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American Journal of Physics

Unified formulation of quantum and statistical mechanics

Z. Onyszkiewicz

Published Sep 1, 1984• 2 citations
Publisher

Abstract

Using one and the same simple variational principle for average energy, a new equation is obtained equivalent to the set of two equations: the time-independent Schrödinger equation and that describing canonical Gibbs distribution.
DOI
10.1119/1.13540

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A path-integral formulation of quantum mechanics is investigated which is closely related to that of Feynman. It differs from Feynman's formulation in that it involves the Hamiltonian function of the canonically conjugate coordinates and momenta. The classical limit yields the variational principle: $\ensuremath{\delta}ff(p\ifmmode\ddagger\else\textdaggerdbl\fi{}\ensuremath{-}N)dt=0$. A path-integral formula is also obtained for the energy eigenstate projection operator associated with the time-independent Schr\"odinger equation. The classical limit of the projection operator formula yields a modified form of the well-known variational principle for the phase-space orbit of given energy. Relativistically covariant Hamiltonian variational principles are analyzed and lead naturally to a relativistic scalar wave equation which involves a proper time variable which is canonically conjugate to the mass in the same manner as the ordinary time variable is conjugate to the energy in nonrelativistic quantum theory.
In a previous article in this series [E. M. Corson, J. Math. Phys. 4, 42(1963); herein referred to as I], we showed that a new variational principle, of Lagrangian structure, includes Hamilton's principle as a unique derived consequent and encompasses both the classical and quantal definitions of ``state'' and the corresponding Lagrangian and Schrödinger equations of motion, respectively. In this theory, the essential difference between classical and quantal domains was shown to arise solely from the superadded postulates of determinism vs indeterminism; other than this, the two basic postulates may be reduced to (a) Newton's equations and (b) the new variation principle. It was shown that in the quantal domain, Schrödinger's equations obtain for the transition amplitudes (propagators) between pure eigenstates of homologous variables in configuration space, at different times, thus clearly implying all the results of conventional Hamiltonian-operator quantum formalism. In the present article we show that our variational formulation, under the familiar classical canonical transformation to momentum space, also automatically leads to the corresponding Schrödinger equations for the transition amplitudes between pure eigenstates of homologous variables in momentum space, at different times, the unitarity of the formalism and the reciprocal Fourier integral relations between coordinate and momentum representations. Thus we bridge a long-standing gap in theory and derive, uniquely and apparently for the first time, the basic quantum commutators (P.B.'s) which are postulated in the more familiar Hamiltonian theory.
We address the paradoxical transformation of a classical-mechanical particle motion when the space and time scales of observation pass below the uncertainty principle threshold. This is analyzed in the language of classical statistical mechanics, considering specifically many-particle systems inhomogeneous along one spatial direction. We employ the density functional formalism in its square-gradient form and find: (i) The macroscopic solution is analogous to the classical trajectory of a particle under a potential of force given by (minus) the free energy density. Whereas, (ii) fluctuations around the solution in (i) are equal to the quantum-mechanical wave functions of a particle under a potential given by the curvature of the free energy density. We illustrate this situation with three textbook examples: A particle in a box, the harmonic oscillator, and the hydrogen atom. We show that their time-independent Schrödinger equation wave functions describe, respectively, the fluctuations of a fluid interface, of critical point fluctuations, and of a confined ideal gas. At large scales, sharp probability distributions make fluctuations irrelevant; the vanishing of the first variation yields the macroscopically observable statistical-mechanical non-uniformity, equivalent to the classical particle trajectory. But at sufficiently small scales, with necessarily very few particles, distributions appear much wider, fluctuations dominate, and one obtains the Schrödinger equation (for the microscopic potential).