Nonadiabatic effects in the double ionization of atoms driven by a circularly polarized laser pulse.

We study the double ionization of atoms subjected to circularly polarized (CP) laser pulses. We analyze two fundamental ionization processes: the sequential (SDI) and nonsequential (NSDI) double ionization in the light of the rotating frame (RF) which naturally embeds nonadiabatic effects in CP pulses. We use and compare two adiabatic approximations: The adiabatic approximation in the laboratory frame (LF) and the adiabatic approximation in the RF. The adiabatic approximation in the RF encapsulates the energy variations of the electrons on subcycle timescales happening in the LF and this, by fully taking into account the ion-electron interaction. This allows us to identify two nonadiabatic effects including the lowering of the threshold intensity at which over-the-barrier ionization happens and the lowering of the ionization time of the electrons. As a consequence, these nonadiabatic effects facilitate over-the-barrier ionization and recollision-induced ionizations. We analyze the outcomes of these nonadiabatic effects on the recollision mechanism. We show that the laser envelope plays an instrumental role in a recollision channel in CP pulses at the heart of NSDI.

Envelope-Driven Recollisions Triggered by an Elliptically Polarized Pulse.

Increasing ellipticity usually suppresses the recollision probability drastically. In contrast, we report on a recollision channel with large return energy and a substantial probability, regardless of the ellipticity. The laser envelope plays a dominant role in the energy gained by the electron, and in the conditions under which the electron comes back to the core. We show that this recollision channel efficiently triggers various nonlinear and nonperturbative phenomena-such as multiple ionization-with an elliptically polarized pulse.

Capturing Photoelectron Motion with Guiding Centers.

Electron motion in combined strong laser and Coulomb fields is central to laser-matter interactions. By mapping this problem onto the motion of a guiding center, we derive a reduced model which naturally embeds important Coulomb effects such as focusing and asymmetry, and clearly distinguishes direct versus rescattered electron ionization processes. We demonstrate the power of this tool by unraveling the bifurcation in photoelectron momentum distributions seen in experiments.

Recollision scenario without tunneling: role of the ionic core potential.

We present a purely classical recollision scenario, i.e., without tunneling, which, in contrast to the standard three-step model, takes into account the ionic core potential fully at all stages of the recollision process and is valid at all intensities. We find that a key periodic orbit drives the recollisions by guiding electrons away and back to the core. At sufficiently high intensity, we connect our scenario to the three-step model, and explain why the three-step model leads to good agreement with the cutoff in high harmonic generation despite neglecting the core potential after tunneling.

How key periodic orbits drive recollisions in a circularly polarized laser field.

We show that a family of key periodic orbits drives the recollision process in a strong circularly polarized laser field. These orbits, coined recolliding periodic orbits, exist for a wide range of parameters, and their relative influence changes as the laser and atomic parameters are varied. We find the necessary conditions for recollision-driven nonsequential double ionization to occur. The outlined mechanism is universal in that it applies equally well beyond atoms: The internal structure of the target species plays a minor role in the recollision process.

Delayed double ionization as a signature of Hamiltonian chaos.

We analyze the dynamical processes behind delayed double ionization of atoms subjected to strong laser pulses. Using reduced models, we show that these processes are a signature of Hamiltonian chaos which results from the competition between the laser field and the Coulomb attraction to the nucleus. In particular, we exhibit the paramount role of the unstable manifold of selected periodic orbits which lead to a delay in these double ionizations. Among delayed double ionizations, we consider the case of recollision excitation with subsequent ionization (RESI) and, as a hallmark of this mechanism, we predict oscillations in the ratio of RESI to double ionization yields versus laser intensity. We discuss the significance of the dimensionality of the reduced models for the analysis of the dynamical processes behind delayed double ionization.

Annular billiard dynamics in a circularly polarized strong laser field.

