Electron-Impact Uncertainty Analysis and its Impact on Certain Temperature Diagnostics

In this study we calculate the electron-impact uncertainties in atomic data for direct ionization and recombination and investigate the role of these uncertainties on spectral diagnostics. We outline a systematic approach to assigning meaningful uncertainties that vary with electron temperature. Once these uncertainty parameters have been evaluated, we can then calculate the uncertainties on key diagnostics through a Monte Carlo routine, using the Astrophysical Emission Code (APEC) [Smith et al. 2001]. We incorporate these uncertainties into well known temperature diagnostics, such as the Lyman alpha versus resonance line ratio and the G ratio. We compare these calculations to a study performed by [Testa et al. 2004], where significant discrepancies in the two diagnostic ratios were observed. We conclude that while the atomic physics uncertainties play a noticeable role in the discrepancies observed by Testa, they do not explain all of them. This indicates that there is another physical process occurring in the system that is not being taken into account. This work is supported in part by the National Science Foundation REU and Department of Defense ASSURE programs under NSF Grant no. 1262851 and by the Smithsonian Institution.

Electron-impact excitation of Xe 26+ and its resultant spectral signature

We have carried out a 129 close-coupling level Dirac-Coulomb R-matrix calculation for the electron-impact excitation of Ni-like Xe. We have utilized this data to generate the spectral signature of Xe26+ in terms of feature photon-emissivity coefficients (F-PεCs). We have compared these F-PεCs with those generated using semi-relativistic plane-wave Born excitation data, which forms the heavy species baseline for the Atomic Data and Analysis Structure (ADAS), We find that the Born-based F-PεCs give a reasonable qualitative description of the spectral signature but that, quantitatively, the R-matrix-based F-PεCs differ by up to a factor of 2. The spectral signature of heavy species is key to diagnosing hot plasmas such as will be found in the International Thermonuclear Experimental Reactor.

Do spectral gamma ray data really reflect humid-arid palaeoclimates? A test from the Palaeogene Interbasaltic weathered horizons at the Giant’s Causeway, N.Ireland

Since 1999, the rapid, inexpensive and non-destructive use of Th/K and Th/U ratios from spectral gamma ray measurements have been used as a proxy for changes in palaeo-hinterland weathering. This model is tested here by analysis of in situ palaeoweathering horizons where clay mineral contents are well-known. A residual palaeoweathered horizon of Palaeogene laterite (developed on basalt) has been logged at 14 locations across N. Ireland using spectral gamma ray detectors. The results are compared to published elemental and mineralogical data. While the model of K and U loss during the early stages of weathering to smectite and kaolinite is supported, the formation (during progressively more advanced weathering) of gibbsite and iron oxides has reversed the predicted pattern and caused U and Th retention in the weathering profile. The severity (duration, humidity) of weathering and palaeoweathering may be estimated using Th/K ratios as a proxy. The use of Th/U ratios is more problematic should detrital gibbsite (or similar clays) or iron oxides be detected. Mineralogical analysis is needed in order to evaluate the hosts for K, U and Th: nonetheless, the spectral gamma ray machine offers a real-time, inexpensive and effective tool for the preliminary or conjunctive assessment of degrees of weathering or palaeoweathering.

Power Spectral Density Side-Channel Attack Overlapping Window Method

Cryptographic algorithms have been designed to be computationally secure, however it has been shown that when they are implemented in hardware, that these devices leak side channel information that can be used to mount an attack that recovers the secret encryption key. In this paper an overlapping window power spectral density (PSD) side channel attack, targeting an FPGA device running the Advanced Encryption Standard is proposed. This improves upon previous research into PSD attacks by reducing the amount of pre-processing (effort) required. It is shown that the proposed overlapping window method requires less processing effort than that of using a sliding window approach, whilst overcoming the issues of sampling boundaries. The method is shown to be effective for both aligned and misaligned data sets and is therefore recommended as an improved approach in comparison with existing time domain based correlation attacks.

Variable Window Power Spectral Density Attack

Side channel attacks permit the recovery of the secret key held within a cryptographic device. This paper presents a new EM attack in the frequency domain, using a power spectral density analysis that permits the use of variable spectral window widths for each trace of the data set and demonstrates how this attack can therefore overcome both inter-and intra-round random insertion type countermeasures. We also propose a novel re-alignment method exploiting the minimal power markers exhibited by electromagnetic emanations. The technique can be used for the extraction and re-alignment of round data in the time domain.

Compression Efficiency Analysis of Wyner-Ziv Video Coding with Motion Compensated Side Information Interpolation

The Wyner-Ziv video coding (WZVC) rate distortion performance is highly dependent on the quality of the side information, an estimation of the original frame, created at the decoder. This paper, characterizes the WZVC efficiency when motion compensated frame interpolation (MCFI) techniques are used to generate the side information, a difficult problem in WZVC especially because the decoder only has available some reference decoded frames. The proposed WZVC compression efficiency rate model relates the power spectral of the estimation error to the accuracy of the MCFI motion field. Then, some interesting conclusions may be derived related to the impact of the motion field smoothness and the correlation to the true motion trajectories on the compression performance.

