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Replicating the Second Law by Macroscopic Thermodynamic Theory derived from Quantum Mechanics

Hiroyasu Tajima, Eyuri Wakakuwa

Published Jan 4, 2016• 0 citations
OpenAlex

Abstract

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 $\vec{a}=(a_1,\cdots,a_L)$, which represents coarse-grained values of a set of physical quantities, and (2) An adiabatic transformation from an equilibrium state $\vec{a}$ to another state $\vec{a}'$ is possible if and only if $s_{\vec{a}}\le s_{\vec{a}'}$ holds. Here, $s_{\vec{a}}$ is a real-valued function corresponding to the thermodynamical entropy, which depends only on macroscopic variables $\vec{a}$. 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 $(U,V,N)$ expression of thermodynamics satisfying (1) and (2), using a toy model of free particles in a box.

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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.
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 second law of thermodynamics for adiabatic operations -- constraints on state transitions in closed systems under external control -- is one of the fundamental principles of thermodynamics. On the other hand, it is recently established that even pure quantum states can represent thermal equilibrium. However, pure quantum states do not satisfy the second law in that they are not passive, i.e., work can be extracted from them if arbitrary unitary operations are allowed. It therefore remains unresolved how quantum mechanics can be reconciled with thermodynamics. Here, based on our key quantum-mechanical notions of thermal equilibrium and adiabatic operations, we address the emergence of the second law for adiabatic operations in the thermodynamics limit. We first introduce infinite-observable macroscopic thermal equilibrium (iMATE); a quantum state, including pure states, is in iMATE if the expectation values of all additive observables agree with their equilibrium values. We also introduce a macroscopic operation as unitary evolution generated by a time-dependent additive Hamiltonian, which is regarded as corresponding to adiabatic operations. Employing these concepts, we show that no extensive work can be extracted from any quantum state in iMATE through any macroscopic operations. Furthermore, we introduce a quantum-mechanical form of entropy density such that it agrees with thermodynamic entropy density for any quantum state in iMATE. We then prove that for any initial state in iMATE, this entropy density cannot be decreased by any macroscopic operations, followed by a time-independent relaxation process. Our theory thus proves two different forms of the second law, by adopting macroscopically reasonable classes of observables, equilibrium states, and operations. We also discuss the time scales of macroscopic operations in these results.
Deriving the laws of thermodynamics from a microscopic picture is a central quest of statistical mechanics.This tutorial focuses on the derivation of the first and second law for isolated and open quantum systems far from equilibrium, where such foundational questions also become practically relevant for emergent nanotechnologies.The derivation is based on a microscopic definition of five essential quantities: internal energy, thermodynamic entropy, work, heat, and temperature.These definitions are shown to satisfy the phenomenological laws of nonequilibrium thermodynamics for a large class of states and processes.The consistency with previous results is demonstrated.The framework applies to multiple baths including particle transport and accounts for processes with, e.g., a changing temperature of the bath, which is determined microscopically.An integral fluctuation theorem for entropy production is satisfied.In summary, this tutorial introduces a consistent and versatile framework to understand and apply the laws of thermodynamics in the quantum regime and beyond.
Thermodynamics is commonly presented as a theory of macroscopic systems in stable equilibrium, built upon assumptions of extensivity and scaling with system size. In this paper, we present a universal formulation of the elementary foundations of thermodynamics, in which entropy and energy are defined and employed beyond equilibrium and without assuming extensivity. The formulation applies to all systems -- large and small, with many or few particles -- and to all states, whether equilibrium or nonequilibrium, by relying on carefully stated operational definitions and existence principles rather than macroscopic idealizations. Key thermodynamic concepts, including adiabatic availability and available energy, are developed and illustrated using the energy-entropy diagram representation of nonequilibrium states, which provides geometric insight into irreversibility and the limits of work extraction for systems of any size. A substantial part of the paper is devoted to the analysis of entropy transfer in non-work interactions, leading to precise definitions of heat interactions and heat-and-diffusion interactions of central importance in mesoscopic continuum theories of nonequilibrium behavior in simple and complex solids and fluids. As a direct consequence of this analysis, Clausius inequalities and the Clausius statement of the second law are derived in forms explicitly extended to nonequilibrium processes. The resulting framework presents thermodynamics as a universal theory whose concepts apply uniformly to all systems, large and small, and provides a coherent foundation for both teaching and modern applications.
We investigate fundamental connections between thermodynamics and quantum information theory. First, we show that the operational framework of thermal operations is nonequivalent to the framework of Gibbs-preserving maps, and we comment on this gap. We then introduce a fully information-theoretic framework generalizing the above by making further abstraction of physical quantities such as energy. It is technically convenient to work with and reproduces known results for finite-size quantum thermodynamics. With our framework we may determine the minimal work cost of implementing any logical process. In the case of information processing on memory registers with a degenerate Hamiltonian, the answer is given by the max-entropy, a measure of information known from quantum information theory. In the general case, we obtain a new information measure, the "coherent relative entropy", which generalizes both the conditional entropy and the relative entropy. It satisfies a collection of properties which justifies its interpretation as an entropy measure and which connects it to known quantities. We then present how, from our framework, macroscopic thermodynamics emerges by typicality, after singling out an appropriate class of thermodynamic states possessing some suitable reversibility property. A natural thermodynamic potential emerges, dictating possible state transformations, and whose differential describes the physics of the system. The textbook thermodynamics of a gas is recovered as well as the form of the second law relating thermodynamic entropy and heat exchange. Finally, noting that quantum states are relative to the observer, we see that the procedure above gives rise to a natural form of coarse-graining in quantum mechanics: Each observer can consistently apply the formalism of quantum information according to their own fundamental unit of information.
We treat the problem of the approach to thermal equilibrium by only resorting to quantum dynamics of an isolated macroscopic system. Inspired by the two important works in 2009 and in 1929, we have noted that a condition we call "thermodynamic normality" for a macroscopic observable guarantees the approach to equilibrium (in the sense that a measurement of the observable at time ttt almost certainly yields a result close to the corresponding microcanonical average for a sufficiently long and typical ttt). A crucial point is that we make no assumptions on the initial state of the system, except that its energy is distributed close to a certain macroscopic value. We also present three (rather artificial) models in which the thermodynamic normality can be established, thus providing concrete examples in which the approach to equilibrium is rigorously justified. Note that this kind of results which hold for ANY initial state are never possible in classical systems. We are thus dealing with a mechanism which is peculiar to quantum systems. The present note is written in a self-contained (and hopefully readable) manner. It only requires basic knowledge in quantum physics and equilibrium statistical mechanics.