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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
321

Superfluids of Fermions in Spin-Orbit Coupled Systems and Photons inside a Cavity

Yu, Yi-Xiang 11 December 2015 (has links)
This dissertation introduces some new properties of both superfluid phases of fermions with spin-orbit coupling (SOC) and superradiant phases of photons in an optical cavity. The effects of SOC on the phase transition between normal and superfluid phase are revealed; an unconventional crossover driven by SOC from the Bardeen-Cooper-Schrieffer (BCS) state to the Bose-Einstein condensate (BEC) state is verified in three different systems; and two kinds of excitations, a Goldstone mode and a Higgs mode, are demonstrated to occur in a quantum optical system. We investigate the BCS superfluid state of two-component atomic Fermi gases in the presence of three kinds of SOCs. We find that SOC drives a class of BCS to BEC crossover that is different from the conventional one without SOC. Here, we extend the concepts of the coherence length and Cooper-pair size in the absence of SOC to Fermi systems with SOC. We study the dependence of chemical potential, coherence length, and Cooper-pair size on the SOC strength and the scattering length in three dimensions (3D) (or the twobody binding energy in two dimensions (2D)) for three attractively interacting Fermi gases with 3D Rashba, 3D Weyl, and 2D Rashba SOC respectively. By adding a population imbalance to a Fermi gas with Rashba-type SOC, we also map out the finite-temperature phase diagram. Due to a competition between SOC and population imbalance, the finite-temperature phase diagram reveals a large variety of new features, including the expanding of the superfluid state regime and the shrinking of both the phase separation and the normal regimes. We find that the tricritical point moves toward a regime of low temperature, high magnetic field, and high polarization as the SOC strength increases. Besides Fermi fluids, this dissertation also gives a new angle of view on the superradiant phase in the Dicke model. Here, we demonstrate that Goldstone and Higgs modes can be observed in an optical system with only a few atoms inside a cavity. The model we study is the U(1)/Z2 Dicke model with N qubits (two-level atoms) coupled to a single photon mode.
322

Calculation of Nuclear Level Densities Near the Drip Lines

Shukla, Shaleen 22 July 2008 (has links)
No description available.
323

Pair Cascades in Blazars and Radio Galaxies

Roustazadeh Sheikhyousefi, Parisa 18 April 2012 (has links)
No description available.
324

Exploiting Fermi Surface Anisotropy for Low-Dissipation Interconnects: A Study on Niobium Phosphide / Utnyttjande av Fermiytans anisotropi för låg-dissipativa förbindelser: En studie på niobiumfosfid

Mariani, Gianluca January 2024 (has links)
The increasing energy consumption of ICT technologies, driven by the rise in AI and data processing, requires the development of low-dissipation interconnects. This thesis addresses the challenge of increased resistivity in chip interconnects due to miniaturization, which stems from enhanced electron scattering at the boundaries. The study focuses on the anisotropy in the Fermi surface as a strategy to mitigate resistivity increase. Experimental methods, including the fabrication of devices made from niobium phosphide (NbP) using focused ion beam (FIB) techniques, are employed. Theoretical models predict that materials with an anisotropic Fermi surface can minimize resistivity by aligning electron velocities with the transport direction. Experimental results confirm significant anisotropy in the transport properties of NbP at reduced dimensions, validating the theoretical predictions. The findings suggest that exploiting Fermi surface anisotropy is a promising approach for developing low-dissipation interconnects, potentially contributing to the continued scaling of integrated circuits and reducing power consumption in ICT applications. / Den ökande energiförbrukningen hos IKT-teknologier, driven av ökningen inom AI och databehandling, kräver utvecklingen av lågförlustiga förbindelser. Denna avhandling tar upp utmaningen med ökad resistivitet i chipförbindelser på grund av miniatyrisering, vilket beror på ökad elektronsspridning vid gränsytorna. Studien fokuserar på anisotropin i Fermi-ytan som en strategi för att minska resistiviteten. Experimentella metoder, inklusive tillverkning av enheter gjorda av niobiumfosfid (NbP) med hjälp av fokuserad jonstråleteknik (FIB), används. Teoretiska modeller förutspår att material med en anisotrop Fermi-yta kan minimera resistiviteten genom att anpassa elektronernas hastigheter med transport riktningen. Experimentella resultat bekräftar betydande anisotropi i transportegenskaperna hos NbP vid reducerade dimensioner, vilket validerar de teoretiska förutsägelserna. Resultaten antyder att utnyttjandet av Fermi-yta anisotropi är ett lovande tillvägagångssätt för att utveckla lågförlustiga förbindelser, vilket potentiellt kan bidra till fortsatt skalförändring av integrerade kretsar och minska energiförbrukningen i IKT-applikationer.
325

