At the heart of high harmonic generation lies a combination of optical and collision physics entwined by a strong laser field. An electron, initially tunnel-ionized by the field, driven away then back in the continuum, finally recombines back to rest in its initial ground state via a radiative transition. The emitted attosecond (atto=10^-18) XUV light pulse carries all the information (polarization, amplitude and phase) about the photorecombination continuum-to-ground transition dipolar field. Photorecombination is related to the time-reversed photoionization process. In this perspective, high-harmonic spectroscopy extends well-established photoelectron spectroscopy, based on charged particle detection, to a fully coherent one, based on light characterization. The main achievement presented in this thesis is to use high harmonic generation to probe femtosecond (femto=10^-15) chemical dynamics for the first time. Thanks to the coherence imposed by the strong driving laser field, homodyne detection of attosecond pulses from excited molecules undergoing dynamics is achieved, the signal from unexcited molecules acting as the reference local oscillator. First, applying time-resolved high-harmonic spectroscopy to the photodissociation of a diatomic molecule, Br2 to Br + Br, allows us to follow the break of a chemical bond occurring in a few hundreds of femtoseconds. Second, extending it to a triatomic (NO2) lets us observe both the previously unseen (but predicted) early femtosecond conical intersection dynamics followed by the late picosecond statistical photodissociation taking place in the reaction NO2 to NO + O. Another important realization of this thesis is the development of a complementary technique to time-resolved high-harmonic spectroscopy called LAPIN, for Linked Attosecond Phase INterferometry. When combined together, time-resolved high-harmonic spectroscopy and LAPIN give access to the complex photorecombination dipole of aligned excited molecules. These achievements lay the basis for electron recollision tomographic imaging of a chemical reaction with unprecedented angstrom (1 angstrom= 0.1 nanometer) spatial resolution. Other contributions dedicated to the development of attosecond science and the generalization of high-harmonic spectroscopy as a novel, fully coherent molecular spectroscopy will also be presented in this thesis.

The main topic of this thesis is the development of novel diagnostics for the characterisation of infrared femtosecond and extreme-ultraviolet (XUV) attosecond pulses. High-resolution interferometric methods are applied to high harmonic radiation, both to measure the properties of the XUV light and to relate this information to the physics of the fundamental generation process. To do so, a complete high harmonic beamline has been built and optimised to enable the observation of strong signatures of the macroscopic response of the medium. The distinct spatial characteristics of long and short trajectories are studied, as well as the interference between them. An interferometric measurement allows the extraction of the atomic dipole phase, which gives direct access to the sub-cycle electron dynamics. A major focus of this thesis is on the development of a novel method which simultaneously characterises two independent electric fields as a function of any degree of freedom in which it is possible to shear one of the beams. Since each field alternately takes the role of the reference to retrieve the other field, this technique is referred to as mutual interferometric characterisation of electric-fields (MICE). One of the key features of MICE is that no sheared but otherwise identical replica of the test pulse needs to be generated, which is a typical requirement of self-referencing techniques. Furthermore, no a priori information is needed for the reconstruction. The strength and the wide applicability of MICE are demonstrated using two fundamentally different examples. First, the temporal pulse profiles of two infrared femtosecond pulses are simultaneously reconstructed in a single laser shot. In the second demonstration, the MICE approach is used to simultaneously reconstruct the wavefronts of two high harmonic beams. Having this new technique at hand, the phase properties of the different quantum trajectories are compared. All pulse characterisation techniques implicitly assume full coherence of the beam. This, however, is often not the case in practice, in particular when dealing with complex XUV light sources. Here the standard characterisation techniques fail to provide an accurate description of the electric field. Instead, the electric field must be seen as a statistical mixture of different contributions to the overall field. Here an interferometric experiment is first proposed and then performed involving multiple lateral shears to measure the two-point correlation function of high harmonic radiation. This directly provides information about the existence and the magnitude of partial coherence of high harmonics.

