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Journal of physics / B 56(5), 054002 (2023). doi:10.1088/1361-6455/acb872, Imaging the microscopic world in real space and real time is a grand challenge of science. In the landscape of time-resolved imaging techniques, laser-induced electron diffraction (LIED) has recently shown to be a promising candidate to push the frontiers of ultrafast molecular imaging. In this work, we review the main achievements of LIED research in terms of experimental results and advanced modelling. We also envision interesting perspectives toward the future advancement of time-resolved LIED imaging., Published by IOP Publ., Bristol

JPhys photonics 4, 034003 (2022). doi:10.1088/2515-7647/ac6ea5 special issue: "Focus on Nanophotonics and Biophotonics for Biomedical and Environmental Applications", The dynamics of biologically relevant molecules exposed to ionizing radiation contains many facets and spans several orders of magnitude in time and energy. In the extreme ultraviolet (XUV) spectral range, multi-electronic phenomena and bands of correlated states with inner-valence holes must be accounted for in addition to a plethora of vibrational modes and available dissociation channels. The ability to track changes in charge density and bond length during ultrafast reactions is an important endeavor toward more general abilities to simulate and control photochemical processes, possibly inspired by those that have evolved biologically. By using attosecond XUV pulses extending up to 35 eV and few-femtosecond near-infrared pulses, we have previously time-resolved correlated electronic dynamics and charge migration occurring in the biologically relevant molecule adenine after XUV-induced sudden ionization. Here, using additional experimental data, we comprehensively report on both electronic and vibrational dynamics of this nucleobase in an energy range little explored to date with high temporal resolution. The time-dependent yields of parent and fragment ions in the mass spectra are analyzed to extract exponential time constants and oscillation periods. Together with time-dependent density functional theory and ab-initio Green's function methods, we identify different vibrational and electronic processes. Beyond providing further insights into the XUV-induced dynamics of an important nucleobase, our work demonstrates that yields of specific dissociation outcomes can be influenced by sufficiently well-timed ultrashort pulses, therefore providing a new route for the control of the multi-electronic and dissociative dynamics of a DNA building block., Published by IOP Publishing, Bristol

We demonstrate sub-20 fs single-stage post-compression of an Ytterbium-doped fiber laser. Dispersion-engineered dielectric cavity mirrors are used to control spectral broadening in a gas-filled multi-pass cell supporting a throughput of 98%.

A novel light source delivering few-cycle UV pulses is used to reveal an ultrafast modulation of the chiroptical properties of photoexcited chiral molecules, probed by time-resolved photoelectron circular dichroism. We report a periodic inversion of photoelectron emission direction in methyl-lactate on a timescale as short as 6fs.

Chapter 5 describes the efforts being made to reach the few-optical-cycle regime for ultraviolet pulses. The main route to achieve this task is to exploit low dispersion gas media for frequency up-conversion of Ti:Sa and Ytterbium:YAG laser sources. UV generation methods to obtain few-fs (sub 3-fs) pulse duration are discussed, providing state-of-the-art UV sources as a key ingredient in the field of ultrafast UV spectroscopy. Applications to study in real time the ultrafast response of photoexcited states of matter are discussed by the authors.

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] .

As an important branch of molecular science, time-resolved ultraviolet (UV) spectroscopy promises to address ultrafast photochemical and photobiological processes that play key roles in nature, from ozone photolysis to UV-induced DNA damage [1] , [2] . At the few-femtosecond and attosecond timescales, the study of UV-induced molecular dynamics has been hampered due to the technical challenges for the generation and manipulation of ultrabroadband, few-cycle UV pulses [3] – [5] .

The field of ultrafast spectroscopy is based on lasers being able to produce pulses that are as short as a few femtoseconds. Due to their broad bandwidth, these ultrashort light transients are strongly affected by propagation through materials. Therefore, a careful characterization of their temporal profile is required before any application. We propose a scheme for their characterization in situ, ensuring that the pulse parameters are measured in the region where the interaction with the sample takes place. Our method is based on first-principles calculations for strong-field ionization of rare-gas atoms and autocorrelation. We introduce a machine-learning algorithm, called vector space Newton interpolation cage (VSNIC), that uses the results from the first-principles calculations as input and reconstructs from a strong-field autocorrelation pattern for an unknown pulse the pulse length and spectral width by narrow margins.

