The Arabian-Nubian Shield is an excellent natural laboratory to study crust formation processes during the Neoproterozoic. It is one of the largest juvenile tracts of continental crust formed during this time. It diachronously evolved between the breakup of Rodinia (c.780 Ma) and amalgamation of Gondwana (c.550 Ma). New SIMS zircon U-Pb, whole-rock Sm-Nd isotopic and geochemical data are presented. The results are used to establish the geochronology of the Abas terrane and constrain its crustal evolution. The U-Pb data show bimodal age distribution: an older age group c. 790-760 Ma, which corresponds to the arc-forming stage of the ANS and a younger group c. 625-590 Ma, belonging to post-collisional episode in the region. The oldest sample in the post-collisional tectonomagmatic group is slightly deformed indicating that pervasive deformation in the area was decaying by c. 625 Ma. The inherited zircons documented range in age from Meso-to-Paleoproterozoic. Although few, these inherited zircons indicate that crust material of that age was assimilated during the Neoproterozoic magmatic events. The U-Pb geochronologic also resolved the temporal transition from high-K calc-alkaline to alkaline magmatism in the post-collisional suits. This transition commonly marks the end of orogeny. Almost all samples studied exhibit a strongly enriched initial εNd compositions and Nd model ages that predate the crystallization ages of the rocks by several hundred million years. These features highlight the sharp contrast in the magmatic sources between the Abas granitoids and the rest of the ANS, which is dominantly juvenile except that of the Afif terrane of Saudi Arabia. This suggests that the Abas terrane of Yemen had a distinctive crustal evolution history compared to the rest of the shield and these features provide evidence for the presence of pre-Neoproterozoic crust at depth in this region.

An investigation into the relaxation of highly vibrationally excited trifluorobenzene and tetrafluorobenzene following collisions with carbon dioxide was performed using diode laser transient absorption spectroscopy. A 248 nm excimer laser prepared the vibrationally hot (E'~41,000 cm-1) fluorobenzene molecules. Large amounts of translational and rotational energy are transferred through collisions between the hot donor molecule and CO2. Rate constants and collisional probabilities were calculated by probing the high J states (J=58~80) of CO2 in the vibrational ground state, 0000, with measurements taken 1 µsec, ¼ the mean gas collision time, following each excimer laser pulse. The energy transfer probability distribution function, P(E,E'), was calculated for each molecule using the state-resolved probabilities and the energy gain of the bath. The study found a relationship between the fraction of strong collisions and the donor's dipole moment. Additionally, these findings support an application of Fermi's Golden rule to collisional energy transfer by linking the shape of P(E,E') to the shape of the donor's density of states as a function of ΔE.

Unimolecular reactions based on the Lindemann - Hinchelwood mechanism are important to understanding combustion and atmospheric processes. The main feature of this mechanism is the energy transfer probability distribution function, P(E',E). We have chosen to study P(E',E) through gas phase collisional dynamics probed with IR transient absorption spectroscopy. Post-collision absorption line widths for the pyrazine-N2O system are used to calculate lab frame translational temperatures. The translational temperatures reveal that collisions with large rotational energy transfer also transfer large amounts of translational energy. For J states >47 the relationship is linear indicating a constant impact parameter. Line widths for J=47 through J=59 also showed that there is no out-scattering from these states, in contrast to work performed previously in the Sevy group. The discrepancy between these measurements prompted a complete analysis of the causes of noise in the experimental system. Defective instruments were identified and noise sources localized, including IR diode frequency jitter. Improved experimental techniques and troubleshooting guides are explained for future researchers in the Sevy group.

