During the last decades, there have been many theoretical and experimental advances both in the extension of thermodynamics to comprise microscopic systems out-of-equilibrium and in the understanding of quantum mechanics. Along with the state-of-the-art capability of controlling fragile quantum systems in a wide variety of physical platforms, this context has paved the way for the current strategic efforts to develop a thermodynamic theory of quantum systems. In this sense, the research field coined as quantum thermodynamics (QT) already plays a key role in the design and development of future quantum-based technologies. More specifically, QT aims both to apply the usual thermodynamic concepts and notions to describe arbitrary non-equilibrium quantum systems and to understand the emergence of classical thermodynamic behaviour from the underlying fundamentally quantum dynamics. However, despite all current progress, there is still no consolidated formalism for a general thermodynamic description of fully autonomous quantum objects. Besides, the lack of consensus on some central aspects, such as the definitions of quantum counterparts of thermodynamic quantities, is particularly notorious. In this thesis, we focus on the energetic analysis within autonomous quantum systems. To this aim, we propose a novel and general formalism for a dynamic description of the energy exchanges between interacting subsystems. From the Schmidt decomposition approach, we identify effective Hamiltonians as the representative operators for characterizing the local internal energies, whose expectation values satisfy the usual thermodynamic notion of energy additivity. In contrast to the currently used methodologies, such procedure treats the subsystems with equal footing and do not rely on any sort of approximations and additional hypotheses, e.g., semi-classical description, weak-coupling regime, strict energy conservation and Markovian dynamics. In short, our proposal contributes to the development of QT by providing a new formalism that does not suffer from the usual restrictive shortcomings and establishes a new and exact route for defining other general thermodynamic quantities to the quantum regime.
During the last decades, there have been many theoretical and experimental advances both in the extension of thermodynamics to comprise microscopic systems out-of-equilibrium and in the understanding of quantum mechanics. Along with the state-of-the-art capability of controlling fragile quantum systems in a wide variety of physical platforms, this context has paved the way for the current strategic efforts to develop a thermodynamic theory of quantum systems. In this sense, the research field coined as quantum thermodynamics (QT) already plays a key role in the design and development of future quantum-based technologies. More specifically, QT aims both to apply the usual thermodynamic concepts and notions to describe arbitrary non-equilibrium quantum systems and to understand the emergence of classical thermodynamic behaviour from the underlying fundamentally quantum dynamics. However, despite all current progress, there is still no consolidated formalism for a general thermodynamic description of fully autonomous quantum objects. Besides, the lack of consensus on some central aspects, such as the definitions of quantum counterparts of thermodynamic quantities, is particularly notorious. In this thesis, we focus on the energetic analysis within autonomous quantum systems. To this aim, we propose a novel and general formalism for a dynamic description of the energy exchanges between interacting subsystems. From the Schmidt decomposition approach, we identify effective Hamiltonians as the representative operators for characterizing the local internal energies, whose expectation values satisfy the usual thermodynamic notion of energy additivity. In contrast to the currently used methodologies, such procedure treats the subsystems with equal footing and do not rely on any sort of approximations and additional hypotheses, e.g., semi-classical description, weak-coupling regime, strict energy conservation and Markovian dynamics. In short, our proposal contributes to the development of QT by providing a new formalism that does not suffer from the usual restrictive shortcomings and establishes a new and exact route for defining other general thermodynamic quantities to the quantum regime.
During the last decades, there have been many theoretical and experimental advances both in the extension of thermodynamics to comprise microscopic systems out-of-equilibrium and in the understanding of quantum mechanics.Along with the state-of-the-art capability of controlling fragile quantum systems in a wide variety of physical platforms, this context has paved the way for the current strategic efforts to develop a thermodynamic theory of quantum systems.In this sense, the research field coined as quantum thermodynamics (QT) already plays a key role in the design and development of future quantum-based technologies.More specifically, QT aims both to apply the usual thermodynamic concepts and notions to describe arbitrary non-equilibrium quantum systems and to understand the emergence of classical thermodynamic behaviour from the underlying fundamentally quantum dynamics.However, despite all current progress, there is still no consolidated formalism for a general thermodynamic description of fully autonomous quantum objects.Besides, the lack of consensus on some central aspects, such as the definitions of quantum counterparts of thermodynamic quantities, is particularly notorious.In this thesis, we focus on the energetic analysis within autonomous quantum systems.To this aim, we propose a novel and general formalism for a dynamic description of the energy exchanges between interacting subsystems.From the Schmidt decomposition approach, we identify effective Hamiltonians as the representative operators for characterizing the local internal energies, whose expectation values satisfy the usual thermodynamic notion of energy additivity.In contrast to the currently used methodologies, such procedure treats the subsystems with equal footing and do not rely on any sort of approximations and additional hypotheses, e.g., semi-classical description, weak-coupling regime, strict energy conservation and Markovian dynamics.In short, our proposal contributes to the development of QT by providing a new formalism that does not suffer from the usual restrictive shortcomings and establishes a new and exact route for defining other general thermodynamic quantities to the quantum regime.
