xiv, 138 p. : ill. (some col.) / In this dissertation, we demonstrate the generation of optical Raman frequency combs by a single laser pump pulse traveling in hydrogen-filled hollow-core optical fibers. This comb generation process is a cascaded stimulated Raman scattering effect, where higher-order sidebands are produced by lower orders scattered from hydrogen molecules. We observe more than 4 vibrational and 20 rotational Raman sidebands in the comb. They span more than three octaves in optical wavelength, largely thanks to the broadband transmission property of the fiber. We found that there are phase correlations between the generated Raman comb sidebands (spectral lines), although their phases are fluctuating from one pump pulse to another due to the inherit spontaneous initiation of Raman scattering. In the experiment, we generated two Raman combs independently from two fibers and simultaneously observed the single-shot interferences between Stokes and anti-Stokes components from the two fibers. The experimental results clearly showed the strong phase anti-correlation between first-order side bands. We also developed a quantum theory to describe this Raman comb generation process, and it predicts and explains the phase correlations we observe. The phase correlation that we found in optical Raman combs may allow us to synthesize single-cycle optical pulse trains, creating attosecond pulses. However, the vacuum fluctuation in stimulated Raman scattering will result in the fluctuation of carrier envelope phase of the pulse trains. We propose that we can stabilize the comb by simultaneously injecting an auxiliary optical beam, mutually coherent with the main Raman pump laser pulse, which is resonant with the third anti-Stokes field. / Committee in Charge: Dr. Steven van Enk, Chair; Dr. Michael G. Raymer; Dr. Daniel A. Steck; Dr. David M. Strom; Dr. Andrew H. Marcus

Optical frequency comb spectroscopy (OFCS) combines two previously exclusive features, i.e., wide optical bandwidth and high spectral resolution, enabling precise measurements of entire molecular bands and simultaneous monitoring of multiple gas species in a short measurement time. Moreover, the equidistant mode structure of frequency combs enables efficient coupling of the comb power to enhancement resonant cavities, yielding high detection sensitivities. Different broadband detection methods have been developed to exploit the full potential of frequency combs in spectroscopy, based either on Fourier transform spectroscopy or on dispersive elements.There have been two main aims of the research presented in this thesis. The first has been to improve the performance of mechanical Fourier transform spectrometers (FTS) based on frequency combs in terms of sensitivity, resolution and spectral coverage. In pursuit of this aim, we have developed a new spectroscopic technique, so-called noise-immune cavity-enhanced optical frequency comb spectroscopy (NICE-OFCS), and achieved a shot-noise-limited sensitivity and low ppb (parts-per-billion, 10−9) CO2 concentration detection limit in the near-infrared range using commercially available components. We have also realized a novel method for acquisition and analysis of comb-based FTS spectra, a so-called sub-nominal resolution method, which provides ultra-high spectral resolution and frequency accuracy (both in kHz range, limited only by the stability of the comb) over the broadband spectral range of the frequency comb. Finally, we have developed an optical parametric oscillator generating a frequency comb in the mid-infrared range, where the strongest ro-vibrational molecular absorption lines reside. Using this mid-infrared comb and an FTS, we have demonstrated, for the first time, comb spectroscopy above 5 μm, measured broadband spectra of several species and reached low ppb detection limits for CH4, NO and CO in 1 s.The second aim has been more application-oriented, focused on frequency comb spectroscopy in combustion environments and under atmospheric conditions for fast and sensitive multispecies detection. We have demonstrated, for the first time, cavity-enhanced optical frequency comb spectroscopy in a flame, detected broadband high temperature H2O and OH spectra using the FTS in the near-infrared range and showed the potential of the technique for flame thermometry. For applications demanding a short measurement time and high sensitivity under atmospheric pressure conditions, we have implemented continuous-filtering Vernier spectroscopy, a dispersion-based spectroscopic technique, for the first time in the mid-infrared range. The spectrometer was sensitive, fast, robust, and capable of multispecies detection with 2 ppb detection limit for CH4 in 25 ms. / Optisk frekvenskamspektroskopi (OFCS) kombinerar två tidigare icke förenliga egenskaper, dvs. ett brett optiskt frekvensområde med en hög spektral upplösning, vilket möjliggör noggranna mätningar av hela molekylära absorptionsband och detektion av flera gaser samtidigt med en kort mättid. Eftersom frekvenskammar har en regelbunden struktur med