Etude par spectroscopies d'électrons d'interfaces métalliques et semiconductrices / Metallic and semiconducting interfaces studied by electron spectroscopies

Tournier-Colletta, Cédric 13 October 2011 (has links)
Cette thèse présente une étude des propriétés électroniques de systèmes de basse dimension à base de métaux et de semiconducteurs. La première partie de l'étude traite le confinement de l'état de Shockley dans des nanostructures tridimensionnelles d'Ag(111), par des mesures STM/STS à très basse température (5 K). Nous avons d'abord analysé en détail la structure en énergie et la distribution spatiale des modes confinés. Nous avons ensuite mis à profit la nature discrète du spectre en énergie pour étudier le temps de vie des quasiparticules. Un comportement typique de liquide de Fermi est mis en évidence, et nous montrons que le mécanisme de diffusion dominant est associé au couplage électron-phonon. La contribution extrinsèque provenant du confinement partiel de l'onde électronique a également été obtenue. Une loi d'échelle est observée avec la taille des nanostructures, ce qui permet d'extraire un coefficient de réflexion plus important que dans de simples ilôts monoatomiques. La seconde partie de l'étude est consacrée aux couches ultra-minces semiconductrices obtenues par dépôts d'alcalins (K, Rb, Cs) sur la surface Si(111):B-[racine]3. Ce travail résout la controverse concernant la nature de l'état fondamental de ce système, et notamment l'origine de la reconstruction 2[racine]3 obtenue à la saturation du taux de couverture. La compréhension en amont de la structure cristallographique permet d'élucider les propriétés électroniques. Nous montrons qu'une approche à un électron, conduisant à un isolant de bandes, décrit le système de manière convaincante, malgré l'indication de forts effets polaroniques. Ce résultat est le fruit d'une étude approfondie combinant des techniques diverses et complémentaires (LEED, ARPES, XPS, STM/STS et calcul DFT) / This thesis is devoted to the electronic properties of low-dimensional systems based on metal and semiconducting materials. The first part deals with the Shockley state confinement in Ag(111) nanostructures, by means of very-low temperature (5 K) STM/STS measurements. We study the electronic structure and spatial distribution of the confined modes. Then the discrete nature of the electronic spectrum allows one to yield the quasiparticule lifetime. A Fermi-liquid behaviour is evidenced and we show that the dominant decay mechanism is attributed to the electron-phonon coupling. The extrinsic contribution arising from the partial confinement of the electronic wave is obtained as well. A scaling law with the nanostructure width is demonstrated, from which we deduce a higher reflection amplitude than in monoatomic islands. In the second part of the thesis, we study semiconducting ultra-thin films produced by alkali (K, Rb, Cs) deposition on the Si(111):B-[root of]3 surface. This work solves the controversy concerning the ground state of this system, and especially the nature of the 2[root of]3 surface recontruction obtained at saturation coverage. Prior understanding of the crystallographic structure allows to elucidate the electronic properties. We show that a one-electron picture, leading to a band insulator scenario, gives a good description of the system, in spite of strong polaronic effects. This conclusion results from an in-depth, combined study of complementary techniques (LEED, ARPES, XPS, STM/STS and DFT calculations).
326

Modélisation au sein de la DFT des propriétés des structures électronique et magnétique et de liaison chimique des Hydrures d’Intermétalliques / DFT modeling of the electronic and magnetic structures and chemical bonding properties of intermetallic hydrides

