In this work optical properties of two dimensional quantum well structures are studied. Variational calculation of the eigenstates in an isolated quantum well structure with and without the external electrical field is presented. At weak fields a quadratic Stark shift is found whose magnitude depends strongly on the finite well depth. It is observed that under external electrical field, the asymmetries due to lack of inversion symmetry leads to higher order nonlinear optical effects such as second order optical polarization and second order optical susceptibility.

Dye sensitized solar cells (DSSCs) are an attractive way to convert light into electricity. Its development requires a detailed understanding and kinetic optimization of various electronic processes, especially those occurring at the mesoporous TiO2/dye/electrolyte interface. This dissertation work is focused on the exploration of the various electronic processes at the sensitized-electrode/electrolyte interface by using various electrochemical and photochemical methods. Firstly, an alternative redox couple—TEMPO/TEMPO·+ with a relatively high positive redox potential—is explored, aiming to reduce the energy loss during the dye regeneration process. Despite the fast dye regeneration, the charge recombination between the electrons in the conduction band of mesoporous TiO2 and the oxidized redox species is found to be the limiting factor of the device. Further, a more efficient tandem-electrolyte system is developed, leading to DSSCs with the power conversion efficiency of 10.5 % and 11.7 % at 1 sun and 0.5-sun illumination, respectively. An electron-transfer cascade process during dye regeneration by the redox mediators is discovered to be beneficial. Further stability studies on the device suggest the crucial role of TiO2/dye/electrolyte interfaces in the long-term stability of cobalt bipyridyl electrolyte-based DSSCs. On the fundamental level, the local electric field and Stark effects at the TiO2/dye/electrolyte interface are investigated in various aspects—including the charge compensation mechanism, the factors affecting the electric field strength, as well as its impact on charge transfer kinetics. These results give further insights about the TiO2/dye/electrolyte interface, and contribute to the further development and understanding of DSSCs.

No description available.

No description available.

Mineral oxide/aqueous interfaces play an important role in the transport of water through aquafers and streams, erosion, the formation of beaches and river deltas, nuclear waste storage, the sequestration and filtration of small ions, and are widely used in industrial scale catalysis. Unlike metal or semiconductor electrodes, the surface charge resulting from the protonation or deprotonation of insulating mineral oxides is highly localized and heterogeneous in nature. While the unique acid/base chemistry associated with different mineral oxide surfaces leads to their wide variety of applications, the extent to which surface groups found on mineral oxides partake in acid/base chemistry is still controversial due to the difficulty associated with experimentally probing them. Surface specific spectroscopic techniques, such as vibrational Sum Frequency Generation (vSFG), provide an opportunity to investigate how the surface architecture and corresponding chemical nature of various mineral oxide surfaces orient the interfacial solvent at a variety of solvent compositions and surface charges. Although vSFG has been used as a tool to measure the orientation and composition of interfacial O-H species originating from the surface and solvent for many mineral oxide/aqueous interfaces since the late 1990’s, controversy still exists in the assignment of vSFG spectra in the O-H stretching region of SiO2, Al2O3, CaF2, and TiO2/aqueous interfaces. The first section of this dissertation focuses on how the nonlinear optics and computational community’s understanding of the structure associated with mineral oxide/aqueous interfaces has evolved and where it stands now. Of particular interest is how the addition of electrolyte and variation of bulk pH allow modulation of the depth of the interfacial region and surface charge. Electrolyte solutions can vary the length of the interface by screening interfacial charges through non-specific adsorption at the interface, or generating surface charge if accumulation is facilitated by specific adsorption. The specific interaction of small ions with mineral oxide surfaces is relevant in geochemistry and filtration technology, and can also aid in prediction of