We consider open quantum systems weakly coupled to a heat reservoir and driven by arbitrary time-dependent parameters. We derive exact microscopic expressions for the nonequilibrium entropy production and entropy production rate, valid arbitrarily far from equilibrium. By using the two-point energy measurement statistics for system and reservoir, we further obtain a quantum generalization of the integrated fluctuation theorem put forward by Seifert [Phys. Rev. Lett. 95, 040602 (2005)].
We consider open quantum systems weakly coupled to a heat reservoir and driven by arbitrary time-dependent parameters. We derive exact microscopic expressions for the nonequilibrium entropy production and entropy production rate, valid arbitrarily far from equilibrium. By using the two-point energy measurement statistics for system and reservoir, we further obtain a quantum generalization of the integrated fluctuation theorem put forward by Seifert [Phys. Rev. Lett. 95, 040602 (2005)].
Thermodynamics is a phenomenological theory describing the energy conversion of work and heat. At its origins thermodynamics was developed in order to understand and improve heat engines. In conventional thermodynamics, however, only such processes are completely describable which are slow enough to keep the system of interest in an equilibrium state with its thermal environment at all times. On the contrary, all real physical processes are accompanied by non-equilibrium phenomena. These are mathematically described with the help of the irreversible entropy production, i.e. the dissipated work divided by the temperature of the bath. The second law of thermodynamics merely states that the irreversible entropy production is on average always positive. The modern trend of miniaturization, however, leads to smaller and smaller devices. On short length scales thermal noise as well as quantum fluctuations become important. Thus, usual thermodynamic quantities as work and heat acquire stochastic nature. Moreover, in the quantum regime a completely new theory had to be invented, since classical notions of work and heat are no longer valid. The present dissertation contributes to this prevailing field by the derivation of analytical expressions for the entropy production in open and closed quantum system far from thermal equilibrium. The theoretical treatment is motivated by an experimental point of view. The obtained results were derived from the reduced dynamics of the quantum mechanical system, which may be coupled to a thermal bath. To this end, it was dealt with methods and approaches of statistical physics, conventional thermodynamics, quantum information theory and the theory of open quantum systems. In this dissertation the most important physical systems are treated. First, an isolated system is considered before later on a heat bath is included. The limit of weak as well as of strong coupling are analyzed in detail. For isolated systems it turns out that a geometric approach is able to capture the thermodynamic properties, completely. To this end, the irreversible entropy production is sharply estimated from below by the angle between the real non-equilibrium state and the corresponding equilibrium one. Further, it is shown that the Heisenberg uncertainty relation for energy and time can be formulated more precisely in terms of that angle. As experimental system cold ion traps are introduced, in which the theoretical predictions can be verified. For weakly coupled systems, then, the irreversible entropy production is identified and a fluctuation theorem is derived by merely thermodynamic arguments. As experimental system we, again, propose the cold ion traps, where the heat bath can be simulated with the help of LASER light. In the limit of strong coupling a semiclassical description of the reduced quantum system is discussed. Again, an analytically exact expression for the entropy production and the corresponding fluctuation theorem is derived. A physical system, in which strong coupling to the environment can be analyzed, is given by Josephson junctions. This dissertation discusses the entropy production for isolated, weakly coupled, and overdamped quantum systems. For these physical regimes analytical relation are derived and experimental systems proposed, with which the predictions can be verified.
We present a general quantum fluctuation theorem for the entropy production of an open quantum system coupled to multiple environments, not necessarily at equilibrium. Such a general theorem, when restricted to the weak-coupling and Markovian regime, holds for both local and global master equations, corroborating the thermodynamic consistency of local quantum master equations. The theorem is genuinely quantum, as it can be expressed in terms of conservation of a Hermitian operator, describing the dynamics of the system state operator and of the entropy change in the baths. The integral fluctuation theorem follows from the properties of such an operator. Furthermore, it is also valid when the system is described by a time-dependent Hamiltonian. As such, the quantum Jarzynski equality is a particular case of the general result presented here. Moreover, our result can be extended to nonthermal baths, as long as microreversibility is preserved. We present some numerical examples to showcase the exact results previously obtained. We finally generalize the fluctuation theorem to the case where the interaction between the system and the bath is explicitly taken into account. We show that the fluctuation theorem amounts to a relation between time-reversed dynamics of the global density matrix and a two-time correlation function along the forward dynamics involving the baths' entropy alone.
A quantum statistical expression for the entropy of a nonequilibrium system is defined so as to be consistent with Gibbs’ relation, and is shown to corresponds to dynamical variable by introducing analogous to the Heisenberg picture in quantum mechanics. The general relation between system-reservoir interactions and an entropy change operator in an open quantum system, relying just on the framework of statistical mechanics and the definition of von Neumann entropy. By using this formula, we can obtain the correct entropy production in the linear response framework. The present derivation of entropy production is directly based on the first principle of microscopic time-evolution, while the previous standard argument is due to the thermodynamic energy balance.
We study an arbitrary nonequilibrium dynamics of a quantum bipartite system coupled to a reservoir. For its characterization, we present a fluctuation theorem (FT) that explicitly addresses the quantum correlation of subsystems during the thermodynamic evolution. To our aim, we designate the local and the global states altogether in the time-forward and the time-reversed transition probabilities. In view of the two-point measurement scheme, only the global states are subject to measurements whereas the local states are used only as an augmented information on the composite system. We specifically derive a FT in such a form that relates the entropy production of local systems in the time-forward transition to the change of quantum correlation in the time-reversed transition. This also leads to a useful thermodynamic inequality and we illustrate its advantage by an example of an isothermal process on Werner states.
We analyze the production of entropy along nonequilibrium processes in quantum systems coupled to generic environments.First, we show that the entropy production due to final measurements and the loss of correlations obeys a fluctuation theorem in detailed and integral forms.Second, we discuss the decomposition of the entropy production into two positive contributions, adiabatic and nonadiabatic, based on the existence of invariant states of the local dynamics.Fluctuation theorems for both contributions hold only for evolutions verifying a specific condition of quantum origin.We illustrate our results with three relevant examples of quantum thermodynamic processes far from equilibrium.
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.