Al Alam, Adel F. 26 June 2009 (has links)
Cette thèse présente une étude modélisatrice de différentes familles d'intermétalliques et de leurs hydrures qui présentent un intérêt à la fois fondamental et appliqué. Deux méthodes complémentaires construites au sein de la théorie de la fonctionnelle densité (DFT) ont été choisies : d'une part celle à base de pseudo potentiels (VASP) pour l'optimisation géométrique, la recherche structurale et la cartographie de localisation électronique (ELF), d'autre part celle de type "tous-électrons" (ASW), pour une description détaillée de la structure électronique, des propriétés de liaison chimique suivant différents schémas et des quantités impliquant les électrons de c\oe ur comme le champ hyperfin. Un accent particulier est mis sur les rôles compétitifs des effets magnétovolumiques par rapport à ceux chimiques (liaison métal-H) dans les phases hydrurées, binaires de Laves (ex. ScFe2) et de Haucke (ex. LaNi5) et ternaires à base de cérium (ex. CeRhSn) et d'uranium (ex. U2Ni2Sn). / This thesis presents an ab initio study of several classes of intermetallics and their hydrides. These compounds are interesting from both a fundamental and an applied points of view. To achieve this aim two complementary methods, constructed within the DFT, were chosen : (i) pseudo potential based VASP for geometry optimization, structural investigations and electron localization mapping (ELF), and (ii) all-electrons ASW method for a detailed description of the electronic structure, chemical bonding properties following different schemes as well as quantities depending on core electrons such as the hyperfine field. A special interest is given with respect to the interplay between magnetovolume and chemical interactions (metal-H) effects within the following hydrided systems : binary Laves (e.g. ScFe2) and Haucke (e.g. LaNi5) phases on one hand, and ternary cerium based (e.g. CeRhSn) and uranium based (e.g. U2Ni2Sn) alloys on the other hand.
327

Ultrafast vibrational dynamics of nucleobases and base pairs in solution and DNA oligomers

Greve, Christian 26 September 2014 (has links)
Die Energierelaxationsdynamik und strukturelle Dynamik der DNA spielen eine entscheidende Rolle für das Verständnis der photochemischen Eigenschaften und biologischen Funktion von DNA. Die schnellsten Prozesse geschehen dabei auf Zeitskalen im Femto- bis Pikosekundenbereich und können durch zeitaufgelöste (ultraschnelle) Messungen an molekularen Schwingungsanregungen in Echtzeit beobachtet werden. In dieser Arbeit werden NH-Streck Schwingungsmoden der Nukleobasen sowie OH-Streckmoden der Hydrathülle mittels linearer infrarot (IR) Spektroskopie sowie ultraschneller Pump-Probe und zweidimensionaler IR Spektroskopie untersucht. Messungen an monomerartigen Nukleobasen, wasserstoffverbrückten Nukleobasenpaaren und kurzen DNA Fragmenten in Doppelhelixstruktur ermöglichen es, die Effekte der verschiedenen Wasserstoffbrücken und Schwingungskopplungen separat voneinander zu untersuchen. Im Zusammenspiel mit exzitonischen und quantenchemischen Rechnungen werden so weitreichende Einsichten in die spektroskopischen Eigenschaften und die Relaxationsdynamik von Schwingungsanregungen in DNA gewonnen. Es wird u.a. gezeigt, dass Wasserstoffbrücken zwischen Nukleobasen eine Lebensdauer größer 1 ps besitzen und eine beschleunigte Energierelaxation durch Fermiresonanzen mit niederfrequenten Schwingungsmoden des Fingerprintbereichs bewirken. Die DNA-Hydrathülle zeigt eine ultraschnelle strukturelle Dynamik unabhängig von der Basenpaarzusammensetzung und fungiert als effiziente Wärmesenke für hochfrequente Schwingungsanregungen. / Energy relaxation and structural dynamics in DNA play a crucial role for the understanding of the photochemical properties and biological function of DNA. The fastest of such processes occur on the femto- to picosecond time scale and can be followed in real time through time-resolved (ultrafast) measurements on molecular vibrations. In this work, NH stretching excitations of nucleobases and OH stretching modes of the hydration shell are analyzed through linear infrared (IR) spectroscopy as well as ultrafast pump-probe and two-dimensional IR spectroscopy. Measurements on monomeric nucleobases, hydrogen-bonded nucleobase pairs, and short DNA fragments in double helix structure allow one to examine the effects of the different hydrogen bonds and vibrational couplings separately from each other. The combination with excitonic and quantum chemical calculations provides profound new insights into the spectroscopic properties and relaxation dynamics of vibrational excitations in DNA. This work shows that hydrogen bonds between nucleobases have a lifetime greater than 1 ps and lead to an accelerated dissipation of energy due to Fermi resonances with vibrational modes in the fingerprint range. The hydration shell of DNA exhibits ultrafast structural dynamics independent of the base pair composition and serves as an efficient heat sink for high-energy vibrational excitations.
328

