Issue 16, 2000

Isotope effect on unimolecular dissociation of MuO2: a classical trajectory study

Abstract

Classical trajectory calculations have been carried out for the unimolecular dissociation of both rotating and non-rotating MuO2 (Mu=muonium hydrogen isotope analog) over the total internal energy range 55.432⩽Etot/kcal mol−1⩽72.282. For the non-rotating system, various distributions of energy among the three vibrational normal modes have been considered, while in the rotating case, 5 kcal mol−1 of rotational energy has been associated to the principal axis of inertia in four different ways. The calculations employed the realistic DMBE IV potential energy surface for the electronic ground state of HO2 , which allows an assessment of the isotope effects by comparison with our previous work (J. Phys. Chem. A, 1997, 101, 5168). Unlike previous results for HO2 , the reaction MuO2→Mu+O2 shows more than one decay regime even in the absence of rotation. This non-RRKM-type behavior appears to be intrinsic, and has been attributed to the large difference between the Mu–O2 vibrational frequency and those of the other two modes. Inclusion of rotation leads also to deviations from RRKM-type behavior, especially when rotational excitation is associated to the adiabatic Ly and Lz axes of inertia. The role of the MuO2 and HO2 zero-point energies is also analysed.

Article information

Article type
Paper
Submitted
17 Jan 2000
Accepted
20 Jun 2000
First published
21 Jul 2000

Phys. Chem. Chem. Phys., 2000,2, 3583-3589

Isotope effect on unimolecular dissociation of MuO2: a classical trajectory study

J. M. C. Marques, J. L. Llanio-Trujillo and A. J. C. Varandas, Phys. Chem. Chem. Phys., 2000, 2, 3583 DOI: 10.1039/B000469N

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