Neste trabalho estudamos o processo de ressonância colisional o que nos permitiu aumentar a taxa de formação molecular em até seis vezes. Isto foi feito variando-se a temperatura atômica de uma amostra inicialmente aprisionada em uma armadilha magneto óptica (MOT) através de um passo de resfriamento do tipo melaço óptico (molasses). Uma explicação qualitativa foi apresentada para o efeito observando as soluções das funções de ondas parciais para átomos interagentes no estado fundamental. Carregamos uma armadilha óptica de dipolo formada por um laser de Ti:Safira. Por fim, ressaltamos a importância de tais resultados para o nosso grupo de pesquisas e a sua utilização em futuros experimentos. / In this work, we study a partial wave resonance process which allows us to increase the molecule formation rate up to six times. This was done by an atomic temperature variation which was first trapped in a magneto optical trap (MOT) by applying a molasses stage. A qualitative explanation was presented for the observed effect through the partial waves solutions for ground states interacting atoms. We loaded an optical dipole trap formed by a Ti:Sapphire laser. Finally, we discuss the importance of such results for our research and their use in future experiments.

Orientadores: Francisco José Arnold, Leonardo Lorenzo Bravo Roger / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Tecnologia / Made available in DSpace on 2018-08-19T21:46:41Z (GMT). No. of bitstreams: 1 Grilo_Marcus_M.pdf: 4359440 bytes, checksum: 6cae50e622550385b3c928f7055ed0fe (MD5) Previous issue date: 2012 / Resumo: Este trabalho apresenta a análise, o projeto e a construção de uma antena de banda dupla para as faixas de frequências de 915MHz e 2,45GHz, para aplicação em sistemas RFID. A antena é impressa em um substrato de fibra de vidro e possui estrutura dipolar. Os elementos radiadores estão em faces opostas do substrato o que resulta em baixa capacitância do dispositivo. As simulações computacionais, realizadas no programa HFSS, apresentaram boa concordância com os resultados experimentais. Os resultados mostraram importantes vantagens conseguidas com a antena desenvolvida, tais como estrutura simples e independência e facilidade de sintonia. Além disso, os parâmetros característicos (perda de retorno e ganho) de desempenho da antena são bastante satisfatórios. Propostas para trabalhos futuros também são apresentadas / Abstract: This paper presents the analysis, design and construction of a dual band antenna for the frequency bands 915 MHz and 2.45 GHz, for use in RFID systems. The antenna is printed on a substrate of fiberglass and has a dipolar structure. The radiator elements are on opposite faces of the substrate which results in low capacitance of the device. Computer simulations, carried out in the program HFSS, in good agreement with experimental results. The results showed important advantages achieved with the antenna developed, such as simple structure, independence and ease of tuning. Moreover, the characteristic parameters (return loss and gain) antenna performance are quite satisfactory. Proposals for future work are also presented / Mestrado / Tecnologia e Inovação / Mestre em Tecnologia

Ce travail concerne la modélisation, à l’échelle moléculaire, de l’interaction entre des nanoparticules carbonées et le rayonnement électromagnétique. Le but est d’aider à la compréhension des propriétés optiques des particules de suie afin de mieux quantifier l’influence des suies sur l’atmosphère et le climat. L’étude de l’interaction rayonnement/particules de suie fraîche a été effectuée par la méthode PDI ; il a été montré que : i) le coefficient d’absorption massique (MAC) des particules de suie dépend de la répartition des atomes dans la particule et de leurs liaisons, en particulier entre 200 et 350 nm ; ii) le MAC diffère selon que le cœur de la particule carbonée est occupé ou non par des plans graphitiques ; iii) un modèle analytique n’est pas adapté pour calculer le MAC d’une nanoparticule carbonée présentant des défauts structuraux. De plus, des méthodes de chimie quantique ont été utilisées pour caractériser le vieillissement des suies. Les résultats montrent que : i) NO, Cl, et HCl sont physisorbées sur une surface carbonée parfaite alors que sur une surface défective, ces espèces sont chimisorbées et conduisent à une modification de la surface ; ii) la présence de Cl conduit à un piégeage fort des molécules d’eau supérieur à celui obtenu lorsqu’un site oxygéné est présent sur la surface carbonée, expliquant ainsi le caractère hydrophile des suies émises lors d’incendies dans des milieux industriels. Enfin, la méthode PDI a été appliquée au calcul de la polarisabilité de HAP afin d’interpréter des spectres d’absorption des grains carbonés du milieu interstellaire, en incluant des molécules pour lesquelles aucune donnée n’était actuellement disponible. / This work concerns the modeling, at the molecular level, of the interaction between carbonaceous particles of nanometric size and the electromagnetic radiation. The goal is to improve our understanding of the optical properties of soot particles, to better quantify the influence of soot on the atmosphere and on climate change. The study of the interaction between radiation and fresh soot particles was carried out using the point dipole interaction method; it has been shown that: i) the mass absorption coefficient (MAC) of these soot nanoparticles may significantly depend on their atomistic details, especially between 200 and 350 nm; ii) the MAC depends on whether the heart of the carbonaceous particle is occupied or not by graphite planes; iii) an analytical model is not suitable for calculating the MAC of carbonaceous nanoparticles having structural defects. In addition, quantum chemical methods have been used to characterize the ageing of soot. The results obtained are i) NO, Cl, and HCl are physisorbed on a perfect carbonaceous surface whereas on a defective surface, these species are chemisorbed and lead to a modification of the surface; ii) on a carbonaceous surface, the presence of adsorbed Cl atoms leads to a strong trapping of the surrounding water molecules. This may be related to the highly hydrophilic nature of soot emitted during fires in industrial environments. Finally, the PDI method was applied to calculate the polarizability of PAHs to help at interpreting the absorption spectra of carbonaceous grains in the interstellar medium, including molecules for which no data was currently available.

