Understanding thermodynamics far from equilibrium at the quantum scale remains a fundamental challenge, particularly in the presence of quantum coherence. Here we develop a first-principles framework for nonequilibrium quantum thermodynamics by integrating quantum resource theory of coherence with thermodynamic laws. We derive a previously unexplored entropy balance relation that explicitly separates entropy flux due to heat exchange from entropy production arising from the loss of quantum coherence. This formulation identifies the appropriate thermodynamic entropy in nonequilibrium quantum processes as the energy entropy associated with energy measurements, demonstrating that the von Neumann entropy does not, in general, represent thermodynamic entropy away from equilibrium. Within this framework, dynamical temperature, free energy, work, and heat are consistently defined, and both the first and second laws are shown to hold far from equilibrium. Applying the theory to an exactly solvable open quantum system, we reveal how equilibrium thermodynamics emerges dynamically in the weak-coupling limit. Our results establish a unified and operational foundation for nonequilibrium quantum thermodynamics and clarify the fundamental thermodynamic role of quantum coherence.
Understanding thermodynamics far from equilibrium at the quantum scale remains a fundamental challenge, particularly in the presence of quantum coherence. Here we develop a first-principles framework for nonequilibrium quantum thermodynamics by integrating quantum resource theory of coherence with thermodynamic laws. We derive a previously unexplored entropy balance relation that explicitly separates entropy flux due to heat exchange from entropy production arising from the loss of quantum coherence. This formulation identifies the appropriate thermodynamic entropy in nonequilibrium quantum processes as the energy entropy associated with energy measurements, demonstrating that the von Neumann entropy does not, in general, represent thermodynamic entropy away from equilibrium. Within this framework, dynamical temperature, free energy, work, and heat are consistently defined, and both the first and second laws are shown to hold far from equilibrium. Applying the theory to an exactly solvable open quantum system, we reveal how equilibrium thermodynamics emerges dynamically in the weak-coupling limit. Our results establish a unified and operational foundation for nonequilibrium quantum thermodynamics and clarify the fundamental thermodynamic role of quantum coherence.
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.
This paper presents a comprehensive exposition of quantum thermodynamics, aiming to bridge the foundational concepts of classical thermodynamics and quantum mechanics.Beginning with a rigorous overview of classical thermodynamic laws and statistical ensembles, the work transitions into the quantum domain by introducing quantum states, density operators, and von Neumann entropy.Core thermodynamic quantities such as work, heat, energy, and entropy are redefined in the quantum regime, with emphasis on operational frameworks like the twopoint measurement scheme.The study explores the role of quantum resource theories in formulating generalizations of the second law and delves into the intricacies of nonequilibrium thermodynamics through fluctuation theorems, such as the Jarzynski equality and Crooks theorem.Special attention is given to the influence of coherence, entanglement, and measurement backaction, which contribute uniquely to quantum thermodynamic behavior.The treatise concludes with a discussion on quantum heat engines, thermodynamic consistency of quantum master equations, and information-theoretic approaches, establishing quantum thermodynamics as a vital framework for understanding energy and information flow at the quantum scale.
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.
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.
Deriving the laws of thermodynamics from a microscopic picture is a central quest of statistical mechanics.This tutorial focuses on the derivation of the first and second law for isolated and open quantum systems far from equilibrium, where such foundational questions also become practically relevant for emergent nanotechnologies.The derivation is based on a microscopic definition of five essential quantities: internal energy, thermodynamic entropy, work, heat, and temperature.These definitions are shown to satisfy the phenomenological laws of nonequilibrium thermodynamics for a large class of states and processes.The consistency with previous results is demonstrated.The framework applies to multiple baths including particle transport and accounts for processes with, e.g., a changing temperature of the bath, which is determined microscopically.An integral fluctuation theorem for entropy production is satisfied.In summary, this tutorial introduces a consistent and versatile framework to understand and apply the laws of thermodynamics in the quantum regime and beyond.
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.