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Quantum macrostates, equivalence of ensembles. and an Htheorem

Wojciech De Roeck, Christian Maes

Published Sep 13, 2013• 18 citations
OpenAlex

Abstract

Dedicated to André Verbeure on the occasion of his 65th birthday. Abstract: Before the thermodynamic limit, macroscopic averages need not commute for a quantum system. As a consequence, aspects of macroscopic fluctuations or of constrained equilibrium require a careful analysis, when dealing with several observables. We propose an implementation of ideas that go back to John von Neumann’s writing about the macroscopic measurement. We apply our scheme to the relation between macroscopic autonomy and an H−theorem, and to the problem of equivalence of ensembles. In particular, we prove a quantum version of the asymptotic equipartition theorem. The main point of departure is an expression of a law of large numbers for a sequence of states that start to concentrate, as the size of the system gets larger, on the macroscopic values for the different macroscopic observables. Deviations from that law are governed by the entropy.

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Before the thermodynamic limit, macroscopic averages need not commute for a quantum system. As a consequence, aspects of macroscopic fluctuations or of constrained equilibrium require a careful analysis, when dealing with several observables. We propose an implementation of ideas that go back to John von Neumann’s writing about the macroscopic measurement. We apply our scheme to the relation between macroscopic autonomy and an H-theorem, and to the problem of equivalence of ensembles. In particular, we show how the latter is related to the asymptotic equipartition theorem. The main point of departure is an expression of a law of large numbers for a sequence of states that start to concentrate, as the size of the system gets larger, on the macroscopic values for the different macroscopic observables. Deviations from that law are governed by the entropy.

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von Neumann has proved a quantum-mechanical ergodic theorem which deals with a closed macroscopic system and macroscopic observables. Certain unsatisfactory features of this theorem are probably due to the overly-strong idealization of a completely closed system.Since the claims of statistical mechanics go beyond macroscopic systems, there is a need for a more general theorem. The present paper deals with a system of any number of degrees of freedom and with any observable, during interaction with a temperature bath. In order to avoid an assumption of randomness, the bath must be described explicitly and precisely by a time-independent Hamiltonian. The model of the bath is obtained by taking the Gibbs ensemble seriously, i.e., as a set of $N$ identical systems interacting through a potential $\ensuremath{\lambda}V$.The following theorem is proved. The time average of the quantum-mechanical expectation value of any observable with respect to any initial state is equal to its statistical average, in the double limit $N\ensuremath{\rightarrow}\ensuremath{\infty}$, $\ensuremath{\lambda}\ensuremath{\rightarrow}0$, for the overwhelming majority of all interaction potentials $V$.

