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arXiv:2409.07899 · Science Advances

Correlated quantum machines beyond the standard second law

Milton Aguilar, Eric Lutz

Published Oct 10, 2025• 13 citations
arXivHTMLPDF

Abstract

The laws of thermodynamics strongly restrict the performance of thermal machines. Standard thermodynamics, initially developed for uncorrelated macroscopic systems, does not hold for microscopic systems correlated with their environments. We here derive an exact formula for the efficiency of any cyclically driven quantum engine by using generalized laws of quantum thermodynamics that account for all possible correlations between all involved parties, including initial correlations. Furthermore, we demonstrate the existence of two basic modes of engine operation: the usual thermal case, where heat is converted into work, and an athermal regime, where work is extracted from entropic resources, such as system-bath correlations. In the latter regime, the efficiency is not bounded by the usual Carnot formula. Our results provide a unified formalism to determine the efficiency of correlated microscopic quantum machines.

DOI
10.1126/sciadv.adw8462

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•Jan 1, 2017•0 citations
The laws of thermodynamics strongly restrict the performance of thermal machines. Standard thermodynamics, initially developed for uncorrelated macroscopic systems, does not hold for microscopic systems correlated with their environments. We here derive an exact formula for the efficiency of any cyclically driven quantum engine by using generalized laws of quantum thermodynamics that account for all possible correlations between all involved parties, including initial correlations. Furthermore, we demonstrate the existence of two basic modes of engine operation: the usual thermal case, where heat is converted into work, and an athermal regime, where work is extracted from entropic resources, such as system-bath correlations. In the latter regime, the efficiency is not bounded by the usual Carnot formula. Our results provide a unified formalism to determine the efficiency of correlated microscopic quantum machines.
Thermodynamics at the nanoscale is known to differ significantly from its familiar macroscopic counterpart: The possibility of state transitions is not determined by free energy alone but by an infinite family of free-energy-like quantities; strong fluctuations (possibly of quantum origin) allow one to extract less work reliably than what is expected from computing the free-energy difference.However, these known results rely crucially on the assumption that the thermal machine is not only exactly preserved in every cycle but also kept uncorrelated from the quantum systems on which it acts.Here, we lift this restriction: We allow the machine to become correlated with the microscopic systems on which it acts while still exactly preserving its own state.Surprisingly, we show that this possibility restores the second law in its original form: Free energy alone determines the possible state transitions, and the corresponding amount of work can be invested or extracted from single systems exactly and without any fluctuations.At the same time, the work reservoir remains uncorrelated from all other systems and parts of the machine.Thus, microscopic machines can increase their efficiency via clever "correlation engineering" in a perfectly cyclic manner, which is achieved by a catalytic system that can sometimes be as small as a single qubit (though some setups require very large catalysts).Our results also solve some open mathematical problems on majorization which may lead to further applications in entanglement theory.
According to the second law, the efficiency of cyclic heat engines is limited by the Carnot bound that is attained by engines that operate between two thermal baths under the reversibility condition whereby the total entropy does not increase. Quantum engines operating between a thermal and a squeezed-thermal bath have been shown to surpass this bound. Yet, their maximum efficiency cannot be determined by the reversibility condition, which may yield an unachievable efficiency bound above unity. Here we identify the fraction of the exchanged energy between a quantum system and a bath that necessarily causes an entropy change and derive an inequality for this change. This inequality reveals an efficiency bound for quantum engines energised by a non-thermal bath. This bound does not imply reversibility, unless the two baths are thermal. It cannot be solely deduced from the laws of thermodynamics.
Abstract According to the second law, the efficiency of cyclic heat engines is limited by the Carnot bound that is attained by engines that operate between two thermal baths under the reversibility condition whereby the total entropy does not increase. Quantum engines operating between a thermal and a squeezed-thermal bath have been shown to surpass this bound. Yet, their maximum efficiency cannot be determined by the reversibility condition, which may yield an unachievable efficiency bound above unity. Here we identify the fraction of the exchanged energy between a quantum system and a bath that necessarily causes an entropy change and derive an inequality for this change. This inequality reveals an efficiency bound for quantum engines energised by a non-thermal bath. This bound does not imply reversibility, unless the two baths are thermal. It cannot be solely deduced from the laws of thermodynamics.
We derive a bound on the efficiency of thermal engines that can be sharper than Carnot's limit. It is a function of statistical correlations between the engine internal state and Hamiltonian, can be saturated even in finite-time cycles, and applies to both classical and quantum engines. Specifically, the bound establishes the exact maximal efficiency of engines operating with multiple baths, tightening the upper limit set by Carnot's theorem. Then, we show that an engine made of a quantum dot coupled with fermionic baths can achieve the bound, even when operating beyond the quasistatic regime. The result provides a design principle for realistic energy harvesting machines.
How much work can be extracted from a heat bath using a thermal machine? The study of this question has a very long history in statistical physics in the weak-coupling limit, when applied to macroscopic systems. However, the assumption that thermal heat baths remain uncorrelated with associated physical systems is less reasonable on the nano-scale and in the quantum setting. In this work, we establish a framework of work extraction in the presence of quantum correlations. We show in a mathematically rigorous and quantitative fashion that quantum correlations and entanglement emerge as limitations to work extraction compared to what would be allowed by the second law of thermodynamics. At the heart of the approach are operations that capture the naturally non-equilibrium dynamics encountered when putting physical systems into contact with each other. We discuss various limits that relate to known results and put our work into the context of approaches to finite-time quantum thermodynamics.
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.