Situations where a spontaneous process of energy or matter transfer is enhanced by an external device are widespread in nature (human sweating system, enzyme catalysis, facilitated diffusion across bio-membranes, industrial heat exchangers). The thermodynamics of such processes remains however open. Here we study enhanced heat transfer by a model junction immersed between two thermal baths at different temperatures $T_h$ and $T_c$ ($T_h>T_c$). The transferred heat power is enhanced via controlling the junction by means of external time-dependent fields. Provided that the spontaneous heat flow process is optimized over the junction Hamiltonian, any enhancement of this spontaneous process does demand consumption and subsequent dissipation of work. The efficiency of enhancement is defined via the increment in the heat power divided over the amount of consumed work. We show that this efficiency is bounded from above by $T_c/(T_h-T_c)$. Formally this is identical to the Carnot bound for the efficiency of ordinary refrigerators which transfer heat from cold to hot. It also shares some (but not all) physical features of the Carnot bound.
Heat engines are fundamental physical objects to develop nonequilibrium thermodynamics. The thermodynamic performance of the heat engine is determined by the choice of cycle and time-dependence of parameters. Here, we propose a systematic numerical method to find a heat engine cycle to optimize some target functions. We apply the method to heat engines with slowly varying parameters and show that the method works well. Our numerical method is based on the genetic algorithm which is widely applied to various optimization problems.
The aim of this paper is to determine lost works in a molecular engine and compare results with macro (classical) heat engines. Firstly, irreversible thermodynamics are reviewed for macro and molecular cycles. Secondly, irreversible thermodynamics approaches are applied for a quantum heat engine with -1/2 spin system. Finally, lost works are determined for considered system and results show that macro and molecular heat engines obey same limitations. Moreover, a quantum thermodynamic approach is suggested in order to explain the results previously obtained from an atomic viewpoint.
Explaining the influence of strong coupling in the dynamics of open quantum systems is one of the most challenging issues in the rapidly growing field of quantum thermodynamics. By using a particular definition of heat, we develop a new approach to study thermodynamics in the strong coupling regime, which takes into account quantum resources as coherence and entanglement. We apply the method to calculate the time-dependent thermodynamic properties of a system and an environment interacting via the generalized amplitude-damping channel (GADC). The results indicate that the transient imbalance b…
Thermodynamics has recently been extended to small scales with resource theories that model heat exchanges. Real physical systems exchange diverse quantities: heat, particles, angular momentum, etc. We generalize thermodynamic resource theories to exchanges of observables other than heat, to baths other than heat baths, and to free energies other than the Helmholtz free energy. These generalizations are illustrated with "grand-potential" theories that model movements of heat and particles. Free operations include unitaries that conserve energy and particle number. From this conservation law an…
We present a detailed thermodynamic analysis of a three-level quantum heat engine coupled continuously to hot and cold reservoirs. The system is driven by an oscillating external field and is described by the Markovian quantum master equation. We use the general form of the dissipator which is consistent with thermodynamics. We calculate the heat, power, and efficiency of the system for the heat-engine operating regime and also examine the thermodynamic uncertainty relation. The efficiency of the system is strongly dependent on the structure of the dissipator, and the correlations between diff…
We study the heat statistics of a quantum Brownian motion described by the Caldeira-Leggett model. By using the path integral approach, we introduce a novel concept of the quantum heat functional along every pair of Feynman paths. This approach has an advantage of improving our understanding about heat in quantum systems. First, we demonstrate the microscopic reversibility of the system by connecting the heat functional to the forward and its time-reversed probabilities. Second, we analytically prove the quantum-classical correspondence of the heat functional and their statistics, which allows…
We consider a situation where an $N$-level system (NLS) is coupled successively to two heat baths with different temperatures without being necessarily thermalized and approaches a steady state. For this situation we apply a general Jarzinski-type equation and conclude that heat and entropy is flowing from the hot bath to the cold one. The Clausius relation between increase of entropy and transfer of heat divided by a suitable temperature assumes the form of two inequalities. Our approach is illustrated by an analytical example. For the linear regime, i.~e., for small temperature differences b…
We consider a situation where an $N$-level system (NLS) is coupled to a heat bath without being necessarily thermalized. For this situation we derive general Jarzinski-type equations and conclude that heat and entropy is flowing from the hot bath to the cold NLS and, vice versa, from the hot NLS to the cold bath. The Clausius relation between increase of entropy and transfer of heat divided by a suitable temperature assumes the form of two inequalities which have already been considered in the literature. Our approach is illustrated by an analytical example.
