Coherent control of laser induced processes is based on the quantum interference among multiple excitation pathways. Progress in the field has been fueled by advances in pulse shaping techniques, allowing modulation of phase and amplitude across the bandwidth of ultra short pulses. This dissertation makes use of coherent control technique for the optimization of two-photon fluorescence (TPF) and its applications in selective excitation for biomedical imaging. Different physical processes, e.g. TPF, second harmonic generation (SHG) and their ratios (e.g. TPF/SHG) were optimized by using feedback control pulse shaping technique with an evolutionary algorithm. Various nonlinear effects, e.g. filamentation, intensity clamping and white light generation were studied using two-photon fluorescence and Z-scan technique with different dyes and biomarkers. Simultaneous measurements of different nonlinear effects were performed. Novel methods were proposed and implemented to obtain two-photon excitation characteristics in intensity-resolved manner. Understanding of these nonlinear effects can give new solution to the issues of spatial resolution and molecular contrast for cellular and tissue imaging.

The SPECIFIC method a fast and accurate method for generating shaped femtosecond laser pulses. The femtosecond pulses are user specified from pulse parameters in the temporal domain. The measured spectral and recovered temporal phase and amplitudes from SEA TADPOLE are compared with the theoretical pulse profile from the user specified input. The SPECIFIC method has been shown to be a technique that can generate a diverse array of spectral/temporal phase and amplitude as well as polarization pulse shapes for numerous scientific applications. The spatio -temporal -spectral properties of focusing femtosecond laser pulses are studied for several pulse shapes that are important for non-linear spectroscopic studies. We have shown with scanning SEA TADPOLE that the spatio-spectral phase of focusing double pulse profile changes across the laterally across the beam profile. The spectral features of the sinusoidal spectral phase shaped pulse has been shown to tilt at with a changing angle away from the focus of the lens. Using spatio-spectral coupling, we have shown that multiple spatio-temporal foci can be generated along and perpendicular to the focusing direction of a femtosecond laser pulse. The spatial position of the spatio-temporal foci is controlled optically. Using sinusoidal spectral phase modulated pulse trains fragment ion production from Benzonitrile parent molecule can be controlled. A spectral transmission window perturbed the temporal pulse amplitudes resulting in fragment ion production dependant on spectral window position. The spectral window ion production was shown to also be dependant on temporal phase sequence. / Chemistry

Experimental investigations of the optical properties of InGaN/GaN quantum dots are presented. A pulsed laser is used to perform time-integrated and time-resolved microphotoluminescence, photoluminescence excitation, and polarisation-resolved spectroscopy of single InGaN quantum dots under a non-linear excitation regime. The first micro-photoluminescence results from InGaN/GaN quantum dots grown on a non-polar crystal plane (11^-<sub style='position: relative;left: -.4em;'>2</sub>0) are presented. Time-resolved studies reveal an order of magnitude increase in the oscillator strength of the exciton transition when compared to InGaN quantum dots grown on the polar (0001) plane, suggesting a significantly reduced internal electric field in non-polar InGaN quantum dots. Polarisation resolved spectroscopy of non-polar InGaN quantum dots reveals 100% linearly polarised emission for many quantum dots. For quantum dot emissions with a polarisation degree less than unity, a fine structure splitting between two orthogonal polarisation axes can be resolved in an optical setup with a simple top-down excitation geometry. A statistical investigation into the origins of spectral diffusion in polar InGaN quantum dots is presented, and spectral diffusion is attributed to charge carriers trapped at threading dislocations, and itinerant and trapped carriers in the underlying quantum well layer which forms during the growth procedure. Incorporating quantum dots into the intrinsic region of a p-i-n diode structure and applying a reverse bias is suggested as a method to reduce spectral diffusion. Coherent control of the excited state exciton in a non-polar InGaN quantum dot is experimentally demonstrated by observation of Rabi rotation between the excited state exciton and the crystal ground state. The exciton ground state photoluminescence is used as an indirect measurement of the excited state population.

