a precise knowledge of the transition state is not required. This revised form of the theory is applied to a realistic two (J=0) and three degree of freedom model (J not equal 0) of the isomerization HCN reversible arrow CNH. The detailed reaction dynamics is examined and understood in terms of the cylindrical manifolds embedded in the molecular phase space. Of special interest we find a T-shaped conformer in addition to the HCN and CNH moieties at J=0. Rates of unimolecular decay are examined by numerical simulation and theory. Good agreement is found between theory and simulation except for a case where a substantial amount of phase space is consumed by regular motion. In all cases studied, the theory is a significant improvement over the Rice-Ramsperger-Kassel-Marcus (RRKM) theory, which is up to three orders of magnitude too large.
Keywords:PHASE-SPACE BOTTLENECKS;UNIMOLECULAR CONFORMATIONAL ISOMERIZATION;CHEMICAL-REACTION DYNAMICS;POTENTIAL SURFACE;VARIATIONAL CALCULATIONS;ENERGY REDISTRIBUTION;CYLINDRICAL MANIFOLDS;VIBRATIONAL-STATES;HCN/HNC;HNC