Various gold complexes were computationally investigated, to probe their photophysical, geometric, and bonding properties. The geometry of AuI complexes (ground state singlet) is very sensitive to the electronic nature of the ligands: σ-donors gave a two-coordinate, linear shape; however, σ-acceptors yielded a three-coordinate, trigonal planar geometry. Doublet AuIIL3 complexes distort to T-shape, and are thus ground state models of the corresponding triplet AuIL3. The disproportionation of AuIIL3 to AuIL3 and AuIIIL3 is endothermic for all ligands investigated, however, σ-donors are better experimental targets for AuII complexes. For dimeric AuI complexes, only one gold center in the optimized triplet exciton displays a Jahn-Teller distortion, and the Au---Au distance is reduced versus the ground state distance (i.e., two reasons for large Stokes' shifts).

First-order viscous relativistic hydrodynamics has long been thought to be unsta- ble and acausal. This is not true; it is only with certain definitions of the hydrody- namic variables that the equations of motion display these properties. It is possible to define the hydrodynamic variables such that a fluid is both stable and causal at first order. This thesis does so for both uncharged and charged fluids, mostly for fluids at rest. Work has also been done in limited cases on fluids in motion. A class of stable and causal theories is identified via constraints on transport coefficients derived from linearized perturbations of the equilibrium state. Causality conditions are also derived for the full non-linear hydrodynamic equations. / Graduate

Quantum chemical methods have been used to model a variety of p- and f-block chemical species to gain insight about their energetic and spectroscopic properties. As well, the studies have provided understanding about the utility of the quantum mechanical approaches employed for the third-row and lanthanide species. The multireference ab initio correlation consistent Composite Approach (MR-ccCA) was utilized to predict dissociation energies for main group third-row molecular species, achieving energies within 1 kcal mol-1 on average from those of experiment and providing the first demonstration of the utility of MR-ccCA for third-row species. Multireference perturbation theory was utilized to calculate the electronic states and dissociation energies of NdF2+, providing a good model of the Nd-F bond in NdF3 from an electronic standpoint. In further work, the states and energies of NdF+ were determined using an equation of motion coupled cluster approach and the similarities for both NdF2+ and NdF were noted. Finally, time-dependent density functional theory and the static exchange approximation for Hartree-Fock in conjunction with a fully relativistic framework were used to calculate the L3 ionization energies and electronic excitation spectra as a means of characterizing uranyl (UO22+) and the isoelectronic compounds NUO+ and UN2.

No description available.

The experience of time passing is a fundamental part of the human experience, but what is the relationship between conscious experiences in time and the relativistic nature of space and time? It is natural to think that our phenomenal experiences are realised by neuralevents in our brains. And it seems plausible that the order of these neural events makes a difference to our phenomenology. Yet, relativity theory entails that in some cases these neural events lack objective temporal orders. Instead, their temporal order is different relative to different, equally valid frames of reference. How then is this relativity compatible that intuitively there is only a single, objective way in which things appear to us? This question is at the centre of this thesis. I will present the context of the debate within the theory of Special Relativity and how different problems seem to arise between consciousness and Special Relativity. I will then introduce some basic key concepts for understanding Special Relativity. After introducing the foundation of the problem and a specific formulation that provides the structure of the rest of the thesis, I will present four different possible solutions to the problems, analysing their strengths and weaknesses. Finally, I will use one of the proposed solutions, the objective objection, to argue that the problem never actually arises to begin with and that it is based on a misreading of Special Relativity. I also argue that the objective objection is much more general than its originator proposes. / Att uppleva att tiden går är en central del av våra medvetna upplevelser, men vad är relationen mellan medvetna upplevelser i tiden och den relativistiska rumtiden? Våra fenomenologiska upplevelser måste vara formade av den temporala ordningen av neurologiska händelser och olika ordningar bör då ge upphov till olika fenomenologiska upplevelser. Den speciella teorin om relativitet tillåter olika ordningar av neurologiska händelser men detta står i kontrast med det faktum att vi endast kan ha en fenomenologisk upplevelse. I denna uppsats kommer jag undersöka relationen mellan speciell relativitet och medvetandet och varför det verkar som om relativitetsteorin ger upphov till flera fenomenologiska upplevelser när vi bara upplever en. Jag kommer presentera speciell relativitet och dess kontext i debatten om medvetandet och tid samt även ett par problem som verkar dyka upp mellan medvetandet och speciell relativitet. Därefter kommer jag att introducera några nyckelbegrepp för att underlätta förståelsen av speciell relativitet. Efter attha lagt fram problemet som uppsatsen undersöker kommer jag presentera fyra möjliga lösningar som jag har identifierat och deras styrkor samt svagheter. Slutligen kommer jag diskutera den lösning som jag tycker är mest sannolik, vilket är den objektiva invändningen, men jag argumenterar även att invändningen är mycket mer generell än dess ursprungliga författare föreslår och att problemet med flera sekvenser av neurologiska händer endast uppstår på grund av en missuppfattning om speciell relativitet.

