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We publish three Roadmaps on photonic, electronic and atomic collision physics in order to celebrate the 60th anniversary of the ICPEAC conference. In Roadmap I, we focus on the light-matter interaction. In this area, studies of ultrafast electronic and molecular dynamics have been rapidly growing, with the advent of new light sources such as attosecond lasers and x-ray free electron lasers. In parallel, experiments with established synchrotron radiation sources and femtosecond lasers using cutting-edge detection schemes are revealing new scientific insights that have never been exploited. Relevant theories are also being rapidly developed. Target samples for photon-impact experiments are expanding from atoms and small molecules to complex systems such as biomolecules, fullerene, clusters and solids. This Roadmap aims to look back along the road, explaining the development of these fields, and look forward, collecting contributions from twenty leading groups from the field.

In this paper, we analyze the dynamic effect of a reservoir computer (RC) on its performance. Modified Kuramoto's coupled oscillators are used to model the RC, and synchronization, Lyapunov spectrum (and dimension), Shannon entropy, and the upper bound of the Kolmogorov-Sinai entropy are employed to characterize the dynamics of the RC. The performance of the RC is analyzed by reproducing the distribution of random, Gaussian, and quantum jumps series (shelved states) since a replica of the time evolution of a completely random series is not possible to generate. We demonstrate that hyperchaotic motion, moderate Shannon entropy, and a higher degree of synchronization of Kuramoto's oscillators lead to the best performance of the RC. Therefore, an appropriate balance of irregularity and order in the oscillator's dynamics leads to better performances., (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)

The nature of time as emergent for a system by separating it from its environment has been put forward by Page and Wootters [Phys. Rev. D 27, 2885 (1983)PRVDAQ0556-282110.1103/PhysRevD.27.2885] in a quantum mechanical setting neglecting interaction between system and environment. Here, we add strong support to the relational concept of time by deriving the time-dependent Schrödinger equation for a system from an energy eigenstate of the global Hamiltonian consisting of system, environment, and their interaction. Our results are consistent with concepts for the emergence of time where interaction has been taken into account at the expense of a semiclassical treatment of the environment. Including the coupling between system and environment without approximation adds a missing link to the relational time approach opening it to dynamical phenomena of interacting systems and entangled quantum states.

Tunable attosecond pulses are necessary for various attosecond resolved spectroscopic applications, which can potentially be obtained through the tuning of high harmonic generation. Here we show theoretically, using the time-dependent Schrödinger equation and strong field approximation, a continuously tunable spectral shift of high-order harmonics by exploiting the interaction of two delayed identical infrared (IR) pulses within the single-atom response. The tuning spans more than twice the driving frequency (∼2ω) range, for several near-cutoff harmonics, with respect to only one control parameter: the change in delay between the two IR pulses. We show that two distinct mechanisms contribute to the spectral shift of the harmonic spectra. The dominant part of the spectral shift of the harmonics is due to the modulation of the central frequency of the composite IR-IR pulse with respect to delay. The second contribution comes from the non-adiabatic phase-shift of the recolliding electron wavepacket due to the change in amplitude of the subcycle electric field within the double pulse envelope. For optical few-cycle pulses this scheme can produce tunable attosecond pulse trains (APT), and in the single-cycle regime the same can be used for tuning isolated attosecond pulses (IAP). We quantify the dependence of tuning range and tuning rate on the laser pulse duration. We envision that the proposed scheme can be easily implemented with compact in-line setups for generating frequency tunable APT/IAP.

We elucidate the mechanism of strong laser pulse excitation in pristine graphene with multi-harmonic pulses, linearly polarized parallel to the line connecting the two different Dirac points in the Brillouin zone and with a maximal vector potential given by the distance of those points. The latter two conditions have emerged from our previous work [Kelardeh et al. , Phys. Rev. Res. , 2022, 4 , L022014] as favorable for large valley polarization. We introduce a novel compacted representation for excitation, locally resolved in the initial conditions for the crystal momenta. These maps are our main tool to gain insight into the excitation dynamics. They also help with understanding the effect of dephasing. We work out why a long wavelength and a moderate number of overtones in the harmonic pulse generate the largest valley polarizations.

