The scientific relevance and potential for technological applications of complex materials have made them the focus of active investigation in order to fully charac- terize the competition and interactions between their electronic, structural, orbital, and spin degrees of freedom. Optical and terahertz (THz) spectroscopy provide ac- cess to electronic and low frequency quasiparticle responses, and therefore play a key role in understanding the fundamental mechanisms which dictate the macroscopic properties of complex materials. Time-resolved experiments, in turn, have the po- tential to disentangle the various coexisting energy scales through a careful selection of the pump and probe characteristics. This work investigates the role played by the electronic, structural and magnetic excitations in the insulator-to-metal transi- tions (IMT) of VO2, V2O3 and NdNiO3, through studies under different conditions of temperature, strain, doping and photoexcitation. Our work shows that a complete understanding of the IMT in VO2 requires sev- eral length scales and time scales to be considered. Indeed, epitaxial strain leads to anisotropy in the IMT characteristics of thin films of (100) and (110) VO2/TiO2, measured using THz spectroscopy, which can be explained by strain induced modi- fications both in the (microscopic) V3d orbitals and in the geometry of mesoscopic metallic domains. On the other hand, ultrafast studies which track, with femtosecond resolution, the electronic and structural dynamics of VO2 thin films following THz excitation reveal a delay in the onset of the structural response with respect to the electronic one, lending support to the correlation rather than Peierls driven picture of the IMT in this material. As for V2O3, the IMT is seen to occur via nucleation and growth of metallic domains, as previously reported in VO2. However, a scaling of the photoinduced conductivity dynamics rise time is further identified, which reveals the temperature and fluence dependence of the nucleation and growth process. Finally, strained NdNiO3 films exhibit a two step dynamical conductivity response following optical excitation, different from that of the vanadates with which they share a complex, albeit more tunable, phase diagram. This hints at a significant role being played by the magnetic structure during the IMT in NdNiO3.

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xvi, 143 p. : ill. (some col.) / Electron spins form a two-level quantum system in which the remarkable properties of quantum mechanics can be probed and utilized for many applications. By learning to manipulate these spins, it may be possible to construct a completely new form of technology based on the electron spin degree of freedom, known as spintronics. The most ambitious goal of spintronics is the development of quantum computing, in which electron spins are utilized as quantum bits, or qubits, with properties that are not possible with classical bits. Before these ideas can become reality, a system must be found in which spin lifetimes are long enough and in which spins can be completely controlled. Semiconductors are an excellent candidate for electron spin control since they can be integrated into on-chip devices and produced on a scalable level. The focus of this dissertation is on electron spin control in two different semiconductor systems, namely a two-dimensional electron gas in a modulation-doped quantum well and donor-bound electrons in bulk semiconductors. Both systems have been studied extensively for a variety of purposes. However, the ability to manipulate spins has been elusive. In this dissertation, the first experimentally successful demonstration of electron spin control in a two-dimensional electron gas is presented, in which ultrafast optical pulses induce spin rotations via the optical Stark effect. Donor-bound electron spin manipulation in bulk semiconductors is also investigated in this dissertation. Important information was obtained on the limiting factors that serve to prohibit spin control in this system. By taking these new factors into account, it is our hope that full electron spin control can eventually be accomplished in this system. Finally, through the course of investigating electron spin dynamics, a strange nonlinear optical behavior was observed in a bilayer system, which was determined to result from a coupling of optical interactions with tunneling rates between layers. The data suggest that there is a strong interplay between interlayer and intralayer correlations in this system. Investigations into the nature of this interaction were undertaken and are presented in the last part of this dissertation. This dissertation includes previously published and unpublished co-authored material. / Committee in charge: Dr. Daniel Steck, Chair; Dr. Hailin Wang, Advisor; Dr. Jens Nockel, Inside; Dr. John Toner, Inside; Dr. Andrew Marcus, Outside

ROLE ASOVÉ 'KÁLY INTERAKCE SYSTÉM-LÁZE VE FOTOSYNTETICKÉM P ENOSU EXCITANÍ ENERGIE Tato práce se věnuje vlivu rychlého a pomalého molekulárno pohybu na přenos excitační energie ve fotosyntetick- ých světlosběrných komplexech. Vyvinuli jsme nový teoretický popis vnitromolekulárních vibračních mod· a zjistili jsme, že jejich resonance s energetickými rozdíly mezi fotosyntetickými pigmenty m·že vést ke zrychlení přenosu energie. Použitím jednomolekulární spektroskopie jsme pozorovali jak pomalé změny bílkovinné konformace mohou zcela změnit stav světlosběrného komplexu LHCII vyšších rostlin. Také jsme vyvinuli novou experimentální techniku, dvoupulzní ultrarychlou jednomolekulární spektroskopii. S její pomocí m·žeme pozorovat jak pomalý pohyb bílkoviny bakteriální antény LH2 ovlivňuje ultrarychlou relaxaci energie uvnitř komplexu. Konstrukcí jednotného modelu pro ultrarychlé objemové a jednomolekulární experimenty se nám podařilo zakomponovat rychlou a pomalou časovou škálu molekulárního pohybu do jednoho pohledu na fotosyntetický sběr světla.

