Abstract Recent studies have pointed out the intrinsic dependence of figures of merit of thermodynamic relevance—such as work, heat and entropy production—on the amount of quantum coherences that is made available to a system. However, whether coherences hinder or enhance the value taken by such quantifiers of thermodynamic performance is yet to be ascertained. We show that, when considering entropy production generated in a process taking a finite-size bipartite quantum system out of equilibrium through local non-unitary channels, no general monotonicity relationship exists between the entropy production and degree of quantum coherence in the state of the system. A direct correspondence between such quantities can be retrieved when considering specific forms of open-system dynamics applied to suitably chosen initial states. Our results call for a systematic study of the role of genuine quantum features in the non-equilibrium thermodynamics of quantum processes.
Abstract Recent studies have pointed out the intrinsic dependence of figures of merit of thermodynamic relevance—such as work, heat and entropy production—on the amount of quantum coherences that is made available to a system. However, whether coherences hinder or enhance the value taken by such quantifiers of thermodynamic performance is yet to be ascertained. We show that, when considering entropy production generated in a process taking a finite-size bipartite quantum system out of equilibrium through local non-unitary channels, no general monotonicity relationship exists between the entropy production and degree of quantum coherence in the state of the system. A direct correspondence between such quantities can be retrieved when considering specific forms of open-system dynamics applied to suitably chosen initial states. Our results call for a systematic study of the role of genuine quantum features in the non-equilibrium thermodynamics of quantum processes.
The second law of thermodynamics can be expressed in terms of entropy production, which can be used to quantify the degree of irreversibility of a process. In this Chapter, we consider the standard scenario of open quantum systems, where a system irreversibly interacts with an external environment. We show that the standard approach, based on von Neumann entropy, can be replaced by a phase-space formulation of the problem. In particular, we focus on spin systems that can be described using the so-called spin coherent states. We deploy this formalism to study the interplay between the entropy production rate and the initial quantum coherence available to the system.
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.
Abstract We report on the experimental quantification of the contribution to non-equilibrium entropy production stemming from the quantum coherence content in the initial state of a qubit exposed to both coherent driving and dissipation. Our experimental demonstration builds on the exquisite experimental control of the spin state of a nitrogen-vacancy defect in diamond and is underpinned, theoretically, by the formulation of a generalized fluctuation theorem designed to track the effects of quantum coherence. Our results provide significant evidence of the possibility to pinpoint the genuinely quantum mechanical contributions to the thermodynamics of non-equilibrium quantum processes in an open quantum systems scenario.
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.
Abstract The entropy produced when a quantum system at thermal equilibrium is driven to a non-equilibrium state can be considered as having components from coherence generation and from a population mismatch. The entropy component which is related to coherence represents a truly quantum effect and can be calculated using two different decompositions, based on either the relative entropy of coherence or on the thermal state corresponding to the Hamiltonian dephased in the eigen basis of the actual state. However, the decomposition based on the relative entropy was unable to quantify highly coherent processes or processes occurring in the low temperature regime. We experimentally explored a general driving scheme (a non-equilibrium process) on a nuclear magnetic resonance quantum processor, and were able to isolate the contribution of coherence to irreversible entropy generation. Furthermore, we numerically explored an infinitesimal driving process to distinguish between high and low temperature limits. The thermal equilibrium temperature and the final energy gap were varied to establish the relationship among temperature, energy level spacing, entropy production and coherence generation. Our results indicate that the contribution to entropy from coherence is higher in the low temperature regime. We also verified a generalized Clausius inequality, which affirms that the irreversible entropy production is lower-bounded.
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.