This thesis examines the modeling of the shock-layer radiative heating associated with hypersonic vehicles entering the atmospheres of Earth and Titan. For Earth entry, flight conditions characteristic of lunar-return are considered, while for Titan entry, the Huygens probe trajectory is considered. For both cases, the stagnation region flowfield is modeled using a two-temperature chemical nonequilibrium viscous shock layer (VSL) approach. This model is shown to provide results that are in agreement with the more computationally expensive Navier-Stokes solutions. A new radiation model is developed that applies the most up-to-date atomic and molecular data for both the spectrum and non-Boltzmann modeling. This model includes a new set of atomic-lines, which are shown to provide a significant increase in the radiation (relative to previous models) resulting from the 1 - 2 eV spectral range. A new set of electronic-impact excitation rates was compiled for the non-Boltzmann modeling of the atomic and molecular electronic states. Based on these new rates, a novel approach of curve-fitting the non-Boltzmann population of the radiating atomic and molecular states was developed. This new approach provides a simple and accurate method for calculating the atomic and molecular non-Boltzmann populations. The newly-developed nonequilibrium VSL flowfield and nonequilibrium radiation models were applied to the Fire II and Apollo 4 cases, and the resulting radiation predictions were compared with the flight data. For the Fire II case, the present radiation-coupled flowfield model provides intensity values at the wall that predicted the flight data better than any other previous study, on average, throughout the trajectory for the both the 0.2 - 6.0 eV and 2.2 - 4.1 eV spectral ranges. The present results over-predicted the calorimeter measurements of total heat flux over most of the trajectory. This was shown to possibly be a result of the super-catalytic assumption for the wall boundary condition, which caused the predicted convective heating to be too high. For the Apollo 4 case, over most of the trajectory the present model over-predicted the flight data for the wall radiative intensity values between 0.2 - 6.2 eV. For the analysis of Huygens entry into Titan, the focus of the radiation model was the CN violet band. An efficient and accurate method of modeling the radiation from this band system was developed based on a simple modification to the smeared rotational band (SRB) model. This modified approach, labeled herein as SRBC, was compared with a detailed line-by-line (LBL) calculation and shown to compare within 5% in all cases. The SRBC method requires many orders-of-magnitude less computational time than the LBL method, which makes it ideal for coupling to the flowfield. The non-Boltzmann modeling of the CN electronic states, which govern the radiation for Huygens entry, is discussed and applied. The radiation prediction resulting from the non-Boltzmann model is up to 70% lower than the Boltzmann result. A new method for treating the escape factor in detail, rather than assuming a value equal to one, was developed. This treatment is shown to increase the radiation from the non-Boltzmann model by about 10%. / Ph. D.

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No description available.

No description available.

The cyclic peroxides: diphenoyl peroxide (1), spiro-adamantyl-1,2-dioxetanone (2) and 4-(3-tert-butyldimethylsilyloxyphenyl)-4-methoxyspiro[1.2-dioxetane-3.2\'-adamantane] (3) synthesized, purified and characterized, also their kinetic and chemiluminescence (CL) properties were determined. The influence of solvent polarity on the chemiexcitation parameters of the catalyzed decomposition of 1 and 2, as well as the induced decomposition of 3 were examined in several binary solvent mixtures with different polarity and polarizability parameters, but similar viscosities. For solvents with low polarity, singlet quantum yields for the intermolecular catalyzed decomposition of diphenoyl peroxide (1,) and 1,2-dioxetanone (2) increase in function of medium polarity, showing maximum values in mediums of intermediate polarity, and decreasing in highly polar mixtures. For the induced decomposition of 3, the quantum yield showed to increase with increasing solvent polarity, including high