We demonstrate a dispersion-free wavefront splitting attosecond resolved interferometric delay line for easy ultrafast metrology of broadband femtosecond pulses. Using a pair of knife-edge prisms, we symmetrically split and later recombine the two wavefronts with a few tens of attosecond resolution and stability and employ a single-pixel analysis of interference fringes with good contrast using a phone camera without any iris or nonlinear detector. Our all-reflective delay line is theoretically analyzed and experimentally validated by measuring 1st and 2nd order autocorrelations and the SHG-FROG trace of a NIR femtosecond pulse. Our setup is compact, offers attosecond stability with flexibility for independent beam-shaping of the two arms. Furthermore, we suggest that our compact and in-line setup can be employed for attosecond resolved pump-probe experiments of matter with few-cycle pulses., (© 2022. The Author(s).)

Measured angular distributions of photoelectrons from size-selected copper and sodium cluster anions are demonstrated to exhibit a universal behavior independent of the initial electron state, cluster size, or material, which can be traced back to momentum conservation upon photoemission. Quantum simulations reproduce the universality under the assumption that multielectron dynamics localizes the emission on the cluster surface and renders the cluster opaque to photoelectrons, thereby quenching interference effects that would otherwise obscure this almost classical behavior.

We have constructed deep neural networks, which can map fluctuating photo-electron spectra obtained from noisy pulses to spectra from noise-free pulses. The network is trained on spectra from noisy pulses in combination with random Hamilton matrices, representing systems which could exist but do not necessarily exist. In [Giri et al., Phys. Rev. Lett., 2020, 124, 113201] we performed a purification of fluctuating spectra, that is, mapping them to those from Fourier-limited Gaussian pulses. Here, we investigate the performance of such neural-network-based maps for predicting spectra of double pulses, pulses with a chirp and even partially-coherent pulses from fluctuating spectra generated by noisy pulses. Secondly, we demonstrate that along with purification of a fluctuating double-pulse spectrum, one can estimate the time-delay of the underlying double pulse, an attractive feature for single-shot spectra from SASE FELs. We demonstrate our approach with resonant two-photon ionization, a non-linear process, sensitive to details of the laser pulse.

We predict the existence of a universal class of ultralong-range Rydberg molecular states whose vibrational spectra form trimmed Rydberg series. A dressed ion-pair model captures the physical origin of these exotic molecules, accurately predicts their properties, and reveals features of ultralong-range Rydberg molecules and heavy Rydberg states with a surprisingly small Rydberg constant. The latter is determined by the small effective charge of the dressed anion, which outweighs the contribution of the molecule's large reduced mass. This renders these molecules the only known few-body systems to have a Rydberg constant smaller than R_{∞}/2.

We introduce an ultra-thin attosecond optical delay line based on controlled wavefront division of a femtosecond infrared pulse after transmission through a pair of micrometer-thin glass plates with negligible dispersion effects. The time delay between the two pulses is controlled by rotating one of the glass plates from absolute zero to several optical cycles, with 2.5 as to tens of attosecond resolution with 2 as stability, as determined by interferometric self-calibration. The performance of the delay line is validated by observing attosecond-resolved oscillations in the yield of high harmonics induced by time delayed infrared pulses, in agreement with a numerical simulation for a simple model atom. This approach can be extended in the future for performing XUV-IR attosecond pump-probe experiments.