jämnt separerade laser moder kan man effektivt koppla kammen till en optisk kavitet och därmed möjliggöra frekvenskamsdetektion med hög känslighet. Olika metoder har utvecklats för att utnyttja frekvenskammarnas fulla potential för spektroskopi, baserad på antingen Fouriertransform-spektroskopi eller dispersiva element.Forskningen som presenteras i denna avhandling har haft två huvudmål. Det första har varit att förbättra prestandan hos mekaniska Fourier-transformspektrometrar (FTS) baserat på frekvenskammar med avseende på känslighet, upplösning och spektral täckning. I strävan efter detta har vi utvecklat en ny spektroskopisk teknik, benämnd brusimmun kavitetsförstärkt optisk frekvenskamspektroskopi (NICE-OFCS), och uppnått en hagelbrusbegränsad känslighet och detektionsgränser ner till låga ppb koncentrationer (miljarddelar, 10−9) för CO2 i det när-infraröda frekvensområdet enbart med användning av kommersiellt tillgängliga komponenter. Vi har också utvecklat en ny metod för insamling och analys av kambaserade FTS-spektra, som betecknas ha sub-nominell upplösning. Metoden gör det möjligt att uppnå ultrahög spektral upplösning och hög frekvensnoggrannhet (båda i kHz-området, endast begränsad av kammens stabilitet) över kammens hela frekvensområde. Slutligen har vi utvecklat en optisk parametrisk oscillator som genererar en frekvenskam i det mid-infraröda frekvensområdet, där de starkaste rotations-vibrationsmolekylära absorptionslinjerna finns. Med hjälp av denna kam och en FTS har vi för första gången demonstrerat frekvenskamspektroskopi över 5 μm. Vi har detekterat bredbandsspektra av flera molekylära gaser och har, för mättider på 1 s, uppnått detektionsgränser ner till låga ppb halter för CH4, NO och CO.Det andra syftet har varit mer applikationsorienterat: att använda frekvenskamspektroskopi i förbränningsmiljö och under atmosfäriska förhållanden för snabb och känslig multiämnesdetektion. Vi har för första gången demonstrerat kavitetsförstärkt optisk frekvenskamspektroskopi i en flamma, där vi har detekterat högtemperaturspektra av H2O och OH i det när-infraröda området med användning av FTS och visat teknikens potential för termometrisk karakterisering av flammor. För applikationer som kräver en kort mättid och hög känslighet under atmosfäriska förhållanden har vi utvecklat ett detektionssystem baserat på Vernier-spektroskopi med kontinuerlig filtrering, vilket är en dispersionsbaserad teknik, för första gången i det mid-infraröda frekvensområdet. Det befanns att spektrometern var känslig, snabb, robust och kapabel till multiämnesdetektion med en detektionsgräns på 2 ppb för CH4 för korta mättider (25 ms).

In this work, resonant laser spectroscopy has been utilized in two major projects --resonance fluorescence measurements in solid-state quantum-confined nanostructures and laser-induced fluorescence measurements in gases. The first project focuses on studying resonant light-matter interactions in semiconductor quantum dots "artificial atoms" with potential applications in quantum information science. Of primary interest is the understanding of fundamental processes and how they are affected by the solid-state matrix. Unlike atoms, quantum dots are susceptible to a variety of environmental influences such as phonon scattering and spectral diffusion. These interactions alter the desired properties of the scattered light and hinder uses in certain single photon source applications. One application of current interest is the use of quantum dots in “quantum repeaters” for which two-photon interference is key. Motivated by such an application we have explored the limits imposed by environmental effects on two quantum dots in the same sample, the scattered light from which is being interfered. We find that both one-photon and two-photon interference, although substantial, are affected in a variety of ways, in particular by spectral diffusion. These observations are discussed and compared with a theoretical model. We further investigated correlations in pulsed resonance fluorescence, and found significant unexpected spectral and temporal deviations from those studied under continuous wave excitation. Under these conditions, the scattered light exhibits Rabi oscillations and photon anti-bunching, while maintaining a rich spectrum containing many spectral features. These observations are discussed and compared with a theoretical model. In the second project, the focus is on the investigation of the possibility of detecting N2+ ions in air using laser induced fluorescence, with potential applications in detection of fissile materials at a distance. A photon-counting analysis reveals that the fluorescence decay rate rapidly increases with increasing N2 pressure and thus limits the detection at elevated pressures, in particular at atmospheric pressure. We show that time-gated detection can be used to isolate N2+ fluorescence from delayed N2 emission. Based on the spontaneous Raman signal from N2 simultaneously observed with N2+ fluorescence, we could estimate a limit of detection in air of order 108-1010 cm3.