Neste trabalho foi investigado o controle do processo de fluorescência excitada por absorção de dois fótons no polímero conjugado MEH-PPV, utilizando um sistema de formatação espectral da fase dos pulsos ultracurtos. Para tal estudo, foi utilizado um oscilador laser de Ti:Safira (15 fs, ~ 800 nm e largura de banda de 60 nm). Através de dois distintos métodos de formatação, observa-se a influência destes no processo de fotodegradação do MEHPPV, inferido pela diminuição da intensidade do sinal de fluorescência. No primeiro método de formatação, é estudada a influência de diferentes chirps impostos aos pulsos no processo de fluorescência do MEH-PPV. Observa-se uma menor taxa de fotodegradação para pulsos com maiores chirps, independente do sinal, em comparação a pulsos no limite de transformada. Esse efeito foi relacionado ao acréscimo na duração temporal dos pulsos com chirp, com consequente diminuição da intensidade. Numa segunda etapa, através do uso de um espelho deformável, a fase espectral do pulso é formatada usando uma máscara de fase senoidal. Neste caso, a intensidade de fluorescência foi modulada em aproximadamente 25%, num claro processo de controle coerente, sem nenhuma diferença apreciável no processo de fotodegradação. Desta forma, técnicas de controle coerente com formatação espectral da fase poderiam ser utilizadas para modular a intensidade do sinal de fluorescência no MEH-PPV, sem detrimento ao processo fotodegradativo. / In this work we studied the control of two-photon excited fluorescence in the conjugated polymer MEH-PPV, using pulse-shaping techniques to manipulate the pulse spectral phase. The experiments were carried out with a Ti:sapphire laser oscillator (15 fs, ~ 800 nm and 60 nm of bandwidth). We investigated the influence of two distinct pulse-shaping methods in the MEH-PPV photodegradation, inferred by the decrease in the fluorescence intensity. In the first method, we studied the effect of different pulse chirps on the MEH-PPV fluorescence. A smaller photodegradation rate was observed for pulses with higher chirps, independently of its sing, in comparison with pulses close to the Fourier Transform limit. This effect was attributed to the increase in the pulse duration for chirped pulses, and consequent decrease in the pulse intensity. In a second stage, we modulate the pulse spectral phase by employing a senoidal phase mask though a deformable mirror. In this case, a 25% modulation in the fluorescence intensity was determined, whereas no considerable effect was observed in the photodegradation. In this way, coherent control techniques employing spectral phase pulse-shaping could be used to modulate MEH-PPV fluorescence, without any negative effect to its photodegradation.

The resonant absorption, emission, and scattering of light are the fundamental optical processes that have been used both to probe matter and to manipulate light itself. In the last decade there has been essential progress in coherent control of both linear and nonlinear optical responses based on resonant excitation of atomic coherence in multilevel quantum systems. Some interesting and useful phenomena, resulting from coherent control of absorption and the group index, such as electromagnetically induced transparency, lasing without inversion, and ultra-slow group velocity of light have been widely studied. This work is focused on coherent control of refractive index and resonant fluorescence in multilevel medium. We suggest two promising schemes for resonant enhancement of the refractive index with eliminated absorption and propose their implementation in transition element doped crystals with excited state absorption and in a cell of Rb atoms at natural abundance. We show how to use one of these schemes for spatial variation of the refractive index via its periodic resonant increase/decrease, remarkably keeping at the same time zero absorption/gain. It opens the way to production of transparent photonic structures (such as distributed Bragg reflectors, holey fibers, or photonic crystals) in a homogeneous resonant atomic media such as dielectrics with homogeneously distributed impurities, atomic, or molecular gases. These optically produced photonic structures could easily be controlled (including switching on/off, changing amplitude and period of modulation) and would be highly selective in frequency, naturally limited by the width of the optical resonance. We also derive the optical fluorescence spectra of a three-level medium driven by two coherent fields at the adjacent transitions in a general case when all three transitions are allowed. We show that coherent driving can efficiently control the distribution of intensities between the fluorescent channels. In particular, the total intensity of fluorescence at the transition which is not driven by the optical fields may essentially exceed the fluorescence intensity at the driven transitions under the condition of two-photon resonance. This counter-intuitive effect is due to depletion of the intermediate state via atomic interference.