The thermodynamics of small quantum many-body systems strongly coupled to a heat bath at low temperatures with non-Markovian behavior are new challenges for quantum thermodynamics, as traditional thermodynamics is built on large systems vanishingly weakly coupled to a non-dynamical reservoir. Important also are the quantum attributes, as in quantum coherence, correlations, entanglement and fluctuations. All told, one needs to reexamine the meaning of the thermodynamic functions, the viability of the thermodynamic relations and the validity of the thermodynamic laws anew. In one popular approac…
A new thermodynamic inequality is derived which leads to the maximum work that can be extracted from multi-heat baths with the assistance of discrete quantum feedback control. The maximum work is determined by the free-energy difference and a generalized mutual information content between the thermodynamic system and the feedback controller. This maximum work can exceed that in conventional thermodynamics and, in the case of a heat cycle with two heat baths, the heat efficiency can be greater than that of the Carnot cycle. The consistency of our results with the second law of thermodynamics is…
Toward the formulation of the operational approach to quantum thermodynamics, the heat-up operator is explicitly constructed. This quantum operation generates for a generic system an irreversible transformation from a pure ground state at zero temperature to a state at finite temperature. The fixed point analysis shows that repeated applications of the operation map from an arbitrary state to the completely random state realized in the high-temperature limit. The change of the von Neumann entropy is evaluated for a simple bipartite spin-1/2 system. It is shown that remarkably, the second law o…
We investigate the thermodynamic uncertainty relation (TUR), \textit{i.e.} a trade-off between entropy production rate and relative power fluctuations, for nondegenerate three-level and degenerate four-level maser heat engines. In the nondegenerate case, we consider two slightly different configurations of three-level maser heat engine and contrast their degree of violation of standard TUR. In the high-temperature limit, standard TUR relation is always violated for both configurations. We also uncover an invariance of TUR under simultaneous rescaling of the matter-field coupling constant and s…
Small systems (of interest in the areas of nanophysics, quantum information, etc.) are particularly vulnerable to environmental effects. Thus, we determine various thermodynamic functions for an oscillator in an arbitrary heat bath at arbitrary temperatures. Explicit results are presented for the most commonly discussed heat bath models: Ohmic, single relaxation time and blackbody radiation.
We show that non-Markovian effects of the reservoirs can be used as a resource to extract work from an Otto cycle. The state transformation under non-Markovian dynamics is achieved via a two-step process, namely an isothermal process using a Markovian reservoir followed by an adiabatic process. From second law of thermodynamics, we show that the maximum amount of extractable work from the state prepared under the non-Markovian dynamics quantifies a lower bound of non-Markovianity. We illustrate our ideas with an explicit example of non-Markovian evolution.
The direction of the steady-state heat currents across a generic quantum system connected to multiple baths may be engineered so as to realize virtually any thermodynamic cycle. In spite of their versatility such continuous energy-conversion systems are generally unable to operate at maximum efficiency due to non-negligible sources of irreversible entropy production. In this paper we introduce a minimal model of irreversible absorption chiller. We identify and characterize the different mechanisms responsible for its irreversibility, namely heat leaks and internal dissipation, and gauge their …
Thermodynamics and Dynamic Stability: Extended Theories of Heat Conduction
HUN-REN Wigner Research Centre for Physics（匈牙利研究与教育网络维格纳物理研究中心）；Eötvös Loránd University（厄特沃什·罗兰大学）；Montavid Thermodynamic Research Group（蒙塔维德热力学研究组）；University of Messina（墨西拿大学）；Budapest University of Technology and Economics（布达佩斯技术与经济大学）
The concepts of quantity of heat and work are deduced in the non-extensive statistical mechanics context, following steps in parallel to those employed in the extensive statistical mechanics.
