Potential Nonstatistical Effects on the Unimolecular Decomposition of H₂O₂

An attempt is made to evaluate the nonstatistical effects in the thermal decomposition of hydrogen peroxide (H₂O₂). Previous experimental studies on this reaction reported an unusual pressure dependence of the rate constant indicating broader falloff behavior than expected from conventional theory. In this work, the possibility that the rate constant is affected by nonstatistical effects is investigated based on classical trajectory calculations on the global potential energy surfaces of H₂O₂ and H₂O₂ + Ar. The emphasis is on the intramolecular energy redistribution from the K-rotor, that is, the external rotor for rotation around the principal axis of least moment of inertia. The calculations for the H₂O₂ molecules excited above the dissociation threshold suggest that the energy redistribution from the torsion and K-rotor to vibrations can be competitive with dissociation. In particular, the slow redistribution of the energy associated with the K-rotor significantly affects the dissociation rate. The successive trajectory calculations for collisions of H₂O₂ with Ar show that the energy associated with the K-rotor can be collisionally transferred more efficiently than the vibrational energy. On the basis of these results and several assumptions, a simple model is proposed to account for the nonstatistical effects on the pressure-dependent thermal rate constants. The model predicts significant broadening of the falloff curve of the rate constants but still cannot fully explain the experimental data.