A great deal of theoretical activity has resulted from blending the fields of computer science and quantum mechanics. Out of this work has come the concept of a quantum computer, which promises to solve problems currently intractable for classical computers. This promise has, in turn, generated a large amount of effort directed toward investigating quantum computing experimentally. ¶ Quantum computing is difficult because fragile quantum superposition states of the computer’s register must be protected from the environment. This is made more difficult by the need to manipulate and measure these states. ¶ This thesis describes work that was carried out both to investigate and to demonstrate the utility of rare earth ion dopants for quantum computation. Dopants in solids are seen by many as a potential means of achieving scalable quantum computing. Rare earth ion dopants are an obvious choice for investigating such quantum computation. Long coherence times for both optical and nuclear spin transitions have been observed as well as optical manipulation of the spin states. The advantage that the scheme developed here has over nearly all of its competitors is that no complex nanofabrication is required. The advantages of avoiding nano-fabrication are two fold. Firstly, coherence times are likely to be adversely effected by the “damage” to the crystal structure that this manufacture represents. Secondly, the nano-fabrication presents a very serious difficulty in itself. ¶ Because of these advantages it was possible to perform two-qubit operations between independent qubits. This is the first time that such operations have been performed and presents a milestone in quantum computation using dopants in solids. It is only the second time two-qubit operations have been demonstrated in a solid. ¶ The experiments performed in this thesis were in two main areas: The first was the characterisation of hyperfine interactions in rare earth ion dopants; the second, simple demonstrations directly related to quantum computation. ¶ The first experiments that were carried out were to characterise the hyperfine interactions in Pr[superscript 3]+:Y[subscript 2]SiO[subscript 5]. The characterisation was the first carried out for the dopants in a site of such low symmetry. The resulting information about oscillator strengths and transition frequencies should prove indispensable when using such a system for quantum computation. It has already enabled an increase in the coherence times of nuclear spin transitions by two orders of magnitudes. ¶ The experiments directly related to the demonstration of quantum computation were all carried out using ensembles. The presence of a significant distribution of resonant frequencies, or inhomogeneous broadening, meant that many different sub-ensembles could be addressed, based on their resonant frequencies. Furthermore, the properties of the sub-ensembles could be engineered by optically pumping unwanted members to different hyperfine states away from resonance with the laser. ¶ A previously demonstrated technique for realising ensembles that could be used as single qubits was investigated and improved. Also, experiments were carried out to demonstrate the resulting ensembles’ utility as qubits. Further to this, ions from one of the ensembles were selected out, based on their interaction with the ions of another. Elementary two qubit operations were then demonstrated using these ensembles.

Le traitement de l’information quantique, en particulier celui utilisant les centres colorés du diamant et la manipulation cohérente des ions de terre rare incorporés dans des matrices solides (Pr3+, Eu3+) et la spectroscopie à ultra-haute résolution, nécessitent des sources accordables ayant une faible largeur de raie. Or, dans la gamme rouge-orange (570-635 nm) où les diodes lasers font défaut et les lasers solides restent très peu développés, les lasers à colorants sont actuellement les seules sources de rayonnement cohérent disponibles. En revanche, ce type de laser est assez complexe et difficile à stabiliser au niveau du kHz à cause des bruits à haute fréquence générés par le jet de colorant.Pour répondre aux besoins des expériences citées ci-dessus, cette thèse vise à proposer une alternative “tout solide” aux lasers à colorants en explorant différentes possibilités pour la construction d’une source stable émettant dans l’orange-rouge. Dans ce but, nous avons proposé deux solutions:1. La première consiste à développer des oscillateurs paramétriques optiques. Dans cette voie, nous avons développé un OPO simplement résonant à doublage de fréquence intra-cavité et stabilisé en frequence au niveau du kHz.2. La deuxième consiste en un laser à base de fluorures dopés au Pr3+pompé par diode. / The quantum information processing using diamond color center or the coherent manipulation of rare earth ion embedded in solid state matrices (Pr3+, Eu3+) or the high resolution spectroscopy, require narrow linewidth tunable laser sources.However in the orange-red range (570-635 nm) where laser diodes are lacking and solid-state lasers are poorly developed, only dye lasers are currently available. Nevertheless these sources are complex and difficult to stabilize at the kHz level because of the high frequency noise induced by dye jet.The aim of this thesis is to give an all-solid state alternative of dye lasers. For this purpose, two solutions have been studied:1. The first approach consists on the development of an intracavity frequency doubled singly resonant optical parametric oscillator (OPO) and frequency stabilized at the kHz level.2. The second approach consists on the development of a diode pumped Pr-doped fluoride laser.