In attosecond science it is assumed that Wigner-Smith time delays, known from scattering theory, are determined by measuring streaking shifts. Despite their wide use from atoms to solids this has never been proven. Analyzing the underlying process-energy absorption from the streaking light-we derive this relation. It reveals that only under specific conditions streaking shifts measure Wigner-Smith time delays. For the most relevant case, interactions containing long-range Coulomb tails, we show that finite streaking shifts, including relative shifts from two different orbitals, are misleading. We devise a new time-delay definition and describe a measurement technique that avoids the record of a complete streaking scan, as suggested by the relation between time delays and streaking shifts.

Rescattering by electrons on classical trajectories is central to understand photoelectron and high-harmonic emission from isolated atoms or molecules in intense laser pulses. By controlling the cluster size and the quiver amplitude of electrons, we demonstrate how rescattering influences the energy distribution of photoelectrons emitted from noble gas nanoclusters. Our experiments reveal a universal dependence of photoelectron energy distributions on the cluster size when scaled by the field driven electron excursion, establishing a unified rescattering picture for extended systems with the known atomic dynamics as the limit of zero extension. The result is supported by molecular dynamics calculations and rationalized with a one-dimensional classical model.

Photoelectron spectra obtained with intense pulses generated by free-electron lasers through self-amplified spontaneous emission are intrinsically noisy and vary from shot to shot. We extract the purified spectrum, corresponding to a Fourier-limited pulse, with the help of a deep neural network. It is trained on a huge number of spectra, which was made possible by an extremely efficient propagation of the Schrödinger equation with synthetic Hamilton matrices and random realizations of fluctuating pulses. We show that the trained network is sufficiently generic such that it can purify atomic or molecular spectra, dominated by resonant two- or three-photon ionization, nonlinear processes which are particularly sensitive to pulse fluctuations. This is possible without training on those systems.

We present experimental results on the characteristic sharing of available excess energy, ranging from 11-221 eV, between two electrons in single-photon direct double ionization of He. An effective parametrization of the sharing distributions is presented along with an empirical model that describes the complete shape of the distribution based on a single experimentally determinable parameter. The measured total energy sharing distributions are separated into two distributions representing the shake-off and knock-out parts by simulating the sharing distribution curves expected from a pure wave collapse after a sudden removal of the primary electron. In this way, empirical knock-out distributions are extracted and both the shake-off and knock-out distributions are parametrized. These results suggest a simple method that can be applied to other atomic and molecular systems to experimentally study important aspects of the direct double ionization process.

The molecular association process in a thermal gas of ^{85}Rb is investigated where the effects of the envelope of the radio-frequency field are taken into account. For experimentally relevant parameters our analysis shows that with increasing pulse length the corresponding molecular conversion efficiency exhibits low-frequency interference fringes which are robust under thermal averaging over a wide range of temperatures. This dynamical interference phenomenon is attributed to Stückelberg phase accumulation between the low-energy continuum states and the dressed molecular state which exhibits a shift proportional to the envelope of the radio-frequency pulse intensity.

We theoretically investigate the deformation of atomic p_{±} orbitals driven by strong elliptically polarized (EP) laser fields and the role it plays in tunnel ionization. Our study reveals that different Stark effects induced by orthogonal components of the EP field give rise to subcycle rearrangement of the bound electron density, rendering the initial p_{+} and p_{-} orbitals deformed and polarized along distinctively tilted angles with respect to the polarization ellipse of the EP field. As a consequence, the instantaneous tunneling rates change such that for few-cycle EP laser pulses the bound electron initially counterrotating (corotating) with the electric field is most likely released before (after) the peak of the electric field. We demonstrate that with a sequential-pulse setup one can exploit this effect to spatially separate the photoelectrons detached from p_{+} and p_{-} orbitals, paving the way towards robust control of spin-resolved photoemission in laser-matter interactions.

We demonstrate that, by changing the direction of the chirp in vacuum-ultraviolet pulses, one can switch between excitation and ionization with very high contrast, if the carrier frequency of the light is resonant with two bound states. This is a surprising consequence of rapid adiabatic passage if extended to include transitions to the continuum. The chirp phase locks the linear combination of the two resonantly coupled bound states whose ionization amplitudes interfere constructively or destructively depending on the chirp direction under suitable conditions. We derive the phenomenon in a minimal model and verify the effect with calculations for helium as a realistic example.

