Extreme light confinement in plasmonic nanosystems enables novel applications in photonics, sensor technology, energy harvesting, biology, and quantum information processing. Fullerenes represent an extreme case for nanoplasmonics: They are subnanometer carbon-based molecules showing high-energy and ultrabroad plasmon resonances; however, the fundamental mechanisms driving the plasmonic response and the corresponding collective electron dynamics are still elusive. Here, we uncover the dominant role of electron correlations in the dynamics of the giant plasmon resonance (GPR) of the subnanometer system C 60 by using attosecond photoemission chronoscopy. We find a characteristic photoemission delay of up to about 300 attoseconds that is purely induced by coherent large-scale electron correlations in the plasmonic potential. These results provide insights into the nature of the plasmon resonances in subnanometer systems and open perspectives for advancing nanoplasmonic applications.

The free expansion of a planar plasma surface is a fundamental non-equilibrium process relevant for various fields but as-yet experimentally still difficult to capture. The significance of the associated spatiotemporal plasma motion ranges from astrophysics and controlled fusion to laser machining, surface high-harmonic generation, plasma mirrors, and laser-driven particle acceleration. Here, we show that x-ray coherent diffractive imaging can surpass existing approaches and enables the quantitative real-time analysis of the sudden free expansion of laser-heated nanoplasmas. For laser-ionized SiO2 nanospheres, we resolve the formation of the emerging nearly self-similar plasma profile evolution and expose the so far inaccessible shell-wise expansion dynamics including the associated startup delay and rarefaction front velocity. Our results establish time-resolved diffractive imaging as an accurate quantitative diagnostic platform for tracing and characterizing plasma expansion and indicate the possibility to resolve various laser-driven processes including shock formation and wave-breaking phenomena with unprecedented resolution.

The strong-field control of plasmonic nanosystems opens up new perspectives for nonlinear plasmonic spectroscopy and petahertz electronics. Questions, however, remain regarding the nature of nonlinear light-matter interactions at sub-wavelength spatial and ultrafast temporal scales. Addressing this challenge, we investigated the strong-field control of the plasmonic response of Au nanoshells with a SiO_2 core to an intense laser pulse. We show that the photoelectron energy spectrum from these core-shell nanoparticles displays a striking transition between the weak and strong-field regime. This observed transition agrees with the prediction of our modified Mie-theory simulation that incorporates the nonlinear dielectric nanoshell response. The demonstrated intensity-dependent optical control of the plasmonic response in prototypical core-shell nanoparticles paves the way towards ultrafast switching and opto-electronic signal modulation with more complex nanostructures.

Fullerenes have unique physical and chemical properties that are associated with their delocalized conjugated electronic structure. Among them, there is a giant ultra-broadband - and therefore ultrafast - plasmon resonance, which for C_60 is in the extreme-ultraviolet energy range. While this peculiar resonance has attracted considerable interest for the potential downscaling of nanoplasmonic applications such as sensing, drug delivery and photocatalysis at the atomic level, its electronic character has remained elusive. The ultrafast decay time of this collective excitation demands attosecond techniques for real-time access to the photoinduced dynamics. Here, we uncover the role of electron correlations in the giant plasmon resonance of C_60 by employing attosecond photoemission chronoscopy. We find a characteristic photoemission delay of up to 200 attoseconds pertaining to the plasmon that is purely induced by coherent large-scale correlations. This result provides novel insight into the quantum nature of plasmonic resonances, and sets a benchmark for advancing nanoplasmonic applications.

Regarded as the most important ion in interstellar chemistry, the trihydrogen cation, H_3^+ , plays a vital role in the formation of water and many complex organic molecules believed to be responsible for life in our universe. Apart from traditional plasma discharges, recent laboratory studies have focused on forming the trihydrogen cation from large organic molecules during their interactions with intense radiation and charged particles. In contrast, we present results on forming H_3^+ from bimolecular reactions that involve only an inorganic molecule, namely water, without the presence of any organic molecules to facilitate its formation. This generation of H_3^+ is enabled by “engineering” a suitable reaction environment comprising water-covered silica nanoparticles exposed to intense, femtosecond laser pulses. Similar, naturally-occurring, environments might exist in astrophysical settings where hydrated nanometer-sized dust particles are impacted by cosmic rays of charged particles or solar wind ions. Our results are a clear manifestation of how aerosolized nanoparticles in intense femtosecond laser fields can serve as a catalysts that enable exotic molecular entities to be produced via non-traditional routes.

The free expansion of a planar plasma surface is a fundamental non-equilibrium process relevant for various fields but as-yet experimentally still difficult to capture. The significance of the associated spatiotemporal plasma motion ranges from astrophysics and controlled fusion to laser machining, surface high-harmonic generation, plasma mirrors, and laser-particle acceleration. Here, we show that x-ray coherent diffractive imaging can surpass existing approaches and enables the quantitative real-time analysis of the sudden free expansion of nanoplasmas. For laser-ionized SiO$_2$ nanospheres, we resolve the formation of the emerging nearly self-similar plasma profile evolution and expose the so far inaccessible shell-wise expansion dynamics including the associated startup delay and rarefaction front velocity. Our results establish time-resolved diffractive imaging as an accurate quantitative diagnostic platform for tracing and characterizing plasma expansion and indicate the possibility to resolve various laser-driven processes including shock formation and wave-breaking phenomena with unprecedented resolution.

