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arXiv:2604.21509 · Physical Review A

Catalytic quantum thermodynamics beyond additivity and reduced-state monotones

Ali Can Günhan, Onur Pusuluk, Thomas Oikonomou, G. Baris Bagci

quant-phSubmitted Apr 23, 2026• Announced Apr 24, 2026• 0 citations
v1 · Apr 23, 2026v2 · Sep 27, 2026
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Abstract

The generalized second laws of quantum thermodynamics are usually formulated in terms of Rényi divergences and the associated family of generalized free energies. In catalytic thermal transformations, this framework typically certifies the existence of a suitable catalyst but does not make the catalytic contribution explicit in the resulting system-level inequalities. Here we develop a complementary formulation based on non-additive divergences, whose pseudo-additive structure yields a family of generalized free energies with an explicit catalyst-dependent correction term. For uncorrelated catalytic thermal transformations, we show that this leads to non-additive second-law relations that make the catalytic contribution explicit and provide nontrivial constraints on admissible catalysts when the catalyst is returned only approximately. We also analyze correlated catalytic thermal transformations and show, through explicit finite-dimensional examples, that reduced-state data are generally insufficient to characterize thermodynamic accessibility: the thermo-majorization behavior of the joint transformation can change while the system and catalyst marginals remain fixed, and even states with identical marginals and the same mutual information can exhibit different thermo-majorization accessibility. Our results show that non-additivity can be thermodynamically informative in uncorrelated catalysis, whereas correlated catalysis generally requires a genuinely joint-state-sensitive description beyond reduced-state monotones.

Journal reference
Phys. Rev. A 114, 042437 (2026)
DOI
10.1103/9lj4-y5m1
Comments
34 pages, 1 figure

