The electric charge distribution of molecules such as H₂ and D₂ is inversion-symmetric so that permanent dipole moments do not exist: such molecules are infrared-inactive. It is therefore interesting that gaseous, liquid, and solid hydrogen and its isotopes actually absorb infrared radiation, for example if gas densities are sufficiently high. The observed absorption arises from electric dipole moments induced by intermolecular interactions. It is of a supermolecular origin, due to binary (or higher-order) molecular complexes that may be transient (i.e., in a collisional encounter) or relatively stable (van-der-Waals molecule). Interaction-induced electric dipoles arise from the same mechanisms that generate the intermolecular forces: exchange forces, dispersion forces, and multipolar induction. Recently the induced dipole and potential energy surfaces of H₂ pairs have been obtained by advanced quantum-chemical calculations. Interaction-induced absorption, more commonly called collision-induced absorption (CIA), by H₂ pairs is an important opacity source in the atmospheres of various types of planets and cool stars, such as late stars, low-mass stars, brown dwarfs, certain white dwarfs, etc., and therefore of special astronomical interest. The emission spectra of cool white dwarf stars differ significantly from the expected blackbody spectra of their cores, mainly due to collision-induced absorption by collisional complexes of hydrogen and helium in the stellar atmospheres. Before proceeding to the frequencies and temperatures of interest it is good to check the new potential energy surface and induced dipole surface in all possible ways by comparison with existing isotopic laboratory measurements. Furthermore, the new potential energy surface is directly compared with previously available, well established intermolecular potential energy surfaces. The electric charge distributions of deuterium and hydrogen are very similar. The new potential energy and induced dipole surfaces were originally obtained to facilitate the computation of the collision-induced absorption of hydrogen. However, by replacing the rotovibrational wavefunctions of H₂ with those of D₂ the surfaces can also be used to calculate the collision-induced absorption of deuterium pairs, thereby probing them further. At the temperature of 298K existing measurements of the collision-induced absorption of D₂--D₂ gas are compared with our quantum scattering calculations in the D₂ fundamental band (approximately 2,500cm⁻¹ to 4,500cm⁻¹). Furthermore, measurements of the collision-induced absorption of deuterium (D₂) in the D₂ first overtone band (about 5,250cm⁻¹ to 7,250cm⁻¹) at 201K are reported. These measurements are compared with ab initio calculations of the absorption spectra. Close agreement of measured and calculated spectra is seen.

Electrification of low-income rural areas that have a limited connection or no access to electrical grids is one of the most demanding challenges in developing countries such as Peru. The international commitment to stop global warming and the reduction in the cost of renewable sources of energy have reduced the prices of fossil fuels in some cases. This has opened the way to the current research which proposes a hybrid energy system (HES) based on the use of renewable sources of energy. Therefore, a renewable electricity system (HRES) was set up at the village of Monte-Catache in the Cajamarca region, which is one of the poorest areas of Peru. Surveys and field studies were used to evaluate the socioeconomic characteristics, availability of renewable energy resources, and energy demand of this region. Potential energy sources were evaluated, and isolated photovoltaic systems with a battery bank were found to be the most appropriate according to the results obtained in the simulation with HOMER. This proposal constitutes an interesting contribution for future energy solutions in isolated and low-income rural areas. / Revisión por pares

