The observation of chemical reactions on the time scale of the motion of electrons and nuclei has been made possible by lasers with ever shortened pulse lengths. Superfluid helium represents a special solvent that permits the synthesis of novel classes of molecules that have eluded dynamical studies so far. However, photoexcitation inside this quantum solvent triggers a pronounced response of the solvation shell, which is not well understood. Here, we present a mechanistic description of the solvent response to photoexcitation of indium (In) dopant atoms inside helium nanodroplets (HeN), obtained from femtosecond pump–probe spectroscopy and time-dependent density functional theory simulations. For the In–HeN system, part of the excited state electronic energy leads to expansion of the solvation shell within 600 fs, initiating a collective shell oscillation with a period of about 30 ps. These coupled electronic and nuclear dynamics will be superimposed on intrinsic photoinduced processes of molecular systems inside helium droplets.

Laser-assisted electron scattering (LAES), a light–matter interaction process that facilitates energy transfer between strong light fields and free electrons, has so far been observed only in gas phase. Here we report on the observation of LAES at condensed phase particle densities, for which we create nano-structured systems consisting of a single atom or molecule surrounded by a superfluid He shell of variable thickness (32–340 Å). We observe that free electrons, generated by femtosecond strong-field ionization of the core particle, can gain several tens of photon energies due to multiple LAES processes within the liquid He shell. Supported by Monte Carlo 3D LAES and elastic scattering simulations, these results provide the first insight into the interplay of LAES energy gain/loss and dissipative electron movement in a liquid. Condensed-phase LAES creates new possibilities for space-time studies of solids and for real-time tracing of free electrons in liquids.

Helium nanodroplets can serve as reaction containers for photoinduced time-resolved studies of cold, isolated molecular systems that are otherwise inaccessible. Recently, three different dynamical processes, triggered by photoexcitation of a single atom inside a droplet, were observed in their natural time scale: Expansion of the He solvation shell (He bubble) within 600 fs initiates a collective bubble oscillation with a ∼30 ps oscillation period, followed by dopant ejection after ∼60 ps. Here, we present a systematic investigation of these processes by combining time-resolved photoelectron and photoion spectroscopy with time-dependent He density functional theory simulations. By variation of the photoexcitation energy, we find that the full excess excitation energy, represented by the blue-shifted in-droplet excitation band, is completely transferred to the He environment during the bubble expansion. Surprisingly, we find that variation of the droplet size has only a minor influence on the ejection time, providing insight into the spatial distribution of the ground-state atoms before photoexcitation. Simulated particle trajectories after photoexcitation are in agreement with experimental observations and suggest that the majority of ground-state atoms are located at around 16 Å below the droplet surface. Bubble expansion and oscillation are purely local effects, depending only on the ultimate dopant environment. These solvation-induced dynamics will be superimposed on intramolecular dynamics of molecular systems, and a mechanistic description is fundamental for the interpretation of future experiments.

Laser-assisted electron scattering (LAES), a light-matter interaction process that facilitates energy transfer between strong light fields and free electrons, has so far been observed only in gas phase. Here we report on the observation of LAES at condensed phase particle densities, for which we create nano-structured systems consisting of a single atom or molecule surrounded by a superfluid He shell of variable thickness (32-340 Å). We observe that free electrons, generated by femtosecond strong-field ionization of the core particle, can gain several tens of photon energies due to multiple LAES processes within the liquid He shell. Supported by 3D scattering simulations, these results provide the first insight into the interplay of LAES energy gain/loss and dissipative electron movement in a liquid. Our results reveal that LAES could significantly increase the temporal resolution of ultrafast electron microscopy, potentially to the attosecond regime.

Laser-assisted electron scattering (LAES) is a fundamental three body interaction process that enables energy transfer between electrons and photons in the presence of matter. Here, we focus on the multiscattering regime of electrons generated by above-threshold ionization (ATI) of In atoms inside a high-density nanostructure, helium nanodroplets (HeN) of ∼40 Å radius. The stochastic nature of the multiscattering regime results in photoelectron spectra independent of laser polarization. Numerical simulations via tunnel-type ionization followed by applying the Kroll–Watson approximation for LAES are in agreement with experimental spectra and yield a mechanistic description of electron generation and the LAES energy modulation processes. We find a negligible influence of the electron start position inside the helium droplet on the simulated electron energy spectrum. Further, our simulations shine light on the interplay of electron time of birth, number of LAES gain/loss events, and final kinetic energy; early ionization leads to the largest number of scattering events and thereby the highest electron kinetic energy.