The present thesis is devoted to theoretical studies of resonant X-ray scattering and propagation of strong X-ray pulses. In the first part of the thesis the nuclear dynamics of different molecules is studied using resonant X-ray Raman and resonant Auger scattering techniques. We show that the shortening of the scattering duration by the detuning results in a purification of the Raman spectra from overtones and soft vibrational modes. The simulations are in a good agreement with measurements, performed at the MAX-II and the Swiss Light Source with vibrational resolution. We explain why the scattering to the ground state nicely displays the vibrational structure of liquid acetone in contrast to excited final state. Theory of resonant X-ray scattering by liquids is developed. We show that, contrary to aqueous acetone, the environmental broadening in pure liquid acetone is twice smaller than the broadening by soft vibrational modes significantly populated at room temperature. Similar to acetone, the "elastic" band of X-ray Raman spectra of molecular oxygen is strongly affected by the Thomson scattering. The Raman spectrum demonstrates spatial quantum beats caused by two interfering wave packets with different momenta as the oxygen atoms separate. It is found that the vibrational scattering anisotropy caused by the interference of the "inelastic" Thomson and resonant scattering channels in O2. A new spin selection rule is established in inelastic X-ray Raman spectra of O2. It is shown that the breakdown of the symmetry selection rule based on the parity of the core hole, as the core hole and excited electron swap parity. Multimode calculations explain the two thresholds of formation of the resonant Auger spectra of the ethene molecule by the double-edge structure of absorption spectrum caused by the out-of- and in-plane modes. We predict the rotational Doppler effect and related broadening of X-ray photoelectron and resonant Auger spectra, which has the same magnitude as its counterpart-the translational Doppler effect. The second part of the thesis explores the interaction of the medium with strong X-ray free-electron laser (XFEL) fields. We perform simulations of nonlinear propagation of femtosecond XFEL pulses in atomic vapors by solving coupled Maxwell's and density matrix equations. We show that self-seeded stimulated X-ray Raman scattering strongly influences the temporal and spectral structure of the XFEL pulse. The generation of Stokes and four-wave mixing fields starts from the seed field created during pulse propagation due to the formation of extensive ringing pattern with long spectral tail. We demonstrate a compression into the attosecond region and a slowdown of the XFEL pulse up to two orders of magnitude. In the course of pulse propagation, the Auger yield is strongly suppressed due to the competitive channel of stimulated emission. We predict a strong X-ray fluorescence from the two-core-hole states of Ne created in the course of the two-photon X-ray absorption. / QC 20110426

The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

The possibility and feasibility is investigated of including in the modelling of nuclear cluster reactions a unified treatment of the effects both of the non-orthogonalities between transfer channels, and of the antisymmetrisation required by the Pauli Principle. The deuteron - nucleus interaction, the simplest cluster reaction, is considered in detail within the Coupled Channels framework. The Coupled Channels formalism was chosen because it accurately handles inelastic and transfer couplings of arbitary strengths. The fact that transfer channels are orthogonal to each other only asymptotically is taken into account by reallocating the wave function in the internal region, from the deuteron channels to the transfer channels, taking components from the deuteron channels in ways exactly analogous to the way the antisymmetrisation requirements remove blocked deuteron-core components. Thus a unified treatment of the two effects is facilitated. It is found further that when all possible transfer channels are included, along with all Pauli blockings from the core nucleons, then under certain conditions at low energies, the wave function in the deuteron channel is small and oscillatory in the internal region, leaving the deuteron as a cluster to have largely asymptotic significance. In this limit, the exact non-local potential governing the deuteron channel simplifies considerably in one approximation to be replaceable by just several orthogonality conditions, and these are easily modelled in solving the coupled equations for the radial wave functions. This simplified and unified model has the advantage, since the deuteron's internal wave form is significant only asymptotically, of allowing automatically for arbitary deuteron polarisation by the core (though not vice-versa). Furthermore, the asymptotic matching is not at a fixed radius as in R-matrix theory, but is a continuous process that depends on the binding energies of the actual proton & neutron bound states in the residual nucleus.

Les fontaines atomiques, basées sur une transition micro-onde du Césium ou du Rubidium, constituent l'état de l'art des horloges atomiques, avec une exactitude relative avoisinant 10^{-16}. Il apparaît cependant clairement aujourd'hui qu'il sera difficile de dépasser significativement ce niveau de performance avec un dispositif de ce type.<br /><br />L'utilisation d'une transition optique, toutes choses étant égales par ailleurs, ouvre la perspective d'une amélioration de 4 ou 5 ordres de grandeur de la stabilité et de l'incertitude relative sur la plupart des effets systématiques. Les effets liés au mouvement des atomes peuvent être, quant à eux, contrôlés d'une façon totalement différente, en les piégeant dans un réseau optique pour éviter la phase de vol ballistique caractéristique des fontaines. Le point clef de cette approche réside dans le fait que les paramètres de ce piège peuvent être ajustés de façon à s'affranchir du déplacement lumineux si l'on sélectionne une transition d'horloge faiblement permise J=0 -> J=0.<br /><br />A cet égard, l'atome de strontium est l'un des candidats les plus prometteurs, la transition ^1S_0 -> ^3P_0 présente une largeur naturelle de 1 mHz, et plusieurs autres transitions facilement accessibles peuvent être utilisées en vue d'un refroidissement laser efficace des atomes jusqu'à une température de 10 µK. Ce manuscrit de thèse d'une part démontre la faisabilité expérimentale d'une horloge à réseau optique basée sur l'atome de strontium, et d'autre part expose une évaluation préliminaire de l'exactitude relative avec l'isotope fermionique ^{87}Sr, à un niveau de quelques 10^{-15}.