We analyze the dynamics of a valence electron of the buckminsterfullerene molecule (C60) subjected to a circularly polarized laser field by modeling it with the motion of a classical particle in an annular billiard. We show that the phase space of the billiard model gives rise to three distinct trajectories: "whispering gallery orbits," which hit only the outer billiard wall; "daisy orbits," which hit both billiard walls (while rotating solely clockwise or counterclockwise for all time); and orbits that only visit the downfield part of the billiard, as measured relative to the laser term. These trajectories, in general, maintain their distinct features, even as the intensity is increased from 10(10) to 10(14) Wcm-2. We attribute this robust separation of phase space to the existence of twistless tori.

Mechanism of delayed double ionization in a strong laser field.

When intense laser pulses release electrons nonsequentially, the time delay between the last recollision and the subsequent ionization may last longer than what is expected from a direct impact scenario [recollision excitation with subsequent ionization (RESI)]. We show that the resulting delayed ionization stems from the inner electron being promoted to a sticky region. We identify the mechanism that traps and releases the electron from this region. As a signature of this mechanism, we predict oscillations in the ratio of RESI to double ionization yields versus laser intensity.

Controlling double ionization of atoms in an intense bichromatic laser pulse.

We consider the classical dynamics of a two-electron system subjected to an intense bichromatic linearly polarized laser pulse. By varying the parameters of the field, such as the phase lag and the relative amplitude between the two colors of the field, we observe several trends from the statistical analysis of a large ensemble of trajectories initially in the ground-state energy of the helium atom: high sensitivity of the sequential double-ionization component, low sensitivity of the intensities where nonsequential double ionization occurs, while the corresponding yields can vary drastically. All these trends hold irrespective of which parameter is varied: the phase lag or the relative amplitude. We rationalize these observations by an analysis of the phase-space structures that drive the dynamics of this system and determine the extent of double ionization. These trends turn out to be mainly regulated by the dynamics of the inner electron.

Recollisions and correlated double ionization with circularly polarized light.

It is generally believed that the recollision mechanism of atomic nonsequential double ionization is suppressed in circularly polarized laser fields because the returning electron is unlikely to encounter the core. On the contrary, we find that recollision can and does significantly enhance double ionization, even to the extent of forming a "knee," the signature of the nonsequential process. Using a classical model, we explain two apparently contradictory experiments, the absence of a knee for helium and its presence for magnesium.

From recollisions to the knee: a road map for double ionization in intense laser fields.

We examine the nature and statistical properties of electron-electron collisions in the recollision process in a strong laser field. The separation of the double ionization yield into sequential and nonsequential components leads to a bell-shaped curve for the nonsequential probability and a monotonically rising one for the sequential process. We identify key features of the nonsequential process and connect our findings in a simplified model which reproduces the knee shape for the probability of double ionization with laser intensity and associated trends.

Strong field double ionization: the phase space perspective.

We identify the phase-space structures that regulate atomic double ionization in strong ultrashort laser pulses. The emerging dynamical picture complements the recollision scenario by clarifying the distinct roles played by the recolliding and core electrons, and leads to verifiable predictions on the characteristic features of the "knee", a hallmark of the nonsequential process.

Bottlenecks to vibrational energy flow in carbonyl sulfide: structures and mechanisms.

Finding the causes for the nonstatistical vibrational energy relaxation in the planar carbonyl sulfide (OCS) molecule is a longstanding problem in chemical physics: Not only is the relaxation incomplete long past the predicted statistical relaxation time but it also consists of a sequence of abrupt transitions between long-lived regions of localized energy modes. We report on the phase space bottlenecks responsible for this slow and uneven vibrational energy flow in this Hamiltonian system with three degrees of freedom. They belong to a particular class of two-dimensional invariant tori which are organized around elliptic periodic orbits. We relate the trapping and transition mechanisms with the linear stability of these structures.

Bifurcations as dissociation mechanism in bichromatically driven diatomic molecules.