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Dedicated to André Verbeure on the occasion of his 65th birthday. Abstract: Before the thermodynamic limit, macroscopic averages need not commute for a quantum system. As a consequence, aspects of macroscopic fluctuations or of constrained equilibrium require a careful analysis, when dealing with several observables. We propose an implementation of ideas that go back to John von Neumann’s writing about the macroscopic measurement. We apply our scheme to the relation between macroscopic autonomy and an H−theorem, and to the problem of equivalence of ensembles. In particular, we prove a quantum version of the asymptotic equipartition theorem. The main point of departure is an expression of a law of large numbers for a sequence of states that start to concentrate, as the size of the system gets larger, on the macroscopic values for the different macroscopic observables. Deviations from that law are governed by the entropy.
Before the thermodynamic limit, macroscopic averages need not commute for a quantum system. As a consequence, aspects of macroscopic fluctuations or of constrained equilibrium require a careful analysis, when dealing with several observables. We propose an implementation of ideas that go back to John von Neumann’s writing about the macroscopic measurement. We apply our scheme to the relation between macroscopic autonomy and an H-theorem, and to the problem of equivalence of ensembles. In particular, we show how the latter is related to the asymptotic equipartition theorem. The main point of departure is an expression of a law of large numbers for a sequence of states that start to concentrate, as the size of the system gets larger, on the macroscopic values for the different macroscopic observables. Deviations from that law are governed by the entropy.
We build a framework for the thermodynamics of macroscopic quantum systems. In contrast with approaches requiring access to the full density matrix, our framework relies on a coarse-grained description, based on measurement statistics of a few observables. When these observables commute, the outcomes define classical macrostates whose entropy is quantified by observational entropy, accounting for uncertainty about both the macrostate and the microstate within it. We extend this notion to non-commuting observables forming a subalgebra of the operator space, and use Jaynes' principle to define an algebra-dependent entropy interpolating between von Neumann and observational entropies. Given initial and final measurement sets, connected by internal and/or environment-induced dynamics, we derive a second law for the coarse-grained dynamics. Unlike formulations based on von Neumann entropy, our inequality captures irreversibility from both non-unitary environment-induced dynamics and internal equilibration. It takes the usual form of a positive entropy production when the system is initially at internal equilibrium, while correction terms capture nonequilibrium resources ignored by the coarse-graining. We also derive fluctuation theorems for coarse-grained thermodynamic quantities. Along a quasi-static path of measurement schemes, we identify quantum macroscopic notions of work and heat fulfilling the first and second laws, including an additional work contribution from manipulating the algebra to which the system is confined, through external constraints or quantum measurement backaction. Finally, we apply our framework to examples illustrating the impact of varying the coarse-graining scheme. Our approach unifies macroscopic and stochastic thermodynamics in a genuinely quantum framework, laying the basis for a versatile, experimentally friendly toolbox to analyze complex quantum dynamics.
The two criteria of ensemble equivalence, i.e., macrostate equivalence and measure equivalence, are investigated for a general pair of states. Macrostate equivalence implies the two ensembles are indistinguishable by the measurement of macroscopic quantities obeying the large-deviation principle, and measure equivalence means that the specific relative entropy of these two states vanishes in the thermodynamic limit. It is shown that measure equivalence implies a macrostate equivalence for a general pair of states by deriving an inequality connecting the large-deviation rate functions to the specific relative Renyi entropies. The result is applicable to both quantum and classical systems. As applications, a sufficient condition for thermalization, the time scale of quantum dynamics of macrovariables, and the second law with strict irreversibility in a quantum quench are discussed.
We construct a macroscopic thermodynamical theory that satisfies the second law of thermodynamics, based on quantum mechanics. More concretely, our macroscopic theory satisfies the following two features: (1) A macroscopic equilibrium state is expressed as a set of macroscopic variables a⃗=(a1,⋯ ,aL)\vec{a}=(a_1,\cdots,a_L)a=(a1​,⋯,aL​), which represents coarse-grained values of a set of physical quantities, and (2) An adiabatic transformation from an equilibrium state a⃗\vec{a}a to another state a⃗′\vec{a}'a′ is possible if and only if sa⃗≤sa⃗′s_{\vec{a}}\le s_{\vec{a}'}sa​≤sa′​ holds. Here, sa⃗s_{\vec{a}}sa​ is a real-valued function corresponding to the thermodynamical entropy, which depends only on macroscopic variables a⃗\vec{a}a. We show that such a macroscopic thermodynamical theory can be consistently constructed if the von-Neumann entropy of a generalized microcanonical state satisfies a generalized central limit theorem. We also show that even when the von-Neumann entropies do not satisfy the condition, a macroscopic thermodynamic-like theory with a similar structure exists, which could be at the foundations of nonequilibrium thermodynamics. Finally, we make a replica of (U,V,N)(U,V,N)(U,V,N) expression of thermodynamics satisfying (1) and (2), using a toy model of free particles in a box.
This chapter considers what would happen to a mixture with the statistical operator 𝗨 if a quantity 𝖱 with operator 𝖱 is measured in it. It then investigates the thermodynamics of quantum mechanical ensembles from two different points of view. First, the chapter assumes the validity of both of the fundamental laws of thermodynamics, and proceeds on this basis to calculation of the entropy of ensembles. In this effort the normal methods of phenomenological thermodynamics are applied, and quantum mechanics plays a role only insofar as these thermodynamic observations relate to objects whose behavior is regulated by the laws of quantum. Afterwards this chapter proves the validity of these fundamental laws in quantum mechanics. Next, the chapter introduces some reversibility and equilibrium problems. Finally, this chapter discusses the macroscopic measurement.
von Neumann has proved a quantum-mechanical ergodic theorem which deals with a closed macroscopic system and macroscopic observables. Certain unsatisfactory features of this theorem are probably due to the overly-strong idealization of a completely closed system.Since the claims of statistical mechanics go beyond macroscopic systems, there is a need for a more general theorem. The present paper deals with a system of any number of degrees of freedom and with any observable, during interaction with a temperature bath. In order to avoid an assumption of randomness, the bath must be described explicitly and precisely by a time-independent Hamiltonian. The model of the bath is obtained by taking the Gibbs ensemble seriously, i.e., as a set of NNN identical systems interacting through a potential $\ensuremath{\lambda}V$.The following theorem is proved. The time average of the quantum-mechanical expectation value of any observable with respect to any initial state is equal to its statistical average, in the double limit $N\ensuremath{\rightarrow}\ensuremath{\infty}$, $\ensuremath{\lambda}\ensuremath{\rightarrow}0$, for the overwhelming majority of all interaction potentials VVV.