The present work provides charge state fractions that may be used to generate TEAMS relative sensitivity factors for impurities in semiconductor materials.

Distortions in the perception of time historically have been associated with dissociation and psychosis in clinical populations. However, the relations among dissociation, psychosis, and time perception in sub-clinical populations have not been investigated. In the present study, college undergraduates scoring either normally or deviantly high on the Per-Mag were given a Dissociative Experiences Scale (DES) and a computerized time-estimation/production task. Participants scoring high on the Per-Mag obtained higher scores on the DES than participants scoring low on the Per- Mag. Per-Mag scores also correlated positively with DES scores across 608 total participants screened. The relation between dissociative and psychotic symptomatology is discussed considering dichotomous versus continuous conceptualizations of psychopathology. The effects of intelligence, social desirability, malingering, gender, and post-traumatic stress on the measures used are also discussed.

Cette thèse présente une étude expérimentale et théorique de peptides protonés contenant plusieurs dizaines d’atomes en phase gazeuse. Le premier objectif de ce travail consistait à coupler trois techniques expérimentales complémentaires, la spectroscopie IRMPD, la spectrométrie de mobilité ionique et la dissociation induite par attachement d’électron (ECD), afin de caractériser la structure des peptides amyloïdes Aβ₁₂-₂₈ et de tryptophane zippers TZ1 et TZ4. L’originalité de cette étude porte sur l’analyse de la distribution d’intensité des fragments c/z obtenus en ECD en relation avec les informations structurelles obtenues par mobilité et IRMPD. Grâce à cette approche combinée, nous avons pu proposer les structures les plus probables adoptées en phase gazeuse par ces peptides flexibles. Nous avons montré que la structure native des peptides n’était pas conservée au passage en phase gazeuse. L’interprétation des données expérimentales repose sur un travail théorique important alliant des dynamiques moléculaires utilisant un champ de force AMBER aux méthodes de chimie quantique au niveau DFT pour simuler les spectres vibrationnels des peptides. Le second axe de ce travail a porté sur la conception, la réalisation et la caractérisation d’une nouvelle technique de mise en phase gazeuse de biomolécules et leurs complexes non-covalents par désorption laser IR sur une micro-gouttelette liquide directement sous vide. Cette technique originale pourrait être une alternative aux techniques ESI et MALDI. Nous avons obtenu les premiers spectres de masse et optimisé les paramètres importants de l’expérience : longueur d’onde, intensité laser, résolution en masse du spectromètre à temps de vol. D’autres développements sont en cours pour améliorer la détection et la résolution en masse de ce type de source qui produit des ions avec une grande dispersion en énergie cinétique : piéger les ions dans une trappe quadrupolaire et entraîner les ions dans une détente supersonique. / Gas-phase studies of large biological molecules have emerged with the advent of soft production methods of biomolecular ions under vacuum (like ESI or MALDI) combined to mass spectrometry. The first aim of this work was to use three complementary experimental techniques, namely IRMPD spectroscopy, ion mobility mass spectrometry and electron capture dissociation ECD to probe the gas-phase structures of amyloïd Aβ₁₂-₂₈ and tryptophan zippers TZ1 and TZ4 peptides. The main originality of this study is to analyse the specific c/z product ion abundances in ECD experiments with the structural information gained through IR spectroscopy and ion mobility experiments. With this complementary approach, we were able to assign the most probable gas-phase structures of these flexible peptides. In particular, it is shown that the native structure of the peptides is not conserved in the gas phase. This study relies on the interplay between experiments and theoretical calculations. To that end, we used several theoretical methods, ranging for molecular dynamics using a classical force field (AMBER) to quantum mechanics calculations to simulate the vibrational spectra of the peptides. The second aim of this work was to design, develop and optimize a unique device, coupling a novel source introducing biomolecules in the gas phase, based on laser desorption from liquid micro-droplets directly into vacuum, coupled with a time-of-flight mass spectrometer. This desorption source is an original alternative to the usual methods (ESI or MALDI). Through mass spectrometry techniques, it should allow investigating the complexation processes of non-covalently bound species in conditions as close as the ones encountered in solution. We have recently obtained the first mass spectra. Due to the high velocity spread of the desorbed ions, new developments are needed to improve the mass resolution. In particular, we plan to transfer the ions in a quadrupole ion trap and to perform the laser desorption in front a pulsed valve to stream the ions in the supersonic expansion.

