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Physical Review

Equations of Motion in Nonequilibrium Statistical Mechanics

Baldwin Robertson

Published Apr 8, 1966• 399 citations
Publisher

Abstract

Exact equations of motion for the space- and time-dependent thermodynamic coordinates of a many-body system are derived directly from the Liouville equation. This is done by definining a generalized canonical density operator depending only upon present values of the thermodynamic coordinates. This operator is used no matter how far the system is from equilibrium. An explicit expression for the entropy of a system possibly not in equilibrium is given in terms of this operator. The equation of motion for the operator is derived, and the coupled, nonlinear, integrodifferential equations of motion for the thermodynamic coordinates follow immediately.

DOI
10.1103/physrev.144.151

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Exact equations of motion for the space- and time-dependent thermodynamic coordinates of a many-body system are derived directly from the Liouville equation. This is done by definining a generalized canonical density operator depending only upon present values of the thermodynamic coordinates. This operator is used no matter how far the system is from equilibrium. An explicit expression for the entropy of a system possibly not in equilibrium is given in terms of this operator. The equation of motion for the operator is derived, and the coupled, nonlinear, integrodifferential equations of motion for the thermodynamic coordinates follow immediately.
Differential conservation equations are derived for the mass-, momentum-, and energy-density operators for a 1-component simple fluid of Bose or Fermi particles with arbitrary pairwise interactions. These equations are used in a statistical mechanical derivation of exact equations of motion for the expectations of these operators. The equations of motion are coupled to equations relating these expectations to the local temperature, chemical potential, and fluid velocity. The coupled equations are closed in the sense that the expectations and their thermodynamic conjugates listed above are the only unknowns, although some of the dependence in the equations on the conjugates is expressed only implicitly. The equations of motion are memory-retaining nonlocal generalizations of the classical hydrodynamic equations and apply to a normal fluid arbitrarily far from equilibrium. The formalism is not carried as far as has the corresponding classical formalism because the local equilibrium expectation of the momentum density here does not equal the fluid velocity times the expectation of the mass density as is true in classical statistical mechanics.
Entropy in nonequilibrium statistical mechanics is investigated theoretically so as to extend the well-established equilibrium framework to open nonequilibrium systems. We first derive a microscopic expression of nonequilibrium entropy for an assembly of identical bosons/fermions interacting via a two-body potential. This is performed by starting from the Dyson equation on the Keldysh contour and following closely the procedure of Ivanov, Knoll and Voskresensky [Nucl. Phys. A {\bf 672} (2000) 313]. The obtained expression is identical in form with an exact expression of equilibrium entropy and obeys an equation of motion which satisfies the HHH-theorem in a limiting case. Thus, entropy can be defined unambiguously in nonequilibrium systems so as to embrace equilibrium statistical mechanics. This expression, however, differs from the one obtained by Ivanov {\em et al}., and we show explicitly that their ``memory corrections'' are not necessary. Based on our expression of nonequilibrium entropy, we then propose the following principle of maximum entropy for nonequilibrium steady states: ``The state which is realized most probably among possible steady states without time evolution is the one that makes entropy maximum as a function of mechanical variables, such as the total particle number, energy, momentum, energy flux, etc.'' During the course of the study, we also develop a compact real-time perturbation expansion in terms of the matrix Keldysh Green's function.
The dynamics of a quantum system coupled to a classical environment and subject to constraints that drive it out of equilibrium are described. The evolution of the system is governed by the quantum-classical Liouville equation. Rather than evaluating the evolution of the mixed quantum-classical density operator, we derive exact equations of motion for the nonequilibrium average values of a set of operators or variables, along with correlation function expressions for the dissipative coefficients that enter these equations. These equations are obtained by requiring that the exact nonequilibrium averages are equal to local nonequilibrium averages that depend on auxiliary fields whose values satisfy evolution equations obtained using projection operator methods. The results are illustrated by deriving reaction-diffusion equations coupled to fluid hydrodynamic equations for a solution of quantum particles that can exist in two metastable states. Nonequilibrium steady states are discussed along with the reaction rate and diffusion correlation functions that characterize such states.
The nonlinear equation of motion that accomplishes a self-consistent unification of quantum mechanics (QM) and thermodynamics conceptually different from the (von Neumann) foundations of quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but which reduces to the same mathematics for the thermodynamic equilibrium (TE) states, and contains standard QM in that it reduces to the time-dependent Schrodinger equation for zero entropy states is discussed in full mathematical detail. By restricting the discussion to a strictly isolated system (noninteracting, disentangled and uncorrelated), we show how the theory departs from the conventional QSM/QIT rationalization of the second law of thermodynamics, which instead emerges in QT (quantum thermodynamics) as a theorem of existence and uniqueness of a stable equilibrium state for each set of mean values of the energy and the number of constituent particles. To achieve this, the theory assumes Trρ lnρ B −k for the physical entropy and is designed to implement two fundamental ansatzs: (1) that in addition to the standard QM states described by idempotent density operators (zero entropy), a strictly isolated and uncorrelated system admits also states that must be described by non-idempotent density operators (nonzero entropy); (2) that for such additional states the law of causal evolution is determined by the simultaneous action of a Schrodinger-von Neumann-type Hamiltonian generator and a nonlinear dissipative generator which conserves the mean values of the energy and the number of constituent particles, and in forward time drives the density operator in the 'direction' of steepest entropy ascent (maximal entropy generation). The resulting dynamics is well defined for all non-equilibrium states, no matter how far from TE. Existence and uniqueness of solutions of the Cauchy initial value problem for all density operators implies that the equation of motion can be solved not only in forward time, to describe relaxation towards TE, but also in backward time, to reconstruct the 'ancestral' or primordial lowest entropy state or limit cycle from which the system originates. Zero entropy states as well as a well defined family of non-dissipative states evolve unitarily according to pure Hamiltonian dynamics and can be viewed as unstable limit cycles of the general nonlinear dynamics.
A theory of non-equilibrium thermodynamics is developed. The general method to derive the closed set of kinetic equations for expectation values of physical quantities is developed, by making use of the functional Taylor expansion with respect to expectation values of physical quantities around the reference state. For this purpose, a definition of the thermodynamic state in the system whose state changes with time is presented in order to describe the general state of the many-body system from the unified point of view. The statistical mechanical probability distribution functions for the quantum-mechanical expectation values at the stationary state are developed, without making use of the concept of the constant of the motion. The relation between the expectation value and the most probable value for the probability distribution function is discussed, and it is found that both values are equivalent to each other, if the system is extended infinitely in space and time. Thus the condition for the thermodynamic limit may be defined in a generalized way. Our method is looked as a perturbational one in the equilibrium statistical mechanics, though the choice of the reference state is arbitrary.
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.