Many of the core concepts and (especially field-theoretic) tools of statistical mechanics have developed within the context of thermodynamic equilibrium, where state variables are all taken to be charges, meaning that their values are inherently preserved under reversal of the direction of time. A principle concern of nonequilibrium statistical mechanics is to understand the emergence and stability of currents, quantities whose values change sign under time reversal. Whereas the correspondence between classical charge-valued state variables and their underlying statistical or quantum ensembles is quite well understood, the study of currents away from equilibrium has been more fragmentary, with classical descriptions relying on the asymmetric auxiliary-field formalism of Martin, Siggia, and Rose (and often restricted to the Markovian assumption of Doi and Peliti), while quantum descriptions employ a symmetric two-field formalism introduced by Schwinger and further clarified by Keldysh. In this paper we demonstrate that for quantum ensembles in which superposition is not violated by very strong conditions of decoherence, there is a large natural generalization of the principles and tools of equilibrium, which not only admits but requires the introduction of current-valued state variables. For these systems, not only do Martin-Siggia-Rose (MSR) and Schwinger-Keldysh (SK) field methods both exist, in some cases they provide inequivalent classical and quantum descriptions of identical ensembles. With these systems for examples, we can both study the correspondence between classical and quantum descriptions of currents, and also clarify the nature of the mapping between the structurally homologous but interpretationally different MSR and SK formalisms.
Many of the core concepts and (especially field-theoretic) tools of statistical mechanics have developed within the context of thermodynamic equilibrium, where state variables are all taken to be charges, meaning that their values are inherently preserved under reversal of the direction of time. A principle concern of nonequilibrium statistical mechanics is to understand the emergence and stability of currents, quantities whose values change sign under time reversal. Whereas the correspondence between classical charge-valued state variables and their underlying statistical or quantum ensembles is quite well understood, the study of currents away from equilibrium has been more fragmentary, with classical descriptions relying on the asymmetric auxiliary-field formalism of Martin, Siggia, and Rose (and often restricted to the Markovian assumption of Doi and Peliti), while quantum descriptions employ a symmetric two-field formalism introduced by Schwinger and further clarified by Keldysh. In this paper we demonstrate that for quantum ensembles in which superposition is not violated by very strong conditions of decoherence, there is a large natural generalization of the principles and tools of equilibrium, which not only admits but requires the introduction of current-valued state variables. For these systems, not only do Martin-Siggia-Rose (MSR) and Schwinger-Keldysh (SK) field methods both exist, in some cases they provide inequivalent classical and quantum descriptions of identical ensembles. With these systems for examples, we can both study the correspondence between classical and quantum descriptions of currents, and also clarify the nature of the mapping between the structurally homologous but interpretationally different MSR and SK formalisms.
This chapter examines the Schwinger-Keldysh technique, applying path integrals, and the functional method of 2PI effective actions—with the latter serving to construct powerful symmetry-preserving nonperturbative approximations for equilibrium as well as nonequilibrium descriptions of strongly interacting quantum many-body systems. It provides a rigorous mathematical basis for exploring the quantum mechanical basis of thermalization and decoherence. Mesoscopic systems with quantum processes, in particular, play a key role. The domain of nonequilibrium mesoscopic systems is flooded with open questions some of which are solved but still others have provisional or incomplete solutions. A correlation function encodes the correlation between the field operators at different times and is an inference to all thermodynamic quantities. The beauty of the Keldysh time path is the definition of the Green's function, which plays an analogous role in the nonequilibrium formalism similar to the role the causal Green's function plays in the equilibrium theory.
In the previous chapter we have seen that departures from equilibrium generate a plethora of new phenomena in statistical physics. While our discussion so far has been limited to classical phenomena, in this chapter we want to ask how quantum mechanics interferes with the conditions of nonequilibrium. Experience shows that, in some cases, nonequilibrium quantum systems can be understood in terms of reasonably straightforward quantization of their classical limits. In others, an interplay of quantum coherence and nonequilibrium driving leads to entirely new phenomena – such as lasing, a paradigm for a steady state nonequilibrium quantum system. At any rate, we have every reason to anticipate that quantum nonequilibrium physics will be as diverse and colourful as its classical counterpart. Even minor departures from equilibrium call for a theoretical description entirely different from the ‘Matsubara formalism’ developed in earlier chapters of this book. The applicability of the latter is rigidly tied to the existence of a quantum grand canonical density operator, the hallmark of a many particle equilibrium system. But how then, can an functional theory of nonequilibrium quantum systems be developed? An obvious idea would be to once more go through the different elements of classical nonequilibrium theory developed in the previous chapter, and subject every one of them to an individual quantization scheme. Luckily, there are more efficient ways to achieve our goal: some decades ago, a many particle formalism suitable to describe nonequilibrium systems under the most general conditions was introduced by Keldysh.
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.
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)].
Investigation on foundational aspects of quantum statistical mechanics recently entered a renaissance period due to novel intuitions from quantum information theory and to increasing attention on the dynamical aspects of single quantum systems. In the present contribution a simple but effective theoretical framework is introduced to clarify the connections between a purely mechanical description and the thermodynamic characterization of the equilibrium state of an isolated quantum system. A salient feature of our approach is the very transparent distinction between the statistical aspects and the dynamical aspects in the description of isolated quantum systems. Like in the classical statistical mechanics, the equilibrium distribution of any property is identified on the basis of the time evolution of the considered system. As a consequence equilibrium properties of quantum system appear to depend on the details of the initial state due to the abundance of constants of the motion in the Schrodinger dynamics. On the other hand the study of the probability distributions of some functions, such as the entropy or the equilibrium state of a subsystem, in statistical ensembles of pure states reveals the crucial role of typicality as the bridge between macroscopic thermodynamics and microscopic quantum dynamics. We shall consider two particular ensembles: the random pure state ensemble and the fixed expectation energy ensemble. The relation between the introduced ensembles, the properties of a given isolated system, and the standard quantum statistical description are discussed throughout the presentation. Finally we point out the conditions which should be satisfied by an ensemble in order to get meaningful thermodynamical characterization of an isolated quantum system.
Focusing on isolated macroscopic systems, described in terms of either a quantum mechanical or a classical model, our two key questions are how far does an initial ensemble (usually far from equilibrium and largely unknown in detail) evolve towards a stationary long-time behavior (equilibration) and how far is this steady state in agreement with the microcanonical ensemble as predicted by statistical mechanics (thermalization). A recently developed quantum mechanical treatment of the problem is briefly summarized, putting particular emphasis on the realistic modeling of experimental measurements and nonequilibrium initial conditions. Within this framework, equilibration can be proven under very weak assumptions about those measurements and initial conditions, while thermalization still requires quite strong additional hypotheses. An analogous approach within the framework of classical mechanics is developed and compared with the quantum case. In particular, the assumptions to guarantee classical equilibration are now rather strong, while thermalization then follows under relatively weak additional conditions.