The second law of classical equilibrium thermodynamics, based on the positivity of entropy production, asserts that any process occurs only in a direction that some information may be lost (flow out of the system) due to the irreversibility inside the system. However, any thermodynamic system can exhibit fluctuations in which negative entropy production may be observed. In particular, in stochastic quantum processes due to quantum correlations and also memory effects we may see the reversal energy flow (heat flow from the cold system to the hot system) and the backflow of information into the system that leads to the negativity of the entropy production which is an apparent violation of the Second Law. In order to resolve this apparent violation, we will try to properly extend the Second Law to quantum processes by incorporating information explicitly into the Second Law. We will also provide a thermodynamic operational meaning for the flow and backflow of information. Finally, it is shown that negative and positive entropy production can be described by a quantum thermodynamic force.
The second law of classical equilibrium thermodynamics, based on the positivity of entropy production, asserts that any process occurs only in a direction that some information may be lost (flow out of the system) due to the irreversibility inside the system. However, any thermodynamic system can exhibit fluctuations in which negative entropy production may be observed. In particular, in stochastic quantum processes due to quantum correlations and also memory effects we may see the reversal energy flow (heat flow from the cold system to the hot system) and the backflow of information into the system that leads to the negativity of the entropy production which is an apparent violation of the Second Law. In order to resolve this apparent violation, we will try to properly extend the Second Law to quantum processes by incorporating information explicitly into the Second Law. We will also provide a thermodynamic operational meaning for the flow and backflow of information. Finally, it is shown that negative and positive entropy production can be described by a quantum thermodynamic force.
Irreversibility is characterized by the entropy production. The second law of classical thermodynamics, based on the positivity of the entropy production, only holds for deterministic processes. Therefore the Second Law in quantum thermodynamics, which is a stochastic thermodynamics, may not hold. By making a fundamental connection between thermodynamics and information theory we will introduce a new way of defining the Second Law which holds for both classical and quantum thermodynamics. Our work incorporate information well into the Second Law and also provide a thermodynamic operational meaning for negative and positive entropy production.
Information thermodynamics is a generalization of thermodynamics to quantum systems and includes information as an analogy of negative entropy. This leads to a generalization of the second law in which the presence of quantum information is taken into account. Whether this information corresponds to conscious information, is left open. In an article published by Minagawa et al in Nature, a more rigorous proof than before is represented for the statement that the second law of thermodynamics is also valid in quantum theory with information included. The presence of information makes possible an apparent local violation of the second law in the sense that the system can do more work than the Carnot law allows. However, Maxwell's demon requires metabolic energy to function and it loses it when demonizing. This energy must be compensated and the conclusion is that the second law of thermodynamics is valid.
Why do quantum evolutions occur and why do they stop at certain points? In classical thermodynamics affinity was introduced to predict in which direction an irreversible process proceeds. In this paper the quantum mechanical counterpart of classical affinity is found. It is shown that the quantum version of affinity can predict in which direction a process evolves. A new version of the second law of thermodynamics is derived through quantum affinity for energy-incoherent state interconversion under thermal operations. we will also see that the quantum affinity can be a good candidate to be responsible, as a force, for driving the flow and backflow of information in Markovian and non-Markovian evolutions. Finally we show that the rate of quantum coherence can be interpreted as the pure quantum mechanical contribution of the total thermodynamic force and flow. Thus It is seen that, from a thermodynamic point of view, any interaction from the outside with the system or any measurement on the system may be represented by a quantum affinity.
Why do quantum evolutions occur and why do they stop at certain points? In classical thermodynamics affinity was introduced to predict in which direction an irreversible process proceeds. In this paper the quantum mechanical counterpart of the classical affinity is found. It is shown that the quantum version of affinity can predict in which direction a process evolves. A new version of the second law of thermodynamics is derived through quantum affinity for energy-incoherent state interconversion under thermal operations. we will also see that the quantum affinity can be a good candidate to be responsible, as a force, for driving the flow and backflow of information in Markovian and non-Markovian evolutions. Finally we show that the rate of quantum coherence can be interpreted as the pure quantum mechanical contribution of the total thermodynamic force and flow. Thus it is seen that, from a thermodynamic point of view, any interaction from the outside with the system or any measurement on the system may be represented by a quantum affinity.
The entropy production in dissipative processes is the essence of the arrow of time and the second law of thermodynamics. For dissipation of quantum systems, it was recently shown that the entropy production contains indeed two contributions: a classical one and a quantum one. Here we show that for degenerate (or near-degenerate) quantum systems there are additional quantum contributions which, remarkably, can become negative. Furthermore, such negative contributions are related to significant changes in the ongoing thermodynamics. This includes phenomena such as generation of coherences between degenerate energy levels (called horizontal coherences), alteration of energy exchanges, and, last but not least, reversal of the natural convergence of the populations toward the thermal equilibrium state. Going further, we establish a complementarity relation between horizontal coherences and population convergence, which is particularly enlightening for understanding heat flow reversals. Conservation laws of the different types of coherences are derived. Some consequences for thermal machines and resource theory of coherence are suggested.
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.