Detailed knowledge about photo-induced electron dynamics in water is key to the understanding of several biological and chemical mechanisms, in particular for those resulting from ionizing radiation [1] . While several studies reporting on detailed low-energy electron scattering cross sections in amorphous ice, liquid water and large water clusters [2] and a time-resolved approach to investigate electron scattering in water has been reported [3] , such investigations in gas-phase water clusters have shown to be a promising bridge in between the gas and liquid phase, allowing for many technological limitations to be overcome and setting a clear route to perform attosecond-resolved spectroscopy of hydrated molecules. Indeed, extreme ultraviolet (XUV) attosecond pulses may be used to photo-ionize a water sample and to investigate the electron dynamics and transport properties with extremely high temporal resolution [4] .

Ultrafast light-induced molecular reactions on aerosolized nanoparticles may elucidate early steps in the photoactivity of nanoparticles with potential impact in fields ranging from chemistry and medicine to climate science. In situ morphology discrimination for nanoparticle streams when measuring light-induced reaction yields is crucial, but lacking. Here, we experimentally demonstrate, using the reaction nano-scopy technique, that proton momenta from deprotonation reactions induced by intense femtosecond pulses exhibit clear, distinguishable signatures for single silica nanospheres and their clusters. Our findings are supported by classical trajectory Monte Carlo simulations. The results demonstrate an in situ single-shot discrimination method between reaction yields from photoinduced processes on single particles and their clusters. We find that the ionization of clusters dominates at sufficiently low intensities, providing an explanation to resolve previously observed discrepancies between experimental data and theoretical treatments, which considered only single nanoparticles.

Theoretical studies indicated that C_{60} exposed to linearly polarized intense infrared pulses undergoes periodic cage structural distortions with typical periods around 100 fs (1  fs=10^{-15}  s). Here, we use the laser-driven self-imaging electron diffraction technique, previously developed for atoms and small molecules, to measure laser-induced deformation of C_{60} in an intense 3.6  μm laser field. A prolate molecular elongation along the laser polarization axis is determined to be (6.1±1.4)% via both angular- and energy-resolved measurements of electrons that are released, driven back, and diffracted from the molecule within the same laser field. The observed deformation is confirmed by density functional theory simulations of nuclear dynamics on time-dependent adiabatic states and indicates a nonadiabatic excitation of the h_{g}(1) prolate-oblate mode. The results demonstrate the applicability of laser-driven electron diffraction methods for studying macromolecular structural dynamics in four dimensions with atomic time and spatial resolutions.

Field localization by nanostructures illuminated with laser pulses of well-defined waveform enables spatio-temporal tailoring of the near-fields for sub-cycle control of electron dynamics at the nanoscale. Here, we apply intense linearly-polarized two-color laser pulses for all-optical control of the highest energy electron emission from SiO 2 nanoparticles. For the size regime where light propagation effects become important, we demonstrate the possibility to control the preferential emission angle of a considerable fraction of the fastest electrons by varying the relative phase of the two-color field. Trajectory based semi-classical simulations show that for the investigated nanoparticle size range the directional steering can be attributed to the two-color effect on the electron trajectories, while the accompanied modification of the spatial distribution of the ionization rate on the nanoparticle surface has only a minor effect.

We present the results of a systematic study of photoelectron emission from isolated dielectric nanoparticles (SiO2) irradiated by intense 25 fs, 780 nm linearly polarized laser pulses as a function of particle size (20 nm to 750 nm in diameter) and laser intensity. We also introduce an experimental technique to reduce the effects of focal volume averaging. The highest photoelectron energies show a strong size dependence, increasing by a factor of six over the range of particles sizes studied at a fixed intensity. For smaller particle sizes (up to 200 nm), our findings agree well with earlier results obtained with few-cycle, ∼4 fs pulses. For large nanoparticles, which exhibit stronger near-field localization due to field-propagation effects, we observe the emission of much more energetic electrons, reaching energies up to ∼200 times the ponderomotive energy. This strong deviation in maximum photoelectron energy is attributed to the increase in ionization and charge interaction for many-cycle pulses at similar intensities.

Nanoparticles offer unique properties as photocatalysts with large surface areas. Under irradiation with light, the associated near-fields can induce, enhance, and control molecular adsorbate reactions on the nanoscale. So far, however, there is no simple method available to spatially resolve the near-field induced reaction yield on the surface of nanoparticles. Here we close this gap by introducing reaction nanoscopy based on three-dimensional momentum-resolved photoionization. The technique is demonstrated for the spatially selective proton generation in few-cycle laser-induced dissociative ionization of ethanol and water on SiO 2 nanoparticles, resolving a pronounced variation across the particle surface. The results are modeled and reproduced qualitatively by electrostatic and quasi-classical mean-field Mie Monte-Carlo (M 3 C) calculations. Reaction nanoscopy is suited for a wide range of isolated nanosystems and can provide spatially resolved ultrafast reaction dynamics on nanoparticles, clusters, and droplets.

