Rozprawy doktorskie na temat „Ultrafast Raman Spectroscopy”

This work is devoted to formulation and development of a laser spectroscopic technique for rapid detection of biohazards, such as Bacillus anthracis spores. Coherent anti-Stokes Raman scattering (CARS) is used as an underlying process for active retrieval of species-specific characteristics of an analyte. Vibrational modes of constituent molecules are Raman-excited by a pair of ultrashort, femtosecond laser pulses, and then probed through inelastic scattering of a third, time-delayed laser field. We first employ the already known time-resolved CARS technique. We apply it to the spectroscopy of easy-to-handle methanol-water mixtures, and then continue building our expertise on solutions of dipicolinic acid (DPA) and its salts, which happen to be marker molecules for bacterial spores. Various acquisition schemes are evaluated, and the preference is given to multi-channel frequency-resolved detection, when the whole CARS spectrum is recorded as a function of the probe pulse delay. We demonstrate a simple detection algorithm that manages to differentiate DPA solution from common interferents. We investigate experimentally the advantages and disadvantages of near-resonant probing of the excited molecular coherence, and finally observe the indicative backscattered CARS signal from DPA and NaDPA powders. The possibility of selective Raman excitation via pulse shaping of the preparation pulses is also demonstrated. The analysis of time-resolved CARS experiments on powders and B. subtilis spores, a harmless surrogate for B. anthracis, facilitates the formulation of a new approach, where we take full advantage of the multi-channel frequency-resolved acquisition and spectrally discriminate the Raman-resonant CARS signal from the background due to other instantaneous four-wave mixing (FWM) processes. Using narrowband probing, we decrease the magnitude of the nonresonant FWM, which is further suppressed by the timing of the laser pulses. The devised technique, referred to as hybrid CARS, leads to a single-shot detection of as few as 104 bacterial spores, bringing CARS spectroscopy to the forefront of potential candidates for real-time biohazard detection. It also gives promise to many other applications of CARS, hindered so far by the presence of the overwhelming nonresonant FWM background, mentioned above.

Thesis (Ph. D.)--University of Oregon, 2005.
Typescript. Includes vita and abstract. Includes bibliographical references (leaves 79-80). Also available for download via the World Wide Web; free to University of Oregon users.

Coherent anti-Stokes Raman scattering microscopy is a versatile technique for label-free imaging and spectroscopy of systems of biophysical interest. Due to the coherent nature of the generated signals, CARS images and spectra can often be difficult to interpret. In this thesis, we document how distortions and enhancements can be produced in CARS hyperspectroscopy as a result of the instrument, geometrical optical effects, or unique molecular states, and discuss how these effects may be suppressed or exploited in various CARS applications.

Chemistry
Ph.D.
Femtosecond laser filamentation in gaseous media is a new source of broadband, ultrashort radiation that has the potential for application to many fields of research. In this dissertation filamentation is studied with a view to understanding the underlying physics governing the formation and propagation dynamics of filamentation, as well as to developing a method for vibrational spectroscopy based on the filament-induced impulsive vibrational excitation of molecules in the filamentation region. In pursuit of a better understanding of the underlying physical processes driving filamentation, the development of a new method for characterizing high intensity ultrashort laser pulses is presented, wherein two laser beams generate a transient grating in a noble gas, causing the pulse undergoing filamentation to diffract from the grating. Measuring the spectrum as a function of time delay between the filament and probe beams generates a spectrogram that can be inverted to recover the spectral and temporal phase and amplitude of the filamentary pulse. This technique enables measurement of the filamentary pulse in its native environment, offering a window into the pulse dynamics as a function of propagation distance. The intrinsic pulse shortening observed during filamentation leads to the impulsive excitation of molecular vibrations, which can be used to understand the dynamics of filamentation as well. Combined measurements of the longitudinally-resolved filament Raman spectrum, power spectrum, and fluorescence intensity confirm the propagation dynamics inferred from pulse measurements and show that filamentation provides a viable route to impulsive vibrational spectroscopy at remote distances from the laser source. The technique is applied to thermometry in air and in flames, and an analytical expression is derived to describe the short-time dynamics of the rovibrational wave-packet dispersion experienced by diatomic molecules in the wave of the filament. It is found that no energy is initially partitioned into the distribution of rovibrational states during the filamentation process. Filament-assisted impulsive stimulated Raman spectroscopy of more complex systems is also performed, showing that filament-assisted vibrational measurements can be used as an analytical tool for gas phase measurements and has potential for use as a method for standoff detection. Finally, a study of the nonlinear optical mechanisms driving the filamentation process is conducted using spectrally-resolved pump-probe measurements of the transient birefringence of air. Comparison to two proposed theories shows that a newly described effect, ionization grating-induced birefringence, is largely responsible for saturation and sign inversion of the birefringence at 400 nm and 800 nm, while the magnitude of contributions described by a competing theory that relies on negative terms in the power series expansion of the bound electron response remain undetermined.
Temple University--Theses

The advent of ultrafast lasers has enabled micromachining schemes that cannot be achieved by other current techniques. Laser direct writing has emerged as one of the possible routes for fabrication of optical waveguides in transparent materials. In this thesis, the advantages and limitations of this technique are explored. Two extended-cavity ultrafast lasers were built and characterized as the laser sources for this study, with improved performance over existing systems. Waveguides are fabricated in oxide glass, chalcogenide glass, and polymers, these being the three major classes of materials for the telecommunication industry. Standard waveguide metrology is performed on the fabricated waveguides, including refractive index profiling and mode analysis. Furthermore, a finite-difference beam propagation method for wave propagation in 3D-waveguides is proposed. The photo-structural modifications underlying the changes in the material optical properties after exposure are investigated. The highly nonlinear processes of the light/matter interaction during the writing process are described using a free electron model. UV/visible absorption spectroscopy, photoluminescence spectroscopy and Raman spectroscopy are used to assess the changes occurring at the atomic level. Finally, the impact of laser direct writing on nonlinear waveguide applications is discussed.
Ph.D.
Other
Optics and Photonics
Optics

In this thesis, the effect of the sample properties on the characteristics of the hot carrier luminescence in graphene is investigated. The present work focuses on the two main issues described below. The first issue is the modification effects of near-infrared pulsed laser excitation on graphene. For excitation fluences several orders of magnitude lower than the optical damage threshold, the interaction with ultrafast laser pulses is found to cause a stable change in the properties of graphene. This photomodification also results in a decrease of the hot photoluminescence intensity. The detailed analysis shows that ultrafast photoexcitation leads to an increase in the local level of hole doping, as well as a change in the mechanical strain. The variation of doping and strain are linked with the enhanced adsorption of atmospheric oxygen caused by the distortion of the graphene surface. These findings demonstrate that ultrashort pulsed excitation can be invasive even if a relatively low laser power is used. Secondly, the variation of the hot photoluminescence intensity with the increasing charge carrier density in graphene is investigated. The electro-optical measurements performed using graphene field-effect transistors show a strong dependence of the photoluminescence intensity on the intrinsic carrier concentration. The emission intensity has a maximum value in undoped graphene and decreases with the increasing doping level. The theoretical calculations performed using a refined two-temperature model suggest that the reduction of the photoluminescence intensity is caused by an increase in the hot carrier relaxation rate. The modification of the carrier relaxation dynamics caused by photoinduced doping is probed directly using the two-pulse correlation measurements. The discovered sensitivity of the hot photoluminescence to the intrinsic carrier concentration can be utilised for spatially-resolved measurements of the Fermi level position in graphene samples, offering an advantage in resolution and speed.

Carbon nanomaterials encompass the newly discovered allotropes of carbon with at least one of its spatial dimensions on the order of a few nanometers. The physical properties of these nanomaterials differ substantially from the bulk carbon allotropes such as graphite and diamond. Of these nanomaterials, single-walled carbon nanotubes (SWNTs) and graphene have illicited much of the attention owing to their unique and attractive electronic, optical, thermal, and mechanical properties which have found numerous applications in emerging technologies. Raman spectroscopy is an invaluable technique in the characterisation of these materials as it allows for both a rapid and non-destructive analysis of these nanomaterials. We examined a number of methodologies for the synthesis of “bulk” quantities of graphene, and using Raman spectroscopy, analysed these samples to critically assess their crystalline quality, finding that many of the bulk methods produce material which could be considered as amorphous, rather than crystalline, having crystalline domain sizes less than a few nanometers. An important finding, as many of graphene’s unique properties are severely attenuated with increasing defects. Using these findings, we utilised the non-linear optical properties of graphene, namely its property of saturable absorption (wherby its light absorption decreases with increasing light intensitiy), to create saturable absorber mirrors (SAMs) which are used in the mode-locking of lasers creating pulses of light on the order femtoseconds with very high peak power. We developed graphene SAMs from the bulk synthetic methods which we found to have good crystalline quality and attempted to use them to passively mode-lock an Er:fiber laser operating at t 1560 nm. We successfully mode-locked the laser with graphene produced from the ultrasound induced exfoliation of graphite generating pules of sub-200 fs duration with low nonsaturable loss, and large modulation depths allowing use in low-gain lasers.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Biomolecular and Physical Sciences
Science, Environment, Engineering and Technology
Full Text