The main motivation of this thesis is to study the long standing problem of mixed alkali effect (MAE) in oxyfluro vanadate glass systems from the point of view of structural arrangement and to investigate the effect of two rare earth ions, namely, erbium and europium on the structure of tellurium dioxide based glass. In glass science, it is well known that when one alkali in a glass matrix is gradually replaced by another alkali, leads to a non-linear variation in some of the physical properties. There are many a theories trying to explain this effect. Recently the renewed interest lies in explaining MAE in-terms of structural consideration. Rare earth (RE) ion doped glasses are of interest in a variety of applications in photonics because of the special optical properties exhibited by these materials. Atomic like f-f transitions of RE ions depend on the local environment of the these ions. A particular glass matrix may be able to bring out the optical properties of a RE ion better than the other matrix. In this regard structural characterization of a glass matrix with different RE ions for optical properties is of importance. Spectroscopic tech-niques are best suited to investigate structural arrangement in glasses and in this thesis we have used techniques like Raman, electron paramagnetic resonance (EPR), impedance, photoluminescence and UV- visible absorption spectroscopies. The thesis comprises of five chapters and an appendix. Chapter 1 consists of brief introduction of general properties of glasses and their behavior under different spectroscopic techniques. Chapter 2 deals with the sample preparation and the experimental techniques used in this work. Chapter 3 elaborates on the Raman and EPR spectroscopic studies on the structural arrangement of the mixed alkali oxyfluro vanadate glass systems. Chapter 4 focuses on the ac and electrical modulus analysis to study the MAE in the above samples. Chapter 5 deals with the optical spectroscopic techniques used to study the compatibility of RE ions (erbium and europium) with the tellurium dioxide based glass matrix. Chapter 1: Disordered materials pose a challenge to understand their structure mainly because of their random arrangement of the constituent units. In this chapter the glassy systems and the different experimental techniques used to study them are discussed in general. The behavior of glassy systems to the external stimuli in various frequency ranges is highlighted. A short review of mixed alkali effect in glasses mainly covering the advances in the last two decades is given. Brief outline of the theory of Raman, EPR and ac impedance spectroscopy are given. Chapter 2: This chapter discusses the major experimental techniques used in the thesis to study the glass systems at block diagram level. The Raman and EPR spectrometers are discussed. Experimental technique used in ac impedance measurement is outlined. Different methods of preparing glass are listed and melt quenching technique is discussed in detail. Chapter 3: This chapter discusses the results and analysis of Raman and EPR study in oxyfluoro vanadate glasses emphasizing MAE. The glass having batch formula 40V2O5 - 30BaF2 - (30 - x) LiF - xRbF (x = 0 – 30) is prepared by melt quenching technique. Raman spectroscopic study in back scattering geometry is performed to see the effect of alkali ions on the V – O bond length of VO6 polyhedra in the glass. The de-convoluted Raman peaks corresponding to V = O and VO2 are considered and the effect of alkali mixture on these bonds are studied. • The peak shift of V = O and VO2 bonds shows that V = O is affected only a little by the replacement of lithium (Li) by rubidium (Rb), while VO2 bond gets affected to a larger extent. • From the peak shift the most probable value of the bond length and the spread in it are estimated. The bond length corresponding to V = O is found to increase and that of VO2 decrease as a consequence of alkali replacement. • From the FWHM of the corresponding Raman peaks, it is concluded that O - Rb coordination sphere around VO6 polyhedra is more homogeneous than