A general comment is made on the existence of various baths in quantum thermodynamics, and a brief explanation is presented about the concept of weak invariants. Then, the isoenergetic process is studied for a spin in a magnetic field that slowly varies in time. In the Markovian approximation, the corresponding Lindbladian operators are constructed without recourse to detailed information about the coupling of the subsystem with the environment called the energy bath. The entropy production rate under the resulting Lindblad equation is shown to be positive. The leading-order expressions of the power output and work done along the isoenergetic process are obtained.
A general comment is made on the existence of various baths in quantum thermodynamics, and a brief explanation is presented about the concept of weak invariants. Then, the isoenergetic process is studied for a spin in a magnetic field that slowly varies in time. In the Markovian approximation, the corresponding Lindbladian operators are constructed without recourse to detailed information about the coupling of the subsystem with the environment called the energy bath. The entropy production rate under the resulting Lindblad equation is shown to be positive. The leading-order expressions of the power output and work done along the isoenergetic process are obtained.
The concept of weak invariants is examined in the thermodynamic context. Discussions are made about the temporally local equilibrium states, corrections to them, and isoenergetic processes based on the quantum master equations of the Lindblad type that admit time-dependent Hamiltonians as weak invariants. The method for determining the correction presented here may be thought of as a quantum-mechanical analog of the Chapman-Enskog expansion in nonequilibrium classical statistical mechanics. Then, the theory is applied to the time-dependent harmonic oscillator as a simple example, and the power output and the work along an isoenergetic process are evaluated within the framework of finite-time quantum thermodynamics.
A brief review of two recent topics on the Lindblad equation is presented. One is concerned with time evolution of the quantum Renyi entropy under the equation. The lower bound of the entropy rate is derived in a compact form. The other is about the concept of weak invariants, which generalize the Lewis-Riesenfeld invariant and are defined in such a way that they are not constant but their expectation values remain invariant in time. The Lindbladian operator describing the time-dependent damped quantum oscillator is identified, and the corresponding weak invariant is explicitly constructed as an example.
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.
The thermodynamics of a qubit undergoing dephasing due to the coupling with the external environment is discussed. First of all, we assume the dynamics of the system to be described by a master equation in Lindblad form. In this framework, we review a standard formulation of the first and second law of thermodynamics that has been known in literature for a long time. After that, we explicitly model the environment with a set of quantum harmonic oscillators choosing the interaction such that the global dynamics of system and bath is analytically solvable and the Lindblad master equation is recovered in the weak-coupling limit. In this generalized setting, we can show that the correlations between system and bath play a fundamental role in the heat exchange. Moreover, the internal entropy production of the qubit is proven to be positive for arbitrary coupling strength.
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.
It is very common in the literature to write a Markovian quantum master equation in Lindblad form to describe a system with multiple degrees of freedom and weakly connected to multiple thermal baths which can, in general, be at different temperatures and chemical potentials. However, the microscopically derived quantum master equation up to leading order in a system-bath coupling is of the so-called Redfield form, which is known to not preserve complete positivity in most cases. Additional approximations to the Redfield equation are required to obtain a Lindblad form. We lay down some fundamental requirements for any further approximations to the Redfield equation, which, if violated, leads to physical inconsistencies such as inaccuracies in the leading order populations and coherences in the energy eigenbasis, violation of thermalization, and violation of local conservation laws at the nonequilibrium steady state. We argue that one or more of these conditions will generically be violated in all the weak system-bath-coupling Lindblad descriptions existing in the literature to our knowledge. As an example, we study the recently derived universal Lindblad equation and use these conditions to show the violation of local conservation laws due to inaccurate coherences but accurate populations in the energy eigenbasis. Finally, we exemplify our analytical results numerically in an interacting open quantum spin system.