H. pylori est une bactérie à Gram négatif qui infecte l'estomac de près de 50% de la population mondiale. L'infection, en général asymptomatique, peut évoluer vers l'ulcère gastrique (15% des cas) ou le cancer de l'estomac (1% des cas). L'infection à H. pylori est traitée par antibiothérapie mais ces dernières années ont vu une augmentation du nombre de souches résistantes. Cette augmentation et la forte prévalence d'H. pylori sont probablement dues à son importante variabilité génétique qui a pour origine un fort taux de mutagénèse spontanée, associée à une recombinaison efficace et un important transfert horizontal de gènes. H. pylori est en effet naturellement compétente pour la transformation qui est le processus biologique permettant la capture, l'internalisation et l'intégration d'ADN exogène dans le génome de la bactérie. Ce processus favorise la diversité génétique au sein d'une population et peut permettre son adaptation rapide aux changements environnementaux. Durant ma thèse, j'ai participé au développement d'une méthode permettant de visualiser la transformation d'ADN fluorescent dans des cellules de H. pylori vivante. Cette méthode nous a permis, pour la première fois, de visualiser directement l'entrée d'un ADN transformant dans le cytoplasme d'une bactérie compétente. Elle nous a également permis de confirmer le rôle de la protéine ComEC dans l'internalisation de l'ADN dans le cytoplasme. Le travail que j'ai réalisé a également permis de mettre en évidence que le niveau de transformation de H. pylori est déterminé par le niveau d'expression du complexe membranaire d'internalisation. La quantité d'ADN capturée serait alors un facteur limitant pour la transformation. / H. pylori is a Gram negative flagellar bacterium that colonizes nearly 50% of the world population. Infection is generally asymptotic but can evolve to ulcerous gastritis (15% of the cases) or stomach cancer (1% of the cases). H. pylori infection is usually treated with antibiotic but the last years saw a dramatic increase in the number of resistant strains. This increase, and the high prevalence of H. pylori, are probably caused by its huge genetic variability likely due to a strong mutagenesis rate associated with efficient recombination and horizontal gene transfer. H. pylori is indeed naturally competent for transformation which is the biological process allowing capture, internalization and integration of exogenous DNA in the genome of a bacterium. This process promotes genetic diversity in a population and could permit rapid adaptation to environmental changes. During my thesis, I participated to the development of a method to visualize transformation in H. pylori living cells. Using fluorescently labelled DNA, this method allowed us for the first time to follow directly the entry of a transforming DNA into the cytoplasm of competent bacteria. It also allowed us to confirm the role of the ComEC protein in the internalization of the DNA in the cytoplasm. The work I performed also allowed to show that the level of expression of the uptake complex determines the transformation efficiency of H. pylori. The amount of captured DNA would then be a limiting factor for the transformation in this bacterium. Finally, I initiated the biochemical and genetic characterization of the NucT protein, a nuclease associated to the membrane and implicated in the transformation.