either O – Li or O - Li /Rb coordination. These results are published in J. Non-Cryst. Solids 370 (2013) 6. EPR studies on the samples are carried out in X band frequency and spin – Hamilto-nian parameters were extracted by simulating and fitting the EPR spectra to experimental data using EasySpin which is a Matlab toolbox. • it is observed that the ratio 4gjj=4g?, which is a measure of tetragonality of octa-hedral crystal symmetry of V2O5, varies non-monotonically with Rb content. • A model based on this observation is proposed. The essential idea of this model is that Rb atoms that are substituted for Li atoms initially prefer terminal positions over planar positions. Continued substitution then replaces planar Li atoms. It is seen that this model of “preferential substitution” explains the observation very well. • Another observation is that the EPR signal intensity, which is due to concentration of V4+ ions, also shows non-monotonous behavior with Rb content. This is also explained using preferential substitution, taking into consideration the oxidation states of the vanadium ions. • The value of 4gjj=4g?, is a minimum for all rubidium environments around V2O5, which infers that Rb coordination is more symmetric than all Li or Li−Rb. • A good correlation is found between Raman and EPR study of the above system. These results are published in J. Phys. Chem. A 118 (2014) 573. Chapter 4: The chapter brings out the results of ac conductivity and electrical mod-ulus study of MAE in the glass system mentioned above. The Agilent 4294A precision impedance analyzer operating in frequency range 40 Hz to 110 MHz, is used for per-forming impedance and capacitance experiments carried out in this thesis. Impedance measurements in our studies are performed in sandwich geometry. • Room temperature dc conductivity shows a decrease as Li is replaced by Rb and reaches its minimum - five orders less than its all Li value at 0.33 molar fraction of Rb, which is attributed to MAE. This observation is explained using the structural aspect. • Using the linear response theory the number of mobile ions participating in the conduction is estimated. • Imaginary part of the electrical modulus is fitted to Kohlrausch – Williams – Watts (KWW) relation by using a complex nonlinear least squares fitting procedure given by Bergmann. • The stretching parameter b estimated from the above procedure is found to exhibit MAE. The observed variation in b with Rb mole fraction is explained by taking into considerations the contributions from fast and slow processes, and coupling between different relaxing sites. The manuscript is under preparation. Chapter 5: This chapter illustrates the optical study of RE doped TeO2 based glasses to determine the suitability of a particular RE ion with a given glass matrix. TeO2 based glasses having a general formula (in mol %) 65TeO2 – 5BaF2 – 30ZnF2 (TBZ) were prepared by usual melt quenching technique. RE doping was done at the expense of TeO2. 3 mol % of Eu or Er are added to prepare RE doped glass. Raman, PL, UV-visible absorption studies are carried out on the glass samples. • From the peak shift, intensity variation and FWHM of the Raman spectra of the glass samples it is observed that Eu doped TBZ glass has a greater tendency towards depolymerizing the glass matrix by influencing the conversion of TeO4 units into the formation of TeO3 units. • PL spectra of the glass samples shows emission due to different possible transitions. Position of the peak of the de-convoluted spectra shows the position of the particular Stark component and the FWHM is a measure of the inhomogeneous broadening. • The UV-visible absorption spectra are used to calculate the optical density and fitted to the Mott equation to determine the band edge of the glass samples. It is seen that Eu doped TBZ glass has a lesser band gap than that of Er doped glass. The manuscript is submitted to Bul. Mat. Sci. Appendix : This consists of a collection of details of EDS study carried on the VBL series glasses and some MATLAB codes used to simulate the EPR spectrum for VBL series glasses.