Studies of the hyperfine splitting in hydrogen are strongly motivated by the level of accuracy achieved in recent atomic physics experiments, which yield finally model-independent informations about nuclear structure parameters with utmost precision. Considering the current status of the determination of corrections to the hyperfine splitting of the ground state in hydrogen, this thesis provides further improved calculations by taking into account the most recent value for the proton charge radius. Comparing theoretical and experimental data of the hyperfine splitting in hydrogen the proton-size contribution is extracted and a relativistic formula for this contribution is derived in terms of moments of the nuclear charge and magnetization distributions. An iterative scheme for the determination of the Zemach and magnetic radii of the proton is proposed. As a result, the Zemach and magnetic radii are determined and the values are compared with the corresponding ones deduced from data obtained in electron-proton scattering experiments. The extraction of the Zemach radius from a rescaled difference between the hyperfine splitting in hydrogen and in muonium is considered as well. Investigations of forbidden radiative transitions in few-electron ions within ab initio QED provide a most sensitive tool for probing the influence of relativistic electron-correlation and QED corrections to the transition rates. Accordingly, a major part of this thesis is devoted to detailed studies of radiative and interelectronic-interaction effects to the transition probabilities. The renormalized expressions for the corresponding corrections in one- and two-electron ions as well as for ions with one electron over closed shells are derived employing the two-time Green's function method. Numerical results for the correlation corrections to magnetic transition rates in He-like ions are presented. For the first time also the frequency-dependent contribution is calculated, which has to be accounted for preserving gauge invariance. One-loop QED corrections to the magnetic-dipole transition amplitude between the fine-structure levels 2p_{3/2} and 2p_{1/2} are calculated to all orders in \alpha Z. Taking into account consistently relativistic, interelectronic-interaction, and QED corrections to the magnetic-dipole transition amplitude allows for predictions of the lifetimes of the states (1s^2 2s^2 2p)^2P_{3/2} in B-like ions and (1s^2 2s 2p)^3P_2 in Be-like ions with utmost precision. The results of corresponding calculations are compared with experimental data obtained in recent measurements at the Heidelberg EBIT. Finally, for He-like ions with nonzero-spin nuclei the effect of hyperfine quenching on the lifetimes of the 2^3P_{0,2} states is investigated and again compared available experimental data.

Studies of the hyperfine splitting in hydrogen are strongly motivated by the level of accuracy achieved in recent atomic physics experiments, which yield finally model-independent informations about nuclear structure parameters with utmost precision. Considering the current status of the determination of corrections to the hyperfine splitting of the ground state in hydrogen, this thesis provides further improved calculations by taking into account the most recent value for the proton charge radius. Comparing theoretical and experimental data of the hyperfine splitting in hydrogen the proton-size contribution is extracted and a relativistic formula for this contribution is derived in terms of moments of the nuclear charge and magnetization distributions. An iterative scheme for the determination of the Zemach and magnetic radii of the proton is proposed. As a result, the Zemach and magnetic radii are determined and the values are compared with the corresponding ones deduced from data obtained in electron-proton scattering experiments. The extraction of the Zemach radius from a rescaled difference between the hyperfine splitting in hydrogen and in muonium is considered as well. Investigations of forbidden radiative transitions in few-electron ions within ab initio QED provide a most sensitive tool for probing the influence of relativistic electron-correlation and QED corrections to the transition rates. Accordingly, a major part of this thesis is devoted to detailed studies of radiative and interelectronic-interaction effects to the transition probabilities. The renormalized expressions for the corresponding corrections in one- and two-electron ions as well as for ions with one electron over closed shells are derived employing the two-time Green's function method. Numerical results for the correlation corrections to magnetic transition rates in He-like ions are presented. For the first time also the frequency-dependent contribution is calculated, which has to be accounted for preserving gauge invariance. One-loop QED corrections to the magnetic-dipole transition amplitude between the fine-structure levels 2p_{3/2} and 2p_{1/2} are calculated to all orders in \alpha Z. Taking into account consistently relativistic, interelectronic-interaction, and QED corrections to the magnetic-dipole transition amplitude allows for predictions of the lifetimes of the states (1s^2 2s^2 2p)^2P_{3/2} in B-like ions and (1s^2 2s 2p)^3P_2 in Be-like ions with utmost precision. The results of corresponding calculations are compared with experimental data obtained in recent measurements at the Heidelberg EBIT. Finally, for He-like ions with nonzero-spin nuclei the effect of hyperfine quenching on the lifetimes of the 2^3P_{0,2} states is investigated and again compared available experimental data.

