Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Log inSign up
Challenges
Datasets
Workspaces
Papers
Discussions
Leaderboard
Blog
Job Board
Q3AS

© 2026 Aqora Quantum S.A.S.

TermsPrivacyLegal Notice

WORLD SCIENTIFIC eBooks

Gibbs and Boltzmann Entropy in Classical and Quantum Mechanics

Sheldon Goldstein, Joel L. Lebowitz, Roderich Tumulka, Nino Zanghı̀

Published Apr 21, 2020• 62 citations
Publisher

Abstract

The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular, in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.

DOI
10.1142/9789811211720_0014

Related papers

Gibbs and boltzmann entropy in classical and quantum mechanics

Sheldon Goldstein, Joel L. Lebowitz, Roderich Tumulka +1 more

The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.

arXiv:1903.11870•Mar 28, 2019•17 citations

Quantum coarse-grained entropy and thermalization in closed systems

Dominik Šafránek, Joshua M. Deutsch, Anthony N. Aguirre

We investigate the detailed properties of observational entropy, introduced by \ifmmode \check{S}\else \v{S}\fi{}afr\'anek et al. [Phys. Rev. A 99, 010101 (2019)] as a generalization of Boltzmann entropy to quantum mechanics. This quantity can involve multiple coarse grainings, even those that do not commute with each other, without losing any of its properties. It is well-defined out of equilibrium, and for some coarse grainings it generically rises to the correct thermodynamic value even in a genuinely isolated quantum system. The quantity contains several other entropy definitions as special cases, it has interesting information-theoretic interpretations, and mathematical properties---such as extensivity and upper and lower bounds---suitable for an entropy. Here we describe and provide proofs for many of its properties, discuss its interpretation and connection to other quantities, and provide numerous simulations and analytic arguments supporting the claims of its relationship to thermodynamic entropy. This quantity may thus provide a clear and well-defined foundation on which to build a satisfactory understanding of the second thermodynamical law in quantum mechanics.

arXiv:1803.00665•Physical Review A•Jan 7, 2019•72 citations

Boltzmann entropy for quantum field systems

Kyo Yoshida

A way to construct Boltzmann entropy, i.e., the entropy as a function of a microscopic pure state, for quantum field systems is proposed. Operators that shift the field in wave-vector space are used in the construction. By employing an assumption that some terms emerging due to the shift are negligible in the thermodynamic limit, it is shown that, for almost all states in the ensemble of pure states corresponding to a thermodynamic state, the value of the proposed Boltzmann entropy coincides with that of the thermodynamic entropy for the thermodynamic state. For general self-interacting fields, the Boltzmann entropy evolves with time under Hamiltonian dynamics, so that it is capable of characterizing the thermalization of isolated quantum field systems.

arXiv:1909.00961•Physical Review A•Mar 16, 2020•2 citations

Quantum corrections to the entropy and its application in the study of quantum Carnot engines

Tian Qiu, Zhaoyu Fei, Rui Pan +1 more

Entropy is one of the most basic concepts in thermodynamics and statistical mechanics. The most widely used definition of statistical mechanical entropy for a quantum system is introduced by von Neumann. While in classical systems, the statistical mechanical entropy is defined by Gibbs. The relation between these two definitions of entropy is still not fully explored. In this work, we study this problem by employing the phase-space formulation of quantum mechanics. For those quantum states having well-defined classical counterparts, we study the quantum-classical correspondence and quantum corrections of the entropy. We expand the von Neumann entropy in powers of ℏ by using the phase-space formulation, and the zeroth-order term reproduces the Gibbs entropy. We also obtain the explicit expression of the quantum corrections of the entropy. Moreover, we find that for the thermodynamic equilibrium state, all terms odd in ℏ are exactly zero. As an application, we derive quantum corrections for the net work extraction during a quantum Carnot cycle. Our results bring important insights into the understanding of quantum entropy and may have potential applications in the study of quantum heat engines.

arXiv:1912.11429•Physical review. E•Mar 10, 2020•7 citations

Maximum entropy distributions of wavefunctions at thermal equilibrium

Jacob T. Willson, Henrik J. Heelweg, Adam P. Willard

Statistical mechanics reveals that the properties of a macroscopic physical system emerge as an average over an ensemble of statistically independent microscopic subsystems, each occupying a specific microstate. In the study of quantum systems, these microstates can be chosen to correspond to the pure state wavefunctions of individual quantum systems. However, the physical principles that govern the distribution of a pure state wavefunction ensemble, even under conditions of thermal equilibrium, are not well established. For instance, the canonical Boltzmann distribution cannot be applied to wavefunctions because they lack a definite energy. In this manuscript, we present a maximum entropy principle for the quantum wavefunction ensemble at thermal equilibrium, the so-called Scrooge ensemble. We highlight that a constraint on the energy expectation value, or even the shape of the associated eigenstate distribution, fails to yield a valid equilibrium state. We find that in addition to these constraints, one must also constrain the measurement entropy to be equal to the Rényi divergence of the ensemble with respect to the Gibbs state, indicating that the Rényi divergence may have uninvestigated physical importance to thermal equilibrium in quantum systems.

