The question whether and how closed quantum systems equilibrate is still debated today. In this thesis a generic spin system is analysed and criteria to classify unique equilibration dynamics are developed. Furthermore, the eigenstate thermalization hypothesis is investigated as a possible cause for the unique equilibrium. For both problems novel numerical methods for solving the time-dependent Schroedinger equation based on series expansions and typicality are developed. Furthermore, the problem of markovian dynamics on the level of single measurements is discussed.

Getriebener Transport wechselwirkender Teilchen ist im direkten oder übertragenen Sinne von großer Bedeutung für viele Forschungsfelder. Zur Untersuchung grundlegender Fragestellungen wird auf einfache Modellsysteme zurückgegriffen, die analytische Zugänge ermöglichen und zugleich wesentliche Aspekte der Nichtgleichgewichtsdynamik in realen Applikationen erfassen. Im ersten Teil dieser Arbeit wird ein eindimensionales Gittergas mit Nächsten-Nachbar-Wechselwirkungen betrachtet, um den Einfluss von Wechselwirkungen auf den Teilchentransport in getriebenen Diffusionsprozessen zu studieren. Mit einem auf der zeitabhängigen Dichtefunktionaltheorie klassischer Fluide basierenden Verfahren werden Evolutionsgleichungen für Dichten, Korrelationsfunktionen und Ströme aufgestellt, deren numerische Lösung eine gute Beschreibung der Transportkinetik liefert. Für Sprungdynamiken, welche bestimmte Relationen erfüllen, werden exakte Strom-Dichte-Beziehungen in geschlossenen Ringsystemen hergeleitet. Hierzu zählen insbesondere die für viele Applikationen relevanten Glauber-Raten. In offenen Kanälen, die zwei Reservoire verbinden, kommt es zu Phasenübergängen der Teilchendichte im Inneren des Kanals. Anhand allgemeiner Überlegungen auf Grundlage der Extremalprinzipien bezüglich des Stroms und der Strom-Dichte-Relation im Bulk kann ein Überblick aller möglichen Phasen, ungeachtet der konkreten System-Reservoir-Kopplung, erhalten werden. Welche Phasen im randinduzierten Phasendiagramm erscheinen, wird durch die System-Reservoir-Kopplung festgelegt. Dies wird anhand zweier unterschiedlicher Randankopplungen demonstriert. Im zweiten Teil der Dissertationsschrift werden stochastische Transportvorgänge in Brownschen Pumpen und in organischen Solarzellen mit Heteroübergang modelliert. Hierbei zeigen Brownsche Pumpen Phasenübergänge in periodengemittelten Dichten und Strömen, falls Ausschlusswechselwirkungen berücksichtigt werden. Ein Minimalmodell organischer Solarzellen erlaubt Elementarprozesse an der Donator-Akzeptor-Grenzfläche abzubilden, wodurch Einblicke in das Strom- und Effizienzverhalten des photovoltaischen Systems gewonnen werden.

Our everyday experiences teach us that any imbalance like temperature gradients, non-uniform particle-densities etc. will approach some equilibrium state if not subjected to any external force. Phenomenological descriptions of these empirical findings reach back to the 19th century where Fourier and Fick presented descriptions of relaxation for macroscopic systems by stochastic approaches. However, one of the main goals of thermodynamics remained the derivation of these phenomenological description from basic microscopic principles. This task has gained much attraction since the foundation of quantum mechanics about 100 years ago. However, up to now no such conclusive derivation is presented. In this dissertation we will investigate whether closed quantum systems may show equilibration, and if so, to what extend such dynamics are in accordance with standard thermodynamic behavior as described by stochastic approaches. To this end we consider i.a. Markovian dynamics, Fokker-Planck and diffusion equations. Furthermore, we consider fluctuation theorems as given e.g. by the Jarzynski relation beyond strict Gibbsian initial states. After all we find indeed good agreement for selected quantum systems.

