arXiv:cond-mat/0408697

The second law and fluctuations of work: The case against quantum fluctuation theorems

ARMEN E. ALLAHVERDYAN, Theo M. Nieuwenhuizen

Published Aug 31, 2004• 1 citation

Abstract

We study how Thomson's formulation of the second law: no work is extracted from an equilibrium ensemble by a cyclic process, emerges in the quantum situation through the averaging over fluctuations of work. The latter concept is carefully defined for an ensemble of quantum systems interacting with macroscopic sources of work. The approach is based on first splitting a mixed quantum ensemble into pure subensembles, which according to quantum mechanics are maximally complete and irreducible. The splitting is done by filtering the outcomes of a measurement process. A critical review is given of two other approaches to fluctuations of work proposed in the literature. It is shown that in contrast to those ones, the present definition {\it i)} is consistent with the physical meaning of the concept of work as mechanical energy lost by the macroscopic sources, or, equivalently, as the average energy acquired by the ensemble; {\it ii)} applies to an arbitrary non-equilibrium state. There is no direct generalization of the classical work-fluctuation theorem to the proper quantum domain. This implies some non-classical scenarios for the emergence of the second law.

DOI: 10.48550/arxiv.cond-mat/0408697

Related papers

The second law and fluctuations of work: The case against quantum fluctuation theorems.

M. Nieuwenhuizen

We study how Thomson’s formulation of the second law: no work is extracted from an equilibrium ensemble by a cyclic process, emerges in the quantum situation through the averaging over fluctuations of work. The latter concept is carefully defined for an ensemble of quantum systems interacting with macroscopic sources of work. The approach is based on first splitting a mixed quantum ensemble into pure subensembles, which according to quantum mechanics are maximally complete and irreducible. The splitting is done by filtering the outcomes of a measurement process. A critical review is given of two other approaches to fluctuations of work proposed in the literature. It is shown that in contrast to those ones, the present definition i) is consistent with the physical meaning of the concept of work as mechanical energy lost by the macroscopic sources, or, equivalently, as the average energy acquired by the ensemble; ii) applies to an arbitrary nonequilibrium state. There is no direct generalization of the classical work-fluctuation theorem to the proper quantum domain. This implies some non-classical scenarios for the emergence of the second law.

Aug 31, 20042 citations

Fluctuations of work from quantum subensembles: The case against quantum work-fluctuation theorems

ARMEN E. ALLAHVERDYAN, Theo M. Nieuwenhuizen

We study how Thomson's formulation of the second law of thermodynamics (no work is extracted from an equilibrium ensemble by a cyclic process) emerges in the quantum situation through the averaging over fluctuations of work. The latter concept is carefully defined for an ensemble of quantum systems, the members of which interact with macroscopic sources of work. The approach is based on splitting a mixed quantum ensemble into pure subensembles, which according to quantum mechanics are maximally complete and irreducible. The splitting is done by filtering the outcomes of a measurement process. The approach is corroborated by comparing to relevant experiments in quantum optics. A critical review is given of two other approaches to fluctuations of work proposed in the literature. It is shown that in contrast to those, the present definition (i) is consistent with the physical meaning of the concept of work as mechanical energy lost by the macroscopic sources, or, equivalently, as the average energy acquired by the ensemble; (ii) applies to an arbitrary nonequilibrium state. There is no direct generalization of the classical work-fluctuation theorem to the proper quantum domain. This implies nonclassical scenarios for the emergence of the second law.

