Abstract Environments in quantum thermodynamics usually take the role of heat baths. These baths are Markovian, weakly coupled to the system, and initialized in a thermal state. Whenever one of these properties is missing, standard quantum thermodynamics is no longer suitable to treat the thermodynamic properties of the system that result from the interaction with the environment. Using a recently proposed framework for open system quantum thermodynamics which is valid for arbitrary couplings and non-Markovian effects, we show that within the very same model, described by a Fano–Anderson Hamiltonian, the environment can take three different thermodynamic roles: a standard heat bath, exchanging only heat with the system, a work reservoir, exchanging only work, and a hybrid environment, providing both types of energy exchange. The exact role of the environment is determined by the strength and structure of the coupling, and by its initial state. The latter also dictates the long time behaviour of the open system, leading to thermal equilibrium for an initial thermal state and to a nonequilibrium steady state when there are displaced environmental modes.
Abstract Environments in quantum thermodynamics usually take the role of heat baths. These baths are Markovian, weakly coupled to the system, and initialized in a thermal state. Whenever one of these properties is missing, standard quantum thermodynamics is no longer suitable to treat the thermodynamic properties of the system that result from the interaction with the environment. Using a recently proposed framework for open system quantum thermodynamics which is valid for arbitrary couplings and non-Markovian effects, we show that within the very same model, described by a Fano–Anderson Hamiltonian, the environment can take three different thermodynamic roles: a standard heat bath, exchanging only heat with the system, a work reservoir, exchanging only work, and a hybrid environment, providing both types of energy exchange. The exact role of the environment is determined by the strength and structure of the coupling, and by its initial state. The latter also dictates the long time behaviour of the open system, leading to thermal equilibrium for an initial thermal state and to a nonequilibrium steady state when there are displaced environmental modes.
It is known that the origin of the deviations from standard thermodynamics proceed from the strong coupling to the bath. Here, it is shown that these deviations are related to the power spectrum of the bath. Specifically, it is shown that the system thermal-equilibrium-state cannot be characterized by the canonical Boltzmann's distribution in quantum mechanics. This is because the uncertainty principle imposed a lower bound of the dispersion of the total energy of the system that is dominated by the spectral density of the bath. However, in the classical case, for a wide class of systems that interact via central forces with pairwise-self-interacting environment, the system thermal equilibrium state is exactly characterized by the canonical Boltzmann distribution. As a consequence of this analysis and taking into account all energy scales in the system and reservoir interaction, an effective coupling to the environment is introduced. Sample computations in different regimes predicted by this effective coupling are shown. Specifically, in the strong coupling effective regime, the system exhibits deviations from standard thermodynamics and in the weak coupling effective regime, quantum features such as stationary entanglement are possible at high temperatures. Moreover, it is known that the spectrum of thermal baths depends on the non-Markovian character. Hence, non-Markovian interactions have a important role in the thermal equilibrium state of physical systems. For example, in quantum optomechanics is looked up to cool the mechanical system through an auxiliary system which generally is a cavity. This cooling process takes into account the non-Markovian interaction and as it is shown here, it is more effective than if we use only the Markovian approximation in the equation of motion for the different modes.
Abstract Understanding how to assign internal energy, heat, and work in quantum systems beyond weak coupling remains a central problem in quantum thermodynamics, particularly as the difference between competing definitions becomes increasingly relevant. We identify two common sets of definitions for first-law quantities that are used to describe the thermodynamics of quantum systems coupled to thermal environments. Both are conceptually non-symmetric, treating one part of the bipartition (the ‘system’) differently from the other (the ‘bath’). We analyze these in a setting where such roles are not easily assigned—two large (but finite) sets of thermal harmonic oscillators interacting with each other. We further compare them with a third set of definitions based on a local, conceptually symmetric open-system approach (‘minimal dissipation’) and discuss their quantitative and structural differences. In particular, we observe that all three sets of definitions differ substantially even when the two subsystems are weakly coupled and far detuned, and that the minimal dissipation approach features distinct work peaks that increase with the coupling strength.
The focus is on understanding the quantum thermodynamics of strongly coupled non-Markovian quantum systems. To this end, a non-trivial, non-Markovian model of a central spin surrounded by a spin bath is taken up, and its exact evolution is derived for arbitrary system-bath couplings. The fundamental quantum thermodynamic quantities, such as system and bath internal energies, work, heat, entropy production, and ergotropy, are calculated using the dynamics and the original system (bath) Hamiltonian. An explicit expression for the work, a mismatch between the system and bath internal energies, is derived. The thermodynamic entropy of the system at thermal equilibrium is studied using the Hamiltonian of mean force in the strong coupling regime. The role of a canonical Hamiltonian in calculating the above thermodynamic quantities, a recently developed technique, is also investigated. Furthermore, an interesting observation relevant to the spin bath acting as a charger is made in a scenario where the central spin is envisaged as a quantum battery.
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.
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.
A general thermodynamic framework is presented for open quantum systems in fixed contact with a thermal reservoir. The first and second law are obtained for arbitrary system-reservoir coupling strengths, and including both factorized and correlated initial conditions. The thermodynamic properties are adapted to the generally strong coupling regime, approaching the ones defined for equilibrium, and their standard weak-coupling counterparts as appropriate limits. Moreover, they can be inferred from measurements involving only system observables. Finally, a thermodynamic signature of non-Markovianity is formulated in the form of a negative entropy production rate.