It is assumed that the quantum state that may describe a macroscopic system at a given instant of time is one of the eigenstates of the reduced density matrix calculated from the wave function of the system plus its environment. This implies that the above quantum state is a member of a special orthonormed set of states. Using a suitable Monte-Carlo simulation, this property is shown to be consistent with the extremely small standard deviation for the coordinates and the momenta of macroscopic systems. Consequences for statistical mechanics and possible observable effects are discussed.
It is assumed that the quantum state that may describe a macroscopic system at a given instant of time is one of the eigenstates of the reduced density matrix calculated from the wave function of the system plus its environment. This implies that the above quantum state is a member of a special orthonormed set of states. Using a suitable Monte-Carlo simulation, this property is shown to be consistent with the extremely small standard deviation for the coordinates and the momenta of macroscopic systems. Consequences for statistical mechanics and possible observable effects are discussed.
The conventional quantum theory gives no real, that is, independent of the observer, natural description. If it is required that it must give an absolute reality of the natural phenomena at least in the macroscopic region, then the quantum theory must be changed. One possibility of that kind is discussed. A model of a quantum theory, which for small systems agrees with the usual theory, but for large systems deviates so much from them that the absolute reality of macroscopic size remains steady, is described. This was achieved by means of an additional term in the motion equation for the density matrix. This additional term plays no role for the small system. For macroscopic ion of the density matrix as if'' all macroscopic size of the system was observed perennially. (tr-auth)
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)].
A small quantum scattering system (the microsystem) is studied in interaction with a large system (the macrosystem) described by unknown stochastic variables. The interaction between the two systems is diagonal for the microsystem in a certain orthonormal basis, and the interaction gives an imprint on the macrosystem. Moreover, the interaction is assumed to involve only small transfers of energy and momentum between the two systems (as compared to typical energies/momenta within the microsystem). The analysis is carried out within scattering theory. Calculated in the conventional way, the transition amplitude for the whole system factorizes. The interaction taking place within the macrosystem is assumed to depend on the stochastic variables in such a way that, on the average, no particular basis vector state of the microsystem is favoured. The density matrix is studied in a formalism which includes generation of the ingoing state and absorption of the final state. Then the dependence of the final state on the conventional scattering amplitude for the microsystem is highly non-linear. In the thermodynamic limit of the macrosystem, the density matrix of the ensemble (of microsystem plus macrosystem) develops into a final state which involves a set of macroscopically distinguishable states, each with the microsystem in one of the basis vector states and the macrosystem in an entangled state. For an element of the ensemble, i.e., for a single measurement, the result is instead a random walk, where the microsystem ends up in one of the basis vector states (reduction of the wave packet).
Descriptions of molecular systems usually refer to two distinct theoretical frameworks. On the one hand the quantum pure state, i.e., the wavefunction, of an isolated system is determined to calculate molecular properties and their time evolution according to the unitary Schrödinger equation. On the other hand a mixed state, i.e., a statistical density matrix, is the standard formalism to account for thermal equilibrium, as postulated in the microcanonical quantum statistics. In the present paper an alternative treatment relying on a statistical analysis of the possible wavefunctions of an isolated system is presented. In analogy with the classical ergodic theory, the time evolution of the wavefunction determines the probability distribution in the phase space pertaining to an isolated system. However, this alone cannot account for a well defined thermodynamical description of the system in the macroscopic limit, unless a suitable probability distribution for the quantum constants of motion is introduced. We present a workable formalism assuring the emergence of typical values of thermodynamic functions, such as the internal energy and the entropy, in the large size limit of the system. This allows the identification of macroscopic properties independently of the specific realization of the quantum state. A description of material systems in agreement with equilibrium thermodynamics is then derived without constraints on the physical constituents and interactions of the system. Furthermore, the canonical statistics is recovered in all generality for the reduced density matrix of a subsystem.
In classical mechanics the state of a dynamical system at any particular time can be described by the values of a set of coordinates and their conjugate momenta, thus, if the system has n degrees of freedom, by 2n numbers. In quantum mechanics, on the other hand, we have to describe a state of the system by a wave function involving a set of coordinates, thus by a function of n variables. The quantum description is, therefore, much more complicated than the classical one. Let us consider, however, an ensemble of systems in Gibbs' sense, i.e. not a large number of actual systems which could, perhaps, interact with one another, but a large number of hypothetical systems which are introduced to describe one actual system of which our knowledge is only of a statistical nature. The basis of the quantum treatment of such an ensemble has been given by Neumann. The description obtained by Neumann of an ensemble on the quantum theory is no more complicated than the corresponding classical description. Thus the quantum theory, which appears to such a disadvantage on the score of complication when applied to individual systems, recovers its own when applied to an ensemble. It is the object of the present note to examine this question more closely and to show how complete the analogy is between the quantum and classical treatments of an ensemble.
The basic concepts and rules of quantum mechanics are shown to be immediate consequences, on the basis of simple reasoning, of a postulate of continuity in the domain of macroscopic thermodynamics. The continuity principle leads first to the concept of a fractional likeness between two states in general, as opposed to the classical alternative of either like or unlike. Then all possible states of a system can be arranged in sets of mutually unlike or “orthogonal” states, with members A and B of different sets interconnected by fractional likeness factors q(A, B) between zero and unity. These factors q are identical with the relative intensities in a splitting effect of a state into components, ruled by probability relations and by the basic principle of quantum statistics of not counting permutations of individual particles. The problem of relation between the various fractional likenesses, or probabilities of transition under analysis, is a purely mathematical problem and is solved by the introduction of probability amplitudes necessarily subject to a matrix law of multiplication, i.e., to the principle of superposition. Thus, starting from the continuity postulate of thermodynamics, quantum theory in its general outline is obtained by simple reasoning. All further details, such as the duality of waves and particles, the uncertainty relation, and the mechanics of special systems, need only one more bit of empirical information, namely, the symmetric and periodic form of the amplitude ψ of fractional likeness between a state of given coordinate and a state of given momentum.