We demonstrate that ultrashort pulses carry the possibility for a new regime of light-matter interaction with nonadiabatic electron processes sensitive to the envelope derivative of the light pulse. A standard single pulse with its two peaks in the derivative separated by the width of the pulse acts in this regime like a traditional double pulse. The two ensuing nonadiabatic ionization bursts have slightly different ionization amplitudes. This difference is due to the redistribution of continuum electron energy during the bursts, negligible in standard photoionization. A time-dependent close-coupling approach based on cycle-averaged potentials in the Kramers-Henneberger reference frame permits a detailed understanding of light-pulse derivative-driven electron dynamics.

Trilobites are exotic giant dimers with enormous dipole moments. They consist of a Rydberg atom and a distant ground-state atom bound together by short-range electron-neutral attraction. We show that highly polar, polyatomic trilobite states unexpectedly persist and thrive in a dense ultracold gas of randomly positioned atoms. This is caused by perturbation-induced quantum scarring and the localization of electron density on randomly occurring atom clusters. At certain densities these states also mix with an s state, overcoming selection rules that hinder the photoassociation of ordinary trilobites.

We provide the necessary framework for carrying out stochastic positive-P and gauge-P simulations of bosonic systems with long-range interactions. In these approaches, the quantum evolution is sampled by trajectories in phase space, allowing calculation of correlations without truncation of the Hilbert space or other approximations to the quantum state. The main drawback is that the simulation time is limited by noise arising from interactions. We show that the long-range character of these interactions does not further increase the limitations of these methods, in contrast to the situation for alternatives such as the density matrix renormalization group. Furthermore, stochastic gauge techniques can also successfully extend simulation times in the long-range-interaction case, by making using of parameters that affect the noise properties of trajectories, without affecting physical observables. We derive essential results that significantly aid the use of these methods: estimates of the available simulation time, optimized stochastic gauges, a general form of the characteristic stochastic variance, and adaptations for very large systems. Testing the performance of particular drift and diffusion gauges for nonlocal interactions, we find that, for small to medium systems, drift gauges are beneficial, whereas for sufficiently large systems, it is optimal to use only a diffusion gauge. The methods are illustrated with direct numerical simulations of interaction quenches in extended Bose-Hubbard lattice systems and the excitation of Rydberg states in a Bose-Einstein condensate, also without the need for the typical frozen gas approximation. We demonstrate that gauges can indeed lengthen the useful simulation time.

We develop general quantitative criteria for dynamic interference, a manifestation of a double-slit interference in time which should be realizable with brilliant state-of-the-art high-frequency laser sources. Our analysis reveals that the observation of dynamic interference hinges upon maximizing the difference between the dynamic polarization of the initial bound and the final continuum states of the electron during the light pulse while keeping depletion of the initial state small. These two properties, Stark shift and depletion, can be determined from electronic structure calculations avoiding expensive propagation in time. Confirmed by numerical results, we predict that this is impossible for the hydrogen ground state but feasible for excited states; this has been exemplified for the case of the hydrogen 2p state.

We determine the ionization time in tunneling ionization by an elliptically polarized light pulse relative to its maximum. This is achieved by a full quantum propagation of the electron wave function forward in time, followed by a classical backpropagation to identify tunneling parameters, in particular, the fraction of electrons that has tunneled out. We find that the ionization time is close to zero for single active electrons in helium and in hydrogen if the fraction of tunneled electrons is large. We expect our analysis to be essential to quantify ionization times for correlated electron motion.

The dynamics of ultraslow electrons in the combined potential of an ionic core and a static electric field is discussed. With state-of-the-art detection it is possible to create such electrons through strong intense-field photoabsorption and to detect them via high-resolution time-of-flight spectroscopy despite their very low kinetic energy. The characteristic feature of their momentum spectrum, which emerges at the same position for different laser orientations, is derived and could be revealed experimentally with an energy resolution of the order of 1 meV.

