<p dir="ltr">Laser absorption spectroscopy (LAS) is a widely used technique to acquire path-integrated measurements of gas properties such as temperature and mole fraction. Although extremely useful, the application of LAS to study heterogeneous combustion environments can be challenging. For example, beam steering can be one such challenge that arises during measurements in heterogeneous combustion environments such as metallized propellant flames or measurements at high-pressure conditions. The ability to only obtain path integrated measurements has been a major challenge of conventional LAS techniques, especially in characterizing combustion environments with a non-uniform thermo-chemical distribution along the line of sight (LOS). Additionally, simultaneous measurements of multiple species using LAS with narrow-bandwidth lasers often necessitates employing multiple light sources. Aerospace applications, such as characterizing hypersonic flows may require ultrashort time resolution to study fast-evolving chemistry. Similarly, atmospheric entry most often requires measurements of atoms and molecules that absorb at wavelengths ranging from ultraviolet to mid-infrared. The availability of appropriate light sources for such measurements has been limited. In the past, several researchers have come up with diagnostic techniques to overcome the above-mentioned challenges to a certain extent. Most often, these solutions have been need-based while compromising on other diagnostic capabilities. Therefore, LAS diagnostics capable of acquiring broadband measurements with ultrafast time resolution and the ability to acquire measurements at wavelengths in ultraviolet through mid-infrared is required to study advanced combustion systems and for the development of advanced aerospace systems for future space missions. Ultrafast laser absorption spectroscopy is one such technique that provides broadband measurements, enabling simultaneous multi-species and high-pressure measurements. The light source utilized for ULAS provides the ultrafast time resolution necessary for resolving fast-occurring chemistry and more importantly the ability to acquire measurements at a wide range of wavelengths ranging from ultraviolet to far-infrared. The development and application of ULAS for characterizing propellant flames and hypersonic flows under non-equilibrium conditions by overcoming the above-mentioned challenges is presented here. </p><p>This work describes the development of a single-shot ultrafast laser absorption spectroscopy (ULAS) diagnostic for simultaneous measurements of temperature and concentrations of CO, NO, and H₂O in flames and aluminized fireballs of HMX (C₄H₈N₈O₈). Ultrashort (55 fs) pulses from a Ti:Sapphire oscillator emitting near 800 nm were amplified and converted into the mid-infrared through optical parametric amplification (OPA) at a repetition rate of 5 kHz. Ultimately, pulses with a spectral bandwidth of ≈600 cm^-1 centered near 4.9 µm were utilized in combination with a mid-infrared spectrograph to measure absorbance spectra of CO, NO, and H₂O across a 30 nm bandwidth with a spectral resolution of 0.3 nm. The gas temperature and species concentrations were determined by least-squares fitting simulated absorbance spectra to measured absorbance spectra. Measurements of temperature, CO, NO, and H₂O were acquired in an HMX flame burning in air at atmospheric pressure and the measurements agree well with previously published results. Measurements were also acquired in fireballs of HMX with and without 16.7 wt% H-5 micro-aluminum. Time histories of temperature and column densities are reported with a 1-σ precision of 0.4% for temperature and 0.3% (CO), 0.6% (NO), and 0.5% (H₂O), and 95% confidence intervals (C.I.) of 2.5% for temperature and 2.5% (CO), 11% (NO), and 7% (H₂O), thereby demonstrating the ability of ULAS to provide high-fidelity, multi-parameter measurements in harsh combustion environments. The results indicate that the addition of the micron-aluminum increases the fireball peak temperature by ≈100 K and leads to larger concentrations of CO. The addition of aluminum also increases the duration fireballs remain at elevated temperatures above 2000 K.