polar solvent systems. In the binary solvent systems studied, the polarizability parameter showed to be contrary to the polarity values, therefore, it might appear that an increase of polarizability leads to a decrease in the singlet quantum yields for catalyzed decomposition of diphenoyl peroxide (1) and the induced decomposition of 3, however an increase in the singlet quantum yields for 1,2-dioxetanone 2. The three CL systems were also studied in binary solvent mixtures with different viscosities but similar polarity and polarizability parameters and singlet quantum yields showed an increase with increasing medium viscosity. Data were analyzed by using the collisional and the free volume models. The highly efficient intramolecular system induced 1,2-dioxetane 3 decomposition showed to be much more sensible to viscosity effects than the inefficient intermolecular systems. This surprising fact indicates that, even showing a significant solvent-cage effect, the induced 1,2-dioxetane should occur by an intramolecular electron back transfer. Moreover, chemiluminescence parameters of these systems were studied in several pure solvents. The obtained singlet quantum yields were correlated with viscosity, polarizability and polarity parameters by using multiple linear regression analysis. / Os peróxidos cíclicos: peróxido de difenoila (1), spiro-adamantil-1,2-dioxetanona (2) e 4-(3-terc-butildimetilsililoxifenil)-4-metoxispiro[1,2-dioxetano-3.2\'-adamantano] (3) foram sintetizados, purificados e caracterizados e as suas propriedades cinéticas e de quimiluminescência (CL) determinadas. A influência da polaridade do solvente sobre os parâmetros de quimi-excitação da decomposição catalisada de 1 e 2, e a decomposição induzida de 3 foi examinada em diversas misturas binárias de solventes com parâmetros de polaridade e polarizabilidade diferente, mas viscosidades semelhantes. Para solventes com baixa polaridade, os rendimentos quânticos singlete para a decomposição catalisada intermolecular do peróxido de difenoila (1) e 1,2-dioxetanona (2) aumentam em função da polaridade do meio, mostrando valores máximos em meios com polaridade intermediária, e diminuim para misturas altamente polares. Para a decomposição induzida de 3, o rendimento quântico mostrou aumentar com o aumento da polaridade do solvente, inclusive para sistemas com alta polaridade. Nos sistemas binários de solventes estudados, os parâmetros de polarizabilidade mostraram-se contrários aos valores de polaridade, portanto, parece que um aumento da polarizability leva a uma diminuição nos rendimentos quânticos singlete para a decomposição catalisada do peróxido de difenoila (1) e a decomposição induzida de 3, no entanto, um aumento nos rendimentos quânticos singlete para a 1,2-dioxetanona 2. Os três sistemas de CL também foram estudados em misturas binárias de solventes com diferentes viscosidades, mas com parâmetros de polaridade e polarizabilidade semelhantes e os rendimentos quânticos singlete mostraram aumentar com o aumento da viscosidade do meio. Os dados foram analisados usando tanto o modelos colisional quando o modelo de volume livre. Surpreendentemente, o sistema altamente eficiente decomposição induzida intramolecular do 1,2-dioxetano 3 mostrou-se muito mais sensível aos efeitos da viscosidade do que os sistemas intermoleculares ineficientes, o que indica claramente que a decomposição induzida do 1,2-dioxetano deve ocorrer por um processo de retro-transferência de elétron intramolecular. Além disso, os parâmetros de quimiluminescência destes sistemas foram estudados em vários solventes puros. Os rendimentos quânticos singlete obtidos foram correlacionados com parâmetros de viscosidade, polarizabilidade e polaridade usando análise de regressão linear múltipla.

