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This thesis reports on the setup of a new ion trap apparatus designed for experiments with single ⁴⁰Ca⁺ ions to perform molecular spectroscopy. The calcium ion is laser cooled, allowing for sympathetic cooling of the nonfluorescing molecular ion. The aim of these experiments is to explore loading and identifying molecular ions in RF-Paul traps, as well as developing new spectroscopic tools to measure transitions of molecular ions via the fluorescence of co-trapped ⁴⁰Ca⁺ ions. Ground state cooling of a mixed ion pair is implemented as a first step towards increasing the sensitivity of our technique to the level necessary to measure transitions with low scattering rates (like those present in molecular ions). Doppler cooling on the S(1/2)->P(1/2) transition of the calcium ion results in the formation of a Coulomb crystal, the behavior of which may be used to infer properties of the molecular ion. Following cooling, sideband spectroscopy on the narrow S(1/2)->D(5/2) quadrupole transition of calcium may be used to identify the mass of single molecular ions. This method is verified via a non-destructive measurement on ⁴⁰CaH⁺ and ⁴⁰Ca¹⁶O⁺. The normal modes of the Coulomb crystal can also be used to extract information from the target ion to the control ion. By driving the blue side of a transition, laser induced heating can be put into the two ion system, which leads to changes in fluorescence of the ⁴⁰Ca⁺ ion, first demonstrated with two Ca⁺ isotopes. Increasing the sensitivity of this technique requires ground state cooling of both the ⁴⁰Ca⁺ ion and the ion of interest, enabling the transfer of the ion's motional state into the ground state with high probability. This thesis demonstrates ground state cooling of the atomic ion and sympathetic cooling of a second ion (⁴⁴Ca⁺). Once in the ground state, heating of the Coulomb crystal by scattering photons off of the spectroscopy ion can be measured by monitoring the resolved motional sidebands of the S(1/2)->D(5/2) transition of ⁴⁰Ca⁺, allowing for spectral lines to be inferred. Future experiments will investigate this technique with molecular ions.

This thesis aims to investigate the possibility of developing spectroscopic techniques for trace gas detection, with particular emphasis on their applicability to breath analysis and medical diagnostics. Whilst key breath molecules such as methane and carbon dioxide will feature throughout this work, the focus of the research is on the detection of breath acetone, a molecule strongly linked with the diabetic condition. Preliminary studies into the suitability of cavity enhanced absorption spectroscopy (CEAS) for the analysis of breath are carried out on methane, a molecule found in varying quantities in breath depending on whether the subject is a methane-producer or not. A telecommunications near-infrared semiconductor diode laser (1.6 µm) is used with an optical cavity based detection system to probe transitions within the vibrational overtone of methane. Achieving a minimum detectable sensitivity of 600 ppb, the device is used to analyse the breath of 48 volunteers, identifying approximately one in three as methane producers. Following this, a second type of laser source, the novel and widely tunable Digital Supermode Distributed Bragg Reflector (DS-DBR) laser, is characterised and the first demonstration of its use in spectroscopy documented. Particular emphasis is given to its application to CEAS and to probing the transitions of the two Fermi resonance components of the CO_2 3ν_1 + ν_3 combination bands found within the spectral range (1.56 - 1.61 µm) of the laser, providing the means to determine accurate ^{13}CO_2/^{12}CO_2 ratios for use in the urea breath test. Not all molecules exhibit narrow, well-resolved ro-vibrational transitions and the next section of the thesis focuses on the detection of molecules, such as acetone, with broad, congested absorption features which are not readily discernible using narrowband laser sources. To provide the necessary specificity for these molecules, two types of broadband source, a Superluminescent Light Emitting Diode (SLED) and a Supercontinuum source (SC), both emitting over the 1.6 - 1.7 µm region, are used in the development of a series of broadband cavity enhanced absorption (BB-CEAS) spectrometers. The three broadband absorbers investigated here, butadiene, acetone and isoprene, all exhibit overtone and combination bands in this spectral region