We discuss the influence of periodic orbits on the dissociation of a model diatomic molecule driven by a strong bichromatic laser fields. Through the stability of periodic orbits, we analyze the dissociation probability when parameters, such as the two amplitudes and the phase lag between the laser fields, are varied. We find that qualitative features of dissociation can be reproduced by considering a small set of short periodic orbits. The good agreement with direct simulations demonstrates the importance of bifurcations of short periodic orbits in the dissociation dynamics of diatomic molecules.

Dynamical bottlenecks to intramolecular energy flow.

Vibrational energy flows unevenly in molecules, repeatedly going back and forth between trapping and roaming. We identify bottlenecks between diffusive and chaotic behavior, and describe generic mechanisms of these transitions, taking the carbonyl sulfide molecule OCS as a case study. The bottlenecks are found to be lower-dimensional tori; their bifurcations and unstable manifolds govern the transition mechanisms.

Transition-state theory rate calculations with a recrossing-free moving dividing surface.

Two different methods for transition-state theory (TST) rate calculations are presented that use the recently developed notions of the moving dividing surface and the associated moving separatrices: one is based on the flux-over-population approach and the other on the calculation of the reactive flux. The flux-over-population rate can be calculated in two ways by averaging the flux first over the noise and then over the initial conditions or vice versa. The former entails the calculation of reaction probabilities and is closely related to previous TST rate derivations. The latter results in an expression for the transmission factor as the noise average of a stochastic variable that is given explicitly as a function of the moving separatrices. Both the reactive-flux and flux-over-population methods suggest possible new ways of calculating approximate rates in anharmonic systems. In particular, numerical simulations of harmonic and anharmonic systems have been used to calculate reaction rates based on the reactive flux calculation using the fixed and moving dividing surfaces so as to illustrate the computational advantages of the latter.

Transition state theory for laser-driven reactions.

Recent developments in transition state theory brought about by dynamical systems theory are extended to time-dependent systems such as laser-driven reactions. Using time-dependent normal form theory, the authors construct a reaction coordinate with regular dynamics inside the transition region. The conservation of the associated action enables one to extract time-dependent invariant manifolds that act as separatrices between reactive and nonreactive trajectories and thus make it possible to predict the ultimate fate of a trajectory. They illustrate the power of our approach on a driven Henon-Heiles system, which serves as a simple example of a reactive system with several open channels. The present generalization of transition state theory to driven systems will allow one to study processes such as the control of chemical reactions through laser pulses.

Extracting multidimensional phase space topology from periodic orbits.

We establish a hierarchical ordering of periodic orbits in a strongly coupled multidimensional Hamiltonian system. Phase space structures can be reconstructed quantitatively from the knowledge of periodic orbits alone. We illustrate our findings for the hydrogen atom in crossed electric and magnetic fields.

Identifying reactive trajectories using a moving transition state.

A time-dependent no-recrossing dividing surface is shown to lead to a new criterion for identifying reactive trajectories well before they are evolved to infinite time. Numerical dynamics simulations of a dissipative anharmonic two-dimensional system confirm the efficiency of this approach. The results are compared to the standard fixed transition state dividing surface that is well-known to suffer from recrossings and therefore requires trajectories to be evolved over a long time interval before they can reliably be classified as reactive or nonreactive. The moving dividing surface can be used to identify reactive trajectories in harmonic or moderately anharmonic systems with considerably lower numerical effort or even without any simulation at all.

Stochastic transition states: reaction geometry amidst noise.

Classical transition state theory (TST) is the cornerstone of reaction-rate theory. It postulates a partition of phase space into reactant and product regions, which are separated by a dividing surface that reactive trajectories must cross. In order not to overestimate the reaction rate, the dynamics must be free of recrossings of the dividing surface. This no-recrossing rule is difficult (and sometimes impossible) to enforce, however, when a chemical reaction takes place in a fluctuating environment such as a liquid. High-accuracy approximations to the rate are well known when the solvent forces are treated using stochastic representations, though again, exact no-recrossing surfaces have not been available. To generalize the exact limit of TST to reactive systems driven by noise, we introduce a time-dependent dividing surface that is stochastically moving in phase space, such that it is crossed once and only once by each transition path.