Application of continuous wavelet transform to the analysis of the modulus of the fractional Fourier transform bands for resolving two component mixture

In this paper, the fractional Fourier transform (FrFT) is applied to the spectral bands of two component mixture containing oxfendazole and oxyclozanide to provide the multicomponent quantitative prediction of the related substances. With this aim in mind, the modulus of FrFT spectral bands are processed by the continuous Mexican Hat family of wavelets, being denoted by MEXH-CWT-MOFrFT. Four modulus sets are obtained for the parameter a of the FrFT going from 0.6 up to 0.9 in order to compare their effects upon the spectral and quantitative resolutions. Four linear regression plots for each substance were obtained by measuring the MEXH-CWT-MOFrFT amplitudes in the application of the MEXH family to the modulus of the FrFT. This new combined powerful tool is validated by analyzing the artificial samples of the related drugs, and it is applied to the quality control of the commercial veterinary samples.

Application of Continuous Wavelet Transform to the Analysis of the Modulus of the Fractional Fourier Transform Bands for Resolving Two Component Mixture

In this paper, the fractional Fourier transform (FrFT) is applied to the spectral bands of two component mixture containing oxfendazole and oxyclozanide to provide the multicomponent quantitative prediction of the related substances. With this aim in mind, the modulus of FrFT spectral bands are processed by the continuous Mexican Hat family of wavelets, being denoted by MEXH-CWT-MOFrFT. Four modulus sets are obtained for the parameter a of the FrFT going from 0.6 up to 0.9 in order to compare their effects upon the spectral and quantitative resolutions. Four linear regression plots for each substance were obtained by measuring the MEXH-CWT-MOFrFT amplitudes in the application of the MEXH family to the modulus of the FrFT. This new combined powerful tool is validated by analyzing the artificial samples of the related drugs, and it is applied to the quality control of the commercial veterinary samples.

The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halide molecules /

TITLE: The normal co-ordinate analysis, vibrational spectra and theoretical infrared intensities of some thiocarbonyl halides. AUTHOR: J. L. Brema SUPERVISOR: Dr. D. C. Moule NUMBER OF PAGES: 89 ABSTRACT: The vibrational assignment of the five-in-plane fundamental modes of CSClBr has been made on the basis of infrared gas phase and liquid Raman spectral analyses to supplement our earlier vibrational studies. Even though the one out-of-plane fundamental was not observed spectroscopically an attempt has been made to predict its frequency. The vibrational spectra contained impurity bands and the CSClBr assignment was made only after a thorough analysis of the impurities themselves. A normal co-ordinate analysis calculation was performed assuming a Urey-Bradley force field. This calculation yielded the fundamental frequencies in good agreement with those observed after refinement of the originally transferred force constants. The theoretical frequencies are the eigenvalues of the secular equation and the calculation also gave the corresponding eigenvectors in the form of the very important LLj matrix. The [l] matrix is the transfoirmation between internal co-ordinates and normal co-ordinates and it is essential for Franck-Condon calculations on electronically excited molecules and for infrared Integrated band intensity studies. Using a self-consistent molecular orbital calculation termed "complete neglect of differential overlap" (CNDO/2) , theoretical values of equilibrium bond lengths and angleswere calcuted for a series of carbonyl and thlocarbonyl molecules. From these calculations valence force field force constants were also determined but with limited success. With the CNIX)/2 method theoretical dipole moment derivatives with respect to symmetrized internal co-ordinates were calculated and the results should be useful in a correlation with experimentally determined values.

Synthesis and spectral studies of methyl heterocylic systems

2-Carboxy-2?-methyldiphenyl sulfide was prepared by the Ullmann reaction and cyclodehydrated by sulfuric acid to afford 4-methylthioxanthone. 1-Methylthioxanthone was separated from the reaction mixture obtained upon cyclodehydration of 2-carboxy-3f-methyldiphenyl sulfide. In addition, 1-, 2-, 3- and 4-methylthioxanthone 10,10-dioxides were synthesized by oxidation of the corresponding thioxanthones. o-, m- and p-N-Tolylanthranilic acids were prepared by the Ullmann reaction and used as precursors for the preparation of 1-, 2- and 4- methyl-9-chloroacridine and finally 1-, 2-, 3- and 4-methylacridone. High resolution, 60 MHz PMR spectra were obtained on the four monomethyl isomers of xanthone, thioxanthone, thioxanthone 10,10-dioxide and acridone, and on 1-, 2- and 4-methyl-9-chloroacridine. For some compounds, coupling of all three different aromatic protons to the methyl was observed, two of the couplings typically being smaller than the third. With the large (ortho) coupling being on the order of 0.5 to 1.0 Hz, it was necessary to decouple the aromatic part of the spectrum. The magnitude of the ortho benzylic constant may be related to an incomplete Tr-bond delocalization in the molecules.