At the heart of high harmonic generation lies a combination of optical and collision physics entwined by a strong laser field. An electron, initially tunnel-ionized by the field, driven away then back in the continuum, finally recombines back to rest in its initial ground state via a radiative transition. The emitted attosecond (atto=10^-18) XUV light pulse carries all the information (polarization, amplitude and phase) about the photorecombination continuum-to-ground transition dipolar field. Photorecombination is related to the time-reversed photoionization process. In this perspective, high-harmonic spectroscopy extends well-established photoelectron spectroscopy, based on charged particle detection, to a fully coherent one, based on light characterization. The main achievement presented in this thesis is to use high harmonic generation to probe femtosecond (femto=10^-15) chemical dynamics for the first time. Thanks to the coherence imposed by the strong driving laser field, homodyne detection of attosecond pulses from excited molecules undergoing dynamics is achieved, the signal from unexcited molecules acting as the reference local oscillator. First, applying time-resolved high-harmonic spectroscopy to the photodissociation of a diatomic molecule, Br2 to Br + Br, allows us to follow the break of a chemical bond occurring in a few hundreds of femtoseconds. Second, extending it to a triatomic (NO2) lets us observe both the previously unseen (but predicted) early femtosecond conical intersection dynamics followed by the late picosecond statistical photodissociation taking place in the reaction NO2 to NO + O. Another important realization of this thesis is the development of a complementary technique to time-resolved high-harmonic spectroscopy called LAPIN, for Linked Attosecond Phase INterferometry. When combined together, time-resolved high-harmonic spectroscopy and LAPIN give access to the complex photorecombination dipole of aligned excited molecules. These achievements lay the basis for electron recollision tomographic imaging of a chemical reaction with unprecedented angstrom (1 angstrom= 0.1 nanometer) spatial resolution. Other contributions dedicated to the development of attosecond science and the generalization of high-harmonic spectroscopy as a novel, fully coherent molecular spectroscopy will also be presented in this thesis.

To capture electronic rearrangements inside a molecule or during chemical reactions, attosecond (as, 1 as =10−18 s) time resolution is needed. To create a light pulse with this duration, the central frequency has to be in the XUV range and cover several tens of eVs. Moreover, the frequency components have to be synchronized. The so called High Harmonic Generation (HHG) in gases well suits this task. During this process a high intensity laser pulse is focused in a gas jet, where its electric field bends the potential barrier of an atom allowing an electron wave packet (EWP) to tunnel ionize. Following the electric field of the laser the EWP gets accelerated, gaining a large kinetic energy that may be released as a high energy (XUV) photon in the event of a re-collision with the ionic core. These recolliding EWP probe the structure and dynamics of the core in a self-probing scheme: the EWP, that is emitted by the molecule at a certain time, probes itself later. More precisely, this "self-probing" scheme gives access to the complex valued recombination dipole moment (RDM) of the molecule which is determined by both the nuclear and electronic structure. The recombination encodes these characteristics into the spectral amplitude, phase and polarization state of the harmonic radiation emitted by the dipole. Due to the coherent nature of HHG it is possible to measure all these three parameters. Moreover, it is in principle possible through a tomographic procedure to reconstruct the radiating orbital.The objective of my thesis was two-fold. By implementing advanced characterization techniques of the harmonic amplitude, phase and polarization we studied i) the electronic structure of N2 and laser induced multi-channel tunnel ionization. We presented the reconstruction of molecular orbitals and revealed the ionization channel dependent ultrafast nuclear vibration. We also studied ii) the reflectivity and dispersion of recently designed chirped XUV mirrors that can shape the temporal profile of attosecond pulses. With these mirrors we could control the spectral phase over 20 eV and compensate the GDD of the harmonics or introduce a TOD. We also proposed a novel attosecond pulse shaper.

At the heart of high harmonic generation lies a combination of optical and collision physics entwined by a strong laser field. An electron, initially tunnel-ionized by the field, driven away then back in the continuum, finally recombines back to rest in its initial ground state via a radiative transition. The emitted attosecond (atto=10^-18) XUV light pulse carries all the information (polarization, amplitude and phase) about the photorecombination continuum-to-ground transition dipolar field. Photorecombination is related to the time-reversed photoionization process. In this perspective, high-harmonic spectroscopy extends well-established photoelectron spectroscopy, based on charged particle detection, to a fully coherent one, based on light characterization. The main achievement presented in this thesis is to use high harmonic generation to probe femtosecond (femto=10^-15) chemical dynamics for the first time. Thanks to the coherence imposed by the strong driving laser field, homodyne detection of attosecond pulses from excited molecules undergoing dynamics is achieved, the signal from unexcited molecules acting as the reference local oscillator. First, applying time-resolved high-harmonic spectroscopy to the photodissociation of a diatomic molecule, Br2 to Br + Br, allows us to follow the break of a chemical bond occurring in a few hundreds of femtoseconds. Second, extending it to a triatomic (NO2) lets us observe both the previously unseen (but predicted) early femtosecond conical intersection dynamics followed by the late picosecond statistical photodissociation taking place in the reaction NO2 to NO + O. Another important realization of this thesis is the development of a complementary technique to time-resolved high-harmonic spectroscopy called LAPIN, for Linked Attosecond Phase INterferometry. When combined together, time-resolved high-harmonic spectroscopy and LAPIN give access to the complex photorecombination dipole of aligned excited molecules. These achievements lay the basis for electron recollision tomographic imaging of a chemical reaction with unprecedented angstrom (1 angstrom= 0.1 nanometer) spatial resolution. Other contributions dedicated to the development of attosecond science and the generalization of high-harmonic spectroscopy as a novel, fully coherent molecular spectroscopy will also be presented in this thesis.

