"Boltzmann's problem" of statistical thermodynamics, is that of eliminating the paradoxical incompatibility of structure, existing between the irreversibility of the classical phenomenological thermodynamics, and the reversibility of any purely kinetic model, one could ever think of for these phenomena. One finds that, in order to construct kinetic "analogs" to the laws of phenomenological thermodynamics, the dynamics of large assemblies of molecules (Liouville theorem, etc,\cdots) must be completed by some hypotheses of randomness. Once established, this randomness can be followed up in its development, with no new conceptual paradox (although with great technical difficulty: there is a great amount of current work on this topic). But the introduction of randomness still raises entirely uncleared problems. Since, therefore, the kinetic foundations of thermodynamics are not sufficient in the absence of further hypotheses of randomness, are they still quite necessary in the presence of such hypotheses? Or else, could not one "short-circuit" the atoms, by centering upon any elements of randomness, for example those introduced by the process of observation? Our aim is to show (partly after Szilard) that a substantial part of the results, usually obtained through kinetic arguments, could be obtained by postulating from the outset a statistical distribution for the properties of a system, and following up with a purely phenomenological argument. The spirit of the theory is extremely close to that of the conventional (Copenhagen) approach to quantum theory, and the results are quite parallel, although the mathematics is quite different. Randomness is introduced by following the modern statistical theory of the estimation of non directly observable intensive variables of state, such as the temperature. The discussion of the methodological foundations of modern statistics can thus be translated into a full-fledged, and possibly significant , counterpart of the discussion of the kinetic foundations of thermodynamics. Statistics is thus provided with a particularly concrete example for some of its more involved methods; thermodynamics appears clarified in its classical aspects, and is further completed with an apparently new uncertainty relationship. It may also be of interest to the communication engineer to have a unified treatment of the foundations of fluctuation phenomena, and of methods of fighting noise : a discussion of entropy and information performed in this spirit, will be given in Part II of the paper.
"Boltzmann's problem" of statistical thermodynamics, is that of eliminating the paradoxical incompatibility of structure, existing between the irreversibility of the classical phenomenological thermodynamics, and the reversibility of any purely kinetic model, one could ever think of for these phenomena. One finds that, in order to construct kinetic "analogs" to the laws of phenomenological thermodynamics, the dynamics of large assemblies of molecules (Liouville theorem, etc,\cdots) must be completed by some hypotheses of randomness. Once established, this randomness can be followed up in its development, with no new conceptual paradox (although with great technical difficulty: there is a great amount of current work on this topic). But the introduction of randomness still raises entirely uncleared problems. Since, therefore, the kinetic foundations of thermodynamics are not sufficient in the absence of further hypotheses of randomness, are they still quite necessary in the presence of such hypotheses? Or else, could not one "short-circuit" the atoms, by centering upon any elements of randomness, for example those introduced by the process of observation? Our aim is to show (partly after Szilard) that a substantial part of the results, usually obtained through kinetic arguments, could be obtained by postulating from the outset a statistical distribution for the properties of a system, and following up with a purely phenomenological argument. The spirit of the theory is extremely close to that of the conventional (Copenhagen) approach to quantum theory, and the results are quite parallel, although the mathematics is quite different. Randomness is introduced by following the modern statistical theory of the estimation of non directly observable intensive variables of state, such as the temperature. The discussion of the methodological foundations of modern statistics can thus be translated into a full-fledged, and possibly significant , counterpart of the discussion of the kinetic foundations of thermodynamics. Statistics is thus provided with a particularly concrete example for some of its more involved methods; thermodynamics appears clarified in its classical aspects, and is further completed with an apparently new uncertainty relationship. It may also be of interest to the communication engineer to have a unified treatment of the foundations of fluctuation phenomena, and of methods of fighting noise : a discussion of entropy and information performed in this spirit, will be given in Part II of the paper.
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.
Quantum thermodynamics is a blossoming research program that uses tools and ideas from quantum information theory to extend the laws of thermodynamics to the domain of systems to which the laws of quantum mechanics apply and the thermodynamic limit does not necessarily apply. The contributions of this program are both foundational, in providing an approach to constructively derive the laws of phenomenological thermodynamics from the postulates of unitary quantum mechanics in a rigorous and bottom-up fashion, but also prac- tical, in providing the theory for an increasing number of experiments that attempt to build thermodynamic machines at scales that were previously inaccessible. One key mathematical tool used in quantum thermodynamics is the framework of resource theories, specifically the resource theory of thermal operations, in which the thermodynamic interaction of a system with a heat bath and various additional components such as work batteries, clocks or catalysts are modeled. In this cumulative thesis, various extensions and modifications of this framework are studied in order to derive novel results and insights about the possible thermodynamic evolution of quantum systems. In particular, following a system- atic exposition of the resource theory of thermal operations from first principles, I develop answers to the following questions: i) What is the smallest heat bath required to provide the necessary randomness for a system to undergo a given stochastic or thermodynamical evolution? ii) Does this size differ depending on whether the interaction between bath and system is quantum or classical? iii) How can quantum systems thermodynamically evolve in the presence of catalytic bystander systems and how can this be put to use? iv) What are the thermodynamic state transitions that an agent can operationally affect when she only has access to partial information about the underlying states of system and bath? v) How can we understand the emergence of the canonical ensemble in statistical thermodynamics from quantum mechanics? These questions cover a wide ground, but it will become clear that they can in fact all be discussed using the same formal tools. As such, the answers to the above questions provided in this thesis are both interesting in their own right — showing for example that there exists a gap in how efficiently randomness can be exploited quantumly as compared to classically or that catalytic bystander systems can be used to extract finite amounts of work per particle from macroscopic systems with non-vanishing probability — as well as illustrate the power of quantum thermodynamics as a set of tools to connect quantum mechanics and the theory of thermodynamics more generally.
