Generalized master equations determining the time dependence of both diagonal and off-diagonal density matrix elements are derived. The equations are valid for systems of arbitrary size and initial conditions, and have all the generality of the von Neumann equation for the density matrix. They are general enough for use in determining all higher-order contributions to transport coefficients. Their advantage over the von Neumann equation is that they are in forms suited to reduction by time-independent many-body approximation techniques.
For a system described in a phase space of generalized coordinates w and momenta J, the generalized master equation gives the time evolution of the reduced-density distribution function ρ(t, J) for the momenta. A generalization of the generalized master equation, having a similar non-Markoffian form, is derived for the full distribution function ρ(t, w, J). This equation is an alternate form of the Liouville equation. The derivation is an extension of a previous derivation of the generalized master equation from the Liouville equation utilizing projection operators in a Hilbert space. The time-evolution equation for the reduced distribution function ρr(t, wr, J), depending on the subset wr of the set of coordinates w, is derived. The approach to a stationary state for t → ∞ is discussed.
A formal density expansion of transport coefficients expressed in terms of momentum autocorrelation functions is derived for a degenerate quantum gas (Bose-Einstein or Fermi-Dirac statistics) at any frequency and for noncentral as well as central forces. The result to lowest order in density is reduced to the solution of a well-defined quantum two-body problem, and the first density correction is reduced to the solution of a well-defined quantum three-body problem. It is confirmed that at zero frequency one only needs the asymptotic forms of the collision operator to calculate quantum transport coefficients. It is further pointed out that the coefficients of the third- and higher order terms of the density expansion diverge at zero frequency, in analogy with the classical case. A "renormalization" is suggested which, it is believed, leads to a nonanalytic density dependence for quantum gases distinct from the nonanalytic behavior associated with degeneracy statistics.
A method, similar to the one previously used by the author in his derivation of a generalized classical virial theorem (see ibid., vol.10, no.4, p.507 (1977)), is used to derive a generalized quantum virial equation. This equation is applicable to any part of a larger system of particles. Furthermore, by the introduction of a flux density operator, it is possible to express the quantum surface flux virial in two alternative forms, as easily interpreted as the classical form. As an intermediate result, an equation of continuity for a general one-particle observable is obtained. In an appendix, an equation of motion of the reduced density matrix of the first order is derived.
In a previous paper we showed how time-dependent projection operators may be employed to enable the Nakajima-Zwanzig projection-operator technique for deriving exact master equations to deal efficiently with two or more coupled classical or quantum systems, neither of which is reservoir like. We considered in detail the case where the relevant part of the classical-system probability-density function (PDF) or quantumsystem density operator (DO) is a product of the PDF's or DO's for the separate subsystems, and we applied the techniques developed to problems in quantum optics and in the kinetic theory of dilute nonideal gases. In this paper we make the time-dependent projection-operator approach useful for a greater variety of systems by allowing the relevant part of the PDF or DO to include correlations between two of the interacting subsystems. This extension allows us to describe well the dynamics of strongly interacting systems in a low degree of approximation while avoiding the use of infinite resummations. We derive exact generalized master equations in this manner for the same two cases as in our earlier work, namely a classical gas of
N molecules interacting via a two-body potential and a quantum-optical system of
N two-level atoms interacting with an electromagnetic field. In the former case, the relevant part of the PDF contains two-body correlations, and we obtain two exact coupled master equations for the singlet and doublet PDF's
F1(t) and
F2(t). In the latter case, the relevant part of the DO contains atom-field correlations, and the result is three exact coupled equations for the single-atom DO ${\ensuremath{\rho}}_{1}(t)$, the field DO
R(t), and the DO for one atom plus the field $\ensuremath{\chi}(t)$. From the exact equations we derive approximate equations by making simplifying assumptions. In the case of the gas we carry out a straightforward density expansion of the ${\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{F}}_{2}$ master equation and obtain a set of kinetic equations for dense gases, which have been derived previously by Frieman, Goldman, and Dorfman and which describe well effects due to the finite mean free path. In the quantum-optical case we derive kinetic equations for a single-mode laser by treating the $\stackrel{\ifmmode \dot{}\else \.{}\fi{}}{\ensuremath{\chi}}$ equation in the Born-Markoff approximation. The equations describe gain saturation and other effects on the field dynamics which are of infinite order in the atom-field coupling constant. It is shown that these equations reduce to previously derived laser master equations if atom-atom correlations can be neglected. Finally, we mention possible generalizations of the time-dependent projection-operator approach used in this paper and briefly discuss its application to other problems, including the kinetics of liquids, collisional line broadening, superradiance, and amplified spontaneous emission.
We consider a system perturbed by an external field and subject to dissipative processes. From the von Neumann equation for such a system in the weak coupling limit we derive an inhomogeneous master equation, i.e., a master equation with dissipative terms and streaming terms, using Zwanzig’s projection operator technique in Liouville space. From this equation the response function, as well as expressions for the generalized conductivity and susceptibility, is obtained. It is shown that for large times only the diagonal part of the density operator is required. The various expressions are found to be in complete harmony with previous results (Part I) obtained via the van Hove limit of the Kubo–Green linear response formulas. In order to account for the properties at quantum frequencies, the evolution of the nondiagonal part in the weak coupling limit is also established. The complete time dependent behavior of the dynamic variables in the van Hove limit is expressed by B (t) =exp[−(Λd−iℒ0) t] B, where Λd is the master operator and L0 the Liouville operator in the interaction picture. The cause of irreversibility is discussed. Finally, the inhomogeneous master equation is employed to obtain as first moment equation a Boltzmann equation with streaming terms, applicable to quantum systems.