Doctor of Philosophy / Department of Physics / Artem Rudenko / Carlos Trallero-Herrero / Ultrafast laser systems (pulse durations 10-100 femtoseconds) allow for the practical production of intense fields (≥ 10¹⁴ W/cm²) in a table-top, laboratory setup. The development of this technology has opened the door to studying the interaction of intense laser fields with atoms, molecules, and solid media. These experiments revealed a wealth of dynamics and interplay between the field, ion, and the freed electron, which has led to the production of first attosecond pulses and opened the field of attosecond science. The dynamics of the electron in an intense laser field are fundamental to strong- field phenomena such as higher-order harmonic generation, high energy above threshold ionization, and non-sequential double ionization. As the electron can be strongly accelerated by the instantaneous field, the dynamics depend on both the field's amplitude and wavelength. The latter dependence comes from the fact that the period of the field increases with wavelength. Thus, the electron is accelerated for a longer time and the energy gained is proportional to the wavelength squared. Recent evidence supports the claim that the electron- field interaction at longer wavelengths must include the contribution of the magnetic field and/or the radiation pressure of the field, adding to the wealth of effects associated with strong- field interactions. This thesis explores several routes towards fulfilling gaps in our understanding of the wavelength-scaling of strong- field interactions. I first demonstrate several important developments that reduce the complexity of generating non-sinusoidal, light transient waveforms in the near-infrared, opening the ability to tailor waveforms for more control on strong- field interactions. Next, I demonstrate the development of a strong- field, femtosecond source at wavelengths from 5 micrometers to 9 micrometers. To date, this is the first few-cycle, strong- field (≥ 10¹⁴ W/cm²) source in the long-wave infrared. An important advantage to this design is the wavelength tunability, which provides a control knob for understanding strong- field interactions across a broad wavelength range. Afterwards, I present applications of wavelength tunable sources in strong- field absorption in semiconductors. Specifically, I measure the absorbance of a strong laser field in gallium arsenide as a function of laser polarization, which varies the density of states available to the electron. This is performed for four laser wavelengths spanning 1.2 micrometers to 2.4 micrometers. With these absorbance measurements, we can compare the dependence of the photoexcitation rate on several parameters and compare it to theory. We find that the change in absorbance with density of states deviates from theoretical predictions as the photon order for the photoexcitation increases from two to three. This could be attributed to the field modifying the energy-momentum relationship of the conduction band. To conclude the thesis, I present simulations on a recent experimentally demonstrated technique for amplifying few-cycle electric fields. Due to the difficulty in making these sources, the model I developed includes many of the parameters involved in designing the system. This simulation can be used to plan design criteria, such as nonlinear crystal thickness, for peak performance of the amplification process.

abstract: The structure-function relation in Biology suggests that every biological molecule has evolved its structure to carry out a specific function. However, for many of these processes (such as those with catalytic activity) the structure of the biomolecule changes during the course of a reaction. Understanding the structure-function relation thus becomes a question of understanding biomolecular dynamics that span a variety of timescales (from electronic rearrangements in the femtoseconds to side-chain alteration in the microseconds and more). This dissertation deals with the study of biomolecular dynamics in the ultrafast timescales (fs-ns) using electron and X-ray probes in both time and frequency domains. It starts with establishing the limitations of traditional electron diffraction coupled with molecular replacement to study biomolecular structure and proceeds to suggest a pulsed electron source Hollow-Cone Transmission Electron Microscope as an alternative scheme to pursue ultrafast biomolecular imaging. In frequency domain, the use of Electron Energy Loss Spectroscopy as a tool to access ultrafast nuclear dynamics in the steady state, is detailed with the new monochromated NiON UltraSTEM and examples demonstrating this instrument’s capability are provided. Ultrafast X-ray spectroscopy as a tool to elucidate biomolecular dynamics is presented in studying X-ray as a probe, with the study of the photolysis of Methylcobalamin using time-resolved laser pump – X-ray probe absorption spectroscopy. The analysis in comparison to prior literature as well as DFT based XAS simulations offer good agreement and understanding to the steady state spectra but are so far inadequate in explaining the time-resolved data. However, the trends in the absorption simulations for the transient intermediates show a strong anisotropic dependence on the axial ligation, which would define the direction for future studies on this material to achieve a solution. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2016

