This paper addresses fundamental aspects of statistical mechanics such as the motivation of a classical state space with spontaneous transitions, the meaning of non-equilibrium in the context of thermalization, and the justification of these concepts from the quantum-mechanical point of view. After an introductory part we focus on the problem of entropy production in non-equilibrium systems. In particular, the generally accepted formula for entropy production in the environment is analyzed from a critical perspective. It is shown that this formula is only valid in the limit of separated time scales of the system's and the environmental degrees of freedom. Finally, we present an alternative simple proof of the fluctuation theorem.
This paper addresses fundamental aspects of statistical mechanics such as the motivation of a classical state space with spontaneous transitions, the meaning of non-equilibrium in the context of thermalization, and the justification of these concepts from the quantum-mechanical point of view. After an introductory part we focus on the problem of entropy production in non-equilibrium systems. In particular, the generally accepted formula for entropy production in the environment is analyzed from a critical perspective. It is shown that this formula is only valid in the limit of separated time scales of the system's and the environmental degrees of freedom. Finally, we present an alternative simple proof of the fluctuation theorem.
This paper addresses fundamental aspects of statistical mechanics such as the motivation of a classical state space with spontaneous transitions, the meaning of non-equilibrium in the context of thermalization, and the justification of these concepts from the quantum-mechanical point of view. After an introductory part we focus on the problem of entropy production in non-equilibrium systems. In particular, the generally accepted formula for entropy production in the environment is analyzed from a critical perspective. It is shown that this formula is only valid in the limit of separated time scales of the system's and the environmental degrees of freedom. Finally, we present an alternative simple proof of the fluctuation theorem.
Thermodynamics is a phenomenological theory describing the energy conversion of work and heat. At its origins thermodynamics was developed in order to understand and improve heat engines. In conventional thermodynamics, however, only such processes are completely describable which are slow enough to keep the system of interest in an equilibrium state with its thermal environment at all times. On the contrary, all real physical processes are accompanied by non-equilibrium phenomena. These are mathematically described with the help of the irreversible entropy production, i.e. the dissipated work divided by the temperature of the bath. The second law of thermodynamics merely states that the irreversible entropy production is on average always positive. The modern trend of miniaturization, however, leads to smaller and smaller devices. On short length scales thermal noise as well as quantum fluctuations become important. Thus, usual thermodynamic quantities as work and heat acquire stochastic nature. Moreover, in the quantum regime a completely new theory had to be invented, since classical notions of work and heat are no longer valid. The present dissertation contributes to this prevailing field by the derivation of analytical expressions for the entropy production in open and closed quantum system far from thermal equilibrium. The theoretical treatment is motivated by an experimental point of view. The obtained results were derived from the reduced dynamics of the quantum mechanical system, which may be coupled to a thermal bath. To this end, it was dealt with methods and approaches of statistical physics, conventional thermodynamics, quantum information theory and the theory of open quantum systems. In this dissertation the most important physical systems are treated. First, an isolated system is considered before later on a heat bath is included. The limit of weak as well as of strong coupling are analyzed in detail. For isolated systems it turns out that a geometric approach is able to capture the thermodynamic properties, completely. To this end, the irreversible entropy production is sharply estimated from below by the angle between the real non-equilibrium state and the corresponding equilibrium one. Further, it is shown that the Heisenberg uncertainty relation for energy and time can be formulated more precisely in terms of that angle. As experimental system cold ion traps are introduced, in which the theoretical predictions can be verified. For weakly coupled systems, then, the irreversible entropy production is identified and a fluctuation theorem is derived by merely thermodynamic arguments. As experimental system we, again, propose the cold ion traps, where the heat bath can be simulated with the help of LASER light. In the limit of strong coupling a semiclassical description of the reduced quantum system is discussed. Again, an analytically exact expression for the entropy production and the corresponding fluctuation theorem is derived. A physical system, in which strong coupling to the environment can be analyzed, is given by Josephson junctions. This dissertation discusses the entropy production for isolated, weakly coupled, and overdamped quantum systems. For these physical regimes analytical relation are derived and experimental systems proposed, with which the predictions can be verified.