Orientador: René Alfonso Nome Silva
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: A espectroscopia vibracional de femtossegundos da vizinhança é ideal para caracterizar os movimentos moleculares da vizinhança acoplados com o sistema eletrônico captador de luz. No caso dos movimentos nucleares intramoleculares, isto pode ser realizado tanto por infravermelho quanto por Raman, ambos de femtossegundos. No caso de movimentos intermoleculares, a dinâmica de femtossegundos somente pode ser caracterizada com experimento Raman coerente, e, por essa razão, é importante sabermos qual é o comportamento do clorofórmio em um experimento de femtossegundo. Dessa forma, pode-se realizar a comparação entre os dados experimentais e teóricos e concluir se o comportamento observado experimentalmente é o mesmo que o esperado. Este trabalho explora a análise de Franck-Condon para os espectros de emissão do pireno com dependência da temperatura. Assume-se que uma progressão vibrônica de bandas no formato de Lorenzianas pode representar o formato das bandas de emissão do fluoróforo. Consequentemente, é possível obter alguns parâmetros, como a largura de linha das bandas obtidas, as intensidades relativas dos picos observados (valores que são utilizados para encontrar os fatores de Huang-Rhys), a variação do comprimento de onda de emissão com o aumento da temperatura e a área integrada dos espectros
Abstract: The femtosecond vibrational spectroscopy of the neighborhood is ideal to characterize the molecular movements of the neighborhood coupled with the electronics pickup light. In the case of intra-molecular nuclear movements, this can be accomplished either by infrared and Raman both femtosecond. In the case of intermolecular movements, the dynamics of femtosecond can only be characterized with coherent Raman experiment, and so it is important to know the behavior of chloroform in a femtosecond experiment. Thus, it is possible to make a comparison between experimental and theoretical data and conclude that the observed experimentally is the same behavior expected. This work explores the Franck-Condon analysis for the emission spectra of pyrene in dependence on temperature. It is assumed that a vibronic bands in the progression Lorenzianas shape may represent the format of fluorophore emission bands. Consequently, it is possible to obtain some parameters such as the line width of the bands obtained, the relative intensities of the observed peaks (values that are used to find the Huang-Rhys factors), the variation of emission wavelength with increasing temperature and the integrated area of the spectra
Mestrado
Físico-Química
Mestre em Química

Die Kombination aus Breit-Band Spektroskopie-Methoden ermöglicht eine umfassende Einsicht in das elektronische System von Molekülen im angeregten Zustand. Am Beispiel des Riboflavin in saurer Umgebung wird der Protonen-Transfer aus der Lösung auf den Chromophor mittels transienter Absorption und -Fluoreszenz im S1-Zustand beobachtet. Mittels transienter Absorption- und Femtosekunden-stimulierter Raman-Spektroskopie wird der Populationstransfer in den elektronischen Grundzustand im beta-Karotin verfolgt und charakterisiert werden.
The combination of broadband spectroscopic methods allows a comprehensive view of the electronic system of molecules in the excited state. On riboflavin in acidic environment the proton-transfer is observed with transient absorption and -flurescence in the S1-state. With transient absorption and femtosecond-stimulated Raman-spectroscopy the population transfer into the electronic ground-state is followed and characterized.

Local refractive index changes (RIC) are the building blocks of laser-induced optical functions in bulk transparent materials, where the use of a fused silica as a target material plays a paramount role. Depending on the regime of laser interaction ultra-short pulses can induce positive isotropic refractive index changes (usually denoted as type I) or produce self-arranged nano-scale layered structures resulting in form birefringence (type II). In this thesis we have studied two objectives related to these material transformations. From the one side, we qualitatively determined the effects of the focused ultra-short laser pulses on the fused silica and borosilicate glasses. With the independent control of the energetic dose, pulse duration and focusing conditions, the isotropic type I and birefringent type II traces could be performed with the certain optical properties. Finally, complex polarization sensitive devices were designed and fabricated. From the other side, as these types of RIC have consequences in the functionality and the performances of 3D embedded optical devices, an investigation of the laser-induced structures is particularly useful. We applied photoluminescence and Raman microscopy (RM) to investigate defect formation and glass network reorganization paths. The proposed spectroscopy study distinguishes type I and type II regions by presence and distribution of silicon clusters and non-bridging oxygen hole centers (NBOHC). RM reveals signs of compaction of the glass network in the RIC regions. At the same time, zones with high concentration of NBOHC where no visible RIC and densification signs were detected. Assuming that these zones are precursors of permanent visible modification, we propose a scenario of cold defect-assisted densification realized in type I irradiation regime. This, thereby, revises the densification paths in fused silica

In dieser Arbeit wird das Wachstum von dünnen quasi-kristallinen Ge-Sb-Te (GST) Schichten mittels Molekularstrahlepitaxie demonstriert, die zu einer geordneten Konfiguration von intrinsischen Kristallgitterfehlstellen führen. Es wird gezeigt, wie es eine Strukturanalyse basierend auf Röntgenstrahlbeugungssimulationen, Dichtefunktionaltheorie und Transmissionselektronenmikroskopie ermöglicht, eine eindeutige Beurteilung der Kristallgitterlückenanordnung in den GST-Proben vorzunehmen. Das Verständnis für die Ordnungsprozesse der Gitterfehlstellen erlaubt eine gezielte Einstellung des Ordnungsgrades selbst, der mit der Zusammensetzung und der Kristallphase des Materials in Zusammenhang steht. Auf dieser Basis wurde ein Phasendiagramm mit verschiedenen Wachstumsfenstern für GST erstellt. Des Weiteren wird gezeigt, dass man eine hohe Ordnung der Gitterfehlstellen in GST auch durch Ausheizprozesse und anhand von Femtosekunden-gepulster Laserkristallisation von amorphem Material erhält, das zuvor auf einem als Kristallisationsgrundlage dienenden Substrat abgeschiedenen wurde. Diese Erkenntnis ist bemerkenswert, da sie zeigt, dass sich kristalline GST Schichten mit geordneten Kristallgitterlücken durch verschiedene Herstellungsprozesse realisieren lassen. Darüber hinaus wurde das Wachstum von GeTe/Sb2Te3 Übergittern durchgeführt, deren Struktur die von GST mit geordneten Gitterfehlstellen widerspiegelt. Die Möglichkeit den Grad der Gitterfehlstellenordung in GST gezielt zu manipulieren wurde mit einer Studie der Transporteigenschaften kombiniert. Die Anwendung von großflächigen Charakterisierungsmethoden wie XRD, Raman und IR-Spektroskopie, erlaubte die Bestimmung der Phase und des Fehlstellenordnungsgrades von GST und zeigte eindeutig, dass die Fehlstellenordnung für den Metall-Isolator-Übergang (MIT) verantwortlich ist. Insbesondere wird durch das Vergleichen von XRD-Messungen mit elektrischen Messungen gezeigt, dass der Übergang von isolierend zu leitend erfolgt, sobald eine Ordnung der Kristallgitterlücken einsetzt. Dieses Phänomen tritt in der kubischen Kristallphase auf, wenn Gitterfehlstellen in GST von einem ungeordneten in einen geordneten Zustand übergehen. Im zweiten Teil des Kapitels wird eine Kombination aus FIR- und Raman-Spektroskopie zur Untersuchung der Vibrationsmoden und des Ladungsträgerverhaltens in der amorphen und der kristallinen Phase angewendet, um Aktivierungsenergien für die Elektronenleitung, sowohl für die kubische, als auch für die trigonale Kristallphase von GST zu bestimmen. Hier ist es wichtig zu erwähnen, dass, in Übereinstimmung mit Ergebnissen aus anderen Untersuchungen, das Auftauchen eines MIT beim Übergang zwischen der ungeordneten und der geordneten kubischen Phase beobachtet wurde. Schlussendlich wurden verschiedene sogenannte Pump/Probe Technik, bei der man das Material mit dem Laser anregt und die Röntgenstrahlung oder Terahertz (THz)-spektroskopie als Sonde nutzt, angewandt. Dies dient um ultra-schnelle Dynamiken zu erfassen, die zum Verständnis der Umschaltmechanismen nötig sind. Die Empfindlichkeit der THz-Messungen hinsichtlich der Leitfähigkeit, sowohl in GST, als auch in GeTe/Sb2Te3 Übergittern zeigte, dass die nicht-thermische Natur der Übergitterumschaltprozesse mit Grenzflächeneffekten zusammenhängt und . Der Ablauf wird mit beeindruckender geringer Laser-Fluenz erreicht. Dieses Ergebnis stimmt mit Berichten aus der Literatur überein, in denen ein Kristall-zu Kristallwechsel von auf Übergittern basierenden Speicherzellen für effizienter gehalten wird als GST Schmelzen, was zu einen ultra-schwachen Energieverbrauch führt.
The growth by molecular beam epitaxy of Ge-Sb-Te (GST) alloys resulting in quasi-single-crystalline films with ordered configuration of intrinsic vacancies is demonstrated. It is shown how a structural characterization based on transmission electron microscopy, X-ray diffraction and density functional theory, allowed to unequivocally assess the vacancy ordering in GST samples, which was so far only predicted. The understanding of the ordering process enabled the realization of a fine tuning of the ordering degree itself, which is linked to composition and crystalline phase. A phase diagram with the different growth windows for GST is obtained. High degree of vacancy ordering in GST is also obtained through annealing and via femtosecond-pulsed laser crystallization of amorphous material deposited on a crystalline substrate, which acts as a template for the crystallization. This finding is remarkable as it demonstrates that it is possible to create a crystalline GST with ordered vacancies by using different fabrication procedures. Growth and structural characterization of GeTe/Sb2Te3 superlattices is also obtained. Their structure resembles that of ordered GST, with exception of the Sb and Ge layers stacking sequence. The possibility to tune the degree of vacancy ordering in GST has been combined with a study of its transport properties. Employing global characterization methods such as XRD, Raman and Far-Infrared spectroscopy, the phase and ordering degree of the GST was assessed, and unequivocally demonstrated that vacancy ordering in GST drives the metal-insulator transition (MIT). In particular, first it is shown that by comparing electrical measurements to XRD, the transition from insulating to metallic behavior is obtained as soon as vacancies start to order. This phenomenon occurs within the cubic phase, when GST evolves from disordered to ordered. In the second part of the chapter, a combination of Far-Infrared and Raman spectroscopy is employed to investigate vibrational modes and the carrier behavior in amorphous and crystalline phases, enabling to extract activation energies for the electron conduction for both cubic and trigonal GST phases. Most important, a MIT is clearly identified to occur at the onset of the transition between the disordered and the ordered cubic phase, consistently with the electrical study. Finally, pump/probe schemes based on optical-pump/X-ray absorption and Terahertz (THz) spectroscopy-probes have been employed to access ultrafast dynamics necessary for the understanding of switching mechanisms. The sensitivity of THz-probe to conductivity in both GST and GeTe/Sb2Te3 superlattices showed that the non-thermal nature of switching in superlattices is related to interface effects, and can be triggered by employing up to one order less laser fluences if compared to GST. Such result agrees with literature, in which a crystal to crystal switching of superlattice based memory cells is expected to be more efficient than GST melting, therefore enabling ultra-low energy consumption.