Dans cette thèse, on a étudié la formation de monocouches auto-assemblées de différentes molécules de chalcogénure et de films minces de semiconducteurs organiques. Leurs caractéristiques électroniques et structurelles ont été étudiées principalement par la spectroscopie de photoélectron à rayons X à base de rayonnement synchrotron, la spectroscopie d’adsorption de rayons X à proximité de seuil, la microscopie à force atomique et la diffraction d'électrons à faible énergie. En outre, les caractéristiques d'adsorption du sélénium et du soufre ont été étudiées comme complément à l'étude des adsorptions des molécules comportant des atomes de chalcogène. Le XPS à haute résolution a été utilisé pour enquêter sur les monocouches auto-assemblées de benzèneselénol et de sélénophène sur Cu (111). L'étude détaillée des pics caractéristiques des niveaux du coeur a démontré l'existence de différents sites d'absorption des molécules et aussi avec les mesures NEXAFS l'apparition du clivage de la liaison Se-C. Ces conclusions sont étayées par l'étude de l’adsorption de sélénium atomique montrant également différents sites d'absorption pour le sélénium atomique avec différents environnements chimiques basés sur une étude XPS haute résolution des spectres caractéristiques Se3d, Se3p et l'imagerie LEED. On a étudié les adsorptions de molécules de polythiophène (nT, n = 1-4, 6) ainsi que pour le α, ω-diquaterthiophène (DH4T) et le dihexylsexithiophène (DH6T) sur les films Au (111) et films de Au sur le mica. Les résultats indiquent que les pics XPS S2p ont des contributions de molécules intactes sur différents sites d'adsorption et des molécules cassées. Ces conclusions sont étayées par les calculs DFT existants. La dissociation spontanée apparaît dans une mesure variable dans différents cas, ce qui pourrait être lié à différentes morphologies de surface, à l'existence de défauts et à la réactivité différentes liés a ces défauts. Des films ultra-minces d'α-sexithiophène (6T) ont été déposés sur des surfaces planes de CaF2 (111) / Si (111) et sur des surfaces striées de CaF2 (110) / Si (001) par épitaxie par faisceau moléculaire. L'image AFM de 6T sur CaF2 (111) montre de grandes îles avec des terrasses plates sans préférence dans le plan, tandis que des îlots étroits et allongés suivant l'ondulation du substrat sont formés pour 6T sur CaF2 (110). Les spectres XPS et NEXAFS indiquent que les interactions entre 6T et les surfaces sont négligeables et que les molécules s'alignent avec leur long axe perpendiculaire aux surfaces pour les deux cas. / In this thesis, formation of self-assembled monolayers of different chalcogenide molecules and organic semiconductor thin films was investigated. Their electronic and structural characteristics have been investigated primarily by synchrotron based X-ray photoelectron, near edge X-ray absorption fine structure spectroscopy, Atomic force microscopy and low energy electron diffraction. In addition, the adsorption characteristics of selenium and sulfur were studied as a complement to the study of adsorptions of chalcogen headgroup molecules. The high resolution XPS was employed to investigate the self assembled monolayers of benzeneselenol and selenophene on Cu(111). The detailed study of characteristic core level peaks demonstrated the existence of different absorption sites of the molecules and also along with NEXAFS measurements the occurrence of Se-C bond cleavage. These conclusions are supported by the study of atomic selenium adsorptions showing also different absorption sites for the atomic selenium with different chemical environments based on high resolution XPS study of characteristic Se3d, Se3p spectra and LEED imaging. The adsorptions of polythiophene molecules (nT, n=1-4, 6) as well as for α, ω-diquaterthiophene (DH4T) and dihexylsexithiophene (DH6T) on Au(111) and Au films grown on mica was studied. The results indicate that the XPS S2p peaks have contributions from intact molecules on different adsorption sites and broken molecules complemented. These conclusions are supported by existing DFT calculations. Spontaneous dissociation appears to a variable extent in different cases, which could be related to different surface morphologies, existence of defects and ensuing differences reactivity.α-Sexithiophene (6T) ultrathin films were grown on CaF2(111)/Si(111) planar surfaces and on CaF2(110)/Si(001) ridged surfaces by molecular beam epitaxy. The AFM image of 6T on CaF2(111) shows large islands with flat terraces without in-plane preference, while narrow and elongated islands following the substrate corrugation are formed for 6T on CaF2(110). XPS and NEXAFS spectra indicate that the interactions between 6T and surfaces are negligible, and the molecules align with their long axis perpendicular to the surfaces for both cases.