contaminant mobility in ground water systems. Chapters two and three discuss the theory and application of vSFG, and the experimental setup used to capture vSFG spectra in this work, respectively. The fourth chapter investigates how monovalent or divalent cations accumulate at alpha-Al2O3(0001)/H2O interfaces and reorganize the interfacial solvent structure. The reactivity of these interfaces is strongly impacted by the presence of ions. Thus, it is critical to understand how ions alter the interfacial environment. This is achieved by measuring the changes in the structure and vibrational dynamics of interfacial water induced by the presence of ions in close vicinity to the mineral surface. The alpha-Al2O3(0001) surface represents a flexible platform to study the effect of ions on interfacial aqueous environments at positive, neutral and negative surface charge. Using vibrational sum frequency generation (vSFG) in the frequency and time domain, we investigate how monovalent and divalent cations affect the hydrogen bonding environment of the first few layers of interfacial water next to an alpha-Al2O3(0001) surface. Our results indicate that monovalent cations, such as Li+, Na+, K+, and Cs+, appear to have lower adsorption affinities for the interface compared to Ca2+, Sr2+, and Ba2+. This leads to an interfacial region that is structured in a cation valence dependent manner. Time resolved vSFG measurements reveal that the O-H vibrational lifetime (T1) of interfacial species at pH 10 conditions in the presence of NaCl and BaCl2 remains similar, but restructuring of the surface seen in steady state vSFG is manifested in the degree to which strongly hydrogen bonded species recover to their original populations post excitation. By tracking the accumulation of ions at the interface via the vSFG response, we can characterize the unique surface arrangements of interfacial water molecules induced by a range of monovalent and divalent cations at the alpha-Al2O3(0001)/water interface. In the fifth chapter the Stark active C ≡ N stretch of potassium thiocyanate is used as a molecular probe of interfacial electrostatic potential at the alpha-Al2O3(0001)/H2O interface. We confirm the presence of the thiocyanate ion in the interfacial region via reorganization of surface waters in the O-H stretching region. Changes in electrostatic potential are then tracked via Stark shifts of the vibrational frequency of the C ≡ N stretch. Our vSFG measurements show that we can simultaneously measure the SFG response of SCN- ions experiencing charged and neutral surface sites and assign a local potential of + 308 mV and -154 mV to positively and negatively charged aluminol groups, respectively. Thiocyanate anions at charged surface sites adopt similar relative orientations independent of surface charge, but adopt an opposite orientation at neutral surface sites. MD-DFT simulations of SCN- near the neutral alpha-Al2O3(0001)//H2O interface show that the vSFG response in the C ≡ N stretch region originates from a SCN-H-O-Al complex, suggesting the surface site specificity of these experiments. By tracking how this molecular probe responds to local surface charges we offer insight into the local electrostatic potential at neutral and charged surface aluminol groups. Chapter six investigates the vibrational dynamics of potassium thiocyanate at the alumina/water interface. Here, we leverage the sensitivity of the C ≡ N stretch vibrational lifetime of potassium thiocyanate to measure the local electrostatic potential at the alpha-Al2O3(0001)/H2O interface. To accomplish this, KSCN was investigated using free induction decay vSFG (FID-vSFG) and time resolved pump probe (TR-vSFG) measurements, which measure the total dephasing time and vibrational lifetime of the excited C ≡ N stretch, respectively. Our FID-vSFG spectra suggest that at all surface charges the total dephasing time of SCN- is on the order of ~300-600 fs. TR-vSFG characterizations of potassium thiocyanate report the vibrational lifetime of the excited C ≡ N stretch between ~0.5-2 ps. TR-vSFG measurements show two distinct vibrational relaxation rates, which are assigned the CN stretch and the HOH bend plus libration combination band of interfacial water. The variation in the T1 lifetime of the CN stretch with bulk pH show that changes in the SCN- net orientation measured using steady-state vSFG can be correlated to the vibrational dynamics in the interfacial region. The energy transfer to the bend plus libration combination band of water is also sensitive to the surface charge, as the lifetime of this species becomes shorter as the bulk pH is increased. Lastly, in chapter seven this thesis is summarized, and future directions of the experiments presented here are discussed. / Chemistry