The study of supercooled liquids and glasses remains one of the most divisive and divided fields in modern physics. Despite a vast amount of effort and research time invested in this topic, the answers to many central questions remain disputed and incomplete. However, the link between the behaviour of supercooled liquids and their energy landscapes is well established and widely accepted. Understanding this link would be a key step towards resolving many of the mysteries and controversies surrounding the glass transition. Therefore the study of glassy energy landscapes is an important area of research. In this thesis, I report some of the most detailed computational studies of glassy potential energy landscapes ever performed. Using geometry optimisation techniques, I have sampled the local minima and saddle points of the landscapes for several supercooled liquids to analyse their dynamics and thermodynamics. Some of my analysis follows previous work on the binary Lennard-Jones fluid (BLJ), a model atomic liquid. BLJ is a fragile glass former, meaning that its transport coefficients have super-Arrhenius temperature dependence, rather than the more usual Arrhenius behaviour exhibited by strong liquids. The difference in behaviour between these two classes of liquid has previously been attributed to differing degrees of structure in the relevant energy landscapes. I have studied models for both fragile and strong glass formers: the molecular liquid ortho-terphenyl (OTP) and viscous silica (SiO$_{2}$) respectively. My results for OTP agree closely with trends observed for BLJ, suggesting that the same diffusion mechanism is applicable to fragile molecular liquids as well as to atomic. However, the dynamics and energy landscape of OTP are made complicated by the molecular orientational degrees of freedom, making the analysis more challenging for this system. Dynamics of BLJ, OTP and silica are all dominated by cage-breaking events: structural rearrangements in which atoms change their nearest neighbours. I propose a robust and general method to identify cage breaks for small rigid molecules, and compare some properties of cage breaks between strong and fragile systems. The energy landscapes of BLJ and OTP both display hierarchical ordering of potential energy minima into metabasins. These metabasins can be detected by the cage-breaking method. It has previously been suggested that metabasins are responsible for super-Arrhenius behaviour, and are absent from the landscapes of strong liquids such as SiO2. My results indicate that metabasins are present on the silica landscape, but that they each contain fewer minima than metabasins in BLJ or OTP. Metabasins are associated with anticorrelated particle motion, mediated by reversed transitions between minima of the potential energy landscape. I show that accounting for time-correlation of particle displacement vectors is essential to describe super-Arrhenius behaviour in BLJ and OTP, but also required to reproduce strong behaviour in silica. I hypothesise that the difference between strong and fragile liquids arises from a longer correlation timescale in the latter case, and I suggest a number of ways in which this proposition could be tested. I have investigated the effect on the landscape of freezing the positions of some particles in a BLJ fluid. This “pinning” procedure induces a dynamical crossover that has been described as an equilibrium “pinning transition”, related to the hypothetical ideal glass transition. I show that the pinning transition is related to (and probably caused by) a dramatic change in the potential energy landscape. Pinning a large fraction of the particles in a supercooled liquid causes its energy landscape to acquire global structure and hence structure-seeking behaviour, very different from the landscape of a typical supercooled liquid. I provide a detailed description of this change in structure, and investigate the mechanism underlying it. I introduce a new algorithm for identifying hierarchical organisation of a landsape, which uses concepts related to the pinning transition but is applicable to unpinned liquids as well. This definition is complementary to metabasins, but the two methods often identify the same higher-order structures. The new “packings” algorithm offers a route to test thermodynamic theories of the glass transition in the context of the potential energy landscape. Over the course of this thesis, I discuss several different terms and methods to identify higher-order structures in the landscapes of model glass formers, and investigate how this organisation varies between different systems. Although little variation is immediately apparent between most glassy landscapes, deeper analysis reveals a surprising diversity, which has important implications for dynamical behaviour in the vicinity of the glass transition.

