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Journal of Mathematical Physics

Derivation of the Generalized Boltzmann Equation in Quantum Statistical Mechanics

Tohru Morita

Published Jun 1, 1966• 8 citations
Publisher

Abstract

The hierarchy of the equations of motion for the reduced density matrices in quantum statistical mechanics is solved and the (cumulant) reduced density matrices at a time t are expressed in terms of those at an earlier time t0. Diagrams are introduced to express the results. With the aid of the technique of partial summations, the general term in the kinetic equation for the one-particle reduced density matrix or the generalized Boltzmann equation in quantum statistical mechanics is obtained. The equation is non-Markovian. A method of reducing the equation to Markovian is sketched.

DOI
10.1063/1.1704996

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The hierarchy of the equations of motion for the reduced density matrices in quantum statistical mechanics is solved and the (cumulant) reduced density matrices at a time t are expressed in terms of those at an earlier time t0. Diagrams are introduced to express the results. With the aid of the technique of partial summations, the general term in the kinetic equation for the one-particle reduced density matrix or the generalized Boltzmann equation in quantum statistical mechanics is obtained. The equation is non-Markovian. A method of reducing the equation to Markovian is sketched.
By means of the time-smoothing method developed in the previous papers of this series, the quantum kinetic equation is derived from the principles of statistical mechanics. In this paper, we avoid the BBGKY hierarchy; instead we use the Liouville-von Neumann equation for the time-smoothed density matrix. The Boltzmann distribution function is defined in terms of this time-smoothed density matrix. The present scheme may be applied to strong-coupling systems even if they are not in near equilibrium.
The rigorous evolution equation for the one-body density matrix n ( t ) describing a quantum system of interacting particles is not closed according to the investigations of Bogoliubov, Born, Green, Kirkwood, Yvon and others (B-B-G-K-Y hierarchy). The analysis of this equation is made in terms of connected diagrams. It is found that in the limits of large volume and time this equation can be reduced to a generalized Boltzmann equation which is a closed equation with respect to n ( t ) and which can rigorously describe linear and non-linear transport coefficients.
A recently developed method [Semkat et al., Phys. Rev. E 59, 1557 (1999); Kremp et al., in Progress in Nonequilibrium Green’s Functions (World Scientific, Singapore, 2000), p. 34] for incorporating initial binary correlations into the Kadanoff–Baym equations (KBE) is used to derive a generalized T-matrix approximation for the self-energies. It is shown that the T-matrix obtains additional contributions arising from initial correlations. Using these results and taking the time-diagonal limit of the KBE, a generalized quantum kinetic equation in binary collision approximation is derived. This equation is a far-reaching generalization of Boltzmann-type kinetic equations: It self-consistently includes memory effects (retardation, off-shell T-matrices) as well as many-particle effects (damping, in-medium T-matrices) and spin-statistics effects (Pauli-blocking).
The new approach in quantum statistical mechanics proposed by the author in previous publications is extended to systems of nonzero-spin particles. It is shown that properties of particles relevant to their spin can well be incorporated into the approach proposed. In so doing the principal ideas of the approach undergo no changes and lead to a hierarchy of equations for reduced density matrices at thermodynamic equilibrium that generalizes the hierarchy obtained earlier for spinless particles. Thermodynamics based on the hierarchy is worked out as well. The hierarchy and relevant thermodynamics enable one to calculate both thermodynamical properties of a system of particles and structural ones. With the help of perturbation expansions it is shown that the hierarchy has a solution and the solution is unique at least in the case of a weakly interacting system. Using the example of a hard-sphere system wherein triplet correlations are disregarded it is demonstrated that the hierarchy may serve as basis for deriving various results. Comparison of these results with results of other theoretical treatments evidences complete agreement within the limits allowed by the approximation used.
Abstract In this chapter, we continue our parallel exploration of statistical and computational physics, but now move to the field of quantum mechanics, where the density matrix generalizes the classical Boltzmann distribution. The density matrix constructs the quantum statistical probabilities from their two origins: the quantum mechanical wave functions and the Boltzmann probabilities of the energy levels. The density matrix can thus be defined in terms of the complete solution of the quantum problem (wave functions, energies), but all this information is available only in simple examples, such as the free particle or the harmonic oscillator. A simple general expression exists for the density matrix only at high temperature.