To understand in detail the relation between unitary quantum theory that describes our world at the microscopic scale and thermodynamics, which was long believed only to apply to macroscopic objects, is one of the most interesting and long-standing problems in physics. Recently, this problem has received renewed attention, in particular from the community of quantum information theory, but also from the field of statistical mechanics, inspired from stochastic thermodynamics. These results suggest that thermodynamics is also relevant for individual quantum systems, provided that they can be brought into contact with thermal baths. In this thesis, I use recently developed tools to provide new results both on fundamental questions, but also on questions which are of practical relevance for potential miniaturized thermal machines. In terms of fundamental questions, the results in this thesis contribute to understanding how the basic laws of thermodynamics and statistical mechanics can be understood directly from unitary quantum mechanics. In particular, I discuss and answer the following questions: i) How can we quantify the third law of thermodynamics using information theoretic methods? ii) How can we quantify the "thermodynamic value" of a state-transition in quantum systems? iii) How can we axiomatically characterize the non-equilibrium free energy and relative entropy? iv) How can we justify statistical ensembles from an operational perspective, without having to introduce either some probability measures or an information theoretic entropy measure? v) How can we understand the equilibration of closed quantum systems, how long does it take and how difficult is it to avoid? In the second part of the thesis I discuss in detail how experimental restrictions, which become important at the quantum scale, influence the ultimate thermodynamic bounds for thermal machines. In particular, the results in this thesis provide thermodynamic bounds on work-extraction and efficiencies of thermal machines in situations where 1.) an experimenter only has limited field strengths available, 2.) an experimenter cannot control the interactions between particles, but external fields arbitrarily well, and 3.) situations in which a small quantum system can only be strongly coupled to heat baths. These bounds are tight and I provide explicit examples illustrating the different behaviours. Finally, I come back to a classic problem in statistical physics: The emergence of spontaneous symmetry breaking. Here, I provide general and rigorous new results that show how symmetry-breaking stationary states emerge from fluctuations in order parameters in dissipative lattice models.
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)].
Abstract It is well known that a new form of statistical mechanics has been recently developed by Einstein for an ideal gas of structureless mass-points. This starts from a discussion by Bose of the laws of temperature radiation based on the light quantum hypothesis, and has been further analysed by Schrödinger. Yet another new form has been proposed independently by Fermi and Dirac. The latter based his theory on a discussion of lightly coupled systems with the help of Schrödinger’s equation. Combined with Heisenberg’s work on the many-body problem, Dirac’s work forces us to conclude at least that the classical form of statistical mechanics must be changed. It indicates that the true form, which satisfies the laws of the new mechanics, is almost certainly that of Fermi and Dirac, which is the natural generalization of Pauli’s principle of exclusion for electronic orbits in an atom. The work of Heisenberg and Dirac already quoted has shown that Pauli’s principle and its extension are satisfied in the new mechanics by a complete self-consistent solution of the equations of motion. So far as I am aware, the discussions of the new forms have as yet dealt only with the statistics of a gas of structureless mass-points (and, of course, temperature radiation). There has, moreover, been as yet no attempt to define the entropy (and the absolute temperature) in strict analogy with rational thermodynamics by means of the equation dQ = TdS. If another definition is preferred, then this equation must be deduced from it. It has, therefore, seemed worth while to reopen the discussion by examining ab initio a quite general form of statistical mechanics of which the classical form and instein’s and Fermi-Dirac’s are special cases. This is rendered possible by using the powerful method of complex integration already applied to the classical form. The sequence of the argument is then to take the general form, which covers a very large range of ways of assigning possibilities and counting complexions, and construct on that basis exact integral expressions for the number of complexions possible to the assembly and for the average number of systems of the assembly in their various quantum states. We then derive from these the average energies and external reactions and so the form of dQ, deduce from dQ the existence of S and so define S and T. This can be done in the general form for assemblies of ideal systems just as general as can be handled in the classical way—ideal gases of molecules of any structure and crystals and radiation. Such assemblies are in all cases thermodynamical systems.
ABSTRACT. What is the physical significance of entropy? What is the physical origin of irreversibility? Do entropy and irreversibility exist only for complex and macroscopic systems? Most physicists still accept and teach that the rationalization of these fundamental ques-tions is given by Statistical Mechanics. Indeed, for everyday laboratory physics, the math-ematical formalism of Statistical Mechanics (canonical and grand-canonical, Boltzmann, Bose-Einstein and Fermi-Dirac distributions) allows a successful description of the ther-modynamic equilibrium properties of matter, including entropy values. However, as al-ready recognized by Schrödinger in 1936, Statistical Mechanics is impaired by conceptual ambiguities and logical inconsistencies, both in its explanation of the meaning of entropy and in its implications on the concept of state of a system. An alternative theory has been developed by Gyftopoulos, Hatsopoulos and the present author to eliminate these stumbling conceptual blocks while maintaining the mathematical formalism so successful in applications. To resolve both the problem of the meaning of entropy and that of the origin of irreversibility we have built entropy and irreversibility