Phase Space Transition State Theory Research Articles

A Saddle in a Corner—A Model of Collinear Triatomic Chemical Reactions

A geometrical model which captures the main ingredients governing atom-diatom collinear chemical reactions is proposed. This model is neither near-integrable nor hyperbolic, yet it is amenable to analysis using a combination of the recently developed tools for studying systems with steep potentials and the study of the phase space structure near a center-saddle equilibrium. The nontrivial dependence of the reaction rates on parameters, initial conditions, and energy is thus qualitatively explained. Conditions under which the phase space transition state theory assumptions are satisfied and conditions under which they fail are derived.

Noise-Enhanced Trapping in Chaotic Scattering

We show that noise enhances the trapping of trajectories in scattering systems. In fully chaotic systems, the decay rate can decrease with increasing noise due to a generic mismatch between the noiseless escape rate and the value predicted by the Liouville measure of the exit set. In Hamiltonian systems with mixed phase space we show that noise leads to a slower algebraic decay due to trajectories performing a random walk inside Kolmogorov-Arnold-Moser islands. We argue that these noise-enhanced trapping mechanisms exist in most scattering systems and are likely to be dominant for small noise intensities, which is confirmed through a detailed investigation in the Hénon map. Our results can be tested in fluid experiments, affect the fractal Weyl's law of quantum systems, and modify the estimations of chemical reaction rates based on phase-space transition state theory.

Rydberg hydrogen atom near a metallic surface: Stark regime and ionization dynamics

We investigate the classical dynamics of a hydrogen atom near a metallic surface in the presence of a uniform electric field. To describe the atom-surface interaction we use a simple electrostatic image model. Owing to the axial symmetry of the system, the $z$-component of the canonical angular momentum ${P}_{\ensuremath{\phi}}$ is an integral and the electronic dynamics is modeled by a two degrees of freedom Hamiltonian in cylindrical coordinates. The structure and evolution of the phase space as a function of the electric field strength is explored extensively by means of numerical techniques of continuation of families of periodic orbits and Poincar\'e surfaces of section. We find that, due to the presence of the electric field, the atom is strongly polarized through two consecutive pitchfork bifurcations that strongly change the phase space structure. Finally, by means of the phase space transition state theory and the classical spectral theorem, the ionization dynamics of the atom is studied.

Efficient Procedure to Compute the Microcanonical Volume of Initial Conditions that Lead to Escape Trajectories from a Multidimensional Potential Well

A procedure is presented for computing the phase space volume of initial conditions for trajectories that escape or "react" from a multidimensional potential well. The procedure combines a phase space transition state theory, which allows one to construct dividing surfaces that are free of local recrossing and that minimize the directional flux, and a classical spectral theorem. The procedure gives the volume of reactive initial conditions in terms of a sum over each entrance channel of the well of the product of the phase space flux across the dividing surface associated with the channel and the mean residence time in the well of trajectories which enter through the channel. This approach is illustrated for HCN isomerization in three dimensions, for which the method is several orders of magnitude more efficient than standard Monte Carlo sampling.