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arXiv:2603.19887

Macroscopic Thermodynamic Framework for the Mpemba Effect

Yun-Qian Lin, Z. C. Tu, Yu-Han Ma

cond-mat.stat-mechphysics.class-phquant-phSubmitted Mar 20, 2026• Announced Mar 23, 2026• Revised May 20, 2026 (v2)
v1 · Mar 20, 2026v2 · May 20, 2026
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Abstract

The counterintuitive Mpemba effect, wherein a hotter system cools faster, critically lacks a general macroscopic theory. Here, starting from linear irreversible thermodynamics, we formulate a generalized Newton's cooling law, $\mathrm{d}T/\mathrm{d}t = -[γ_0 + \mathcal{M}Q(t)](T-T_r)$, for a system at temperature $T$ relaxing in a thermal reservoir at $T_r$, where the bare relaxation rate $γ_0$ is modified by an initial-state memory term, $Q(t) \propto T(0)-T_r$. Arising from the interplay between heat flux and structural evolution, the coefficient $\mathcal{M}$ governs anomalous relaxation behaviors, where $\mathcal{M} > 0$ ($\mathcal{M} < 0$) induces the (inverse) Mpemba effect. This universal thermodynamic framework maps out phase diagram to provide general criteria for the Mpemba effect in complex systems, offering a macroscopic picture that bridges disparate microscopic approaches.

Comments
Bringing Mpemba research back to the macroscopic world. Never forget the original inquiry, and the ultimate truth shall be reached