Abstract Thermodynamic irreversibility is well characterized by the entropy production arising from non-equilibrium quantum processes. We show that the entropy production of a quantum system undergoing open-system dynamics can be formally split into a term that only depends on population unbalances, and one that is underpinned by quantum coherences. This allows us to identify a genuine quantum contribution to the entropy production in non-equilibrium quantum processes. We discuss how these features emerge both in Lindblad-Davies differential maps and finite maps subject to the constraints of thermal operations. We also show how this separation naturally leads to two independent entropic conservation laws for the global system-environment dynamics, one referring to the redistribution of populations between system and environment and the other describing how the coherence initially present in the system is distributed into local coherences in the environment and non-local coherences in the system-environment state. Finally, we discuss how the processing of quantum coherences and the incompatibility of non-commuting measurements leads to fundamental limitations in the description of quantum trajectories and fluctuation theorems.
Phase transitions represent fundamental transformations of matter, characterized by abrupt changes in macroscopic properties and often associated with singular behavior at critical points. While equilibrium aspects of phase transitions, particularly universal critical exponents and scaling laws, are well-understood, the non-equilibrium processes occurring near criticality, especially the production of entropy, remain a rich area of investigation. This paper explores the intricate relationship between critical entropy production and the emergence of scaling laws in systems undergoing phase transitions. We delve into how the rate of entropy production diverges or exhibits anomalous scaling near critical points, reflecting the system's attempts to dissipate energy and respond to external perturbations as it approaches a state of macroscopic change. By integrating concepts from non-equilibrium thermodynamics, statistical mechanics, and renormalization group theory, we aim to elucidate the underlying mechanisms that govern entropy generation in these critical regimes. We discuss theoretical frameworks that predict universal scaling behaviors for entropy production rates, analogous to those observed for equilibrium order parameters and susceptibilities. The implications of these scaling laws extend beyond theoretical physics, offering insights into complex systems, far-from-equilibrium dynamics, and the efficiency of energy conversion processes in critical environments. Our analysis highlights the critical entropy production as a unique signature of non-equilibrium dynamics during phase transitions, providing a deeper understanding of the interplay between fluctuations, dissipation, and universality near points of instability.
A consistent theory of non-equilibrium thermodynamics for Markovian open quantum systems has been developed in the late seventies in analogy with Classical Irreversible Thermodynamics. The time-evolution of these open systems is usually described by means of effective master equations in Lindblad form, that turn out to be reliable when there is a separation of time-scales between system and environment, such that memory effects are negligible and the so-called Markovian approximation is justified. In this framework, the variations of energy and entropy in the system are consistently described, distinguishing between heat and work contributions and providing a statement of the second law of thermodynamics as positivity of the entropy production.\nHowever, there is empirical evidence that many physical systems like photosynthetic complexes,\nopto-mechanical resonators and superconducting qubits, just to mention a few, experience more general non-Markovian dynamics. The formulation of the laws of thermodynamics in a non-Markovian setting is matter of current research and represents the main topic of the present work. As a first step, we show that the entropy production defined as in the Markovian case can be negative for a class of non-Markovian dynamics. We argue that this outcome should not be interpreted as a violation of the second law of thermodynamics because the environment must be explicitly taken into account in the balance of entropy in the non-Markovian setting. In order to justify this claim we adopt a more general point of view, studying a closed bipartite quantum system, such that each of the two subsystems plays the role of a finite environment out of equilibrium for the other one. We concentrate on the balance of energy first and construct an effective Hamiltonian for each subsystem using physically reasonable requirements; then we define heat and work as in the standard Markovian treatment, with the effective Hamiltonian replacing the free Hamiltonian. It turns out that, in our framework, the work power is perfectly balanced between subsystems, while the correlations can store a part of energy locally inaccessible and exchange it with both subsystems in the form of heat.\nConcerning the balance of entropy, a quite general formulation of the second law of thermodynamics can be given as follows: under the assumption of a factorized initial state for the compound system, the sum of the total variations of the entropies in the two subsystems is always nonnegative. We show with an explicit example that this general formulation does not correspond to the statement presented in the framework of Markovian master equations, which should not be considered a priori the second law of thermodynamics.\nIn the last part of the thesis we concentrate of the so-called fluctuation relations, that are results extending the thermodynamic formalism beyond the behavior of average quantities. After reviewing the main theoretical outcomes, such as the Jarzynski equality and the Crooks fluctuation theorem, we describe a proposal to access experimentally the work performed on an ensemble of diatomic molecules by a time-dependent electric field coupled with their vibrational degree of freedom. This procedure could then be used to test the quantum Jarzynski equality. With respect to the results so far appeared in the literature, in which the left-hand side of the equality is inferred from an experiment and the right-hand side is computed according to a model, in our proposed setting we should be able to estimate from the experiment both the left-hand side and the right-hand side of the equality, independently.
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.