Chemische Reaktionen in der Natur sowie Prozesse in synthetischen Materialien werden oft erst durch die Wechselwirkung von Licht mit Materie ausgelöst. Üblicherweise werden diese komplexen Prozesse mit Hilfe von Näherungen beschrieben. Im ersten Teil der Arbeit wird die Gültigkeit der Born-Oppenheimer Näherung in einem vibronischen Modellsystem (Trans-Polyacetylene) unter Photoelektronenspektroskopie im Gleichgewicht sowie zeitaufgelöster Photoelektronenspektroskopie im Nichtgleichgewicht überprüft. Die vibronische Spektralfunktion zeigt aufgrund des faktorisierten Anfangs- und Endzustandes in der Born-Oppenheimer Näherung zusätzliche Peaks, die in der exakten Spektralfunktion nicht auftreten. Im Nichtgleichgewicht zeigen wir für eine Franck-Condon Anregung und eine Anregung mit Pump-Probe Puls, wie die Bewegung des vibronischen Wellenpaktes im zeitabhängigen Photoelektronenspektrum verfolgt werden kann. Im zweiten Teil der Arbeit werden sowohl die Materie als auch das Licht quantisiert behandelt. Für eine volle quantenmechanische Beschreibung des Elektron-Licht Systems, verwenden wir die kürzlich entwickelte quantenelektrodynamische Dichtefunktionaltheorie (QEDFT) für gekoppelte Elektron-Photon Systeme. Wir zeigen erste numerische QEDFT-Berechnungen voll quantisierter Atome und Moleküle in optischen Kavitäten, die an das quantisierte elektromagnetische Feld gekoppelt sind. Mit Hilfe von Fixpunktiterationen berechnen wir das exakte Kohn-Sham Potential im diskreten Ortsraum, wobei unser Hauptaugenmerk auf dem Austausch-Korrelations-Potential liegt. Wir zeigen die erste Näherung des Austausch-Korrelations-Potentials mit Hilfe eines optimierten effektiven Potential Ansatzes angewandt auf einen Jaynes-Cummings-Dimer. Die dieser Arbeit zugrunde liegenden Erkenntnisse und Näherungen ermöglichen es neuartige Phänomene an der Schnittstelle zwischen den Materialwissenschaften und der Quantenoptik zu beschreiben. / Many natural and synthetic processes are triggered by the interaction of light and matter. All these complex processes are routinely explained by employing various approximations. In the first part of this work, we assess the validity of the Born-Oppenheimer approximation in the case of equilibrium and time-resolved nonequilibrium photoelectron spectra for a vibronic model system of Trans-Polyacetylene. We show that spurious peaks appear for the vibronic spectral function in the Born-Oppenheimer approximation, which are not present in the exact spectral function of the system. This effect can be traced back to the factorized nature of the Born-Oppenheimer initial and final photoemission states. In the nonequilibrium case, we illustrate for an initial Franck-Condon excitation and an explicit pump-pulse excitation how the vibronic wave packet motion can be traced in the time-resolved photoelectron spectra as function of the pump-probe delay. In the second part of this work, we aim at treating both, matter and light, on an equal quantized footing. We apply the recently developed quantum electrodynamical density-functional theory, (QEDFT), which allows to describe electron-photon systems fully quantum mechanically. We present the first numerical calculations in the framework of QEDFT. We focus on the electron-photon exchange-correlation contribution by calculating exact Kohn-Sham potentials in real space using fixed-point inversions and present the performance of the first approximate exchange-correlation potential based on an optimized effective potential approach for a Jaynes-Cummings-Hubbard dimer. This work opens new research lines at the interface between materials science and quantum optics.