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arXiv:1307.0610

Direct derivation of microcanonical ensemble average from many-particle quantum mechanics

T. Saso

Published Jul 2, 2013• 0 citations
arXivHTMLPDF

Abstract

Starting from the quantum mechanics for $N$ particles, we show that we can directly derive the microcanonical ensemble average of the physical quantity $A$ by using only the long time average and the equal probability assumption for the equal energy states. The system is considered to be embedded in the outer world and we describe them in terms of the density matrix method.

DOI
10.48550/arxiv.1307.0610

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Starting from the quantum mechanics for NNN particles, we show that we can directly derive the microcanonical ensemble average of the physical quantity AAA by using only the long time average and the equal probability assumption for the equal energy states. The system is considered to be embedded in the outer world and we describe them in terms of the density matrix method.
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We propose a new approach to justify the use of the microcanonical ensemble for isolated macroscopic quantum systems. Since there are huge number of independent observables in a macroscopic system, we cannot see all of them. Actually what we observe can be written in a rather simple combination of local observables. Considering this limitation, we show that almost all states in a energy shell are practically indistinguishable from one another, and hence from the microcanonical ensemble. In particular, the expectation value of a macroscopic observable is very close to its microcanonical ensemble average for almost all states.
We develop a regularization of the quantum microcanonical ensemble, called a Gaussian ensemble, which can be used for derivation of the canonical ensemble from microcanonical principles. The derivation differs from the usual methods by giving an explanation for the, at the first sight unreasonable, effectiveness of the canonical ensemble when applied to certain small, isolated, systems. This method also allows a direct identification between the parameters of the microcanonical and the canonical ensemble and it yields simple indicators and rigorous bounds for the effectiveness of the approximation. Finally, we derive an asymptotic expansion of the microcanonical corrections to the canonical ensemble for those systems, which are near, but not quite, at the thermodynamical limit and show how and why the canonical ensemble can be applied also for systems with an exponentially increasing density of states. The aim throughout the paper is to keep mathematical rigour intact while attempting to produce results which are both physically and practically interesting.
The study of quantum statistical mechanics begins with a review of the basic principles of quantum mechanics. Schrödinger’s equation is introduced and Eigenstates (or stationary states) are defined. Model probability for quantum statistics is assumed to have a uniform distribution in phases. Wave functions for many-body systems are defined. The density matrix is introduced. The Planck entropy and the microcanonical ensemble are defined. The differences between classical and quantum statistical mechanics are all based on the differing concepts of a microscopic ‘state’. While the classical microscopic state (specified by a point in phase space) determines the exact position and momentum of every particle, the quantum mechanical state determines neither; quantum states can only provide probability distributions for observable quantities.
Classical statistical mechanics tries to derive the macroscopic properties of matter starting from the mechanical laws that rule the behaviour of single particles. To describe equilibrium states, only observables accounting for correlations among states are considered, and only systems consisting of a large number of particles are taken into account. The observables are described by continuous functions on phase space, and the states are represented by linear assignments of a number to each observable. Within the framework of the canonical ensemble, one deals with mechanical systems in thermal equilibrium with a thermal reservoir, and the equilibrium state is reached as a result of the interaction with the external world. The external world may be really external, or equally well, the unrecognized internal degrees of freedom, like in the calculation of viscosity or thermal conductivity. If really only the external world is the cause we may expect some surface dependence while an internal unrecognized degree of freedom would have a volume effect, unless the interactions are long range. The microcanonical ensemble is instead introduced to study isolated mechanical systems, and the equilibrium is viewed as a temporal average, rather than as a limit. Attention is then focused on partition functions, the theorem of equipartition of energy and an elementary theory of specific heats. In the second part, the Planck derivation of the law of black-body radiation is analysed, presenting in chronological order the Kirchhoff theorem, the Stefan law, the Wien displacement law, the Rayleigh–Jeans formula and the Planck hypothesis. Further topics discussed are the Einstein and Debye quantum models for specific heats of solids. These topics prepare the ground for the introduction of quantum statistical mechanics. The third part is, in fact, devoted to the analysis of identical particles in quantum mechanics.