The origin of the Mixed Glass Former Effect (MGFE) is studied, which manifests itself in a non-monotonic behavior of the activation energy for long-range ion transport as a function of the mixing ratio of two glass formers. Two theoretical models are developed, the mixed barrier model and the network unit trap model, which consider different possible mechanisms for the occurrence of the MGFE. The mixed barrier model is based on the assumption that energy barriers are reduced for ionic jumps in regions of mixed composition. By employing percolation theory it is shown that this mechanism can successfully account for the behavior of the activation energy in various ion conducting mixed glass former glasses. The network unit trap model is based on the fact that a variety of network forming units, the so-called Q(n) species, can be associated with one glass former. Using a thermodynamic approach, the change of the concentration of these units in dependence of ionic concentration and the glass former mixing ratio is successfully predicted for alkali borate, phosphate and borophosphate glasses. In a second step, the charge distribution of the various units is considered and related to it, the binding energies to alkali ions. This gives rise to a modeling of the ionic transport in an energy landscape that changes in a defined manner with the glass former mixing ratio. Kinetic Monte Carlo simulations for alkali borophosphate glasses, which serve as a representative system for the MGFE in the literature, demonstrate that this approach succeeds to predict the behavior of the activation energy. In a further part of the thesis, Reverse Monte Carlo (RMC) simulations for the atomic structure of sodium borophosphate glasses are carried out with X-ray and neutron diffraction data as further input from experiments. Three-dimensional structures could be successfully generated that are in agreement with all experimental and theoretical constraints. Volume fractions of the ionic conduction pathways determined from these structures, however, do not show a substantial relationship to the activation energy, as earlier proposed in the iterature for alkali borate and alkali phosphate glasses.

We present a novel approach to the investigation of transport coefficients in condensed matter systems, which is based on a pertinent time-convolutionless (TCL) projection operator technique. In this context we analyze in advance the convergence of the corresponding perturbation expansion and the influence of the occurring inhomogeneity. The TCL method is used to establish a formalism for a consistent derivation of a Boltzmann equation from the underlying quantum dynamics, which is meant to apply to non-ideal quantum gases. We obtain a linear(ized) collision term that results as a finite non-singular rate matrix and is thus adequate for further considerations, e.g., the calculation of transport coefficients. In the work at hand we apply the provided scheme to numerically compute the diffusion coefficient of an atomic wire and especially analyze its dependence on certain model properties, in particular on the width of the wire.

The first part of the present Phd thesis is devoted to transport investigations in disordered quantum systems. We aim at quantitatively determining transport parameters like conductivity, mean free path, etc., for simple models of spatially disordered and/or percolated quantum systems in the limit of high temperatures and low fillings using linear response theory. We find the transport behavior for some models to be in accord with a Boltzmann equation, i.e., long mean free paths, exponentially decaying currents although there are no band-structures to start from, while this does not apply to other models even though they are also almost completely delocalized. The second part of the present PhD thesis addresses the issue of initial state independence (ISI) in closed quantum system. The relevance of the eigenstate thermalization hypothesis (ETH) for the emergence of ISI equilibration is to some extent addressed. To this end, we investigate the Heisenberg spin-ladder and check the validity of the ETH for the energy difference operator by examining the scaling behavior of the corresponding ETH-fluctuations, which we compute using an innovative numerical method based on typicality related arguments. While, the ETH turns out to hold for the generic non-integrable models and may therefore serve as the key mechanism for ISI for this cases, it does not hold for the integrable Heisenberg-chain. However, close analysis on the dynamic of substantially out-of-equilibrium initial states indicates the occurrence of ISI equillibration in the thermodynamic limit regardless of whether the ETH is violated. Thus, we introduce a new parameter $v$, which we propose as an alternative of the ETH to indicate ISI equillibration in cases, in which the ETH does not strictly apply.

Based on the publications [P1–P6], the cumulative dissertation at hand addresses quite diverse aspects of non-equilibrium behavior in isolated quantum systems. The works presented in publications [P1, P2] concern the issue of finding generally valid upper bounds on equilibration times, which ensure the eventual occurrence of equilibration in isolated quantum systems. Recently, a particularly compelling bound for physically relevant observables has been proposed. Said bound is examined analytically as well as numerically. It is found that the bound fails to give meaningful results in a number of standard physical scenarios. Continuing, publication [P4] examines a particular integral fluctuation theorem (IFT) for the total entropy production of a small system coupled to a substantially larger but finite bath. While said IFT is known to hold for canonical states, it is shown to be valid for microcanonical and even pure energy eigenstates as well by invoking the physically natural conditions of “stiffness” and “smoothness” of transition probabilities. The validity of the IFT and the existence of stiffness and smoothness are numerically investigated for various lattice models. Furthermore, this dissertation puts emphasis on the issue of the route to equilibrium, i.e., to explain the omnipresence of certain relaxation dynamics in nature, while other, more exotic relaxation patterns are practically never observed, even though they are a priori not disfavored by the microscopic laws of motion. Regarding this question, the existence of stability in a larger class of dynamics consisting of exponentially damped oscillations is corroborated in publication [P6]. In the same vein, existing theories on the ubiquity of certain dynamics are numerically scrutinized in publication [P3]. Finally, in publication [P5], the recently proposed “universal operator growth hypothesis”, which characterizes the complexity growth of operators during unitary time evolution, is numerically probed for various spin-based systems in the thermodynamic limit. The hypothesis is found to be valid within the limits of the numerical approach.

