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Thermodynamic laws beyond free energy relations

Matteo Lostaglio, David Jennings, Terry Rudolph

Published May 9, 2014• 3 citations
OpenAlex

Abstract

Recent studies have developed fundamental limitations on nanoscale thermodynamics, in terms of a set of independent free energy relations. Here we show that free energy relations cannot properly describe quantum coherence in thermodynamic processes. By casting time-asymmetry as a quantifiable, fundamental resource of a quantum state we arrive at an additional, independent set of thermodynamic laws, that naturally extend the existing ones. These asymmetry relations reveal that the traditional Szilard engine argument does not extend automatically to quantum coherences, but instead only relational coherences in a multipartite scenario can contribute to thermodynamic work. We find that coherence transformations are always irreversible. Our results also reveal additional structural parallels between thermodynamics and entanglement theory.

Related papers

Description of quantum coherence in thermodynamic processes requires constraints beyond free energy

Matteo Lostaglio, David Jennings, Terry Rudolph

Recent studies have developed fundamental limitations on nanoscale thermodynamics, in terms of a set of independent free energy relations. Here we show that free energy relations cannot properly describe quantum coherence in thermodynamic processes. By casting time-asymmetry as a quantifiable, fundamental resource of a quantum state, we arrive at an additional, independent set of thermodynamic constraints that naturally extend the existing ones. These asymmetry relations reveal that the traditional Szilárd engine argument does not extend automatically to quantum coherences, but instead only relational coherences in a multipartite scenario can contribute to thermodynamic work. We find that coherence transformations are always irreversible. Our results also reveal additional structural parallels between thermodynamics and the theory of entanglement.

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Coherence Manipulation in Asymmetry and Thermodynamics

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In the classical regime, thermodynamic state transformations are governed by the free energy. This is also called as the second law of thermodynamics. Previous works showed that, access to a catalytic system allows us to restore the second law in the quantum regime when we ignore coherence. However, in the quantum regime, coherence and free energy are two independent resources. Therefore, coherence places additional nontrivial restrictions on the state transformations that remain elusive. In order to close this gap, we isolate and study the nature of coherence, i.e., we assume access to a source of free energy. We show that allowing catalysis along with a source of free energy allows us to amplify any quantum coherence present in the quantum state arbitrarily. Additionally, any correlations between the system and the catalyst can be suppressed arbitrarily. Therefore, our results provide a key step in formulating a fully general law of quantum thermodynamics.

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The resource theory of quantum thermodynamics

Matteo Lostaglio

Planck found, when attempting to describe the way in which hot bodies glow, that energy at microscopic scales often comes in discrete chunks. Thus began the long and intimate relationship between the field of thermodynamics, which explores our ability to manipulate heat and other energy transfers between macroscopic systems, and quantum mechanics, which explains the dynamics of individual microscopic systems. Even as both our technology and our theoretical investigations have extended to ever-smaller devices, our understanding of quantum effects on thermodynamics has remained almost exclusively limited to the quantized nature of energy. There is much more, however, to quantum theory than energy quantization. In this thesis we focus on the property of quantum coherence, the ability of quantum systems to emulate Schrodinger’s cat and somehow be neither dead nor alive, but something completely different altogether. We provide a simple and elegant formulation for the processing of coherence in thermodynamics, relying on the fact that thermodynamical processes possess an underlying time-translation symmetry. This fact allows us to quantify the ways in which coherence can play an active role, facilitating otherwise impossible thermodynamic transformations. We argue that coherence should be thought of as a distinctly quantum-mechanical thermodynamic resource. By considering an isolated quantum system connected, for some period of time, to a thermal bath, we give fundamental limitations on how coherence can be irreversibly manipulated. These limitations are related to those dictated on energy transfer by the second law of thermodynamics. Others topics that are investigated here is what is the role of correlations at the smallest scales and the conversion of quantum coherence into work. It has long been appreciated that thermodynamics is subtly interlinked with the notion of information. This work provides evidence that, to apply the laws of thermodynamics to the smallest systems around us, we must develop deeper insights into the nature of quantum information.

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Coherence, thermodynamics and uncertainty relations

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The principle of superposition is one of the main building blocks of quantum physics and has tremendous consequences both for our fundamental understanding of nature and for technological applications. In particular, the existence of coherent superposition leads to the concept of unavoidable quantum uncertainty. The role played by this "coherent" uncertainty within thermodynamics, as well as its relationship to classical lack of knowledge, is the main subject of this thesis. In Part I we study thermodynamic limitations of processing quantum coherence within a resource-theoretic framework. Using the time-translation symmetry that arises from the first law of thermodynamics, we find constraints on possible manipulations of coherence and prove their irreversibility due to the second law. We also generalise to the quantum domain Szilard's concept of converting information into work. Namely, we show how, in the presence of a heat bath, coherence of a system can be exploited to perform mechanical work. Finally, we analyse the effect that coherence has on the structure of the thermodynamic arrow of time, i.e., on the set of states into which a given state can freely evolve under thermodynamic constraints. In Part II we focus on the interplay between quantum and classical uncertainty manifested in uncertainty relations. We show that separating the total uncertainty into these two distinct components leads to a new type of "fixed-entropy" uncertainty relation. We also analyse how classical ignorance affects the structure of states that minimise the unavoidable uncertainty arising from the noncommutativity of two observables. Finally, we study error-disturbance trade-off relations and, by proving that quantum uncertainty can be simultaneously maximised for any two observables, we clarify the unphysical nature of state-dependent relations.