This thesis describes the development of several spectroscopic methods based on impulsive vibrational spectroscopy as well as of the technique itself. The first chapter describes the ultrafast time domain Raman spectrometer including the development of two noncollinear optical parametric amplifiers for sub-10 fs pulse generation with 343 or 515 nm pumping. In the first spectroscopic study we demonstrate, for the first time, that impulsive vibrational spectroscopy can be used for recording transient Raman spectra of molecules in excited electronic states. We obtain spectra of beta-carotene with comparable, or better, quality than established frequency domain based nonlinear Raman techniques. The following two chapters address the questions on the fate of vibrational coherences when generated on a reactive potential energy surface. We photoexcite bacteriorhodopsin and observe anharmonic coupling mediated vibrational coherence transfer to initially silent vibrational modes. Additionally, we are able to correlate the vibrational coherence activation with the efficiency of the isomerisation reaction in bR. Upon generation of vibrational coherence in the second excited electronic state of beta-carotene, by excitation from the ground electronic state, we are able to follow the wavepacket motion out of the Franck-Condon region. We observe vibrationally coherent internal conversion, through a conical intersection, into the first excited electronic state and are hence able to demonstrate that electronic surface crossings can occur in a vibrationally coherent fashion. Additionally, we find strong evidence for vibronic coupling mediated back and forth crossing between the two electronic states. As a combination of this work we develop a IVS based technique that allows for the direct recording of background and baseline free Raman spectra in the time domain. Several proof of principle experiments highlight the capabilities of this technique for time resolved Raman spectroscopy. In the final chapter we present work on weak-field coherent control. Here, we address the question of whether a photochemical reaction can be controlled by the phase term of an electric excitation field, in the one photon excitation limit. We study the systems rhodamine 101, bacteriorhodopsin, rhodopsin and isorhodopsin and, contrary to previous reports, find no evidence for one photon control.

The vibrational wave-packet dynamics of diatomic rubidium molecules (Rb2) in triplet states formed on the surface of superfluid helium nanodroplets is investigated both experimentally and theoretically. Detailed comparison of experimental femtosecond pump–probe spectra with dissipative quantum dynamics simulations reveals that vibrational relaxation is the main source of dephasing. The rate constant for vibrational relaxation in the first excited triplet state 13Σ+g is found to be constant γ ≈ 0.5 ns−1 for the lowest vibrational levels v [less, similar] 15 and to increase sharply when exciting to higher energies
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich

The vibrational wave-packet dynamics of diatomic rubidium molecules (Rb2) in triplet states formed on the surface of superfluid helium nanodroplets is investigated both experimentally and theoretically. Detailed comparison of experimental femtosecond pump–probe spectra with dissipative quantum dynamics simulations reveals that vibrational relaxation is the main source of dephasing. The rate constant for vibrational relaxation in the first excited triplet state 13Σ+g is found to be constant γ ≈ 0.5 ns−1 for the lowest vibrational levels v [less, similar] 15 and to increase sharply when exciting to higher energies.
Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Lasers find a wide range of applications in many areas including photo-biology, photo-chemistry, materials processing, imaging and telecommunications. However, the practical use of such sources is often limited by the bulky nature of existing systems. By fabricating channel waveguides in solid-state laser-gain materials more compact laser systems can be designed and fabricated, providing user-friendly sources. Other advantages inherent in the use of waveguide gain media include the maintenance of high intensities over extended interaction lengths, reducing laser thresholds. This thesis presents the development of Yb:tungstate lasers operating around 1μm in waveguide geometries. An Yb:KY(WO₄)₂ planar waveguide laser grown by liquid phase epitaxy is demonstrated with output powers up to 190 mW and 76 % slope efficiency. This is similar to the performance from bulk lasers but in a very compact design. Excellent thresholds of only 40 mW absorbed pump power are realised. The propagation loss is found to be less than 0.1 dBcm⁻¹ and Q-switched operation is also demonstrated. Channel waveguides are fabricated in Yb:KGd(WO₄)₂ and Yb:KY(WO₄)₂ using ultrafast laser inscription. Several of these waveguides lase in compact monolithic cavities. A maximum output power of 18.6 mW is observed, with a propagation loss of ~2 dBcm⁻¹. By using a variety of writing conditions the optimum writing pulse energy is identified. Micro-spectroscopy experiments are performed to enable a fuller understanding of the induced crystal modification. Observations include frequency shifts of Raman lines which are attributed to densification of WO₂W bonds in the crystal. Yb:tungstate lasers can generate ultrashort pulses and some preliminary work is done to investigate the use of quantum dot devices as saturable absorbers. These are shown to have reduced saturation fluence compared to quantum well devices, making them particularly suitable for future integration with Yb:tungstate waveguides for the creation of ultrafast, compact and high repetition rate lasers.

L’engouement mondial pour les appareils nomades et la course à la sobriété énergétique font de la diminution de la taille des systèmes microélectroniques (MEMS) un enjeu majeur pour les prochaines années. Les micro batteries au lithium sont aujourd'hui le moyen le plus efficace pour stocker et alimenter des dispositifs avec une très forte densité énergétique. Les incorporer dans des cartes de crédit comportant un écran et des touches intégrés est l’un des défis que relèvent les multinationales comme ST Micro Electronics. Ces micro batteries contiennent cependant du lithium métallique qui peut s'avérer très dangereux quand il est en contact avec de l’eau ou de l’air humide. Ainsi, afin de protéger les composants à une exposition à l’humidité, une encapsulation de l’ensemble de la batterie est nécessaire. L'encapsulation polymère a l’avantage, comparativement à d’autres matériaux, de présenter un faible coût de mise en forme et un faible poids. Cependant, de tels systèmes d'encapsulation sont aujourd'hui insuffisants pour garantir une durée de vie de plusieurs années des composants car en présence d’humidité ou d’une variation de température importante la tenue mécanique des assemblages peut être fragilisée. L'objectif de la thèse est donc de réaliser et d'étudier le comportement mécanique et structural d’assemblage de couches minces de polymères et de métaux en température et en humidité. Deux types de polymères ont été choisis pour ce projet :1. Le chlorure de polyvinylidène (PVDC), un polymère commercial très utilisé pour ses bonnes propriétés barrières à l'eau 2. Un oligomère acrylate reticulable par voie thermique et UV synthétisé au sein de l'IMMM
The increasing number of mobile devices and the race to energy sobriety make the decrease of the size of microelectronic systems (MEMS) a major challenge. Today, Lithium micro batteries are currently the best solution for high-power-and-energy applications. Incorporate them into credit cards containing a screen or associate them to electronic sensors for the supervision is the challenge which raises international companies such as ST Microelectronics. However, these micro batteries contain some lithium metal which can be dangerous if the metallic lithium is in contact with water or humid air. In addition, the substance can spontaneously ignite in the contact of the humidity. So, in order to avoid the problems of safety, we absolutely have to protect the lithium contained in our micro batteries using an encapsulation layer. Polymeric encapsulation has the advantage, compared with other materials (ceramic, metal), to present a moderate cost of shaping and a low weight. However, such systems of encapsulation are today insufficient to guarantee a satisfactory life cycle of components. Indeed, in the presence of humidity or of a too important temperature variation, the mechanical assemblies can be weakened and engender an irreparable break. The objective of the thesis is therefore to realize and study the mechanical and structural behavior of assembly of thin layers of polymers and metals in temperature and humidity.Two types of polymers were selected for this project:1. Polyvinylidene chloride (PVDC), a commercial polymer widely used for its good barrier properties to water.2. A thermally and UV-crosslinkable acrylate oligomer synthesized in the IMMM