Heterogeneous reactions between gas-phase oxidants and particulate-phase organic compounds impact many important atmospheric chemical processes. For example, little is known about the reaction dynamics of gaseous oxidants with organic compounds found in the atmosphere. The first step of the reaction between gaseous ozone and solid pentacene was investigated using Reflection Absorption Infrared Spectroscopy (RAIRS). Ozone was found to add to pentacene non-selectively and form a range of products after heavy ozone exposure. The rate limiting step had an activation energy of 17 kJ/mol, which is consistent with the findings of previous ozone oxidation studies for the cleavage of a carbon-carbon double bond. Unfortunately the products could not be used to distinguish between probable reaction mechanisms. Hydroxyl radicals (•OH) play a major role processing atmospheric hydrocarbons. Due to their short lifetimes, not much is known about the dynamics of the first steps of •OH reactions. To investigate these reactions, a rotational state-selector was constructed to filter a molecular beam of •OH for reaction dynamics investigations with organic surfaces. The rotational state-selector was designed to leverage the linear Stark effect to pass only suitable molecules in a particular rotational state and block the flow of any other atoms, molecules and ions in a molecular beam. The state-selector was validated and used to positively deflect molecular beams of methyl iodide and D₂O via the linear Stark effect. Future studies with the rotational state-selector will investigate the initial steps of •OH reactions with solid organic compounds. / Master of Science

Die vorliegende Arbeit beschäftigt sich mit optischen Untersuchungen von MBE-gewachsenen hexagonalen Gruppe-III-Nitridheterostrukturen. Dafür wird die Photolumineszenz von InGaN/GaN- und GaN/AlGaN-Mehrfachquantengrabenstrukturen umfangreich zeitintegriert und zeitaufgelöst studiert. Die Proben unterscheiden sich in den Dicken der Quantengräben und Barrieren (InGaN) bzw. in der kristallografischen Orientierung (AlGaN). Als Ergebnis der großen, für das Materialsystem charakteristischen, elektrostatischen Felder zeigen die konventionell [0001]-orientierten Heterostrukturen eine verringerte Übergangsenergie und längere Lebensdauern mit zunehmender Quantengrabenbreite und höherem Indiumgehalt in den Gräben. Der beobachtete Einfluss des Quantumconfined Stark-Effektes (QCSE) auf diese Größen kann auch durch Modellrechnungen quantitativ gezeigt werden. In der Arbeit wird erstmals eine umfangreiche optische Charakterisierung einer neuartigen [1-100]-orientierten GaN-Heterostruktur auf Gamma-LiAlO2 geboten. Zum Vergleich wird das Verhalten einer identisch aufgebauten, [0001]-orientierten Struktur auf SiC ebenfalls diskutiert. Die (1-100)-Probe ist in Wachstumsrichtung frei von elektrostatischen Feldern und unterscheidet sich damit deutlich von den herkömmlichen Nitridstrukturen mit [0001]-Orientierung, deren interne Felder im MV/cm-Bereich liegen. Die spektrale Lage der Photolumineszenz bei geringen Anregungsdichten bestätigt die Flachbandsituation in der Probe. Aufgrund des bei dieser Probe nicht auftretenden QCSE ist hier eine deutlich verkürzte Lebensdauer festzustellen. Entsprechend der Auswahlregeln für hexagonales GaN weist die [1-100]-orientierte Probe eine sehr starke Polarisation der Photolumineszenz bezogen auf die Lage der [0001]-Achse auf. Die geringe Abweichung des ermittelten Polarisationsgrades von der, für A-Exzitonen in Volumen-GaN zu erwartenden, totalen Polarisation kann durch das Konfinement in den Quantengräben erklärt werden. Ein Schwerpunkt der Arbeit ist die Untersuchung der Rekombinationsmechanismen der Proben in Abhängigkeit von der induzierten Ladungsträgerdichte. Diese wird in einem Bereich von sehr geringer Dichte bis über die Mottdichte variiert. Eine Abschirmung der elektrostatischen Felder mit zunehmender Ladungsträgerdichte wird festgestellt. Dabei kann bei einer InGaN/GaN-Probe mit 3.1 nm breiten Gräben gezeigt werden, dass neben den internen piezoelektrischen Feldern die in der Literatur diskutierte Lokalisation von Exzitonen an Stöchiometrieschwankungen des Quantengrabens entscheidend die Rekombinationsdynamik in der Probe beeinflusst. Dies spiegelt sich in einer Abhängigkeit der Quantengrabeneigenschaften von den Anfangsbedingungen des Abklingprozesses und damit einem nicht existierenden allgemein