Development and characterization of concentric capillary nebulizer used in inductively coupled plasma analysis /

A simple, low-cost concentric capillary nebulizer (CCN) was developed and evaluated for ICP spectrometry. The CCN could be operated at sample uptake rates of 0.050-1.00 ml min'^ and under oscillating and non-oscillating conditions. Aerosol characteristics for the CCN were studied using a laser Fraunhofter diffraction analyzer. Solvent transport efficiencies and transport rates, detection limits, and short- and long-term stabilities were evaluated for the CCN with a modified cyclonic spray chamber at different sample uptake rates. The Mg II (280.2nm)/l\/lg 1(285.2nm) ratio was used for matrix effect studies. Results were compared to those with conventional nebulizers, a cross-flow nebulizer with a Scott-type spray chamber, a GemCone nebulizer with a cyclonic spray chamber, and a Meinhard TR-30-K3 concentric nebulizer with a cyclonic spray chamber. Transport efficiencies of up to 57% were obtained for the CCN. For the elements tested, short- and long-term precisions and detection limits obtained with the CCN at 0.050-0.500 ml min'^ are similar to, or better than, those obtained on the same instrument using the conventional nebulizers (at 1.0 ml min'^). The depressive and enhancement effects of easily ionizable element Na, sulfuric acid, and dodecylamine surfactant on analyte signals with the CCN are similar to, or better than, those obtained with the conventional nebulizers. However, capillary clog was observed when the sample solution with high dissolved solids was nebulized for more than 40 min. The effects of data acquisition and data processing on detection limits were studied using inductively coupled plasma-atomic emission spectrometry. The study examined the effects of different detection limit approaches, the effects of data integration modes, the effects of regression modes, the effects of the standard concentration range and the number of standards, the effects of sample uptake rate, and the effect of Integration time. All the experiments followed the same protocols. Three detection limit approaches were examined, lUPAC method, the residual standard deviation (RSD), and the signal-to-background ratio and relative standard deviation of the background (SBR-RSDB). The study demonstrated that the different approaches, the integration modes, the regression methods, and the sample uptake rates can have an effect on detection limits. The study also showed that the different approaches give different detection limits and some methods (for example, RSD) are susceptible to the quality of calibration curves. Multicomponents spectral fitting (MSF) gave the best results among these three integration modes, peak height, peak area, and MSF. Weighted least squares method showed the ability to obtain better quality calibration curves. Although an effect of the number of standards on detection limits was not observed, multiple standards are recommended because they provide more reliable calibration curves. An increase of sample uptake rate and integration time could improve detection limits. However, an improvement with increased integration time on detection limits was not observed because the auto integration mode was used.

Spectral Reflectance Characteristics of Kimberlite Indicator Minerals and Other Selected Mineral Grains

High chromium content in kimberlite indicator minerals such as pyrope garnet and diopside is often correlated with the presence of diamonds. In this study, kimberlite indicator minerals were examined using visible light reflectance spectroscopy to determine if chromium content can be correlated with spectral absorption features. The depth of absorption features in the visible spectral region were correlated with the molecular percentage of chromium and other first series transition metal elements obtained by electron microprobe data. In the visible part of the spectrum, chromium is evident by 3 absorption features in the pyrope reflectance spectrum; one isolated and narrow feature at the wavelength 689 nm was used to correlate with the chromium mol %. The isolation of this feature in the pyrope spectra is advantageous since it is not directly affected by other proximal absorption bands that could be caused by other transition metals. Analysis of the feature indicates that as grain volume increases the depth of the absorption feature will also increase. Clustering grain volumes into fractions yields better correlation between absorption depth and mol % chromium. Other types of garnet (almandine, grossular, spessartine) and kimberlite indicator minerals (olivine, diopside, chromite, ilmenite) were analyzed to determine if other absorption features could be used to predict the proportion of specific transition metal elements. Diopside in particular illustrates the same isolated chromium absorption feature as pyrope and may indicate mol percent but needs further study with larger sample sets.