L’étude expérimentale des processus physico-chimiques de la combustion nécessite de disposer de diagnostics non-intrusifs. Le présent manuscrit reporte le développement du diagnostic laser de mesure de température DRASC (Diffusion Raman anti-Stokes Cohérente) en régime d’impulsions laser femtoseconde pour lequel la configuration à sonde à dérive de fréquence (CPP) a permis d’effectuer des mesures instantanées de température à 1kHz. Un travail à la fois théorique, numérique et expérimental a permis d’extraire la température des spectres DRASC instantanés acquis dans des mélanges air/argon (300-600K) et en flamme prémélangée CH4/Air avec une précision de l’ordre de 1% à 2100 K. La validité de ces résultats est obtenues par des confrontations numérique/expérimental pour différentes grandeurs d’influence. Cette étude permettra dans un proche futur d’appliquer le diagnostic DRASC fs CPP dans des flammes turbulentes représentatives d’écoulements réels observés en combustion aéronautique
The experimental study of the physico-chemical processes of combustion requires the use of non-intrusive diagnostics. This manuscript reports the development of the CARS (Coherent Anti-Stokes Raman Scattering)) laser diagnostic in the femtosecond pulse regime for which the Chirped Pulse Probe (CPP) configuration enabled instantaneous measurements of temperature at 1kHz. A theoretical, numerical and experimental study allowed highlighting the possibility to measure temperature from the data processing of instantaneous DRASC spectra acquired in air/argon mixtures (300-600K) and in premixed flame CH4/Air with an accuracy of 1% at 2100 K. Validity of these results was obtained from numerical/experimental confrontations for different scalar parameters configurations. This study would enable in the near future the application of the CPP fs CARS diagnostic in turbulent flames representative of real flows observed in aeronautical combustion

Contemporary laser research involves the development of spectroscopic techniques to understand the microscopic structural aspects of a simple molecular system in chemical and materials to more complex biological systems such as cells. In particular, Raman spectroscopy, which provides bond specific information, has attracted considerable attention. Further with the advent of femtosecond (fs) laser, the recent trend in the field of fs chemistry is to develop nonlinear Raman techniques that allow one to acquire vibrational structural information with both fs temporal resolution as well as good spectral resolution. Among many advanced nonlinear Raman techniques, the development of fs Stimulated Raman scattering (SRS) has gathered momentum in the recent decade due to its ability to (1) provide vibrational structural information of various system including fluorescent molecules with good signal to noise ratio and (2) circumvent the limitation imposed on the spectral resolution by the necessary pulse durations according to the energy-time uncertainty principle where ‘K’ is a constant that depends on the pulse shape) unlike in the case of fs normal resonance Raman spectroscopy. We have developed a technique named “Ultrafast Raman loss spectroscopy (URLS)” that is analogues to SRS, but is more advantageous as compared to SRS and has the potential to be an alternative if not competitive tool as a vibrational structure elucidating technique. The concept and the design of this novel technique, URLS, form the core of the thesis entitled “Ultrafast Raman Loss Spectroscopy (URLS)”. Chapter 1 lays the theoretical groundwork for ultra-short pulses and nonlinear spectroscopy which forms the heart of URLS. It presents a detailed discussion on the basis behind the elementary experimental problems associated with the ultra-short laser pulses when they travel through a medium, the characterization of these ultrashort pulses as well as various non-linear phenomena induced within a medium due to the propagation of these pulses. Chapter 2 focuses on the concept of SRS which resulted into the foundation of URLS. It illustrates the theoretical as well as the experimental aspects of SRS and demonstrates the sensitivity of SRS over normal Raman spectroscopy. Chapter 3 introduces the conceptual and the technical basis which ensued into the development of URLS while Chapter 4 demonstrates its application and efficiency over its analogue SRS. URLS involves the interaction of two laser sources, viz. a picosecond (ps) pulse and a fs white light (WL), with a sample leading to the generation of loss signal on the higher energy (blue) side with respect to the wavelength of the ps pulse unlike the gain signal observed on the lower energy (red) side in SRS. These loss signals are at least 1.5 times more intense than SRS signals. Also, the very prerequisite of the experimental protocol for signal detection to be on the higher energy side by design eliminates the interference from fluorescence, which appears on the red side. Thus, the rapid data acquisition, 100% natural fluorescence rejection and experimental ease ascertain “Ultrafast Raman Loss Spectroscopy (URLS)” as a unique valuable structure determining technique. Further, the effect of resonance on the line shape of the URLS signal has been studied which forms the subject of discussion in Chapter 5. The objective of the study is to verify whether the variation of resonance Raman line shapes in URLS could provide an understanding of the mode specific response on ultrafast excitation. It is found that the URLS signal’s line shape is mode dependent and can provide information similar to Raman excitation profile (REP) in the normal Raman studies. This information can have impact on the study of various dynamical process involving vibrational modes like structural dynamics and coherent control. Chapter 6 demonstrates the application of URLS as a structure elucidating technique for monitoring ultrafast structural and reaction dynamics in both chemical and biological systems using α-terthiophene (3T) as the model system. The objective is to understand the mechanism of the molecular structure dependent electronic relaxation of the first singlet excited state, S1, of α-terthiophene using fs URLS. The URLS data along with the ab-initio calculations indicate that the electronic transition is associated with a structural rearrangement from a non-planar to a planar configuration in the singlet manifold along the ring deformation co-ordinate. The experimental findings suggest that the singlet state decays exponentially with a decay time constant ( 1/e) of about 145 ps and this decay could be assigned to the intersystem crossing (ISC) pathway from the relaxed S1 state to the vibrationally hot triplet state, T1*. Lastly, Chapter 7 summarizes the entire thesis and presents some possible future prospects for URLS. Considering the advantages of URLS, it is proposed that URLS can be exploited [1] to determine the structure of any fluorescent/non-florescent condensed materials and biological systems with a very good spectral resolution (10- 40 cm-1); [2] to obtain the vibrational signature of weak Raman scattering molecules and vibrational modes with relatively small Raman cross-section owing to its high detection sensitivity with good signal to noise ratio; [3] for performing fs time-resolved study by introducing an additional fs pulse for photo-excitation of the molecule and using URLS to probe the excited state dynamics with good temporal (fs) and spectral (10-40 cm-1) resolution; and lastly, [4] the high chemical selectivity of URLS and the fact that the signal is generated only within the focal volume of the lasers where all the beams overlap can be utilized for developing this method into a microscopy for labeled-free effective vibrational study of biological samples. Consequently, it is hoped that this technique, “Ultrafast Raman Loss Spectroscopy (URLS)”, would be a suitable alternative to other nonlinear Raman methods like coherent anti-Stokes Raman spectroscopy (CARS) that has made major inroads into biology, medicine and materials.

Contemporary laser research involves the development of spectroscopic techniques to understand the microscopic structural aspects of a simple molecular system in chemical and materials to more complex biological systems such as cells. In particular, Raman spectroscopy, which provides bond specific information, has attracted considerable attention. Further with the advent of femtosecond (fs) laser, the recent trend in the field of fs chemistry is to develop nonlinear Raman techniques that allow one to acquire vibrational structural information with both fs temporal resolution as well as good spectral resolution. Among many advanced nonlinear Raman techniques, the development of fs Stimulated Raman scattering (SRS) has gathered momentum in the recent decade due to its ability to (1) provide vibrational structural information of various system including fluorescent molecules with good signal to noise ratio and (2) circumvent the limitation imposed on the spectral resolution by the necessary pulse durations according to the energy-time uncertainty principle where ‘K’ is a constant that depends on the pulse shape) unlike in the case of fs normal resonance Raman spectroscopy. We have developed a technique named “Ultrafast Raman loss spectroscopy (URLS)” that is analogues to SRS, but is more advantageous as compared to SRS and has the potential to be an alternative if not competitive tool as a vibrational structure elucidating technique. The concept and the design of this novel technique, URLS, form the core of the thesis entitled “Ultrafast Raman Loss Spectroscopy (URLS)”. Chapter 1 lays the theoretical groundwork for ultra-short pulses and nonlinear spectroscopy which forms the heart of URLS. It presents a detailed discussion on the basis behind the elementary experimental problems associated with the ultra-short laser pulses when they travel through a medium, the characterization of these ultrashort pulses as well as various non-linear phenomena induced within a medium due to the propagation of these pulses. Chapter 2 focuses on the concept of SRS which resulted into the foundation of URLS. It illustrates the theoretical as well as the experimental aspects of SRS and demonstrates the sensitivity of SRS over normal Raman spectroscopy. Chapter 3 introduces the conceptual and the technical basis which ensued into the development of URLS while Chapter 4 demonstrates its application and efficiency over its analogue SRS. URLS involves the interaction of two laser sources, viz. a picosecond (ps) pulse and a fs white light (WL), with a sample leading to the generation of loss signal on the higher energy (blue) side with respect to the wavelength of the ps pulse unlike the gain signal observed on the lower energy (red) side in SRS. These loss signals are at least 1.5 times more intense than SRS signals. Also, the very prerequisite of the experimental protocol for signal detection to be on the higher energy side by design eliminates the interference from fluorescence, which appears on the red side. Thus, the rapid data acquisition, 100% natural fluorescence rejection and experimental ease ascertain “Ultrafast Raman Loss Spectroscopy (URLS)” as a unique valuable structure determining technique. Further, the effect of resonance on the line shape of the URLS signal has been studied which forms the subject of discussion in Chapter 5. The objective of the study is to verify whether the variation of resonance Raman line shapes in URLS could provide an understanding of the mode specific response on ultrafast excitation. It is found that the URLS signal’s line shape is mode dependent and can provide information similar to Raman excitation profile (REP) in the normal Raman studies. This information can have impact on the study of various dynamical process involving vibrational modes like structural dynamics and coherent control. Chapter 6 demonstrates the application of URLS as a structure elucidating technique for monitoring ultrafast structural and reaction dynamics in both chemical and biological systems using α-terthiophene (3T) as the model system. The objective is to understand the mechanism of the molecular structure dependent electronic relaxation of the first singlet excited state, S1, of α-terthiophene using fs URLS. The URLS data along with the ab-initio calculations indicate that the electronic transition is associated with a structural rearrangement from a non-planar to a planar configuration in the singlet manifold along the ring deformation co-ordinate. The experimental findings suggest that the singlet state decays exponentially with a decay time constant ( 1/e) of about 145 ps and this decay could be assigned to the intersystem crossing (ISC) pathway from the relaxed S1 state to the vibrationally hot triplet state, T1*. Lastly, Chapter 7 summarizes the entire thesis and presents some possible future prospects for URLS. Considering the advantages of URLS, it is proposed that URLS can be exploited [1] to determine the structure of any fluorescent/non-florescent condensed materials and biological systems with a very good spectral resolution (10- 40 cm-1); [2] to obtain the vibrational signature of weak Raman scattering molecules and vibrational modes with relatively small Raman cross-section owing to its high detection sensitivity with good signal to noise ratio; [3] for performing fs time-resolved study by introducing an additional fs pulse for photo-excitation of the molecule and using URLS to probe the excited state dynamics with good temporal (fs) and spectral (10-40 cm-1) resolution; and lastly, [4] the high chemical selectivity of URLS and the fact that the signal is generated only within the focal volume of the lasers where all the beams overlap can be utilized for developing this method into a microscopy for labeled-free effective vibrational study of biological samples. Consequently, it is hoped that this technique, “Ultrafast Raman Loss Spectroscopy (URLS)”, would be a suitable alternative to other nonlinear Raman methods like coherent anti-Stokes Raman spectroscopy (CARS) that has made major inroads into biology, medicine and materials.