La chiralité est une propriété géométrique caractérisant les objets qui ne sont pas superposables à leur image dans un miroir. Nos mains en sont un exemple emblématique, puisqu’elles existent sous deux formes différentes droite et gauche. Si la chiralité s'observe à toutes les échelles de l'univers, elle joue un rôle particulièrement important en chimie. Une molécule chirale et son image miroir peuvent réagir différemment avec leur environnement et être thérapeutiques ou toxiques. Ces effets ont évidemment d'immenses répercussions sur le règne animal et végétal. Il apparaît alors clairement qu'il est essentiel d’étudier précisément les dynamiques des réactions chimiques chirales.Dans cette thèse, nous avons étudié les dynamiques ultrarapides de molécules chirales par des sources lasers de durée femtosecondes).($10^{-15}$ s). La chiralité moléculaire étant généralement difficile à détecter, nous avons ici utilisé une technique récente, le dichroïsme circulaire de photoélectrons (PECD) qui permet de générer un signal chiral très important. Nous avons ainsi observé des dynamiques moléculaires ultrarapides jusqu'à l'échelle attoseconde ($10^{-18}$ s), et mis en avant des dynamiques de relaxation et d'ionisation encore jamais observées.Parallèlement à ces études résolues en temps, nous avons développé plusieurs expériences employant une nouvelle source laser Yb fibrée à haute cadence et grande puissance moyenne. Nous avons développé une nouvelle méthode, par extension du PECD, qui nous a permis de mesurer la compositions d'échantillons chiraux rapidement avec une grande précision. Enfin, nous avons développé une ligne de lumière XUV ultrabrève de très haute brillance ($sim 2$ mW). Cette source, couplée à un détecteur de photoélectrons et photoions en coïncidence, servira à étudier les mécanismes de reconnaissance chirale. / Chirality is a geometric property that characterizes objects that cannot be superposed on their mirror image. Our hands are an emblematic example of this, since they exist in two different forms, right and left. While chirality is observed at all scales in the universe, it plays a particularly important role in chemistry. A chiral molecule and its mirror image can react differently with their environment and be therapeutic or toxic. These effects obviously have immense repercussions on the animal and plant kingdom. It then becomes clear that it is essential to study precisely the dynamics of chiral chemical reactions.In this thesis, we studied the ultrafast dynamics of chiral molecules by laser sources of femtosecond duration ($10^{-15}$ s). Molecular chirality is generally difficult to detect, so we have used a recent technique, circular photoelectron dichroism (PECD), to generate a very important chiral signal. We have thus observed ultrafast molecular dynamics at the attosecond scale ($10^{-18}$ s), and highlighted relaxation and ionization dynamics never observed before.In parallel to these time-resolved studies, we have developed several experiments using a new high repetition rate, high mean power Yb fiber laser. We have developed a new method, by extending the PECD, that has allowed us to measure the composition of chiral samples quickly and accurately. Finally, we have developed an ultra-short XUV beamline with very high brightness ($sim 2$ mW). This source, coupled with a photoelectron and photoion coincidence detector, will be used to study chiral recognition mechanisms.