Análise conformacional e estudo das interações eletrônicas de algumas (α-oxa-α-tio-) e (α-oxa-α-seleno-) acetofenonas-para-substituídas / Conformational analysis and electronic interactions study of some (α-oxa-α-thio-) and (α-oxa-α-seleno-) acetophenones-para-substituted

Traesel, Henrique Joel 26 October 2018 (has links)
A presente tese trata da análise conformacional e estudo das interações eletrônicas de algumas 2-(fenilselanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série I) e das 2-(4-substituídasfenilsulfanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série II) contendo grupos doadores, hidrogênio e atraentes de elétrons na posição para dos anéis fenacílico [4\'-Y-PhC(O)] e fenilsulfanílico (S-Ph-4-X). Através da resolução das bandas de νCO, foi constatada a ocorrência de isomerismo conformacional nos solventes de constante dielétrica crescente (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) em ambas as séries. Cinco compostos da série II apresentaram ressonância de Fermi (RF) no infravermelho e precisaram ser deuterados. Os dados espectroscópicos são concordantes tanto com os resultados dos cálculos de otimização e frequência em fase gasosa quanto com a simulação do efeito do solvente (PCM), no nível de teoria B3LYP/6-31+G(d,p). Em ambas as séries, foram encontradas três conformações estáveis c1, c2 e c3, sendo que c2 é significativamente mais estável que c1 e c3. O confôrmero c1 possui o oxigênio metoxílico e o carbonílico em sinperiplanar enquanto os grupos -SePh/- SPh estão em anticlinal. Os confôrmeros c2 e c3 possuem o hidrogênio metínico em sinperiplanar com a carbonila enquanto os grupos -OMe e -SePh/-SPh estão na anticlinal. O confôrmero c1 pode ser atribuído ao componente de banda (IR) de maior frequência νCO. Da mesma forma, c2 e c3 são o componente de frequência intermediária e de menor frequência, respectivamente, na série I enquanto que na série II eles coalescem em apenas um componente de menor frequência. Os cálculos de PCM mimetizam os dados espectroscópicos, i.e. é possível constatar a inversão populacional entre c1 e c2, conforme a polaridade do solvente aumenta. Através do cálculo de frequências anarmônicas e construção da PED, foram encontrados dois modos vibracionais que combinados interagem com νCO originando a RF (série II). Um modo é de alta frequência e envolve uma porcentagem considerável de &#948C-H(metínico), o outro modo é esqueletal. A análise das interações orbitalares (NBO) mostrou que os confôrmeros c1 e c2 são estabilizados pela transferência de cargas entre LpO5→σ*CS/Se (ca. 18 kcal mol-1) enquanto c3 é estabilizado pela interação menos intensa LpO5→σ*C-C (ca. 9,5 kcal mol-1). As interações eletrônicas foram investigadas a partir dos contatos interatômicoscurtos com apoio das cargas atômicas parciais. Apesar de c1 e c2 apresentarem praticamente a mesma estabilidade em termos de interações orbitalares, o primeiro é fortemente desestabilizado pela repulsão eletrostática entre os átomos O&#948-CO...O&#948-OMe negativamente carregados separados por uma distância menor que a soma dos raios de van der Waals. Este contato curto entre os dipolos C&#948+=O&#948- e C&#948+−O&#948- é responsável pela maior frequência de νCO de c1 frente c2 e c3. A maior estabilidade de c1 nos solventes mais polares, porém, deve-se à melhor solvatação local destes dipolos. As análises dos monocristais (raios-X) indicou que os compostos assumem, no estado sólido, a conformação menos estável c1, obtida em fase gasosa. Não foram encontradas diferenças significativas no que se refere aos substituintes Y e X. Conclui-se que a estabilidade global das conformações é determinada pelo balanço energético entre as interações orbitalares e eletrostáticas, nas duas séries estudadas. / This thesis reports the conformational analysis and the electronic interactions study of some 2-(phenylselanyl)-2-(methoxy)-4\'-substituted-acetophenones (series I) and 2-(4-substitutedphenylsulphanyl)-2-(methoxy)-4\'-substituted-acetophenones (series II) bearing electron donating, hydrogen and electron attracting substituents in the para position of the phenacyl [4\'-Y-PhC(O)] and phenylsulphanyl (S-Ph-4-X). The occurrence of conformational isomerism in crescent dielectric constant solvents (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) in the two series was studied through the νCO infrared band decomposition. From the series II compounds, five presented Fermi resonance (FR) and had to be deuterated. The spectroscopic data are in line with theoretical calculations results for optimization and frequency in gas phase as well as for solvent effect simulation (PCM), both in B3LYP/6-31+G(d,p) level. Three stable conformers (c1, c2 and c3) were found for both series being the c2 significantly more stable than c1 and c3. Particularly in the c1 conformer, the methoxyl and the carbonyl oxygens are in sinperiplanar orientation while the -SePh/-SPh groups are in anticlinal. In the c2 and c3 conformers the methyne hydrogen assume a sinperiplanar geometry with respect to the carbonyl whereas both -OMe and -SePh/-SPh are in anticlinal. The c1 conformer can be ascribed to the highest frequency νCO band component (IR). So, c2 and c3 ones can be ascribed to the medium and the lowest frequency νCO component, respectively, in the series I whereas in the series II they come together (coalescence) in one single band component. The PCM calculations are in good agreement with spectroscopic data i.e. it is possible to observe a populational inversion between c1 and c2 conformers as the solvent polarity increases. The anharmonic frequencies and PED theoretical treatment revealed that the combination of two vibrational modes interact with the νCO giving rise to the FR (series II): the high frequency one involves a considerable δC-H(methyne) percentage; whilst the other is skeletal. The orbital interactions analysis (NBO) showed that the c1 and c2 conformers are mainly stabilized by charge transfer LpO5→σ*CS/Se (ca. 18 kcal mol-1) while c3 is stabilized by the less intense interaction LpO5→σ*C-C (ca. 9,5 kcal mol-1). The electronic interactions were investigated by means of interatomic short contacts supported by partial atomic charges calculations. In contrast with the almost similar orbital interactions stability of c1 and c2, the former is strongly destabilized by the electrostatic repulsion between Oδ-CO...Oδ-OMe atoms which are negatively charged separated by a distance shorter than the van der Waals radius sum. This short contact between Cδ+=Oδ- and Cδ+−Oδ- dipoles is responsible for the highest νCO frequency of c1 compared to c2 and c3. In the other hand, the greater stabilization of c1 in the more polar solvents is due to the better solvation of those local dipoles. Last, but not least, the X-ray analysis showed that the compounds in the solid state assume the less stable conformation c1, obtained in gas phase. No significative differences were found in terms of the Y and X substituents. It is suggestive that an energetic balance between orbital and electrostatic interactions determines the global stability of conformations in both studied series.
329