</p><p dir="ltr">Next, the application of ULAS for dual-zone temperature and multi-species (CO, NO, H₂O, CO₂, HCl, and HF) measurements in solid-propellant flames is presented. ULAS measurements were acquired at three different central wavelengths (5.121 µm, 4.18 µm, and 3.044 µm) for simultaneous measurements of temperature and: 1) CO, NO, and H₂O, 2) CO₂ and HCl, and 3) HF and H₂O. Absorption measurements with a spectral resolution of 0.35 nm and bandwidth of 7 cm^-1, 18 cm^-1, and 35 cm^-1, respectively were acquired. In some cases, a dual-zone absorption spectroscopy model was implemented to accurately determine the gas temperature in the hot flame core and cold flame boundary layer via broadband absorption measurements of CO₂, thereby overcoming the impact of line-of-sight non-uniformities. Results illustrate that the hot-zone temperature of CO₂ agrees well with the equilibrium flame temperature and single-zone thermometry of CO, the latter of which is insensitive to the cold boundary layer due to the corresponding oxidation of CO to CO₂.</p><p dir="ltr">The initial development and implementation of an ultraviolet and broadband ultrafast-laser-absorption-imaging (UV-ULAI) diagnostic for one dimensional (1D) imaging of temperature and CN via its <i>B</i>²Σ⁺←<i>X</i>²Σ⁺absorption bands near 385 nm. The diagnostic was demonstrated by acquiring single-shot measurements of 1D temperature and CN profiles in HMX flames at a repetition rate of 25 Hz. Ultrashort pulses (55 fs) at 800 nm were generated using a Ti:Sapphire oscillator and then amplification and wavelength conversion to the ultraviolet was carried out utilizing an optical parametric amplifier and frequency doubling crystals. The broadband pulses were spectrally resolved using a 1200 l/mm grating and imaged on an EMCCD camera to obtain CN absorbance spectra with a resolution of ≈0.065 nm and a bandwidth of ≈4 nm (i.e. 260 cm^-1). Simulated absorbance spectra of CN were fit to the measured absorbance spectra using non-linear curve fitting to determine the gas properties. The spatial evolution of gas temperature and CN concentration near the burning surface of an HMX flame was measured with a spatial resolution of ≈10 µm. 1D profiles of temperature and CN concentration were obtained with a 1-σ spatial precision of 49.3 K and 4 ppm. This work demonstrates the ability of UV-ULAI to acquire high-precision, spatially resolved absorption measurements with unprecedented temporal and spatial resolution. Further, this work lays the foundation for ultraviolet imaging of numerous atomic and molecular species with ultrafast time resolution.</p><p dir="ltr">Ultraviolet ULAS was applied to characterize the temporal evolution of non-Boltzmann CN (<i>X</i>²Σ⁺) formed behind strong shock waves in N₂-CH₄ mixtures at conditions relevant to entry into Titan's atmosphere. An ultrafast (femtosecond) light source was utilized to produce 55 fs pulses near 385 nm at a repetition rate of 5 kHz and a spectrometer with a 2400 lines/mm grating was utilized to spectrally resolve the pulses after passing through the Purdue High-Pressure Shock Tube. This enabled broadband single-shot absorption measurements of CN to be acquired with a spectral resolution and bandwidth of ≈0.02 nm and ≈6 nm (≈402 cm^-1 at these wavelengths), respectively. A line-by-line absorption spectroscopy model for the <i>B</i>²Σ⁺←<i>X</i>²Σ⁺ system of CN was developed and utilized to determine six internal temperatures (two vibrational temperatures, four rotational) of CN from the (0,0), (1,1), (2,2) and (3,3) absorption bands. Measurements were acquired behind reflected shock waves in 5.65% CH₄ and 94.35% N₂ with an initial pressure of 1.56 mbar and incident shock speed of ≈2.1 km/s. For this test condition, the chemically and vibrationally frozen temperature of the mixture behind the reflected shock was 5000 K and the pressure was 0.6 atm. The high repeatability of the shock-tube experiments (0.3% variation in shock speed across tests) enabled multi-shock time histories of CN mole fraction and six internal temperatures to be acquired with a single-shot time resolution of less than 1 ns. The measurements revealed that CN <i>X</i>²Σ⁺ is non-Boltzmann rotationally and vibrationally for greater than 200 µs, thereby strongly suggesting that chemical reactions are responsible for the non-Boltzmann population distributions. </p><p><br></p>

<p>Bose-Einstein condensates (BECs) in light-induced synthetic gauge fields and spaces can provide a highly-tunable platform for quantum simulations. Chapter 1 presents a short introduction to the concepts of BECs and our BEC machine. Chapter 2 introduces some basic ideas of how to use light-matter interactions to create synthetic gauge fields and spaces for neutral atoms. Three main research topics of the thesis are summarized below.</p> <p>Chapter 3: Recently, using bosonic quasiparticles (including their condensates) as spin carriers in spintronics has become promising for coherent spin transport over macroscopic distances. However, understanding the effects of spin-orbit (SO) coupling and many-body interactions on such a spin transport is barely explored. We study the effects of synthetic SO coupling (which can be turned on and off, not allowed in usual materials) and atomic interactions on the spin transport in an atomic BEC.