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A theory of thermodynamics for nanoscale quantum systems

N. H. Y. Ng

Thermodynamics is one of the main pillars of theoretical physics, and it has a special appeal of having wide applicability to a large variety of different physical systems. However, many assumptions in thermodynamics apply only to systems which are bulk material, i.e. consisting a large number of microscopic classical particles. Due to the advancement of designing nanoscale engines, especially in the light of devices that are used today in the processing of quantum information, is thermodynamics still applicable? Can we refine the core principles of thermodynamics to suit such nanoscale quantum systems as well? The central aim of this thesis is to construct a theory of thermodynamics that holds for nanoscale quantum systems, even those as small and simple as a single qubit. We do this by starting out from the core basics of quantum theory: unitary dynamics on closed quantum systems. We adapt a resource theoretic approach inspired by quantum information theory, which defines the quantum states and operations allowed to be used in a thermodynamic evolution. With this framework that naturally adopts the first law as an energy preserving condition, we show the refinement of both the zeroeth and second law of thermodynamics. The zeroeth law explains the physical significance of the Gibbs thermal state. On the other hand, we show that the second law sees refinement in the quantum nanoregime: instead of having the free energy as the sole quantity dictating the possibility of a thermodynamic state transition, we derive a family of generalized free energies that also constitute necessary conditions for a transition to occur. Moreover, these conditions become sufficient for states which are block-diagonal in the energy eigenbasis. In this thesis, we also brought our approach of thermodynamics to the next step: we apply our findings on the second laws, in order to analyze the maximum achievable efficiency for quantum heat engines. In classical thermodynamics, the Carnot efficiency has been long known as the theoretical maximum which does not depend on the specific structure of the thermal baths used, but only on its temperature. With the additional free energies we discover, we show that although quantum heat engines may achieve the Carnot efficiency, such an achievability is no longer independent of the Hamiltonians of the thermal baths. In other words, we find additional restrictions that surface in the study of quantum nanoscale heat engines, which are a direct consequence of the generalized second laws. This has provided us with a deeper understanding into the fundamental limitations of how efficient devices can be made in the realm of microscopic quantum systems.

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Thermodynamics Beyond Equilibrium in Coherent Quantum Systems

Md Manirul Ali, Po-Wen Chen

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.

