We report the first observation of intermolecular Coulombic decay (ICD) in liquid water following inner-valence ionization. By combining a monochromatized tabletop high-harmonic source with a liquid microjet, we record electron-electron coincidence spectra at two photon energies that identify the ICD electrons, together with the photoelectrons originating from the $2a_1$ inner-valence band of liquid water. Our results confirm the importance of ICD as a source of low-energy electrons in bulk liquid water and provide quantitative results for modeling the velocity distribution of the slow electrons that are thought to dominate radiation damage in aqueous environments.

Our study reveals the detailed influence of elastic and inelastic mean-free paths on the complete photoelectron spectra of liquid water, including the low-energy electron distributions and the reshaping of the primary photoelectron bands.

We experimentally and theoretically demonstrate that electron correlation can cause the bond-length sensitivity of a shape resonance to induce an unexpected vibrational state–dependent ionization delay in a nonresonant channel. This discovery was enabled by a high-resolution attosecond-interferometry experiment based on a 400-nm driving and dressing wavelength. The short-wavelength driver results in a 6.2–electron volt separation between harmonics, markedly reducing the spectral overlap in the measured interferogram. We demonstrate the promise of this method on O ₂ , a system characterized by broad vibrational progressions and a dense photoelectron spectrum. We measure a 40-attosecond variation of the photoionization delays over the X ² Π _g vibrational progression. Multichannel calculations show that this variation originates from a strong bond-length dependence of the energetic position of a shape resonance in the b 4 Σ g − channel, which translates to the observed effects through electron correlation. The unprecedented energy resolution and delay accuracies demonstrate the promise of visible-light–driven molecular attosecond interferometry.

Attosecond Pulse Trains (APT) generated by high-harmonic generation (HHG) of high-intensity near-infrared (IR) laser pulses have proven valuable for studying the electronic dynamics of atomic and molecular species. However, the high intensities required for high-photon-energy, high-flux HHG usually limit the class of adequate laser systems to repetition rates below 10 kHz. Here, APT’s generated from the 100 kHz, 160 W, 40 fs laser system (HR-1) currently under commissioning at the extreme light infrastructure attosecond light pulse source (ELI-ALPS) are reconstructed using the reconstruction of attosecond beating by interference of two-photon Transitions (RABBIT) technique. These experiments constitute the first attosecond time-resolved photoelectron spectroscopy measurements with attosecond pulses performed at 100 kHz repetition rate and one of the first experiments performed at ELI-ALPS in the framework of projects commissioning its newly installed technologies. These RABBIT measurements were taken with an additional IR field temporally locked to the extreme-ultraviolet APT, resulting in an atypical ω beating. We show that the phase of the 2ω beating recorded under these conditions is strictly identical to that observed in standard RABBIT measurements within second-order perturbation theory. This work highlights an experimental simplification for future experiments based on attosecond interferometry (or RABBIT), which is particularly useful when lasers with high average powers are used.

We report the first systematic photoelectron measurements of the three outer-valence bands of liquid water as a function of the ionizing photon energy in the near-threshold region. We use extreme-ultraviolet (XUV) radiation tunable between ∼17.1 and 35.6 eV, obtained through monochromatization of a high-harmonic source. We show that the absolute values of the apparent vertical ionization energies and their respective peak widths show a decreasing trend of their magnitudes with increasing photon energy close to the ionization threshold. We find that the observed effects do not only depend on the electron kinetic energy but are also different for the various outer-valence bands. These observations are consistent with, but not fully explained by, the effects of inelastic electron scattering.