Abstract We present a Gedankenexperiment that leads to a violation of detailed balance if quantum mechanical transition probabilities are treated in the usual way by applying Fermi’s “golden rule”. This Gedankenexperiment introduces a collection of two-level systems that absorb and emit radiation randomly through non-reciprocal coupling to a waveguide, as realized in specific chiral quantum optical systems. The non-reciprocal coupling is modeled by a hermitean Hamiltonian and is compatible with the time-reversal invariance of unitary quantum dynamics. Surprisingly, the combination of non-reciprocity with probabilistic radiation processes entails negative entropy production. Although the considered system appears to fulfill all conditions for Markovian stochastic dynamics, such a dynamics violates the Clausius inequality, a formulation of the second law of thermodynamics. Several implications concerning the interpretation of the quantum mechanical formalism are discussed.
Abstract We present a Gedankenexperiment that leads to a violation of detailed balance if quantum mechanical transition probabilities are treated in the usual way by applying Fermi’s “golden rule”. This Gedankenexperiment introduces a collection of two-level systems that absorb and emit radiation randomly through non-reciprocal coupling to a waveguide, as realized in specific chiral quantum optical systems. The non-reciprocal coupling is modeled by a hermitean Hamiltonian and is compatible with the time-reversal invariance of unitary quantum dynamics. Surprisingly, the combination of non-reciprocity with probabilistic radiation processes entails negative entropy production. Although the considered system appears to fulfill all conditions for Markovian stochastic dynamics, such a dynamics violates the Clausius inequality, a formulation of the second law of thermodynamics. Several implications concerning the interpretation of the quantum mechanical formalism are discussed.
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 Brownian motion of a harmonically bound quantum particle and coupled to a harmonic quantum bath is exactly solvable. At low enough temperatures the stationary state is non-Gibbsian due to an entanglement with the bath. This happens when a cloud of bath modes around the particle is formed. Equilibrium thermodynamics for particle plus bath together, does not imply standard thermodynamics for the particle itself at low T. Various formulations of the second law are then invalid. First, the Clausius inequality can be violated. Second, when the width of the confining potential is suddenly changed, there occurs a relaxation to equilibrium during which the rate of entropy production is partly negative. Third, for non-adiabatic changes of system parameters the rate of energy dissipation can be negative, and, out of equilibrium, cyclic processes are possible which extract work from the bath. Conditions are put forward under which perpetuum mobile of the second kind, having several work extraction cycles, enter the realm of condensed matter physics. Introduction. There are not two fundamental theories of nature, quantum mechanics and thermodynamics. There is only one: quantum mechanics, while thermodynamics must emerge from it. The universal character of equilibrium thermodynamics led to the general expectation that in one way or another, thermodynamics will apply to the full
Abstract We introduce a concept of non-coherent evolution of macroscopic quantum systems. We show that for weakly interacting systems such evolution is a Markovian stochastic process. The transition rates between system states, which characterize the process, are determined by Fermi’s golden rule. Such evolution is time-irreversible and leads to the equidistribution of probabilities across every state of the system. Furthermore, we investigate the time dependence of the mean numbers of particles in single-particle states and find that, under the given assumptions, it is governed by the Boltzmann collision integral. The proposed mechanism that transforms time-reversible unitary evolution into time-irreversible stochastic evolution is non-coherence. In the presented theory, the non-coherence is not associated with interaction with a heat bath, but rather with the finite spectral width of quantum states. This understanding of non-coherence is analogous to the one used in wave optics. Thus, we present a novel approach to the famous arrow of time problem.
The Brownian motion of a harmonically bound quantum particle and coupled to a harmonic quantum bath is exactly solvable. At low enough temperatures the stationary state is non‐Gibbsian due to an entanglement with the bath. This happens when a cloud of bath modes around the particle is formed. Equilibrium thermodynamics for particle plus bath together, does not imply standard thermodynamics for the particle itself at low T. Various formulations of the second law are then invalid. First, the Clausius inequality can be violated. Second, when the width of the confining potential is suddenly changed, there occurs a relaxation to equilibrium during which the rate of entropy production is partly negative. Third, for non‐adiabatic changes of system parameters the rate of energy dissipation can be negative, and, out of equilibrium, cyclic processes are possible which extract work from the bath. Conditions are put forward under which perpetuum mobile of the second kind, having several work extraction cycles, enter the realm of condensed matter physics.
The Second Law of Thermodynamics is considered to be one of the most fundamental and important laws of Physics. Both Clausius and Kelvin reformulated the Second Law as statements concerning the behaviour of two communicating systems, set to interact at different temperatures. The average positive entropy production of any process, described by the Second Law, is often understood as a "thermodynamic arrow of time" capable of discerning the direction in which physical events should arrange. By studying a microscopic system described by two initially correlated qubits, in this thesis we explore the phenomenon of reverse energy flow. Differently from an often standard uncorrelated case, the correlated one shows properties that seem to suggest that a further generalization of both Clausius and Kelvin's statements is needed
In the weak-coupling limit approach to open quantum systems, the presence of the bath is eliminated and accounted for by a master equation that introduces dissipative contributions to the system reduced dynamics: within this framework, there are no bath entropy contributions to the entropy balance. We show that, as a consequence, the entropy production fails to be positive for a class of physically legitimate, that is completely positive and trace preserving, non-Markovian dynamical maps. Moreover, in absence of the semigroup property, if the reduced dynamics has a thermal asymptotic state, this need not be stationary. Then even the integrated entropy production becomes negative. These observations imply that, when the conditions leading to reduced dynamics of semigroup type are relaxed, a consistent formulation of the second law of thermodynamics requires that the environment contribution to the entropy balance be explicitly taken into account.