</p> <p>Chapter 4: Interplay between matter and fields in physical spaces with nontrivial geometries can lead to phenomena unattainable in planar spaces. However, realizing such spaces is often impeded by experimental challenges. We synthesize real and curved synthetic dimensions into a Hall cylinder for a BEC, which develops symmetry-protected topological states absent in the planar counterpart. Our work opens the door to engineering synthetic gauge fields in spaces with a wide range of geometries and observing novel phenomena inherent to such spaces.</p> <p>Chapter 5: Rotational properties of a BEC are important to study its superfluidity. Recent studies have found that SO coupling can change a BEC's rotational and superfluid properties, but this topic is barely explored experimentally. We study rotational dynamics of a SO-coupled BEC in an effective rotating frame induced by a synthetic magnetic field. Our work may allow for studying how SO coupling modify a BEC's rotational and superfluid properties.</p> <p>Chapter 6 presents some possible future directions.</p>

A Emodina (EMH) é uma das antraquinonas mais abundantes na natureza. Essa molécula vem sendo largamente usada como material de estudo científico por apresentar diversas atividades farmacológicas, tais como antiviral, antitumoral, antifungal, digestiva e outras. É conhecido que a Emodina em solução aquosa alcalina pode sofrer mais de um processo de desprotonação, apresentando-se na forma desprotonada, EM-, após a primeira desprotonação. Nesta tese de doutorado estudamos as propriedades estruturais e eletrônicas da molécula Emodina em meio solvente e em bicamadas lipídicas a fim de caracterizar as propriedades relacionadas à espectroscopia UV-Vis, à reatividade e à termodinâmica dessa molécula nesses ambientes. Realizamos cálculos quânticos com a Emodina em vácuo e em meio solvente, onde consideramos todos os possíveis sítios de desprotonação. Como resultados desses cálculos, identificamos os sítios da primeira, segunda e terceira desprotonação. Calculamos o pKa1 da Emodina em água e o pK*a1 em metanol através de simulações computacionais com o método Monte Carlo e cálculos quânticos, com o solvente descrito com o modelo contínuo polarizável. Nossos melhores valores para o pKa1 da Emodina determinados nesses solventes foram 8.4±0.5 e 10.3±1.5, que estão em boa concordância com os valores experimentais, (pKa1=8.0±0.2 e pK*a1=11.1±0.1) obtidos nesta tese para Emodina em água e metanol, respectivamente. Adicionalmente realizamos simulações com Dinâmica Molecular com as espécies EMH e EM- em bicamada lipídica de DMPC, para investigar a nível atômico as interações dessas espécies com a bicamada e determinar as posições preferenciais dessas espécies nesse ambiente anfifílico. Os resultados dessas simulações mostraram que as espécies EMH e EM- ficam inseridas na bicamada, na região polar dos lipídios, próximos aos gliceróis. Esses resultados corroboram as nossas medidas do espectro de absorção dessas espécies em bicamada lipídica, onde mostramos de forma qualitativa, que ambas as espécies ficam inseridas na bicamada, na região das cabeças polares dos lipídios. A análise das propriedades estruturais da bicamada na vizinhança das espécies da Emodina como área por lipídio e densidade eletrônica dos lipídios, mostrou que o efeito da EM- na estrutura da bicamada lipídica é maior do que o da EMH. Esses resultados corroboram as nossas medidas de DSC(Differential Scanning Calorimetry) das espécies da Emodina na bicamada. / Emodin (EMH) is one of the most abundant anthraquinone derivatives found in nature. This molecule has been used widely as research material, due to its biological and pharmacological activities such as antiviral, anticancer, antifungal, digestive and antibacterial activities. It is known that Emodin in alkaline aqueous solution can undergo more than one deprotonation, leading to the specie EM- in the first deprotonation process. In this PhD thesis, we studied the structural and electronic properties of this molecule in several solvents and lipid bilayers, in order to characterize the properties related to UV-Vis absorption spectroscopy, reactivity and thermodynamics of this molecule in these environments. Performing quantum mechanics (QM) calculations for all possible deprotonation sites and tautomeric isomers of Emodin in vacuum and in water, we identified the sites of the first, second and third deprotonations. We calculated the pKa1 of Emodin in water and pK*a1 in methanol with free energy perturbation method, implemented in the Monte Carlo simulation, and with QM calculations, where the solvent was treated as a polarizable continuum medium. Our best