No description available.

Neste trabalho usamos um modelo hidrodinâmico com condições iniciais flutuantes evento a evento para estudar alguns observáveis em colisões de íons pesados relativísticos. Mostramos que a introdução de flutuações, caracterizadas por tubos longitudinais de alta densidade de energia, torna o cálculo dos observáveis mais próximo dos dados, em comparação à abordagem tradicional, na qual as condições iniciais são parametrizadas através de funções suaves e simétricas. No caso da distribuição de partículas em função do momento transversal, observamos um aumento do número de partículas na região onde p_t>2.0GeV, como consequência da expansão rápida dos tubos de alta densidade de energia, principalmente os tubos próximos à superfície da matéria, que chamamos de tubos periféricos. No caso de v_2 em função do momento transversal, observamos uma redução do fluxo elíptico na mesma região, devido à expansão isotrópica dos tubos periféricos. No caso de v_2 em função da pseudo-rapidez, observamos, com o uso das condições iniciais flutuantes, uma curva com um perfil triangular muito próximo dos dados. No caso da função de correlação de duas partículas, observamos que os tubos periféricos dão origem às chamadas estruturas de Ridge. Estas estruturas representam correlações de longo alcance, na direção longitudinal, entre as partículas trigger e as partículas associadas. Obtivemos uma função de correlação com três Ridges, respectivamente, nas posições: \\Delta\\phi=0, \\Delta\\phi=2 e \\Delta\\phi=-2. Mostramos, também, que o modelo reproduz o chamado efeito in-plane/out-of-plane, que está relacionado com a dependência da função de correlação de duas partículas em relação ao ângulo azimutal do momento da partícula trigger. De modo geral, observamos que, com o ajuste correto dos parâmetros do modelo, como por exemplo, a distribuição de densidade de energia inicial média e a temperatura de desacoplamento, todos os observáveis discutidos nesta tese apresentam um razoável acordo com os dados. / In this work we apply a hydrodynamic model with fluctuating initial conditions in a event by event basis to study some observables in relativistic heavy ion collisions. We show that the introduction of fluctuations, characterized by longitudinal high energy density tubes, turn the computation of the observables closer to data, in comparison to the traditional approach, in which the initial conditions are parametrized by using smooth and symmetrical functions. In the case of the transverse momentum distribution, we observe an enhancement of the number of particles in the region where p_t>2.0GeV, as a consequence of the fast expansion of the high energy density tubes, mainly the tubes that are close to the surface of the matter, called peripheral tubes. In the case of v_2 as a function of the transverse momentum, we observe a reduction of the elliptic flow at the same region, due to the isotropic expansion of the peripheral tubes. In the case of v_2 as a function of the pseudorapidity, we observe, by using the fluctuating initial conditions, a curve with a triangular shape very close to data. In the case of the two particle correlation function, we observed that the peripheral tubes give rise to the Ridge structures. These structures represent a long range correlation, in the longitudinal direction, between the trigger particles and the associated particles. We got a two particle correlation function with three Ridges, respectively, at the positions: \\Delta\\phi=0, \\Delta\\phi=2 and \\Delta\\phi=-2. In addition, we show that the model reproduces the in-plane/out-of-plane effect, which is related with the two particle correlation function dependence on the azimuthal angle of the momentum of the trigger particle. Generally, we observed that, with the proper adjustment of the parameters of the model, as, for example, the average initial energy density and the freeze-out temperature, all observables discussed in this thesis show a reasonable agreement with data.

