This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.

This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.

Thesis (Ph.D.); Submitted to the Massachusetts Inst. of Tech., Cambridge, MA (US); 1 Oct 2003. / Published through the Information Bridge: DOE Scientific and Technical Information. "JLAB-PHY-03-174" "DOE/ER/40150-2571" Zhengwei Chai. 10/01/2003. Report is also available in paper and microfiche from NTIS.

This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.

Le secteur du bâtiment représente 35% des la consommations énergétiques dans les pays membres de l’agence international de l’énergie en 2010 et 39,8% aux Etats-Unis en 2015. Plus de 50% de cette consommation a été utilisée pour la production de chaleur et de froid. Néanmoins cette consommation peut être réduite par l'amélioration la performance énergétique du bâtiment. La performance thermique de l'enveloppe du bâtiment joue un rôle primordial. Par conséquent, le diagnostic thermique de l'enveloppe du bâtiment est nécessaire pour, par exemple, la réception de nouvelles constructions, l'amélioration de la performance énergétique des anciens bâtiments, ainsi que la vente et la location des logements. Pourtant, il existe très peu de méthodes quantitatives pour la caractérisation des parois épaisses. L'objectif de cette étude est d'explorer des méthodes quantitatives innovantes de diagnostic thermique de l'enveloppe du bâtiment. Des mesures expérimentales ont été réalisées en laboratoire (à l’IFSTTAR à Nantes) et in situ (à l’IUT de Bordeaux). Différents capteurs et méthodes d'instrumentation ont été étudiés pour mesurer la densité de flux et la température de surfaces des parois, afin de procurer des recommandations pour le choix des capteurs ainsi que des protocoles de traitement de données. A partir des données mesurées (température et densité de flux des surfaces de l'enveloppe), trois approches numériques ont été proposées pour estimer des paramètres thermiques des parois multicouches épaisses : par méthode inverse, par réponse à un échelon et par réponse impulsionnelle. En outre, une méthode innovante non-destructive utilisant la rayonnement térahertz a été étudiée. Les mesures ont été effectuées au sein du laboratoire I2M. Cette méthode permet de caractériser le coefficient d'absorption des matériaux constructifs ordinaires comme isolation, plâtre, béton, bois… Elle pourrait postérieurement être combinée avec une méthode thermique pour apporter des informations complémentaires. / Buildings represent a large share in terms of energy consumption, such as 35% in the member countries of IEA (2010) and 39.8% in U.S. (2015). Climate controlling (space heating and space cooling) occupies more than half of the consumption. While this consumption can be reduced by improving the building energy efficiency, in which the thermal performance of building envelope plays a critical role. Therefore, the thermal diagnosis of building envelope is of great important, for example, in the case of new building accreditation, retrofitting energy efficiency of old building and the building resale and renting. However, very few diagnostic methods exist for the characterization of thick walls. The present measurement standards that based on steady state heat transfer regime need a long time (several days). The classical transient technologies, such as flash method, are difficult to implement on the walls because of the large thickness of walls and the complex conditions in situ. This thesis aims to explore innovative methodologies for thermal quantitative diagnosis of building envelope. Two experimental cases were carried out: one is in laboratory (IFSTTAR, Nantes) and the other is in situ (IUT, Bordeaux). Different sensors and instruments were studied to measure the wall heat flux and surface temperature, and provided some guidelines for the choice of sensors and data processing protocols as well. Using these measured data, three estimation approaches were proposed to estimate the thermal parameters of the multilayer thick wall: pulse response curve method, step response curve method and inverse method, which can be applied for different diagnostic situations. In addition, an innovative NDE (non-destructive evaluation) method using terahertz (THz) radiation was also investigated. Measurements were carried out in I2M laboratory to characterize the absorption coefficient of standard building materials (insulation, plaster, concrete, wood ...). This THz method can be combined with a previous thermal method to provide some complementary information.

