Electron correlation and multielectron effects are fundamental interactions that govern many physical and chemical processes in atomic, molecular and solid state systems. The process of autoionization, induced by resonant excitation of electrons into discrete states present in the spectral continuum of atomic and molecular targets, is mediated by electron correlation. Here we investigate the attosecond photoemission dynamics in argon in the 20-40 eV spectral range, in the vicinity of the 3s(-1)np autoionizing resonances. We present measurements of the differential photoionization cross section and extract energy and angle-dependent atomic time delays with an attosecond interferometric method. With the support of a theoretical model, we are able to attribute a large part of the measured time delay anisotropy to the presence of autoionizing resonances, which not only distort the phase of the emitted photoelectron wave packet but also introduce an angular dependence.

We study laser-assisted photodetachment time delays by attosecond pulse trains from the closed-shell negative ions F- and Cl. We investigate the separability of the delay into two contributions: (i) the Wigner-like delay associated with one-photon ionization by the attosecond pulse train and (ii) the delay associated with the exchange of an additional laser photon in the presence of the potential of the remaining target. Based on the asymptotic form of the wave packet, the latter term is expected to be negligible because the ion is neutralized, leading to a vanishing laser-ion interaction with increasing electron-atom separation. While this asymptotic behavior is verified at high photoelectron energies, we also quantify sharp deviations at low photoelectron energies. Further, these low-energy delays are clearly different for the two studied anions, indicating a breakdown of the universality of laser-ion-induced delays. The fact that the short-range potential can induce a delay of as much as 50 as can have implications for the interpretation of delay measurements also in other systems that lack long-range potential.

We present a study of high-order-harmonic generation (HHG) assisted by extreme ultraviolet (XUV) attosecond pulses, which can lead to the excitation of inner-shell electrons and the generation of a second HHG plateau. With the treatment of a one-dimensional model of krypton, based on time-dependent configuration interaction singles (TDCIS) of an effective two-electron system, we show that the XUV-assisted HHG spectrum reveals the duration of the semiclassical electron trajectories. The results are interpreted by the strong-field approximation (SFA) and the importance of the hole transfer during the tunneling process is emphasized. Finally, coherent population transfer between the inner and outer holes with attosecond pulse trains is discussed.

We investigate the possibility of using transient absorption of a coherent bound electron wave packet in hydrogen as an attosecond pulse characterization technique. In a recent work, we have shown that photoionization of such a coherent bound electron wave packet opens up for pulse characterization with unprecedented temporal accuracy-independent of the atomic structure-with maximal photoemission at all kinetic energies given a wave packet with zero relative phase (Pabst and Dahlstrom Phys. Rev. A 94 13411 (2016)). Here, we perform numerical propagation of the time-dependent Schrodinger equation and analytical calculations based on perturbation theory to show that the energy-resolved maximal absorption of photons from the attosecond pulse does not uniquely occur at a zero relative phase of the initial wave packet. Instead, maximal absorption occurs at different relative wave packet phases, distributed as a non-monotonous function with a smooth -pi/2 shift across the central photon energy (given a Fourier-limited Gaussian pulse). Similar results are also found in helium. Our finding is surprising, because it implies that the energy-resolved photoelectrons are not mapped one-to-one with the energy-resolved absorbed photons of the attosecond pulse.

Attosecond x-ray pulses offer unprecedented opportunities for probing and triggering new types of ultrafast motion. At the same time, pulse characterization of x-rays presents new challenges that do not exist in the UV regime. Inner-shell ionization is the dominant ionization mechanism for x-rays and it is followed by secondary processes like fluorescence, Auger decay, and shake-up. In general, we find that inner-shell ionization and secondary processes can create additional delay-dependent modulations that will affect pulse reconstruction schemes. Our recently proposed pulse characterization method (Pabst and Dahlstrom 2016 Phys. Rev. A 94 013411), where a bound electron wavepacket is sequentially photoionized by the attosecond pulse, can be adapted to mitigate the impact of these effects, thus opening up an avenue for reliable pulse reconstruction in the x-ray regime.

Ultrafast processes in matter, such as the electron emission after light absorption, can now be studied using ultrashort light pulses of attosecond duration (10-18 seconds) in the extreme ultraviolet spectral range. The lack of spectral resolution due to the use of short light pulses has raised issues in the interpretation of the experimental results and the comparison with theoretical calculations. We determine photoionization time delays in neon atoms over a 40-electron volt energy range with an interferometric technique combining high temporal and spectral resolution. We spectrally disentangle direct ionization from ionization with shake-up, in which a second electron is left in an excited state, and obtain excellent agreement with theoretical calculations, thereby solving a puzzle raised by 7-year-old measurements.

Time delays of electrons emitted from an isotropic initial state with the absorption of a single photon and leaving behind an isotropic ion are angle independent. Using an interferometric method involving XUV attosecond pulse trains and an IR-probe field in combination with a detection scheme, which allows for full three-dimensional momentum resolution, we show that measured time delays between electrons liberated from the 1s(2) spherically symmetric ground state of helium depend on the emission direction of the electrons relative to the common linear polarization axis of the ionizing XUV light and the IR-probing field. Such time delay anisotropy, for which we measure values as large as 60 as, is caused by the interplay between final quantum states with different symmetry and arises naturally whenever the photoionization process involves the exchange of more than one photon. With the support of accurate theoretical models, the angular dependence of the time delay is attributed to small phase differences that are induced in the laser-driven continuum transitions to the final states. Since most measurement techniques tracing attosecond electron dynamics involve the exchange of at least two photons, this is a general and significant effect that must be taken into account in all measurements of time delays involving photoionization processes.

We investigate ionization of neon atoms by an isolated attosecond pump pulse in the presence of two coherent extreme ultraviolet or x-ray probe fields. The probe fields are tuned to a core-valence transition in the residual ion and induce spectral shearing of the photoelectron distributions. We show that the photoelectron-ion coincidence signal contains an interference pattern that depends on the temporal structure of the attosecond pump pulse and the stimulated core-valence transition. Many-body perturbation theory is used to compute atomic response times for the processes and we find strikingly different behavior for stimulation to the outer-core hole (2p <-> 2s) and stimulation to the inner-core hole (2p <-> 1s). The response time of the inner-core transition is found to be comparable to that of state-of-the-art laser-based characterization techniques for attosecond pulses.

We propose a technique to fully characterize the temporal structure of extreme ultraviolet pulses by ionizing a bound coherent electronic wave packet. The influence of the dipole phase, which is the main obstacle for state-of-the-art pulse characterization schemes, can be eliminated by angle integration of the photoelectron spectrum. We show that in particular, atomic Rydberg wave packets are ideal and that wave packets involving multiple electronic states provide redundant information that can be used to cross-check the consistency of the phase reconstruction.

The material presented in this chapter is based on important advances realized in attophysics which make feasible to follow the motion of electrons in atoms and molecules with attosecond-level time resolution. In this context, time-delays have been recently determined in the process of photoionization by extreme-ultra- violet (XUV) pulses and the question of the significance of these measured delays arises. As we shall outline here, numerical experiments show that they are intimately related to the structure of the ionized species' continuous spectrum. Another point addressed here is that, in experiments, the measurements have the common characteristic to be performed in the presence of an auxiliary infra-red (IR) field, used to clock the timing of the process. This implies to adapt the theory treatment to handle such two-color photoionization processes. We review a systematic analysis of these features that are characteristic of this class of electronic transitions, when viewed in the time domain.