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arXiv:2309.04170

Comment on "Extending the Laws of Thermodynamics for Arbitrary Autonomous Quantum Systems"

Philipp Strasberg

Published Sep 8, 2023• 0 citations
arXivHTMLPDF

Abstract

Recently, Elouard and Lombard Latune [PRX Quantum 4, 020309 (2023)] claimed to extend the laws of thermodynamics to "arbitrary quantum systems" valid "at any scale" using "consistent" definitions allowing them to "recover known results" from the literature. I show that their definitions are in conflict with textbook thermodynamics and over- or underestimate the real entropy production by orders of magnitude. The cause of this problem is traced back to problematic definitions of entropy and temperature, the latter, for instance, violates the zeroth law. It is pointed out that another framework presented in PRX Quantum 2, 030202 (2021) does not suffer from these problems, while Elouard and Lombard Latune falsely claim that it only provides a positive entropy production for a smaller class of initial states. A simple way to unify both approaches is also presented.

DOI
10.48550/arxiv.2309.04170

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In his Comment [1], Philip Strasberg (PS) argues from the analysis of different examples that the framework we have presented in [2] does not recover known results of macroscopic textbook thermodynamics. Here, we show that such apparent contradictions disappear when the necessary assumptions the aforementioned known results pre-suppose are applied. Those assumptions concern the control ability of the observer, the nature of the described degree of freedom, or the scale of the systems. The ability to relax those assumptions is precisely a motivation of our framework, which can explore the capacity of quantum systems to exchange work and heat even at scales not captured by textbook thermodynamics. We take the opportunity of this reply to further expand on the use of our framework and its connections with traditional thermodynamics.

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The example provided in the comment [arXiv:0803.2241] concerns a situation where the system is initially at negative temperature. It is known that in such cases the Law of Entropy Decrease holds. Nevertheless, this does not challenge the validity of the Second Law of Thermodynamics.

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•Feb 6, 2018•1 citation
Recently, Elouard and Lombard Latune [PRX Quantum 4, 020309 (2023)] claimed to extend the laws of thermodynamics to "arbitrary quantum systems" valid "at any scale" using "consistent" definitions allowing them to "recover known results" from the literature. I show that their definitions are in conflict with textbook thermodynamics and over- or underestimate the real entropy production by orders of magnitude. The cause of this problem is traced back to problematic definitions of entropy and temperature, the latter, for instance, violates the zeroth law. It is pointed out that another framework presented in PRX Quantum 2, 030202 (2021) does not suffer from these problems, while Elouard and Lombard Latune falsely claim that it only provides a positive entropy production for a smaller class of initial states. A simple way to unify both approaches is also presented.
In his Comment [1], Philip Strasberg (PS) argues from the analysis of different examples that the framework we have presented in [2] does not recover known results of macroscopic textbook thermodynamics. Here, we show that such apparent contradictions disappear when the necessary assumptions the aforementioned known results pre-suppose are applied. Those assumptions concern the control ability of the observer, the nature of the described degree of freedom, or the scale of the systems. The ability to relax those assumptions is precisely a motivation of our framework, which can explore the capacity of quantum systems to exchange work and heat even at scales not captured by textbook thermodynamics. We take the opportunity of this reply to further expand on the use of our framework and its connections with traditional thermodynamics.
Originally formulated for macroscopic machines, the laws of thermodynamics were recently shown to hold for quantum systems coupled to ideal sources of work (external classical fields) and heat (systems at equilibrium). Ongoing efforts have been focusing on extending the validity of thermodynamic laws to more realistic, non-ideal energy sources. Here, we go beyond these extensions and show that energy exchanges between arbitrary quantum systems are structured by the laws of thermodynamics. We first generalize the second law and identify the associated work and heat exchanges. After recovering known results from ideal work and heat sources, we analyze some consequences of hybrid work and heat sources. We illustrate our general laws with microscopic machines realizing thermodynamic tasks in which the roles of heat and work sources are simultaneously played by elementary quantum systems. Our results open perspectives to understand and optimize the energetic performances of realistic quantum devices, at any scale.
The recent experimental realization of exotic matter states in isolated quantum systems and the ensuing controversy about the existence of negative absolute temperatures demand a careful analysis of the conceptual foundations underlying microcanonical thermostatistics. Here we provide a detailed comparison of the most commonly considered microcanonical entropy definitions, focusing specifically on whether they satisfy or violate the zeroth, first, and second laws of thermodynamics. Our analysis shows that, for a broad class of systems that includes all standard classical Hamiltonian systems, only the Gibbs volume entropy fulfills all three laws simultaneously. To avoid ambiguities, the discussion is restricted to exact results and analytically tractable examples.
Deriving the laws of thermodynamics from an underlying microscopic picture is a central quest of statistical mechanics. The present article focuses on the derivation of the first and second law of thermodynamics for closed and open quantum systems, where such foundational questions in addition become practically relevant for emergent nanotechnologies. Recent progress is presented in a self-contained way, with an emphasis on general ideas and useful tools instead of particular applications. We identify limits and conceptual shortcomings of previous approaches. Then, we propose a novel, unifying perspective, which starts from a microscopic definition of nonequilibrium thermodynamic entropy. The change of this entropy is identified with the entropy production, which satisfies a fluctuation theorem for a large class of initial states. Moreover, this entropy production can be naturally separated into a quantum and a classical component. Within our framework, we introduce the notions of recoverable work and remaining heat. In the case of a weakly perturbed ideal thermal bath this approach is in quantitative agreement with previous ones, thus ensuring their thermodynamic consistency.
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.