The advent of the fourth industrial revolution (Industry 4.0) aims at increasing automation and efficiency in manufacturing processes by the adoption of information and communication technologies. Several of the proposed solutions rely on precise localization of material, equipment, or operators. This article investigates the employment of ultrawideband (UWB) real-time location systems (RTLS) in a factory environment and proposes an augmentation technique to mitigate the impairments that arise in such a complex scenario. A Bayesian filtering method is developed to jointly track the motion dynamics and the time-varying visibility conditions of the UWB antennas, with particle-based implementation to deal with the nonlinearity of the UWB measurements. Laboratory tests and industrial experiments are carried out to evaluate the performance of three commercial off-the-shelf UWB technologies: Decawave, Sewio, and Ubisense. The experimental data are then used to calibrate and test the developed filtering technique, showing that it is possible to significantly reduce the positioning error originating from dense multipath and NLOS effects by jointly tracking the target dynamics and visibility conditions.

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. Here we report a method to obtain photoelectron spectra from neutral water clusters following ionization by an extreme-ultraviolet (XUV) attosecond pulse train, representing a first step towards a time-resolved analysis. Typically, a large background signal in the experiment arises from water monomers and carrier gas used in the cluster source. We report a protocol to quantify this background in order to eliminate it from the experimental spectra. We disentangle the accumulated XUV photoionization signal into contributions from the background species and the photoelectron spectra from the clusters. This proof-of-principle study demonstrates feasibility of background free photoelectron spectra of neutral water clusters ionized by XUV combs and paves the way for the detailed time-resolved analysis of the underlying dynamics., JPhys Photonics, 2 (3), ISSN:2515-7647

The journal of physical chemistry letters 11(3), 891 - 899 (2020). doi:10.1021/acs.jpclett.9b03517, Extreme-ultraviolet-induced charge migration in biorelevant molecules is a fundamental step in the complex path leading to photodamage. In this work we propose a simple interpretation of the charge migration recently observed in an attosecond pump–probe experiment on the amino acid tryptophan. We find that the decay of the prominent low-frequency spectral structure with increasing pump–probe delay is due to a quantum beating between two geometrically distinct, almost degenerate charge oscillations. Quantum beating is ubiquitous in these systems, and at least on the few-to-tens of femtosecond time scales, it may dominate over decoherence the line intensities of time-resolved spectra. We also address the experimentally observed phase shift in the charge oscillations of two different amino acids, tryptophan and phenylalanine. Our results indicate that a beyond mean-field treatment of the electron dynamics is necessary to reproduce the correct behavior., Published by ACS, Washington, DC

We demonstrate post-compression of 1.2 ps pulses to the few-cycle regime via multi-pass spectral broadening. We achieve compression factors of 40 via single and >90 via dual stage compression employing mJ pulses.

9th EPS-QEOD Europhoton Conference on Solid-State, Fibre, and Waveguide Coherent Light Sources, EUROPHOTON 2020, Online, Online, 30 Aug 2020 - 4 Sep 2020; The European physical journal / Web of Conferences 243, 21002 (2020). doi:10.1051/epjconf/202024321002, Published by EDP Sciences, Les Ulis

We report post-compression of 1.2 ps pulses into the few-cycle regime via multi-pass spectral broadening. We achieve compression factors of 40 in single and 93 in a dual stage scheme using a compact setup.

We performed angle-resolved photoelectron spectroscopy of water clusters ionized by an extreme-ultraviolet attosecond pulse train. A clean signature of the clusters was isolated from the water monomer contribution, to be used for time-resolved attosecond spectroscopy.

Generation of few-femtosecond (fs) pulses in the ultraviolet (UV) is important in ultrafast spectroscopy since several bio-relevant molecules, including DNA bases, possess electronic transitions in this spectral region [1]. Exploiting nonlinear processes driven by intense laser pulses has led to several advances to meet this challenge. We developed a source delivering 1.9 fs (2.2 cycles at 255 nm) deep-UV pulses with 150 nJ of energy on target [2].