La mesure de l’émittance transverse du faisceau est fondamentale pour tous les accélérateurs, et en particulier pour les collisionneurs, son évaluation precise étant essentielle pour maximiser la luminosité et ainsi la performance des faisceaux de collision.Le rayonnement synchrotron (SR) est un outil polyvalent pour le diagnostic non-destructif de faisceau, exploité au CERN pour mesurer la taille des faisceaux de protons des deux machines du complexe dont l’énergie est la plus élevée, le SPS et le LHC où l’intensité du faisceau ne permet plus les techniques invasives.Le travail de thèse documenté dans ce rapport s’est concentré sur la conception, le développement, la caractérisation et l’optimisation des moniteurs de taille de faisceau basés sur le SR. Cette étude est fondée sur un ensemble de calculs théoriques, de simulation numériques et d’expériences conduite au sein des laboratoires et accélérateurs du CERN. Un outil de simulation puissant a été développé, combinant des logiciels classiques de simulation de SR et de propagation optique, permettant ainsi la caractérisation complète d’un moniteur SR de la source jusqu’au détecteur.La source SR a pu être entièrement caractérisée par cette technique, puis les résultats validés par observation directe et par la calibration à basse énergie basée sur les mesures effectuées avec les wire-scanners (WS), qui sont la référence en terme de mesure de taille de faisceau, ou telles que la comparaison directe avec la taille des faisceaux obtenue par déconvolution de la luminosité instantanée du LHC.Avec l’augmentation de l’énergie dans le LHC (7TeV), le faisceau verra sa taille diminuer jusqu’à atteindre la limite de la technique d’imagerie du SR. Ainsi, plusieurs solutions ont été investiguées afin d’améliorer la performance du système: la sélection d’une des deux polarisations du SR, la réduction des effets liés à la profondeur de champ par l’utilisation de fentes optiques et l’utilisation d’une longueur d’onde réduite à 250 nm.En parallèle à l’effort de réduction de la diffraction optique, le miroir d’extraction du SR qui s’était avéré être la source principale des aberrations du système a été entièrement reconçu. En effet, la détérioration du miroir a été causée par son couplage EM avec les champs du faisceau, ce qui a conduit à une surchauffe du coating et à sa dégradation. Une nouvelle géométrie de miroir et de son support permettant une douce transition en termes de couplage d’impédance longitudinale dans le beam pipe a été définie et caractérisée par la technique dite du “streched wire”. Egalement, comme méthode alternative à l’imagerie directe, un nouveau moniteur basé sur la technique d’interférométrie à deux fentes du SR, non limité par la diffraction, a également été développé. Le principe de cette méthode est basé sur la relation directe entre la visibilité des franges d’interférence et la taille de faisceau.Comme l’emittance du faisceau est la donnée d’intérêt pour la performance du LHC, il est aussi important de caractériser avec précision l’optique du LHC à la source du SR. Dans ce but, la méthode “K-modulation” a été utilisée pour la première fois au LHC en IR4. Les β ont été mesurés à l’emplacement de tous les quadrupoles et ont été évalués via deux algorithmes de propagation différents au BSRT et au WS. / Measuring the beam transverse emittance is fundamental in every accelerator, in particular for colliders, where its precise determination is essential to maximize the luminosity and thus the performance of the colliding beams.
 Synchrotron Radiation (SR) is a versatile tool for non-destructive beam diagnostics, since its characteristics are closely related to those of the source beam. At CERN, being the only available diagnostics at high beam intensity and energy, SR monitors are exploited as the proton beam size monitor of the two higher energy machines, the Super Proton Synchrotron (SPS) and the Large Hadron Collider (LHC). The thesis work documented in this report focused on the design, development, characterization and optimization of these beam size monitors. Such studies were based on a comprehensive set of theoretical calculations, numerical simulations and experiments.A powerful simulation tool has been developed combining conventional softwares for SR simulation and optics design, thus allowing the description of an SR monitor from its source up to the detector. 
The simulations were confirmed by direct observations, and a detailed performance studies of the operational SR imaging monitor in the LHC, where different techniques for experimentally validating the system were applied, such as cross-calibrations with the wire scanners at low intensity (that are considered as a reference) and direct comparison with beam sizes de-convoluted from the LHC luminosity measurements.In 2015, the beam sizes to be measured with the further increase of the LHC beam energy to 7 TeV will decrease down to ∼190 μm. In these conditions, the SR imaging technique was found at its limits of applicability since the error on the beam size determination is proportional to the ratio of the system resolution and the measured beam size. Therefore, various solutions were probed to improve the system’s performance such as the choice of one light polarization, the reduction of depth of field effect and the reduction of the imaging wavelength down to 250 nm.In parallel to reducing the diffraction contribution to the resolution broadening, the extraction mirror, found as the main sources of aberrations in the system was redesigned. Its failure was caused by the EM coupling with the beam’s fields that led to overheating and deterioration of the coating. A new system’s geometry featuring a smoother transition in the beam pipe was qualified in terms of longitudinal coupling impedance via the stretched wire technique. A comparison with the older system was carried out and resulted in a reduction of the total power dissipated in the extraction system by at least a factor of four.A new, non-diffraction limited, SR-based monitor based on double slit interferometry was designed as well as an alternative method to the direct imaging. Its principle is based on the direct relation between the interferogram fringes visibility and the beam size.Since the beam emittance is the physical quantity of interest in the performance analysis of the LHC, determining the optical functions at the SR monitors is as relevant as measuring the beam size. The “K-modulation” method for the optical function determination was applied for the first time in the LHC IR4, where most of the profile monitors sit. The βs at the quadrupoles were measured and via two different propagation algorithms the βs at the BSRT and the WS were obtained reducing significantly the uncertainty at the monitors location.