values for pKa1 of Emodin in these solvents were 8.4±0.5 and 10.3±1.5, which are in very good agreement with the experimental values obtained in this thesis pKa1=8.0±0.2 and pK*a1=11.1±0.1, for water and methanol, respectively. Additionally, we performed molecular dynamics simulations of both species in fully hydrated lipid bilayers of DMPC to investigate at atomic detail the molecular mechanism of the interaction of these species with lipid membrane and its preferred positions in this amphiphilic environment. As results of these simulations, we obtained that both species of Emodin have a strong tendency to insert into the lipid bilayer, remaining near the glycerol group of DMPC. These results corroborate our measured absorption spectra of these species in the bilayer, which qualitatively showed that both species are within the bilayer, inserted in the lipid headgroup region. Our results also show that the effect of EM- specie in the lipid bilayer structure is stronger than the EMH, which corroborate our DSC(Differential Scanning Calorimetry) measurements.

<p>Atoms, molecules and clusters all constitute building blocks of macroscopic matter. Therefore, understanding the electronic and geometrical properties of such systems is the key to understanding the properties of solid state objects.</p><p>In this thesis, some atomic, molecular and cluster systems (clusters of O₂, CH₃Br, Ar/O₂, Ar/Xe and Ar/Kr; dimers of Na; Na and K atoms) have been investigated using synchrotron radiation, and in the two last instances, laser light. We have performed x-ray photoelectron spectroscopy (XPS) on all of these systems. We have also applied ultraviolet photoelectron spectroscopy (UPS), resonant Auger spectroscopy (RAS) and near-edge x-ray absorption spectroscopy (NEXAFS) to study many of the systems. Calculations using <i>ab initio</i> methods, namely density functional theory (DFT) and Møller-Plesset perturbation theory (MP), were employed for electronic structure calculations. The geometrical structure was studied using a combination of <i>ab initio</i> and molecular dynamics (MD) methods.</p><p>Results on the dissociation behavior of CH₃Br and O₂ molecules in clusters are presented. The dissociation of the Na₂ molecule has been characterized and the molecular field splitting of the Na 2<i>p</i> level in the dimer has been measured. The molecular field splitting of the CH₃Br 3<i>d</i> level has been measured and the structure of CH₃Br clusters has been determined to be similar to the structure of the bulk solid. The diffusion behavior of O₂, Kr and Xe on large Ar clusters, as a function of doping rate, has been investigated. The shake-down process has been observed from excited states of Na and K. Laser excited Na atoms have been shown to be magnetically aligned. The shake-down process was used to characterize the origin of various final states that can be observed in the spectrum of ground-state K.</p>

Atoms, molecules and clusters all constitute building blocks of macroscopic matter. Therefore, understanding the electronic and geometrical properties of such systems is the key to understanding the properties of solid state objects. In this thesis, some atomic, molecular and cluster systems (clusters of O2, CH3Br, Ar/O2, Ar/Xe and Ar/Kr; dimers of Na; Na and K atoms) have been investigated using synchrotron radiation, and in the two last instances, laser light. We have performed x-ray photoelectron spectroscopy (XPS) on all of these systems. We have also applied ultraviolet photoelectron spectroscopy (UPS), resonant Auger spectroscopy (RAS) and near-edge x-ray absorption spectroscopy (NEXAFS) to study many of the systems. Calculations using ab initio methods, namely density functional theory (DFT) and Møller-Plesset perturbation theory (MP), were employed for electronic structure calculations. The geometrical structure was studied using a combination of ab initio and molecular dynamics (MD) methods. Results on the dissociation behavior of CH3Br and O2 molecules in clusters are presented. The dissociation of the Na2 molecule has been characterized and the molecular field splitting of the Na 2p level in the dimer has been measured. The molecular field splitting of the CH3Br 3d level has been measured and the structure of CH3Br clusters has been determined to be similar to the structure of the bulk solid. The diffusion behavior of O2, Kr and Xe on large Ar clusters, as a function of doping rate, has been investigated. The shake-down process has been observed from excited states of Na and K. Laser excited Na atoms have been shown to be magnetically aligned. The shake-down process was used to characterize the origin of various final states that can be observed in the spectrum of ground-state K.