Esta dissertação faz parte de um projeto que tem como objetivo investigar a origem e evolução do magmatismo de arco e pós-colisional do Escudo Sul-rio-grandense (ESRG), caracterizando a partir de estudos geoquímicos, estruturais e petrográficos os Granitóides Sanga do Areal (GSA), localizados na região de Quitéria, porção leste do Escudo Sul-rio-grandense. Estes granitóides consistem de dois corpos principais, alongados na direção NE-SW, com aproximadamente 14 km de extensão e 2 km de largura, e também de diversas intrusões menores, posicionadas, preferencialmente, na porção mediana de alta deformação cisalhante do Complexo Arroio dos Ratos. Estão em contato na porção NW com metatonalitos, metagranodioritos e gnaisses tonalíticos a dioríticos de idade paleoproterozóica do referido complexo e com horblenda-biotita granodioritos da unidade neoproterozóica Granodiorito Cruzeiro do Sul. Na porção SE o contato se dá com tonalitos a dioritos relacionados aos Granitóides Arroio Divisa de idade neoproterozóica. Os GSA são biotita monzogranitos de textura porfirítica em seu termo principal, com cerca de 30% de megacristais de até 5 cm de comprimento de plagioclásio e K-feldspato. A matriz heterogranular média a grossa é composta por quartzo fitado, feldspato parcialmente recristalizado e biotita. Subordinadamente, observam-se corpos de espessura centimétrica a métrica de biotita granodiorito equigranular médio, com fenocristais esparsos de feldspatos alinhados na foliação. Raramente ocorrem enclaves microgranulares máficos. A foliação milonítica é bem marcada pela orientação da biotita, dos megacristais lenticulares e do quartzo fitado e tem direção E-W, com alto ângulo de mergulho para N e para S, contendo lineação de estiramento direcional, com baixo caimento para W a SW. A foliação ígnea primária, concordante a sub-concordante com a foliação milonítica, tem ocorrência restrita e é marcada pela orientação dos megacristais não deformados e das lamelas de biotita. Estruturas S-C, caudas assimétricas em porfiroclastos de feldspatos, biotita fish e fitas assimétricas de quartzo são consistentes e indicam movimento transcorrente sinistral. Os Granitóides Sanga do Areal têm afinidade sub-alcalina médio a alto K, provavelmente toleítica, compatível com ambiente pós-colisional, onde foram deformados e controlados por zonas de cisalhamento transcorrente sub-verticais. Foi obtida uma idade U-Pb em zircão dos granitóides de 626,6±4,9 Ma (MSWD=2.2), coerente com as relações de campo. / This research investigates the evolution of arc to post-collisional magmatism in the Sul-rio-grandense Shield (ESGR), using geochemistry, structural and petrographic studies of the Sanga do Areal Granitoids (GSA). These granitoids are located in the Quitéria region, east of ESRG. The GSA form two main, NE-striking intrusions, and several other small ones, mainly within the shear zone croscutting the central portion of the Arroio dos Ratos Complex. The two main bodies are about 14 km long and 2 km wide. To the northwest, the GSA rocks are in contact with Paleoproterozoic metatonalites, metagranodiorites, tonalitic to dioritic gneisses of the Complex, and Neoproterozoic horblende-biotite granodiorites of the Cruzeiro do Sul unit. To the southeast, they are surrounded by tonalitic to dioritic rocks, related to the Neoproterozoic Arroio da Divisa Granitoids. The GSA rocks are composed mainly of porphyritic biotite monzogranites, with about 30% megacrysts of plagioclase and 5 cm long K-feldspar. The medium to coarse grained heterogranular groundmass is composed of microcrystalline ribbon quartz, partially re-crystallized feldspar and biotite. Medium-grained equigranular granodiorite occurs as centimeter to meter- thick bodies, with sparse feldspar megacrysts aligned on the foliation plane. Microgranular mafic enclaves are rarely observed within the GSA rocks. The mylonitic foliation is well-developed and marked by biotite, oriented lenticular megacrysts, as well as quartz ribbons. It strikes E-W and dips at high angles either N or S. The stretching lineation within the foliation shows shallow plunges, preferentially W-SW. A primary igneous foliation is sometimes observed, and it is concordant or sub-concordant with the mylonitic one, and marked by orientation of igneous megacrysts and biotite lamellae. S-C structures, asymetric tails in feldspar porphyroclasts, biotite fish, and asymetric quartz ribbons indicate transcurrent movement with consistent sinistral shear sense. The Sanga do Areal Granitoids show subalkaline medium- to high-K affinity, probably tholeiitic, and trace element composition consistent with sources related to post-collisional settings, which were deformed and controlled by E-NE and NE sub-vertical transcurrent shear zones. A U-Pb age in zircon grains from Sanga do Areal Granitoids of 626.6 ± 4.6Ma ((MSWD=2.2) was obtained and considered coherent with stratigraphic relations.

