In this thesis, we investigate the emergence of kinetic processes in finite quantum systems. We first generalize the Redfield theory to describe the dynamics of a small quantum system weakly interacting with an environment of finite heat capacity. We then study in detail the spin-GORM model, a model made of a two-level system interacting with a random matrix environment. By doing this, we verify our new theory and find a critical size of the environment over which kinetic processes occur. We finally study the emergence of a diffusive transport process, on a finite tight-binding subsystem interacting with a fast environment, when the size of subsystem exceeds a critical value.
In this thesis, we investigate the emergence of kinetic processes in finite quantum systems. We first generalize the Redfield theory to describe the dynamics of a small quantum system weakly interacting with an environment of finite heat capacity. We then study in detail the spin-GORM model, a model made of a two-level system interacting with a random matrix environment. By doing this, we verify our new theory and find a critical size of the environment over which kinetic processes occur. We finally study the emergence of a diffusive transport process, on a finite tight-binding subsystem interacting with a fast environment, when the size of subsystem exceeds a critical value.
We study the emergence of diffusion for a quantum particle moving in a finite and translationally invariant one-dimensional subsystem described by a tight-binding Hamiltonian with a single energy band and interacting with its environment by an interaction energy proportional to some coupling parameter. We show that there exists a crossover between a nondiffusive relaxation regime for small sizes or low values of the coupling parameter and a diffusive regime above a critical size or for higher values of the coupling parameter. In the nondiffusive regime, the relaxation is characterized by oscillations decaying at rates independent of the size and proportional to the square of the coupling parameter and the temperature of the environment. In the diffusive regime, the damped oscillations have disappeared and the relaxation rate is inversely proportional to the square of the size. The diffusion coefficient is proportional to the square of the energy bandwidth of the subsystem and inversely proportional to the temperature of the environment and the square of the coupling parameter. The critical size where the crossover happens is obtained analytically.
A new perturbative quantum master equation is presented for the dissipative dynamics of a subsystem inside a nanosystem with a constant and finite total energy. The degrees of freedom besides those of the subsystem play the role of the environment. Our equation rules the time evolution of the distribution functions of the subsystem populations and coherences over the energy of the environment. Thanks to these distribution functions, we can take into account the effects of the conservation of the total energy. This equation is more general than the standard perturbative equations used for describing a subsystem interacting with an environment (such as the Redfield or Cohen-Tannoudji equations) because these latter equations can be deduced from it in the limit of an infinitely large environment. We numerically apply this equation to the spin-GORM model for the interaction of a two-level subsystem with an environment described by random matrices. We compare our equation with the exact von Neumann equation of the total system and show its superiority compared to the Redfield equation (in the Markovian and non-Markovian cases).
Recently, the possibility of investigating single molecule, or single spin observables, as well as the necessity of a better understanding of the mechanisms underlying quantum dynamics in order to obtain nanoscale devices and nanostructered materials suitable for quantum computing tasks, have revived the interest in foundational aspects of quantum statistical mechanics. This thesis aims to give a contribution to this field by re-considering the statistical characterization of a quantum system at the light of some paradigmatic changes in our understanding of quantum theory which have taken place in the last two decades. In particular the impressive development of quantum information theory has changed the perceptions of quantum entanglement: for a long time it has been considered a somewhat paradoxical property of the matter at the atomic scale, but now it is regarded as an essential and ubiquitous phenomenon whose consequences are affecting the very macroscopic world that we experience. Still the decoherence program has brought out the importance of considering a quantum system together with its environment in order to clarify some key aspects of quantum dynamics. Thus, we start from the idea that quantum correlations are ubiquitous and somewhat uncontrollable in systems with many degrees of freedom which are typically considered in statistical mechanics. As a consequence we assume the standpoint that quantum statistical mechanics has not to be based on the underlying idea of a collection of many, independent quantum systems but rather it has to emerge at the level of a global wavefunction (pure state) which describes the system as well as its environment as a whole. In order to investigate the consequences of these assumptions we study the equilibrium distribution of an isolated quantum system. This is defined, in analogy with the ergodic foundations of classical statistical mechanics, on the basis of the time evolution of the quantum state. Then, we study the emergence of thermodynamic properties in a quantum system by studying the probability distribution of some function of interests, as the entropy and the equilibrium state of a subsystem, on Ensembles of Pure States. Such a probability distribution is derived from the geometry of the Hilbert space, and the theoretical tools suitable for its characterization are developed. On the one hand we perform a numerical sampling of the ensemble distributions by employing Monte Carlo techniques, on the other hand simpler analytical approximation of the geometrical distributions are derived by means of a maximum entropy principle. Model systems composed of an ensemble of spins are chosen to illustrate the salient features which emerge from the developed theoretical framework: the main point is that the Ensemble Distributions of “thermodynamic observables” (entropy or equilibrium state of a subsystem) are sharply peaked around a typical value. From the analysis it emerges that each of the overwhelming majority of the wavefunctions which has appreciable weight in the considered ensemble, is characterized by the same value of the “macroscopic” functions. This is a striking evidence of the “typicality” of these properties. In the essence, our impossibility to know the state of the system in detail does not matter, just for the remarkable fact that almost all quantum states behave essentially in the same way. By virtue of this typicality the study of the behaviour of the typical values of the thermodynamic function become meaningful. Notably, under certain conditions, one recovers the results of standard statistical mechanics, that is, the equilibrium average of the state of a subsystem can be cast in the Boltzmann canonical form at the temperature given by the usual thermodynamical relation . In the second part of the thesis we consider the dynamical aspects of the equilibrium state of a subsystem interacting with its environment. The fluctuations around the equilibrium average critically depends on the entanglement between the system and the environment and on the form of the interaction Hamiltonian. The connection between the dynamics of the fluctuations of an observable at the equilibrium and the relaxation toward the equilibrium from a “non typical” initial value is also investigated with the aid of simple model systems. The study presented in this thesis was partly motivated by a critical analysis of the statistical methods available for the theoretical modelling of magnetic resonance experiments. One of these, the Stochastic Liouville Equation, has been employed in a work completed during the first year of my Ph.D. program in order to interpret some feature of a two dimensional electron spin resonance experiment, [Fresch B., Frezzato D., Moro G. J., Kothe G., Freed J. H.; J. Phys. Chem. B., 110, 24238, (2006)].