Objectives: This thesis aimed to investigate whether a history of childhood trauma was indirectly associated with eating psychopathology through mediation by dissociation and/or emotion dysregulation. Method: Firstly, a systematic review was conducted to appraise the current level of evidence within the literature that supported dissociation as a potential mediator. To this end, studies that assessed the variables of childhood trauma, dissociation and eating psychopathology within a single study were identified and systematically reviewed. Secondly, an empirical cross-sectional study was undertaken to investigate a multiple mediation model of the association between childhood trauma and eating psychopathology which included dissociation and emotion dysregulation as potential mediators. 165 undergraduate Psychology students took part in this study. Participants completed measures of childhood trauma, eating psychopathology, dissociation and emotion dysregulation. Experiences of multiple forms of childhood trauma were assessed, including emotional abuse (CEA), physical abuse (CPA), sexual abuse (CSA), emotional neglect (CEN) and physical neglect (CPN). Results: The results of the systematic review were inconclusive regarding the potential role of dissociation as a mediator in the relationships between childhood trauma and eating psychopathology. Findings within the reviewed studies generally offered more support for associations between childhood trauma and dissociation and dissociation and eating psychopathology. Studies reported more inconsistent findings regarding the association between childhood trauma and eating psychopathology. The results from the empirical study indicated that CEA and CEN were both significantly associated with increased eating psychopathology within the whole sample. These relationships were significantly mediated by both dissociation and emotion dysregulation. A separate analysis with female participants only, indicated that CPA and CPN in addition to CEA and CEN were significantly associated with increased eating psychopathology. The associations between CEA, CEN, CPN and eating psychopathology were all significantly mediated by both dissociation and emotion dysregulation. Dissociation and emotion dysregulation did not mediate the association between CPA and eating psychopathology. Conclusions: The studies included within the systematic review offered tentative support for an indirect relationship between childhood trauma and eating psychopathology through dissociation. Firm conclusions were limited, however, due to a number of methodological shortcomings identified within the included studies. The main methodological shortcomings concerned the definition and measurement of childhood trauma and the failure of a number of studies to address theoretical models within their research design. Addressing both of these methodological limitations, the results of the empirical study provided support for the growing consensus that emotional maltreatment may be an important risk factor for the development of eating psychopathology. Further, the results of this study indicate that childhood trauma impacts indirectly on eating psychopathology through an enduring effect on both dissociative and emotion regulation processes.

By a dominant account, memory is composed of multiple storage systems, each operating according to unique principles. By an alternative account, memory is a single storage system and operates according to a single set of principles. Selective memory impairments in amnesia serve as the primary evidence for the multiple-system perspective. This thesis reports a critical appraisal of the multiple-system perspective using a combination of computational and empirical methods. In the computational analysis, I adopt the Holographic Exemplar Model, a single-system model of memory based on Hintzman’s (1986) classic MINERVA2 model. I simulate amnesia by manipulating the quality with which items are encoded in memory. In the empirical analysis, I simulate amnesia by manipulating peoples’ quality of encoding by limiting the time given to study stimuli. Simulations 1-2 and Experiments 1-2 simulate a dissociation between classification and recognition. All four analyses are consistent with the original results. Simulation 3 and Experiment 3 simulate single and double dissociations between tachistoscopic identification and recognition. The analyses were consistent with the single but not double dissociation. Simulation 4 and Experiment 4 simulate a dissociation among word-stem completion, cued recall, and recognition. Both analyses were only partially consistent with the original results, representing a failure overall. Simulation 5 and Experiment 5 derived a novel prediction from artificial grammar learning, predicting a non-dissociation between string completion and recognition. The mixed results provide some support for a single-system account of memory and opens opportunities for future work. I argue that the analysis is best considered in convergence with previous work moving toward a more integrated account of memory / February 2017

It is important that accurate estimates of crew exposure to radiation are obtained for future long - term space missions. To predict the radiation environment, a few space radiation transport codes exist, all of which use basic nuclear cross section information for transport of radiation through materials. Little theoretical and experimental work has been conducted on reactions induced by the electromagnetic (EM) force, especially with regard to di?erential cross sections. Therefore, radiation transport codes have typically neglected to incorporate EM nuclear collision cross sections. EM cross sections for single nucleon removal have been included in some radiation codes, but better values can be obtained by using an energy dependent branching ratio. Most previous theoretical and experimental work has been devoted to total cross sections. Therefore, the energy dependent branching ratios presented can be extensively compared to past theory and experiment. Such comparisons indicate that using energy dependent branching ratios yield better estimates of total cross sections. Differential cross sections for electromagnetic dissociation in nuclear collisions are calculated for the first time. In order to be useful for three - dimensional transport codes, these cross sections have been calculated in both the projectile and lab frames. The formulas for these cross sections are such that they can be immediately used in space radiation transport codes. Only a limited amount of data exists, but the comparison between theory and experiment is good.