Análise conformacional e estudo das interações eletrônicas de algumas (α-oxa-α-tio-) e (α-oxa-α-seleno-) acetofenonas-para-substituídas / Conformational analysis and electronic interactions study of some (α-oxa-α-thio-) and (α-oxa-α-seleno-) acetophenones-para-substituted

Henrique Joel Traesel 26 October 2018 (has links)
A presente tese trata da análise conformacional e estudo das interações eletrônicas de algumas 2-(fenilselanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série I) e das 2-(4-substituídasfenilsulfanil)-2-(metoxi)-4\'-substituídas-acetofenonas (série II) contendo grupos doadores, hidrogênio e atraentes de elétrons na posição para dos anéis fenacílico [4\'-Y-PhC(O)] e fenilsulfanílico (S-Ph-4-X). Através da resolução das bandas de νCO, foi constatada a ocorrência de isomerismo conformacional nos solventes de constante dielétrica crescente (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) em ambas as séries. Cinco compostos da série II apresentaram ressonância de Fermi (RF) no infravermelho e precisaram ser deuterados. Os dados espectroscópicos são concordantes tanto com os resultados dos cálculos de otimização e frequência em fase gasosa quanto com a simulação do efeito do solvente (PCM), no nível de teoria B3LYP/6-31+G(d,p). Em ambas as séries, foram encontradas três conformações estáveis c1, c2 e c3, sendo que c2 é significativamente mais estável que c1 e c3. O confôrmero c1 possui o oxigênio metoxílico e o carbonílico em sinperiplanar enquanto os grupos -SePh/- SPh estão em anticlinal. Os confôrmeros c2 e c3 possuem o hidrogênio metínico em sinperiplanar com a carbonila enquanto os grupos -OMe e -SePh/-SPh estão na anticlinal. O confôrmero c1 pode ser atribuído ao componente de banda (IR) de maior frequência νCO. Da mesma forma, c2 e c3 são o componente de frequência intermediária e de menor frequência, respectivamente, na série I enquanto que na série II eles coalescem em apenas um componente de menor frequência. Os cálculos de PCM mimetizam os dados espectroscópicos, i.e. é possível constatar a inversão populacional entre c1 e c2, conforme a polaridade do solvente aumenta. Através do cálculo de frequências anarmônicas e construção da PED, foram encontrados dois modos vibracionais que combinados interagem com νCO originando a RF (série II). Um modo é de alta frequência e envolve uma porcentagem considerável de &#948C-H(metínico), o outro modo é esqueletal. A análise das interações orbitalares (NBO) mostrou que os confôrmeros c1 e c2 são estabilizados pela transferência de cargas entre LpO5→σ*CS/Se (ca. 18 kcal mol-1) enquanto c3 é estabilizado pela interação menos intensa LpO5→σ*C-C (ca. 9,5 kcal mol-1). As interações eletrônicas foram investigadas a partir dos contatos interatômicoscurtos com apoio das cargas atômicas parciais. Apesar de c1 e c2 apresentarem praticamente a mesma estabilidade em termos de interações orbitalares, o primeiro é fortemente desestabilizado pela repulsão eletrostática entre os átomos O&#948-CO...O&#948-OMe negativamente carregados separados por uma distância menor que a soma dos raios de van der Waals. Este contato curto entre os dipolos C&#948+=O&#948- e C&#948+−O&#948- é responsável pela maior frequência de νCO de c1 frente c2 e c3. A maior estabilidade de c1 nos solventes mais polares, porém, deve-se à melhor solvatação local destes dipolos. As análises dos monocristais (raios-X) indicou que os compostos assumem, no estado sólido, a conformação menos estável c1, obtida em fase gasosa. Não foram encontradas diferenças significativas no que se refere aos