and direct absorption measurements are taken to determine absorption cross-sections for all three molecules. The first BB-CEAS spectrometer couples the SLED device with a dispersive monochromator, attaining a minimum detectable sensitivity of 6 x 10^{-8} cm^{-1}, which is further enhanced to 1.5 x 10^{-8} cm^{-1} on replacing the monochromator with a Fourier Transform interferometer. The spectral coverage is then extended to 1.5 - 1.7 µm by coupling the first SLED with a second device, providing a demonstration of simultaneous multiple species detection. Finally, a SC source is used to provide greater power and uniform spectral intensity, resulting in an improved minimum detectable sensitivity of 5 x 10^{-9} cm^{-1}, or 200 ppb, 400 ppb and 200 ppb for butadiene, acetone and isoprene respectively. This device is then applied to acetone-enriched breath samples; the resulting spectra are fitted with a simulation to return the acetone levels present in the breath-matrix. Following this, the development of a prototype breath acetone analyser, carried out at Oxford Medical Diagnostics Ltd. (OMD), is described. To fulfill the requirements of a compact and commercially-viable device, a diode laser-based system is used, which necessitates a thorough investigation into all possible sources of absorption level change. Most notably, this includes a study into the removal and negating of interfering species, such as water vapour, and to a lesser extent, methane. A novel solution is presented, utilising a water-removal device in conjunction with molecular sieve so that each breath sample generates its own background, which has allowed breath acetone levels to be measured within an uncertainty of 200 ppb. Spectroscopic detection then moves to the mid-infrared with the demonstration of a continuous wave 8 µm quantum cascade laser, which allows the larger absorption cross-sections associated with fundamental vibrational modes to be probed. Following the laser's characterisation using methane, including a wavelength modulation spectroscopy study, the low effective laser linewidth is utilised to resolve rotational structure in low pressure samples of pure acetone. Absorption cross-sections are determined before the sensitivity of the system is enhanced for the detection of dilute concentrations of acetone using two types of multipass cells, firstly a White cell and secondly a home-built Herriott cell. This allows an acetone minimum detectable absorption of 350 ppb and 20 ppb to be attained, respectively. Following this, an optical cavity is constructed and, on treating breath samples in a water-removal device prior to analysis, breath acetone levels determined and corroborated with a mass spectrometer. Finally, a preliminary study probing acetone in the ultraviolet is presented. Utilising an LED centred at 280 nm with a low finesse optical cavity and an imaging spectrograph, detection of 25 ppm of acetone is demonstrated and possible vibronic structure resolved. Combining large absorption cross-sections with the potential to be compact and commercially viable, further development of this arrangement could ultimately represent the optimum solution for breath acetone detection.

by Clifford Sanders. / Thesis (M.S.)--Florida Atlantic University, 2009. / Includes bibliography. / Electronic reproduction. Boca Raton, Fla., 2009. Mode of access: World Wide Web. / Ethylene is the simplest alkene. The carbon-carbon double bond is ubiquitous in the field of chemistry. Ethylene serves as the basis for understanding these molecules. Thus, the assignment of the electronic transitions in ethylene is an important endeavor that many scientists have undertaken, but are yet to decipher theoretically or experimentally. Synchrotron Radiation in the vacuum ultraviolet region allows for magnetic circular dichroism (MCD) measurements of ethylene and other simple alkenes. Studies of ethylene and propylene revealed that the páap* (AgáaB1u ethylene notation) transition is not the lowest energy transition. The páa3s(R) (AgáaB3u ethylene notation) is the lowest energy transition. To further this investigation, MCD and absorption measurement were carried out on isobutene. The isobutene spectra clearly showed four electronic transitions in the 156 to 212 nm wavelength region. These four isobutene transitions have been assigned as páa3s, páap*, páa3p(Sv (Band páa3px proceeding from lower energy to higher energy. The present results support the assignments in ethylene and propylene.

