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Physical Review A

Alternative derivation of the classical second law of thermodynamics

Ian M. Bassett

Published Nov 1, 1978• 36 citations
Publisher

Abstract

One of the classical statements of the second law of thermodynamics is derived from an assumption about the behavior of an isolated heat reservoir, together with a further assumption, which seems to be a rather weak one, about initial states. The derivation is otherwise based on the unitary property of time evolution in quantum mechanics. An analogous derivation, within the framework of classical mechanics, is also given; in this case Liouville's theorem substitutes for unitarity.

DOI
10.1103/physreva.18.2356

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One of the classical statements of the second law of thermodynamics is derived from an assumption about the behavior of an isolated heat reservoir, together with a further assumption, which seems to be a rather weak one, about initial states. The derivation is otherwise based on the unitary property of time evolution in quantum mechanics. An analogous derivation, within the framework of classical mechanics, is also given; in this case Liouville's theorem substitutes for unitarity.
The second law of thermodynamics states that the entropy of an isolated system can only increase over time. This appears to conflict with the reversible evolution of isolated quantum systems under the Schrödinger equation, which preserves the von Neumann entropy. Nonetheless, one finds that with respect to many observables, expectation values approach a fixed value—their equilibrium value. This ultimately raises the question: ? For classical systems, one introduces the assumption of a low-entropy initial state along with the concept of ignorance about the microscopic details of the physical system, leading to a statistical interpretation of the second law. By considering the observables through which we examine quantum systems, both these assumptions can be incorporated, building upon recent studies of the of observables. While the statistical behavior of observable expectation values is well established, a quantitative connection to entropy increase has been lacking so far. In deriving novel bounds for the equilibration of observables, and considering the entropy of the system relative to observables, we recover a variant of the second law: the entropy with respect to a given observable tends toward its equilibrium value in the course of the system’s unitary evolution. These results also support recent findings that question the necessity of nonintegrability for equilibration in quantum systems. We further illustrate our bounds using numerical results from the paradigmatic example of a quantum Ising model on a chain of spins. There, we observe entropy increasing up to equilibrium values, as well as fluctuations, which expose the underlying reversible evolution in accordance with the derived bounds.
A version of the second law of thermodynamics states that one cannot lower the energy of an isolated system by a cyclic operation. We prove this law without introducing statistical ensembles and by resorting only to quantum mechanics. We choose the initial state as a pure quantum state whose energy is almost E_0 but not too sharply concentrated at energy eigenvalues. Then after an arbitrary unitary time evolution which follows a typical "waiting time", the probability of observing the energy lower than E_0 is proved to be negligibly small.
The second law of thermodynamics states that for a thermally isolated system entropy never decreases. Most physical processes we observe in nature involve variations of macroscopic quantities over spatial and temporal scales much larger than microscopic molecular collision scales and thus can be considered as in local equilibrium. For a many-body system in local equilibrium a stronger version of the second law applies which says that the entropy production at each spacetime point should be non-negative. In this paper we provide a proof of the second law for such systems and a first derivation of the local second law. For this purpose we develop a general non-equilibrium effective field theory of slow degrees of freedom from integrating out fast degrees of freedom in a quantum many-body system and consider its classical limit. The key elements of the proof are the presence of a Z2Z_2Z2​ symmetry, which can be considered as a proxy for local equilibrium and micro-time-reversibility, and a classical remnant of quantum unitarity. The Z2Z_2Z2​ symmetry leads to a local current from a procedure analogous to that used in the Noether theorem. Unitarity leads to a definite sign of the divergence of the current. We also discuss the origin of an arrow of time, as well as the coincidence of causal and thermodynamical arrows of time. Applied to hydrodynamics, the proof gives a first-principle derivation of the phenomenological entropy current condition and provides a constructive procedure for obtaining the entropy current.
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.
We treat a quantum mechanical system with certain general properties which are expected to be common in macroscopic quantum systems. Starting from a PURE initial state (which may not describe an equilibrium) in which energy is mildly concentrated at a single value, we consider a time evolution determined by a time-dependent Hamiltonian as a model of an adiabatic operation in thermodynamics. We take a family of operations with the same procedure and various ``waiting times.'' Then the Minimum Work Principle is rigorously proved for almost all choices of the waiting time.