Thermodynamic processes in finite time are in general irreversible. But there are chances to avoid irreversibility. For instance, there are canonical ensembles of special quantum systems with a given probability distribution describing the likelihood to find the system at time t=0 in a particular state with energy E_i(0), which can be controlled in a specific way, such that the initial probability distribution is recovered at the end of the process (t=T), but the state energies did change, hence E_i(0) is not equal to E_i(T). This allows to change thermodynamic quantities (expectation values) adiabatically, reversibly and in finite time. Such special processes are called Shortcuts to Adiabaticity. The presented thesis analyzes the origin of these shortcuts utilizing special Hamiltonian systems with dynamical algebra. Their main feature is to provide canonical invariance, which means a canonical ensemble stays canonical under Hamiltonian dynamics. This invariance carried by the dynamical algebra will be discussed using Lie group theory. In addition, the persistence of the dynamical algebra with respect to calculating expectation values will be deduced. This allows to benefit from all intrinsic symmetries within the discussion of ensemble trajectories. In consequence, these trajectories will evolve under Hamiltonian dynamics on a specific manifold given by the so-called Casimir companion. In addition, the deformation of this manifold due to non-Hamiltonian (dissipative) dynamics will be discussed, which allows to present a framework for modeling irreversible processes based on Hamiltonian systems with dynamical algebra. An application of this framework based on the parametric harmonic oscillator will be presented by determining time-optimal controls for transitions between two equilibrium as well as between non-equilibrium and equilibrium states. The latter one will lead to time-optimal equilibration strategies for a statistical ensemble of parametric harmonic oscillators. / Thermodynamische Prozesse in endlicher Zeit sind im Allgemeinen irreversibel. Es gibt jedoch Möglichkeiten, diese Irreversibilität zu umgehen. Ein kanonisches Ensemble eines speziellen quantenmechanischen Systems kann zum Beispiel auf eine ganz spezielle Art und Weise gesteuert werden, sodass nach endlicher Zeit T wieder eine kanonische Besetzungverteilung hergestellt ist, sich aber dennoch die Energie des Systems geändert hat (E(0) ungleich E(T)). Solche Prozesse erlauben das Ändern thermodynamischer Größen (Ensemblemittelwerte) der erwähnten speziellen Systeme in endlicher Zeit und auf eine adiabatische und reversible Art. Man nennt diese Art von speziellen Prozessen Shortcuts to Adiabaticity und die speziellen Systeme hamiltonsche Systeme mit dynamischer Algebra. Die vorliegende Dissertation hat zum Ziel den Ursprung dieser Shortcuts to Adiabaticity zu analysieren und eine Methodik zu entwickeln, die es erlaubt irreversible thermodynamische Prozesse adequat mittels dieser speziellen Systeme zu modellieren. Dazu wird deren besondere Eigenschaft ausgenutzt, die kanonische Invarianz, d.h. ein kanonisches Ensemble bleibt kanonisch bezüglich hamiltonscher Dynamik. Der Ursprung dieser Invarianz liegt in der dynamischen Algebra, die mit Hilfe der Theorie der Lie-Gruppen näher betrachtet wird. Dies erlaubt, eine weitere besondere Eigenschaft abzuleiten: Die Ensemblemittelwerte unterliegen ebenfalls den Symmetrien, die die dynamische Algebra widerspiegelt. Bei näherer Betrachtung befinden sich alle Trajektorien der Ensemblemittelwerte auf einer Mannigfaltigkeit, die durch den sogenannten Casimir Companion beschrieben wird. Darüber hinaus wird nicht-hamiltonsche/dissipative Dynamik betrachtet, welche zu einer Deformation der Mannigfaltigkeit führt. Abschließend wird eine Zusammenfassung der grundlegenden Methodik zur Modellierung irreversibler Prozesse mittels hamiltonscher Systeme mit dynamischer Algebra gegeben. Zum besseren Verständnis wird ein ausführliches Anwendungsbeispiel dieser Methodik präsentiert, in dem die zeitoptimale Steuerung eines Ensembles des harmonischen Oszillators zwischen zwei Gleichgewichtszuständen sowie zwischen Gleichgewichts- und Nichtgleichgewichtszuständen abgeleitet wird.

