Extreme ultraviolet (XUV) frequency combs exhibit promise for enabling high-precision spectroscopic measurements of myriad chemical species for the first time. Coherent XUV radiation can be generated through high harmonic generation (HHG) in femtosecond enhancement cavities. HHG efficiency is limited by nonlinear phase shifts induced by residual intracavity plasma. The goal of this work is to gain insight regarding plasma dynamics in order to allay the detrimental effects of plasma interactions. Our approach is to conduct simulations of cavity pump-probe experiments by probing with higher-order transverse modes. We propose methods for estimating spatial plasma profiles, gas jet velocities, and the plasma recombination coefficient based on measurements of plasma-induced phase shifts. Beam distortion due to plasma interaction is analyzed and used as another reference for plasma dynamics.

Advancements in spectroscopy rely on the improvement of two fundamental characteristics: spatial and temporal resolutions. High harmonic spectroscopy (HHS) is an emerging technology that promises the capability of studying the fastest processes that exist today: electronic motion with angstrom spatial and attosecond temporal resolution. HHS is based on the process of high harmonic generation (HHG) which arises from the nonlinear interaction between an intense, infrared laser pulse and an atomic or molecular gaseous medium, producing coherent, attosecond-duration bursts of extreme ultraviolet (XUV) light. In order to utilize the attosecond pulses for spectroscopic measurements, it is necessary to improve the conversion efficiency of HHG. Chapter 2 of this thesis describes the improvements we make to the HHG source in order to obtain high XUV photon flux and we report on the nonlinear ionization of atomic systems using these pulses in Chapter 6. In Chapters 3 - 5, we describe several HHG experiments in complex, polyatomic molecules in order to promote the use of HHS as a general spectroscopic tool. Amplitude modulations in high harmonic spectra of complex molecules can be attributed to several types of interference conditions that depend on a system's molecular or electronic structure such as recombination with multiple centres or dynamical interference from multi-orbital contributions to ionization. Our results demonstrate the capability of HHS to extract useful information on molecular and electronic structure from large, polyatomic molecules directly from their high harmonic spectra. Furthermore, we use HHS to investigate the suppression of ionization in complex molecules due to quantum destructive interference during ionization as well as the distinguishability of emitted harmonic spectra from molecular isomers. Chapter 6 explores the study of multi-electron dynamics in complex molecules using XUV multiphoton ionization of atoms and molecules as well as the ionization and fragmentation of C60 which has hundreds of delocalized valence electrons. This thesis also describes the author's role in the design and fabrication of a time-of- flight mass spectrometer (Section 6.1) as well as an HHG detector system (Appendix A).

La physique attoseconde est un domaine en pleine expansion, intrinsèquement lié au processus de génération d’harmoniques d’ordre élevé. Cette émission, sous forme d’un train d’impulsions attosecondes ou d’une impulsion attoseconde isolée, constitue une source de lumière dans le domaine spectral extrême-UV (XUV), ultra-brève, cohérente, parfaitement synchrone du champ générateur. Deux thématiques ont été abordées. La première consiste en la caractérisation complète de l’état de polarisation des harmoniques par Polarimétrie Moléculaire en collaboration avec l’ISMO-Orsay. Cette technique est basée sur la mesure de la distribution angulaire des photoélectrons dans le référentiel moléculaire lors de l’ionisation dissociative de la molécule de NO. Nous l’appliquons à trois configurations produisant un rayonnement harmonique polarisé elliptiquement. Nous obtenons ainsi, pour la première fois, la valeur absolue de l’ellipticité harmonique, son signe, ainsi que le taux de dépolarisation.La seconde thématique est la photoionisation attoseconde résonante : nous avons étudié la photoionisation de l’hélium au voisinage de la résonance d'autoionisation 2s2p à 60.15eV, excitée par une impulsion XUV accordable et sondée par une impulsion laser IR en utilisant la technique RABBIT, qui permet la mesure de l’amplitude et de la phase spectrales de la transition résonante à deux photons. Il est ainsi possible de reconstruire dans le domaine temporel, le paquet d'ondes électronique (POE) à 2 photons. Ces mesures ont été complétées par des simulations effectuées par nos collaborateurs à UAM-Madrid et au LCPMR-Paris, qui montrent que, dans nos conditions expérimentales, ce paquet à deux photons est une image fidèle du paquet résonant à un photon. Ceci représente la première reconstruction de la dynamique temporelle d’une résonance non perturbée par le champ laser, avec une résolution attoseconde. / Attosecond physics is an expending field, intrinsically linked to the High Harmonic Generation process. This emission, which can be either an attosecond pulse train or an isolated attosecond pulse, constitutes a light source in the extreme-UV (XUV) spectral domain, coherent, perfectly synchronous of the generating field. Two thematic have been studied. The first one consists in the complete characterization of the harmonic emission through Molecular Polarimetry, in collaboration with ISMO-Orsay. This technique is based on the measurement of the Molecular Frame PhotoElectron Angular Distribution, during the dissociative ionization of NO molecules. We applied this technique to three configurations producing an elliptically polarized light. For the first time, we obtain the absolute value of the ellipticity, its sign and the depolarization rate. The second topic is the resonant attosecond photoionization: we studied the photoionization of helium, close to the 2s2p autoionization resonance at 60.15 eV, excited by a tunable XUV pulse and probed by an IR pulse, using RABBIT technique, enabling the measurement of the spectral amplitude and phase of the two photons resonant transition. From this, we can reconstruct the two-photons electron wave packets (EWP). These measurements have been completed by simulations done by our collaborator from UAM-Madrid and LCPMR-Paris, showing that, in our experimental conditions, this two photons EWP corresponds to the image of the one-photon EWP. This measurement is the first reconstruction of the temporal dynamic of a resonance non-perturbed by a laser field, with an attosecond resolution.