We explore the possibility for orientation recovery in single-molecule coherent diffractive imaging with diffusion map. This algorithm approximates the Laplace-Beltrami operator, which we diagonalize with a metric that corresponds to the mapping of Euler angles onto scattering images. While suitable for images of objects with specific properties we show why this approach fails for realistic molecules. We introduce a modification of the form factor in the scattering images which facilitates the orientation recovery and should be suitable for all recovery algorithms based on the distance of individual images.

Objective: Long-term studies regarding the effect of a structured physical exercise programme (SPEP) during haemodialysis (HD) assessing compliance and clinical benefit are scarce., Study Design: A single-centre clinical trial, non-randomised, investigating 46 patients with HD (63.2 ± 16.3 years, male/female 24/22, dialysis vintage 4.4 years) performing an SPEP over 5 years. The SPEP (twice/week for 60 min during haemodialysis) consisted of a combined resistance (8 muscle groups) and endurance (supine bicycle ergometry) training. Exercise intensity was continuously adjusted to improvements of performance testing. Changes in endurance and resistance capacity, physical functioning and quality of life (QoL) were analysed over 1 year in addition to long-term adherence and economics of the programme over 5 years. Average power per training session, maximal strength tests (maximal exercise repetitions/min), three performance-based tests for physical function, SF36 for QoL were assessed in the beginning and every 6 months thereafter., Results: 78% of the patients completed the programme after 1 year and 43% after 5 years. Participants were divided--according to adherence to the programme--into three groups: (1) high adherence group (HA, >80% of 104 training sessions within 12 months), (2) moderate adherence (MA, 60-80%), and 3. Low adherence group (LA, <60%)) with HA and MA evaluated quantitatively. One-year follow-up data revealed significant (p<0.05) improvement for both groups in all measured parameters: exercise capacity (HA: 55%, MA: 45%), strength (HA: >120%, MA: 40-50%), QoL in three scores of SF36 subscales and physical function in the three tests taken between 11% and 31%. Moreover, a quantitative correlation analysis revealed a close association (r=0.8) between large improvement of endurance capacity and weak physical condition (HA)., Conclusions: The exercise programme described improves physical function significantly and can be integrated into a HD routine with a high long-term adherence., (Published by the BMJ Publishing Group Limited. For permission to use (where not already granted under a licence) please go to http://group.bmj.com/group/rights-licensing/permissions.)

Exciton pulses transport excitation and entanglement adiabatically through Rydberg aggregates, assemblies of highly excited light atoms, which are set into directed motion by resonant dipole-dipole interaction. Here, we demonstrate the coherent splitting of such pulses as well as the spatial segregation of electronic excitation and atomic motion. Both mechanisms exploit local nonadiabatic effects at a conical intersection, turning them from a decoherence source into an asset. The intersection provides a sensitive knob controlling the propagation direction and coherence properties of exciton pulses. The fundamental ideas discussed here have general implications for excitons on a dynamic network.

X-ray photoabsorption from intense short pulses by a molecule triggers complicated electron and subsequently ion dynamics, leading to photoelectron spectra, which are difficult to interpret. Illuminating fullerenes offers a way to separate out the electron dynamics since the cage structure confines spatially the origin of photo- and Auger electrons. Together with the sequential nature of the photoprocesses at intensities available at x-ray free-electron lasers, this allows for a remarkably detailed interpretation of the photoelectron spectra, as we will demonstrate. The general features derived can serve as a paradigm for less well-defined situations in other large molecules or clusters.

