Abstract Markovian master equations provide a versatile tool for describing open quantum systems when memory effects of the environment may be neglected. As these equations are of an approximate nature, they often do not respect the laws of thermodynamics when no secular approximation is performed in their derivation. Here we introduce a Markovian master equation that is thermodynamically consistent and provides an accurate description whenever memory effects can be neglected. The thermodynamic consistency is obtained through a rescaled Hamiltonian for the thermodynamic bookkeeping, exploiting the fact that a Markovian description implies a limited resolution for heat. Our results enable a thermodynamically consistent description of a variety of systems where the secular approximation breaks down.
Abstract Markovian master equations provide a versatile tool for describing open quantum systems when memory effects of the environment may be neglected. As these equations are of an approximate nature, they often do not respect the laws of thermodynamics when no secular approximation is performed in their derivation. Here we introduce a Markovian master equation that is thermodynamically consistent and provides an accurate description whenever memory effects can be neglected. The thermodynamic consistency is obtained through a rescaled Hamiltonian for the thermodynamic bookkeeping, exploiting the fact that a Markovian description implies a limited resolution for heat. Our results enable a thermodynamically consistent description of a variety of systems where the secular approximation breaks down.
Periodically driven open quantum systems are central to quantum thermodynamics and quantum control. These systems are typically described using Floquet-Born-Markov master equations, derived with the use of a full secular approximation, and whose thermodynamic implications are often overlooked. In this context, we show that such a strong secular approximation may lead to unphysical predictions for steady state energy currents. We then demonstrate that a coarse-grained formulation of the master equation can regularize these issues while yielding completely positive dynamics and consistent energy currents. The coarse-graining time has a clear physical interpretation, as it defines the temporal resolution at which a Markovian master equation can describe the evolution of the periodically driven system. We show the consistency and validity of our approach by comparing to an exact non-Markovian simulation in paradigmatic examples: a driven two-level system and a three-level maser coupled to hot and cold thermal reservoirs. Our work provides a practical framework for correctly applying the secular approximation in periodically driven-dissipative systems and for assessing the accuracy of master equations of the GKSL form.
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.
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.
Thermodynamics entails a set of mathematical conditions on quantum Markovian dynamics.In particular, strict energy conservation between the system and environment implies that the dissipative dynamical map commutes with the map of the system's unitary evolution.Employing spectral analysis, we prove the general form of the ensuing master equation.The obtained structure extends thermodynamical considerations to dynamical processes.Comparing this form with master equations obtained from microscopic derivations allows validating their compatibility with thermodynamics.It predicts that coherence is not generated spontaneously under steady-state transport.Moreover, for a bipartite system-environment it singles out the global master equation as the thermodynamically compatible choice for nondriven systems, as well as supplying insight into the validity of the secular approximation.
We provide a rigorous construction of Markovian master equations for a wide class of quantum systems that encompass quadratic models of finite size, linearly coupled to an environment modeled by a set of independent thermal baths. Our theory can be applied for both fermionic and bosonic models in any number of physical dimensions and does not require any particular spatial symmetry of the global system. We show that, for nondegenerate systems under a full secular approximation, the effective Lindblad operators are the normal modes of the system, with coupling constants that explicitly depend on the transformation matrices that diagonalize the Hamiltonian. Both the dynamics and the steady-state (guaranteed to be unique) properties can be obtained with a polynomial amount of resources in the system size. We also address the particle and energy current flowing through the system in a minimal two-bath scheme and find that they hold the structure of Landauer's formula, being thermodynamically consistent.
We investigate the dynamics of a qubit chain locally coupled to a thermal reservoir, modeled through repeated collisions with particles drawn from a heat bath. Under suitable conditions, the resulting Lindblad equation is thermodynamically consistent -- it drives the system toward thermal equilibrium -- while remaining local at short times. This framework reveals a crossover between the global Lindblad equation derived from the secular approximation in weak-coupling theory and the local dissipative models often employed in the literature, which generally fail to ensure thermodynamic consistency.