gültigen Zusammenhang zwischen der Lebensdauer und der Ladungsträgerdichte wider. Die zeitaufgelösten Lumineszenzspektren der InGaN/GaN-Strukturen zeigen als Folge der mit höheren Ladungsträgerdichten zunehmenden Abschirmung eine verringerte Lebensdauer durch die vergrößerte Überlappung von Elektron- und Lochwellenfunktionen. Aufgrund der wieder abnehmenden Abschirmung während des Rekombinationsprozesses verändert sich die Lebensdauer im Laufe der Zeit. Gleichzeitig kommt es zu einer Verringerung der Übergangsenergie des Lumineszenzmaximums durch den weniger abgeschirmten QCSE. Die zeitintegrierten Photolumineszenzspektren zeigen ebenfalls eine deutliche Abhängigkeit von der Anregungsdichte. Während bei der feldfreien (1-100)-Probe keine Kompensationseffekte erwartet werden, weisen die Resultate für die konventionellen Proben auf einen, die Ladungsträgerdichte wesentlich beeinflussenden Effekt hin. Die Abhängigkeit der Intensität der Photolumineszenz von der Ladungsträgerdichte deutet ab einer bestimmten Anregungsdichte auf einen zusätzlichen Prozess, welcher die Ladungsträgerdichte reduziert, sich aber nicht im Lumineszenzspektrum widerspiegelt. Als Erklärung dafür wird die Absorption von stimulierter Emission im Substrat oder in der Pufferschicht angenommen. Bei den InGaN-Proben schiebt die Übergangsenergie mit höheren Dichten zu größeren Energien und nähert sich bis 10e5 W/cm2 einem Sättigungswert an. Dieser Wert entspricht trotz Dichten oberhalb der Mottdichte noch nicht der Flachbandsituation bei vollständig kompensierten internen Feldern. Als Ursache dafür wird der genannte, bei hohen Ladungsträgerdichten einsetzende Konkurrenzprozess gesehen. Bei den GaN/AlGaN-Proben kann im untersuchten Bereich der Anregungsdichte keine spektrale Verschiebung im Photolumineszenzspektrum festgestellt werden. Zum ersten Mal werden experimentelle Untersuchungen zur stimulierten Emission einer [1-100]-orientierten GaN-Probe durchgeführt und das optische Gewinnspektrum analysiert. Die Messungen zeigen einen maximalen Nettogewinn von ca. 50 1/cm. Aus der rechnerischen Analyse der Modenausbreitung lässt sich dafür ein Materialgewinn für GaN(1-100) von 1.1x10e4 1/cm ableiten. Die Ergebnisse zeigen außerdem, dass die Rekombination eines Elektron-Loch-Plasmas der Mechanismus für die stimulierte Emission ist. Dies entspricht dem überwiegenden Teil der in der Literatur veröffentlichten Beobachtungen für [0001]-orientierte Nitridstrukturen. Ein direkter Vergleich mit der parallel untersuchten GaN/AlGaN(0001)-Probe ist aufgrund der starken Substratabsorption nicht möglich. Es zeigt sich, dass für [1-100]-orientierte GaN-Heterostrukturen gute Ausgangsbedingungen für die Realisierung von Laserdioden gegeben sind. Zu den untersuchten Heterostrukturen wird die Wellenführung in den Proben simuliert. Bei den auf SiC gewachsenen Schichten werden die sich ausbreitenden Moden wegen des deutlich höheren Brechungsindexes des Substrates vornehmlich dort geführt. Die Überlappung der Moden mit dem aktiven Schichtpaket ist äußerst gering. Es ist für die Proben auf SiC kein optischer Gewinn zu erwarten. Die [1-100]-orientierte GaN/AlGaN-Probe besitzt eine deutlich bessere Wellenführung, da das LiAlO2 einen vergleichsweise kleinen Brechungsindex besitzt. Es wird ein Zusammenhang zwischen experimentell ermitteltem optischen Gewinn und dem Materialgewinn gebildet und das Ergebnis mit Rechnungen aus der Literatur verglichen. Ein Vorschlag für eine optimierte Wellenführung in allen untersuchten Proben wird gegeben. / In this thesis, the optical properties of molecular beam epitaxy grown hexagonal group-III nitride heterostructures are studied. The photoluminescence (PL) characteristics of InGaN/GaN and GaN/AlGAN multiple quantum well structures are investigated by time-integrated and time-resolved measurements. The analyzed specimens differ in the width of the quantum wells and barriers (InGaN) and in the crystallographic orientation (AlGaN), respectively. As a result of the large characteristic electrostatic fields, conventional [0001]-oriented heterostructures show a reduced transistion energy and longer lifetimes with increasing well width and higher Indium content in the wells. The observed impact of the Quantum Confined Stark Effect (QCSE) on these quantities is quantitatively shown in model calculations. In this work, a first extensive optical characterization of a novel [1-100]-oriented GaN heterostructure grown on Gamma-LiAlO2 is presented. For comparison, an identically designed [0001]-oriented structure on SiC is discussed. The (1-100)-grown specimen is free of electrostatic