Neste trabalho usamos um modelo hidrodinâmico com condições iniciais flutuantes evento a evento para estudar alguns observáveis em colisões de íons pesados relativísticos. Mostramos que a introdução de flutuações, caracterizadas por tubos longitudinais de alta densidade de energia, torna o cálculo dos observáveis mais próximo dos dados, em comparação à abordagem tradicional, na qual as condições iniciais são parametrizadas através de funções suaves e simétricas. No caso da distribuição de partículas em função do momento transversal, observamos um aumento do número de partículas na região onde p_t>2.0GeV, como consequência da expansão rápida dos tubos de alta densidade de energia, principalmente os tubos próximos à superfície da matéria, que chamamos de tubos periféricos. No caso de v_2 em função do momento transversal, observamos uma redução do fluxo elíptico na mesma região, devido à expansão isotrópica dos tubos periféricos. No caso de v_2 em função da pseudo-rapidez, observamos, com o uso das condições iniciais flutuantes, uma curva com um perfil triangular muito próximo dos dados. No caso da função de correlação de duas partículas, observamos que os tubos periféricos dão origem às chamadas estruturas de Ridge. Estas estruturas representam correlações de longo alcance, na direção longitudinal, entre as partículas trigger e as partículas associadas. Obtivemos uma função de correlação com três Ridges, respectivamente, nas posições: \\Delta\\phi=0, \\Delta\\phi=2 e \\Delta\\phi=-2. Mostramos, também, que o modelo reproduz o chamado efeito in-plane/out-of-plane, que está relacionado com a dependência da função de correlação de duas partículas em relação ao ângulo azimutal do momento da partícula trigger. De modo geral, observamos que, com o ajuste correto dos parâmetros do modelo, como por exemplo, a distribuição de densidade de energia inicial média e a temperatura de desacoplamento, todos os observáveis discutidos nesta tese apresentam um razoável acordo com os dados. / In this work we apply a hydrodynamic model with fluctuating initial conditions in a event by event basis to study some observables in relativistic heavy ion collisions. We show that the introduction of fluctuations, characterized by longitudinal high energy density tubes, turn the computation of the observables closer to data, in comparison to the traditional approach, in which the initial conditions are parametrized by using smooth and symmetrical functions. In the case of the transverse momentum distribution, we observe an enhancement of the number of particles in the region where p_t>2.0GeV, as a consequence of the fast expansion of the high energy density tubes, mainly the tubes that are close to the surface of the matter, called peripheral tubes. In the case of v_2 as a function of the transverse momentum, we observe a reduction of the elliptic flow at the same region, due to the isotropic expansion of the peripheral tubes. In the case of v_2 as a function of the pseudorapidity, we observe, by using the fluctuating initial conditions, a curve with a triangular shape very close to data. In the case of the two particle correlation function, we observed that the peripheral tubes give rise to the Ridge structures. These structures represent a long range correlation, in the longitudinal direction, between the trigger particles and the associated particles. We got a two particle correlation function with three Ridges, respectively, at the positions: \\Delta\\phi=0, \\Delta\\phi=2 and \\Delta\\phi=-2. In addition, we show that the model reproduces the in-plane/out-of-plane effect, which is related with the two particle correlation function dependence on the azimuthal angle of the momentum of the trigger particle. Generally, we observed that, with the proper adjustment of the parameters of the model, as, for example, the average initial energy density and the freeze-out temperature, all observables discussed in this thesis show a reasonable agreement with data.