substituintes Y e X. Conclui-se que a estabilidade global das conformações é determinada pelo balanço energético entre as interações orbitalares e eletrostáticas, nas duas séries estudadas. / This thesis reports the conformational analysis and the electronic interactions study of some 2-(phenylselanyl)-2-(methoxy)-4\'-substituted-acetophenones (series I) and 2-(4-substitutedphenylsulphanyl)-2-(methoxy)-4\'-substituted-acetophenones (series II) bearing electron donating, hydrogen and electron attracting substituents in the para position of the phenacyl [4\'-Y-PhC(O)] and phenylsulphanyl (S-Ph-4-X). The occurrence of conformational isomerism in crescent dielectric constant solvents (n-C6H14, CCl4, CHCl3, CH2Cl2, CH3CN) in the two series was studied through the νCO infrared band decomposition. From the series II compounds, five presented Fermi resonance (FR) and had to be deuterated. The spectroscopic data are in line with theoretical calculations results for optimization and frequency in gas phase as well as for solvent effect simulation (PCM), both in B3LYP/6-31+G(d,p) level. Three stable conformers (c1, c2 and c3) were found for both series being the c2 significantly more stable than c1 and c3. Particularly in the c1 conformer, the methoxyl and the carbonyl oxygens are in sinperiplanar orientation while the -SePh/-SPh groups are in anticlinal. In the c2 and c3 conformers the methyne hydrogen assume a sinperiplanar geometry with respect to the carbonyl whereas both -OMe and -SePh/-SPh are in anticlinal. The c1 conformer can be ascribed to the highest frequency νCO band component (IR). So, c2 and c3 ones can be ascribed to the medium and the lowest frequency νCO component, respectively, in the series I whereas in the series II they come together (coalescence) in one single band component. The PCM calculations are in good agreement with spectroscopic data i.e. it is possible to observe a populational inversion between c1 and c2 conformers as the solvent polarity increases. The anharmonic frequencies and PED theoretical treatment revealed that the combination of two vibrational modes interact with the νCO giving rise to the FR (series II): the high frequency one involves a considerable δC-H(methyne) percentage; whilst the other is skeletal. The orbital interactions analysis (NBO) showed that the c1 and c2 conformers are mainly stabilized by charge transfer LpO5→σ*CS/Se (ca. 18 kcal mol-1) while c3 is stabilized by the less intense interaction LpO5→σ*C-C (ca. 9,5 kcal mol-1). The electronic interactions were investigated by means of interatomic short contacts supported by partial atomic charges calculations. In contrast with the almost similar orbital interactions stability of c1 and c2, the former is strongly destabilized by the electrostatic repulsion between Oδ-CO...Oδ-OMe atoms which are negatively charged separated by a distance shorter than the van der Waals radius sum. This short contact between Cδ+=Oδ- and Cδ+−Oδ- dipoles is responsible for the highest νCO frequency of c1 compared to c2 and c3. In the other hand, the greater stabilization of c1 in the more polar solvents is due to the better solvation of those local dipoles. Last, but not least, the X-ray analysis showed that the compounds in the solid state assume the less stable conformation c1, obtained in gas phase. No significative differences were found in terms of the Y and X substituents. It is suggestive that an energetic balance between orbital and electrostatic interactions determines the global stability of conformations in both studied series.
330

