Attosecond time-resolved photoemission spectroscopy reveals that photoemission from solids is not yet fully understood. The relative emission delays between four photoemission channels measured for the van der Waals crystal tungsten diselenide (WSe) can only be explained by accounting for both propagation and intra-atomic delays. The intra-atomic delay depends on the angular momentum of the initial localized state and is determined by intra-atomic interactions. For the studied case of WSe, the photoemission events are time ordered with rising initial-state angular momentum. Including intra-atomic electron-electron interaction and angular momentum of the initial localized state yields excellent agreement between theory and experiment. This has required a revision of existing models for solid-state photoemission, and thus, attosecond time-resolved photoemission from solids provides important benchmarks for improved future photoemission models.

We report a detailed experimental and theoretical study on high-order harmonic generation of a femtosecond Ti-sapphire laser focused at an intensity of around 1015 W cm−2 onto a high-pressure (50–210 mbar) neon gas cell of variable length (1–3 mm). Using thorough three-dimensional simulations, we discuss the interplay between the different factors influencing the harmonic-generation efficiency, i.e. phase matching determined by the electronic and atomic dispersions, re-absorption of the harmonics by the medium and refraction of the generating laser beam. Generically, we find that, in our generation conditions, the emission yield of harmonics from the plateau region of the spectrum is absorption limited, whereas the emission from harmonics in the cut-off is strongly reduced due to both electron dispersion and ionization-induced refraction of the laser beam. A good agreement between the numerical results and the experimental data is obtained for the harmonic yield dependence on the various generation parameters (gas pressure, medium length and laser intensity).

A time-resolved study of core-level chemical shifts in a monolayer of aromatic molecules reveals complex photoinduced reaction dynamics. The combination of electron spectroscopy for chemical analysis and ultrashort pulse excitation in the extreme ultraviolet allows performing time-correlated 4d-core-level spectroscopy of iodine atoms that probe the local chemical environment in the adsorbate molecule. The selectivity of the method unveils metastable molecular configurations that appear about 50 ps after the excitation and are efficiently quenched back to the ground state.

Self-assembled monolayer films based on iodobenzoyloxy-functionalized resorc[4]arenes were prepared on gold substrates to serve as model systems for future time-resolved studies of molecular recognition, a mechanism of outstanding importance in bioorganic systems. The film properties were tested using X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM) and imaging ellipsometry. An apparatus for time-resolved electron spectroscopy utilizing femtosecond soft X-ray pulses is capable of detecting iodine core-level photolines and the photoinduced dissociation after ultraviolet illumination. The developed technique holds promise for tracking the temporal evolution of chemical shifts of atomic markers as local probes for the dynamics of the guest-host interaction.

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