fields along the growth direction and shows a significant different behavior than conventional [0001]-oriented nitrides with internal fields of several MV/cm. The existing flat band conditions are confirmed by the spectral position of the PL at low excitation densities. Due to the non-existing QCSE at this specimen an significantly reduced lifetime is observed. A strong polarization of the PL is observed for the [1-100]-oriented sample, following the selection rules for hexagonal GaN. The small deviation of the degree of polarization from unity, which is expected in bulk GaN, is attributed to the quantum confinement in the heterostructures. One main topic of this thesis is the analysis of the recombination mechanisms of the specimens depending on the induced carrier density. The carrier density is varied from very low upto densities above the mott density. A screening of the electrostatic fields is observed with increasing carrier density. It is shown, that an InGaN/GaN heterostructure with a well width of 3.1 nm not only is influenced by internal piezoelectric fields but also the localization of excitons at stoichiometric inhomogenities in the quantum well is playing an important role for the recombination dynamics of the structure. This can be seen in the dependence of the decay process on the starting conditions. No general correlation is existing between lifetime and carrier density. Time-resolved PL measurements on InGaN/GaN heterostructures show a reduced lifetime due to an increased overlap of the electron and hole wave functions as a result of the increased screening at increasing carrier densities. During the recombination process the screening decreases again and the lifetime is changed with time. Simultaneously the transistion energy of the PL maximum is reduced by the less screened QCSE. A distinct dependence of the time-integrated PL spectra on the excitation density was also found. While there are no compensation effects expected at the (1-100) structure, which is free of electrostatic fields, the results for the conventional specimens point to an effect which influences the carrier density essentially. The dependence of the PL intensity on the carrier density points to an additional process, which comes into play at a special excitation density. This process reduces the carrier density but is invisible in the PL spectra. As an explanation we assume, that light of stimulated emission is absorbed either in the substrate or in the buffer layer. The transistion energy of the InGaN structures increases with increasing excitation density and reaches a saturation energy at a density of 10e5 W/cm2. Although this density is larger than the mott density, the transistion energy is not equivalent with a transition energy at flat band conditions. The origin of the observed effect is assumed to be the rival process, mentioned above, which comes into play at high carrier densities. For the GaN/AlGaN heterostructures no spectral shift of the PL was observed within the variation of excitation density. For the very first time, the stimulated emission of an [1-100]-oriented GaN structure was analyzed. A maximum netto gain of 50 1/cm was observed. From calculations of the mode propagation, a material gain of 1.1x10e4 1/cm is derived for GaN(1-100). Additionally from the results follows that the recombination of an electron-hole-plasma is the mechanism of the stimulated emission. This is in accordance with most of the published observations for [0001]-oriented GaN heterostructures. A direct comparison of both, the [1-100]-oriented specimen and the GaN/AlGaN(0001) structure, which was investigated parallel, was not possible. The reason for that is the strong absorption of the SiC substrate of the latter mentioned structure. It is generally shown, that [1-100]-oriented GaN heterostructures offers good starting conditions to realize laser diodes. The wave guiding was simulated for all of the used specimens. At structures grown on SiC the propagating modes are mainly guided in the substrate due to the larger refractive index of SiC with respect to GaN. The overlap of the amplified mode and the active layer is very small. No optical gain is expected for these structures. The [1-100]-oriented GaN/AlGaN structure shows a significantly improved wave guiding, due to the small refractive index of LiAlO2 in comparison with GaN. A correlation between the experimentally observed optical gain and the material gain is formed and the results are compared with the literature. A suggestion for an optimized wave guiding in all investigated specimens is given.

