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arXiv:cond-mat/0410623 · Physical Review E

Unified treatment of the quantum fluctuation theorem and the Jarzynski equality in terms of microscopic reversibility

Takaaki Monnai

Published Aug 9, 2005• 79 citations
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Abstract

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.

DOI
10.1103/physreve.72.027102

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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.
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.
For classical systems driven out of equilibrium, Crooks derived a relation (the Crooks-Jarzynski relation), whose special cases include a relation (the Crooks relation) equivalent to the Kawasaki non-linear response relation. We derive a quantum extension of the Crooks-Jarzynski relation without explicitly using the principle of microreversibility. Its special cases lead to the Jarzynski equality and the standard linear response theory with a Green-Kubo formula with a canonical correlation function. We also derive a quantum extension of the Crooks relation using the principle of microreversibility. Its special cases lead to the Jarzynski equality, the Crooks transient fluctuation theorem, and the fluctuation theorem for current or shear stress, which leads to a Green-Kubo formula with a symmetrized correlation function. For each quantum Crooks relation, there exists a corresponding quantum Crooks-Jarzynski relation. Using either relation, we can derive the Jarzynski equality, the fluctuation theorems mentioned above, and the standard linear response theory.
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.
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.
We present a general quantum fluctuation theorem for the entropy production of an open quantum system coupled to multiple environments, not necessarily at equilibrium. Such a general theorem, when restricted to the weak-coupling and Markovian regime, holds for both local and global master equations, corroborating the thermodynamic consistency of local quantum master equations. The theorem is genuinely quantum, as it can be expressed in terms of conservation of a Hermitian operator, describing the dynamics of the system state operator and of the entropy change in the baths. The integral fluctuation theorem follows from the properties of such an operator. Furthermore, it is also valid when the system is described by a time-dependent Hamiltonian. As such, the quantum Jarzynski equality is a particular case of the general result presented here. Moreover, our result can be extended to nonthermal baths, as long as microreversibility is preserved. We present some numerical examples to showcase the exact results previously obtained. We finally generalize the fluctuation theorem to the case where the interaction between the system and the bath is explicitly taken into account. We show that the fluctuation theorem amounts to a relation between time-reversed dynamics of the global density matrix and a two-time correlation function along the forward dynamics involving the baths' entropy alone.
Fluctuation theorems are relations constraining the out-of-equilibrium fluctuations of thermodynamic quantities like the entropy production that were initially introduced for classical or quantum systems in contact with a thermal bath. Here we show, in the absence of thermal bath, the dynamics of continuously measured quantum systems can also be described by a fluctuation theorem, expressed in terms of a recently introduced arrow of time measure. This theorem captures the emergence of irreversible behavior from microscopic reversibility in continuous quantum measurements. From this relation, we demonstrate that measurement-induced wave-function collapse exhibits absolute irreversibility, such that Jarzynski-like equalities are violated, and that this property is inherent to quantum information acquisition. We apply our results to different continuous measurement schemes on a qubit: dispersive measurement, homodyne, and heterodyne detection of qubit's fluorescence.