The entropy production in dissipative processes is the essence of the arrow of time and the second law of thermodynamics. For dissipation of quantum systems, it was recently shown that the entropy production contains indeed two contributions: a classical one and a quantum one. Here we show that for degenerate (or near-degenerate) quantum systems there are additional quantum contributions which, remarkably, can become negative. Furthermore, such negative contributions are related to significant changes in the ongoing thermodynamics. This includes phenomena such as generation of coherences between degenerate energy levels (called horizontal coherences), alteration of energy exchanges, and, last but not least, reversal of the natural convergence of the populations toward the thermal equilibrium state. Going further, we establish a complementarity relation between horizontal coherences and population convergence, which is particularly enlightening for understanding heat flow reversals. Conservation laws of the different types of coherences are derived. Some consequences for thermal machines and resource theory of coherence are suggested.
The entropy production in dissipative processes is the essence of the arrow of time and the second law of thermodynamics. For dissipation of quantum systems, it was recently shown that the entropy production contains indeed two contributions: a classical one and a quantum one. Here we show that for degenerate (or near-degenerate) quantum systems there are additional quantum contributions which, remarkably, can become negative. Furthermore, such negative contributions are related to significant changes in the ongoing thermodynamics. This includes phenomena such as generation of coherences between degenerate energy levels (called horizontal coherences), alteration of energy exchanges, and, last but not least, reversal of the natural convergence of the populations toward the thermal equilibrium state. Going further, we establish a complementarity relation between horizontal coherences and population convergence, which is particularly enlightening for understanding heat flow reversals. Conservation laws of the different types of coherences are derived. Some consequences for thermal machines and resource theory of coherence are suggested.
Abstract The entropy produced when a quantum system is driven away from equilibrium can be decomposed in two parts, one related with populations and the other with quantum coherences. The latter is usually based on the so-called relative entropy of coherence, a widely used quantifier in quantum resource theories. In this paper we argue that, despite satisfying fluctuation theorems and having a clear resource-theoretic interpretation, this splitting has shortcomings. First, it predicts that at low temperatures the entropy production will always be dominated by the classical term, irrespective of the quantum nature of the process. Second, for infinitesimal quenches, the radius of convergence diverges exponentially as the temperature decreases, rendering the functions non-analytic. Motivated by this, we provide here a complementary approach, where the entropy production is split in a way such that the contributions from populations and coherences are written in terms of a thermal state of a specially dephased Hamiltonian. The physical interpretation of our proposal is discussed in detail. We also contrast the two approaches by studying work protocols in a transverse field Ising chain, and a macrospin of varying dimension.
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.
The second law of classical equilibrium thermodynamics, based on the positivity of entropy production, asserts that any process occurs only in a direction that some information may be lost (flow out of the system) due to the irreversibility inside the system. However, any thermodynamic system can exhibit fluctuations in which negative entropy production may be observed. In particular, in stochastic quantum processes due to quantum correlations and also memory effects we may see the reversal energy flow (heat flow from the cold system to the hot system) and the backflow of information into the system that leads to the negativity of the entropy production which is an apparent violation of the Second Law. In order to resolve this apparent violation, we will try to properly extend the Second Law to quantum processes by incorporating information explicitly into the Second Law. We will also provide a thermodynamic operational meaning for the flow and backflow of information. Finally, it is shown that negative and positive entropy production can be described by a quantum thermodynamic force.
Bridging the second law of thermodynamics and microscopic reversible dynamics has been a longstanding problem in statistical physics. Here, we address this problem on the basis of quantum many-body physics, and discuss how the entropy production saturates in isolated quantum systems under unitary dynamics. First, we rigorously prove that the entropy production does indeed saturate in the long time regime, even when the total system is in a pure state. Second, we discuss the non-negativity of the entropy production at saturation, implying the second law of thermodynamics. This is based on the eigenstate thermalization hypothesis, which states that even a single energy eigenstate is thermal. We also numerically demonstrate that the entropy production saturates at a non-negative value even when the initial state of a heat bath is a single energy eigenstate. Our results reveal fundamental properties of the entropy production in isolated quantum systems at late times.
Abstract Thermodynamic irreversibility is well characterized by the entropy production arising from non-equilibrium quantum processes. We show that the entropy production of a quantum system undergoing open-system dynamics can be formally split into a term that only depends on population unbalances, and one that is underpinned by quantum coherences. This allows us to identify a genuine quantum contribution to the entropy production in non-equilibrium quantum processes. We discuss how these features emerge both in Lindblad-Davies differential maps and finite maps subject to the constraints of thermal operations. We also show how this separation naturally leads to two independent entropic conservation laws for the global system-environment dynamics, one referring to the redistribution of populations between system and environment and the other describing how the coherence initially present in the system is distributed into local coherences in the environment and non-local coherences in the system-environment state. Finally, we discuss how the processing of quantum coherences and the incompatibility of non-commuting measurements leads to fundamental limitations in the description of quantum trajectories and fluctuation theorems.
Recent research on the thermodynamic arrow of time, at the microscopic scale, has questioned the universality of its direction. Theoretical studies showed that quantum correlations can be used to revert the natural heat flow (from the hot body to the cold one), posing an apparent challenge to the second law of thermodynamics. Such an "anomalous" heat current was observed in a recent experiment (K. Micadei et al., arXiv:1711.03323), by employing two spin systems initially quantum correlated. Nevertheless, the precise relationship between this intriguing phenomenon and the initial conditions that allow it is not fully evident. Here, we address energy transfer in a wider perspective, identifying a nonclassical contribution that applies to the reversion of the heat flow as well as to more general forms of energy exchange. We derive three theorems that describe the energy transfer between two microscopic systems, for arbitrary initial bipartite states. Using these theorems, we obtain an analytical bound showing that certain type of quantum coherence can optimize such a process, outperforming incoherent states. This genuine quantum advantage is corroborated through a characterization of the energy transfer between two qubits. For this system, it is shown that a large enough amount of coherence is necessary and sufficient to revert the thermodynamic arrow of time. As a second crucial consequence of the presented theorems, we introduce a class of nonequilibrium states that only allow unidirectional energy flow. In this way, we broaden the set where the standard Clausius statement of the second law applies.