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The Journal of Chemical Physics

The Statistical Mechanical Theory of Transport Processes. V. Quantum Hydrodynamics

J. H. Irving, Robert W. Zwanzig

Published Sep 1, 1951• 127 citations
Publisher

Abstract

This paper is concerned with certain extensions of a formal technique devised by Wigner for handling problems in quantum-statistical mechanics, especially to problems in quantum-mechanical transport processes. The approach is to find the closest possible analogy between classical and quantum-statistical mechanics, so that the extensive work in classical statistical mechanics can be utilized. This analogy is attained with the Wigner distribution function, with which averages of dynamical variables in quantum mechanics may be calculated by integrations in phase space. We will first state some basic properties of distribution functions in classical statistical mechanics, and then state the corresponding properties of the density matrix in quantum mechanics. We will define and discuss the Wigner distribution function, show that it has the desired averaging properties, and obtain the analog of the Liouville equation satisfied by this function. We will derive the analog of the Liouville equation in reduced phase space, and then obtain the equations of hydro-dynamics from quantum-statistical mechanics.

DOI
10.1063/1.1748498

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This paper is concerned with certain extensions of a formal technique devised by Wigner for handling problems in quantum-statistical mechanics, especially to problems in quantum-mechanical transport processes. The approach is to find the closest possible analogy between classical and quantum-statistical mechanics, so that the extensive work in classical statistical mechanics can be utilized. This analogy is attained with the Wigner distribution function, with which averages of dynamical variables in quantum mechanics may be calculated by integrations in phase space. We will first state some basic properties of distribution functions in classical statistical mechanics, and then state the corresponding properties of the density matrix in quantum mechanics. We will define and discuss the Wigner distribution function, show that it has the desired averaging properties, and obtain the analog of the Liouville equation satisfied by this function. We will derive the analog of the Liouville equation in reduced phase space, and then obtain the equations of hydro-dynamics from quantum-statistical mechanics.
Abstract For present purposes, the first thing to recall about quantum mechanics is that all dynamical quantities, instead of being functions of the location of a system in phase space as in classical mechanics, are now represented by operators in a Hilbert space of quantum states. In particular, the quantum analog of the classical phase space distribution function is the quantum mechanical density matrix. Since this is seldom discussed in introductory texts on either quantum mechanics or statistical mechanics, it may be helpful to summarize some of its basic properties.
An attempt is made to interpret quantum mechanics as a statistical theory, or more exactly as a form of non-deterministic statistical dynamics. The paper falls into three parts. In the first, the distribution functions of the complete set of dynamical variables specifying a mechanical system (phase-space distributions), which are fundamental in any form of statistical dynamics, are expressed in terms of the wave vectors of quantum theory. This is shown to be equivalent to specifying a theory of functions of non-commuting operators, and may hence be considered as an interpretation of quantum kinematics . In the second part, the laws governing the transformation with time of these phase-space distributions are derived from the equations of motion of quantum dynamics and found to be of the required form for a dynamical stochastic process. It is shown that these phase-space transformation equations can be used as an alternative to the Schrödinger equation in the solution of quantum mechanical problems, such as the evolution with time of wave packets, collision problems and the calculation of transition probabilities in perturbed systems; an approximation method is derived for this purpose. The third part, quantum statistics , deals with the phase-space distribution of members of large assemblies, with a view to applications of quantum mechanics to kinetic theories of matter. Finally, the limitations of the theory, its uniqueness and the possibilities of experimental verification are discussed.
