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arXiv:2412.15316

Statistical entropy of quantum systems

Smitarani Mishra, Shaon Sahoo

Published Dec 19, 2024• 0 citations

Abstract

Statistical formulations of thermodynamic entropy, such as those by Boltzmann and Gibbs, were originally developed for classical systems and are well understood in that context. However, the foundational aspects of quantum statistical mechanics remain an area of active debate and are yet to be fully understood. This work is motivated by the need to develop a comprehensive understanding of the statistical measures of thermodynamic entropy in quantum systems - a topic intimately connected to the phenomenon of quantum thermalization. In particular, we investigate the conditions under which the von Neumann entropy can be regarded as a valid statistical measure of thermodynamic entropy in quantum systems. This paper demonstrates that the equivalence between the von Neumann and thermodynamic entropies is not universal, but instead depends on several subtle and often overlooked assumptions. In this context, we also briefly revisit key criticisms of von Neumann entropy - particularly its time-invariance and subadditivity - and argue that these concerns can be meaningfully addressed in the setting of thermodynamic systems. To substantiate some arguments and to clarify some issues, we provide suitable numerical results from our analysis of a spin-1/2 system.

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Classical formulations of the entropy concept and its interpretation are introduced. This is to motivate the definition of the quantum von Neumann entropy. Some general properties of quantum entropy are developed, such as the quantum entropy which always increases. The current state of the area that includes thermodynamics and quantum mechanics is reviewed. This interaction shall be critical for the development of nonequilibrium thermodynamics. The Jarzynski inequality is developed in two separate but related ways. The nature of irreversibility and its role in physics are considered as well. Finally, a specific quantum spin model is defined and is studied in such a way as to illustrate many of the subjects that have appeared.

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.

The quantum entropy is usually defined using von Neumann's formula, which measures lack of information and vanishes for pure states. In contrast, we obtain a formula for the entropy of a pure state as it is measured from thermodynamic experiments, solely from the self-entanglement of the wave function, and find strong numerical evidence that the two are in agreement for nonintegrable systems, both for energy eigenstates and for states that are obtained at long times under the evolution of more general initial conditions. This is an extension of Boltzmann's hypothesis for classical systems, relating microscopic motion to thermodynamics.

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.