XXI International Conference on Ultrafast Phenomena 2018, UP 2018, Hamburg, Germany, 15 Jul 2018 - 20 Jul 2018; The European physical journal / Web of Conferences 205, 07002 (2019). doi:10.1051/epjconf/201920507002, Laser-aligned carbonyl-sulfide molecules were strong-field ionized using mid-infrared light. Investigating the strong-field effects in the molecular frame allowed to add novel facets to the understanding of the intrinsic nature of strong-field physics., Published by EDP Sciences, Les Ulis

Attosecond pump–probe spectroscopy is a unique tool for the direct observation of the light-activated electronic motion in molecules and it offers the possibility to capture the first instants of a chemical reaction. Recently, advances in attosecond technology allowed the charge migration processes to be revealed in biochemically relevant molecules. Although this purely electronic process might be key for a future chemistry at the electron time scale, the influence of this ultrafast charge flow on the reactivity of a molecule is still debated. In this work, we exploit extreme ultraviolet attosecond pulses to activate charge migration in two aromatic amino acids, namely phenylalanine and tryptophan. Advanced numerical calculations are performed to interpret the experimental data and to discuss the effects of the nuclear dynamics on the activated quantum coherences. By comparing the experimental results obtained in the two molecules, we show that the presence of different functional groups strongly affects the fragmentation pathways, as well as the charge rearrangement. The observed charge dynamics indeed present peculiar aspects, including characteristic periodicities and decoherence times. Numerical results indicate that, even for a very large molecule such as tryptophan, the quantum coherences can survive the nuclear dynamics for several femtoseconds. These results open new and important perspectives for a deeper understanding of the photo-induced charge dynamics, as a promising tool to control the reactivity of bio-relevant molecules via photo-excitation. This article is part of the theme issue ‘Measurement of ultrafast electronic and structural dynamics with X-rays’.

A time resolved setup combining sub-2fs UV pump pulses with attosecond XUV probe pulses is presented. This scheme will allow the UV photo-induced electron dynamics in bio-chemically relevant molecules to be investigated with unprecedented time resolution.

Measurements on the strong-field ionization of carbonyl sulfide molecules by short, intense, 2~\um wavelength laser pulses are presented from experiments where angle-resolved photoelectron distributions were recorded with a high-energy velocity map imaging spectrometer, designed to reach a maximum kinetic energy of 500~eV. The laser-field-free elastic-scattering cross section of carbonyl sulfide was extracted from the measurements and is found in good agreement with previous experiments, performed using conventional electron diffraction. By comparing our measurements to the results of calculations, based on the quantitative rescattering theory (QRS), the bond lengths and molecular geometry were extracted from the experimental differential cross sections to a precision better than $\pm5$~pm and in agreement with the known values.

Nature photonics 13(2), 91 - 95 (2019). doi:10.1038/s41566-018-0308-z, A key challenge in attosecond science is the temporal characterization of attosecond pulses that are essential for understanding the evolution of electronic wavefunctions in atoms, molecules and solids. Current characterization methods, based on nonlinear light–matter interactions, are limited in terms of stability and waveform complexity. Here, we experimentally demonstrate a conceptually new linear and all-optical pulse characterization method, inspired by double-blind holography. Holography is realized by measuring the extreme ultraviolet (XUV) spectra of two unknown attosecond signals and their interference. Assuming a finite pulse duration constraint, we reconstruct the missing spectral phases and characterize the unknown signals in both isolated pulse and double pulse scenarios. This method can be implemented in a wide range of experimental realizations, enabling the study of complex electron dynamics via a single-shot and linear measurement., Published by Nature Publ. Group, London [u.a.]

XXI International Conference on Ultrafast Phenomena 2018, UP 2018, Hamburg, Germany, 15 Jul 2018 - 20 Jul 2018; The European physical journal / Web of Conferences 205, 02009 (2019). doi:10.1051/epjconf/201920502009, Extreme-ultraviolet pulses as short as 5 fs, produced by high- order harmonic generation and selected by a time-delay compensated monochromator, were fully reconstructed thanks to an advanced ptychographic technique, while most commonly used reconstruction methods fail. These pulses constitute the shortest extreme ultraviolet pulses ever achieved via a time-delay compensated monochromator., Published by EDP Sciences, Les Ulis

In the above article [1] , the text in the box of Fig. 9(b) should report $\varepsilon$ @95% = 1.17 m rather than $\varepsilon$ @95% = 0.40 m.

In this work, we demonstrate postcompression of 1.2 ps laser pulses to 13 fs via gas-based multipass spectral broadening. Our results yield a single-stage compression factor of about 40 at 200 W in-burst average power and a total compression factor > 90 at reduced power. The employed scheme represents a route toward compact few-cycle sources driven by industrial-grade Yb:YAG lasers at high average power.