Neste trabalho foi investigado o controle do processo de fluorescência excitada por absorção de dois fótons no polímero conjugado MEH-PPV, utilizando um sistema de formatação espectral da fase dos pulsos ultracurtos. Para tal estudo, foi utilizado um oscilador laser de Ti:Safira (15 fs, ~ 800 nm e largura de banda de 60 nm). Através de dois distintos métodos de formatação, observa-se a influência destes no processo de fotodegradação do MEHPPV, inferido pela diminuição da intensidade do sinal de fluorescência. No primeiro método de formatação, é estudada a influência de diferentes chirps impostos aos pulsos no processo de fluorescência do MEH-PPV. Observa-se uma menor taxa de fotodegradação para pulsos com maiores chirps, independente do sinal, em comparação a pulsos no limite de transformada. Esse efeito foi relacionado ao acréscimo na duração temporal dos pulsos com chirp, com consequente diminuição da intensidade. Numa segunda etapa, através do uso de um espelho deformável, a fase espectral do pulso é formatada usando uma máscara de fase senoidal. Neste caso, a intensidade de fluorescência foi modulada em aproximadamente 25%, num claro processo de controle coerente, sem nenhuma diferença apreciável no processo de fotodegradação. Desta forma, técnicas de controle coerente com formatação espectral da fase poderiam ser utilizadas para modular a intensidade do sinal de fluorescência no MEH-PPV, sem detrimento ao processo fotodegradativo. / In this work we studied the control of two-photon excited fluorescence in the conjugated polymer MEH-PPV, using pulse-shaping techniques to manipulate the pulse spectral phase. The experiments were carried out with a Ti:sapphire laser oscillator (15 fs, ~ 800 nm and 60 nm of bandwidth). We investigated the influence of two distinct pulse-shaping methods in the MEH-PPV photodegradation, inferred by the decrease in the fluorescence intensity. In the first method, we studied the effect of different pulse chirps on the MEH-PPV fluorescence. A smaller photodegradation rate was observed for pulses with higher chirps, independently of its sing, in comparison with pulses close to the Fourier Transform limit. This effect was attributed to the increase in the pulse duration for chirped pulses, and consequent decrease in the pulse intensity. In a second stage, we modulate the pulse spectral phase by employing a senoidal phase mask though a deformable mirror. In this case, a 25% modulation in the fluorescence intensity was determined, whereas no considerable effect was observed in the photodegradation. In this way, coherent control techniques employing spectral phase pulse-shaping could be used to modulate MEH-PPV fluorescence, without any negative effect to its photodegradation.

Master of Science / Department of Physics / Brett D. Esry / In the last 20 years, advancements in laser technology have allowed for the production of intense laser pulses with durations in the femtosecond (10⁻¹⁵ second) regime, giving scientists the ability to probe nuclear dynamics on their natural time scale. Study of the dissociated fragments created by these intense fields can be used to learn about the molecular structure and dynamics. The work presented in this thesis focuses on controlling this light–molecule interaction in such a way that we can preferentially dissociate the molecule to a desired final product. The hydrogen molecular ion, HD⁺, as well as LiF serve as simple systems that can be studied theoretically for a broad range of laser parameters. Our goal in using these relatively simple systems is to capture the essential physics of the light–molecule interaction and develop general methods to describe these interactions in more complex systems.

The main theme covered in this thesis is experimentalstudies of quantum dynamics and coherent control in homonuclearalkali diatomic molecules by ultrafast laser spectroscopy iththe implementation of pump-probe techniques. A series of experiments have been performed on the Rb2molecules in a molecular beam as well as in a thermal oven. Thereal-time molecular quantum dynamics of the predissociatingelectronically excited D(3)1Πu state of Rb2, which couples to/intersects several otherneighbouring states, is investigated using wavepackets. Thepredissociation of the D state, explored by this wavepacketmethod, arises from two independent states, the (4)3Σu+and (1)3∆u, for which the second corresponds to a much fasterdecay channel above a sharp energy threshold around 430 nm. Thelifetime of the D state above the energy threshold is obtained,τ ≈ 5 ps, by measuring the decay time of thewavepacket in a thermal oven. Further experimentalinvestigation performed in a molecular beam together withquantum calculations of wavepacket dynamics on the D state haveexplored new probe channels of wavepacket evolution: theD′(3)1Σu+ channel, which exhibits vibrational motionin a shelf state and the (4)3Σu+ channel, where direct build-up of thewavefunction is observed due to its spin-orbit oupling to the Dstate. The real-time quantum dynamics of wavepackets confined totwo bound states, A1Σu+(0u+) and b3Πu(0u+), have been studied by experiment andcalculations. It is shown that these two states are fullycoupled by spin-orbit interaction, characterised by itsintermediate strength. The intermediate character of thedynamics is established by complicated wavepacket oscillationatterns and a value of 75 cm-1is estimated for the coupling strength at thestate crossing. The experiments on the Li2molecule are performed by coherent control ofrovibrational molecular wavepackets. First, the Deutsch-Jozsaalgorithm is experimentally demonstrated for three-qubitfunctions using a pure coherent superposition of Li2rovibrational eigenstates. The function’scharacter, either constant or balanced, is evaluated by firstimprinting the function, using a phase-tailored femtosecond(fs) pulse, on a coherent superposition of the molecularstates, and then projecting the superposition onto an ionicfinal state using a second fs pulse at a specific delay time.Furthermore, an amplitude-tailored fs pulse is used to exciteselected rovibrational eigenstates and collision induceddephasing of the wavepacket signal, due to Li2-Ar collisions, is studied experimentally. Theintensities of quantum beats decaying with the delay time aremeasured under various pressures and the collisional crosssections are calculated for each well-defined rovibrationalquantum beat, which set the upper limitsfor ure dephasingcross sections. <b>Keywords:</b>Ultrafast laser spectroscopy, pump-probetechnique, predissociation, wavepacket, pin-orbit interaction,coherent control, (pure) dephasing