We propose the concept of global temperature for spatially non-uniform heat conduction systems. With this novel quantity, we present an extended framework of thermodynamics for the whole system such that the fundamental relation of thermodynamics holds, which we call "global thermodynamics" for heat conduction systems. Associated with this global thermodynamics, we formulate a variational principle for determining thermodynamic properties of the liquid-gas phase coexistence in heat conduction, which corresponds to the natural extension of the Maxwell construction for equilibrium systems. We qu…
We propose a quantum-enhanced heat engine with entanglement. The key feature of our scheme is superabsorption, which facilitates enhanced energy absorption by entangled qubits. Whereas a conventional engine with $N$ separable qubits provides power with a scaling of $P = Θ(N)$, our engine uses superabsorption to provide power with a quantum scaling of $P = Θ(N^2)$. This quantum heat engine also exhibits a scaling advantage over classical ones composed of $N$-particle Langevin systems. Our work elucidates the quantum properties allowing for the enhancement of performance.
We take the perspective of open quantum systems and examine from their nonequilibrium dynamics the conditions when the physical quantities, their relations and the laws of thermodynamics become well defined and viable for quantum many body systems. We first describe how an open system nonequilibrium dynamics (ONEq) approach is different from the closed combined system + environment in a global thermal state (CGTs) setup. Only after the open system equilibrates will it be amenable to conventional thermodynamics descriptions, thus quantum thermodynamics (QTD) comes at the end rather than assumed…
Fluctuations of thermodynamic quantities become non-negligible and play an important role when the system size is small. We develop finite-time thermodynamics of fluctuations in microscopic heat engines whose environmental temperature and mechanical parameter are driven periodically in time. Within the slow-driving regime, this formalism universally holds in a coarse-grained time scale whose resolution is much longer than the correlation time of the fluctuations, and is shown to be consistent with the relation analogous to the fluctuation-dissipation relation. Employing a geometric argument, a…
We study energetic exchanges and fluctuations in two-stroke quantum thermodynamic engines where the working fluid is represented by two multilevel quantum systems, i.e. qudits, the heat flow is allowed by relaxation with two thermal reservoirs at different temperatures, and the work exchange is operated by a partial-swap unitary interaction. We identify three regimes of operation (heat engine, refrigerator, and thermal accelerator), present the thermodynamic uncertainty relations between the entropy production and the signal-to-noise ratio of work and heat, and derive the full joint probabilit…
We develop a geometric framework to describe the thermodynamics of microscopic heat engines driven by slow periodic temperature variations and modulations of a mechanical control parameter. Covering both the classical and the quantum regime, our approach reveals a universal trade-off relation between efficiency and power that follows solely from geometric arguments and holds for any thermodynamically consistent microdynamics. Focusing on Lindblad dynamics, we derive a second bound showing that coherence as a genuine quantum effect inevitably reduces the performance of slow engine cycles regard…
Following the proposal of steady state thermodynamics (SST) by Oono and Paniconi, we develop a phenomenological theory for steady nonequilibrium states in systems with heat conduction. We find that there is essentially a unique consistent thermodynamics, and make concrete predictions, i.e, the existence of a new osmotic pressure and a shift in the coexistence temperature. These predictions allow one to test for the quantitative validity of SST by comparing them with experiments.