In the spring of 2018, a prospection and subsequent research excavation of a previously unstudied area related to the rampart of the Viking age town of Birka, Sweden, was undertaken by students and professors from the archaeological science department affiliated with Stockholm University.The purpose of this paper is to examine and categorise the various excavated finds, the ensuing conservation and preservation of the metal objects as well as to investigate the context and possible function of the site regarding the spatial distribution of said finds.The main method used is that of metal conservation with the wet-chemical technique EDTA; a method that was deemed adequate for the treatment of the dry metal finds from the rampart excavation.The conservation and categorisation suggest that the metal posts consist of assorted metal objects, predominately rivets and nails as well as unidentified fragmented objects; the occasional slag fragment was evident. The material category of clay and ceramics contains assorted burnt clay and ceramic sherd fragments, some with decoration. Whetstone (or hone stone) and flint fragments make up most of the stone finds while the category of glass consists of a few bead fragments. The bulk of the osteological material consists of burnt and unburnt animal bones, some with slaughter marks in the form of cuts and hacks. Two human bone fragments were found; a humerus- and cranial fragment.Post holes and charcoal in the context of the rampart suggests the possibility of wooden supports and/or a superimposed wooden structure on the rampart itself that likely burnt at some point in time. The interpretation of the excavated area, based on the distribution of the finds and material categories, is that of a dumping site for discarded town refuse, most likely set against or near a walled construction; the rampart. The dating of the site is based on object similarities as well as stratigraphy and set to; Early to Late Viking Period, c. A.D. 820-1000(1150).The analyses, materials and the stratigraphy of the site together with a contextual analysis of the objects in question furthers the knowledge of Birka’s rampart and will enable future scientific inquiries into this specific rampart as well as similar fortification structures.

In several fields, such as biology, chemistry, combustion and environmental science, laser absorption spectroscopy represents an invaluable tool for the detection and identification of a variety of molecular species in the gas phase. For this detection to be quantitative, it is of paramount importance to rely on accurate spectroscopic parameters for the involved absorption lines in terms of line strength, line center frequency, pressure broadening, and pressure shift coefficients. The mid-infrared region offers the most favorable conditions for sensitive and chemically selective detection. The sensitivity derives from the presence of intense fundamental ro-vibrational transitions of molecules, whereas chemical selectivity relates to the unique absorption spectrum that molecules possess in the mid-IR region, thereby known as the fingerprint region. In this thesis, we combine the accelerating technology of optical frequency combs (OFC), which are powerful tools for accurate optical frequency measurements, with the wide tunability and single line emission in the mid-IR of extended cavity quantum cascade lasers (EC-QCL), to perform highly resolved, accurate and sensitive measurements in the fingerprint region, from 7.25 to 8 μm. Specifically, we have been able to lock for the first time the optical frequency of an EC-QCL to an OFC by utilizing nonlinear optics in the form of sum frequency generation (SFG) (Lamperti, AlSaif et al., 2018) and have exploited this comb-locked EC-QCL for an accurate survey of the entire ν1 ro-vibrational band of one of the most important greenhouse gases, nitrous oxide (N2O). The developed spectrometer is able to operate over a wide region of ~ 100 cm-1, in a fully automated fashion, while affording a 63 kHz uncertainty on the retrieved line center frequencies. The measurement allowed us to determine very accurately rotational constants of both ground and excited states of the ν1 band of N2O through the measurements of tens of lines of the P and R branches (AlSaif et al., JQSRT 2018). The spectrometer was then upgraded with a more recent and narrower linewidth EC-QCL to perform sub-Doppler saturated spectroscopy on the same N2O sample at a spectral resolution below 1 MHz, the sharpest ever observed with this type of laser. Finally, we worked at adding high sensitivity to the apparatus by introducing the gas in a high-finesse passive resonator and by developing a system to measure the intra-cavity absorption with cavity ring-down spectroscopy (CRDS) together with comb calibration.

The thesis deals with a design of a comparing interferometer. It concerns a setup of two interferometers, one of them is a Michelson and another a Fabry-Pérot type. This set-up is made to compare results of length measurements simultaneously performed by each of them. In the Theory, basic principles of Michelson and Fabry-Pérot interferometers are described. A special attention is paid to an innovative method of length measurement with tunable lasers and optical frequency comb. In the Practical Part, so-called Pilot Experimental Setup is described. It is a prototype that has been used to perform basic experiments on comparing of the two above mentioned methods. Based on experimental results and practical experience with the Pilot Experimental Setup, a Final Setup is designed. It comes in a form of a stand-alone instrument.