Dynamics and stability of a Bose-Fermi mixture : counterflow of superfluids and inelastic decay in a strongly interacting gas / Dynamique et stabilité d'un mélange de Bose-Fermi : contre-courant de superfluides et pertes inélastiques dans un gaz fortement corrélé

Laurent, Sébastien 09 October 2017 (has links)
La compréhension des effets des interactions dans un ensemble de particules quantiques représente un enjeu majeur de la physique moderne. Les atomes ultra-froids sont rapidement devenus un outil incomparable pour étudier ces systèmes quantiques fortement corrélés. Dans cette thèse, nous présentons plusieurs travaux portant sur les propriétés d’un mélange de superfluides de Bose et de Fermi créé à l’aide de vapeurs ultra-froides de ⁷Li et de ⁶Li. Nous étudions tout d'abord les propriétés hydrodynamiques du mélange en créant un contre-courant entre les superfluides. L'écoulement est dissipatif uniquement au dessus d'une vitesse critique que nous mesurons dans le crossover BEC-BCS. Une simulation numérique d’un contre-courant de deux condensats permet de mieux comprendre les mécanismes sous-jacents mis en jeu dans la dynamique. En particulier, l'étude numérique fournit des preuves supplémentaires que l'origine de la dissipation dans nos expériences est liée à l'émission d'excitation élémentaires dans chaque superfluide. Finalement, nous nous intéressons aux pertes inélastiques par recombinaison à trois corps qui peuvent limiter la stabilité de nos nuages. Ces pertes sont intimement liées aux corrélations à courte distance présentes dans le système et sont ainsi connectées aux propriétés universelles du gaz quantique. Cela se manifeste notamment par l’apparition de dépendances en densité ou en température inusuelles du taux de perte lorsque le système devient fortement corrélé. Nous démontrons cet effet dans deux exemples où les interactions sont résonantes, le cas du gaz de Bose unitaire et celui de notre mélange de superfluides Bose-Fermi. Plus généralement, nos travaux montrent que ces pertes inélastiques peuvent être utilisées pour sonder les corrélations quantiques dans un système en fortes interactions. / Understanding the effect of interactions in quantum many-body systems presents some of the most compelling challenges in modern physics. Ultracold atoms have emerged as a versatile platform to engineer and investigate these strongly correlated systems. In this thesis, we study the properties of a mixture of Bose and Fermi superfluids with tunable interactions produced using ultracold vapors of ⁷Li and ⁶Li. We first study the hydrodynamic properties of the mixture by creating a counterflow between the superfluids. The relative motion only exhibit dissipation above a critical velocity that we measure in the BEC-BCS crossover. A numerical simulation of counterflowing condensates allows for a better understanding of the underlying mechanisms at play in the dynamics. In particular, this numerical study provides additional evidence that the onset of friction in our experiment is due to the simultaneous generation of elementary excitations in both superfluids. Finally, we consider the inelastic losses that occur via three-body recombination in our cold gases. This few-body process is intimately related to short-distance correlations and is thereby connected to the universal properties of the many-body system. This manifests as the apparition of an unusual dependence on density or temperature in the loss rate when increasing the interactions. We demonstrate this effect in two examples where interactions are resonant: the case of a dilute unitary Bose gas and the one of impurities weakly coupled to a unitary Fermi gas. More generally, our work shows that inelastic losses can be used to probe quantum correlations in a many-body system.

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