There is a long-standing question as to whether and to what extent it is possible to describe nonequilibrium systems in stationary states in terms of global thermodynamic functions. The positive answers have been obtained only for isothermal systems or systems with small temperature differences. We formulate thermodynamics of the stationary states of the ideal gas subjected to heat flow in the form of the zeroth, first, and second law. Surprisingly, the formal structure of steady state thermodynamics is the same as in equilibrium thermodynamics. We rigorously show that $U$ satisfies the follow…
Starting from microscopic mechanics, we derive thermodynamic relations for heat conducting nonequilibrium steady states. The extended Clausius relation enables one to experimentally determine nonequilibrium entropy to the second order in the heat current. The associated Shannon-like microscopic expression of the entropy is suggestive. When the heat current is fixed, the extended Gibbs relation provides a unified treatment of thermodynamic forces in linear nonequilibrium regime.
We numerically determine the entropy for heat-conducting states, which is connected to the so-called excess heat considered as a basic quantity for steady-state thermodynamics in nonequilibrium. We adopt an efficient method to estimate the entropy from the bare heat current and find that the obtained entropy agrees with the familiar local equilibrium hypothesis well. Our method possesses a wider applicability than local equilibrium and opens a possibility to compare thermodynamic properties of complex systems with those in the local equilibrium. We further investigate the entropy for heat-cond…
For 1D Hamiltonian systems with periodic solutions, Helmholtz formalism provides a tantalizing interpretation of classical thermodynamics, based on time integrals of purely mechanical quantities and without need of statistical description. Here we extend this approach to include heat flux and pressure at the walls, thereby enabling it to describe actual thermodynamic transformations, such as isothermal compressions and expansions. The presence of hard walls, which gives rise to non zero pressure, is justified by means of the virial theorem, while the heat fluxes are introduced as quasi-static …
In this paper, we consider a model of two-level quantum heat engine to investigate the explicit analytic expression for the thermodynamics quantities in different condition under the finite-time operation. In this engine, the working substance is composed of a spin-half particles immersed in a magnetic field. The finite-time thermodynamic processes consisting of two quantum adiabatic and two quantum isothermal processes. This processes working between two heat reservoirs with an inverse temperatures $β_{1}$ and $β_{2}$ ($<β_{1}$). In this processes, we obtain the work, heat, power and efficien…
Mesoscopic thermoelectric heat engine is much anticipated as a device that allows us to utilize with high efficiency wasted heat inaccessible by conventional heat engines. However, the derivation of the heat current in this engine seems to be either not general or described too briefly, even inappropriate in some cases. In this paper, we give a clear-cut derivation of the heat current of the engine with suitable assumptions beyond the linear-response regime. It resolves the confusion in the definition of the heat current in the linear-response regime. After verifying that we can construct the …
We present results obtained by using nonlinear irreversible models for heat devices. In particular, we focus on the global performance characteristics, the maximum efficiency and the efficiency at maximum power regimes for heat engines, and the maximum coefficient of performance (COP) and the COP at maximum cooling power regimes for refrigerators. We analyze the key role played by the interplay between irreversibilities coming from heat leaks and internal dissipations. We also discuss the relationship between these results and those obtained by different models.
We show that systems with negative specific heat can violate the zeroth law of thermodynamics. By both numerical simulations and by using exact expressions for free energy and microcanonical entropy it is shown that if two systems with the same intensive parameters but with negative specific heat are thermally coupled, they undergo a process in which the total entropy increases irreversibly. The final equilibrium is such that two phases appear, that is, the subsystems have different magnetizations and internal energies at temperatures which are equal in both systems, but that can be different …
Passive filters allowing the exchange of particles in a narrow band of energy are currently used in micro-refrigerators and energy transducers. In this letter, we analyze their thermal properties using linear irreversible thermodynamics and kinetic theory, and discuss a striking phenomenon: the possibility of increasing or decreasing simultaneously the temperatures of two systems without any supply of energy. This occurs when the filter induces a flow of particles whose energy is between the average energies of the two systems. Here we show that this selective transfer of particles does not ne…
The autonomous heat engine is a model system of autonomous nonequilibrium systems like biological cells, exploiting nonequilibrium flow for operations. As the Carnot engine has essentially contributed to the equilibrium thermodynamics, autonomous heat engine is expected to play a critical role in the challenge of constructing nonequilibrium thermodynamics. However, the high complexity of the engine involving an intricate coupling among heat, gas flow, and mechanics has prevented simple modeling. Here, we experimentally characterized the nonequilibrium dynamics and thermodynamics of a low-tempe…
The impossibility of separating into work and heat the energy transmitted between two subsystems through a movable piston is analyzed in this article. The process here described, although "quasi-static", is not reversible. It is shown that the First Principle, dU=dW+dQ, introduced by Clausius, does not generally allow a physical identification of dW and dQ, although dU=-pdV+TdS is verified along the equilibrium points of each subsystem.