Space and time characterization of laser-induced plasmas for applications in chemical analysis and thin film deposition

Après des décennies de développement, l'ablation laser est devenue une technique importante pour un grand nombre d'applications telles que le dépôt de couches minces, la synthèse de nanoparticules, le micro-usinage, l’analyse chimique, etc. Des études expérimentales ainsi que théoriques ont été menées pour comprendre les mécanismes physiques fondamentaux mis en jeu pendant l'ablation et pour déterminer l’effet de la longueur d'onde, de la durée d'impulsion, de la nature de gaz ambiant et du matériau de la cible. La présente thèse décrit et examine l'importance relative des mécanismes physiques qui influencent les caractéristiques des plasmas d’aluminium induits par laser. Le cadre général de cette recherche forme une étude approfondie de l'interaction entre la dynamique de la plume-plasma et l’atmosphère gazeuse dans laquelle elle se développe. Ceci a été réalisé par imagerie résolue temporellement et spatialement de la plume du plasma en termes d'intensité spectrale, de densité électronique et de température d'excitation dans différentes atmosphères de gaz inertes tel que l’Ar et l’He et réactifs tel que le N2 et ce à des pressions s’étendant de 10‾7 Torr (vide) jusqu’à 760 Torr (pression atmosphérique). Nos résultats montrent que l'intensité d'émission de plasma dépend généralement de la nature de gaz et qu’elle est fortement affectée par sa pression. En outre, pour un délai temporel donné par rapport à l'impulsion laser, la densité électronique ainsi que la température augmentent avec la pression de gaz, ce qui peut être attribué au confinement inertiel du plasma. De plus, on observe que la densité électronique est maximale à proximité de la surface de la cible où le laser est focalisé et qu’elle diminue en s’éloignant (axialement et radialement) de cette position. Malgré la variation axiale importante de la température le long du plasma, on trouve que sa variation radiale est négligeable. La densité électronique et la température ont été trouvées maximales lorsque le gaz est de l’argon et minimales pour l’hélium, tandis que les valeurs sont intermédiaires dans le cas de l’azote. Ceci tient surtout aux propriétés physiques et chimiques du gaz telles que la masse des espèces, leur énergie d'excitation et d'ionisation, la conductivité thermique et la réactivité chimique. L'expansion de la plume du plasma a été étudiée par imagerie résolue spatio-temporellement. Les résultats montrent que la nature de gaz n’affecte pas la dynamique de la plume pour des pressions inférieures à 20 Torr et pour un délai temporel inférieur à 200 ns. Cependant, pour des pressions supérieures à 20 Torr, l'effet de la nature du gaz devient important et la plume la plus courte est obtenue lorsque la masse des espèces du gaz est élevée et lorsque sa conductivité thermique est relativement faible. Ces résultats sont confirmés par la mesure de temps de vol de l’ion Al+ émettant à 281,6 nm. D’autre part, on trouve que la vitesse de propagation des ions d’aluminium est bien définie juste après l’ablation et près de la surface de la cible. Toutefois, pour un délai temporel important, les ions, en traversant la plume, se thermalisent grâce aux collisions avec les espèces du plasma et du gaz.

Structural and Spectral Investigations of Transition Metal Complexes Of Di-2-Pyridyl Ketone N (4), N (4)-Disubstituted Thiosemicarbazones

The study deals with structural and spectral investigations of transition metal complexes of di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones. The main objective and scope of the work deals with di-2-pyridyl ketone N(4),N(4)-disubstituted thiosemicarbazones are quardridentate NNNS donor ligands. To chosen this ligand for study because, the ligands are prepared and characterized for the first time, since there are two pyridyl nitorgens, dimmers and polymers of complexes may result leading to interesting structural aspects. The work includes the preparation of the thiosemicarbzones and their structural and spectral studies, synthesis and spectral characterization of complexes of copper(II),,nickel(II),manganese(II), dioxovanadium(V),cobalt(III),zinc(II),cadmium(II) of the ligand HL, synthesis and spectral characterization of complexes of copper(II),manganese(II), of the ligand HL and the development of X-ray quality crystals and its X-ray diffraction studies. The structural characterization techniques are elemental analysis, conductivity measurements, magnetic measurements, electronic spectroscopy, H NMR spectroscopy, Infrared spectroscopy and X-ray crystallography.

Synthesis and Spectral Characterization of Lanthanide Complexes with Sulfamethoxazole and Their Antibacterial Activity

A series of nonelectrolytic lanthanide(III) complexes, [ ML 2 Cl 3 ] · 2 H 2 O, where M is lanthanum(III), praseodymium(III), neodymium(III), samarium(III), gadolinium(III), terbium(III), dysprosium(III), and yttrium(III), containing sulfamethoxazole ligand (L) are prepared. The structure and bonding of the ligand are studied by elemental analysis, magnetic susceptibility measurements, IR, 1 H NMR, TG / DTA , X-ray diffraction studies, and electronic spectra of the complexes. The stereochemistry around the metal ions is a monocapped trigonal prism in which four of the coordination sites are occupied by two each from two chelating ligands, sulfonyl oxygen, and nitrogen of the amide group and the remaining three positions are occupied by three chlorines. The ligand and the new complexes were tested in vitro to evaluate their activity against the bacteria Escherichia coli and Staphylococcus aureus.