Esta dissertação faz parte de um projeto que tem como objetivo investigar a origem e evolução do magmatismo de arco e pós-colisional do Escudo Sul-rio-grandense (ESRG), caracterizando a partir de estudos geoquímicos, estruturais e petrográficos os Granitóides Sanga do Areal (GSA), localizados na região de Quitéria, porção leste do Escudo Sul-rio-grandense. Estes granitóides consistem de dois corpos principais, alongados na direção NE-SW, com aproximadamente 14 km de extensão e 2 km de largura, e também de diversas intrusões menores, posicionadas, preferencialmente, na porção mediana de alta deformação cisalhante do Complexo Arroio dos Ratos. Estão em contato na porção NW com metatonalitos, metagranodioritos e gnaisses tonalíticos a dioríticos de idade paleoproterozóica do referido complexo e com horblenda-biotita granodioritos da unidade neoproterozóica Granodiorito Cruzeiro do Sul. Na porção SE o contato se dá com tonalitos a dioritos relacionados aos Granitóides Arroio Divisa de idade neoproterozóica. Os GSA são biotita monzogranitos de textura porfirítica em seu termo principal, com cerca de 30% de megacristais de até 5 cm de comprimento de plagioclásio e K-feldspato. A matriz heterogranular média a grossa é composta por quartzo fitado, feldspato parcialmente recristalizado e biotita. Subordinadamente, observam-se corpos de espessura centimétrica a métrica de biotita granodiorito equigranular médio, com fenocristais esparsos de feldspatos alinhados na foliação. Raramente ocorrem enclaves microgranulares máficos. A foliação milonítica é bem marcada pela orientação da biotita, dos megacristais lenticulares e do quartzo fitado e tem direção E-W, com alto ângulo de mergulho para N e para S, contendo lineação de estiramento direcional, com baixo caimento para W a SW. A foliação ígnea primária, concordante a sub-concordante com a foliação milonítica, tem ocorrência restrita e é marcada pela orientação dos megacristais não deformados e das lamelas de biotita. Estruturas S-C, caudas assimétricas em porfiroclastos de feldspatos, biotita fish e fitas assimétricas de quartzo são consistentes e indicam movimento transcorrente sinistral. Os Granitóides Sanga do Areal têm afinidade sub-alcalina médio a alto K, provavelmente toleítica, compatível com ambiente pós-colisional, onde foram deformados e controlados por zonas de cisalhamento transcorrente sub-verticais. Foi obtida uma idade U-Pb em zircão dos granitóides de 626,6±4,9 Ma (MSWD=2.2), coerente com as relações de campo. / This research investigates the evolution of arc to post-collisional magmatism in the Sul-rio-grandense Shield (ESGR), using geochemistry, structural and petrographic studies of the Sanga do Areal Granitoids (GSA). These granitoids are located in the Quitéria region, east of ESRG. The GSA form two main, NE-striking intrusions, and several other small ones, mainly within the shear zone croscutting the central portion of the Arroio dos Ratos Complex. The two main bodies are about 14 km long and 2 km wide. To the northwest, the GSA rocks are in contact with Paleoproterozoic metatonalites, metagranodiorites, tonalitic to dioritic gneisses of the Complex, and Neoproterozoic horblende-biotite granodiorites of the Cruzeiro do Sul unit. To the southeast, they are surrounded by tonalitic to dioritic rocks, related to the Neoproterozoic Arroio da Divisa Granitoids. The GSA rocks are composed mainly of porphyritic biotite monzogranites, with about 30% megacrysts of plagioclase and 5 cm long K-feldspar. The medium to coarse grained heterogranular groundmass is composed of microcrystalline ribbon quartz, partially re-crystallized feldspar and biotite. Medium-grained equigranular granodiorite occurs as centimeter to meter- thick bodies, with sparse feldspar megacrysts aligned on the foliation plane. Microgranular mafic enclaves are rarely observed within the GSA rocks. The mylonitic foliation is well-developed and marked by biotite, oriented lenticular megacrysts, as well as quartz ribbons. It strikes E-W and dips at high angles either N or S. The stretching lineation within the foliation shows shallow plunges, preferentially W-SW. A primary igneous foliation is sometimes observed, and it is concordant or sub-concordant with the mylonitic one, and marked by orientation of igneous megacrysts and biotite lamellae. S-C structures, asymetric tails in feldspar porphyroclasts, biotite fish, and asymetric quartz ribbons indicate transcurrent movement with consistent sinistral shear sense. The Sanga do Areal Granitoids show subalkaline medium- to high-K affinity, probably tholeiitic, and trace element composition consistent with sources related to post-collisional settings, which were deformed and controlled by E-NE and NE sub-vertical transcurrent shear zones. A U-Pb age in zircon grains from Sanga do Areal Granitoids of 626.6 ± 4.6Ma ((MSWD=2.2) was obtained and considered coherent with stratigraphic relations.