Raman spectroscopy involves change in the polarizability of the molecular system on excitation and is based on scattering process. Spontaneous Raman scattering is a two photon process, in which the input light initiates the excitation, which then leads to an emission of another photon due to scattering. It is extensively used to understand molecular properties. As spontaneous Raman scattering is a weak process, the detection of these weak Raman photons are rather difficult. Alternatively, resonance Raman (RR) scattering is another technique where the excitation wavelength is chosen according to the material under study. The excitation wavelength is chosen to be within the absorption spectrum of the material under study. RR spectroscopy not only provides considerable improvement in the intensity of the Raman signal, but also provides mode specific information i.e. the modes which are Franck-Condon active in that transition can be observed. There are reports on RR studies of many systems using pulsed light as an excitation source. It is necessary to use at least two pulsed laser sources for carrying out the time resolved RR spectroscopy. A single pulse source for excitation would lead to compromise either with temporal or spectral resolution which is due to the uncertainty principle. If an excitation pulse has pulse width of ~100 femtoseconds then the spectral resolution will be ~ 150 cm-1. It is clear now that for improving the temporal and spectral resolution simultaneously, usage of single pulse for Raman experiments (spontaneous scattering) is not adequate. The usage of multiple laser pulses may provide the way out to improve the resolutions. Nonlinear spectroscopy in a broad view helps in understanding the structural and dynamical properties of the molecular systems in a deeper manner. There are a number of techniques as a part of nonlinear spectroscopy that have emerged in due course to meet different requirements and to overcome some difficulties while understanding the molecular properties. Stimulated Raman (SRS) gain, coherent anti-Stokes Raman scattering (CARS) and the inverse Raman spectroscopy are a few to mention as third order nonlinear spectroscopic techniques which give the similar kind of information about the molecular systems. Stimulated Raman scattering is a more general process involved in nonlinear Raman processes. SRS involves at least two laser pulses and the difference in their frequencies should match with the vibrational frequency of the molecule. The polarization has to be matched between the Raman pump and the Raman probe pulses. We have developed a new nonlinear Raman technique in our laboratory named as ultrafast Raman loss spectroscopy (URLS) using the principles of nonlinear Raman scattering. It involves the Raman pump (~ 1 picosecond (ps) or ~ 15 cm-1spectral resolution) and Raman probe as a white light continuum (100 fs) whose frequency components ranges from 400-900 nm. The laser system consists of Tsunami which is pumped by a Millennia laser and Spitfire-Pro, a regenerative amplifier which is pumped by an Empower laser. Tsunami provides a 100 fs, 780 nm centered, 80 MHz and ~6 nJ energy laser pulses. The Tsunami output is fed into Spitfire to amplify its energy and change the repetition rate to 1 KHz. The pulse length of the input pulse is preserved in amplification. The output of amplifier is split into two equal parts; one part is used to pump the Optical Parametric Amplifier (OPA) in order to generate wavelengths in the range 480-800 nm. The output of the OPA is utilized to generate Raman pump which has to be in ps in order to get the best spectral resolution. A small portion of the other part of amplifier output is utilized to generate white light source for the Raman probe. The remaining part of the amplifier output is used to pump TOPAS to generate wavelengths in the ultraviolet region. URLS has been applied to many molecular systems which range from non-fluorescent to highly fluorescent. URLS has been demonstrated to be very sensitive and useful while dealing with highly fluorescent systems. URLS is a unique technique due to its high sensitivity and the Raman loss signal intensity is at least 1.5-2 times higher as compared to the Raman gain signal intensities. Cresyl violet perchlorate (CVP) is a highly fluorescent system. URLS has been applied to study CVP even at resonance excitation. Rhodamine B has also been studied using URLS. Spontaneous Raman scattering is very difficult to observe experimentally in such high quantum yield fluorescent systems. The variation in the lineshapes of the Raman bands for different RP excitation wavelengths in URLS spectra shows the mode dependent behavior of the absorption spectrum. The experimental observation of variation in the lineshape has been accounted using theoretical formalism. The thesis is focused on discussing the development of the new nonlinear Raman spectroscopic technique URLS in detail and its applicability to molecular systems for better understanding. A theoretical formalism for accounting the uniqueness of URLS among the other nonlinear Raman techniques is developed and discussed in various pictorial representations i.e. ladder, Feynman and closed loop diagrams. A brief overview of nonlinear spectroscopy and nonlinear Raman spectroscopy is presented for demonstrating the difference between the URLS and the other nonlinear Raman techniques.

Raman spectroscopy involves change in the polarizability of the molecular system on excitation and is based on scattering process. Spontaneous Raman scattering is a two photon process, in which the input light initiates the excitation, which then leads to an emission of another photon due to scattering. It is extensively used to understand molecular properties. As spontaneous Raman scattering is a weak process, the detection of these weak Raman photons are rather difficult. Alternatively, resonance Raman (RR) scattering is another technique where the excitation wavelength is chosen according to the material under study. The excitation wavelength is chosen to be within the absorption spectrum of the material under study. RR spectroscopy not only provides considerable improvement in the intensity of the Raman signal, but also provides mode specific information i.e. the modes which are Franck-Condon active in that transition can be observed. There are reports on RR studies of many systems using pulsed light as an excitation source. It is necessary to use at least two pulsed laser sources for carrying out the time resolved RR spectroscopy. A single pulse source for excitation would lead to compromise either with temporal or spectral resolution which is due to the uncertainty principle. If an excitation pulse has pulse width of ~100 femtoseconds then the spectral resolution will be ~ 150 cm-1. It is clear now that for improving the temporal and spectral resolution simultaneously, usage of single pulse for Raman experiments (spontaneous scattering) is not adequate. The usage of multiple laser pulses may provide the way out to improve the resolutions. Nonlinear spectroscopy in a broad view helps in understanding the structural and dynamical properties of the molecular systems in a deeper manner. There are a number of techniques as a part of nonlinear spectroscopy that have emerged in due course to meet different requirements and to overcome some difficulties while understanding the molecular properties. Stimulated Raman (SRS) gain, coherent anti-Stokes Raman scattering (CARS) and the inverse Raman spectroscopy are a few to mention as third order nonlinear spectroscopic techniques which give the similar kind of information about the molecular systems. Stimulated Raman scattering is a more general process involved in nonlinear Raman processes. SRS involves at least two laser pulses and the difference in their frequencies should match with the vibrational frequency of the molecule. The polarization has to be matched between the Raman pump and the Raman probe pulses. We have developed a new nonlinear Raman technique in our laboratory named as ultrafast Raman loss spectroscopy (URLS) using the principles of nonlinear Raman scattering. It involves the Raman pump (~ 1 picosecond (ps) or ~ 15 cm-1spectral resolution) and Raman probe as a white light continuum (100 fs) whose frequency components ranges from 400-900 nm. The laser system consists of Tsunami which is pumped by a Millennia laser and Spitfire-Pro, a regenerative amplifier which is pumped by an Empower laser. Tsunami provides a 100 fs, 780 nm centered, 80 MHz and ~6 nJ energy laser pulses. The Tsunami output is fed into Spitfire to amplify its energy and change the repetition rate to 1 KHz. The pulse length of the input pulse is preserved in amplification. The output of amplifier is split into two equal parts; one part is used to pump the Optical Parametric Amplifier (OPA) in order to generate wavelengths in the range 480-800 nm. The output of the OPA is utilized to generate Raman pump which has to be in ps in order to get the best spectral resolution. A small portion of the other part of amplifier output is utilized to generate white light source for the Raman probe. The remaining part of the amplifier output is used to pump TOPAS to generate wavelengths in the ultraviolet region. URLS has been applied to many molecular systems which range from non-fluorescent to highly fluorescent. URLS has been demonstrated to be very sensitive and useful while dealing with highly fluorescent systems. URLS is a unique technique due to its high sensitivity and the Raman loss signal intensity is at least 1.5-2 times higher as compared to the Raman gain signal intensities. Cresyl violet perchlorate (CVP) is a highly fluorescent system. URLS has been applied to study CVP even at resonance excitation. Rhodamine B has also been studied using URLS. Spontaneous Raman scattering is very difficult to observe experimentally in such high quantum yield fluorescent systems. The variation in the lineshapes of the Raman bands for different RP excitation wavelengths in URLS spectra shows the mode dependent behavior of the absorption spectrum. The experimental observation of variation in the lineshape has been accounted using theoretical formalism. The thesis is focused on discussing the development of the new nonlinear Raman spectroscopic technique URLS in detail and its applicability to molecular systems for better understanding. A theoretical formalism for accounting the uniqueness of URLS among the other nonlinear Raman techniques is developed and discussed in various pictorial representations i.e. ladder, Feynman and closed loop diagrams. A brief overview of nonlinear spectroscopy and nonlinear Raman spectroscopy is presented for demonstrating the difference between the URLS and the other nonlinear Raman techniques.