Contributions to the second order collision efficiency function S ⁽²⁾ (b), used in semiclassical perturbation approaches to pressure broadening of microwave and infrared spectra, due to several leading terms, dipole and quadrupole components, in the expansion of the intermolecular interaction energy are derived by method of irreducible spherical tensor operators for molecules of arbitrary symmetry. Results are given explicitly in terms of dipole and quadrupole line strengths. General expressions for dipole moment line strength in the asymmetric rotor basis as well as quadrupole moment line strength for the special case of molecules with two independent quadrupole moment components are derived. Computer programs for calculating linewidth parameters in the rotational spectrum of ¹⁴NO₂ based on Anderson and Murphy and Boggs theories are presented.

Quaternary ammonium salts are surface active bactericides. A mechanism of their biological activity has been well studied experimentally, and it encompasses two stages. The first stage involves electrostatic interactions of polar functional groups of the salts with oppositely charged functional groups on a bacterial cell surface, and the second stage includes incorporation of their lipophilic groups into a bacterial cell membrane. However, despite numerous experimental studies, computational modelling of this mechanism with the aim to support experimental observations with theoretical conclusions, to the author's knowledge, has not yet been reported. In the current study, linear regression models correlating theoretical descriptors of lipophilicity and electronic properties of mono- and disubstituted imidazolium carboxylates with their biological activity towards Escherichia coli have been developed. These models established that biological activity of these salts is governed by the chemical structures of imidazolium cations, and that the centre of this biological activity is located in the long alkyl side chains of the cations. It was also found that these side chains have an intrinsic electronic potential to form internal C-H- -H-C electrostatic interactions when their lengths reach seven carbon atoms. Additionally, the nature of the C-H- -O-C inter-ionic electrostatic interactions in imidazolium carboxylates has been explored via a topological analysis of these interactions in 1-ethyl-3-methylimidazolium acetate. Thus, it was established that these electrostatic interactions are hydrogen bonds.

L'insertion de couches minces d'oxyde métallique (MO) à l'interface entre les électrodes conductrices (FTO / ITO, Métaux) et la couche active (polymère, pérovskite) constitue une solution prometteuse pour améliorer les performances des dispositifs photovoltaïques organiques et hybrides. La procédure consiste à introduire des couches MO fonctionnalisées par des monocouches auto-assemblées dipolaires (SAMs) à l'interface entre l'électrode conductrice et la couche active. Les couches SAMs supportant des dipôles perpendiculaires à la surface peuvent avoir un impact important sur les dispositifs électroniques à la fois en affectant la croissance et l'organisation de la couche organique active et en accordant le travail de sortie des couches MO. Dans ce travail, nous montrons que le greffage des molécules dipolaires sur des couches minces de MO peut affecter considérablement les performances des cellules photovoltaïques. Cet impact dépend fortement de l'orientation du dipôle permanent situé sur la molécule SAM. / The insertion of very thin metal-oxide (MO) layers at the interface between the conductive electrodes (FTO/ITO, Metals) and the active layer (polymer, perovskite) presents a promising solution to improve the performances of organic and hybrid photovoltaic devices. The procedure is about introducing MO layers functionalized by dipolar self-assembling monolayer’s (SAMs) at the interface between the conductive electrode and the active layer. The SAM layers bearing dipoles perpendicular to the surface that can have a large impact on the electronic devices both by affecting the growth and organization of active organic layer and by tuning the work function of the MO layers. In this work we show that the grafting of dipole molecular on top of MO thin films can considerably affect the performance of the photovoltaic cell. The impact on these performances depends strongly on the orientation of the permanent dipole lying on the SAM molecule.