<p>The main theme covered in this thesis is experimentalstudies of quantum dynamics and coherent control in homonuclearalkali diatomic molecules by ultrafast laser spectroscopy iththe implementation of pump-probe techniques.</p><p>A series of experiments have been performed on the Rb2molecules in a molecular beam as well as in a thermal oven. Thereal-time molecular quantum dynamics of the predissociatingelectronically excited D(3)¹Πu state of Rb₂, which couples to/intersects several otherneighbouring states, is investigated using wavepackets. Thepredissociation of the D state, explored by this wavepacketmethod, arises from two independent states, the (4)³Σ_u⁺and (1)³∆_u, for which the second corresponds to a much fasterdecay channel above a sharp energy threshold around 430 nm. Thelifetime of the D state above the energy threshold is obtained,τ ≈ 5 ps, by measuring the decay time of thewavepacket in a thermal oven. Further experimentalinvestigation performed in a molecular beam together withquantum calculations of wavepacket dynamics on the D state haveexplored new probe channels of wavepacket evolution: theD′(3)1Σu+ channel, which exhibits vibrational motionin a shelf state and the (4)³Σu+ channel, where direct build-up of thewavefunction is observed due to its spin-orbit oupling to the Dstate.</p><p>The real-time quantum dynamics of wavepackets confined totwo bound states, A¹Σ_u⁺(0_u⁺) and b³Π_u(0_u⁺), have been studied by experiment andcalculations. It is shown that these two states are fullycoupled by spin-orbit interaction, characterised by itsintermediate strength. The intermediate character of thedynamics is established by complicated wavepacket oscillationatterns and a value of 75 cm^-1is estimated for the coupling strength at thestate crossing.</p><p>The experiments on the Li₂molecule are performed by coherent control ofrovibrational molecular wavepackets. First, the Deutsch-Jozsaalgorithm is experimentally demonstrated for three-qubitfunctions using a pure coherent superposition of Li₂rovibrational eigenstates. The function’scharacter, either constant or balanced, is evaluated by firstimprinting the function, using a phase-tailored femtosecond(fs) pulse, on a coherent superposition of the molecularstates, and then projecting the superposition onto an ionicfinal state using a second fs pulse at a specific delay time.Furthermore, an amplitude-tailored fs pulse is used to exciteselected rovibrational eigenstates and collision induceddephasing of the wavepacket signal, due to Li₂-Ar collisions, is studied experimentally. Theintensities of quantum beats decaying with the delay time aremeasured under various pressures and the collisional crosssections are calculated for each well-defined rovibrationalquantum beat, which set the upper limitsfor ure dephasingcross sections.</p><p><b>Keywords:</b>Ultrafast laser spectroscopy, pump-probetechnique, predissociation, wavepacket, pin-orbit interaction,coherent control, (pure) dephasing</p>

Quantum mechanics, arguably one of the greatest achievements of modern physics, has not only fundamentally changed our understanding of nature but is also taking an ever increasing role in engineering. Today, the control of quantum systems has already had a far-reaching impact on time and frequency metrology. By gaining further control over a large variety of different quantum systems, many potential applications are emerging. Those applications range from the development of quantum sensors and new quantum metrological approaches to the realization of quantum information processors and quantum networks. Unfortunately most quantum systems are very fragile objects that require tremendous experimental effort to avoid dephasing. Being able to control the interaction between a quantum system with its local environment embodies therefore an important aspect for application and hence is at the focus of this thesis. / Physics