Collect. Czech. Chem. Commun. 1992, 57, 1173-1176

Distribution of the Lifetimes of Energized Polyatomic Molecules in the Harmonic Model

Milan Šolc

Institute of Inorganic Chemistry, Czechoslovak Academy of Sciences, 160 00 Prague 6


In the harmonic model of unimolecular reactions of polyatomic molecules, the decay of a molecule is defined as the passage of an internal coordinate (given by the superposition of normal vibrations) over a critical value. A numerical study of the behaviour of the superposition of harmonic vibrations with frequencies linearly independent in the field of rationals has shown that the distribution of time gaps between upzeros of the superposition over the critical value is not exponential. For molecules with uniform density of phases, however, the lifetime distribution is close to an exponential one.