<p>Studier på barn med en dissociativ problematik utifrån ett familje- eller gruppterapeutiskt perspektiv är ovanliga. Enligt Waters (1998) bör familjeterapin fokusera på rak och tydlig kommunikation. Silberg (1997) anser att barngruppsterapin bör ha ett psykopedagogiskt förhållningssätt. Denna studie studerade behandlingseffekterna av familjeterapi, barngruppsterapi och ingen terapi alls för barn med en dissociativ problematik Studien gjordes på en barnpsykiatrisk mottagning och pågick under sex månader, behandling och uppföljning. Urvalet baserades på mottagningens population och egna kriterier. Arton barn, tio pojkar och åtta flickor, i åldern 10 – 14 delades upp i tre grupper. Utfallet av behandlingsmetoderna baserades på antalet återbesök gjorda under en tre månaders period efter avslutad behandling. En MANOVA visade inte på någon skillnad mellan familjeterapi, barngruppsterapi eller ingen terapi alls.</p>

Graduation date: 1968

Reliable measurements of the thermodynamics of the carbonate system are needed to better understand the CO2 system in natural waters. New measurements of the carbonic acid pK1* and pK2* in seawater have been made over a wide range of temperatures (1 to 50°C) and salinities. The commonly used CO2 constants of Mehrbach et al., (1973) were limited to salinities (19 to 43) and temperatures (2 to 35°C). They cannot be used to study estuarine or fresh waters. The results of these measured pK1* and pK2* values are in good agreement with those determined using the Miami Pitzer equations (Millero and Pierrot, 1998). The results in this dissertation can be demonstrates the validity of the model that can be used to study the carbonate system in most natural waters. The so called Miami model is presently being used to examine the effect of ocean acidification on natural waters. The boric acid effect on the dissociation constants in seawater and NaCl solutions was tested. The addition of boric acid has little or no effect on pK1* values. However, the values of pK2*, decreases with the addition of small amounts of boric acid to ASW in agreement with the work of Mojica-Prieto and Millero, (2002). The addition of larger concentrations of boric acid cause the values of pK2* to increase. These effects have been attributed to the interactions of boric acid with the carbonate ion (CO32-) in seawater (Mojica-Prieto and Millero, 2002). The addition of boric acid to NaCl solutions in contrast, caused the values of pK1* and pK2* to decrease. This has been attributed to the interactions of borate ions with Mg2+ and Ca2+ in seawater. Further measurements in Na-Mg-Cl and Na-Ca-Cl solutions are needed to prove that this is the case. The boric acid effect on the carbonate constants indicate that an increase in boric acid has no affect on pK1*, but does change the values of pK2*. At low concentrations of boric acid, pK*2 decreases, and at higher concentrations it increases. These results indicate that boric acid has some ionic interactions with the carbonate ion. Similar studies in NaCl indicate that both pK1* and pK2* decrease when boric acid is added. The differences between seawater and NaCl may be related to the interactions of Mg2+ and Ca2+ with borate anions. Further studies of NaCl with additions of MgCl2 and CaCl2 are needed to examine the effects in detail. Preliminary studies on the effect of DOC on the carbonate constants are not definitive. The change of the DOC concentration from 50 to 100 µmol kg-1 has little effect on the values of pK1* and pK2*. Dilutions of seawater with artificial seawater are complicated by changes in the concentration of boric acid. Earlier studies indicated that DOC may cause the 8 mu-mol kg-1 increase in total alkalinity of seawater needed to balance the thermodynamics of the system (Millero et al., 2002). This may be partially due to the new values for the B/Cl ratio in seawater found by Lee et al., (2010) that increases the TA by ~ 6 µmol kg-1. Further studies are needed to examine the effect of humic compounds in estuarine waters on the carbonate system. Measurements of pH or pCO2 along with TA and TCO2 can be used to separate the effect of organic ligands on TA. If DOC measurements are also made, one can relate the effect to organic ligands that can accept a proton. The cruises in the Little Bahama Banks show for the first time the active precipitation of CaCO3 (Bustos-Serrano et al., 2009). This causes measured decreases of TA, TCO2 and pH and increases in pCO2 in the whitings. This is in contrast to earlier studies on the Grand Bahama Banks where no active precipitation of CaCO3 was every found (Morse et al., 2003; Millero et al., 2005). The differences appear to be due to the movement of fresh saturated seawater from the Gulf Stream into the LBB. The Gulf Stream water enters the GBB in the winter, and the precipitation occurs on the suspended sediment over the year. Observations are needed on the Grand Bahama Banks in the winter and throughout the year to prove that this is the case.