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arXiv:quant-ph/9703006

Quantum Mechanics as a Classical Theory XV: Thermodynamical Derivation

L. S. F. Olavo

Published Mar 5, 1997• 2 citations
arXivHTMLPDF

Abstract

We present in this continuation paper a new axiomatic derivation of the Schrödinger equation from three basic postulates. This new derivation sheds some light on the thermodynamic character of the quantum formalism. We also show the formal connection between this derivation and the one previously done by other means. Some considerations about metaestability are also drawn. We return to an example previously developed to show how the connection between both derivations works.

DOI
10.48550/arxiv.quant-ph/9703006

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We present in this continuation paper a new axiomatic derivation of the Schrödinger equation from three basic postulates. This new derivation sheds some light on the thermodynamic character of the quantum formalism. We also show the formal connection between this derivation and the one previously done by other means. Some considerations about metaestability are also drawn. We return to an example previously developed to show how the connection between both derivations works.
In a previous paper, we have mathematically derived the Schrödinger equation using the construct of a Characteristic Function. We have shown that this derivation has a great number of consequences and may help to understand what Quantum Mechanics is really about. In this paper, we present another axiomatic mathematical derivation based on the construct of Boltzmann’s entropy. We also show how these two derivations are mathematically connected and obtain, from this, the positive definite phase space probability distribution function. This probability distribution function is shown to be the only one that reproduces the Schrödinger equation and maximizes entropy, while minimizing the energy. Bohmian Mechanics is considered and reinterpreted from the perspective of the mathematical results of the present approach. Some examples are worked out to give teachers interested in using this material in their classrooms some concreteness.
An axiomatic approach to quantum mechanics that has, as a theorem, the Schrödinger equation may be of enormous value to cope with interpretation issues, since all the interpretation constructs must be present in the axioms, or directly derived by them from their mathematical unfolding. Thus, it is critical to show that this axiomatic derivation is reliable beyond any possible doubt. To show this, it is possible to make generalizations and extensions of the axioms to derive the Schrödinger equation in the underlying generalized or extended formats. In previous papers, we have shown that the axiomatic approach we propose can be used to derive the Schrödinger equation as a direct axiom. Since then, we have also shown that it was possible to generalize that derivation to coordinate systems other than the Cartesian, as well as its relativistic extensions that lead to the relativistic wave equations. An extension to dissipative systems was also performed, allowing us to mathematically derive the Caldirola–Kanai equation from first principles. All these derivations were performed using pure states and in the absence of the electromagnetic field. This means that we can further generalize the approach to embrace these two possibilities. Being an axiomatic approach, we show that we need only to slightly modify the axioms to derive the Schrödinger equation for these two contexts. Despite being quite direct, the algebraic complexity of these derivations should give the reader the desired confidence in the proposed axioms.
We found in the previous chapter that the molecular partition function is required to determine the thermodynamic properties of an ideal gas. To evaluate the partition function, specification of pertinent energy levels and degeneracies is necessary. Such knowledge demands that we investigate at least the rudiments of quantum mechanics, and especially those quantum concepts required for subsequent applications to statistical thermodynamics. For this reason, we concentrate in the next few chapters on the Schrödinger wave equation, whose various solutions provide the ε j 's and g j 's needed for the eventual calculation of thermodynamic properties. Depending on your academic background, you might thus consider reviewing classical mechanics (Appendix G) and operator theory (Appendix H) in preparation for your upcoming study of quantum mechanics. We begin this chapter with a historical review of the developments leading to the formulation of quantum mechanics, subsequently focusing on the Bohr model for atomic hydrogen and the de Broglie hypothesis for matter waves. We then introduce the Schrödinger wave equation, the basic postulates of quantum mechanics, and salient insights from these postulates germane to the development of statistical thermodynamics. We next apply the Schrödinger wave equation to the translation energy mode of an atom or molecule. This application conveniently explains both quantum states and quantum numbers, including their relation to our previous notions of microstate and macrostate. We end this chapter by discussing the Heisenberg uncertainty principle, including its utility in defining indistinguishability and symmetry conditions for multiparticle systems.
It is shown that Schrödinger's equation may be derived from three postulates. The first is a kind of statistical metamorphosis of classical mechanics, a set of two relations which are obtained from the canonical equations of particle mechanics by replacing all observables by statistical averages. The second is a local conservation law of probability with a probability current which takes the form of a gradient. The third is a principle of maximal disorder as realized by the requirement of minimal Fisher information. The rule for calculating expectation values is obtained from a fourth postulate, the requirement of energy conservation in the mean. The fact that all these basic relations of quantum theory may be derived from premises which are statistical in character is interpreted as a strong argument in favor of the statistical interpretation of quantum mechanics. The structures of quantum theory and classical statistical theories are compared, and some fundamental differences are identified.
An alternative method is proposed for deriving the time dependent Schroedinger equation from the pictures of wave and matrix mechanics. The derivation is of a mixed classical quantum character, since time is treated as a classical variable, thus avoiding any controversy over its meaning in quantum mechanics. The derivation method proposed in this paper requires no ad hoc assumption and avoids going through a second-order differential equation that can be reduced to the well known time-dependent Schroedinger equation only postulating a complex wavefunction with an exponential time dependence, as did by Schroedinger in its original paper of 1926.
In this continuation paper the theory is further extended to reveal the connection between its formal aparatus, dealing with microscopic quantities, and the formal aparatus of thermodynamics, related to macroscopic properties of large systems. We will also derive the Born-Sommerfeld quantization rules from the formalism of the infinitesimal Wigner-Moyal transformations and, as a consequence of this result, we will also make a connection between the later and the path integral approach of Feynman. Some insights of the relation between quantum mechanics and equilibrium states will be given as a natural development of the interpretation of the above results.