In this study we investigate the dissociative photoionization of molecular hydrogen H-2, addressing the influence of autoionizing states and nuclear motion on the photoelectron dynamics. Experimental results are compared with ab initio calculations.

The interaction of an extreme-ultraviolet attosecond pulse with a molecular system suddenly removes electrons, which can lead to significant changes in the chemical bonding and hence to rearrangements of the residual molecular cation. The timescales of the electronic and nuclear dynamics are usually very different, thus supporting separate treatment. However, when light nuclei are involved, as in most organic and biological molecules containing atomic hydrogen, the correlation between electronic and nuclear motion cannot be ignored. Using an advanced attosecond pump–probe spectroscopic method, we show that the coupling between electronic and nuclear motion in H2 leaves a clear trace in the phase of the entangled electron–nuclear wave packet. This requires us to re-evaluate the physical meaning of the measured phase, which depends on the energy distribution between electrons and nuclei. The conclusions are supported by ab initio calculations that explicitly account for the coupling between electronic and nuclear dynamics. Attosecond XUV spectroscopy is reported, focussing on non-Born–Oppenheimer dynamics in molecular gases of light elements. It is shown that the phase of the detected photoelectrons carries information from both vibrational and electronic degrees of freedom.

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-1np 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.

This corrects the article DOI: 10.1103/PhysRevLett.115.133001.

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 $1{s}^{2}$ 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 present measurements of single-photon ionization time delays between the outermost valence electrons of argon and neon using a coincidence detection technique that allows for the simultaneous measurement of both species under identical conditions. The analysis of the measured traces reveals energy-dependent time delays of a few tens of attoseconds with high energy resolution. In contrast to photoelectrons ejected through tunneling, single-photon ionization can be well described in the framework of Wigner time delays. Accordingly, the overall trend of our data is reproduced by recent Wigner time delay calculations. However, besides the general trend we observe resonance features occurring at specific photon energies. These features have been qualitatively reproduced and identified by a calculation using the multiconfigurational Hartree-Fock method, including the influence of doubly excited states and ionization thresholds.

Time is not an operator in quantum mechanics, and therefore not a direct observable [1]. As a consequence, timing information on any physical process has to be extracted indirectly by choosing other measurable observables. Following the peak of an electron wavepacket for determining photoionization time delays, for example, can be tricky and often misleading. In contrast to a light pulse, an electron wavepacket disperses even in vacuum. Since the propagation of the peak of a wavepacket follows by definition the group delay, almost any group delay can be measured during propagation in combination with an appropriate energy-dependent transmission filter. This explains why in the multi-photon or tunnel ionization regime the group delay (or the related, although not exactly equivalent, Wigner delay) gives the wrong explanation for the measured delay [2,3], whereas in the single-photon ionization regime we can show experimentally that the Wigner time delay explains the general trend correctly although it does not capture all the observed features (Fig. 1c).

We present photoemission time-delay measurements between electrons originating from the valence shells of neon and argon obtained by attosecond streaking. After giving a brief review of the different techniques, we focus on more detailed analysis using the attosecond streaking technique. We show that the temporal structure of the ionizing single attosecond pulse may significantly affect the obtained time delays, and we propose a procedure how to take this contribution properly into account. Our analysis reveals a delay of a few tens of attoseconds in a photon energy range between 28 and 40 eV in the emission of electrons ionized from argon with respect to those liberated from neon.

Here, we present the first experiments addressing the single-photon ionization time delay for randomly oriented molecular hydrogen (H2), the simplest non-charged molecule. We measure the difference \( \varDelta \tau_{\text{m}}^{\text{Ar,H2}} \) in time delays between electrons emitted from the 3p6 shell of argon (Ar) and the highest occupied molecular orbital of H2 by means of two distinct methods, employing attosecond streaking and RABBITT.

In contrast to expectations, we observe that the photoionization time delay from the 1s2 spherically symmetric ground state of He depend on the electron emission direction with respect to an external reference. We attribute the observed anisotropy to the interplay between different final quantum states, which become accessible once two photons are involved in the photoionization process. This is a universal effect, which needs to be taken into account for any study dealing with photoionization dynamics.

For the first time, we implemented both RABBITT and attosecond energy streaking using an AttoCOLTRIMS apparatus and exploit its advantages to determine energy-and angle-resolved single-photon ionization time delays for different noble gases.

The question of how long a tunneling particle spends inside the barrier region has remained unresolved since the early days of quantum mechanics. The main theoretical contenders, such as the Buttiker–Landauer, Eisenbud–Wigner, and Larmor time, give contradictory answers. On the other hand, recent attempts at reconstructing valence electron dynamics in atoms and molecules have entered a regime where the tunneling time genuinely matters. Here, we compare the main competing theories of tunneling time against experimental measurements using the attoclock in strong laser field ionization of helium atoms. The attoclock uses a close to circularly polarized femtosecond laser pulse, mapping the angle of rotation of the laser field vector to time similar to the hand of a watch. Refined attoclock measurements reveal a real (not instantaneous) tunneling delay time over a large intensity regime, using two independent experimental apparatus. Only two theoretical predictions are compatible within our experimental error: the Larmor time and the probability distribution of tunneling times constructed using a Feynman Path Integral formulation. The latter better matches the observed qualitative change in tunneling time over a wide intensity range, and predicts a broad tunneling time distribution with a long tail. The implication of such a probability distribution of tunneling times, as opposed to a distinct tunneling time, would imply that one must account for a significant, though bounded and measurable, uncertainty as to when the hole dynamics begin to evolve. We therefore expect our results to impact the reconstruction of attosecond electron dynamics following tunnel ionization.

Here we present a successful combination of an attosecond beamline with a COLTRIMS apparatus, which we refer to as AttoCOLTRIMS. The setup provides either single attosecond pulses or attosecond pulse trains for extreme ultraviolet-infrared pump-probe experiments. We achieve full attosecond stability by using an active interferometer stabilization. The capability of the setup is demonstrated by means of two measurements, which lie at the heart of the COLTRIMS detector: firstly, we resolve the rotating electric field vector of an elliptically polarized few-cycle infrared laser field by attosecond streaking exploiting the access to the 3D momentum space of the charged particles. Secondly, we show streaking measurements on different atomic species obtained simultaneously in a single measurement making use of the advantage of measuring ions and electrons in coincidence. Both of these studies demonstrate the potential of the AttoCOLTRIMS for attosecond science.

We combine an attosecond beamline with a 3D momentum imaging spectrometer to achieve coincidence pump probe experiments with unprecedented attosecond time-resolution. Besides technical details, first coincidence and pump-probe experiments are presented.

Recent measurements have demonstrated the possibility of probing single-photon ionization time delays of electrons originating from different initial states [1,2]. Here, we show for the first time the importance of the temporal structure of the ionizing single attosecond pulse (i.e. attochirp) in the extraction of time delays in attosecond streaking experiments. We have demonstrated this by measuring the time delay between valence electrons from different atomic species by combining attosecond streaking with a coincidence detection scheme. This novel technique allows for the simultaneous measurement of both species under identical conditions. We find that the attochirp introduces an artificial time delay that may exceed the atomic time delay and present a general procedure, which corrects for this contribution. Our analysis, exemplarily applied to argon (Ar) and neon (Ne), reveals an energy-dependent atomic time delay of a few tens of attoseconds in agreement with theoretical predictions.