The Phthalocyanines (Pc’s) are a group of macro-cyclic molecules, widely investigated due to the possibility to use them in a variety of applications. Electronic and geometrical structure investigations of molecular model systems of Pc’s adsorbed on surfaces are important for a deeper understanding of the functionality of different Pc-based devices. Here, Pc’s monolayers and films, deposited on different surfaces, were investigated by X-ray Photoelectron Spectroscopy (XPS), X-ray Absorption Spectroscopy (XAS) and Scanning Tunneling Microscopy (STM). In addition Density Functional Theory (DFT) simulations were performed. For molecular films of Metal-free (H2Pc) and Iron (FePc) Pc’s, on surfaces, it is found that the intermolecular interaction is weak and the molecules arrange with their molecular plane mainly perpendicular to the surface. Several monolayer systems were characterized, namely H2Pc and FePc adsorbed on Graphite, ZnPc on InSb(001)-c(8x2), H2Pc on Al(110) and on Au(111). For all the studied monolayers it was found that the molecules are oriented with their molecular plane parallel to the surface. The electronic structure of the molecules is differently influenced by interaction with the surfaces. For H2Pc adsorbed on Graphite the nearly negligible effect of the surface on the molecular electronic structure allowed STM characterization of different molecular orbitals. A strong interaction is instead found in the case of H2Pc on Al(110) resulting in molecules strongly adsorbed, and partly dissociated. Modifications of the electronic and geometrical structure induced by alkali doping of H2Pc films and monolayers were characterized. It is found both for the H2Pc film on Al(110) and monolayer adsorbed on Au(111), that the molecular arrangement is changed upon doping by Potassium and Rubidium, respectively. Potassium doping of the H2Pc films results in a filling of previously empty molecular orbitals by a charge transfer from the alkali to the molecule, with significant modification of the molecular electronic structure.

A Emodina (EMH) é uma das antraquinonas mais abundantes na natureza. Essa molécula vem sendo largamente usada como material de estudo científico por apresentar diversas atividades farmacológicas, tais como antiviral, antitumoral, antifungal, digestiva e outras. É conhecido que a Emodina em solução aquosa alcalina pode sofrer mais de um processo de desprotonação, apresentando-se na forma desprotonada, EM-, após a primeira desprotonação. Nesta tese de doutorado estudamos as propriedades estruturais e eletrônicas da molécula Emodina em meio solvente e em bicamadas lipídicas a fim de caracterizar as propriedades relacionadas à espectroscopia UV-Vis, à reatividade e à termodinâmica dessa molécula nesses ambientes. Realizamos cálculos quânticos com a Emodina em vácuo e em meio solvente, onde consideramos todos os possíveis sítios de desprotonação. Como resultados desses cálculos, identificamos os sítios da primeira, segunda e terceira desprotonação. Calculamos o pKa1 da Emodina em água e o pK*a1 em metanol através de simulações computacionais com o método Monte Carlo e cálculos quânticos, com o solvente descrito com o modelo contínuo polarizável. Nossos melhores valores para o pKa1 da Emodina determinados nesses solventes foram 8.4±0.5 e 10.3±1.5, que estão em boa concordância com os valores