arXiv:2603.19060•Mar 19, 2026•0 citations

The generalized Boltzmann distribution is the only distribution in which the Gibbs-Shannon entropy equals the thermodynamic entropy

Xiang Gao, Emilio Gallicchio, Adrian E. Roitberg

We show that the generalized Boltzmann distribution is the only distribution for which the Gibbs-Shannon entropy equals the thermodynamic entropy. This result means that the thermodynamic entropy and the Gibbs-Shannon entropy are not generally equal, but rather the equality holds only in the special case where a system is in equilibrium with a reservoir.

arXiv:1903.02121•The Journal of Chemical Physics•Jul 19, 2019•37 citations
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular, in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
The Gibbs entropy of a macroscopic classical system is a function of a probability distribution over phase space, i.e., of an ensemble. In contrast, the Boltzmann entropy is a function on phase space, and is thus defined for an individual system. Our aim is to discuss and compare these two notions of entropy, along with the associated ensemblist and individualist views of thermal equilibrium. Using the Gibbsian ensembles for the computation of the Gibbs entropy, the two notions yield the same (leading order) values for the entropy of a macroscopic system in thermal equilibrium. The two approaches do not, however, necessarily agree for non-equilibrium systems. For those, we argue that the Boltzmann entropy is the one that corresponds to thermodynamic entropy, in particular in connection with the second law of thermodynamics. Moreover, we describe the quantum analog of the Boltzmann entropy, and we argue that the individualist (Boltzmannian) concept of equilibrium is supported by the recent works on thermalization of closed quantum systems.
We investigate the detailed properties of observational entropy, introduced by \ifmmode \check{S}\else \v{S}\fi{}afr\'anek et al. [Phys. Rev. A 99, 010101 (2019)] as a generalization of Boltzmann entropy to quantum mechanics. This quantity can involve multiple coarse grainings, even those that do not commute with each other, without losing any of its properties. It is well-defined out of equilibrium, and for some coarse grainings it generically rises to the correct thermodynamic value even in a genuinely isolated quantum system. The quantity contains several other entropy definitions as special cases, it has interesting information-theoretic interpretations, and mathematical properties---such as extensivity and upper and lower bounds---suitable for an entropy. Here we describe and provide proofs for many of its properties, discuss its interpretation and connection to other quantities, and provide numerous simulations and analytic arguments supporting the claims of its relationship to thermodynamic entropy. This quantity may thus provide a clear and well-defined foundation on which to build a satisfactory understanding of the second thermodynamical law in quantum mechanics.
A way to construct Boltzmann entropy, i.e., the entropy as a function of a microscopic pure state, for quantum field systems is proposed. Operators that shift the field in wave-vector space are used in the construction. By employing an assumption that some terms emerging due to the shift are negligible in the thermodynamic limit, it is shown that, for almost all states in the ensemble of pure states corresponding to a thermodynamic state, the value of the proposed Boltzmann entropy coincides with that of the thermodynamic entropy for the thermodynamic state. For general self-interacting fields, the Boltzmann entropy evolves with time under Hamiltonian dynamics, so that it is capable of characterizing the thermalization of isolated quantum field systems.
Entropy is one of the most basic concepts in thermodynamics and statistical mechanics. The most widely used definition of statistical mechanical entropy for a quantum system is introduced by von Neumann. While in classical systems, the statistical mechanical entropy is defined by Gibbs. The relation between these two definitions of entropy is still not fully explored. In this work, we study this problem by employing the phase-space formulation of quantum mechanics. For those quantum states having well-defined classical counterparts, we study the quantum-classical correspondence and quantum corrections of the entropy. We expand the von Neumann entropy in powers of ℏ by using the phase-space formulation, and the zeroth-order term reproduces the Gibbs entropy. We also obtain the explicit expression of the quantum corrections of the entropy. Moreover, we find that for the thermodynamic equilibrium state, all terms odd in ℏ are exactly zero. As an application, we derive quantum corrections for the net work extraction during a quantum Carnot cycle. Our results bring important insights into the understanding of quantum entropy and may have potential applications in the study of quantum heat engines.
Statistical mechanics reveals that the properties of a macroscopic physical system emerge as an average over an ensemble of statistically independent microscopic subsystems, each occupying a specific microstate. In the study of quantum systems, these microstates can be chosen to correspond to the pure state wavefunctions of individual quantum systems. However, the physical principles that govern the distribution of a pure state wavefunction ensemble, even under conditions of thermal equilibrium, are not well established. For instance, the canonical Boltzmann distribution cannot be applied to wavefunctions because they lack a definite energy. In this manuscript, we present a maximum entropy principle for the quantum wavefunction ensemble at thermal equilibrium, the so-called Scrooge ensemble. We highlight that a constraint on the energy expectation value, or even the shape of the associated eigenstate distribution, fails to yield a valid equilibrium state. We find that in addition to these constraints, one must also constrain the measurement entropy to be equal to the Rényi divergence of the ensemble with respect to the Gibbs state, indicating that the Rényi divergence may have uninvestigated physical importance to thermal equilibrium in quantum systems.