Le principal objectif de ce travail de thèse a été de développer de nouvelles techniques de spectroscopie moléculaire afin obtenir de nouvelles données spectroscopiques dans le visible et le proche infrarouge pour des molécules, radicaux ou ions d’intérêt astrophysiques. La première partie de ce travail a consisté en l’étude d’harmoniques élevés, très faibles en intensité, de bandes vibrationnelles de la molécule HC₃N (cyanoacetylène), par la technique de spectroscopie CRDS. La deuxième partie a consisté en l’étude spectroscopique d’espèces instables radicalaires. Pour cela, une décharge inductive Radio Fréquence a été couplée au montage CRDS. Le plasma ainsi créé a été caractérisé et sa capacité à produire des anions a été démontrée via notamment la mesure quantitative du rapport C₂ / C₂⁻pour une grande variété de conditions expérimentales. De même, une analyse spectroscopique quantitative a été menée sur les radicaux isotopomères ¹⁴NH₂ et ¹⁵NH₂. Cette étude valide certaines hypothèses faites dans de précédents travaux ayant permis de mesurer le rapport isotopique ¹⁵N/¹⁴N dans les comètes, pour la première fois à partir de raies d’émission de ces 2 isotopomères portant un groupe amino. La troisième et dernière partie de ce travail a consisté en le développement d’une nouvelle technique expérimentale appelée Broad-Band Dual Etalon Frequency COMb. Cette technique expérimentale basée sur l’utilisation de 2 cavités optiques de haute finesse devrait permettre d’obtenir une spectroscopie avec une résolution spectrale ultime non limitée par la source laser nanoseconde large bande mais par l’intervalle spectral libre des cavités de haute finesse utilisées. / The main objective of this PhD was to develop spectroscopic techniques using high finesse optical cavities. These were applied to the measurement of quantitative spectroscopic data for neutral, radical and ionic molecular species of astrophysical interest in the near infrared and visible spectral range. The first part was devoted to the measurement of the oscillator strength of high vibrational overtone bands of the cyanoacetylene (HC₃N) molecule with the Cavity Ring Down Spectroscopy (CRDS) technique. The second part was devoted to the study of the spectroscopy of transient neutral and ionic species. For that, an inductively radio frequency (RF) discharged has been coupled to the CRDS set up. The pertinence of this plasma to efficiently produce anions was demonstrated via the quantitative measurement of the C₂ / C₂⁻ ratio in a wide variety of conditions. A quantitative spectral analysis of the radical isotopomers ¹⁴NH₂ and ¹⁵NH₂ was also performed for the first time. This study provides experimental data that will allow to better constraint the ¹⁵N/¹⁴N isotopic ratio in comets through the emission lines of these two amino bearing isotopomers. The third and last part of the work was devoted to the development of a CRDS scheme called Broad Band Dual Etalon Frequency Comb Ring Down Spectroscopy. This new heterodyne technique, based on the use of the microsecond frequency combs generated by two high finesse optical cavities, should allow performing molecular spectroscopy with ultrahigh spectral resolution. First proof experiments were performed and perspective’s for improvement of the method is provided.

Despite the potential benefits of modifying behaviour according to changing ecological conditions, many populations comprise individuals that differ consistently in behaviour across situations, contexts and points in time (i.e. individuals show personality). If personalities are adaptive, the balance between consistency and flexibility of behavioural traits should reflect the ability of individuals to detect and respond to changing conditions in an appropriate and timely manner and, thus, depend upon the pace and predictability of changing conditions. We investigated the balance between individual consistency and flexibility in the subsocial spider Anelosimus studiosus by assaying boldness across the diel cycle and correlating these data with patterns of prey and threat abundance in the natural habitat. We found significant diel flexibility in boldness correlating with drastic and predictable changes in prey availability. Moreover, the strength of within-individual flexibility in boldness was comparable to the strength of rank-order consistency among individuals. We also found evidence that mean boldness level and among-individual variation in boldness are correlated with reproductive status. These data emphasize the interplay between behavioural consistency and flexibility and suggest that temporal characteristics of ecological conditions may be vital in assessing the strength, stability and adaptive value of animal personalities.

