Heat and work for quantum systems governed by dissipative master equations with a time-dependent driving field were introduced in the pioneering work of Alicki [J. Phys. A 12, L103 (1979)]. Alicki's work was in the Schr\"odinger picture; here we extend these definitions to the Heisenberg and interaction pictures. We show that, in order to avoid consistency problems, the full time derivatives in the definitions for heat flux and power (work flux) should be replaced by partial time derivatives. We also present an alternative approach to the partitioning of the energy flux which differs from that of Alicki in that the instantaneous interaction energy with the external field is not included directly. We then proceed to generalize Alicki's definition of power by replacing the original system and its external driving field with a larger, bipartite system, governed by a time-independent Hamiltonian. Using the definition of heat flux and the generalized definition of power, we derive the first law of thermodynamics in differential form, for both the full bipartite system and the partially traced subsystems. Although the second law (Clausius formulation) is satisfied for the full bipartite system, we find that in general there is no rigorous formulation of the second law for the partially traced subsystem unless certain additional requirements are met. Once these requirements are satisfied, however, both the Carnot and the Clausius formulations of the second law are satisfied. We illustrate this thermodynamic analysis on both the simple Jaynes-Cummings model and an extended dissipative Jaynes-Cummings model, which is a model for a quantum amplifier.
Heat and work for quantum systems governed by dissipative master equations with a time-dependent driving field were introduced in the pioneering work of Alicki [J. Phys. A 12, L103 (1979)]. Alicki's work was in the Schr"odinger picture; here we extend these definitions to the Heisenberg and interaction pictures. We show that, in order to avoid consistency problems, the full time derivatives in the definitions for heat flux and power (work flux) should be replaced by partial time derivatives. We also present an alternative approach to the partitioning of the energy flux which differs from that of Alicki in that the instantaneous interaction energy with the external field is not included directly. We then proceed to generalize Alicki's definition of power by replacing the original system and its external driving field with a larger, bipartite system, governed by a time-independent Hamiltonian. Using the definition of heat flux and the generalized definition of power, we derive the first law of thermodynamics in differential form, for both the full bipartite system and the partially traced subsystems. Although the second law (Clausius formulation) is satisfied for the full bipartite system, we find that in general there is no rigorous formulation of the second law for the partially traced subsystem unless certain additional requirements are met. Once these requirements are satisfied, however, both the Carnot and the Clausius formulations of the second law are satisfied. We illustrate this thermodynamic analysis on both the simple Jaynes-Cummings model and an extended dissipative Jaynes-Cummings model, which is a model for a quantum amplifier.
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 question of with what we associate work and heat in a quantum thermodynamic process has been extensively discussed, mostly for systems with time-dependent Hamiltonians. In this paper, we aim to investigate the energy exchanged between two quantum systems through interaction where the Hamiltonian of the system is time-independent. An entropy-based re-definitions of heat and work are presented for these quantum thermodynamic systems therefore an entropy-based formalism of both the first and the second laws of thermodynamics are introduced. We will use the genuine reasoning based on which Clausius originally defined work and heat. The change in the energy which is accompanied by a change in the entropy is identified as heat, while any change in the energy which does not lead to a change in the entropy is known as work. It will be seen that quantum coherence does not allow all the energy exchanged between two quantum systems to be only of the heat form. Several examples will also be discussed. Finally, we will examine irreversibility from our entropy-based formalism of quantum thermodynamics.
Thermodynamics of a three-level maser was studied in the pioneering work of Scovil and Schulz-DuBois [Phys. Rev. Lett. 2, 262 (1959)]. In this work we consider the same three-level model, but treat both the matter and the light quantum mechanically. Specifically, we analyze an extended (three-level) dissipative (ED) Jaynes-Cummings model (JCM) within the framework of a quantum heat engine, using formulas for heat flux and power in bipartite systems introduced in our previous work [E. Boukobza and D. J. Tannor Phys. Rev. A 74, 063823 (2006)] Amplification of the selected cavity mode occurs even in this simple model, as seen by a positive steady state power. However, initial field coherence is lost, as seen by the decaying off-diagonal field density matrix elements, and by the Husimi-Kano Q function. We show that after an initial transient time the field's entropy rises linearly during the operation of the engine, which we attribute to the dissipative nature of the evolution and not to matter-field entanglement. We show that the second law of thermodynamics is satisfied in two formulations (Clausius, Carnot) and that the efficiency of the ED JCM heat engine agrees with that defined intuitively by Scovil and Schulz-DuBois. Finally, we compare the steady state heat flux and power of the fully quantum model with the semiclassical counterpart of the ED JCM, and derive the engine efficiency formula of Scovil and Schulz-DuBois analytically from fundamental thermodynamic fluxes.
We provide a characterization of energy in the form of exchanged heat and work between two interacting constituents of a closed, bipartite, correlated quantum system. By defining a binding energy we derive a consistent quantum formulation of the first law of thermodynamics, in which the role of correlations becomes evident, and this formulation reduces to the standard classical picture in relevant systems. We next discuss the emergence of the second law of thermodynamics under certain-but fairly general-conditions such as the Markovian assumption. We illustrate the role of correlations and interactions in thermodynamics through two examples.
The internal energy of individual subsystems is not well defined in interacting quantum systems, leading to ambiguities in the definition of thermodynamic quantities. Applying the Schmidt basis formalism to general bipartite autonomous quantum systems, we demonstrate that the master equation describing subsystem evolution adheres to the principle of minimal dissipation. This enables to define internal energy of each subsystem in a consistent way. Moreover, by utilizing general aspects of open quantum systems, we show that this master equation is unique. We analyze heat and work for each subsystem as derived from this formalism, providing deeper insights into the thermodynamics of interacting quantum systems.
In quantum thermodynamics, the decomposition of energy exchanges into heat and work remains an open problem beyond weak-coupling and slow-driving regimes. Recent formulations have shown that quantum coherence introduces additional energy contributions whose thermodynamic interpretation is still under debate, raising fundamental questions about the structure of the quantum first law. In this work, we investigate this problem through a time-dependent perturbative framework applied to the first law of quantum thermodynamics. By expanding the thermodynamic quantities up to second order, we derive explicit perturbative corrections for work, heat, and coherence contributions. Our results show that the coherence term can be consistently decomposed into coherent heat and coherent work, demonstrating that quantum coherence does not require the introduction of an independent energetic contribution beyond heat and work. The formalism resolves inconsistencies associated with previous formulations of the quantum first law, including the interpretation of coherence contributions and their connection with entropy fluxes. At second order, the perturbative corrections become directly connected to transition rates governed by Fermi's golden rule, establishing a bridge between microscopic quantum transitions and macroscopic thermodynamic quantities. These results provide a physically transparent framework to investigate coherence-driven thermodynamic processes and offer new perspectives for the analysis of driven quantum systems and nonequilibrium quantum technologies.