We study thermodynamic processes in contact with a heat bath that may have an arbitrary time-varying periodic temperature profile. Within the framework of stochastic thermodynamics, and for models of thermo-dynamic engines in the idealized case of underdamped particles in the low-friction regime, we derive explicit bounds as well as optimal control protocols that draw maximum power and achieve maximum efficiency at any specified level of power.
Macroscopic nonextensive thermodynamics is studied without recourse to microscopic statistical mechanics. It is shown that if entropy is nonextensive, the concept of physical temperature introduced through the generalized zeroth law of thermodynamics necessarily leads to modifications of the first law of thermodynamics and some of thermodynamic relations including Clausius definition of thermodynamic entropy. It is also shown, by applying this generalized Clausius entropy to a composite nonextensive system, how the nonextensive entropy and the quantity of heat consistently behave in an arbitra…
As an extension to our earlier work \cite{Mirza2}, we employ the Nambu brackets to prove that the divergences of heat capacities correspond to their counterparts in thermodynamic geometry. We also obtain a simple representation for the conformal transformations that connect different thermodynamics metrics to each other. Using our bracket approach, we obtain interesting exact relations between the Hessian matrix with any number of parameters and specific heat capacities. Finally, we employ this approach to investigate some thermodynamic properties of the Meyers-Perry black holes with three spi…
I discuss in parallel two universal phenomena: the independence of statistics of the heat capacity and entropy of ideal gases of the same, constant, density of states, on one hand, and the independence of statistics of the heat and entropy transport through one-dimensional channels, on the other hand. I show that there is a close similarity between the microscopic explanations of each of these phenomena.
Low-temperature-differential (LTD) Stirling heat engines are able to operate with a small temperature difference between low-temperature heat reservoirs that exist in our daily lives, and thus they are considered to be an important sustainable energy technology. The author recently proposed a nonlinear dynamics model of an LTD kinematic Stirling heat engine to study the rotational mechanism of the engine [Y. Izumida, EPL \textbf{121}, 50004 (2018)]. This paper presents our study of the nonequilibrium thermodynamics analysis of this engine model, where a load torque against which the engine doe…
Development of steady state thermodynamics and statistical mechanics depends crucially on our ability to develop notions of equilibrium thermodynamics for nonequilibrium steady states (NESS). The present paper considers the development of heat capacity. A modified definition is proposed which continues to maintain the same relation to steady state Shannon entropy as in equilibrium, thus providing a thermodynamically consistent treatment of NESS heat capacity.
