We investigate a total thermodynamic entropy production rate of an isolated quantum system. In particular, we consider a quantum model of coupled harmonic oscillators in a star configuration, where a central harmonic oscillator (system) is coupled to a finite number of surrounding harmonic oscillators (bath). In this model, when the initial state of the total system is given by the tensor product of the Gibbs states of the system and the bath, every harmonic oscillator is always in a Gibbs state with a time-dependent temperature. This enables us to define time-dependent thermo-dynamic entropy for each harmonic oscillator and total non-equilibrium thermodynamic entropy as the summation of them. We analytically confirm that the total thermodynamic entropy satisfies the third law of thermodynamics. Our numerical solutions show that, even when the dynamics of the system is well approximated by the Gorini-Kossakowski-Sudarshan-Lindblad (GKSL)-type Markovian master equation, the total thermodynamic entropy production rate can be negative, while the total thermodynamic entropy satisfies the second law of thermodynamics. This result is a counterexample to the common belief that the total entropy production rate is non-negative when the system is under the GKSL-type Markovian dynamics.
We investigate a total thermodynamic entropy production rate of an isolated quantum system. In particular, we consider a quantum model of coupled harmonic oscillators in a star configuration, where a central harmonic oscillator (system) is coupled to a finite number of surrounding harmonic oscillators (bath). In this model, when the initial state of the total system is given by the tensor product of the Gibbs states of the system and the bath, every harmonic oscillator is always in a Gibbs state with a time-dependent temperature. This enables us to define time-dependent thermo-dynamic entropy for each harmonic oscillator and total non-equilibrium thermodynamic entropy as the summation of them. We analytically confirm that the total thermodynamic entropy satisfies the third law of thermodynamics. Our numerical solutions show that, even when the dynamics of the system is well approximated by the Gorini-Kossakowski-Sudarshan-Lindblad (GKSL)-type Markovian master equation, the total thermodynamic entropy production rate can be negative, while the total thermodynamic entropy satisfies the second law of thermodynamics. This result is a counterexample to the common belief that the total entropy production rate is non-negative when the system is under the GKSL-type Markovian dynamics.
We investigate a total thermodynamic entropy production rate of an isolated quantum system. In particular, we consider a quantum model of coupled harmonic oscillators in a star configuration, where a central harmonic oscillator (system) is coupled to a finite number of surrounding harmonic oscillators (bath). In this model, when the initial state of the total system is given by the tensor product of the Gibbs states of the system and the bath, every harmonic oscillator is always in a Gibbs state with a time-dependent temperature. This enables us to define time-dependent thermodynamic entropy for each harmonic oscillator and total nonequilibrium thermodynamic entropy as the summation of them. We analytically confirm that the total thermodynamic entropy satisfies the third law of thermodynamics. Our numerical solutions show that, even when the dynamics of the system is well approximated by the Gorini-Kossakowski-Sudarshan-Lindblad (GKSL)-type Markovian master equation, the total thermodynamic entropy production rate can be negative, while the total thermodynamic entropy satisfies the second law of thermodynamics. This result is a counterexample to the common belief that the total entropy production rate is non-negative when the system is under the GKSL-type Markovian dynamics.
Entropy production provides a general way to state the second law of thermodynamics for nonequilibrium scenarios.In open quantum system dynamics, it also serves as a useful quantifier of the degree of irreversibility.In this work we shed light on the relation between correlations, initial preparation of the system, and non-Markovianity by studying a system of two harmonic oscillators independently interacting with their local baths.Their dynamics, described by a time-local master equation, is solved to show, both numerically and analytically, that the global purity of the initial state of the system influences the behavior of the entropy production rate and that the latter depends algebraically on the entanglement that characterizes the initial state.
We discuss fundamental features of the local expression for the entropy production rate of the nonequilibrium quantum dynamics of open systems and its relations to memory effects and the spectrum of the generator of the dynamics. Defining the entropy production rate as negative rate of change of the relative entropy with respect to an instantaneous fixed point, it is shown that positivity of the entropy production rate for all possible initial states implies that the real parts of the eigenvalues of the time-local generator for the quantum master equation are always negative. It is further demonstrated that Markovian dynamics, identified as P-divisibility of the quantum dynamical map, implies positivity of entropy production rate, thus providing a kind of generalized second law in the nonequilibrium regime. We also prove by means of the counterexample of a phase covariant quantum master equation that the converse of this statement is not true, i.e., there are non-Markovian dynamics for which the entropy production rate is always positive. Thus, we conclude that the emergence of negative entropy production rates is a sufficient but not necessary condition for non-Markovianity of the quantum dynamics. Finally, we also consider a recently introduced map-based notion of entropy production and show the equivalence between its positivity and Markovianity for general finite-dimensional systems.
We present a systematic thermodynamic analysis of nonsecular GKLS master equations. When some energy transitions in the system are comparable with the dissipative rate, the secular approximation is not valid, and the positivity of the dynamics must be ensured via other approximations. The dynamics then presents features reminiscent from strong coupling to the environment: e.g. the equilibrium state with an environment at thermal equilibrium is not a Gibbs state of the local system Hamiltonian and the dynamics couples energy coherences and populations. Nonetheless, we build a unified, consistent thermodynamic framework for those dynamics. We focus on two approximations beyond the full secular approximation (the local and the more accurate geometric-arithmetic approximations), and then employ systematic perturbation theory on microscopic expressions for the first and second law of thermodynamics which relate irreversibility to the increase of system-environment correlations. We show that, in spite of the weak system-bath coupling, the system-bath interaction energy participates to the energy balance, and is directly linked to the Lamb-shift Hamiltonian. We compare this microscopic entropy production with the definition based on the contractivity of the reduced system dynamics (Spohn inequality). We show that, unlike for secular master equations, the two entropy production rates differ because of the presence of non-vanishing stationary coherences in the energy eigenbasis. However, in the case of a single thermal bath, the difference is purely transient, and no work can be cyclically extracted from the steady-state despite its non-Gibbs form. Finally, we illustrate our results with simple examples, clarifying and completing the thermodynamic picture of Markovian dynamics in the quantum regime.
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.
Entropy production plays a fundamental role in nonequilibrium thermodynamics to quantify the irreversibility of open systems. Its positivity can be ensured for a wide class of setups, but the entropy production rate can become negative sometimes. This is often taken as an indicator of non-Markovianity. We make this link precise by showing under which conditions a negative entropy production rate implies non-Markovianity and when it does not. For a system coupled to a single heat bath, this can be established within a unified language for two setups: (i) the dynamics resulting from a coarse-grained description of a Markovian master equation and (ii) the classical Hamiltonian dynamics of a system coupled to a bath. The quantum version of the latter result is shown not to hold despite the fact that the integrated thermodynamic description is formally equivalent to the classical case. The instantaneous fixed point of a non-Markovian dynamics plays an important role in our study. Our key contribution is to provide a consistent theoretical framework to study the finite-time thermodynamics of a large class of dynamics with a precise link to its non-Markovianity.