Correct use of the Wigner representation of quantum mechanics, which is realized with joint distributions of quasiprobabilities in phase space, requires the use of certain specific rules and attention to a number of properties which distinguish the quasiprobability from a true probability. This paper is mainly concerned with these problems. In the Wigner representation the quantum Liouville equation appears instead of the Schroedinger equation. The solution may have no physical meaning unless it is subjected to a necessary and sufficient condition which selects an allowed class of distributions which describe quantum-mechanical pure states. This condition contains Planck's constant and imposes, besides the uncertainty relations, severe restrictions on the possible form of the Wigner function. When this condition is satisfied, one can reconstruct the wave function from the Wigner function. In the case of an oscillator, the quantization condition for the energies of the stationary states does not follow from the Liouville equation, but from this supplementary condition. Unlike the true probability density, any Wigner function (except Gaussian ones) of a pure state takes on negative values. Another important peculiarity is that the quasiprobability is not concentrated on certain hypersurfaces, but is smeared out over the entire phase space. These and other features considered in this paper should be kept in mind when using the Wigner representation in quantum-mechanical problems.
By means of a quantum mechanical phase space distribution function introduced by von Roos, the Schroedinger equation for a non-relativistic system of N identical particles with scalar interactions is transformed into a quantum mechanical generalization of the Liouville equation, thereby formulating the problem in terms of a generalized density in phase space, a quantity of primary interest in most treatments of the corresponding classical system (or plasma). This transformation permits a parallel development of the theories of classical and quantum plasmas and thus allows the quantum many-body problem to be discussed virtually completely in classical terms. In particular, a kinetic theory of quantum plasmas is obtained by deriving the quantum analogue of the BBGKY hierarchy, and applying thereto approximation techniques similar to those of Rostocker and Rosenbluth, and Bogoliubov. The point of departure from similar previous studies based on the Wigner distribution function is that the proper exchange symmetry can be tractably introduced into the formalism. Attention is first focused on the Hartree and Hartree-Fock approximations, in which case the quantum BBGKY system reduces to a simple quantum generalization of the Vlasov equation. This equation is used to study the response of spatially homogeneous systems to weak external forces, and the associated problems of plasmon and spin-wave excitations. It is also used to derive the quantum and exchange corrected equations of inviscid hydrodynamical transport which are then applied to the problem of sound propagation in the degenerate electron gas. The second part of the study is concerned with the theory of the many-electron atom in the Hartree and Hartree-Fock approximations. The relevant quantum Vlasov equations lead naturally to a statistical theory of the atom which reduces to the Thomas-Fermi-Amaldi and Thomas Fermi models (respectively) as ħ → 0. For ħ ≠ 0, the quantum and exchange corrections to these models are simultaneously generated. The quantum hydrodynamical theory developed earlier is used to determine the influence of these corrections on the boundary conditions of the model, and a theory of the compressed atom is consequently obtained. Considered in somewhat less detail are the effects of non-zero temperature, net orbital angular momentum, relativity and correlations, as well as time dependent processes. The final part deals with the problem of the degenerate electron gas with a uniform neutralizing background. Going beyond the Hartree-Fock approximation, the pair functions for particles with parallel and anti-parallel spin are obtained by neglecting three particle correlations. From these functions, a quantum-mechanical collision integral is derived which differs from that obtained by Silin and Guernsey and conjectured by Wyld and Pines in that dynamical exchange effects are included. Also obtained from the pair function is an expression for the correlation which reduces in the high density limit to the result of Gell-Mann and Brueckner. At intermediate densities an additional term appears in the energy due to the screening of the exchange interaction by the dielectric properties of the medium. It is evaluated in the high density limit and found to be -0.151 r_s ln r_s Ryd/electron in marked disagreement with the corresponding value obtained by DuBois.
A derivation of the quantum-mechanical analog of the Maxwell-Boltzmann equation of transport for gases at low density is presented. The analysis requires: the definition of a time differential which is necessary for the selection of only secular variations in the time dependence of the distribution functions (coarse-graining in time); a binary collision approximation; the connection between the phase-space transformation function, relating the Wigner distribution function at different times, and the transition matrix in the theory of scattering of two particles; and a coarse graining in configuration space leading to a kinetic equation for spatially nonuniform systems. A consequence of the binary collision approximation is the exclusion of the effects of symmetrization (Bose-Einstein or Fermi-Dirac statistics) resulting in density-dependent terms.