The present thesis deals with the detailed ultrafast experimental studies on the ex-cited state vibrational dynamics of model chemical systems in condensed phase. The molecular systems are studied by means of Ultrafast Raman Loss Spectroscopy (URLS) and femtosecond transient absorption (TA) spectroscopy. The primary objective of the current thesis is to look at structural dynamics immediately after Franck-Condon excitation, influenced by surrounding solvent molecules. The thesis is divided into six chapters and a brief summary of each chapter is given below. In Chapter 1, I have included the concept of femtosecond time-resolved spectroscopy and nuclear dynamics. Some important aspects of spontaneous and stimulated Raman scattering are discussed. Subsequently, I have described the theoretical framework and methodologies that are important to understand non-linear spectroscopy. Important aspects of time-resolved stimulated Raman pro-cess are described here. A brief outline of the current thesis is also presented at the end of this chapter. In Chapter 2, I have described in detail the instrumentation and data process-ing methods. A detailed explanation of spectroscopic techniques like transient ab-sorption and femtosecond stimulated Raman spectroscopy and their experimen-tal aspects are discussed. The optimization of the setup, detailed data analysis processes are described. Finally, I have described step-by-step data processing method using DaFitUma software which is developed in our lab. In Chapter 3, I have studied the excited state isomerization dynamics of tetrap-henylethylene in various solvents using femtosecond TA and URLS spectroscopy. Tetraphenylethylene, a model molecular motor, known to exhibit low-frequency torsional dynamics. TA measurements in the S1 state reveal a step-wise struc-tural rearrangement from Franck-Condon (FC) state ! relaxed state ! twisted state on photoexcitation. Furthermore, oscillation in TA kinetics was observed with-in 1 ps. Fourier transformation of this oscillation leads to a 130 cm 1 low-frequency mode which is responsible for the excited state wavepacket dynamics during the course of FC state ! relaxed state structural rearrangement. Two vi-brational marker band Cet=Cet stretching ( 1512 cm 1) and Cph=Cph stretching ( 1584 cm 1) modes appear immediately after photoexcitation in URLS spectra. From the peak frequency shift, we confirm that the initial structural relaxation is dominated by phenyl torsion rather than central Cet=Cet twist. In Chapter 4, the structural dynamics and solvent induced internal conversion of 2-(20-Hydroxyphenyl)benzothiazole (HBT), an extensively studied excited state intramolecular proton transfer (ESIPT) system, are investigated. We have obtained snapshots of vibrational spectra of the photoexcited HBT, by URLS, providing de-tailed structural change at an early time. From the URLS peak amplitude analysis we have observed 400 fs amplitude decay in acetonitrile. This is assigned to a rapid structural change induced by polar acetonitrile due to the torsional mo-tion. The ultrafast amplitude decay is associated with coherent excitation of tor-sional mode ( 40 cm 1). Oscillatory peak position in the high-frequency Raman modes indicates a coupling between low-frequency torsional and high-frequency vibrations. Activation of torsional motion in polar solvents provides an additional route for non-radiative decay, responsible for a short lifetime ( 12 ps) and low fluorescence quantum yield. For hexane, the URLS spectral evolution is assigned to vibrational cooling (2-4 ps) followed by population relaxation (115 ps). Chapter 5, deals with the ultrafast intersystem crossing (ISC) dynamics of thioxanthone (TX) in various solvents. It has striking solvent dependent photo-physical properties. For example, the fluorescence quantum yield ( f ) and life-time ( f ) of the primarily populated singlet (1 *) state strongly depends on the solvent properties. We have studied TX in three different solvents: acetonitrile (ACN; aprotic), methanol (MeOH; polar protic) and in cyclohexane (CX; nonpo-lar). Following electronic excitation to the S1 (1 ) state, the molecule relaxes to the lowest T1 (3 ) state in 50 ps, 4 ps in ACN and in CX respectively. In the case of TX in methanol, two stages of ISC with time constants of 4 ps and > 2ns were obtained. These two stages are assigned to direct ( 4 ps) ISC to the T2 state (1 ! 3n ) followed by slow internal conversion ( 2 ns) to the T1 state (3 ). Analysis of peak position dynamics further allows us to obtain vibrational relaxation times during ISC process. The present study sheds light on a complete understanding of the structural changes accompanying the ISC process. Finally, in Chapter 6, we have briefly summarized the main results of the the-sis. This chapter also includes our comments on some of the future extensions of the present work.

The ability to perceive the dynamics of nature is ultimately limited by the temporal resolution of the instruments available. With the help of the ultrashort optical pulse, people now are able to observe and steer the electronic dynamics on the atomic scale. Meanwhile, high power attainable in such short time scale helps to boost the study of nonlinear physics. Most commercial femtosecond lasers are based on Ti:sapphire, but such systems can only be tuned in a spectral range around 800 nm. Few applications need only a single wavelength in this spectral region and pulses tunable from the UV to the IR are highly desirable. Based on the soliton characteristics of ultrashort laser pulses, we are the first ones who propose to make use of resonant dispersive waves, which are phase-matched non-solitonic linear waves, to extend the spectral tuning range of ultrashort laser without involving complicated amplifiers. Experimentally, we achieve the tuning of dispersive wave wavelengths by changing the dispersion parameters of the laser cavity, and confirm dispersive waves are ultrashort pulses under appropriate conditions. We successfully apply such a system into a multi-wavelength operation Ti:sapphire laser. The proposed idea is general, and can be applied to systems where solitons dominate, for example fiber lasers. Thanks to the newly developed novel fiber -photonic crystal fiber- we obtain widely tunable and gap-free femtosecond pulse by extending this mechanism to waveguides. This is the largest reported tuning range for efficient nonlinear optical frequency conversion obtained with such a simple and low energy laser. We apply such a Ti:sapphire laser to Raman micro-spectroscopy. Because of the different temporal behaviors of the Raman process and other parametric processes, we can efficiently separate the coherent Raman signal from the unwanted background, and obtain a high chemical contrast and high resolution image. This high repetition rate and low energy laser oscillator makes it very suitable for biological Raman micro-spectroscopy, especially living samples for which damage is a big concern.

The subject of this thesis is the design and development of a unified set up for femtosecond transient absorption and ultrafast Raman loss spectroscopy and demonstrate its potential in capturing the ultrafast photophysical and photochemical processes with excellent time and frequency resolution. Ultrafast spectroscopy has been serving as a powerful tool for understanding the structural dynamical properties of molecules in the condensed and gas phase. The advent of ultrashort pulses with their high peak power enables the laser spectroscopic community to study molecular reaction dynamics and photophysics that happen at extremely short timescales, ranging from picosecond to femtosecond. These processes can be measured with extremely high time resolution, which helps to resolve the under-lying molecular process. But in order to understand the global mechanism of the underlying molecular processes, we have to resolve the nuclear dynamics with the proper frequency resolution. However, achieving both, time and frequency resolutions simultaneously is not possible according to the Heisenberg uncertainty principle. Later, this limitation was overcome by femtosecond stimulated Raman spectroscopy (FSRS), a third order non-linear Raman spectroscopy. In this thesis we introduced the ultrafast Raman loss spectroscopic (URLS) technique which is analogous to FSRS, offering the modern ultrafast community to resolve molecular processes with better signal-to-noise ratio along with proper time and frequency resolution. We demonstrate the experimental procedure including the single shot detection scheme to measure whitelight background, ground state Ra-man, transient absorption and transient Raman in shot-to-shot detection fashion. URLS has been applied to understand the excited state planarization dynamics of 1,4-bis(phenylethynyl)benzene (BPEB) in different solvents. In addition, excitation wavelength dependent conformational reorganization dynamics of different sub-sets of thermally activated ground state population of BPEB are also discussed. Using the same techniques along with femtosecond transient absorption, we demonstrate the ultrafast vibrational energy transfer and the role of coherent oscillations of low frequency vibrations on the solution phase photo-isomerization of trans-stilbene from an optically excited state. The effects of solvents on the coherent nuclear motion are also discussed in the context of reaction rates. 2