La physique des collisions d'ions lourds réunit deux domaines : la physique nucléaire et la physique des particules. Les progrès expérimentaux de ces dernières années donne l'opportunité d'étudier la nouvelle matière créée dans les collisions d'ions lourds qui s'appelle le plasma de quarks et de gluons.L'état initial de deux ions qui se collisionnent est affecté par les fluctuations créées par les fonctions d'ondes des nucléons. Ces fluctuations provoquent l'anisotropie de moments de la matière hadronique observée par les détecteurs. Le système créé dans une collision se comporte comme un fluide, donc l'état initial est connecté avec l'état final par l'évolution hydrodynamique. L’hydrodynamique relativiste est utilisée pour décrire l'évolution du fluide créé dans les collisions d'ions lourds. Nos résultats combinés avec les données expérimentales permettent de contraindre l'etat initial donc de faire la «rétro-ingénierie» des collisions d'ions lourds.L'observable qui caractérise l'anisotropie des moments est le flot anisotrope v_n. On présente les premières mesures du premier coefficient de la distribution de Fourier v_1 pour l'accélérateur LHC. v_1 s'appelle le flot dirigé. On effectue aussi les premiers calculs de v_1 à partir de l’hydrodynamique visqueuse. On trouve que v_1 est moins dépendent de la viscosité que les coefficients v_2 et v_3 qui sont respectivement les flots elliptique et triangulaire. On présente aussi les prédictions de v_1 pour l'accélérateur RHIC. Ces résultats ont été confirmés plus tard par les mesures de v_1 par RHIC. On propose aussi deux méthodes pour contraindre les modèles d’état initial: avec les données de v_1 et les données de v_2 et v_3. Ces méthodes donnent l'unique possibilité de contraindre les modèles Monte Carlo d'état initial. A la fin de cette thèse on montre les perspectives de ce domaine et on étudie les corrélations entre les plans des évènements qui ont été mesurées récemment et qui pourraient faire la lumière sur les fluctuations de l'état initial. / Ultra-Relativistic heavy-ion physics is a promising field of high energy physics connecting two fields: nuclear physics and elementary particle physics. Experimental achievements of the last years have provided an opportunity to study the properties of a new state of matter created in heavy-ion collisions called quark-gluon plasma. The initial state of two colliding nuclei is affected by fluctuations coming from wave- functions of nucleons. These fluctuations lead to the momentum anisotropy of the hadronic matter which is observed by the detectors. The system created in the collision behaves like a fluid, so the initial state is connected to the final state via hydrodynamic evolution. In this thesis we model the evolution with relativistic viscous hydrodynamics. Our results, combined with experimental data, give non trivial constraints on the initial state, thus achieving "reverse engineering" of the heavy-ion collisions. The observable which characterizes the momentum anisotropy is the anisotropic flow vn. We present the first measurements of the first harmonic of the anisotropic flow called directed flow v1 in Pb-Pb collisions at the LHC. We then perform the first viscous hydrodynamic modeling of directed flow and show that it is less sensitive to viscosity than higher harmonics. Comparison of these experimental data with the modeling allows to extract the values of the dipole asymmetry of the initial state, which provides constraints on the models of initial states. A prediction for directed flow v1 in Au-Au collisions is also made for RHIC. We then perform a similar modeling of the second and third harmonics of the anisotropic flow, called respectively elliptic v2 and triangular v3 flow. A combined analysis of the elliptic and triangular flow data compared with viscous hydrodynamic calculations allows us to put constraints on initial ellipticity and triangularity of the system. These constraints are then used as a filter for different models of initial state. At the end of this thesis, we show perspectives in the studies of the initial state which are opened by recent measurements of event-plane correlations which could shed light on the initial state fluctuations.

Desde o início do uso de ferramentas computacionais na química, pesquisadores notaram a necessidade de um adequado tratamento da correlação eletrônica para a acurada descrição da estrutura eletrônica. Algum tempo depois, perceberam que, além da correlação, haviam ainda deficiências nos resultados obtidos, as quais estavam relacionadas com efeitos relativísticos, principalmente quando tentavam tratar moléculas com átomos pesados. Um terceiro aspecto a ser levado em consideração nestes estudos diz respeito ao uso de um conjunto acurado de funções de base. No caso específico de cálculos relativísticos, se possível, tais conjuntos ainda precisam garantir a eliminação do prolapso variacional, um problema que está relacionado com uma descrição deficiente da região mais próxima dos núcleos. Com esse propósito, o conjunto RPF-4Z foi desenvolvido recentemente. Sendo assim, este projeto foi voltado para a análise comparativa da qualidade do conjunto RPF-4Z. Desta forma, foram avaliadas propriedades fundamentais das moléculas como, por exemplo, geometrias, momentos de dipolo e constantes espectroscópicas. Simultaneamente, uma propriedade desafiadora, o gradiente de campo elétrico na posição de núcleos de xenônio, também foi considerada. Os resultados obtidos até agora reforçam a eficiência do conjunto RPF-4Z, que é capaz de fornecer valores comparáveis àqueles dados por conjuntos de base de mesma qualidade, mas com menor demanda por recursos computacionais. / Early in the application of computational framework in chemistry, researchers noticed the need for an adequate electronic correlation treatment in order to accurately describe electronic structures. Some years later they realized that, besides correlation, there were also deficiencies in the results, which were related to relativistic effects, especially when dealing with molecules containing heavy atoms. A third aspect to be taken into account is related to the use of an accurate basis set. Specifically for relativistic calculations, these basis sets must also ensure the elimination of variational prolapse if possible, which is a problem related to a poor description of the innermost region close to the nuclei. Thus, the RPF-4Z basis set was recently developed for this aim. This project is focused on a comparative analysis regarding the RPF-4Z basis set\'s quality. Thereby, fundamental properties of molecules were evaluated, such as geometries, dipole moments and spectroscopic constants. At the same time, a challenging property, the electric field gradient at the xenon nuclei, was considered as well. The results obtained so far reinforce the efficiency of the RPF-4Z basis set, which is capable of providing comparable values to those obtained by same quality basis sets but with a lower demand for computational resources.