Neste trabalho usamos simulações computacionais para estudar inicialmente a estrutura das redes de ligação de hidrogênio (HB) formadas pelas misturas de metanol--água e 1-propanol--água e em seguida como essas misturas afetam as propriedades eletrônicas da sonda solvatocrômica 1-metilquinolin-8-olato (QB). Para a primeira parte fizemos uso do formalismo de redes complexas na análise das redes de HB formadas nas misturas. Com essa abordagem foi possível verificar o comportamento do sistema como um todo em diferentes concentrações de água nas misturas por meio do cálculo de diversas propriedades de rede. Da análise dessas propriedades pudemos, por exemplo, constatar bastante similaridade na conectividade dos dois tipos de misturas, entender melhor comportamentos anômalos, observar microssegregação, e verificar uma mudança na conectividade das moléculas de água em misturas com 1-propanol. Na parte seguinte, onde investigamos os efeitos das misturas nas propriedades eletrônicas da QB, foi necessário modelar uma parametrização adequada para o campo de força da sonda utilizado nas simulações. Essa parametrização incluiu adaptação de parâmetros geométricos da sonda e do conjunto de cargas atômicas polarizadas. Nessa último tópico, adaptamos o procedimento iterativo de polarização, dentro de uma abordagem sequencial de mecânica quântica e mecânica molecular. De posse desses parâmetros realizamos a simulação da QB em misturas de álcool--água em sete frações molares de água distintas. Analisamos a distribuição do solvente ao redor da QB e a solvatação preferencial. Em configurações amostradas nas simulações calculamos os efeitos das misturas no dipolo induzido, comprimento de onda de excitação eletrônica, índices globais de reatividade e blindagem magnética da QB. Fomos especialmente atentos em correlacionar esses efeitos com as propriedades estruturais do sistema, e percebemos quais das propriedades eletrônicas calculadas para a QB podem ser divididas nas duas classes: as que são mais susceptíveis às interações de curto alcance, como HB com o solvente e a solvatação preferencial; e as que são mais susceptíveis às interações de longo alcance. / In this work we use computer simulations to initially study the hydrogen bond (HB) networks formed in mixtures of methanol--water and 1-propanol--water and subsequently how these mixtures can affect the electronic properties of the solvatocromic probe 1-methylquinolin-8-olate (QB). For the first part, we use the complex networks formalism to analyse HB networks formed in mixtures. With this approach it was possible to verify the behavior of the system as a whole in different water concentrations by calculating several network properties. As a result we note, for example, the connectivities of the two types of mixtures are quite similar. We were also able to better understand the system anomalous behavior, observe microsegregation and verify a change in the connectivity of water molecules in mixtures with 1-propanol. In the following part, in which we investigated the effects of mixtures on the electronic properties of the QB, it was necessary to model an appropriate parameterization for the force field of the probe used in the simulations. This parameterization included adjustments for both the geometric parameters and the polarized atomic charges. In this last topic, we adapt the iterative polarization process within a sequential approach using quantum mechanics and molecular mechanics. With these parameters we performed the simulation of the QB in mixtures of alcohol--water in seven distinct water fractions. We analyzed the solvent distribution around the QB and the preferential solvation. Using configurations sampled in the simulations we calculate the mixtures effects on induced dipole, wavelength electronic excitation, global indices of reactivity and magnetic shielding of the QB. We were especially attentive to correlate these effects with the structural properties of the system, and realize that of the electronic properties calculated for the QB can be divided into two classes: those that are more susceptible to short-range interactions, such as solute-solvent HB and preferential solvation, and those which are more susceptible to long-range interactions.

As taxas de aniquilação de pósitrons lentos em moléculas são aprimoradas para pósitrons incidentes com energias específicas. Segundo a visão atual do problema, tal fenômeno corresponde a um acoplamento contínuo-discreto do pósitron acompanhado com transições vibracionais na molécula. Este mecanismo é conhecido como ressonância vibracional de Feshbach. Existem basicamente três aspectos que foram desenvolvidos no tempo do mestrado. O primeiro foi a proposta de um modelo analítico para o cálculo das larguras de acoplamento do pósitron em transições vibracionais Raman-Ativas mostrando que sua estimativa pode ser feita a partir de parâmetros da molécula isolada e sua ordem de grandeza é equivalente ao das larguras associadas a transições IR-ativas. O segundo aspecto desenvolvido é a estimativa dos efeitos de correlação elétron pósitron na dinâmica vibracional da molécula principalmente definindo acoplamentos entre modos vibracionais que permitiram a excitação de modos vibracionais, de outro modo, inativos. Foram apresentados, como exemplo, os efeitos de correlação nas moléculas de LiH e NaH. Também foi feita uma estimativa das propriedades de estrutura eletrônica e vibracional para moléculas de mais de um modo normal de vibração. Especificamente, para a molécula de HCN no nível de cálculo MP2, apresentando um método para aproximar, no nível harmônico, os efeitos de correlação elétron-pósitron na superfície de energia potencial. / The annihilation rates for slow positrons in molecules are enhanced for positrons with specific energies. According to the current view of the problem, such phenomenon corresponds to a positron continuum-discrete coupling, accompanied by a coupling of the molecule vibrational states. Such mechanism is described by a vibrational Feshbach resonance. There are, basically, three developed topics in the time of the master degree. The first one is proposing an analytical model for the calculation of the coupling widths of the positron with Raman-Active vibrational transitions. It is showed that this estimation could be computed by some parameters of a single molecule and its order of magnitude is equivalent to coupling widths for IR-active transitions. The second developed topic is the estimation of electron-positron correlation effects in the vibrational dynamics of the molecule mainly by defining couplings between modes which allows excitation of vibrational states, otherwise, inactive. As an example, the effects of the correlation in the NaH and LiH molecules have been presented. An estimation of electronic structure and vibrational properties was also made for molecules with many vibrational normal modes. As an example, the HCN molecule at MP2 level calculation was taken, showing a method to approximate the electron-positron correlation effects, on the potential energy surface, at harmonic level, the electron-positron correlation effects on the potential energy surface.