Free-electron lasers (FELs) are among the world's most intense artificial artificial sources of coherent light and are tunable to various wavelengths, including the X-ray spectrum. X-ray FELs (XFELs) are extremely useful for diffraction experiments to study molecules, materials, and quantum systems. A FEL consists of an electron accelerator and a structure of magnets called an undulator. The undulator has a periodic magnetic field, and when an electron beam passes through the undulator, the Lorentz force forces the electrons to oscillate and emit what is known asspontaneous undulator radiation. Initially, the undulator radiation is spontaneously emitted and incoherent. However, aAs the electrons interact with this initial spontaneous undulator radiation, they change their relative positions and form micro-bunches of electrons. These microbunches are shorter than the undulator radiation wavelength. Hence, the waves emitted by the electrons from the same microbunch arethey become in phase, meaning the radiation is now coherent with the radiation field, and the state of coherence develops. This process is known as self-amplified spontaneous emission (SASE). Due to the coherence, tThe radiation intensity grows exponentially along the undulator, forming several peaks in the radiation pulse known as SASE spikes. One technique for obtaining ultra-short laser pulses is to isolate single SASE spikes by controlling where, along the electron beam, the SASE spikes can grow. This growth limitation is archieved by modulating the electron energies, thus only allowing electrons at specific positions along the electron beam to radiate. In addition, to keep positive interference between undulator radiation from electrons with different energies, the energy modulation must be compensated with a gradient of the magnetic field amplitude of the undulator, so-called tapering. There are plans to implement this technique at one of the beamlines at the European X-ray FEL (EuXFEL) to generate attosecond X-ray pulses and study quantum systems. One goal of the design process is to choose design parameters for the electron beam's modulation amplitude and the undulator's tapering coefficient. These design parameters shall be chosen so that the XFEL will have as short pulse duration as possible while at the same time not getting too low peak power. This thesis aims to study the effect of electron energy modulation and undulator tapering on the SASE and how the modulation amplitude and the tapering coefficient affect the XFEL's peak power and pulse duration. A model was developed to simulate SASE with a modulated electron beam in a tapered undulator. With this model, a parameter scan gave the average peak power and pulse duration as functions of the modulation amplitude and the tapering coefficient. The parameter scan showed that the peak power and the pulse duration decrease as the modulation amplitude and the tapering coefficient increase. Therefore, a trade-off exists between high peak power and short pulse duration. It was possible to exclude sets of the parameters that gave too low peak power or long pulse duration. This study also found an optimum range for the tapering coefficient where the peak power had a local maximum without a significant increase in pulse duration. The physics behind this optimal tapering coefficient is also discussed in connection to the electrons' energy modulation.

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This thesis describes methods for using spectral interferometry for the complete space-time characterisation of few-cycle near-infrared femtosecond pulses and extreme ultraviolet (XUV) attosecond pulses produced via high harmonic generation (HHG). Few-cycle pulses tend to exhibit one or more of the following: (1) an octave-spanning bandwidth, (2) a highly modulated spectrum and (3) space-time coupling. These characteristics, coupled with the desire to measure them in a single-shot (to characterise shot-to-shot fluctuations) and in real-time (for online optimisation and control) causes problems for conventional characterisation techniques. The first half of this thesis describes a method, based on a spatially encoded arrangement for spectral phase interferometry for direct electric-field reconstruction (SEA-SPIDER). SEA-SPIDER is demonstrated for sub-10fs pulses with a central wavelength near 800nm, a bandwidth over 350nm, and a pulse energy of several nano-Joules. In addition, the pulses exhibit a modulated spectrum and space-time coupling. The spatially-dependent temporal intensity of the pulse is reconstructed and compared to other techniques: interferometric frequency-resolved optical gating (IFROG) and spectral phase interferometry for direct electric field reconstruction (SPIDER). SEA-SPIDER will prove useful in both femtoscience, which requires accurate knowledge of the space-time character of few-cycle pulses, and in HHG, which requires the precise knowledge of the driving pulse for seeding into simulations and controlling the generation process itself. Pulses arising from HHG are known to exhibit significant space-time coupling. The second half of this thesis describes how spectral interferometry may be performed to obtain the complete space-time nature of these fields via the use of lateral shearing interferometry. Finally, it is shown, via numerical simulations, how to extend the SPIDER technique for temporal characterisation of XUV pulses from HHG by driving the process with two spectrally-sheared driving pulses. Different experimental configurations and their applicability to different laser systems are discussed. This method recovers the space-time nature of the harmonics in a single shot, thus reducing the stability constraint currently required for photoelectron based techniques and may serve as a complimentary method for studying interactions of XUV attosecond pulses with matter.