Cette thèse porte sur l’étude de l’émissivité et de l’opacité dans les plasmas de fusion inertielle (FCI), et des processus atomiques dans les plasmas de fusion magnétique (FCM).En FCI, nous avons étudié les spectres d’émissivité du hohlraum de l’approche indirecte et d’opacité des dopants de l’ablateur. Leur connaissance permet d’améliorer la compression de la cible de D-T et ainsi favoriser les réactions de fusion. Nous avons caractérisé les spectres lié-lié de l’or, du carbone et du germanium au moyen de méthodes détaillées (code PPP) mais qui s’avèrent coûteuses en temps de calculs et limitées quand le nombre de niveaux/ions augmente. Pour optimiser le temps de calcul sans perdre en précision, une méthode hybride détaillée/statistique (code SCO-RCG) a fait l’objet de comparaison/validation avec le code PPP sur des cas tests. Cette approche a ensuite été appliquée au calcul de l’opacité totale (lié-lié, lié-libre, libre-libre) pour tous les états d’ionisation du germanium et du silicium. Les spectres obtenus sont ensuite comparés dans une large gamme d’énergies en vue d’optimiser la compression de la cible.En FCM, à partir d’expériences effectuées sur les tokamaks Tore Supra (CEA Cadarache) et ASDEX Upgrade (Max Planck Institut, Garching), nous nous proposons de développer une nouvelle base de données de physique atomique (sections efficaces, taux des processus,…) à l’aide du code HULLAC pour analyser des coefficients de transport. Le but de cette étude est la sensibilité aux données atomiques de la reconstruction des coefficients de transport par le code ITC. Pour le cas de l’argon, les sections efficaces de quelques processus sont présentées et les coefficients de taux sont comparés à ceux provenant du consortium ADAS. / The thesis is devoted on the study of emissivity and opacity in inertial confinement fusion plasmas (ICF), and on atomic processes in magnetic fusion plasmas (MCF).In ICF, we have studied the emissivity of the hohlraum and the opacity of ablator’s dopants in the indirect drive scheme. The knowledge of these quantities allows the improvement of the target compression and, as a consequence, the fusion reactions. We have characterized the bound-bound spectrum of gold, carbon and germanium with detailed line calculation (PPP code). Such calculations are time consuming and thus restricted to small numbers of levels/ions. To optimize the time calculation without lack of precision, a hybrid approach statistical/detailed (SCO-RCG code) was compared with the PPP code for test cases. Then the hybrid approach was applied to total opacity calculations (bound-bound, bound-free and free-free transitions) for each ionization state of germanium and silicon. The spectra are compared in a large temperature range in order to optimize the target compression.In MCF, from experiences carried out on Tore Supra (CEA Cadarache) and ASDEX Upgrade (Max Planck Institut, Garching) tokomak, we have provided new atomic data (cross sections, rates of processes) with the HULLAC code in order to analyze the transport coefficients. The aim of this study is the sensitivity of atomic data on the reconstruction of transport coefficients by the ITC code. For the argon case, the cross sections of some processes are presented and the rate coefficients are compared to those of ADAS consortium.