The low-energy photoelectron spectra from strong-field ionization of C-60 fullerenes and noble gases (xenon and krypton) with 3 mu m laser pulses are measured and compared. It is found that the low-energy structure (LES), a universal spikelike feature in the strong-field limit of atoms and small molecules, is significantly suppressed in the C-60 photoelectron distribution. We propose that the large polarizability of the C-60 core disrupts the corresponding electron trajectories. In particular, the induced dipole force repels the electron, which opposes the focusing and bunching due to the Coulomb potential that is responsible for the LES, thus leading to its reduction.

The development of attosecond metrology has enabled time-resolved studies on atoms, molecules, and (nanostructured) solids. Despite a wealth of theoretical work, attosecond experiments on isolated nanotargets, such as nanoparticles, clusters, and droplets have been lacking. Only recently, attosecond streaking metrology could be extended to isolated silica nanospheres, enabling real-time measurements of the inelastic scattering time in dielectric materials. Here, we revisit these experiments and describe the single-shot analysis of velocitymap images, which permits to evaluate the recorded number of electrons. Modeling of the recorded electron histograms allows deriving the irradiated nanoparticle statistics. Theoretically, we analyze the influence of the nanoparticle size on the field-induced delay, which is one of the terms contributing to the measured streaking delay. The obtained new insight into attosecond streaking experiments on nanoparticles is expected to guide wider implementation of the approach on other types of nanoparticles, clusters, and droplets.

Field localization by nanostructures illuminated with laser pulses of well-defined waveform enables spatial-temporal tailoring of the near-fields for sub-cycle control of electron dynamics at the nanoscale [1]. Transition from the ponderomotive to sub-cycle acceleration regime of the near-field-driven electron emission was shown to be determined by the ratio of the near-field decay length and amplitude of the electron quiver motion [2]. Field-propagation-induced shaping of the near-field in turn has been utilized for size-dependent directional tuning of the electron emission from isolated nanospheres [3]. Here, we go beyond these studies and use intense 30 fs two-color laser pulses (780 nm/390 nm) to tailor the spatio-temporal near-fields of SiO2 nanoparticles, enabling the all-optical control of the electron emission direction.

Attosecond streaking is used to study the dynamics of electron scattering in dielectric nanoparticles in real time. Revealing the mechanisms involved is the first step towards understanding electron scattering in more complex dielectrics. The scattering of electrons in dielectric materials is central to laser nanomachining1, light-driven electronics2 and radiation damage3,4,5. Here, we demonstrate real-time access to electron scattering by implementing attosecond streaking spectroscopy on dielectric nanoparticles: photoelectrons are generated inside the nanoparticles and both their transport through the material and photoemission are tracked on an attosecond timescale. We develop a theoretical framework for attosecond streaking spectroscopy in dielectrics and identify that the presence of the internal field inside the material cancels the influence of elastic scattering, enabling the selective characterization of the inelastic scattering time. The approach is demonstrated on silica nanoparticles, where an inelastic mean-free path is extracted for 20–30 eV. Our approach enables the characterization of inelastic scattering in various dielectric solids and liquids, including water, which can be studied in the form of droplets.

We study strong-field ionization of dielectric nanospheres and focus on the enhancement of the cutoff energies for backscattering electrons resulting from charge interaction. Though recent studies clearly demonstrated the decisive impact of a surface trapping field on the electron backscattering process, a clear picture of the underlying mechanism is lacking. Here, we provide this picture and present a simple and transparent extension of the famous three-step model of strong-field science by adding a triangular surface trapping potential. We justify this model for the case of dielectric nanospheres based on high-level transport simulations. The analysis of the trapping field assisted backscattering provides a universal scaling of the maximal recollision and backscattering energies as 9 U-p and 14.5 U-p, respectively, where U-p is the local ponderomotive potential. The universal nature of the enhancement over the conventional three-step model is of particular interest for the generation of attosecond electron bunches via near-field induced photoemission and high harmonic generation at nanostructures.

Summary form only given. Strong-field induced processes in molecules such as ionization and dissociation have been subject to theoretical and experimental investigations for many decades [1]. These processes include, e.g., above threshold ionization, high harmonic generation with the generation of attosecond pulses, and laser induced electron diffraction. Since these effects strongly rely on the exact spatial and temporal evolution of the electric fields they are also influenced and controlled by the presence of enhanced near-fields in the proximity of a nanostructure [2]. Recent theoretical and experimental work focused mainly on either atomic processes in strong near-fields or near-field driven photoemission from nanostructures. Here, we go beyond these studies and investigate the near-field control of one of the most fundamental molecular strong-field processes, namely multiple ionization leading to Coulomb explosion.