Neste trabalho são apresentados estudos referentes a dois grupos de sistemas contendo dióxido de enxofre como principal foco, tendo em vista a importância desta molécula em sistemas ambientais e sua caracteristicas químicas interessantes como seu caráter anfotérico e sua capacidade de interação com sistemas inorgânicos via oxigênio ou enxofre. Tendo como principais feramentas as espectroscopias vibracionais (espalhamento Raman e absorção no Infravermelho), eletrônica (UV-VIS) e Ressonância Magnética Nuclear (RMN) investigou-se as interações inter e intramoleculares dos sistemas de interesse. Primeiramente foi investigada a interação do SO2 com aminoálcoois, sendo que estes sistemas apresentam boa capacidade de absorção do SO2. Destaca-se a formação de zwitteríons pela interação do SO2 com o grupamento alcoólico da molécula, observado apenas quando da presença de grupo amino para estabilização da separação de cargas gerada, mostou-se que o poduto fomado é mais estavél quanto menor a separação das cargas e menor o impedimento estérico na amina. Este sistema foi investigado quanto a sua revesibilidade, que foi observada sempre acompanhada de degradação do aminoálcool. O segundo sistema refere-se a interação do dióxido de enxofre com complexos de níquel em dois estados de oxidação (II/III) com ligante macrocíclico cyclam (1,4,8,11- Tetraazaciclotetradecano); o diferencial deste estudo frente a outros apresentados na literatura é a análise das reações em meio anidro. Nos experimentos em meio livre de O2 obseva-se a redução do complexo de Ni (III) a Ni(II) e em meio contendo O2 observa-se a oxidação do complexo de Ni(II) a Ni(III), mostrando a importância do O2 para a manutenção de um ciclo catalítico capaz de oxidar SO2 a SO42-. Os resultados aqui apresentados indicam que os mecanismos em meio anidro são bastante semelhantes aos observados em meio aquoso. / In this work we focus on two sulfur dioxide containing systems due to the relevance of this molecule in environmental science and its interesting physico-chemical properties as its amphoteric characteristic and ability to interact with inorganic systems through oxygen or sulfur atoms. The main tools for investigation was vibrational spectroscopy (Raman scattering and Infrared absorption), electronic spectroscopy (UV-VIS) and Nuclear Magnetic Resonance (NMR), whereby the intra and intermolecular interactions were probed. The first subject of investigation was the study of interactions between SO2 and amino alcohol. This system shows great ability to capture SO2, highlighting the zwitterionic formation due to the bonding of SO2 via the alcoholic part of the amino alcohol molecule, what is only possible due to the presence of the amino group to stabilize the charge separation, the stability of the poduct depends on the steric hindrance and on the charge separation. The reversibility of the system was investigated and it was always accompanied by degradation of the amino alcohol. The second system consists in the investigation of interactions between SO2 and two nickel-cyclam (1,4,8,11-Tetraazacyclotetradecane) complexes, where the metal is in different oxidation states (II/III). This work is different from previous in the sense that the analyses are carried out in anhydrous environment. In O2 free environment we were able to see the reduction of Ni(III) to Ni(II) complex, and in presence of O2 the oxidation of Ni(II) to Ni(III) complex occurs, showing the relevance of O2 to catalytic cicle that is able to transform SO2 to SO42-. Our results suggest that the mechanisms in aqueous and nonaqueous environments are very similar.