experimentais, (pKa1=8.0±0.2 e pK*a1=11.1±0.1) obtidos nesta tese para Emodina em água e metanol, respectivamente. Adicionalmente realizamos simulações com Dinâmica Molecular com as espécies EMH e EM- em bicamada lipídica de DMPC, para investigar a nível atômico as interações dessas espécies com a bicamada e determinar as posições preferenciais dessas espécies nesse ambiente anfifílico. Os resultados dessas simulações mostraram que as espécies EMH e EM- ficam inseridas na bicamada, na região polar dos lipídios, próximos aos gliceróis. Esses resultados corroboram as nossas medidas do espectro de absorção dessas espécies em bicamada lipídica, onde mostramos de forma qualitativa, que ambas as espécies ficam inseridas na bicamada, na região das cabeças polares dos lipídios. A análise das propriedades estruturais da bicamada na vizinhança das espécies da Emodina como área por lipídio e densidade eletrônica dos lipídios, mostrou que o efeito da EM- na estrutura da bicamada lipídica é maior do que o da EMH. Esses resultados corroboram as nossas medidas de DSC(Differential Scanning Calorimetry) das espécies da Emodina na bicamada. / Emodin (EMH) is one of the most abundant anthraquinone derivatives found in nature. This molecule has been used widely as research material, due to its biological and pharmacological activities such as antiviral, anticancer, antifungal, digestive and antibacterial activities. It is known that Emodin in alkaline aqueous solution can undergo more than one deprotonation, leading to the specie EM- in the first deprotonation process. In this PhD thesis, we studied the structural and electronic properties of this molecule in several solvents and lipid bilayers, in order to characterize the properties related to UV-Vis absorption spectroscopy, reactivity and thermodynamics of this molecule in these environments. Performing quantum mechanics (QM) calculations for all possible deprotonation sites and tautomeric isomers of Emodin in vacuum and in water, we identified the sites of the first, second and third deprotonations. We calculated the pKa1 of Emodin in water and pK*a1 in methanol with free energy perturbation method, implemented in the Monte Carlo simulation, and with QM calculations, where the solvent was treated as a polarizable continuum medium. Our best values for pKa1 of Emodin in these solvents were 8.4±0.5 and 10.3±1.5, which are in very good agreement with the experimental values obtained in this thesis pKa1=8.0±0.2 and pK*a1=11.1±0.1, for water and methanol, respectively. Additionally, we performed molecular dynamics simulations of both species in fully hydrated lipid bilayers of DMPC to investigate at atomic detail the molecular mechanism of the interaction of these species with lipid membrane and its preferred positions in this amphiphilic environment. As results of these simulations, we obtained that both species of Emodin have a strong tendency to insert into the lipid bilayer, remaining near the glycerol group of DMPC. These results corroborate our measured absorption spectra of these species in the bilayer, which qualitatively showed that both species are within the bilayer, inserted in the lipid headgroup region. Our results also show that the effect of EM- specie in the lipid bilayer structure is stronger than the EMH, which corroborate our DSC(Differential Scanning Calorimetry) measurements.

