In this didactical note I review in depth the rationale for using generalised canonical distributions in quantum statistics. Particular attention is paid to the proper definitions of quantum entropy and quantum relative entropy, as well as to quantum state reconstruction on the basis of incomplete data. There are two appendices in which I outline how generalised canonical distributions link to the conventional formulation of statistical mechanics, and how classical probability calculus emerges at the macroscopic level.
In this didactical note I review in depth the rationale for using generalised canonical distributions in quantum statistics. Particular attention is paid to the proper definitions of quantum entropy and quantum relative entropy, as well as to quantum state reconstruction on the basis of incomplete data. There are two appendices in which I outline how generalised canonical distributions link to the conventional formulation of statistical mechanics, and how classical probability calculus emerges at the macroscopic level.
The paper discusses the physical groundlessness of the models used for the derivation of canonical distribution and provides the experimental data demonstrating the incompleteness of quantum mechanics. The possibility of using statistical ensembles is presented as a consequence of the existence of probabilistic processes which are not accounted for by quantum mechanics. The paper provides a new analytical derivation of canonical distribution for macrosystems which takes into account subquantum processes. The paper discusses the possibility of the experimental study of a probability which is beyond quantum mechanics.
The concept of entropy is central to the formulation of the quantum statistical mechanics, and it is linked to the definition of the density operator and the associated probabilities of occupation of quantum states. The extension of this scheme to accommodate for quantum decaying states is conceptually difficult, because of the nature of these states. Here we present a way to treat quantum unstable states in the context of statistical mechanics. We focuss on the definition of the entropy and avoid the use of complex temperatures.
We examine the fundamental aspects of statistical mechanics, dividing the problem into a discussion purely about probability, which we analyse from a Bayesian standpoint. We argue that the existence of a unique maximising probability distribution {p(j∣K)} for states labelled by j given data K implies that the corresponding maximal value of the information entropy σ({(pj∣K)})=−∑j(pj∣K)ln(pj∣K) depends explicitly on the data at equilibrium and on the Hamiltonian of the system. As such, it is a direct measure of our uncertainty about the exact state of the body and can be identified with the traditional thermodynamic entropy. We consider the well known microcanonical, canonical and grand canonical methods and ensure that the fluctuations about mean values are generally minuscule for macroscopic systems before identifying these mean values with experimental observables and thereby connecting to many standard results from thermodynamics. Unexpectedly, we find that it is not generally possible for a quantum process to be both isentropic and reversibly adiabatic. This is in sharp contrast to traditional thermodynamics where it is assumed that isentropic, reversible adiabatic processes can be summoned up on demand and easily realised. By contrast, we find that linear relations between pressures Pj and energies Ej are necessary and sufficient conditions for a quasi-static and adiabatic change to be isentropic, but, of course, this relationship only holds for a few especially simple systems, such as the perfect gas, and is not generally true for more complicated systems. By considering the associated entropy increases up to second order in small volume changes we argue that the consequences are in practice negligible.
