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.
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.
In this paper, unambiguous redefinitions of heat and work are presented for quantum thermodynamic systems. We will use genuine reasoning based on which Clausius originally defined work and heat in establishing thermodynamics. 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, it will be shown that these refined definitions will strongly affect the entropy production of quantum thermodynamic processes giving new insight into the irreversibility of quantum processes.
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.
In bipartite quantum systems commutation relations between the Hamiltonian of each subsystem and the interaction impose fundamental constraints on the dynamics of each partition. Here we investigate work, heat and entropy production in bipartite systems characterized by particular commutators between their local Hamiltonians and the interaction operator. We consider the formalism of (Weimer et al 2008 Europhys. Lett. 83 30008 ), in which heat (work) is identified with energy changes that (do not) alter the local von Neumann entropy, as observed in an effective local measurement basis. We demonstrate the consequences of the commutation relations on the work and heat fluxes into each partition, and extend the formalism to open quantum systems where one, or both, partitions are subject to a Markovian thermal bath. We also discuss the relation between heat and entropy in bipartite quantum systems out of thermal equilibrium, and reconcile the aforementioned approach with the second law of thermodynamics.
A central open question in quantum thermodynamics is the identification of thermodynamic entropy away from equilibrium. Although thermodynamic entropy coincides with the von Neumann entropy for a Gibbs state at equilibrium, the thermodynamic role of quantum coherence generated during nonequilibrium evolution remains unclear. Here, we show that von Neumann entropy does not, in general, represent the thermodynamic entropy governing heat exchange in coherent nonequilibrium quantum systems. By integrating the resource theory of quantum coherence with thermodynamic principles, we develop a general framework for nonequilibrium quantum thermodynamics. We identify thermodynamic entropy with the energy entropy derived from energy-measurement statistics and introduce a dynamical temperature extending the equilibrium concept to nonequilibrium states. Consequently, we obtain an exact entropy-balance relation separating the entropy flux associated with heat exchange from the coherence-loss contribution to entropy production, establishing an operational connection between quantum coherence, heat flow, and total entropy change. Unlike approaches relying on equilibrium reference states or stationary Gibbs ensembles, our framework uses instantaneous dynamical quantities and remains valid throughout transient nonequilibrium evolution. It provides consistent dynamical definitions of temperature, work, heat, and free energy. Applying the formalism to an exactly solvable open quantum system, we show that the first and second laws hold throughout transient evolution and that equilibrium thermodynamics emerges dynamically in the weak-coupling long-time limit. Our results establish a unified framework for coherent nonequilibrium quantum thermodynamics and suggest opportunities for controlling heat dissipation through coherence engineering in quantum thermal technologies.
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.
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.