Abstract Processes at the nanoscale happen far away from the thermodynamic limit, far from equilibrium and are dominated by fluctuations and, perhaps, even quantum effects. This book establishes a consistent thermodynamic framework for such processes by combining tools from non-equilibrium statistical mechanics and the theory of open quantum systems. The book is accessible for graduate students and of interest to all researchers striving for a deeper understanding of the laws of thermodynamics beyond their traditional realm of applicability. It puts most emphasis on the microscopic derivation and understanding of key principles and concepts as well as their interrelation. The topics covered in this book include (quantum) stochastic processes, (quantum) master equations, local detailed balance, classical stochastic thermodynamics, (quantum) fluctuation theorems, strong coupling and non non-Markovian effects, thermodynamic uncertainty relations, operational approaches, Maxwell's demon and time-reversal symmetry, among other topics. Furthermore, the book treats a few applications in detail to illustrate the general theory and its potential for practical applications. These are single-molecule pulling experiments, quantum transport and thermoelectric effects in quantum dots, the micromaser and related set-ups in quantum optics.
Abstract Processes at the nanoscale happen far away from the thermodynamic limit, far from equilibrium and are dominated by fluctuations and, perhaps, even quantum effects. This book establishes a consistent thermodynamic framework for such processes by combining tools from non-equilibrium statistical mechanics and the theory of open quantum systems. The book is accessible for graduate students and of interest to all researchers striving for a deeper understanding of the laws of thermodynamics beyond their traditional realm of applicability. It puts most emphasis on the microscopic derivation and understanding of key principles and concepts as well as their interrelation. The topics covered in this book include (quantum) stochastic processes, (quantum) master equations, local detailed balance, classical stochastic thermodynamics, (quantum) fluctuation theorems, strong coupling and non non-Markovian effects, thermodynamic uncertainty relations, operational approaches, Maxwell's demon and time-reversal symmetry, among other topics. Furthermore, the book treats a few applications in detail to illustrate the general theory and its potential for practical applications. These are single-molecule pulling experiments, quantum transport and thermoelectric effects in quantum dots, the micromaser and related set-ups in quantum optics.
To understand in detail the relation between unitary quantum theory that describes our world at the microscopic scale and thermodynamics, which was long believed only to apply to macroscopic objects, is one of the most interesting and long-standing problems in physics. Recently, this problem has received renewed attention, in particular from the community of quantum information theory, but also from the field of statistical mechanics, inspired from stochastic thermodynamics. These results suggest that thermodynamics is also relevant for individual quantum systems, provided that they can be brought into contact with thermal baths. In this thesis, I use recently developed tools to provide new results both on fundamental questions, but also on questions which are of practical relevance for potential miniaturized thermal machines. In terms of fundamental questions, the results in this thesis contribute to understanding how the basic laws of thermodynamics and statistical mechanics can be understood directly from unitary quantum mechanics. In particular, I discuss and answer the following questions: i) How can we quantify the third law of thermodynamics using information theoretic methods? ii) How can we quantify the "thermodynamic value" of a state-transition in quantum systems? iii) How can we axiomatically characterize the non-equilibrium free energy and relative entropy? iv) How can we justify statistical ensembles from an operational perspective, without having to introduce either some probability measures or an information theoretic entropy measure? v) How can we understand the equilibration of closed quantum systems, how long does it take and how difficult is it to avoid? In the second part of the thesis I discuss in detail how experimental restrictions, which become important at the quantum scale, influence the ultimate thermodynamic bounds for thermal machines. In particular, the results in this thesis provide thermodynamic bounds on work-extraction and efficiencies of thermal machines in situations where 1.) an experimenter only has limited field strengths available, 2.) an experimenter cannot control the interactions between particles, but external fields arbitrarily well, and 3.) situations in which a small quantum system can only be strongly coupled to heat baths. These bounds are tight and I provide explicit examples illustrating the different behaviours. Finally, I come back to a classic problem in statistical physics: The emergence of spontaneous symmetry breaking. Here, I provide general and rigorous new results that show how symmetry-breaking stationary states emerge from fluctuations in order parameters in dissipative lattice models.
