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arXiv:0707.2307 · Physical Review E

Microcanonical quantum fluctuation theorems

Peter Talkner A, Peter Hänggi A, Manuel Morillo

Published May 29, 2008• 79 citations
arXivHTMLPDF

Abstract

Previously derived expressions for the characteristic function of work performed on a quantum system by a classical external force are generalized to arbitrary initial states of the considered system and to Hamiltonians with degenerate spectra. In the particular case of microcanonical initial states, explicit expressions for the characteristic function and the corresponding probability density of work are formulated. Their classical limit as well as their relations to the corresponding canonical expressions are discussed. A fluctuation theorem is derived that expresses the ratio of probabilities of work for a process and its time reversal to the ratio of densities of states of the microcanonical equilibrium systems with corresponding initial and final Hamiltonians. From this Crooks-type fluctuation theorem a relation between entropies of different systems can be derived which does not involve the time-reversed process. This entropy-from-work theorem provides an experimentally accessible way to measure entropies.

DOI
10.1103/physreve.77.051131

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Previously derived expressions for the characteristic function of work performed on a quantum system by a classical external force are generalized to arbitrary initial states of the considered system and to Hamiltonians with degenerate spectra. In the particular case of microcanonical initial states, explicit expressions for the characteristic function and the corresponding probability density of work are formulated. Their classical limit as well as their relations to the corresponding canonical expressions are discussed. A fluctuation theorem is derived that expresses the ratio of probabilities of work for a process and its time reversal to the ratio of densities of states of the microcanonical equilibrium systems with corresponding initial and final Hamiltonians. From this Crooks-type fluctuation theorem a relation between entropies of different systems can be derived which does not involve the time-reversed process. This entropy-from-work theorem provides an experimentally accessible way to measure entropies.
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.
In the context of nonequilibrium quantum thermodynamics, variables like work behave stochastically. A particular definition of the work probability density function (pdf) for coherent quantum processes allows the verification of the quantum version of the celebrated fluctuation theorems, due to Jarzynski and Crooks, that apply when the system is driven away from an initial equilibrium thermal state. Such a particular pdf depends basically on the details of the initial and final Hamiltonians, on the temperature of the initial thermal state, and on how some external parameter is changed during the coherent process. Using random matrix theory we derive a simple analytic expression that describes the general behavior of the work characteristic function G(u), associated with this particular work pdf for sudden quenches, valid for all the traditional Gaussian ensembles of Hamiltonians matrices. This formula well describes the general behavior of G(u) calculated from single draws of the initial and final Hamiltonians in all ranges of temperatures.
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.
Fluctuation theorems for work provide universal constraints on nonequilibrium fluctuations, yet their quantum generalizations often rely on externally prescribed classical driving protocols. While for classical systems, fluctuation theorems have been extended to autonomous work, where the dynamics of the work source is subject to the backaction of the system, their generalization to the quantum regime is constrained by the uncertainty principle. Here, we extend fluctuation theorems for autonomous work from the classical regime to the quantum regime. By performing successive projective measurements over the work source and the system, we derive Jarzynski-type and Crooks-type fluctuation theorems for autonomous inclusive work from initial mixed thermal states. These relations are analogous to fluctuation theorems for autonomous work in the classical regime and explicitly incorporate the fluctuations of the work source. However, quantum noncommutativity prevents a consistent reduction to the nonautonomous counterparts, even in the limit of a large work source and correspondingly negligible backaction. By contrast, under the exclusive work definition, the nonautonomous limit is recovered when the measured observable of the work source commutes with its bare Hamiltonian and the backaction of the system on the work source is negligible. Our results are illustrated with the Dicke model, where a single-mode radiation field and an ensemble of two-level atoms act as the system of interest and the work source, respectively.