This paper explores the possibility that linear dynamical maps might be used to describe the energy-conserving, entropy-increasing motions which occur in closed thermodynamic systems as they approach canonical thermal equilibrium. ForN-level quantum systems withN>2, we prove that no such maps exist which are independent of the initial state.

Several authors have hypothesized that completely positive maps should provide the means for generalizing quantum dynamics. In a critical analysis of that proposal, we show that such maps are incompatible with the standard phenomenological theory of spin relaxation and that the theoretical argument which has been offered as justification for the hypothesis is fallacious.

In this rejoinder to a critique by Raggio and Primas of our paper, “On Completely Positive Maps in Generalized Quantum Dynamics,” we acknowledge that, contrary to our original assertion, the Bloch equations are indeed completely positive. We then explain briefly why this modification of our analysis does not alter its main conclusions.

Using Schrödinger's generalized probability relations of quantum mechanics, it is possible to generate a canonical ensemble, the ensemble normally associated with thermodynamic equilibrium, by at least two methods, statistical mixing and subensemble selection, that do not involve thermodynamic equilibration. Thus the question arises as to whether an observer making measurements upon systems from a canonical ensemble can determine whether the systems were prepared by mixing, equilibration, or selection. Investigation of this issue exposes antinomies in quantum statistical thermodynamics. It is conjectured (...) that resolution of these paradoxes may involve a new law of motion in quantum dynamics. (shrink)

A dynamical analysis of standard procedures for subensemble selection is used to show that the state restriction violation proposal in Part I of the paper cannot be realized by employing familiar correlation schemes. However, it is shown that measurement of an observable not commuting with the superselection operator is possible, a violation of the observable restrictions. This is interpreted as supporting the position that each of these restrictions is sufficient but not necessary for the superselection rule. The results do constitute (...) a proposal for superselection rule violation in theories requiring both restrictions, e.g., the axiomatic treatment by Bogolubov, Logunov, and Todorov. It is also concluded that superselection rules place restrictions on procedures for selective state preparations using correlations. More generally, it is conjectured that a mathematically conceivable decomposition of a given density operator does not necessarily represent a possibility for partitioning of the corresponding ensemble into subensembles by any physically realizable means. (shrink)

A generalized Onsager reciprocity theorem emerges as an exact consequence of the structure of the nonlinear equation of motion of quantum thermodynamics and is valid for all the dissipative nonequilibrium states, close and far from stable thermodynamic equilibrium, of an isolated system composed of a single constituent of matter with a finite-dimensional Hilbert space. In addition, a dispersion-dissipation theorem results in a precise relation between the generalized dissipative conductivity that describes the mutual interrelation between dissipative rates of a pair of (...) observables and the codispersions of the same observables and the generators of the motion. These results are presented together with a review of quantum thermodynamic postulates and general results. (shrink)