The development of a self-consistent thermodynamic theory of quantum systems is of fundamental importance for modern physics. Still, despite its essential role in quantum science and technology, there is no unifying formalism for characterizing the thermodynamics within general autonomous quantum systems, and many fundamental open questions remain unanswered. Along these lines, most current efforts and approaches restrict the analysis to particular scenarios of approximative descriptions and semi-classical regimes. Here, we propose a novel approach to describe the thermodynamics of arbitrary bipartite autonomous quantum systems based on the well-known Schmidt decomposition. This formalism provides a simple, exact, and symmetrical framework for expressing the energetics between interacting systems, including scenarios beyond the standard description regimes, such as strong coupling. We show that this procedure allows straightforward identification of local effective operators suitable for characterizing the physical local internal energies. We also demonstrate that these quantities naturally satisfy the usual thermodynamic notion of energy additivity.
The quest to develop a general framework for thermodynamics, suitable for the regime of strong coupling and correlations between subsystems of an autonomous quantum "universe," has entailed diverging definitions for basic quantities, including internal energy. While most approaches focus solely on the system of interest, we propose that a universal notion of internal energy should also account for the environment in order to keep consistency with the closed-system energy of the universe. We introduce an abstract framework to describe all effective Hamiltonian-based approaches and address a rigorous definition of energy additivity in this context, in both a weak and a strong form, discussing the underlying subtleties. As an illustration, we study a particular two-qubit universe model, obtaining the exact master equations for both parties and calculating their effective Hamiltonians and internal energies as given by the recently devised minimal dissipation approach. In this case, we show that internal energies are neither additive nor conservative, which leads to unphysical features.
Quantum thermodynamics (QT) is an emerging field of research that aims to investigate how the laws of thermodynamics and quantum mechanics merge together in small quantum systems. With advances at the necessary technology to control and measure those small physical systems this field has acquired even more importance, not only in the sense that it can be tested, which is a good thing for basic research, but that new applications could be implemented at these scales, so a better comprehension of the limitations imposed by quantum thermodynamics turns out to be of crucial importance for these goals, which forces theoreticians to produce experimentally relevant versions of these new concepts. Another important aspect present at those systems is that part of them work in a regime where its constituents are described by non-thermal states, and in particular non-thermal steady states, which brings to light a different thermodynamic description, usually called steady-state thermodynamics, therefore one of the goals that we are willing to achieve with this thesis is to give an introduction to QT of systems out-of-equilibrium. One of the related subtopics that physicists deal with in QT and the one that we will be focusing on this work are the use of non-thermal stationary states to build heat engines in the quantum domain, and the analyses of the features that this new regime could possibly allow, like the use of quantum resources as a way to overcome classical limitations imposed on its performance, like to attain efficiencies higher than Carnots or operate in certain regimes unattainable using only classical resources. Therefore, in order to clarify the underlying physics of those systems in a non-thermal regime, any experimentally well suited content is more than welcome. So keeping that in mind we devised an experimentally relevant thermodynamic cycle for a transmon qubit WS interacting with a non-thermal environment composed by two subsystems, an externally excited cavity and a classical heat bath with temperature T. The WS undergoes a non-conventional cycle (different from Otto, Carnot, etc.) through a succession of non-thermal stationary states obtained by slowly varying its bare frequency and the amplitude of the field applied on the cavity. The efficiency of this engine obtains a maximum value up to 47% in the regime of operation used. We also wanted to look for the role played by the different types of coherences, present at the WS, on the behavior of the engine and its efficiency. By different types of coherence we mean the so called modes of coherence, whose definition is based on how they respond to symmetry transformations. We did that for the trivial case of the qubit, that only contains the modes 1 and -1, and that has shown to be extremely important for the efficiency of the machine. The same procedure was repeated for a 3-level system WS. The modes 1 and -1 was again very important, not only to the absolute value of the engines efficiency but to the regime of operation of the machine. The additional modes, 2 and -2, had a negative impact on the efficiency, reducing its absolute value. This result appears to show some evidences that quantumness wont necessarily bring improvements to the operation of those machines.
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.
Quantum thermodynamics has emerged as a central field for understanding how energy conversion processes occur in microscopic systems. In these systems, effects such as coherence, entanglement, and non-Markovianity play key roles. In this thesis, we explore different ways to describe quantum thermodynamics, using two main approaches: one based on entropy and the other on ergotropy. First, we introduce a generalized approach to quantify non-Markovianity through the breakdown of monotonicity in thermodynamic functions. In this context, the entropy-based heat flow serves as a practical tool to witness and measure quantum memory in unital maps that do not reverse the sign of the internal energy. Next, we analyze the dynamics of ergotropy in open qubits under both Markovian and non-Markovian evolutions. We identify phenomena such as freezing and sudden death of ergotropy, and we establish an analytical relation between the change in ergotropy and the environment-induced work . This provides a clear physical interpretation for the additional term in the first law in the entropy-based formulation. Finally, we propose an ergotropy-based thermodynamic formulation, in which heat is reinterpreted in terms of the change of the passive state associated with the density operator governing the quantum dynamics. This approach allows one to measure non-Markovianity of unital maps more generally and accurately than the entropy-based heat flow. This advantage comes from the direct link between heat and von Neumann entropy, a property ensured by invariance under passive transformations. Moreover, the out-of-equilibrium temperature naturally remains non-negative, similarly to equilibrium thermodynamics.