La mesure de l’émittance transverse du faisceau est fondamentale pour tous les accélérateurs, et en particulier pour les collisionneurs, son évaluation precise étant essentielle pour maximiser la luminosité et ainsi la performance des faisceaux de collision.Le rayonnement synchrotron (SR) est un outil polyvalent pour le diagnostic non-destructif de faisceau, exploité au CERN pour mesurer la taille des faisceaux de protons des deux machines du complexe dont l’énergie est la plus élevée, le SPS et le LHC où l’intensité du faisceau ne permet plus les techniques invasives.Le travail de thèse documenté dans ce rapport s’est concentré sur la conception, le développement, la caractérisation et l’optimisation des moniteurs de taille de faisceau basés sur le SR. Cette étude est fondée sur un ensemble de calculs théoriques, de simulation numériques et d’expériences conduite au sein des laboratoires et accélérateurs du CERN. Un outil de simulation puissant a été développé, combinant des logiciels classiques de simulation de SR et de propagation optique, permettant ainsi la caractérisation complète d’un moniteur SR de la source jusqu’au détecteur.La source SR a pu être entièrement caractérisée par cette technique, puis les résultats validés par observation directe et par la calibration à basse énergie basée sur les mesures effectuées avec les wire-scanners (WS), qui sont la référence en terme de mesure de taille de faisceau, ou telles que la comparaison directe avec la taille des faisceaux obtenue par déconvolution de la luminosité instantanée du LHC.Avec l’augmentation de l’énergie dans le LHC (7TeV), le faisceau verra sa taille diminuer jusqu’à atteindre la limite de la technique d’imagerie du SR. Ainsi, plusieurs solutions ont été investiguées afin d’améliorer la performance du système: la sélection d’une des deux polarisations du SR, la réduction des effets liés à la profondeur de champ par l’utilisation de fentes optiques et l’utilisation d’une longueur d’onde réduite à 250 nm.En parallèle à l’effort de réduction de la diffraction optique, le miroir d’extraction du SR qui s’était avéré être la source principale des aberrations du système a été entièrement reconçu. En effet, la détérioration du miroir a été causée par son couplage EM avec les champs du faisceau, ce qui a conduit à une surchauffe du coating et à sa dégradation. Une nouvelle géométrie de miroir et de son support permettant une douce transition en termes de couplage d’impédance longitudinale dans le beam pipe a été définie et caractérisée par la technique dite du “streched wire”. Egalement, comme méthode alternative à l’imagerie directe, un nouveau moniteur basé sur la technique d’interférométrie à deux fentes du SR, non limité par la diffraction, a également été développé. Le principe de cette méthode est basé sur la relation directe entre la visibilité des franges d’interférence et la taille de faisceau.Comme l’emittance du faisceau est la donnée d’intérêt pour la performance du LHC, il est aussi important de caractériser avec précision l’optique du LHC à la source du SR. Dans ce but, la méthode “K-modulation” a été utilisée pour la première fois au LHC en IR4. Les β ont été mesurés à l’emplacement de tous les quadrupoles et ont été évalués via deux algorithmes de propagation différents au BSRT et au WS. / Measuring the beam transverse emittance is fundamental in every accelerator, in particular for colliders, where its precise determination is essential to maximize the luminosity and thus the performance of the colliding beams.
 Synchrotron Radiation (SR) is a versatile tool for non-destructive beam diagnostics, since its characteristics are closely related to those of the source beam. At CERN, being the only available diagnostics at high beam intensity and energy, SR monitors are exploited as the proton beam size monitor of the two higher energy machines, the Super Proton Synchrotron (SPS) and the Large Hadron Collider (LHC). The thesis work documented in this report focused on the design, development, characterization and optimization of these beam size monitors. Such studies were based on a comprehensive set of theoretical calculations, numerical simulations and experiments.A powerful simulation tool has been developed combining conventional softwares for SR simulation and optics design, thus allowing the description of an SR monitor from its source up to the detector. 
The simulations were confirmed by direct observations, and a detailed performance studies of the operational SR imaging monitor in the LHC, where different techniques for experimentally validating the system were applied, such as cross-calibrations with the wire scanners at low intensity (that are considered as a reference) and direct comparison with beam sizes de-convoluted from the LHC luminosity measurements.In 2015, the beam sizes to be measured with the further increase of the LHC beam energy to 7 TeV will decrease down to ∼190 μm. In these conditions, the SR imaging technique was found at its limits of applicability since the error on the beam size determination is proportional to the ratio of the system resolution and the measured beam size. Therefore, various solutions were probed to improve the system’s performance such as the choice of one light polarization, the reduction of depth of field effect and the reduction of the imaging wavelength down to 250 nm.In parallel to reducing the diffraction contribution to the resolution broadening, the extraction mirror, found as the main sources of aberrations in the system was redesigned. Its failure was caused by the EM coupling with the beam’s fields that led to overheating and deterioration of the coating. A new system’s geometry featuring a smoother transition in the beam pipe was qualified in terms of longitudinal coupling impedance via the stretched wire technique. A comparison with the older system was carried out and resulted in a reduction of the total power dissipated in the extraction system by at least a factor of four.A new, non-diffraction limited, SR-based monitor based on double slit interferometry was designed as well as an alternative method to the direct imaging. Its principle is based on the direct relation between the interferogram fringes visibility and the beam size.Since the beam emittance is the physical quantity of interest in the performance analysis of the LHC, determining the optical functions at the SR monitors is as relevant as measuring the beam size. The “K-modulation” method for the optical function determination was applied for the first time in the LHC IR4, where most of the profile monitors sit. The βs at the quadrupoles were measured and via two different propagation algorithms the βs at the BSRT and the WS were obtained reducing significantly the uncertainty at the monitors location.