<div>The interactions of femtosecond lasers with gold targets were investigated with a numerical method combining molecular dynamics (MD) and the two-temperature model (TTM). Previous works using MD-TTM method did not consider all the thermodynamic parameters and the interatomic potential dependent of the electron temperature simultaneously. Therefore, we developed a LAMMPS function to achieve this. To accurately capture the physics behind the interactions, we also included the electron blast force from free electron pressure and the modified Fourier law with steep electron temperature gradient in our model. For bulk materials, a stress non-reflecting and heat conducting boundary is added between the atomistic and the continuum parts. The modified boundary force in our study greatly reduces the reflectivity of the atomistic-continuum boundary compared with its original form. Our model is the first to consider all these factors simultaneously and manage to predict four femtosecond laser ablation phenomena observed in the experiments. </div><div><br></div><div>In this dissertation, the thermodynamic parameters in the two-temperature model were extensively explored. We considered three different approaches to calculate these parameters: namely interpolation, <i>ab initio</i> calculation, and analytical expression. We found that simple interpolation between solid state and plasma state could lead to high level of inaccuracy, especially for electron thermal conductivity. Therefore, <i>ab initio</i> calculation and analytical expression were used for the calculation of the thermodynamic parameters in more advanced studies. The effects of electron thermal conductivity and electron-phonon coupling factor on electron and lattice temperatures were analyzed.</div><div><br></div><div>Our studies considered electron temperature dependent (ETD) and electron temperature independent (ETI) interatomic potentials. The ETI interatomic potential is easier to implement and therefore it is used in our phase change study to investigate the effects of target thickness on melting. Homogeneous melting occurred for thin films, while melting can be observed through the movement of the solid-liquid interface in thick or bulk materials. However, the ETI potential overestimated the bond strength at high temperatures. Therefore, ablation process was studied with the ETD potential. Three ablation mechanisms were found in our simulations at different laser fluences. Short nonthermal ablation was only observed at the ablation threshold. With increasing laser fluence, spallation was then seen. In high laser fluence regime, phase explosion occurred on the surface and coexisted with spallation.</div><div><br></div><div>Lastly, we researched on the effects of the delay time between two femtosecond laser pulses. Various delay times did not have much influence on melting depth. In low laser fluence regime, with increasing delay time, the target went through nonthermal ablation, to spallation and to no ablation. In high laser fluence regime, longer delay time encouraged phase explosion while suppressed spallation.</div>

Cette thèse fait l'étude expérimentale de dynamiques de relaxations ultrarapides au sein d'atomes et de molécules (Ar, NO2, C2H2). Les méthodes expérimentales qui sont utilisées sont basées sur l'interaction d'un rayonnement laser avec le système atomique ou moléculaire étudié et font intervenir le processus de génération d'harmoniques d'ordres élevés, ainsi que la spectrométrie d'imagerie de vecteur vitesse. Au cours de cette thèse, deux approchesexpérimentales de type pompe-sonde ont été mises en œuvre. Une première approche exploitela sensibilité du processus de génération d'harmoniques à la structure électronique dumilieu pour la sonder. Cette méthode a été utilisée sur la molécule de dioxyde d'azote pourobserver sa relaxation électronique à travers l'intersection conique des états X2A1-A2B2suite à une excitation autour de 400 nm. Une seconde approche utilise le rayonnementharmonique comme source de photons dans le domaine de l'extrême ultraviolet (EUV)pour exciter ou sonder les espèces d'intérêt. Cette approche a été couplée avec l'utilisationd'un spectromètre d'imagerie de vecteur vitesse (VMIS), qui a été développé durant lathèse. Des expériences menées sur un système modèle comme l'argon ont permis de validerle dispositif expérimental, qui a ensuite été mis en application pour étudier la photodissociationde la molécule d'acétylène, après excitation autour de 9,3 eV du complexe deRydberg 3d-4s. Les deux méthodes mises en œuvre permettent toutes-deux de réaliserdes études dynamiques résolues en temps à l'échelle femtoseconde. / Ultrafast atomic and molecular dynamics (Ar, NO2, C2H2) have been experimentally studied during this PhD. The employed techniques use the laser interaction with the atomic or molecular system produced in gas phase. High harmonic generation (HHG) pump-probe studies allow resolving dynamics on a femtosecond scale. Two applications of high harmonic generation have been implemented here. In the first one, the harmonic generation process is the probe of a vibronic relaxation induced by a pump pulse. This application is currently labeled high harmonic spectroscopy. The sensibility of the high harmonic process to the geometry of the atomic or molecular orbitals is exploited to obtain information about the electronic structure of the generating medium. This method have been used to reveal the electronic relaxation of the nitrogen dioxide molecule (NO2) through the X2A1-A2B2 conical intersection.A second way consists to use the harmonic radiation like a source of XUV photons. The produced XUV radiation permits thus to reach electronically excited energy levels of atoms or molecules, pumping only with a one photon transition. XUV photons can also be used like a probe to ionize products of a molecular reaction. Velocity map imaging spectrometer (VMIS) have been designed and built to complete this fs-VUV source. Above threshold ionization (ATI) experiments and pump-probe XUV-400 nm studies have been performed on reference system like Argon to characterize the built experimental setup. The last excitation scheme has been also applied to study the photodissociation of the Acetylene excited in the 3d-4s Rydberg complex.