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arXiv:1003.1052 · Philosophical Transactions of the Royal Society A Mathematical Physical and Engineering Sciences

Quantum Bochkov–Kuzovlev work fluctuation theorems

Michele Campisi, Peter Talkner A, Peter Hänggi A

Published Dec 13, 2010• 40 citations
arXivHTMLPDF

Abstract

The quantum version of the Bochkov-Kuzovlev identity is derived on the basis of the appropriate definition of work as the difference of the measured internal energies of a quantum system at the beginning and the end of an external action on the system given by a prescribed protocol. According to the spirit of the original Bochkov-Kuzovlev approach, we adopt the 'exclusive' viewpoint, meaning that the coupling to the external work source is not counted as part of the internal energy. The corresponding canonical and microcanonical quantum fluctuation theorems are derived as well, and are compared with the respective theorems obtained within the 'inclusive' approach. The relations between the quantum inclusive work w, the exclusive work w(0) and the dissipated work w(dis), are discussed and clarified. We show by an explicit example that w(0) and w(dis) are distinct stochastic quantities obeying different statistics.

DOI
10.1098/rsta.2010.0252

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The quantum version of the Bochkov-Kuzovlev identity is derived on the basis of the appropriate definition of work as the difference of the measured internal energies of a quantum system at the beginning and the end of an external action on the system given by a prescribed protocol. According to the spirit of the original Bochkov-Kuzovlev approach, we adopt the 'exclusive' viewpoint, meaning that the coupling to the external work source is not counted as part of the internal energy. The corresponding canonical and microcanonical quantum fluctuation theorems are derived as well, and are compared with the respective theorems obtained within the 'inclusive' approach. The relations between the quantum inclusive work w, the exclusive work w(0) and the dissipated work w(dis), are discussed and clarified. We show by an explicit example that w(0) and w(dis) are distinct stochastic quantities obeying different statistics.
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.
As quantum systems become more experimentally accessible, we are forced to reconsider the notions of control and work to fully account for quantum effects. To this end, we identify the work injected into a quantum system during a general quantum-mechanical driving protocol and quantify the relevant heat flows. The known results that are applicable in the limit of a classical drive are shown to emerge from our equations as a special case. Using the established framework, we show that the Bochkov-Kuzovlev identity for the exclusive work distribution is modified in a nontrivial way by the accumulation of system-drive correlations resulting from quantum back action. Our results accentuate the conceptual and discernible differences between a fully quantum-mechanical and classical driving protocols of quantum systems.
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 classical Jarzynski equality establishes an exact relation between the stochastic work performed on a system driven out of thermal equilibrium and the free energy difference in a corresponding quasistatic process. This fluctuation theorem bears experimental relevance, as it enables the determination of the free energy difference through the measurement of externally applied work in a nonequilibrium process. In the quantum case, the Jarzynski equality only holds if the measurement procedure of the stochastic work is drastically changed: it is replaced by a so-called two-point measurement scheme that requires the knowledge of the initial and final Hamiltonian and therefore lacks the predictive power for the free energy difference that the classical Jarzynski equation is known for. Here, we propose a quantum fluctuation theorem that is valid for externally measurable quantum work determined during the driving protocol. In contrast to the two-point measurement case, the theorem also applies to open quantum systems and the scenario can be realized without knowing the system Hamiltonian. Our fluctuation theorem comes in the form of an inequality and therefore only yields bounds to the true free energy difference. The inequality is saturated in the quasiclassical case of vanishing energy coherences at the beginning and at the end of the protocol. Thus, there is a clear quantum disadvantage.
We briefly introduce the quantum Jarzynski and Bochkov-Kuzovlev equalities in isolated quantum Hamiltonian systems, which includes the origin of the equalities, their derivations using a quantum Feynman-Kac formula, the quantum Crooks equality, the evolution equations governing the characteristic functions of the probability density functions for the quantum work, the recent experimental verifications. Some results are given here first time. We particularly emphasize the formally structural consistence between these quantum equalities and their classical counterparts, which shall be useful in understanding the existing equalities and pursuing new fluctuation relations in other complex quantum systems.