Potential energy Diagram and Kinetic Parameters

1 High-Pressure Limits Factor (4oo) and Rate Constant k Determination 

The reactions for which thermochemical properties of transition states are calculated by ab initio or Density Functional Theory methods, oo s are fit by three parameters n, and over the temperature range of 298-2000 K, kao = A T)T exp( a/ 7). Entropy differences between the reactants and transition state structures are used to determine the pre-exponential factor. A, via canonical Transition State Theory [197]. 

Corrections for H-atom tunnelling are applied for the intramolecular hydrogen atom transfer reactions of the transition state structures using Wigner 2 order correction [198]. In this study the rate constants of three of our calculated transition states, TSPH OOH and TSC C4DO and TSCDCC DO identified in Table 6.3, are corrected for H-atom tunnelling. 

Unimolecular dissociation and isomerization reactions of chemically activated and stabilized adduct resulting from addition or combination reactions are analyzed by constructing potential energy diagrams. Some high-pressure rate constants for each channel are obtained from literature or referenced estimation techniques. Kinetics parameters for uni-molecular and bimolecular (chemical activation) reactions are then calculated using multifrequency QRRK analysis iork(E) [199, 200, 63]. 

1 Important initial Reaction Paths and Transition States of the Chemically Activated PhOO Adduct 

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