Autoionizing states and their relevance in electron-ion recombination

Atomic physics plays an important role in determining the evolution stages in a wide range of laboratory and cosmic plasmas. Therefore, the main contribution to our ability to model, infer and control plasma sources is the knowledge of underlying atomic processes. Of particular importance are reliable low temperature dielectronic recombination (DR) rate coefficients. This thesis provides systematically calculated DR rate coefficients of lithium-like beryllium and sodium ions via ∆n = 0 doubly excited resonant states. The calculations are based on complex-scaled relativistic many-body perturbation theory in an all-order formulation within the single- and double-excitation coupled-cluster scheme, including radiative corrections. Comparison of DR resonance parameters (energy levels, autoionization widths, radiative transition probabilities and strengths) between our theoretical predictions and the heavy-ion storage rings experiments (CRYRING-Stockholm and TSRHeidelberg) shows good agreement. The intruder state problem is a principal obstacle for general application of the coupled-cluster formalism on doubly excited states. Thus, we have developed a technique designed to avoid the intruder state problem. It is based on a convenient partitioning of the Hilbert space and reformulation of the conventional set of pairequations. The general aspects of this development are discussed, and the effectiveness of its numerical implementation (within the non-relativistic framework) is selectively illustrated on autoionizing doubly excited states of helium.

Supersymmetric Dark Matter : aspects of sfermion coannihilations

There is very strong evidence that ordinary matter in the Universe is outweighed by almost ten times as much so-called dark matter. Dark matter does neither emit nor absorb light and we do not know what it is. One of the theoretically favoured candidates is a so-called neutralino from the supersymmetric extension of the Standard Model of particle physics. A theoretical calculation of the expected cosmic neutralino density must include the so-called coannihilations. Coannihilations are particle processes in the early Universe with any two supersymmetric particles in the initial state and any two Standard Model particles in the final state. In this thesis we discuss the importance of these processes for the calculation of the relic density. We will go through some details in the calculation of coannihilations with one or two so-called sfermions in the initial state. This includes a discussion of Feynman diagrams with clashing arrows, a calculation of colour factors and a discussion of ghosts in non-Abelian field theory. Supersymmetric models contain a large number of free parameters on which the masses and couplings depend. The requirement, that the predicted density of cosmic neutralinos must agree with the density observed for the unknown dark matter, will constrain the parameters. Other constraints come from experiments which are not related to cosmology. For instance, the supersymmetric loop contribution to the rare b -> sγ decay should agree with the measured branching fraction. The principles of the calculation of the rare decay are discussed in this thesis. Also on-going and planned searches for cosmic neutralinos can constrain the parameters. In one of the accompanying papers in the thesis we compare the detection prospects for several current and future searches for neutralino dark matter.

Theoretical studies of mononuclear non-heme iron active sites

The quantum chemical investigations presented in this thesis use hybrid density functional theory to shed light on the catalytic mechanisms of mononuclear non-heme iron oxygenases, accommodating a ferrous ion in their active sites. More specifically, the dioxygen activation process and the subsequent oxidative reactions in the following enzymes were studied: tetrahydrobiopterin-dependent hydroxylases, naphthalene 1,2-dioxygenase and α-ketoglutarate-dependent enzymes. In light of many experimental efforts devoted to the functional mimics of non-heme iron oxygenases, the reactivity of functional analogues was also examined. The computed energetics and the available experimental data served to assess the feasibility of the reaction mechanisms investigated. Dioxygen activation in tetrahydrobiopterin- and α-ketoglutarate-dependent enzymes were found to involve a high-valent iron-oxo species, which was then capable of substrate hydroxylation. In the case of naphthalene 1,2-dioxygenase, the reactivity of an iron(III)-hydroxperoxo species toward the substrate was investigated and compared to the biomimetic counterpart.