We develop Wigner's approach to a dynamical transition state theory in phase space in both the classical and quantum mechanical settings. The key to our development is the construction of a normal form for describing the dynamics in the neighborhood of a specific type of saddle point that governs the evolution from reactants to products in high dimensional systems. In the classical case this is the standard Poincaré-Birkhoff normal form. In the quantum case we develop a normal form based on the Weyl calculus and an explicit algorithm for computing this quantum normal form. The classical normal form allows us to discover and compute the phase space structures that govern classical reaction dynamics. From this knowledge we are able to provide a direct construction of an energy dependent dividing surface in phase space having the properties that trajectories do not locally "re-cross" the surface and the directional flux across the surface is minimal. Using this, we are able to give a formula for the directional flux through the dividing surface that goes beyond the harmonic approximation. We relate this construction to the fluxflux autocorrelation function which is a standard ingredient in the expression for the reaction rate in the chemistry community. We also give a classical mechanical interpretation of the activated complex as a normally hyperbolic invariant manifold (NHIM), and further describe the structure of the NHIM. The quantum normal form provides us with an efficient algorithm to compute quantum reaction rates and we relate this algorithm to the quantum version of the flux-flux autocorrelation function formalism. The significance of the classical phase space structures for the quantum mechanics of reactions is elucidated by studying the phase space distribution of scattering states. The quantum normal form also provides an efficient way of computing Gamov-Siegert resonances. We relate these resonances to the lifetimes of the quantum activated complex. We consider several one, two, and three degree-of-freedom systems and show explicitly how calculations of the above quantities can be carried out. Our theoretical framework is valid for Hamiltonian systems with an arbitrary number of degrees of freedom and we demonstrate that in several situations it gives rise to algorithms that are computationally more efficient than existing methods.

We introduce generalized Husimi functions at the interfaces of dielectric systems. Four different functions can be defined, corresponding to the incident and departing wave on both sides of the interface. These functions allow to identify mechanisms of wave confinement and escape directions in optical microresonators, and give insight into the structure of resonance wave functions. Off resonance, where systematic interference can be neglected, the Husimi functions are related by Snell's law and Fresnel's coefficients.

Abstract. We study the number of bouncing ball modes N bb (E) in a class of two-dimensional quantized billiards with two parallel walls. Using an adiabatic approximation we show that asymptotically N bb (E) ∼ αE δ for E → ∞, where δ ∈] 1 2 , 1[ depends on the shape of the billiard boundary. In particular for the class of two-dimensional Sinai billiards, which are chaotic, one can get arbitrarily close (from below) to δ = 1, which corresponds to the leading term in Weyl's law for the mean behaviour of the counting function of eigenstates. This result shows that one can come arbitrarily close to violating quantum ergodicity. We compare the theoretical results with the numerically determined counting function N bb (E) for the stadium billiard and the cosine billiard and find good agreement.

The quantum evolution of the Wigner function for Gaussian wave packets generated by a non-Hermitian Hamiltonian is investigated. In the semiclassical limith → 0 this yields the non-Hermitian analog of the Ehrenfest theorem for the dynamics of observable expectation values. The lack of Hermiticity reveals the importance of the complex structure on the classical phase space: The resulting equations of motion are coupled to an equation of motion for the phase-space metric-a phenomenon having no analog in Hermitian theories.

Abstract:For a large class of quantized ergodic flows the quantum ergodicity theorem due to Shnirelman, Zelditch, Colin de Verdière and others states that almost all eigenfunctions become equidistributed in the semiclassical limit. In this work we first give a short introduction to the formulation of the quantum ergodicity theorem for general observables in terms of pseudodifferential operators and show that it is equivalent to the semiclassical eigenfunction hypothesis for the Wigner function in the case of ergodic systems. Of great importance is the rate by which the quantum mechanical expectation values of an observable tend to their mean value. This is studied numerically for three Euclidean billiards (stadium, cosine and cardioid billiard) using up to 6000 eigenfunctions. We find that in configuration space the rate of quantum ergodicity is strongly influenced by localized eigenfunctions like bouncing ball modes or scarred eigenfunctions. We give a detailed discussion and explanation of these effects using a simple but powerful model. For the rate of quantum ergodicity in momentum space we observe a slower decay. We also study the suitably normalized fluctuations of the expectation values around their mean, and find good agreement with a Gaussian distribution. †