A evolução continua dos computadores levou a várias modificações na maneira de fazer ciência, fazendo surgir uma infinidade de novas opções para resolvermos problemas científicos. A implementação computacional de métodos teóricos possibilitou a tratamento de sistemas grandes, complexos e em diferentes áreas da ciência.Uma área particularmente em destaque e a química de moléculas, atualmente podemos descrever sistemas moleculares relativamente complexos com extrema precisão. Os métodos teóricos em química molecular podem ser divididos basicamente em métodos clássicos ou quânticos, dependendo do que queremos estudar, podemos também utilizar métodos híbridos ou seqüenciais, contudo para uma descrição detalhada da estrutura eletrônica e de ligações químicas é necessária a utilização de métodos quânticos.Cálculos ab initio da estrutura eletrônica de átomos e especialmente moléculas foram realizados pela primeira vez utilizando-se o método de expansão de Roothaan na década de cinqüenta. Em 1986, uma versão integral das equações de Griffin-Wheele-Hartree-Fock (GW-HF) foi apresentada na literatura , inspirada no Método da Coordenada Geradora (MCG), introduzido por Griffin e Wheeler na década de cinqüenta. A versão integral das equações de Hartree-Fock foi denominada de Método da Coordenada Geradora Hartree-Fock (MCG-HF), e uma de suas primeiras aplicações foi na geração de bases atômicas universais . De fato, uma integração numérica cuidadosa das equações de GW-HF permite a geração de bases universais bem mais generalizadas do que as já publicadas na literatura.Recentemente, Barbosa e da Silva propuseram uma modificação na metodologia da discretização com o intuito de melhorar a obtenção de conjuntos de funções Gaussianas (GTF) por meio do MCG-HF, tornando possível a geração de GTF tão boas ou melhores quanto as até agora obtidas na literatura, porém mais compactas e precisas (acuradas). / The ongoing evolution of computers has led to several changes in the way of doing science, to create a multitude of new options for solving scientific problems. The implementation of computational methods allowed the theoretical treatment of large systems, complex and different areas of science. One area of particular focus and chemistry of molecules, now can describe relatively complex molecular systems with extreme precision. The theoretical methods in molecular chemistry can be basically divided into classical and quantum methods, depending on what we consider, we can also use sequential or hybrid methods, however for a detailed description of the electronic structure and chemical bonds is required the use of quantum methods. Ab initio calculations of the electronic structure of atoms and molecules have been specially made for the first time using the method of Roothaan expansion in the decade of the fifties . In 1986, a full version of the equations of Griffin-Wheeler-Hartree-Fock (HF-GW) was presented in the literature , inspired by the Method of Coordinate Generator (MCG), introduced by Griffin and Wheeler in the decade of fifty . The full equations of the Hartree-Fock method was called the Generator Coordinate Hartree-Fock (HF-MCG) and its first applications was the generation of atomic universal bases In fact, a careful numerical integration of equations of GW-HF allows the generation of universal bases and more widespread than those already published in the literature .Recently, Barbosa and Silva proposed a modification in the methodology of the discretization to improve the collection of sets of Gaussian functions (GTF) by means of MCG-HF, making possible the generation of GTF as good or better as the so far obtained in the literature, but more compact and precise (accurate). A polynomial expansion is proposed as a new way to discretize the Griffin-Wheeler-Hartree-Fock equations of the Generator Coordinate Hartree-Fock method. The implementation of the polynomial expansion in the Generator Coordinate Hartree-Fock method discretizes the Griffin-Wheeler-Hartree-Fock equations through a numerical mesh, which is not equally spaced. This procedure makes the optimization of Gaussian exponents in the Generator Coordinate Hartree-Fock method more flexible and more efficient. The results obtained with the polynomial expansion for atomic Hartree-Fock energies show this technique is very powerful when employed in the design of compact and high accurate Gaussian basis sets used in ab initio non-relativistic (Hartree-Fock) and relativistic (Dirac-Fock) calculations.

By means of N-body simulations we study the ion and electron dynamics in molecular first-row hydride clusters when exposed to intense and short X-ray pulses. We find that, for a particular range of X-ray intensities, fast protons are ejected from the system on a considerably shorter time scale than that of the screened core. As a consequence, the structure of heavy atoms is kept intact", which may be relevant in the context of X-ray based molecular imaging. Moreover the final charge states of the heavy ions are considerably lower than those of the ions in pristine atomic clusters exposed to the same laser pulses, which is in agreement with recent measurement of methane cluster at the LCLS in Stanford.

No description available.