We develop a general theory describing the thermodynamical behavior of open quantum systems coupled to thermal baths beyond perturbation theory. Our approach is based on the exact time-local quantum master equation for the reduced open-system states, and on a principle of minimal dissipation. This principle leads to a unique prescription for the decomposition of the master equation into a Hamiltonian part representing coherent time evolution and a dissipator part describing dissipation and decoherence. Employing this decomposition we demonstrate how to define work, heat, and entropy production, formulate the first and second laws of thermodynamics, and establish the connection between violations of the second law and quantum non-Markovianity.
We develop a general theory describing the thermodynamical behavior of open quantum systems coupled to thermal baths beyond perturbation theory. Our approach is based on the exact time-local quantum master equation for the reduced open-system states, and on a principle of minimal dissipation. This principle leads to a unique prescription for the decomposition of the master equation into a Hamiltonian part representing coherent time evolution and a dissipator part describing dissipation and decoherence. Employing this decomposition we demonstrate how to define work, heat, and entropy production, formulate the first and second laws of thermodynamics, and establish the connection between violations of the second law and quantum non-Markovianity.
We develop a general theory describing the thermodynamical behavior of open quantum systems coupled to thermal baths beyond perturbation theory. Our approach is based on the exact time-local quantum master equation for the reduced open system states, and on a principle of minimal dissipation. This principle leads to a unique prescription for the decomposition of the master equation into a Hamiltonian part representing coherent time evolution and a dissipator part describing dissipation and decoherence. Employing this decomposition we demonstrate how to define work, heat and entropy production, formulate the first and second law of thermodynamics, and establish the connection between violations of the second law and quantum non-Markovianity.
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.
We introduce a systematic framework to derive the effective Hamiltonian governing the coherent dynamics of non-Markovian open quantum systems. By applying the minimal dissipation principle, we uniquely isolate the coherent contribution to the time-local generator of the reduced dynamics. We derive a general expression for the effective Hamiltonian and develop a recursive perturbative expansion that expresses it in terms of system-bath interaction terms and bath correlation functions. This expansion provides a systematic tool for analyzing energy renormalization effects across different coupling regimes. Applying our framework to paradigmatic spin systems, we reveal how environmental correlations influence energy shifts and eigenbasis rotations, offering insights into strong-coupling effects and non-Markovian quantum thermodynamics.
We present a systematic thermodynamic analysis of nonsecular GKLS master equations. When some energy transitions in the system are comparable with the dissipative rate, the secular approximation is not valid, and the positivity of the dynamics must be ensured via other approximations. The dynamics then presents features reminiscent from strong coupling to the environment: e.g. the equilibrium state with an environment at thermal equilibrium is not a Gibbs state of the local system Hamiltonian and the dynamics couples energy coherences and populations. Nonetheless, we build a unified, consistent thermodynamic framework for those dynamics. We focus on two approximations beyond the full secular approximation (the local and the more accurate geometric-arithmetic approximations), and then employ systematic perturbation theory on microscopic expressions for the first and second law of thermodynamics which relate irreversibility to the increase of system-environment correlations. We show that, in spite of the weak system-bath coupling, the system-bath interaction energy participates to the energy balance, and is directly linked to the Lamb-shift Hamiltonian. We compare this microscopic entropy production with the definition based on the contractivity of the reduced system dynamics (Spohn inequality). We show that, unlike for secular master equations, the two entropy production rates differ because of the presence of non-vanishing stationary coherences in the energy eigenbasis. However, in the case of a single thermal bath, the difference is purely transient, and no work can be cyclically extracted from the steady-state despite its non-Gibbs form. Finally, we illustrate our results with simple examples, clarifying and completing the thermodynamic picture of Markovian dynamics in the quantum regime.
We study the nonequilibrium thermodynamics of pure decoherence processes in open quantum systems coupled to a thermal reservoir. We review various definitions of central quantities, such as internal energy, work, heat, and entropy production, developed within local and global approaches to quantum thermodynamics. Within local approaches, thermodynamic quantities only refer to the open system's degrees of freedom, while in the global approaches, certain quantities are defined by referring explicitly to the reservoir degrees of freedom. Employing a microscopic, analytically solvable model, we perform a comparison of these two perspectives, revealing substantial differences in the thermodynamic quantities and in the formulations of the first and second laws. The main reason for these discrepancies is the fact that the global approaches involve the system-reservoir interaction which exchanges a large amount of energy with the environment, while the average open system energy is constant in time because the dynamics represents pure decoherence and does not affect the open system populations.
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.