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The generalized second laws of quantum thermodynamics are usually formulated in terms of Rényi divergences and the associated family of generalized free energies. In catalytic thermal transformations, this framework typically certifies the existence of a suitable catalyst but does not make the catalytic contribution explicit in the resulting system-level inequalities. Here we develop a complementary formulation based on non-additive divergences, whose pseudo-additive structure yields a family of generalized free energies with an explicit catalyst-dependent correction term. For uncorrelated catalytic thermal transformations, we show that this leads to non-additive second-law relations that make the catalytic contribution explicit and provide nontrivial constraints on admissible catalysts when the catalyst is returned only approximately. We also analyze correlated catalytic thermal transformations and show, through explicit finite-dimensional examples, that reduced-state data are generally insufficient to characterize thermodynamic accessibility: the thermo-majorization behavior of the joint transformation can change while the system and catalyst marginals remain fixed, and even states with identical marginals and the same mutual information can exhibit different thermo-majorization accessibility. Our results show that non-additivity can be thermodynamically informative in uncorrelated catalysis, whereas correlated catalysis generally requires a genuinely joint-state-sensitive description beyond reduced-state monotones.
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.
What are the fundamental limits and advantages of using a catalyst to aid thermodynamic transformations between quantum systems? In this paper, we answer this question by focusing on transformations between energy-incoherent states under the most general energy-conserving interactions among the system, the catalyst, and a thermal environment. The sole constraint is that the catalyst must return unperturbed and uncorrelated with the other subsystems. More precisely, we first upper bound the set of states to which a given initial state can thermodynamically evolve (the catalyzable future) or from which it can evolve (the catalyzable past) with the help of a strict catalyst. Secondly, we derive lower bounds on the dimensionality required for the existence of catalysts under thermal process, along with bounds on the catalyst's state preparation. Finally, we quantify the catalytic advantage in terms of the volume of the catalyzable future and demonstrate its utility in an exemplary task of generating entanglement and cooling a quantum system using thermal resources. Published by the American Physical Society 2024
Quantum thermodynamics investigates how robust the second law of thermodynamics serves as the unique fundamental law in the small quantum world. To tackle this problem, the quantum coherence constitutes a major difficulty of investigations, which provides severe constraints hindering the recovery of a single thermodynamic potential. Here we solve this long-standing problem of quantum information theory by revealing that the state convertibility under thermal operations is fully characterized by the second law of thermodynamics. Specifically, we prove that whether a quantum state with quantum coherence is convertible to another by a thermal operation with a correlated catalyst is completely determined by the free energy ordering. Unlike previous attempts, our setting does not resort to any additional external coherent assist, providing a faithful operational characterization of thermodynamic state transformation.
The laws of thermodynamics are usually formulated under the assumption of infinitely large environments. While this idealization facilitates theoretical treatments, real physical systems are always finite and their interaction range is limited. These constraints have consequences for important tasks such as cooling, not directly captured by the second law of thermodynamics. Here, we study catalytic transformations that cannot be achieved when a system exclusively interacts with a finite environment. Our core result consists of constructive conditions for these transformations, which include the corresponding global unitary operation and the explicit states of all the systems involved. From this result we present various findings regarding the use of catalysts for cooling. First, we show that catalytic cooling is always possible if the dimension of the catalyst is sufficiently large. In particular, the cooling of a qubit using a hot qubit can be maximized with a catalyst as small as a three-level system. We also identify catalytic enhancements for tasks whose implementation is possible without a catalyst. For example, we find that in a multiqubit setup catalytic cooling based on a three-body interaction outperforms standard (non-catalytic) cooling using higher order interactions. Another advantage is illustrated in a thermometry scenario, where a qubit is employed to probe the temperature of the environment. In this case, we show that a catalyst allows to surpass the optimal temperature estimation attained only with the probe.
One physical system always evolves from a state of low disorder to another of high disorder. This phenomenon can be identified by increased entropy. As we know, quantum resource theories provide a mathematical framework for examining diverse quantum resources in states, with the primary problem being whether quantum states can be transformed into each other by free operations. Unlike natural transformations, free operations in quantum resource theories never increase the resource measure of a primary system. Generally, the standard approach to this central problem is to study approximate transformations and apply catalysts to broaden the set of possible state transformations. By combining approximate transformations and catalytic transformations, we show that the quantum correlation between the primary system and the catalytic system after approximate catalytic transformations determines quantum resource changes in the primary system as well as the distribution of quantum correlations among different primary systems. We first find and establish that the resource measure of the primary system does not decrease under global free operations on the primary system and the corresponding catalytic system using the universal freezing technology and the catalytic transformation methods. A resource measure is monotonic under free operations, additive on tensor products, and continuous. Using these features, we then access relations between variations in the resource measure of the primary system under global free operations and quantum correlations between the primary and catalytic systems. Therefore, quantum correlations exist between the primary and catalytic systems after catalytic transformations, which are essential for nondecreasing resource measures of the primary system. Finally, we establish relationships among different primary systems after repeatedly applying the same catalyst. The correlation is closely associated with the reuse times of the same catalyst.
The class of possible thermodynamic conversions can be extended by introducing an auxiliary system called catalyst, which assists in state conversion while its own state remains unchanged. We reveal a complete characterization of catalytic state conversion in quantum and single-shot thermodynamics by allowing an infinitesimal correlation between the system and the catalyst. Specifically, we prove that a single thermodynamic potential, which provides the necessary and sufficient condition for the correlated-catalytic state conversion, is given by the standard nonequilibrium free energy defined with the Kullback-Leibler divergence. This resolves the conjecture raised by Wilming, Gallego, and Eisert [Entropy 19, 241 (2017)ENTRFG1099-430010.3390/e19060241] and by Lostaglio and Müller [Phys. Rev. Lett. 123, 020403 (2019)PRLTAO0031-900710.1103/PhysRevLett.123.020403] in the positive. Moreover, we show that, with the aid of the work storage, any quantum state can be converted into another by paying the work cost equal to the nonequilibrium free energy difference. Our result would serve as a step towards establishing resource theories of catalytic state conversion in the fully quantum regime.