We present time-resolved ultraviolet-pump x-ray probe Auger spectra of 2-thiouracil. An ultraviolet induced shift towards higher kinetic energies is observed in the sulfur 2p Auger decay. The difference Auger spectra of pumped and unpumped molecules exhibit ultrafast dynamics in the shift amplitude, in which three phases can be recognized. In the first 100 fs, a shift towards higher kinetic energies is observed, followed by a 400 fs shift back to lower kinetic energies and a 1 ps shift again to higher kinetic energies. We use a simple Coulomb-model, aided by quantum chemical calculations of potential energy states, to deduce a C–S bond expansion within the first 100 fs. The bond elongation triggers internal conversion from the photoexcited S2 to the S1 state. Based on timescales, the subsequent dynamics can be interpreted in terms of S1 nuclear relaxation and S1-triplet internal conversion.

Hydrogen migration in the glycine cation has been investigated using a combination of a short train of attosecond extreme ultraviolet pulses with few-optical-cycle near-infrared pulses. The yield of the photofragments produced has been measured as a function of pump–probe delay. These time-dependent measurements reveal the presence of a hydrogen migration process occurring in 48 fs. Previous mass spectrometric experiments and theoretical calculations have allowed us to identify the conformations and cation states involved in the process induced by the broad band extreme ultraviolet radiation.

Optics express 26(6), 6771 - 6784 (2018). doi:10.1364/OE.26.006771, Sub-10-fs pulses tunable in the extreme-ultraviolet (XUV) spectral region are particularly important in many research fields: from atomic and molecular spectroscopy to the study of relaxation processes in solids and transition phase processes, from holography to free-electron laser injection. A crucial prerequisite for all applications is the accurate measurement of the temporal characteristics of these pulses. To fulfill this purpose, many phase retrieval algorithms have been successfully applied to reconstruct XUV attosecond pulses. Nevertheless, their extension to XUV femtosecond pulses is not trivial and has never been investigated/reported so far. We demonstrate that ultrashort XUV pulses, produced by high-order harmonic generation, spectrally filtered by a time-delay compensated monochromator, can be fully characterized, in terms of temporal intensity and phase, by employing the ptychographic reconstruction technique while other common reconstruction algorithms fail. This allows us to report on the generation and complete temporal characterization of XUV pulses with duration down to 5 fs, which constitute the shortest XUV pulse ever achieved via a time-delay compensated monochromator., Published by OSA, Washington, DC

Nature Communications 9(1), 302 (2018). doi:10.1038/s41467-017-02702-x, Coherent diffractive imaging of individual free nanoparticles has opened routes for the in situ analysis of their transient structural, optical, and electronic properties. So far, single-shot single-particle diffraction was assumed to be feasible only at extreme ultraviolet and X-ray free-electron lasers, restricting this research field to large-scale facilities. Here we demonstrate single-shot imaging of isolated helium nanodroplets using extreme ultraviolet pulses from a femtosecond-laser-driven high harmonic source. We obtain bright wide-angle scattering patterns, that allow us to uniquely identify hitherto unresolved prolate shapes of superfluid helium droplets. Our results mark the advent of single-shot gas-phase nanoscopy with lab-based short-wavelength pulses and pave the way to ultrafast coherent diffractive imaging with phase-controlled multicolor fields and attosecond pulses., Published by Nature Publishing Group UK, [London]

Journal of optics 20, 0024002 (2017). doi:10.1088/2040-8986/aa9b08, 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 velocity-map 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., Published by IOP Publ., Bristol

Attosecond pump-probe experiments performed in small molecules have allowed tracking charge dynamics in the natural time scale of electron motion. That this is also possible in biologically relevant molecules is still a matter of debate, because the large number of available nuclear degrees of freedom might destroy the coherent charge dynamics induced by the attosecond pulse. Here we investigate extreme ultraviolet-induced charge dynamics in the amino acid tryptophan. We find that, although nuclear motion and nonadiabatic effects introduce some decoherence in the moving electron wave packet, these do not significantly modify the coherence induced by the attosecond pulse during the early stages of the dynamics, at least for molecules in their equilibrium geometry. Our conclusions are based on elaborate theoretical calculations and the experimental observation of sub-4 fs dynamics, which can only be reasonably assigned to electronic motion. Hence, attosecond pump-probe spectroscopy appears as a promising approach to induce and image charge dynamics in complex molecules.

We report on single-shot coherent diffractive imaging of isolated helium nanodroplets obtained with intense multicolor XUV pulses from a high harmonic source. The wide-angle scattering patterns yield the droplets’ shapes and refractive indices.