Abstract We derive the basic laws of phenomenological non-equilibrium thermodynamics for small open systems, whose quantum nature can no longer be neglected. Emphasis is put from the beginning on deriving them from an underlying microscopic system on deriving them from an underlying microscopic system–bath picture. Commonly considered approximation schemes (wea k coupling master equations) are reviewed and their thermodynamics is studied. The zeroth law is discussed for small systems and exact identities for the entropy production, valid at strong coupling and in the non non-Markovian regime, are introduced. We discu ss the effect of finite baths even out of equilibrium and use the framework of repeated interactions to study microscopic non-equilibrium resources. The chapter concludes with the study of particle transport and thermoelectric devices, which were realized in experiments. This chapter focuses entirely on the dynamics of a system coupled to a bath without any external interventions.
This innovative and modular textbook combines classical topics in thermodynamics, statistical mechanics and many-body theory with the latest developments in condensed matter physics research. Written by internationally renowned experts and logically structured to cater for undergraduate and postgraduate students and researchers, it covers the underlying theoretical principles and includes numerous problems and worked examples to put this knowledge into practice. Three main streams provide a framework for the book; beginning with thermodynamics and classical statistical mechanics, including mean field approximation, fluctuations and the renormalization group approach to critical phenomena. The authors then examine quantum statistical mechanics, covering key topics such as normal Fermi and Luttinger liquids, superfluidity and superconductivity. Finally, they explore classical and quantum kinetics, Anderson localization and quantum interference, and disordered Fermi liquids. Unique in providing a bridge between thermodynamics and advanced topics in condensed matter, this textbook is an invaluable resource to all students of physics.
Deriving the laws of thermodynamics from a microscopic picture is a central quest of statistical mechanics.This tutorial focuses on the derivation of the first and second law for isolated and open quantum systems far from equilibrium, where such foundational questions also become practically relevant for emergent nanotechnologies.The derivation is based on a microscopic definition of five essential quantities: internal energy, thermodynamic entropy, work, heat, and temperature.These definitions are shown to satisfy the phenomenological laws of nonequilibrium thermodynamics for a large class of states and processes.The consistency with previous results is demonstrated.The framework applies to multiple baths including particle transport and accounts for processes with, e.g., a changing temperature of the bath, which is determined microscopically.An integral fluctuation theorem for entropy production is satisfied.In summary, this tutorial introduces a consistent and versatile framework to understand and apply the laws of thermodynamics in the quantum regime and beyond.
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.
The thermodynamical behavior of quantum systems at the nanoscale is often very difficult to capture via standard frameworks of thermodynamics. The latter is, in fact, an equilibrium theory whose predictions are typically only valid on average, and in regimes where systems are composed of a very large number of constituents. In reality, the thermodynamical behavior of nanoscale systems can be much more constrained that what is predicted by macroscopic thermodynamics, due to the unavoidable impact of fluctuations. As a result, the fundamental limitations to a system's dynamics induced by macroscopic thermodynamics might turn out to be considerably less stringent than what can actually be observed at those scales. The theory of open quantum systems is certainly a powerful tool in this context, and can provide solutions which go beyond equilibrium treatments, but solving the dynamics of an open system requires detailed information about its microscopic structure (e.g. system-environment interactions and coupling strengths). In other words, one of the great advantages of macroscopic thermodynamics, i.e. its universality and independence of microscopic details, might be essentially lost if we can only infer thermodynamical results once we specify the full microscopic structure of our system-environment interaction. This highlights the necessity for a framework of thermodynamics that is well suited for studying the behavior of small quantum systems far from equilibrium, but can still be applied to physical systems in a universal way, i.e., without having to specify full microscopic information. Quantum Resource Theories (QRTs), and in particular the formulations of quantum thermodynamics that have emerged from them, constitute a promising tool in this direction. However, these models of thermodynamics have not yet been extensively applied to realistic physical platform, and their consequences on known thermodynamical processes are still unexplored. Furthermore, going beyond a purely thermodynamical context, a case can be made for the use of general QRTs as benchmarking tools for the certification of certain quantum resources. In other words, QRTs could be used to find fundamental bounds to physical quantities or impossibility results (in the form of no-go theorems) that, when compared to experimental data, can be used to falsify specific hypotheses. In this thesis, both these directions will be explored, by considering resource-theoretical questions that are relevant for different physical platforms. These will include the photochemical process of photoisomerization, heat transport in harmonic systems, and tabletop tests of quantum gravity.