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arXiv:0902.3879 · Physical Review Letters

Fluctuation Theorem for Arbitrary Open Quantum Systems

Michele Campisi, Peter Talkner A, Peter Hänggi A

Published May 26, 2009• 354 citations
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Abstract

Based on the observation that the thermodynamic equilibrium free energy of an open quantum system in contact with a thermal environment is the difference between the free energy of the total system and that of the bare environment, the validity of the Crooks theorem and of the Jarzynski equality is extended to open quantum systems. No restrictions on the nature of the environment or on the strength of the coupling between system and environment need to be imposed. This free energy entering the Crooks theorem and the Jarzynski equality is closely related to the Hamiltonian of mean force that generalizes the classical statistical mechanical concept of the potential of mean force.

DOI
10.1103/physrevlett.102.210401

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Based on the observation that the thermodynamic equilibrium free energy of an open quantum system in contact with a thermal environment is the difference between the free energy of the total system and that of the bare environment, the validity of the Crooks theorem and of the Jarzynski equality is extended to open quantum systems. No restrictions on the nature of the environment or on the strength of the coupling between system and environment need to be imposed. This free energy entering the Crooks theorem and the Jarzynski equality is closely related to the Hamiltonian of mean force that generalizes the classical statistical mechanical concept of the potential of mean force.
In this paper we present a first-principles analysis of the nonequilibrium work distribution and the free energy difference of a quantum system interacting with a general environment (with arbitrary spectral density and for all temperatures) based on a well-understood microphysics (quantum Brownian motion) model under the conditions stipulated by the Jarzynski equality [Jarzynski, Phys. Rev. Lett. 78, 2690 (1997)] and Crooks' fluctuation theorem [Crooks, Phys. Rev. E 60, 2721 (1999)] (in short, fluctuation theorems, FTs). We use the decoherent histories conceptual framework to explain how the notion of trajectories in a quantum system can be made viable and use the environment-induced decoherence scheme to assess the strength of noise that could provide sufficient decoherence to warrant the use of trajectories to define work in open quantum systems. From the solutions to the Langevin equation governing the stochastic dynamics of such systems we were able to produce formal expressions for these quantities entering in the FTs and from them prove explicitly the validity of the FTs at the high temperature limit. At low temperatures our general results would enable one to identify the range of parameters where FTs may not hold or need be expressed differently. We explain the relation between classical and quantum FTs and the advantage of this microphysics open-system approach over the phenomenological modeling and energy-level calculations for substitute closed quantum systems.
We consider the quantum mechanical generalization of Crooks Fluctuation Theorem and Jarzynski Equality for an open quantum system. The explicit expression for microscopic work for an arbitrary prescribed protocol is obtained, and the relation between quantum Crooks Fluctuation Theorem, quantum Jarzynski Equality and their classical counterparts are clarified. Numerical simulations based on a two-level toy model are used to demonstrate the validity of the quantum version of the two theorems beyond linear response theory regime.
The characteristic function for the joint measurement of the changes of two or more commuting observables upon an external forcing of a quantum system is derived. In particular, the statistics of the internal energy, the exchanged heat and the work of a quantum system that weakly couples to its environment are determined in terms of the energy changes of the system and the environment due to the action of a classical, external force on the system. If the system and the environment initially are in a canonical equilibrium, the work performed on the system is shown to satisfy the Tasaki–Crooks theorem and the Jarzynski equality.
The characteristic function for the joint measurement of the changes of two commuting observables upon an external forcing of a quantum system is derived. In particular, the statistics of the internal energy, the exchanged heat and the work of a quantum system that weakly couples to its environment is determined in terms of the energy changes of the system and the environment due to the action of a classical, external force on the system. If the system and environment initially are in a canonical equilibrium, the work performed on the system is shown to satisfy the Tasaki-Crooks theorem and the Jarzynski equality. PACS numbers: 05.30.-d,05.70.Ln,05.40-a
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.
There are two related theorems which hold even in far from equilibrium, namely fluctuation theorem and Jarzynski equality. Fluctuation theorem states the existence of symmetry of fluctuation of entropy production, while the Jarzynski equality enables us to estimate the free energy change between two states by using irreversible processes. On the other hand, the relationship between these theorems was investigated by Crooks [Phys. Rev. E 60, 2721 (1999)] for the classical stochastic systems. In this paper, we derive quantum analogues of fluctuation theorem and Jarzynski equality in terms of microscopic reversibility. In other words, the quantum analog of the work by Crooks is presented. Also, for the quasiclassical Langevin system, microscopically reversible condition is confirmed.