abstract: Vibrational spectroscopy is a ubiquitous characterization tool in elucidating atomic structure at the bulk and nanoscale. The ability to perform high spatial resolution vibrational spectroscopy in a scanning transmission electron microscope (STEM) with electron energy-loss spectroscopy (EELS) has the potential to affect a variety of materials science problems. Since 2014, instrumentation development has pushed for incremental improvements in energy resolution, with the current best being 4.2 meV. Although this is poor in comparison to what is common in photon or neutron vibrational spectroscopies, the spatial resolution offered by vibrational EELS is equal to or better than the best of these other techniques. The major objective of this research program is to investigate the spatial resolution of the monochromated energy-loss signal in the transmission-beam mode and correlate it to the excitation mechanism of the associated vibrational mode. The spatial variation of dipole vibrational signals in SiO2 is investigated as the electron probe is scanned across an atomically abrupt SiO2/Si interface. The Si-O bond stretch signal has a spatial resolution of 2 – 20 nm, depending on whether the interface, bulk, or surface contribution is chosen. For typical TEM specimen thicknesses, coupled surface modes contribute strongly to the spectrum. These coupled surface modes are phonon polaritons, whose intensity and spectral positions are strongly specimen geometry dependent. In a SiO2 thin-film patterned with a 2x2 array, dielectric theory simulations predict the simultaneous excitation of parallel and uncoupled surface polaritons and a very weak excitation of the orthogonal polariton. It is demonstrated that atomic resolution can be achieved with impact vibrational signals from optical and acoustic phonons in a covalently bonded material like Si. Sub-nanometer resolution mapping of the Si-O symmetric bond stretch impact signal can also be performed in an ionic material like SiO2. The visibility of impact energy-loss signals from excitation of Brillouin zone boundary vibrational modes in hexagonal BN is seen to be a strong function of probe convergence, but not as strong a function of spectrometer collection angles. Some preliminary measurements to detect adsorbates on catalyst nanoparticle surfaces with minimum radiation damage in the aloof-beam mode are also presented. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

京都大学 / 新制・課程博士 / 博士(理学) / 甲第22998号 / 理博第4675号 / 新制||理||1670(附属図書館) / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)准教授 金田 佳子, 教授 萩野 浩一, 教授 田中 貴浩 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

In this thesis, research starts by questioning Berry curvature dipole's role in electronic properties in solids. Strongly inspired by the recent studies, we discover a more profound interpretation of the Berry curvature dipole. It is demonstrated that the anomalous correction to the electron acceleration is proportional to the Berry curvature dipole and is responsible for the Non-linear Hall effect recently discovered in materials with broken inversion symmetry. This allows uncovering a deeper meaning of the Berry curvature dipole as a non-linear version of the Drude weight that serves as a measurable order parameter for broken inversion symmetry in metals. Later, we introduce the Quantum Rectification Sum Rule in time-reversal invariant materials is derived by showing that the integral over frequency of the rectification conductivity depends solely on the Berry connection and not on the band energies or relaxation rates. In the final part of the thesis, we use the Keldysch-Floquet formalism to obtain non-perturbative predictions of the optical responses in solids, mainly focusing on the clean limit response of systems with broken time-reversal symmetry.

The method of dipole orientation of protein complexes using electric fields plays a key role in the development of single particle imaging, since it enables orientation of the protein in vacuum. In the orientation process the protein is exposed to an external electric field along which the dipole axis of the protein will eventually align. Earlier studies using molecular dynamics simulations have implemented a constant electric field to examine the dipole orientation process. However, when injected into the electric field the protein experiences a gradually increasing field strength converging to some terminal field strength rather than a constant electric field. In order to examine the effects of the time-dependant nature of the electric field, in comparison to a constant one, fields with different time dependances were implemented in molecular dynamics simulations in vacuum performed with GROMACS. Ubiquitin was chosen as a model protein. The results of the study show time-increasing fields tend to result in slower orientation, but preserve the structure of the protein better than for a constant field. It was also shown that after 10 ns electric field exposure, with terminal field strengths greater  or equal to 0.6Vnm^-1, there was no apparent difference of the average degree of orientation of proteins within the time-increasing fields and the constant one. However, for fields of greater or equal to 1.5Vnm^-1 the constant field tended to result in a larger change of the protein structure.