The heat engine, a machine that extracts useful work from thermal sources, is one of the basic theoretical constructs and fundamental applications of classical thermodynamics. The classical description of a heat engine does not include coherence in its microscopic degrees of freedom. By contrast, a quantum heat engine might possess coherence between its internal states. Although the Carnot efficiency cannot be surpassed, and coherence can be performance degrading in certain conditions, it was recently predicted that even when using only thermal resources, internal coherence can enable a quantu…
Thermodynamics of nanoscale devices is an active area of research. Despite their noisy surround- ing they often produce mechanical work (e.g. micro-heat engines) or display rectified Brownian motion (e.g. molecular motors). This invokes the research in terms of experimentally quantifiable thermodynamic efficiencies. To enhance the efficiency of such devices, close-loop control is an useful technique. Here a single Brownian particle is driven by a harmonic confinement with time-periodic contraction and expansion, together with a velocity feedback that acts on the particle only when the trap con…
A model for the thermodynamics of a quantum heat bath is introduced. Under the assumption that the bath molecules have finitely many degrees of freedom and are weakly interacting, we present a general derivation of the equation of state of the bath in the thermodynamic limit. The relation between the temperature and the specific energy of the bath depends on (i) the spectral properties of the molecules, and (ii) the choice of probability measure on the state space of a representative molecule. The results obtained illustrate how the microscopic features of the molecular constituents determine …
Among various possible routes to extend entropy and thermodynamics to nonequilibrium steady states (NESS), we take the one which is guided by operational thermodynamics and the Clausius relation. In our previous study, we derived the extended Clausius relation for NESS, where the heat in the original relation is replaced by its "renormalized" counterpart called the excess heat, and the Gibbs-Shannon expression for the entropy by a new symmetrized Gibbs-Shannon-like expression. Here we concentrate on Markov processes describing heat conducting systems, and develop a new method for deriving ther…
There is a long-standing question of whether it is possible to extend the formalism of equilibrium thermodynamics to the case of non-equilibrium systems in steady states. We have made such an extension for an ideal gas in a heat flow [Hołyst \emph{et al.}, J. Chem. Phys. 157, 194108 (2022)]. Here we investigate whether such a description exists for the system with interactions: the Van der Waals gas in a heat flow. We introduce the parameters of state, each associated with a single way of changing energy. The first law of non-equilibrium thermodynamics follows from these parameters. The intern…
A linear irreversible thermodynamic framework of heat conduction in rigid conductors is introduced. The deviation from local equilibrium is characterized by a single internal variable and a current intensity factor. A general constitutive evolution equation of the current density of the internal energy is derived by introducing linear relationship between the thermodynamic forces and fluxes. The Fourier, Maxwell-Cattaneo-Vernotte, Guyer-Krumhansl, Jeffreys type and Green-Naghdi type equations of heat conduction are obtained as special cases. The universal character of the approach is demonstra…
A simple and effective approach to thermodynamics is suggested, which solves the major difficulties in the traditional presentation of the subject. The internal energy is introduced from the behavior of deformable bodies, whereas the importance of keeping in mind the microscopic picture is emphasized. A straightforward model is used to show that the internal energy depends on the volume and entropy, from where the relationship between mechanics and thermodynamics is immediate, mechanics corresponding to isentropic thermodynamics. The questions of evolution to equilibrium and irreversibility ar…
The concepts of weighted reciprocal of temperature and weighted thermal flux are proposed for a heat engine operating between two heat baths and outputting mechanical work. With the aid of these two concepts, the generalized thermodynamic fluxes and forces can be expressed in a consistent way within the framework of irreversible thermodynamics. Then the efficiency at maximum power output for a heat engine, one of key topics in finite-time thermodynamics, is investigated on the basis of a generic model under the tight-coupling condition. The corresponding results have the same forms as those of…
In this study, the internal energy and the specific heat of the one- dimensional Ising model obtained in the frame of the generalized statistical thermodynamics by Andrade [Physica A175 (1991) 285], have been extended somewhat and compared with the internal energy and the specific heat which have been calculated in the standard statistical thermodynamics.
In systems described by the scattering theory, there is an upper bound, lower than Carnot, on the efficiency of steady-state heat to work conversion at a given output power. We show that interacting systems can overcome such bound and saturate, in the thermodynamic limit, the much more favorable linear-response bound. This result is rooted in the possibility for interacting systems to achieve the Carnot efficiency at the thermodynamic limit without delta-energy filtering, so that large efficiencies can be obtained without greatly reducing power.
State functions play important roles in thermodynamics. Different from the process function, such as the exchanged heat $δQ$ and the applied work $δW$, the change of the state function can be expressed as an exact differential. We prove here that, for a generic thermodynamic system, only the inverse of the temperature, namely $1/T$, can serve as the integration factor for the exchanged heat $δQ$. The uniqueness of the integration factor invalidates any attempt to define other state functions associated with the exchanged heat, and in turn, reveals the incorrectness of defining the entransy $E_…