No description available.

A variant of RABBITT pump-probe spectroscopy in which the attosecond pulse train comprises both even and odd harmonics of the fundamental IR probe frequency is explored to measure time-resolved photoelectron emission in systems that exhibit autoionizing states. It is shown that the group delay of both one-photon and two-photon resonant transitions is directly encoded in the energy-resolved photoelectron anisotropy as a function of the pump-probe time-delay. This principle is illustrated for a 1D model with symmetric zero-range potentials that supports both bound states and shape-resonances. The model is studied using both perturbation theory and solving the time-dependent Schodinger equation on a grid. Moreover, we study the case of a realistic atomic system, helium. In both cases, we demonstrate faithful reconstruction of the phase information for resonant photoemission.

No description available.

<p dir="ltr">Some of the simplest molecules that are found in abundance in nature, like oxygen, nitrogen, carbon dioxide and water can be playgrounds for complex quantum mechanical phenomenon. Although we can calculate their static properties, like binding energies, equilibrium geometries and ionization/decay rates with extraordinary precision, their dynamics offer new avenues for exploration. Although analytical techniques have been successfully applied in studying single-particle and many-particle systems, few-particle systems like simple molecules are still best understood through a combination of numerical calculations and experimental work. However, the small size of these molecules endows them with dynamics that occur on timescales of a few picoseconds to a few attoseconds, making their experimental study challenging. The overarching goal of this work is the study of such ‘ultrafast’ dynamics in excited state molecules/atoms, by developing and demonstrating novel optical probes of quantum dynamics.</p><p dir="ltr">One way to probe ultrafast dynamics in molecules is by measuring their nonlinear optical response. Such a measurement can potentially track the evolution of the symmetries of excited molecules, shedding light on their transient dynamics. We start chapter 1 with a brief discussion of the formalism behind nonlinear optical spectroscopy. Direct measurement of ultrafast (and ultraweak) optical pulses is discussed as a useful probe of nonlinear processes. After presenting preliminary results on direct electric field reconstruction, experimental work on measuring emitted nonlinear electric fields from impulsively aligned molecules is discussed. In such an experiment, however, contributions from both aligned and unaligned molecules are present, and new experimental capabilities had to be developed to disentangle and measure the ultraweak signal from aligned molecules. Following a detailed discussion of the developed measurement capabilities, results from experiments done on aligned carbon dioxide and nitrogen molecules are discussed.</p><p dir="ltr">Unlike solids, where electronic states can be excited with visible/UV light, binding energies in isolated atoms/molecules are on the order of electron-volts (eVs), and they need vacuum-ultraviolet (VUV) extreme-ultraviolet (EUV) light to excite electronically. Polyatomic molecules, like ethylene, when excited to an electronic state with VUV light, often relax back to the ground state by redistributing energy to their internal degrees of freedom non-adiabatically. These relaxation pathways are important in many chemical and biological systems, and control the yield of chemical reactions ranging from elementary reactions involving few atoms to large biomolecules such as DNA and proteins. For instance, in the photochemical reaction of the protein Rhodopsin, considered to be the primary event in human vision. In chapter 2 we discuss progress made towards extending nonlinear response measurements to study ultrafast dynamics in electronically excited molecules, using a high-harmonic VUV source. Details about the design of the high-harmonic generation beamline, and preliminary experimental data are presented. In chapter 3 we discuss preliminary theoretical work on the development of an EUV entangled-photon source, using two-photon emission from the metastable 2s state in neutral Helium. Such a source, if demonstrated, can possibly even extended to the zeptosecond regime in the future.</p>

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.

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.

I present several new methods for the characterisation of ultrashort pulses using interferometry. A generalisation of the concatenation algorithm for spectral shearing interferometry enables interferograms taken at multiple shears to be combined. This improves the precision of the reconstructed phase in the presence of detector noise, and enables the relative phase between disjoint spectral components to be obtained without decreasing the spectral resolution. The algorithm is applied to experimental data from two different implementations of spectral shearing interferometry for ultrashort optical pulses. In one, the shears are acquired sequentially, and in the other they are acquired simultaneously. I develop a form of spatio-temporal ultrashort pulse characterisation which performs both spatial and spectral shearing interferometry simultaneously. It requires a similar geometrical setup to common implementations of spectral phase interferometry for direct electric-field reconstruction, but provides complete amplitude and phase characterisation in time and one spatial dimension. I develop the theory of lateral shearing interferometry for spectrally resolved wavefront sensing of extended ultraviolet and soft x-ray pulses generated using high-harmonic generation. A comprehensive set of wavefront measurements of harmonics 13-25 in Krypton show good agreement with theory, validating the technique. I propose and numerically demonstrate quantum-path interferometry mediated by a weak control field for high harmonic generation. This is a general technique for measuring the amplitude and relative phases of each contributing quantum path. The control field perturbatively modulates the phase of each path. The differing sensitivity of each path to the parameters of the control field allows their contributions to be distinguished from one another.