Journal of Physical Chemistry A, Vol.103, No.16, 3020-3030, 1999
RRKM theory beyond the separable harmonic approximation: The HCO2 -> H+CO2 unimolecular decomposition
We report variational calculations of a large number of vibrational states of HCO2 and the H ... CO2 transition state for J = 0 using the code MULTIMODE and a realistic six degree-of-freedom potential energy surface. State-dependent rotational constants for both species are calculated for the same sets of vibrational states from exact rotation/vibration calculations for J = 1. The results of these variational calculations are used to obtain RRKM rate constants for the decomposition of HCO2 to form H + CO2. Comparison is made between these nonseparable RRKM results and those obtained from a standard, separable harmonic oscillator/rigid rotor evaluation of the RRKM rate constant expression. Significant differences between the nonseparable and separable results are found.
Keywords:SELF-CONSISTENT-FIELD;TRANSITION-STATE THEORY;CUMULATIVEREACTION PROBABILITIES;ANHARMONIC-FORCE FIELD;MANY-MODESYSTEMS;POLYATOMIC-MOLECULES;VIBRATIONAL ENERGIES;RATECONSTANTS;QUANTUM;ROTATION