<p>In this dissertation is exemplified how different laser based methods are applied in high-resolution spectroscopic studies of internal properties of diatomic molecules.</p><p>A molecular beam apparatus assembly is described, where a laser ablation source is combined with a time-of-flight mass spectrometer. Compounds investigated with this equipment are hafnium sulfide and hafnium oxide. The molecules are excited and ionized applying the resonant two-photon ionization (R2PI) scheme, which is a sensitive absorption and detection technique for probing the population of an excited state.</p><p>By means of the DC Stark effect, permanent electric dipole moments of HfS in the <i>D</i> ¹Π state and HfO in the <i>b</i> ³Π₁ state are determined while the molecules are exposed to a static electric field. Under field-free conditions low temperature rotationally resolved spectra are recorded, generating line positions from which molecular parameters are derived.</p><p>The R2PI method, modified with an adjustable delay time, is also used in lifetime measurements of individual rotational levels of the HfS <i>D</i>¹Π and HfO<i> b</i> ³Π₁ states. Oscillator strengths for transitions from the ground state are calculated, and in this connection basic concepts like Einstein coefficients, line strengths and Hönl-London factors, are surveyed. Theoretical calculation of lifetimes is discussed in view of the fact that a commonly available computer program (LEVEL 7.5 by Le Roy) gives erroneous output.</p><p>Some coherence and quantum interference related phenomena, such as electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting, are presented in the latter part of this thesis. Fundamental concepts and relations are introduced and explained. The driven three-level cascade system is elucidated, including some of its experimental applications to alkali metal dimers, Na₂ and Li₂.</p><p>A triple resonance spectroscopy experiment is described in terms of a three-laser, four-level inverted-Y excitation scheme, implemented in Na₂. The accompanying density matrix formalism, providing the basis for theoretical simulations, is accounted for. From analysis of the results an absolute value of the electric dipole moment matrix element (transition moment) is extracted, using the AC Stark effect.</p><p>Some recently reported unexpected experimental results and unforeseen features, occurring in Doppler broadened samples and related to the open character of molecular systems, are briefly commented.</p>

In this dissertation is exemplified how different laser based methods are applied in high-resolution spectroscopic studies of internal properties of diatomic molecules. A molecular beam apparatus assembly is described, where a laser ablation source is combined with a time-of-flight mass spectrometer. Compounds investigated with this equipment are hafnium sulfide and hafnium oxide. The molecules are excited and ionized applying the resonant two-photon ionization (R2PI) scheme, which is a sensitive absorption and detection technique for probing the population of an excited state. By means of the DC Stark effect, permanent electric dipole moments of HfS in the D 1Π state and HfO in the b 3Π1 state are determined while the molecules are exposed to a static electric field. Under field-free conditions low temperature rotationally resolved spectra are recorded, generating line positions from which molecular parameters are derived. The R2PI method, modified with an adjustable delay time, is also used in lifetime measurements of individual rotational levels of the HfS D 1Π and HfO b 3Π1 states. Oscillator strengths for transitions from the ground state are calculated, and in this connection basic concepts like Einstein coefficients, line strengths and Hönl-London factors, are surveyed. Theoretical calculation of lifetimes is discussed in view of the fact that a commonly available computer program (LEVEL 7.5 by Le Roy) gives erroneous output. Some coherence and quantum interference related phenomena, such as electromagnetically induced transparency (EIT) and Autler-Townes (AT) splitting, are presented in the latter part of this thesis. Fundamental concepts and relations are introduced and explained. The driven three-level cascade system is elucidated, including some of its experimental applications to alkali metal dimers, Na2 and Li2. A triple resonance spectroscopy experiment is described in terms of a three-laser, four-level inverted-Y excitation scheme, implemented in Na2. The accompanying density matrix formalism, providing the basis for theoretical simulations, is accounted for. From analysis of the results an absolute value of the electric dipole moment matrix element (transition moment) is extracted, using the AC Stark effect. Some recently reported unexpected experimental results and unforeseen features, occurring in Doppler broadened samples and related to the open character of molecular systems, are briefly commented.