The subject of this thesis is the design and development of a unified set up for femtosecond transient absorption and ultrafast Raman loss spectroscopy and demonstrate its potential in capturing the ultrafast photophysical and photochemical processes with excellent time and frequency resolution. Ultrafast spectroscopy has been serving as a powerful tool for understanding the structural dynamical properties of molecules in the condensed and gas phase. The advent of ultrashort pulses with their high peak power enables the laser spectroscopic community to study molecular reaction dynamics and photophysics that happen at extremely short timescales, ranging from picosecond to femtosecond. These processes can be measured with extremely high time resolution, which helps to resolve the under-lying molecular process. But in order to understand the global mechanism of the underlying molecular processes, we have to resolve the nuclear dynamics with the proper frequency resolution. However, achieving both, time and frequency resolutions simultaneously is not possible according to the Heisenberg uncertainty principle. Later, this limitation was overcome by femtosecond stimulated Raman spectroscopy (FSRS), a third order non-linear Raman spectroscopy. In this thesis we introduced the ultrafast Raman loss spectroscopic (URLS) technique which is analogous to FSRS, offering the modern ultrafast community to resolve molecular processes with better signal-to-noise ratio along with proper time and frequency resolution. We demonstrate the experimental procedure including the single shot detection scheme to measure whitelight background, ground state Ra-man, transient absorption and transient Raman in shot-to-shot detection fashion. URLS has been applied to understand the excited state planarization dynamics of 1,4-bis(phenylethynyl)benzene (BPEB) in different solvents. In addition, excitation wavelength dependent conformational reorganization dynamics of different sub-sets of thermally activated ground state population of BPEB are also discussed. Using the same techniques along with femtosecond transient absorption, we demonstrate the ultrafast vibrational energy transfer and the role of coherent oscillations of low frequency vibrations on the solution phase photo-isomerization of trans-stilbene from an optically excited state. The effects of solvents on the coherent nuclear motion are also discussed in the context of reaction rates. 2

Abstract The excited-state dynamics of molecular materials is of great importance to understand early time photodynamics. We have used Femtosecond Transient Absorption (fs-TA) and Ultrafast Raman Loss Spectroscopy (URLS) spectroscopy to understand early time photophysical dynamics in the ultrafast timescale. fs-TA measures the electronic absorption of photoexcited molecule revealing the population dynamics on the complex potential manifold. Whereas, URLS measures the vibrational signature of excited species that depicting the structural dynamics during the evolution. Such ultrafast spectroscopic methods are very essential to unravel the early time events of photophysical and photochemical processes. We performed time-resolved URLS measurements (stimulated Raman scattering based on third-order nonlinear spectroscopic principles) by choosing the actinic pump in the UV-Vis region, Raman pump in the visible region and Raman probe as a broadband white light continuum to understand intricacies related to the excited state dynamics in few interesting systems Singlet Fission (SF), a spin allowed fast internal conversion process of multiexciton generation from photoexcited singlet 〖(S〗_0) exciton in which a pair of correlated triplet exciton 〖(TT)〗^1 is formed. SF can overcome Shockley-queisser limit and vastly improve photo-energy conversion efficiency. We have studied the SF process in the solution phase for 9,10-Bis(phenylethynyl) anthracene (BPEA) to understand the electronic and structural dynamics in ultrafast time-scale. The extent of electronic coupling between singlet exciton and triplet pair state governs the efficiency of SF process. SF is very efficient for crystalline forms, as a consequence tracking the initial events related to evolution from the initial singlet state to two triplet states is non-trivial due to ultrafast in nature. However, in solution, SF is essentially limited by the diffusion. Here, the dynamics of the BPEA (in solution) in the entangled singlet and multi-excitonic states is elucidated in terms of the intricate structural dynamics, which is otherwise non-trivial from fs-TA measurements alone. The study of the effect of coupled electronic states for the SF process in BPEA has been studied next. In BPEA, a strong one-photon allowed electronic transition (B_1u) with long axis polarization is overlapped with moderately allowed short-axis polarized electronic transition (B_2u). These two electronic states are coupled via Pseudo Jahn-Teller coupling along with modes having b_3g symmetry. The TA of the excited species is a result of overlapping spectral signatures from both hot-multiexcitionic and moderately allowed states. The photoexcitation of BPEA in n-hexane (HX) at different wavelengths across the steady-state absorption spectrum exhibits a distinct intensity ratio of these two transient absorption bands although their normalized intensity kinetics show similar behaviour. However, with URLS, it is shown that the modes that are involved in the Pseudo-Jahn-Teller coupling exhibit distinct response as a consequence of quantum interference of the Raman polarizabilities related to such states. We have performed an extensive quantum mechanical calculation by utilizing Gaussian 09 software to understand the experimentally observed absorption, vibrational spectra by means of orbital calculation, orbital symmetry, oscillator strength calculation, vibrational frequency calculation, energy level diagram along specific coordinates. The corroboration of quantum calculation with experimentally observed data provides a deeper understanding of the photodynamics particularly in the excited state analysis. Next, we have investigated the excess energy dissipation and isomerization process in excited t-stilbene in the condensed phase. Upon photoexcitation, the excess energy is deposited in the initially prepared Franck-Condon (FC) excited state. However, such energy is redistributed among intramolecular modes and subsequently dissipated to the solvent molecules through anharmonic coupling and solute-solvent coupling respectively. The energy dissipation process can be described by two exchange parameters i.e., backward exchange rate (W_1) and forward exchange rate (W_2) that are related to the thermally generated exciton in the bath and the low-frequency solute modes respectively. Here, the influence of alkane chain length of solvents on the exchange rates and associated mode coupling is elucidated in terms of the W_2/W_1 ratio. Finally, a detailed analytical calculation has been performed to compute the third- order nonlinear susceptibility that contributes to the URLS signatures. It also depicts the method of identifying the relevant quantum processes using closed path time loop (CPTL) Feynman diagrams. Here, it is clearly demonstrated the underlying reasons for asymmetry in the intensity between gain (Stokes) and loss (anti-Stokes) signatures of URLS process. A model simulation has been carried out with different molecular parameters.

This thesis incorporates the understanding of the ultrafast excited state photoinduced intramolecular charge transfer (ICT) process in liquid phase. The molecular systems are studied by employing Ultrafast Raman Loss Spectroscopy (URLS) and transient absorption (TA) spectroscopy. The primary goal of this thesis is to observe structural dynamics immediately after the formation of Franck-Condon state and the effect of slight modifications in the structure and solvent onto the excited state ICT process.

Understanding the behavior of complex systems is greatly simplified when the proper energy and time scales over which their evolution occurs are investigated. Consequently, deciphering the dynamics of atoms and molecules requires to access the domain of femtoseconds, and even shorter timescales are involved in the case of electrons. Probing such extreme phenomena is the challenging task at which ultrafast spectroscopy aims. In the last forty years, the development of pulsed laser sources and nonlinear optical techniques has allowed the study of phenomena invisible to electronic devices, through the manipulation of matter macroscopic phases on picosecond and sub-picosecond timescales. This technological leap provided sophisticated and customized ultrashort spectroscopic protocols in a wide energy range, from terahertz to x rays, fully realizing the pioneering view of the ultrafast stroboscope, dreamed by the father of femtochemistry Ahmed Zewail. Indeed, using the proper technique, short flashes of light are currently able to record stop-motion images of a dynamic processes as fast as a chemical reaction. The study of the nonlinear response due to external impulsive optical perturbations has been applied to a wide range of scientific cases, fueling a parallel boost in electronic and vibrational spectroscopies. The frontier in ultrafast sciences is now gradually shifting to tackle the interplay between these two degrees of freedom. Vibronic coupling is considered at the grounds of fascinating processes which connect conceptual topics from the foundation of quantum mechanics, as the breakdown of the Born-Oppenheimer approximation, to technological application, as the coherent energy transfer in biomimic photosynthetic devices or the bewildering effects of strong electron-phonon coupling in novel materials as graphene and third generation semiconductors. Probing electronic and vibrational interactions at the same time is complicated by the time and energy scale separation between the two. Thus, one dimensional spectroscopies are weakened by resolution limits which may partially hamper their use in this direction. Multidimensional techniques can cope this limit spreading the information on separate spectroscopic axes, consequently disentangling the relative resolutions. Couplings between different agents in the microscopic description of the sample dynamics are directly revealed through the presence of cross peaks in the multidimensional maps. In this context, the research presented in this thesis has been devoted to the design, realization and interpretation of novel approaches to multidimensional Impulsive Stimulated Raman Spectroscopy (ISRS). Coherent Raman techniques are indeed able to measure vibrational spectra using visible light, which provides at the same time information about the electronic degrees of freedom when tuned resonant with the absorption edges of the sample. A concerted combination between theory and experiments is the key to successfully probe the quantum properties of the matter on which the vibronic interactions rely. For this reason, the experimental efforts have been flanked by a powerful theoretical toolbox given by the nonlinear response formalism. This framework represents a natural link between theory and experiments and supplies a common language to describe very different techniques, gathering their features to design new experimental protocols. We found that the properties of the probe spectral envelope, the wise tuning of resonant conditions and the choice of the pulses scheme may be used to built multidimensional ISRS maps. The developed schemes have been experimentally tested in three different contexts: the coherent control of ground and excited state vibrations in a liquid solvent, the study of charge photogeneration in a hybrid organic-inorganic perovskite and the vibronic coupling in a prototypical fluorescent protein. The research work presented here is structured in seven chapters and one appendix, which summarize the main theoretical and experimental results achieved during the preparation of this doctoral thesis. The core of the thesis is contained in Chapters 4, 5 and 6, which discuss the application of multidimensional ISRS in different scenarios. Since the investigated scientific problems belong to quite different backgrounds, each of these result chapters is introduced by a brief summary of the relevant field. Specifically: In Chapter 1, we introduce the context in which this thesis is developed. The basics features of ultrafast spectroscopy based on the pump-probe scheme and nonlinear Raman techniques are briefly discussed. We then present the classical mechanism underlying spontaneous and coherent Raman effects, while the detailed, microscopic derivation is postponed to Chapter 2. The remaining part of the chapter is devoted to introduce how multidimensional information can be encoded in the parameters of time and frequency domain stimulated Raman spectroscopies, following the key words in the title of the thesis. As an example, the lineshapes from stimulated Raman spectra measured in hemeproteins are studied as a function of the resonance and the vibrational mode. In Chapter 2, the nonlinear response theory is presented as the unifying framework in which all the different experiments in the thesis are conceived, designed and interpreted. In the first part, the principles of quantum mechanics in the density matrix framework are briefly revised, defining the properties of the Liouville space. Then, the concept of nonlinear polarization is introduced and calculated perturbatively in this space. The light matter interaction is derived from both the classical and quantum treatment of electromagnetism, showing that Feynman diagrams are a convenient way to isolate the relevant terms in the perturbative expansion. Finally, we report the rules to derive expressions for the nonlinear signal in the time and frequency domains directly from the diagrams. In Chapter 3, the experimental setups and the data acquisition are described in detail. We analyze the tools and the physical mechanisms at the base of the generation and handling of the ultrashort pulses used in the experiments and also provide an overview of the data analysis routine applied to the impulsive stimulated Raman measurements presented in the thesis. Chapter 4 is the first of the three chapters presenting the main results of this work. Here, we discuss how the broadband envelope of a supercontinuum probe pulse can be shaped to manipulate vibrational coherences in ISRS. In particular, probe wavelength resolved ISRS maps of a liquid solvent are measured changing the chirp of the probe pulse and interpreted in the light of the diagrammatic framework. As a starting point, the effect of the probe chirp and sample length are investigated to rationalize previously unexplained dependencies of low frequency modes on the dispersed probe wavelength. Then, the probe chirp is demonstrated as a control knob to coherently control ISRS modes and to assign spectral features to specific electronic states. In Chapter 5, broadband ISRS is applied to study electron-phonon coupling in lead halide hybrid perovskites. After briefly revising the field of organic-inorganic perovskite optoelectronics, we present experimental measurements on methylammonium lead bromide thin films, comparing the ISRS response of the system upon excitation above and below the band gap. The results are interpreted in the light of the recently proposed polaronic nature of photocarriers in these materials. In Chapter 6, we present a novel multidimensional ISRS scheme, which combines the capabilities of two dimensional Fourier transform techniques with the structural sensitivity of resonant stimulated Raman. We show how this technique can be used to probe mode couplings between different active sites in molecular compounds and determine the shape of vibrationally structured excited state potential energy surfaces. We apply the diagrammatic approach to design 2D ISRS and assign the origin of the different spectral features in a model system. Then, the proposed scheme is benchmarked by addressing vibronic coupling in Green Fluorescent Protein during the first steps of its photoinduced dynamics. Finally, in Chapter 7, the main results obtained in this work are summarized and analyzed under a common perspective. The appendix reports the calculation of transition integrals for the linearly displaced harmonic model. A list of the publications and contributions to international conferences of the author is included at the end of the thesis.