Clusters consisting of small molecules containing hydrogen do eject fast protons when illuminated by short x-ray pulses. A suitable overall charging of the cluster controlled by the x-ray intensity induces electron migration from the surface to the bulk leading to efficient segregation of the protons and to a globally hindered explosion of the heavy atoms even outside the screened volume. We investigate this peculiar effect systematically along the isoelectronic sequence of methane over ammonia and water to the atomic limit of neon as a reference. In contrast to core-shell systems where the outer shell is sacrificed to reduce radiation damage, the intricate proton dynamics of hydride clusters allows one to keep the entire backbone of heavy atoms intact.

We have obtained experimental photo-double- and photo-triple-detachment cross sections for the fullerene negative ion using Advanced Light Source photons of 17-90 eV. The cross sections are 2 and 2.5 times larger than those for C60 and appear to be compressed and shifted in photon energy as compared to C60. Our analysis reveals that the additional electron in C60- primarily produces screening which is responsible for the modification of the spectrum. Both screening effects, the shift and the compression, can be quantitatively accounted for by a linear transformation of the energy axis. Applying the transformation allows us to map the neutral and negative ion cross sections onto each other, pointing out the close relationship of correlated few-electron dynamics in neutral and negatively charged extended systems. In contrast, dynamics of neutral and negatively charged atoms or small molecules are typically not closely related.

We demonstrate that fast removal of many electrons uncovers initial correlations of atoms in a finite sample through a pronounced peak in the kinetic-energy spectrum of the exploding ions. This maximum is the result of an intricate interplay between the composition of the system from discrete particles and its boundary. The formation of the peak can be described analytically, accounting for correlations beyond a mean-field reference model. It can be experimentally detected with short and intense light pulses from 4th-generation light sources.

The phase space dynamics of higher dimensional nonintegrable conservative systems is characterized via the effect of "sticky" motion on the finite time Lyapunov exponents (FTLEs) distribution. Since a chaotic trajectory suffers the sticky effect when chaotic motion is mixed to the regular one, it offers a way to separate the mixed from the totally chaotic regimes. To detect stickiness, four different measures are used, related to the distributions of the positive FTLEs, and provide conditions to characterize the dynamics. Conservative maps are systematically studied from the uncoupled two-dimensional case up to coupled maps of dimension 20. Sticky motion is detected in all unstable directions above a threshold K(d) of the nonlinearity parameter K for the high dimensional cases d = 10, 20. Moreover, as K increases we can clearly identify the transition from mixed to totally chaotic motion which occurs simultaneously in all unstable directions. Results show that all four statistical measures sensitively characterize the motion in high dimensional systems.

Massively parallel ionization of many atoms in a cluster or biomolecule is identified as a new phenomenon of light-matter interaction which becomes feasible through short and intense FEL pulses. Almost simultaneously emitted from the illuminated target the photo-electrons can have such a high density that they interact substantially even after photoionization. This interaction results in a characteristic electron spectrum which can be interpreted as a convolution of a mean-field electron dynamics and binary electron-electron collisions. We demonstrate that this universal spectrum can be obtained analytically by summing synthetic two-body Coulomb collision events. Moreover, we propose an experiment with hydrogen clusters to observe massively parallel ionization.

We introduce soft recollisions in laser-matter interaction. They are characterized by the electron missing the ion upon recollision in contrast with the well-known head-on collisions responsible for high-harmonic generation or above-threshold ionization. We demonstrate analytically that soft recollisions can cause a bunching of photoelectron energies through which a series of low-energy peaks emerges in the electron yield along the laser polarization axis. This peak sequence is universal, it does not depend on the binding potential, and is found below an excess energy of one tenth of the ponderomotive energy., (© 2012 American Physical Society)

Permanent electric dipole moments in molecules require a breaking of parity symmetry. Conventionally, this symmetry breaking relies on the presence of heteronuclear constituents. We report the observation of a permanent electric dipole moment in a homonuclear molecule in which the binding is based on asymmetric electronic excitation between the atoms. These exotic molecules consist of a ground-state rubidium (Rb) atom bound inside a second Rb atom electronically excited to a high-lying Rydberg state. Detailed calculations predict appreciable dipole moments on the order of 1 Debye, in excellent agreement with the observations.