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

Les décharges Nanosecondes Répétitives Pulsées (NRP) dans l'air à pression atmosphérique ont de nombreuses applications potentielles. Ces applications dépendent de la nature des décharges NRP. Les décharges NRP spark stabilisent les flammes pauvres, qui émettent moins d’oxydes d’azote. Un chauffage ultrarapide de plusieurs milliers de degrés en une vingtaine de nanosecondes a également été observé dans de telles décharges, ce qui permettrait par exemple la production de nanomatériaux. Les décharges NRP glow ont l'avantage de produire un grand nombre d'espèces actives comme le radical O tout en échauffant très peu le gaz ambiant, ce qui les rend utilisables dans des applications sensibles à la température comme la bio-décontamination. Dans une première partie, nous validons expérimentalement le mécanisme chimique à l'origine du chauffage ultra-rapide grâce à des mesures résolues en temps de la densité absolue de deux états excités du diazote ainsi que des mesures de température du gaz. Dans un deuxième temps, nous montrons expérimentalement l'existence du régime glow à température ambiante, celui-ci n'ayant été observé jusqu’à présent que pour des températures supérieures à 750 K. En effet, nous avons démontré que son existence dépend de nombreux paramètres : température et pression du gaz, tension entre les électrodes, distance inter-électrodes, durée de l’impulsion de tension, rayon de courbure des électrodes. Grâce à une étude expérimentale paramétrique détaillée et à l’analyse des résultats obtenus, nous avons réussi à identifier les conditions permettant d’obtenir le régime NRP glow à température ambiante et un nouveau régime de décharge de type “multi-canal” a été mis en évidence. / Nanosecond Repetitively Pulsed (NRP) discharges in atmospheric pressure air have many potential applications. Spark NRP discharges have applications in plasma assisted combustion. These discharges tend to stabilize lean flames which produce less NOx. Furthermore, an increase of several hundreds of Kelvins in less than 20 ns has been observed following NRP spark discharges, which could be used to create nanomaterials. NRP glow discharges, while creating an important number of actives species such as atomic oxygen, do not heat the ambient gas, which allows them to be used in temperature-sensitive applications such as bio-decontamination. In the first part of this thesis, we validate experimentally the mechanism that was proposed to explain the ultrafast heating observed. Time-resolved measurements of the absolute densities of two excited states of nitrogen and of the gas temperature have been performed with calibrated Optical Emission Spectroscopy. The second part of the thesis deals with the NRP glow regime. We have shown that its existence depends on several parameters, gas temperature and pressure, voltage across the electrodes, inter-electrode distance, pulse duration, radius of curvature of the electrodes. This regime had not been observed for temperatures lower than 750 K so far. Thanks to a detailed parametrical experimental study and the analysis of the obtained results, we have succeeded in identifying the NRP glow regime at ambient temperature and we observe a new type of “multi-channel” glow regime.

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

Doctor of Philosophy / Department of Physics / Zenghu Chang / It is still a dream to image the dynamics of electrons in atoms and molecules experimentally. This is due to the fact that such motion takes place in an ultra-short time scale; for example, an electron moves around the Bohr orbit in about 150-as (1 as = 10 -18 s), and pulses much shorter than this limit are not currently available to probe such fast dynamics. In recent years, an isolated single attosecond pulse has been produced by extracting the cutoff of harmonic spectrum driven by a laser pulse as short as ~ 5fs (1fs =10-15 s). But, these pulses are still too long in order to make the dream come true. Here, we study the possibility of generation of a much shorter and wavelength tunable single attosecond pulse by using polarization gating. In the experiment, we compressed ~30fs pulses from the laser amplifier down to ~6fs and characterized them. These linearly polarized pulses were converted to ellipticity varying pulses, and by exploiting the property of the strong dependence of the harmonic signal with the ellipticity of the laser, an XUV supercontinuum was produced in the harmonic spectrum which could support 60-as pulses. The bandwidth of such a supercontinuum, and therefore the duration of the attosecond pulses, is limited mainly by the currently available energy of the driving laser pulses at few cycle limits. In this project, we present an approach which allowed us to scale up the energy of such pulses by a factor of 1.5 in “Hollow Core Fiber / Chirped Mirrors Compressor”. Finally, in order to temporarily characterize the attosecond pulses we designed and built an “Attosecond Streak Camera”. Most of such cameras to date are limited to measuring a 1 dimensional energy spectrum and have only a few degrees of acceptance angle. Our camera is capable of measuring 2d momentum of the photoelectrons with large acceptance angle, for example ~ 65o at the photoelectron of energy ~15 eV. Recently, we observed the sidebands in addition to the main peaks in their laser assisted XUV photoelectron spectrum. The single attosecond pulses, after being characterized with this high speed camera, can be used to explore the dynamics of electrons at the attosecond scale.