The phase space geometry underlying roaming reaction dynamics

Recent studies have found an unusual way of dissociation in formaldehyde. It can be characterized by a hydrogen atom that separates from the molecule, but instead of dissociating immediately it roams around the molecule for a considerable amount of time and extracts another hydrogen atom from the molecule prior to dissociation. This phenomenon has been coined roaming and has since been reported in the dissociation of a number of other molecules. In this paper we investigate roaming in Chesnavich's CH$_4^+$ model. During dissociation the free hydrogen must pass through three phase space bottleneck for the classical motion, that can be shown to exist due to unstable periodic orbits. None of these orbits is associated with saddle points of the potential energy surface and hence related to transition states in the usual sense. We explain how the intricate phase space geometry influences the shape and intersections of invariant manifolds that form separatrices, and establish the impact of these phase space structures on residence times and rotation numbers. Ultimately we use this knowledge to attribute the roaming phenomenon to particular heteroclinic intersections

Holonomy reduced dynamics of triatomic molecular systems

Whereas it is easy to reduce the translational symmetry of a molecular system by using, e.g., Jacobi coordinates the situation is much more involved for the rotational symmetry. In this paper we address the latter problem using {\it holonomy reduction}. We suggest that the configuration space may be considered as the reduced holonomy bundle with a connection induced by the mechanical connection. Using the fact that for the special case of the three-body problem, the holonomy group is SO(2) (as opposed to SO(3) like in systems with more than three bodies) we obtain a holonomy reduced configuration space of topology $\mathbf{R}_+^3 \times S^1$. The dynamics then takes place on the cotangent bundle over the holonomy reduced configuration space. On this phase space there is an $S^1$ symmetry action coming from the conserved reduced angular momentum which can be reduced using the standard symplectic reduction method. Using a theorem by Arnold it follows that the resulting symmetry reduced phase space is again a natural mechanical phase space, i.e. a cotangent bundle. This is different from what is obtained from the usual approach where symplectic reduction is used from the outset. This difference is discussed in some detail, and a connection between the reduced dynamics of a triatomic molecule and the motion of a charged particle in a magnetic field is established.Comment: 11 pages, submitted to J. Phys.

Quantum Monodromy in the Isotropic 3-Dimensional Harmonic Oscillator

The isotropic harmonic oscillator in dimension 3 separates in several different coordinate systems. Separating in a particular coordinate system defines a system of three commuting operators, one of which is the Hamiltonian. We show that the joint spectrum of the Hamilton operator, the $z$ component of the angular momentum, and a quartic integral obtained from separation in prolate spheroidal coordinates has quantum monodromy for sufficiently large energies. This means that one cannot globally assign quantum numbers to the joint spectrum. The effect can be classically explained by showing that the corresponding Liouville integrable system has a non-degenerate focus-focus point, and hence Hamiltonian monodromy.Comment: 15 pages, 8 figure

Non-uniqueness of phase shift in central scattering due to monodromy

Scattering at a central potential is completely characterized by the phase shifts which are the differences in phase between outgoing scattered and unscattered partial waves. In this letter it is shown that, for 2D scattering at a repulsive central potential, the phase shift cannot be uniquely defined due to a topological obstruction which is similar to monodromy in bound systems.Comment: to appear in PR

The Quantum Normal Form Approach to Reactive Scattering: The Cumulative Reaction Probability for Collinear Exchange Reactions

The quantum normal form approach to quantum transition state theory is used to compute the cumulative reaction probability for collinear exchange reactions. It is shown that for heavy atom systems like the nitrogen exchange reaction the quantum normal form approach gives excellent results and has major computational benefits over full reactive scattering approaches. For light atom systems like the hydrogen exchange reaction however the quantum normal approach is shown to give only poor results. This failure is attributed to the importance of tunnelling trajectories in light atom reactions that are not captured by the quantum normal form as indicated by the only very slow convergence of the quantum normal form for such systems.Comment: 8 pages, 4 figure

Phase space structures causing the reaction rate decrease in the collinear hydrogen exchange reaction

The collinear hydrogen exchange reaction is a paradigm system for understanding chemical reactions. It is the simplest imaginable atomic system with $2$ degrees of freedom modeling a chemical reaction, yet it exhibits behaviour that is still not well understood - the reaction rate decreases as a function of energy beyond a critical value. Using lobe dynamics we show how invariant manifolds of unstable periodic orbits guide trajectories in phase space. From the structure of the invariant manifolds we deduce that insufficient transfer of energy between the degrees of freedom causes a reaction rate decrease. In physical terms this corresponds to the free hydrogen atom repelling the whole molecule instead of only one atom from the molecule. We further derive upper and lower bounds of the reaction rate, which are desirable for practical reasons

Trace formula for a dielectric microdisk with a point scatterer

Two-dimensional dielectric microcavities are of widespread use in microoptics applications. Recently, a trace formula has been established for dielectric cavities which relates their resonance spectrum to the periodic rays inside the cavity. In the present paper we extend this trace formula to a dielectric disk with a small scatterer. This system has been introduced for microlaser applications, because it has long-lived resonances with strongly directional far field. We show that its resonance spectrum contains signatures not only of periodic rays, but also of diffractive rays that occur in Keller's geometrical theory of diffraction. We compare our results with those for a closed cavity with Dirichlet boundary conditions.Comment: 39 pages, 18 figures, pdflate