A simple, semianalytical model is proposed for nonrelativistic Coulomb explosion of a uniformly charged spheroid. This model allows us to derive the time-dependent particle energy distributions. Simple expressions are also given for the characteristic explosion time and maximum particle energies in the limits of extreme prolate and oblate spheroids as well as for the sphere. Results of particle simulations are found to be in remarkably good agreement with the model.

We demonstrate ultrafast resonant energy absorption of rare-gas doped He nanodroplets from intense few-cycle (~10 fs) laser pulses. We find that less than 10 dopant atoms "ignite" the droplet to generate a nonspherical electronic nanoplasma resulting ultimately in complete ionization and disintegration of all atoms, although the pristine He droplet is transparent for the laser intensities applied. Our calculations at those intensities reveal that the minimal pulse length required for ignition is about 9 fs., (© 2011 American Physical Society)

High-harmonic generation is shown to be capable of providing time-resolved information about the particle density of a complex system. As an example, we study numerically high-harmonic generation from expanding xenon clusters in a pump-probe laser scheme, where the pump laser pulse induces the cluster explosion and the probe pulse generates harmonics in the expanding cluster. We show that the high-harmonic spectra characterize the properties of the expanding cluster. Hence, measuring the dependence of the harmonic signal on the pump-probe delay suggests itself as an experimental tool to monitor many-particle dynamics with unique temporal resolution; based on optical measurements, this technique is naturally free from any spatial charge effects.

We find that energy surfaces of more than two atoms or molecules interacting via transition dipole-dipole potentials generically possess conical intersections (CIs). Typically only few atoms participate strongly in such an intersection. For the fundamental case, a circular trimer, we show how the CI affects adiabatic excitation transport via electronic decoherence or geometric phase interference. These phenomena may be experimentally accessible if the trimer is realized by light alkali atoms in a ring trap, whose interactions are induced by off-resonant dressing with Rydberg states. Such a setup promises a direct probe of the full many-body density dynamics near a CI.

In a combined experimental and theoretical effort we report on two novel types of ultracold long-range Rydberg molecules. First, we demonstrate the creation of triatomic molecules of one Rydberg atom and two ground-state atoms in a single-step photoassociation. Second, we assign a series of excited dimer states that are bound by a so far unexplored mechanism based on internal quantum reflection at a steep potential drop. The properties of the Rydberg molecules identified in this work qualify them as prototypes for a new type of chemistry at ultracold temperatures.

In a regular, flexible chain of Rydberg atoms, a single electronic excitation localizes on two atoms that are in closer mutual proximity than all others. We show how the interplay between excitonic and atomic motion causes electronic excitation and diatomic proximity to propagate through the Rydberg chain as a combined pulse. In this manner entanglement is transferred adiabatically along the chain, reminiscent of momentum transfer in Newton's cradle.

Inner-shell ionization of atoms and molecules leads to the creation of highly excited ionic states that often decay by electron emission. The dynamics of the decay is usually assumed to be exponential and the process is characterized by a decay rate. Here we show that in a multiply ionized cluster created by interaction with a high-intensity free-electron laser (FEL) radiation, trapping of the emitted electron by the neighboring ions changes the character of the decay dynamics qualitatively to the extent that it can become oscillatory instead of exponential. Implications of the predicted effect on Coster-Kronig and interatomic Coulombic decay processes induced by FELs are investigated.

A Rydberg and a ground-state atom can form ultra-long-range diatomic molecules provided the interaction between the ground-state atom and the Rydberg electron is attractive [C. H. Greene, Phys. Rev. Lett. 85, 2458 (2000)10.1103/PhysRevLett.85.2458]. A repulsive interaction does not support bound states. However, as we will show, adding a second ground-state atom, a long-range bound triatomic molecule becomes possible.