Optische Frequenzkämme (OFC) haben eine Vielzahl von Anwendungen in den angewandten Wissenschaften und der Grundlagenforschung, die auf der Bestimmung von absoluten Frequenzen und Frequenzdifferenzen beruhen, revolutioniert. Für letzteres wird nur die Stabilisierung des spektralen Abstandes der individuellen Kammlinien des OFCs benötigt, was erlaubt, den OFCG auf die Anwendung anzupassen und die Systemkomplexität zu reduzieren. Eine solche Anwendung ist der Quantentest der Universalität des Freien Falls (UFF) im Rahmen der Experimentserie QUANTUS. Mit diesem Test soll der Freie Fall zweier atomarer Spezies, Rubidium (Rb) und Kalium (K), in Mikrogravitation vergleichen werden. Das Ziel dieser Doktorarbeit war die Entwicklung eines hochkompakten, robusten, und weltraum-tauglichen diodenlaser-basierten OFCG mit einem modengekoppelten optischen Spektrum im Wellenlängenbereich um 780 nm. Es wurde ein diodenlaser-basierter OFCG entwickelt, der mit einer spektrale Bandbreite von mehr als 16 nm bei 20 dBc, einer optischen Leistung der Kammlinien > 650 nW (bei 20 dBc), einer Pulswiederholrate von 3.4 GHz, und einer RF-Linienbreite der frei-laufenden Pulswiederholrate < 10 kHz die Anforderungen übertrifft. Um ein Proof-of-Concept Demonstratormodul zu realisieren, wurde der diodenlaser-basierte OFCG in eine weltraum-taugliche Technologieplattform, die für die Anwendung in zukünftigen QUANTUS-Experimenten entwickelt wurde, hybrid-integriert. Der Nachweis einer ausreichend hohen RF-Stabilität des OFCGs wurde durch Stabilisierung der Pulswiederholrate auf eine externe RF Referenz erbracht. Dies ermöglichte eine stabilisierte Pulswiederholrate mit einer RF-Linienbreite von weniger als 1.4 Hz (auflösungsbegrenzt), was die die Anforderung übertrifft. Der entwickelte diodenlaser-basierten OFCG ist wichtiger Schritt in Richtung eines verbesserten Vergleichs des Freien Falls von Rb- und K-Quantengasen innerhalb der QUANTUS-Experimente in Mikrogravitation. / Optical frequency combs (OFC) have revolutionized various applications in applied and fundamental sciences that rely on the determination of absolute optical frequencies and frequency differences. The latter requires only stabilization of the spectral distance between the individual comb lines of the OFC, allowing to tailor and reduce system complexity of the OFC generator (OFCG). One such application is the quantum test of the universality of free fall within the QUANTUS experimental series. Within the test, the rate of free fall of two atomic species, Rb and K, in micro-gravity will be compared. The aim of this thesis was the development of a highly compact, robust, and space-suitable diode laser-based OFCG with a mode-locked optical spectrum in the wavelength range around 780 nm. A diode laser-based OFCG was developed, which exceeds the requirements with a spectral bandwidth > 16 nm at 20 dBc, a comb line optical power > 650 nW (at 20 dBc), a pulse repetition rate of 3.4 GHz, and an RF linewidth of the free-running pulse repetition rate < 10 kHz. To realize a proof-of-concept demonstrator module, the diode laser-based OFCG was hybrid-integrated into a space-suitable technology platform that has been developed for future QUANTUS experiments. Proof of sufficient RF stability of the OFCG was provided by stabilizing the pulse repetition rate to an external RF reference. This resulted in a stabilized pulse repetition rate with an RF linewidth smaller than 1.4 Hz (resolution limited), thus exceeding the requirement. The developed diode laser-based OFCG represents an important step towards an improved comparison of the rate of free fall of Rb and K quantum gases within the QUANTUS experiments in micro-gravity.