The method of the nonequilibrium statistical operator developed by D. N. Zubarev is employed to analyze and derive generalized transport and kinetic equations. The degrees of freedom in solids can often be represented as a few interacting subsystems (electrons, spins, phonons, nuclear spins, etc.). Perturbation of one subsystem may produce a nonequilibrium state which is then relaxed to an equilibrium state due to the interaction between particles or with a thermal bath. The generalized kinetic equations were derived for a system weakly coupled to a thermal bath to elucidate the nature of transport and relaxation processes. It was shown that the "collision term" had the same functional form as for the generalized kinetic equations for the system with small interactions among particles. The applicability of the general formalism to physically relevant situations is investigated. It is shown that some known generalized kinetic equations (e.g. kinetic equation for magnons, Peierls equation for phonons) naturally emerges within the NSO formalism. The relaxation of a small dynamic subsystem in contact with a thermal bath is considered on the basis of the derived equations. The Schrödinger-type equation for the average amplitude describing the energy shift and damping of a particle in a thermal bath and the coupled kinetic equation describing the dynamic and statistical aspects of the motion are derived and analyzed. The equations derived can help in the understanding of the origin of irreversible behavior in quantum phenomena.
The method of the nonequilibrium statistical operator developed by D. N. Zubarev is employed to analyze and derive generalized transport and kinetic equations. The degrees of freedom in solids can often be represented as a few interacting subsystems (electrons, spins, phonons, nuclear spins, etc.). Perturbation of one subsystem may produce a nonequilibrium state which is then relaxed to an equilibrium state due to the interaction between particles or with a thermal bath. The generalized kinetic equations were derived for a system weakly coupled to a thermal bath to elucidate the nature of transport and relaxation processes. It was shown that the "collision term" had the same functional form as for the generalized kinetic equations for the system with small interactions among particles. The applicability of the general formalism to physically relevant situations is investigated. It is shown that some known generalized kinetic equations (e.g. kinetic equation for magnons, Peierls equation for phonons) naturally emerges within the NSO formalism. The relaxation of a small dynamic subsystem in contact with a thermal bath is considered on the basis of the derived equations. The Schrödinger-type equation for the average amplitude describing the energy shift and damping of a particle in a thermal bath and the coupled kinetic equation describing the dynamic and statistical aspects of the motion are derived and analyzed. The equations derived can help in the understanding of the origin of irreversible behavior in quantum phenomena.
A large number of multifaceted quantum transport processes in molecular systems and physical nanosystems can be treated in terms of quantum relaxation processes which couple to one or several fluctuating environments. A thermal equilibrium environment can conveniently be modelled by a thermal bath of harmonic oscillators. An archetype situation provides a two-state dissipative quantum dynamics, commonly known under the label of a spin-boson dynamics. An interesting and nontrivial physical situation emerges, however, when the quantum dynamics evolves far away from thermal equilibrium. This occurs, for example, when a charge transferring medium possesses nonequilibrium degrees of freedom, or when a strong time-dependent control field is applied externally. Accordingly, certain parameters of underlying quantum subsystem acquire stochastic character. Herein, we review the general theoretical framework which is based on the method of projector operators, yielding the quantum master equations for systems that are exposed to strong external fields. This allows one to investigate on a common basis the influence of nonequilibrium fluctuations and periodic electrical fields on quantum transport processes. Most importantly, such strong fluctuating fields induce a whole variety of nonlinear and nonequilibrium phenomena. A characteristic feature of such dynamics is the absence of thermal (quantum) detailed balance.