Thermodynamic processes in finite time are in general irreversible. But there are chances to avoid irreversibility. For instance, there are canonical ensembles of special quantum systems with a given probability distribution describing the likelihood to find the system at time t=0 in a particular state with energy E_i(0), which can be controlled in a specific way, such that the initial probability distribution is recovered at the end of the process (t=T), but the state energies did change, hence E_i(0) is not equal to E_i(T). This allows to change thermodynamic quantities (expectation values) adiabatically, reversibly and in finite time. Such special processes are called Shortcuts to Adiabaticity. The presented thesis analyzes the origin of these shortcuts utilizing special Hamiltonian systems with dynamical algebra. Their main feature is to provide canonical invariance, which means a canonical ensemble stays canonical under Hamiltonian dynamics. This invariance carried by the dynamical algebra will be discussed using Lie group theory. In addition, the persistence of the dynamical algebra with respect to calculating expectation values will be deduced. This allows to benefit from all intrinsic symmetries within the discussion of ensemble trajectories. In consequence, these trajectories will evolve under Hamiltonian dynamics on a specific manifold given by the so-called Casimir companion. In addition, the deformation of this manifold due to non-Hamiltonian (dissipative) dynamics will be discussed, which allows to present a framework for modeling irreversible processes based on Hamiltonian systems with dynamical algebra. An application of this framework based on the parametric harmonic oscillator will be presented by determining time-optimal controls for transitions between two equilibrium as well as between non-equilibrium and equilibrium states. The latter one will lead to time-optimal equilibration strategies for a statistical ensemble of parametric harmonic oscillators. / Thermodynamische Prozesse in endlicher Zeit sind im Allgemeinen irreversibel. Es gibt jedoch Möglichkeiten, diese Irreversibilität zu umgehen. Ein kanonisches Ensemble eines speziellen quantenmechanischen Systems kann zum Beispiel auf eine ganz spezielle Art und Weise gesteuert werden, sodass nach endlicher Zeit T wieder eine kanonische Besetzungverteilung hergestellt ist, sich aber dennoch die Energie des Systems geändert hat (E(0) ungleich E(T)). Solche Prozesse erlauben das Ändern thermodynamischer Größen (Ensemblemittelwerte) der erwähnten speziellen Systeme in endlicher Zeit und auf eine adiabatische und reversible Art. Man nennt diese Art von speziellen Prozessen Shortcuts to Adiabaticity und die speziellen Systeme hamiltonsche Systeme mit dynamischer Algebra. Die vorliegende Dissertation hat zum Ziel den Ursprung dieser Shortcuts to Adiabaticity zu analysieren und eine Methodik zu entwickeln, die es erlaubt irreversible thermodynamische Prozesse adequat mittels dieser speziellen Systeme zu modellieren. Dazu wird deren besondere Eigenschaft ausgenutzt, die kanonische Invarianz, d.h. ein kanonisches Ensemble bleibt kanonisch bezüglich hamiltonscher Dynamik. Der Ursprung dieser Invarianz liegt in der dynamischen Algebra, die mit Hilfe der Theorie der Lie-Gruppen näher betrachtet wird. Dies erlaubt, eine weitere besondere Eigenschaft abzuleiten: Die Ensemblemittelwerte unterliegen ebenfalls den Symmetrien, die die dynamische Algebra widerspiegelt. Bei näherer Betrachtung befinden sich alle Trajektorien der Ensemblemittelwerte auf einer Mannigfaltigkeit, die durch den sogenannten Casimir Companion beschrieben wird. Darüber hinaus wird nicht-hamiltonsche/dissipative Dynamik betrachtet, welche zu einer Deformation der Mannigfaltigkeit führt. Abschließend wird eine Zusammenfassung der grundlegenden Methodik zur Modellierung irreversibler Prozesse mittels hamiltonscher Systeme mit dynamischer Algebra gegeben. Zum besseren Verständnis wird ein ausführliches Anwendungsbeispiel dieser Methodik präsentiert, in dem die zeitoptimale Steuerung eines Ensembles des harmonischen Oszillators zwischen zwei Gleichgewichtszuständen sowie zwischen Gleichgewichts- und Nichtgleichgewichtszuständen abgeleitet wird.