quant-pharXiv:2602.09074•APL Quantum•Feb 10, 2026•0 citations
Recent studies have developed fundamental limitations on nanoscale thermodynamics, in terms of a set of independent free energy relations. Here we show that free energy relations cannot properly describe quantum coherence in thermodynamic processes. By casting time-asymmetry as a quantifiable, fundamental resource of a quantum state we arrive at an additional, independent set of thermodynamic laws, that naturally extend the existing ones. These asymmetry relations reveal that the traditional Szilard engine argument does not extend automatically to quantum coherences, but instead only relational coherences in a multipartite scenario can contribute to thermodynamic work. We find that coherence transformations are always irreversible. Our results also reveal additional structural parallels between thermodynamics and entanglement theory.
Recent studies have developed fundamental limitations on nanoscale thermodynamics, in terms of a set of independent free energy relations. Here we show that free energy relations cannot properly describe quantum coherence in thermodynamic processes. By casting time-asymmetry as a quantifiable, fundamental resource of a quantum state, we arrive at an additional, independent set of thermodynamic constraints that naturally extend the existing ones. These asymmetry relations reveal that the traditional Szilárd engine argument does not extend automatically to quantum coherences, but instead only relational coherences in a multipartite scenario can contribute to thermodynamic work. We find that coherence transformations are always irreversible. Our results also reveal additional structural parallels between thermodynamics and the theory of entanglement.
In the classical regime, thermodynamic state transformations are governed by the free energy. This is also called as the second law of thermodynamics. Previous works showed that, access to a catalytic system allows us to restore the second law in the quantum regime when we ignore coherence. However, in the quantum regime, coherence and free energy are two independent resources. Therefore, coherence places additional nontrivial restrictions on the state transformations that remain elusive. In order to close this gap, we isolate and study the nature of coherence, i.e., we assume access to a source of free energy. We show that allowing catalysis along with a source of free energy allows us to amplify any quantum coherence present in the quantum state arbitrarily. Additionally, any correlations between the system and the catalyst can be suppressed arbitrarily. Therefore, our results provide a key step in formulating a fully general law of quantum thermodynamics.
Planck found, when attempting to describe the way in which hot bodies glow, that energy at microscopic scales often comes in discrete chunks. Thus began the long and intimate relationship between the field of thermodynamics, which explores our ability to manipulate heat and other energy transfers between macroscopic systems, and quantum mechanics, which explains the dynamics of individual microscopic systems. Even as both our technology and our theoretical investigations have extended to ever-smaller devices, our understanding of quantum effects on thermodynamics has remained almost exclusively limited to the quantized nature of energy. There is much more, however, to quantum theory than energy quantization. In this thesis we focus on the property of quantum coherence, the ability of quantum systems to emulate Schrodinger’s cat and somehow be neither dead nor alive, but something completely different altogether. We provide a simple and elegant formulation for the processing of coherence in thermodynamics, relying on the fact that thermodynamical processes possess an underlying time-translation symmetry. This fact allows us to quantify the ways in which coherence can play an active role, facilitating otherwise impossible thermodynamic transformations. We argue that coherence should be thought of as a distinctly quantum-mechanical thermodynamic resource. By considering an isolated quantum system connected, for some period of time, to a thermal bath, we give fundamental limitations on how coherence can be irreversibly manipulated. These limitations are related to those dictated on energy transfer by the second law of thermodynamics. Others topics that are investigated here is what is the role of correlations at the smallest scales and the conversion of quantum coherence into work. It has long been appreciated that thermodynamics is subtly interlinked with the notion of information. This work provides evidence that, to apply the laws of thermodynamics to the smallest systems around us, we must develop deeper insights into the nature of quantum information.
The principle of superposition is one of the main building blocks of quantum physics and has tremendous consequences both for our fundamental understanding of nature and for technological applications. In particular, the existence of coherent superposition leads to the concept of unavoidable quantum uncertainty. The role played by this "coherent" uncertainty within thermodynamics, as well as its relationship to classical lack of knowledge, is the main subject of this thesis. In Part I we study thermodynamic limitations of processing quantum coherence within a resource-theoretic framework. Using the time-translation symmetry that arises from the first law of thermodynamics, we find constraints on possible manipulations of coherence and prove their irreversibility due to the second law. We also generalise to the quantum domain Szilard's concept of converting information into work. Namely, we show how, in the presence of a heat bath, coherence of a system can be exploited to perform mechanical work. Finally, we analyse the effect that coherence has on the structure of the thermodynamic arrow of time, i.e., on the set of states into which a given state can freely evolve under thermodynamic constraints. In Part II we focus on the interplay between quantum and classical uncertainty manifested in uncertainty relations. We show that separating the total uncertainty into these two distinct components leads to a new type of "fixed-entropy" uncertainty relation. We also analyse how classical ignorance affects the structure of states that minimise the unavoidable uncertainty arising from the noncommutativity of two observables. Finally, we study error-disturbance trade-off relations and, by proving that quantum uncertainty can be simultaneously maximised for any two observables, we clarify the unphysical nature of state-dependent relations.
Thermodynamics is one of the main pillars of theoretical physics, and it has a special appeal of having wide applicability to a large variety of different physical systems. However, many assumptions in thermodynamics apply only to systems which are bulk material, i.e. consisting a large number of microscopic classical particles. Due to the advancement of designing nanoscale engines, especially in the light of devices that are used today in the processing of quantum information, is thermodynamics still applicable? Can we refine the core principles of thermodynamics to suit such nanoscale quantum systems as well? The central aim of this thesis is to construct a theory of thermodynamics that holds for nanoscale quantum systems, even those as small and simple as a single qubit. We do this by starting out from the core basics of quantum theory: unitary dynamics on closed quantum systems. We adapt a resource theoretic approach inspired by quantum information theory, which defines the quantum states and operations allowed to be used in a thermodynamic evolution. With this framework that naturally adopts the first law as an energy preserving condition, we show the refinement of both the zeroeth and second law of thermodynamics. The zeroeth law explains the physical significance of the Gibbs thermal state. On the other hand, we show that the second law sees refinement in the quantum nanoregime: instead of having the free energy as the sole quantity dictating the possibility of a thermodynamic state transition, we derive a family of generalized free energies that also constitute necessary conditions for a transition to occur. Moreover, these conditions become sufficient for states which are block-diagonal in the energy eigenbasis. In this thesis, we also brought our approach of thermodynamics to the next step: we apply our findings on the second laws, in order to analyze the maximum achievable efficiency for quantum heat engines. In classical thermodynamics, the Carnot efficiency has been long known as the theoretical maximum which does not depend on the specific structure of the thermal baths used, but only on its temperature. With the additional free energies we discover, we show that although quantum heat engines may achieve the Carnot efficiency, such an achievability is no longer independent of the Hamiltonians of the thermal baths. In other words, we find additional restrictions that surface in the study of quantum nanoscale heat engines, which are a direct consequence of the generalized second laws. This has provided us with a deeper understanding into the fundamental limitations of how efficient devices can be made in the realm of microscopic quantum systems.
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.