Coriolis coupling as a source of non-RRKM effects in ozone molecule: Lifetime statistics of vibrationally excited ozone molecules

Abstract

A theory that describes the non-RRKM ͑non-Rice-Ramsperger-Kassel-Marcus͒ effects in the lifetime statistics of activated ozone molecules is derived. The non-RRKM effects are shown to originate due to the diffusive energy exchange between vibrational and rotational degrees of freedom in ozone molecule. The lifetime statistics is found to be intramolecular diffusion controlled at long times. The theoretical results are in good agreement with the direct MD simulations of lifetime statistics.

Coriolis coupling as a source of non-RRKM effects in triatomic near-symmetric top molecules: Diffusive intramolecular energy exchange between rotational and vibrational degrees of freedom

“…During this time ͑diffusion controlled time͒ ozone molecule is likely to undergo a deactivating collision. Thus, the process of ozone formation depends on the Coriolis-driven diffusion of K. In a subsequent paper 18 we show that the observed diffusive energy exchange between the rotational and vibrational degrees of freedom in ozone molecule explains the nonstatistical distribution of lifetimes of the activated ozone molecules observed in Refs. 9 and 10.…”

“…3, the diffusion of K is expected to depend on the symmetry of ozone molecule as well. In a following paper 18 we show that the diffusion of K-component of angular momentum defines the statistics of lifetimes of excited ozone molecules. However, no significant effect of symmetry on the diffusion of K was observed, similar to the classical numerical results for different isotopomers of ozone shown in Ref.…”

“…The mechanism of the K-diffusion controlled dissociation of ozone molecules discussed in the present section also agrees well with the direct numerical simulation for the statistics of lifetimes of vibrationally excited ozone molecules. 18 …”

Theory of mass-independent fractionation of isotopes, phase space accessibility, and a role of isotopic symmetry

“…These frequencies vary with the classical mechanical phase space action variables and so each periodic orbit in phase space is encircled by quasi-periodic orbits, the whole constituting a classical resonance. In Chirikov theory (20) the overlapping of classical resonances leads to classical chaotic and hence statistical behavior (more bifurcations); Coriolis effects have also been implicated in slow intramolecular energy exchange (5,38,39), contributing to some deviation from statistical theory. The overall deviation from statistical theory for the recombination rate constant was (N. Ghaderi) less than a factor of 2.…”

On stabilization of scattering resonances in recombination reaction that forms ozone

“…They hypothesized that this nonstatistical effect may occur during the stabilization step of the recombination reaction, process (2), and argued that in symmetric molecules the density of dynamically active states may be lower, compared to asymmetric molecules. 15 Marcus also discussed several other alternative sources of η-effect, such as spin-orbit coupling 18 in the asymptotic region of the potential energy surface (PES), resonance coupling effect, 19 chaotic behavior of trajectories at high energies 18 and, more recently, the Coriolis coupling effect 20,21 that may be different in symmetric and asymmetric isotopomers of O 3 . While all these are legitimate hypotheses, no convincing proof has ever been shown for any of these.…”