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Physical Review E

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

ARMEN E. ALLAHVERDYAN, Theo M. Nieuwenhuizen

Published Jun 2, 2005• 143 citations
Publisher

Abstract

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.

DOI
10.1103/physreve.71.066102

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

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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.

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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.

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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.
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.
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.
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.
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.
Of indisputable relevance for nonequilibrium thermodynamics, fluctuations theorems have been generalized to the framework of quantum thermodynamics, with the notion of work playing a key role in such contexts. The typical approach consists of treating work as a stochastic variable and the acting system as an eminently classical device with a deterministic dynamics. Inspired by technological advances in the field of quantum machines, here we look for corrections to work fluctuations theorems when the acting system is allowed to enter the quantum domain. This entails including the acting system in the dynamics and letting it share a nonclassical state with the system acted upon. Moreover, favoring a mechanical perspective to this program, we employ a concept of work observable. For simplicity, we choose as theoretical platform the autonomous dynamics of a two-particle system with an elastic coupling. For some specific processes, we derive several fluctuation theorems within both the quantum and classical statistical arenas. In the quantum results, we find that, along with entanglement and quantum coherence, aspects of inertia also play a significant role since they regulate the route to mechanical equilibrium.
Deriving the laws of thermodynamics from a microscopic picture is a central quest of statistical mechanics.This tutorial focuses on the derivation of the first and second law for isolated and open quantum systems far from equilibrium, where such foundational questions also become practically relevant for emergent nanotechnologies.The derivation is based on a microscopic definition of five essential quantities: internal energy, thermodynamic entropy, work, heat, and temperature.These definitions are shown to satisfy the phenomenological laws of nonequilibrium thermodynamics for a large class of states and processes.The consistency with previous results is demonstrated.The framework applies to multiple baths including particle transport and accounts for processes with, e.g., a changing temperature of the bath, which is determined microscopically.An integral fluctuation theorem for entropy production is satisfied.In summary, this tutorial introduces a consistent and versatile framework to understand and apply the laws of thermodynamics in the quantum regime and beyond.