We consider quantum Hamiltonian systems composed of mutually interacting "dynamical subsystem" with one or several degrees of freedom and "thermostat" with arbitrary many degrees of freedom, under assumptions that the interaction ensures irreversible behavior of the dynamical subsystem, that is finite diffusivities of its coordinates in thermodynamically equilibrium state and finite drift velocities and mobilities in non-equilibrium steady state in presence of external driving forces. It is shown that, nevertheless, regardless of characteristics of the interaction, the diffusivity and mobility have no certain values but instead vary from one observation to another and undergo 1/f-type or flicker-type low-frequency fluctuations.
We consider quantum Hamiltonian systems composed of mutually interacting "dynamical subsystem" with one or several degrees of freedom and "thermostat" with arbitrary many degrees of freedom, under assumptions that the interaction ensures irreversible behavior of the dynamical subsystem, that is finite diffusivities of its coordinates in thermodynamically equilibrium state and finite drift velocities and mobilities in non-equilibrium steady state in presence of external driving forces. It is shown that, nevertheless, regardless of characteristics of the interaction, the diffusivity and mobility have no certain values but instead vary from one observation to another and undergo 1/f-type or flicker-type low-frequency fluctuations.
We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.
Complex environments, such as molecular matrices and biological material, play a fundamental role in many important dynamic processes in condensed phases. Because it is extremely difficult to conduct full quantum dynamics simulations on such environments due to their many degrees of freedom, here, we treat in detail the environment only around the main system of interest (the subenvironment), while the other degrees of freedom needed to maintain the equilibrium temperature are described by a simple harmonic bath, which we call a quantum thermostat. The noise generated by the subenvironment is spatially non-local and non-Gaussian and cannot be characterized by the fluctuation-dissipation theorem. We describe this model by simulating the dynamics of a two-level system (TLS) that interacts with a subenvironment consisting of a one-dimensional XXZ spin chain. The hierarchical Schrödinger equations of motion are employed to describe the quantum thermostat, allowing for time-irreversible simulations of the dynamics at arbitrary temperature. To see the effects of a quantum phase transition of the subenvironment, we investigate the decoherence and relaxation processes of the TLS at zero and finite temperatures for various values of the spin anisotropy. We observed the decoherence of the TLS at finite temperature even when the anisotropy of the XXZ model is enormous. We also found that the population-relaxation dynamics of the TLS changed in a complex manner with the change in the anisotropy and the ferromagnetic or antiferromagnetic orders of spins.
The dynamical aspects of quantum Brownian motion at low temperatures are investigated. Exact calculations of quantum entanglement among two Brownian oscillators are given without invoking the Born-Markov or Born approximation widely used for the study of open systems. Nonlocality due to finite oscillator separation is studied. Our approach is applicable for arbitrary time scale, in particular suitable to probe the short-time regime at cold temperatures where many experiments on quantum information processing are performed. We study separability criteria based on the uncertainty relation, negativity, and entanglement of formation. We found a crossover behavior in a disentanglement process between quantum- and thermal-fluctuation-dominated regimes. The fluctuation-dissipation theorem is violated for two Brownian particles interacting with a common environment. The deviation from the relation originates in the interaction mediated by the environment, which drives two particles into a steady oscillatory state, preventing the system from thermalizing. Consequently there is a residual entanglement at low temperatures for arbitrary coupling strength. This entanglement is generated from the environment nonperturbatively even when two modes are not entangled initially. When the distance between two oscillators is varied, competition between entanglement induced from the environment and modified decoherence due to finite separation leads to the characteristic distance where entanglement is minimized.
We study the quantum counterpart of the theorem on energy equipartition for classical systems. We consider a free quantum Brownian particle modeled in terms of the Caldeira-Leggett framework: a system plus thermostat consisting of an infinite number of harmonic oscillators. By virtue of the theorem on the averaged kinetic energy Ek of the quantum particle, it is expressed as ${E}_{k}=\ensuremath{\langle}{\mathcal{E}}_{k}\ensuremath{\rangle}$, where Ek is the thermal kinetic energy of the thermostat per 1 degree of freedom and $\ensuremath{\langle}\ensuremath{\cdots}\ensuremath{\rangle}$ denotes averaging over the frequencies $\ensuremath{\omega}$ of thermostat oscillators which contribute to Ek according to the probability distribution $\mathbb{P}(\ensuremath{\omega})$. We explore the impact of various dissipation mechanisms, via the Drude, Gaussian, algebraic, and Debye spectral density functions, on the characteristic features of $\mathbb{P}(\ensuremath{\omega})$. The role of the system-thermostat coupling strength and the memory time on the most probable thermostat oscillator frequency as well as the kinetic energy Ek of the Brownian particle is analyzed.
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 fluctuations of macroscopic observables in quantum systems which are in a nonequilibrium steady state are studied rigorously in the thermodynamic limit. In particular, the nonequilibrium steady state (NESS) of a quantum spin system that is composed of two infinite reservoirs at different temperatures coupled in a bounded region is considered. Under suitable assumptions on the interaction and the asymptotics of the fluctuations, a nonequilibrium central limit theorem for the fluctuations of the NESS expectation value of the empirical average of observables is proven by showing the analyticity of the corresponding moment generating function in a neighbourhood of the origin using the cluster expansion method. Furthermore, the large deviation principle is proven for a class of observables by establishing the existence and differentiability of the corresponding moment generating function.