The hitherto unexplored two-photon doubly excited states [Ne∗(2p-13s)]2 were experimentally identified using the seeded, fully coherent, intense extreme ultraviolet free-electron laser FERMI. These states undergo ultrafast interatomic Coulombic decay (ICD), which predominantly produces singly ionized dimers. In order to obtain the rate of ICD, the resulting yield of Ne2+ ions was recorded as a function of delay between the extreme ultraviolet pump and UV probe laser pulses. The extracted lifetimes of the long-lived doubly excited states, 390(-130/+450) fs, and of the short-lived ones, less than 150 fs, are in good agreement with ab initio quantum mechanical calculations.

Summary form only given. One of the ultimate goals of molecular physics is the possibility of accessing the structural dynamics of molecules through external fields. To this end, one first has to image the molecular structure and dynamics with few-fs temporal resolution and atomic spatial resolution simultaneously. Laser induced electron diffraction (LIED) is a very promising candidate for the spatiotemporal imaging of small molecules [1]. So far most of the LIED experiments have been performed on isotropic molecular samples [2, 3]. Recently, this technique was used to derive C-C and C-H bond lengths of acetylene from a molecular-frame measurement [4]. Here, we present the investigation of the geometry of strongly aligned OCS molecules by using IR-driven laser induced electron diffraction. In our experimental setup, strongly aligned molecules are prepared in the interaction area by exploiting a combination of quantum-state-selected molecular beams and pulse-shaped laser fields. Molecular orientation can also be achieved by the application of an additional moderately strong DC electric field [5]. The controlled molecules are exposed to IR-driven LIED pulses. The LIED driving field consists of linearly polarised 50-fs pulses, with a tunable wavelength in the range 1.3-2.5 μm and an energy of few hundreds μJ (at 2.5 μm) or higher.

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.

Nature Communications, 8 (1), ISSN:2041-1723

After sudden ionization of a large molecule, the positive charge can migrate throughout the system on a sub-femtosecond time scale, purely guided by electronic coherences. The possibility to actively explore the role of the electron dynamics in the photo-chemistry of bio-relevant molecules is of fundamental interest for understanding, and perhaps ultimately controlling, the processes leading to damage, mutation and, more generally, to the alteration of the biological functions of the macromolecule. Attosecond laser sources can provide the extreme time resolution required to follow this ultrafast charge flow. In this review we will present recent advances in attosecond molecular science: after a brief description of the results obtained for small molecules, recent experimental and theoretical findings on charge migration in bio-relevant molecules will be discussed, We acknowledge the support from the European Research Council under the ERC grants no. 637756 STARLIGHT, no. 227355 ELYCHE and no. 290853 XCHEM, LASERLABEUROPE (grant agreement no. 284464, European Commissions Seventh Framework Programme), European COST Action CM1204 XLIC, the Ministerio de Ciencia e Innovación project FIS2013-42002-R, European grants MC-ITN CORINF and MC-RG ATTOTREND 268284, UKs Science and Technology Facilities Council Laser Loan Scheme, the Engineering and Physical Sciences Research Council (grant EP/J007048/ 1), the Leverhulme Trust (grant RPG-2012-735), and the Northern Ireland Department of Employment and Learning

We used isolated attosecond pulses to trigger pure electron dynamics in aromatic amino acids on a sub-4.5-fs temporal scale. Our work opens new perspectives for attosecond science, moving toward the investigation of bio-relevant systems.

We demonstrate a novel approach for the extension of self-referenced spectral interferometry to the temporal characterization of few-optical cycle pulses. The new experimental setup is characterized by low dispersion and a collinear geometry. 4-fs pulses have been characterized by performing single-shot measurements, with high dynamic range on a broad temporal region. An independent measurement of the pulse duration, obtained by using attosecond streaking, allowed us to cross-check the experimental technique.

Electron transfer is a fundamental process in biochemistry, which triggers a number of biochemical processes such as photosynthesis, cellular respiration and electron transport along DNA [1]. It has been recognized that the evolution of many biological processes is strictly related to the ultrafast time scale of the corresponding electron dynamics. With the advent of attosecond technology, it was proposed to track and control this electron dynamics in real time. Indeed, the electron dynamics occurring in a biomolecule after sudden ionization can be driven by purely electronic effects and charge migration (CM) from one end of the molecule to the other and back has been theoretically predicted to occur within a time scale ranging from few-femtoseconds down to hundreds-attoseconds [2].