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The counterintuitive Mpemba effect, wherein a hotter system cools faster, critically lacks a general macroscopic theory. Here, starting from linear irreversible thermodynamics, we formulate a generalized Newton's cooling law, dT/dt=−[γ0+MQ(t)](T−Tr)\mathrm{d}T/\mathrm{d}t = -[γ_0 + \mathcal{M}Q(t)](T-T_r)dT/dt=−[γ0​+MQ(t)](T−Tr​), for a system at temperature TTT relaxing in a thermal reservoir at TrT_rTr​, where the bare relaxation rate γ0γ_0γ0​ is modified by an initial-state memory term, Q(t)∝T(0)−TrQ(t) \propto T(0)-T_rQ(t)∝T(0)−Tr​. Arising from the interplay between heat flux and structural evolution, the coefficient M\mathcal{M}M governs anomalous relaxation behaviors, where M>0\mathcal{M} > 0M>0 (M<0\mathcal{M} < 0M<0) induces the (inverse) Mpemba effect. This universal thermodynamic framework maps out phase diagram to provide general criteria for the Mpemba effect in complex systems, offering a macroscopic picture that bridges disparate microscopic approaches.
The Mpemba effect originally referred to the observation that, under certain thermalizing dynamics, initially hotter samples can cool faster than colder ones. This effect has since been generalized to other anomalous relaxation behaviors even beyond classical domains, such as symmetry restoration in quantum systems. This work demonstrates that resource theories, widely employed in information theory, provide a unified organizing principle to frame Mpemba physics. We show how the conventional thermal Mpemba effect arises naturally from the resource theory of athermality, while its symmetry-restoring counterpart is fully captured by the resource theories of asymmetry. Leveraging the framework of modes of asymmetry, we demonstrate that the Mpemba effect due to symmetry restoration is governed by the initial overlap with the slowest symmetry-restoring mode, mirroring the role of the slowest Liouvillian eigenmode in thermal Mpemba dynamics. Through this resource-theoretical formalism, we uncover the connection between these seemingly disparate effects and show that the dynamics of thermalization naturally splits into a symmetry-respecting and a symmetry-breaking term.
Quantum thermometry provides a key capability for nanoscale devices and quantum technologies, but most existing strategies rely on probes initialized near equilibrium. This equilibrium paradigm imposes intrinsic limitations: sensitivity is tied to long-time thermalization and often cannot be improved in fast, noisy, or nonstationary settings. In contrast, the \textit{Mpemba effect}, the counterintuitive phenomenon where hotter states relax faster than colder ones, has mostly been viewed as a thermodynamic anomaly. Here, we bridge this gap by proving that Mpemba-type inversions generically yield a finite-time enhancement of the quantum Fisher information (QFI) for temperature estimation, thereby converting an anomalous relaxation effect into a concrete metrological resource. Through explicit analyses of two-level and ΛΛΛ-level probes coupled to bosonic baths, we show that nonequilibrium initializations can transiently outperform both equilibrium strategies and colder states, realizing a \emph{metrological Mpemba effect}. Our results establish anomalous relaxation as a general design principle for nonequilibrium quantum thermometry, enabling ultrafast and nanoscale sensing protocols that exploit, rather than avoid, transient dynamics.
The Mpemba effect, in which a hotter system cools faster than a colder one, remains one of the most intriguing anomalies in thermodynamics. Here, we investigate its microscopic origin within the framework of quantum resource theories and introduce correlations as a new enabling mechanism: classical correlations can support the effect, whereas quantum correlations become relevant only under specific energy-degeneracy conditions. Importantly, correlations are necessary but not sufficient. Whether they induce the effect depends on their distribution across subsystems and on system parameters. Other resources, such as non-Markovian memory effects and Hilbert space dimensionality, primarily modulate the temperature window in which the effect can occur. Finally, by analyzing both didactic multi-qubit instances and a phenomenological single-molecule model of water, we demonstrate that the insufficiency of correlations helps explain the sporadic and sometimes contradictory observations of the Mpemba effect in experiments.
In classical settings, the Mpemba effect occurs when a hotter system cools faster than an initially colder one. In quantum systems, this effect can be reinterpreted exploiting the concept of symmetries, with the asymmetry of a subsystem playing the role of temperature. A quantum Mpemba effect arises when a more asymmetric state restores the symmetry faster than a less asymmetric one. Previous work mainly focuses on closed systems characterized by thermal equilibration and Hamiltonian symmetries. In this paper, we analyze the dynamics of asymmetry in an open quantum many-body system featuring symmetry breaking and uncover dynamical behavior that appears to be unique to these settings. In the symmetric phase, we demonstrate the existence of a quantum Mpemba effect, which emerges as a direct consequence of a non-monotonic evolution of the asymmetry. In the broken-symmetry phase, we analyze the imbalance between the system's ability to increase or to decrease its asymmetry. Our results extend the notion of quantum Mpemba effects to open quantum many-body systems exhibiting symmetry-breaking phase transitions and establish them as a platform for observing and controlling anomalous relaxation phenomena.
The Mpemba effect is a counterintuitive physical phenomenon where a hot system cools faster than a warm one. In recent years, theoretical analyses of the Mpemba effect have been developed for microscopic systems and experimentally verified. However, the conventional theory relies on a specific choice of distance measure to quantify relaxation speed, leading to several theoretical ambiguities. In this Letter, we derive a rigorous quantification of the Mpemba effect based on thermomajorization theory, referred to as the thermomajorization Mpemba effect. This approach resolves all existing ambiguities and provides a unification of the conventional Mpemba effect across all monotone measures. Furthermore, we demonstrate the generality of the thermomajorization Mpemba effect for Markovian dynamics, rigorously proving that it can occur in any temperature regime with fixed energy levels.
The inverse Mpemba effect is a counterintuitive phenomenon in which a system, initially in thermal equilibrium and prepared at different temperatures below that of the final equilibrium state, relaxes to the final state more rapidly when starting from a lower initial temperature. We extend this concept to the relaxation toward a prethermal state in isolated quantum systems. By examining a simple model that exhibits prethermalization, we demonstrate that this effect indeed manifests under periodic driving. We further discuss the realization of this phenomenon in a variety of systems within a unified theoretical framework.