Dynamical tunneling in molecules: Quantum routes to energy flow

Dynamical tunneling, introduced in the molecular context, is more than two decades old and refers to phenomena that are classically forbidden but allowed by quantum mechanics. On the other hand the phenomenon of intramolecular vibrational energy redistribution (IVR) has occupied a central place in the field of chemical physics for a much longer period of time. Although the two phenomena seem to be unrelated several studies indicate that dynamical tunneling, in terms of its mechanism and timescales, can have important implications for IVR. Examples include the observation of local mode doublets, clustering of rotational energy levels, and extremely narrow vibrational features in high resolution molecular spectra. Both the phenomena are strongly influenced by the nature of the underlying classical phase space. This work reviews the current state of understanding of dynamical tunneling from the phase space perspective and the consequences for intramolecular vibrational energy flow in polyatomic molecules.Comment: 37 pages and 23 figures (low resolution); Int. Rev. Phys. Chem. (Review to appear in Oct. 2007

Effective Hamiltonian and unitarity of the S matrix

The properties of open quantum systems are described well by an effective Hamiltonian ${\cal H}$ that consists of two parts: the Hamiltonian $H$ of the closed system with discrete eigenstates and the coupling matrix $W$ between discrete states and continuum. The eigenvalues of ${\cal H}$ determine the poles of the $S$ matrix. The coupling matrix elements $\tilde W_k^{cc'}$ between the eigenstates $k$ of ${\cal H}$ and the continuum may be very different from the coupling matrix elements $W_k^{cc'}$ between the eigenstates of $H$ and the continuum. Due to the unitarity of the $S$ matrix, the \TW_k^{cc'} depend on energy in a non-trivial manner, that conflicts with the assumptions of some approaches to reactions in the overlapping regime. Explicit expressions for the wave functions of the resonance states and for their phases in the neighbourhood of, respectively, avoided level crossings in the complex plane and double poles of the $S$ matrix are given.Comment: 17 pages, 7 figure

A Quantum Mechanical Study of Ozone Isotope Effect

The rate of ozone recombination, O2 + O + M → O3 + M, is strongly sensitive to the masses of the participating oxygen isotopes—the effect ultimately leading to the unconventional fractionations of ozone isotopomers in the Earth atmosphere. The mass dependence for asymmetric molecules is reconstructed, within the strong collision approximation, from the partial widths of narrow resonances of O3 and demonstrated to stem from the contributions of highly rotationally excited ozones