Recently, the possibility of investigating single molecule, or single spin observables, as well as the necessity of a better understanding of the mechanisms underlying quantum dynamics in order to obtain nanoscale devices and nanostructered materials suitable for quantum computing tasks, have revived the interest in foundational aspects of quantum statistical mechanics. This thesis aims to give a contribution to this field by re-considering the statistical characterization of a quantum system at the light of some paradigmatic changes in our understanding of quantum theory which have taken place in the last two decades. In particular the impressive development of quantum information theory has changed the perceptions of quantum entanglement: for a long time it has been considered a somewhat paradoxical property of the matter at the atomic scale, but now it is regarded as an essential and ubiquitous phenomenon whose consequences are affecting the very macroscopic world that we experience. Still the decoherence program has brought out the importance of considering a quantum system together with its environment in order to clarify some key aspects of quantum dynamics. Thus, we start from the idea that quantum correlations are ubiquitous and somewhat uncontrollable in systems with many degrees of freedom which are typically considered in statistical mechanics. As a consequence we assume the standpoint that quantum statistical mechanics has not to be based on the underlying idea of a collection of many, independent quantum systems but rather it has to emerge at the level of a global wavefunction (pure state) which describes the system as well as its environment as a whole. In order to investigate the consequences of these assumptions we study the equilibrium distribution of an isolated quantum system. This is defined, in analogy with the ergodic foundations of classical statistical mechanics, on the basis of the time evolution of the quantum state. Then, we study the emergence of thermodynamic properties in a quantum system by studying the probability distribution of some function of interests, as the entropy and the equilibrium state of a subsystem, on Ensembles of Pure States. Such a probability distribution is derived from the geometry of the Hilbert space, and the theoretical tools suitable for its characterization are developed. On the one hand we perform a numerical sampling of the ensemble distributions by employing Monte Carlo techniques, on the other hand simpler analytical approximation of the geometrical distributions are derived by means of a maximum entropy principle. Model systems composed of an ensemble of spins are chosen to illustrate the salient features which emerge from the developed theoretical framework: the main point is that the Ensemble Distributions of “thermodynamic observables” (entropy or equilibrium state of a subsystem) are sharply peaked around a typical value. From the analysis it emerges that each of the overwhelming majority of the wavefunctions which has appreciable weight in the considered ensemble, is characterized by the same value of the “macroscopic” functions. This is a striking evidence of the “typicality” of these properties. In the essence, our impossibility to know the state of the system in detail does not matter, just for the remarkable fact that almost all quantum states behave essentially in the same way. By virtue of this typicality the study of the behaviour of the typical values of the thermodynamic function become meaningful. Notably, under certain conditions, one recovers the results of standard statistical mechanics, that is, the equilibrium average of the state of a subsystem can be cast in the Boltzmann canonical form at the temperature given by the usual thermodynamical relation . In the second part of the thesis we consider the dynamical aspects of the equilibrium state of a subsystem interacting with its environment. The fluctuations around the equilibrium average critically depends on the entanglement between the system and the environment and on the form of the interaction Hamiltonian. The connection between the dynamics of the fluctuations of an observable at the equilibrium and the relaxation toward the equilibrium from a “non typical” initial value is also investigated with the aid of simple model systems. The study presented in this thesis was partly motivated by a critical analysis of the statistical methods available for the theoretical modelling of magnetic resonance experiments. One of these, the Stochastic Liouville Equation, has been employed in a work completed during the first year of my Ph.D. program in order to interpret some feature of a two dimensional electron spin resonance experiment, [Fresch B., Frezzato D., Moro G. J., Kothe G., Freed J. H.; J. Phys. Chem. B., 110, 24238, (2006)].
The quantum mechanical concepts of states and operators arise naturally from the question how expectation values of observables can be computed in classical statistical systems where only incomplete local information about the probability distribution is available. The notions of evolution and time are related to the translation of the available information between neighboring local regions. The complex structure of quantum mechanics, the superposition of states and the interference effects characteristic for quantum statistics find a simple origin. This suggests the emergence of quantum mechanics from classical statistics with infinitely many degrees of freedom.
Von Neumann's macroscopic entropy definition is not wholly satisfactory because (a) it rests on an unsatisfactory characterization of macroscopic variables, (b) it fails to make satisfactory connection with the Nernst heat theorem, (c) it is based on an unsatisfactory definition of thermal equilibrium, (d) it is not applicable to microscopic systems. It is proved that if two systems initially in independent states are placed in thermal contact and isolated, the sum of their microscopic entropies cannot decrease, but will in general increase. This theorem is a substitute for the usual rule regarding the increase in entropy of a single isolated system. Appreciable departures from the canonical state are shown to have a vanishingly small probability in the case of a system subjected to the thermostat experimental procedure described in a preceding paper.