Physical Review EJun 2, 2005143 citations

Nonequilibrium Quantum Systems: Fluctuations and Interactions

Yiğit Subaşı

We explore some aspects of nonequilibrium statistical mechanics of classical and quantum systems. Two chapters are devoted to fluctuation theorems which were originally derived for classical systems. The main challenge in formulating them in quantum mechanics is the fact that fundamental quantities of interest, like work, are defined via the classical concept of a phase space trajectory. We utilize the decoherent histories conceptual framework, in which classical trajectories emerge in quantum mechanics as a result of coarse graining, and provide a first-principles analysis of the nonequilibrium work relation of Jarzynski and Crooks's fluctuation theorem for a quantum system interacting with a general environment based on the quantum Brownian motion (QBM) model. We indicate a parameter range at low temperatures where the theorems might fail in their original form. Fluctuation theorems of Jarzynski and Crooks for systems obeying classical Hamiltonian dynamics are derived under the assumption that the initial conditions are sampled from a canonical ensemble, even though the equilibrium state of an isolated system is typically associated with the microcanonical ensemble. We address this issue through an exact analysis of the classical Brownian motion model. We argue that a stronger form of ensemble equivalence than usually discussed in equilibrium statistical mechanics is required for these theorems to hold in the infinite environment limit irrespective of the ensemble used, and proceed to prove it for this model. An exact expression for the probability distribution of work is obtained for finite environments. Intuitively one expects a system to relax to an equilibrium state when brought into contact with a thermal environment. Yet it is important to have rigorous results that provide conditions for equilibration and characterize the equilibrium state. We consider the dynamics of open quantum systems using the Langevin and master equations and rigorously show that under fairly general conditions quantum systems interacting with a heat bath relax to the equilibrium state defined as the reduced thermal state of the system plus environment, even in the strong coupling regime. Our proof is valid to second-order in interaction strength for general systems and exact for the linear QBM model, for which we also show the equivalence of multi-time correlations. In the final chapter we give a sampling of our investigations into macroscopic quantum phenomena. We work out in detail a specific example of how and under what conditions the center of mass (CoM) coordinate of a macroscopic object emerges as the relevant degree of freedom. Interaction patterns are studied in terms of the couplings they induce between the CoM and relative coordinates of two macroscopic objects. We discuss the implications of these interaction patterns on macroscopic entanglement.

Jan 1, 20130 citations

Fluctuations, Thermodynamic Equilibrium and Entropy

Edwin C. Kemble

To eliminate exceptions to the second law due to fluctuation phenomena, etc., the following changes are necessary. First we must state the laws of thermodynamics in terms of Gibbsian ensembles rather than of individual systems. Second we must sharpen our conception of the experimental procedure required for producing states of thermodynamic equilibrium. It will not suffice to isolate the system and wait. We must have the positive stirring action of thermal contact with a thermostat. Using the new definition of thermal equilibrium we can place statistical mechanics on a more satisfactory footing by showing that the thermostat experimental procedure leads to the canonical ensemble and maximizes v. Neumann's microscopic entropy. (Details of this proof appear in succeeding paper). Difficulties with his macroscopic definition of entropy are avoided by showing that his original microscopic definition is satisfactory when used in conjunction with a proper operational definition of thermodynamic equilibrium. In conclusion the second law of thermodynamics is derived from quantum statistics on the basis of the microscopic definition of entropy.

Physical ReviewNov 15, 193918 citations

On the non-equilibrium thermodynamics of quantum systems

Stefano Marcantoni

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.

Feb 6, 20181 citation

Nonequilibrium quantum fluctuations of work

ARMEN E. ALLAHVERDYAN

The concept of work is basic for statistical thermodynamics. To gain a fuller understanding of work and its (quantum) features, it needs to be represented as an average of a fluctuating quantity. Here I focus on the work done between two moments of time for a thermally isolated quantum system driven by a time-dependent Hamiltonian. I formulate two natural conditions needed for the fluctuating work to be physically meaningful for a system that starts its evolution from a nonequilibrium state. The existing definitions do not satisfy these conditions due to issues that are traced back to noncommutativity. I propose a definition of fluctuating work that is free of previous drawbacks and that applies for a wide class of nonequilibrium initial states. It allows the deduction of a generalized work-fluctuation theorem that applies for an arbitrary (out-of-equilibrium) initial state.

arXiv:1404.4190Physical Review ESep 26, 2014158 citations