Technological progress in commercializing ultrafast lasers and detectors has allowed realization of cooperative processes on an ultrashort time scale, which demand a re-evaluation of the conventional cooperative phenomena with a new insight. Ultrafast cooperative phenomena in coherently prepared media and various applications of superfluorescence and coherent Raman scattering are studied in this dissertation. In particular, a simple theoretical testimony on analogy between a cooperative emission and coherent Raman scattering is presented by offering an opportunity to perform parallel research on these two processes from a unified point of view. On one hand, the superfluorescent pulse with a time duration of a few tens of picoseconds (ps) from alkali metal vapor is observed for the first time, even though cooperative phenomena in atomic vapor have been extensively studied for more than five decades. A dense rubidium vapor pumped by ultrashort (100 femtosecond, fs) pulses allows a realization of the ultrafast superfluorescence while a time-resolved study of superfluorescence is accomplished by using a streak camera with 2 ps time resolution. Experimental research on quantum nature of cooperative emissions has been “frozen” over the years (three decades) possibly because of the technical difficulties. Quantum fluctuations of superfluorescence development are explored experimentally by taking advantage of the ultra fast streak camera. Presumable applications of the superfluorescent pulse in e.g., a remote sensing, and an ultraviolet upconversion of the input infrared laser pulse are presented. The quantum interference due to different excitation pathways is revealed by the temporal coherent control technique while observing interferometric signals from alkali metal vapors. On the other hand, a new spectroscopic technique based on ultrafast coherent Raman scattering is developed. The key advantage of the presented technique is to suppress the non-resonant background noise which usually obscures possible applications of the other conventional coherent Raman techniques in practice. A reduction of the background noise is achieved by shaping and delaying the third pulse which probes the coherence of the medium (i.e., an enhancement of specific vibrations of the target molecules in unison) firstly prepared by two broadband pulses. We demonstrate a robustness and superiority of signal-to-noise ratio of the developed technique by identifying as few as 10000 bacterial spores at a single laser shot level. Finally, several comparative studies between cooperative and uncooperative processes are presented. A picosecond cooperative phenomenon in a three-photon resonant medium induced by a single as well as two-color ultrashort pulses is investigated. A time-resolved study shows that a picosecond cooperative effect is crucial in the well-established fields of resonant-enhanced multiphoton ionizations and harmonic generations. We also present a quantitative analysis for spontaneous versus broadband coherent Raman scattering on pyridine molecules. The spontaneous Raman signal is enhanced by 5 orders as a result of cooperative phenomena.

Born-Oppenheimer approximation (ABO) is the assumption that the motion of atomic nuclei and electrons in molecules can be separated and independently treated. In solids, ABO is well justified when the energy gap between ground and excited electronic states is larger than the energy scale of the nuclear motion. Graphene represents a notable exception of this acceptantance. In particular, here we unravel the key role of the gapless linear Dirac dispersion in the vibrational Raman response of the system in the case of impulsively photoexcited graphene. First, we unambiguously describe Four-Wave Mixing (FWM) processes in graphene, which depend on the resonant nature of the electronic interactions. Indeed, the overall spectral response is described in terms of a third order diagrammatic description of the light-matter interaction. We disclose that the interference between Coherent anti-Stokes Raman Scattering (CARS) and Non-Vibrationally Resonant Background (NVRB) generates Lorentzian dip spectral profiles. Actually, by introducing an experimental time delayed FWM scheme, able to modify the relative strength of the two contributions, we observe the first evidence of CARS peak equivalent to the Raman spectrum in graphene. Second, we adopt sub picosecond photoexcitation which impulsively localize energy into graphene electronic subsystem. While the response of hot charge carriers is well-characterized, unraveling the behavior of optical phonons under strongly out-of- equilibrium conditions remains a challenge. Using a 3-ps laser excitation, which trades off between impulsive stimulation and spectral resolution, we show how the Raman response of graphene can be detected in presence of an electronic subsystem temperature largely exceeding that of the phonon bath. We find a peculiar behaviour of the period and lifetime of both the G and 2D phonons as function of the carriers temperature in the range 1700-3100 K, suggesting a broadening of the Dirac cones. Accordingly, we reconsider the traditional scenario of the electron-phonon scattering in a highly excited transient regime

Ultrafast laser-based diagnostic techniques are powerful tools for the detailed understanding of highly dynamic combustion chemistry and physics. The ultrashort pulses provide unprecedented temporal resolution along with high peak power for broad spectral range−ideal for nonlinear signal generation at high repetition rate−with applications including next-generation combustors for gas turbines, plasma-assisted combustion, hypersonic flows and rotating detonation engines. The current work focuses on advancing (i) femtosecond (fs) two-photon laser-induced fluorescence, and (ii) hybrid femtosecond/picosecond vibrational and rotational coherent anti-Stokes Raman scattering (fs/ps RCARS and VCARS) to higher pressures for the first time.

Quantitative single-laser-shot kHz-rate concentration measurements of key atomic (O-atom) and molecular (CO) species is presented using femtosecond two-photon laser-induced fluorescence (TP-LIF) for a range of equivalence ratios and pressures in diffusion flames. A multitude of signal-interfering sources and loss mechanisms−relevant to high-pressure fs TP-LIF applications−are also quantified up to 20 atm to ensure high accuracy. The pressure scaling of interferences take into account degradation, attenuation and wave-front distortion of the excitation laser pulse; collisional quenching and pressure dependent transition line-broadening and shifting; photolytic interferences; multi-photon ionization; stimulated emission; and radiation trapping.

Hybrid fs/ps VCARS of N₂ is reported for interference-free temperature measurement at 1300-2300 K in high-pressure, laminar diffusion flames up to 10 atm. A time asymmetric probe pulse allowed for detection of spectrally resolved CARS signals at probe delays as early as ~200-300 fs while being independent of collisions for the full range of pressures and temperatures. Limits of collisional independence, accuracy and precision of the measurement is explored at various probe-pulse delays, pressures and temperatures.

Additionally, a novel all diode-pumped Nd:YAG amplifier design is presented for generation of time-synchronized ps-probe pulses for hybrid fs/ps RCARS of N₂. High-energy, nearly transform-limited, single-mode, chirp-free ps probe-pulses are generated at variable pulsewidths. The detailed architecture and characterization of the laser is presented. kHz-rate RCARS thermometry is presented up to 2400 K. Excellent spatial, spectral, and temporal beam quality allowed for fitting the theoretical spectra with a simple Gaussian model for the probe pulse with temperature accuracies of 1-2%.