The study aims to assess the energy potential of the sewage treatment plant, residential condominiums low income Programa Minha Casa Minha Vida (PMCMV), by performing the following estimates: biogas production, production of electric and thermal energy, energy needs the common area of the condominium and economic evaluation of the project. This work shows the possibility of using methane That is the aggressive environment in the Energy Recovery, encouraging application of this paragraph Service Sustainable Use of Renewable Natural Resources and Energy Efficiency. Were done calculations to estimate the biogas and methane accounting YOUR Losses During the anaerobic treatment process. The production of biogas Estimated Average was 58.78 m³ / d resulting in a possible Availability of Electricity 86.61 kWh / d Able to supply a lighting of the posts of Internal Streets and condominium recreation area (sports court + gourmet space) through the hum Generator 18 hp no EXISTING iN biogas fueled market having Integrated filter System That allows connection directly to the generator biodigester canvas. It was taking a interest rate of 17.88% pa Investment. Besides the possibility to meet the local population, can earn credits reversing the Electricity Generated in Distribution Network through the Electric Power Compensation System ANEEL. The use of biogas as Electricity Generation And Important For the environment, it avoids it be released methane gas and STILL diversification of energy matrix. / O estudo busca avaliar o potencial energético, da estação de tratamento de esgoto, de condomínios residenciais de baixa renda do programa minha casa minha vida (PMCMV), realizando as seguintes estimativas: produção de biogás, produção de energia elétrica e térmica, necessidades de energia da área comum do condomínio e avaliação econômica do projeto. Este trabalho aponta a possibilidade de utilizar o metano que é agressivo ao meio ambiente na recuperação de energia, incentivando a aplicação deste serviço para uso sustentável dos recursos naturais renováveis e eficiência energética. Foram realizados cálculos para a estimativa do biogás e do metano contabilizando suas perdas durante o processo de tratamento anaeróbico. A produção média de biogás estimado foi de 58,78 m³/d resultando em uma possível disponibilidade de energia elétrica de 86,61 kWh/d capaz de abastecer a iluminação dos postes das ruas internas e a área de lazer do condomínio (quadra poliesportiva + espaço gourmet) através de um gerador de 18 cv existente no mercado abastecido por biogás possuindo Sistema de filtro integrado que permite a conexão do gerador diretamente na lona do biodigestor. Foi adotando uma taxa de juros de 17,88 % a.a. para investimento. Além da possibilidade de atender a população local, pode-se ganhar créditos revertendo a energia elétrica gerada na rede de distribuição através do sistema de compensação de energia elétrica da ANEEL. A utilização do biogás como geração de energia elétrica é importante para o meio ambiente, pois evita que seja lançado gás metano e ainda diversifica a matriz energética.

Made available in DSpace on 2014-06-11T19:22:33Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-05-25Bitstream added on 2014-06-13T18:08:30Z : No. of bitstreams: 1 capellette_rf_me_ilha.pdf: 755361 bytes, checksum: 926155dfd9eb5bc008e14cf26a245d48 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / PROPG - Programa de Pós-Graduação / Este trabalho analisa a influência do FACTS TCSC na função energia do sistema, mais especificamente na energia potencial. Também é abordada a influência da compensação dinâmica do TCSC na trajetória do sistema frente a uma grande perturbação, visando a melhoria da estabilidade transitória. A energia potencial é avaliada no espaço das posições angulares dos rotores das máquinas em torno de um ponto de equilíbrio estável levando em conta os efeitos da ação do TCSC. A trajetória do sistema é sobrepostas às curvas equipotenciais, e com isso é possível a avaliar os efeitos da compensação dinâmica do dispositivo nas mesmas. Através das simulações de dois sistemas testes, um sistema considerado de pequeno porte (Sistema de Quatro Máquinas) e outro de maior porte (New England) quando expostos a uma grande perturbação avalia-se a estabilidade de primeira oscilação com o intuito de determinar o tempo crítico de eliminação de uma falta no sistema. Posteriormente verifica-se a possibilidade de deslocar a trajetória do sistema com o propósito de que ela percorra um caminho mais íngreme na superfície da energia potencial, ou seja, idealmente que ela tenha orientação coincidente do gradiente da energia potencial, e analisa-se qual a influência da compensação série na energia potencial, com o intuito de obter tal direcionamento / This dissertation examines the influence of TCSC FACTS on the power system energy function, specifically on the potential energy. The influence of dynamic compensation of the TCSC in the trajectory of the system after a major disruption in order to improve transient stability is also approached. The potential energy is evaluated in the space of machines rotor angular positions around stable equilibrium point taking into account effects of the TCSC action and the trajectory of the system is superimposed with equipotential curves and so it is possible to evaluate the effects of the dynamic compensation. Simulations are performed with two test systems, one being a (four machines system) and the other being the well-know New England system submitted to great disturbances. The stability of the first oscillation in order to determine the critical fault clearing time, is assessed. It is possible to change the system trajectory in order to traverse a more steeply path, i.e. ideally matching orientation with the potential energy gradient. The influence of series compensation in potential energy is taken into account, in order to conduct the system trajectory to the potential energy gradient orientation