Neste trabalho são apresentados estudos referentes a dois grupos de sistemas contendo dióxido de enxofre como principal foco, tendo em vista a importância desta molécula em sistemas ambientais e sua caracteristicas químicas interessantes como seu caráter anfotérico e sua capacidade de interação com sistemas inorgânicos via oxigênio ou enxofre. Tendo como principais feramentas as espectroscopias vibracionais (espalhamento Raman e absorção no Infravermelho), eletrônica (UV-VIS) e Ressonância Magnética Nuclear (RMN) investigou-se as interações inter e intramoleculares dos sistemas de interesse. Primeiramente foi investigada a interação do SO2 com aminoálcoois, sendo que estes sistemas apresentam boa capacidade de absorção do SO2. Destaca-se a formação de zwitteríons pela interação do SO2 com o grupamento alcoólico da molécula, observado apenas quando da presença de grupo amino para estabilização da separação de cargas gerada, mostou-se que o poduto fomado é mais estavél quanto menor a separação das cargas e menor o impedimento estérico na amina. Este sistema foi investigado quanto a sua revesibilidade, que foi observada sempre acompanhada de degradação do aminoálcool. O segundo sistema refere-se a interação do dióxido de enxofre com complexos de níquel em dois estados de oxidação (II/III) com ligante macrocíclico cyclam (1,4,8,11- Tetraazaciclotetradecano); o diferencial deste estudo frente a outros apresentados na literatura é a análise das reações em meio anidro. Nos experimentos em meio livre de O2 obseva-se a redução do complexo de Ni (III) a Ni(II) e em meio contendo O2 observa-se a oxidação do complexo de Ni(II) a Ni(III), mostrando a importância do O2 para a manutenção de um ciclo catalítico capaz de oxidar SO2 a SO42-. Os resultados aqui apresentados indicam que os mecanismos em meio anidro são bastante semelhantes aos observados em meio aquoso. / In this work we focus on two sulfur dioxide containing systems due to the relevance of this molecule in environmental science and its interesting physico-chemical properties as its amphoteric characteristic and ability to interact with inorganic systems through oxygen or sulfur atoms. The main tools for investigation was vibrational spectroscopy (Raman scattering and Infrared absorption), electronic spectroscopy (UV-VIS) and Nuclear Magnetic Resonance (NMR), whereby the intra and intermolecular interactions were probed. The first subject of investigation was the study of interactions between SO2 and amino alcohol. This system shows great ability to capture SO2, highlighting the zwitterionic formation due to the bonding of SO2 via the alcoholic part of the amino alcohol molecule, what is only possible due to the presence of the amino group to stabilize the charge separation, the stability of the poduct depends on the steric hindrance and on the charge separation. The reversibility of the system was investigated and it was always accompanied by degradation of the amino alcohol. The second system consists in the investigation of interactions between SO2 and two nickel-cyclam (1,4,8,11-Tetraazacyclotetradecane) complexes, where the metal is in different oxidation states (II/III). This work is different from previous in the sense that the analyses are carried out in anhydrous environment. In O2 free environment we were able to see the reduction of Ni(III) to Ni(II) complex, and in presence of O2 the oxidation of Ni(II) to Ni(III) complex occurs, showing the relevance of O2 to catalytic cicle that is able to transform SO2 to SO42-. Our results suggest that the mechanisms in aqueous and nonaqueous environments are very similar.

<div>The chemical complexity of hydrocarbon fuels and the fast-expanding list of potential plantderived biofuels pose a challenge to the scientific community seeking to provide a molecular understanding of their combustion. More refined spectroscopic tools and methodologies must be developed to selectively detect and characterize the widening array of fuel components and combustion reactive intermediates. The direct relationship between molecular structure and rotational frequencies makes rotational spectroscopy highly structural specific; therefore, it offers a powerful means of characterizing pyrolysis ntermediates. This thesis describes experimental work using broadband microwave spectroscopy to address a number of challenging problems in the spectroscopy of gas complex mixtures.</div><div><br></div><div>Usually, the observed rotational spectra contain contributions from many distinct species, creating a complicated spectrum with interleaved transitions that make spectral assignment challenging. To assist with the process, a protocol called “strong-field coherence breaking” (SFCB) has been developed. It exploits multi-resonance effects that accompany sweeping the microwave radiation under strong-field conditions to output a set of transitions that can confidently be assigned to a single component in a mixture, thereby reducing the spectral assignment time.</div><div><br></div><div>The broadband chirped pulse Fourier transform microwave (CP-FTMW) spectra of guaiacol, syringol, 4-methyl guaiacol, 4-vinyl guaiacol were recorded under jet- cooled conditions over the 2-18 GHz frequency range. Using data from the 13C isotopomers the r0 structure of guaiacol was determined by means of a Kraitchman analysis. The tunneling due to OH hindered rotation was observed in syringol and the V2 barrier was deduced to be 50% greater than phenol’s barrier. This is due to the intramolecular H-bonding between the hydroxy and the methoxy groups. The internal rotation barrier for the methyl group for 4-methyl guaiacol was also determined. Moreover, the spectral assignment of the two conformers of 4-vinyl guaiacol was sped-up by using SFCB. The main structural insight from these lignin-related molecules was that polar substituents dictate the magnitude and type of structural shift that occurs relative to that of the unsubstituted aromatic ring.</div><div><br></div><div>In the next part of my work, the pyrolysis of 2-methoxy furan was carried out over the 300-1600 K temperature range, with microwave detection in the 2-18 GHz frequency range, using hightemperature flash pyrolysis micro-reactor coupled with a supersonic expansion. The SFCB technique was used to analyze and speed up the line assignment. The 2-furanyloxy radical, a primary, resonance-stabilized radical formed by loss of a methyl group in the pyrolysis of 2-methoxy furan, was detected and its molecular parameters were determined.</div><div><br></div><div>Finally, a unique setup that combines the high-resolution spectroscopic data provided by chirped pulse Fourier transform microwave (CP-FTMW) spectroscopy with photoionization mass spectra from a vacuum ultraviolet (VUV) time-of-flight mass spectrometer (TOF-MS) was used to find optimal conditions to detect reactive intermediates and make full assignments for the microwave spectra of phenoxy radical and o-hydroxy phenoxy radical over the 2-18 GHz range. Phenoxy radical was generated through the pyrolysis of anisole and allyl phenyl ether. Using a combination of data from 13C isotopomers and fully deuterated phenoxy radical, in combination with high level ab initio calculations, a near-complete r0 structure for the radical was obtained. The structural data point to the radical being a primarily carbon-centered rather than oxygencentered radical. Using guaiacol as precursor, we studied the spectroscopy of the o-hydroxy phenoxy radical, whose structural data is compared with that of phenoxy to understand the role played by the hydroxyl group in modifying the resonance stabilization of the radical.</div><div><br></div>

abstract: Transient molecules are of great importance having proposed applications in quantum science and technology and tests of fundamental physics. In the present dissertation, the transient molecules studied are SrOH, ThF, ThCl, YbF and YbOH; each having been selected because of their proposed application. Specifically, SrOH is a candidate of constructing a molecular magneto-optical trap (MOT). The simple actinide molecules, ThF and ThCl, were selected as ligand bonding model systems to gain insight into chemical processing of Spent Nuclear Fuel. The lanthanides YbF and YbOH are venues for the determination of electron electric dipole moment (eEDM) and the studies in this dissertation provide the requisite properties for those experiments. Intense supersonic molecular beams of these transient molecules were generated via laser ablation and spectroscopically characterized using a novel medium-resolution two-dimensional (2D) spectroscopic approach, as well as high-resolution laser induced fluorescence (LIF). The 2D medium resolution approach, which was used in the studies SrOH, ThF, ThCl and YbOH, uses a multiplexing method that simultaneously records dispersed fluorescence and excitation spectra. A significant advantage of 2D-LIF imaging is that all the electronics states can be targeted to determine the electronics states and associated vibrational spacing individually. Consequently, in the 2D spectra of ThF, ThCl and YbOH, several previously unobserved band systems have been detected in one single scan. For the DF spectra of SrOH and YbOH, the determined branching ratios show that the transitions of these molecules are diagonal (i.e. Δv=0), which is essential for the proposed potential for laser cooling. In the high-resolution of YbF, ThF, ThCl and SrOH optical spectra were recorded to an accuracy of ±30 MHz, which represents an unprecedented precision of 1:10+8. In addition to field free spectra, optical Stark and Zeeman studies were performed to determine the most fundamental magneto-and electro-static properties. Effective Hamiltonian operators were employed to analyze the recorded spectra and determine the spectroscopic parameters. This data set also establishes a contribution toward developing new computational methodologies for treating relativistic effects and electron correlation. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2019