An Ab Initio/RRKM study of the reaction mechanism and product branching ratios of neutral-radical ethynyl (C2H) and cyano (CN) radical species with unsaturated hydrocarbons is performed. The reactions studied apply to cold conditions such as planetary atmospheres including Titan, the Interstellar Medium (ISM), icy bodies and molecular clouds. The reactions of C2H and CN additions to gaseous unsaturated hydrocarbons are an active area of study. NASA’s Cassini/Huygens mission found a high concentration of C2H and CN from photolysis of ethyne (C2H2) and hydrogen cyanide (HCN), respectively, in the organic haze layers of the atmosphere of Titan. The reactions involved in the atmospheric chemistry of Titan lead to a vast array of larger, more complex intermediates and products and may also serve as a chemical model of Earth’s primordial atmospheric conditions. The C2H and CN additions are rapid and exothermic, and often occur barrierlessly to various carbon sites of unsaturated hydrocarbons. The reaction mechanism is proposed on the basis of the resulting potential energy surface (PES) that includes all the possible intermediates and transition states that can occur, and all the products that lie on the surface. The B3LYP/6-311g(d,p) level of theory is employed to determine optimized electronic structures, moments of inertia, vibrational frequencies, and zero-point energy. They are followed by single point higher-level CCSD(T)/cc-vtz calculations, including extrapolations to complete basis sets (CBS) of the reactants and products. A microcanonical RRKM study predicts single-collision (zero-pressure limit) rate constants of all reaction paths on the potential energy surface, which is then used to compute the branching ratios of the products that result. These theoretical calculations are conducted either jointly or in parallel to experimental work to elucidate the chemical composition of Titan’s atmosphere, the ISM, and cold celestial bodies.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23220号 / 工博第4864号 / 新制||工||1759(附属図書館) / 京都大学大学院工学研究科分子工学専攻 / (主査)教授 佐藤 啓文, 教授 佐藤 徹, 教授 田中 勝久 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Thermodynamically, native cellulose nano fibrils are more stable in an aggregated state. The aggregated state is however not useful from a material development perspective. Therefore much research has been done to stabilize the dispersal of the fibrils. One method to overcome this instability is by surface substitution of the O6 hydroxyl group with carboxylate groups, to make highly charged fibrils in aqueous solutions. It is therefore of much interest to understand the interaction of highly charged fibrils in aqueous solutions. In this study, we aim to model the interaction potential energy between native and surface modified cellulose nanofibrils in order to understand under what conditions the contribution from the dipole interactions can be neglected. To achieve this we propose to use a continuum electrostatic approach, modeling the electrostatic interactions as a function of the fibrils relative dipole orientation, separation, surface charge as well as ionic strength of the solution, by means of using the Poisson-Boltzmann equation.

The purpose of this study was to examine the effect that load has on the mechanics of the jump shrug. Fifteen track and field and club/intramural athletes (age 21.7 ± 1.3 y, height 180.9 ± 6.6 cm, body mass 84.7 ± 13.2 kg, 1-repetition-maximum (1RM) hang power clean 109.1 ± 17.2 kg) performed repetitions of the jump shrug at 30%, 45%, 65%, and 80% of their 1RM hang power clean. Jump height, peak landing force, and potential energy of the system at jump-shrug apex were compared between loads using a series of 1-way repeated-measures ANOVAs. Statistical differences in jump height (P <.001), peak landing force (P =.012), and potential energy of the system (P <.001) existed; however, there were no statistically significant pairwise comparisons in peak landing force between loads (P >.05). The greatest magnitudes of jump height, peak landing force, and potential energy of the system at the apex of the jump shrug occurred at 30% 1RM hang power clean and decreased as the external load increased from 45% to 80% 1RM hang power clean. Relationships between peak landing force and potential energy of the system at jump-shrug apex indicate that the landing forces produced during the jump shrug may be due to the landing strategy used by the athletes, especially at lighter loads. Practitioners may prescribe heavier loads during the jump-shrug exercise without viewing landing force as a potential limitation.

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20369号 / 工博第4306号 / 新制||工||1667(附属図書館) / 京都大学大学院工学研究科材料工学専攻 / (主査)教授 田中 功, 教授 酒井 明, 教授 中村 裕之 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM