A general quantum theory encompassing Mechanics, Thermodynamics and irreversible dynamics is presented in two parts. The first part is concerned exclusively with the description of the states of any individual physical system. It is based on a new nonlinear quantum equation of motion, which reduces to the Schroedinger equation of motion of motion of conventional quantum dynamics only under special conditions. It accounts for the implications of the laws of Thermodynamics as well as for irreversible phenomena, such as the natural tendency of an isolated system to transit from any non-equilibrium state to an equilibrium state of higher entropy. Conversely, the laws of Thermodynamics and irreversibility emerge as manifestations of the fundamental quantum dynamical behaviour of the elementary constituents of any material system. We call this part Quantum Thermodynamics. The second part of the theory, which contains the first as a special case, is concerned with the description of stochastic distributions of states in an ensemble of identical physical systems each of which individually obeys the laws of Quantum Thermodynamics. It is based on a new measure-theoretic description of ensembles. It accounts unambiguously for the essential distinction between two types of uncertainties that are generally present in an ensemble, namely, quantal uncertainties due to the inherent quantal nature of the states of each individual member system and nonquantal uncertainties due to the stochastic distribution of states. We call this part Quantum Statistical Thermodynamics.
A general quantum theory encompassing Mechanics, Thermodynamics and irreversible dynamics is presented in two parts. The first part is concerned exclusively with the description of the states of any individual physical system. It is based on a new nonlinear quantum equation of motion, which reduces to the Schroedinger equation of motion of motion of conventional quantum dynamics only under special conditions. It accounts for the implications of the laws of Thermodynamics as well as for irreversible phenomena, such as the natural tendency of an isolated system to transit from any non-equilibrium state to an equilibrium state of higher entropy. Conversely, the laws of Thermodynamics and irreversibility emerge as manifestations of the fundamental quantum dynamical behaviour of the elementary constituents of any material system. We call this part Quantum Thermodynamics. The second part of the theory, which contains the first as a special case, is concerned with the description of stochastic distributions of states in an ensemble of identical physical systems each of which individually obeys the laws of Quantum Thermodynamics. It is based on a new measure-theoretic description of ensembles. It accounts unambiguously for the essential distinction between two types of uncertainties that are generally present in an ensemble, namely, quantal uncertainties due to the inherent quantal nature of the states of each individual member system and nonquantal uncertainties due to the stochastic distribution of states. We call this part Quantum Statistical Thermodynamics.
Entropy is the distinguishing and most important concept of our efforts to understand and regularize our observations of a very large class of natural phenomena, and yet, it is one of the most contentious concepts of physics. In this article, we review two expositions of thermodynamics, one without reference to quantum theory, and the other quantum mechanical without probabilities of statistical mechanics. In the first, we show that entropy is an inherent property of any system in any state, and that its analytical expression must conform to eight criteria. In the second, we recognize that quantum thermodynamics: (i) admits quantum probabilities described either by wave functions or by nonstatistical density operators; and (ii) requires a nonlinear equation of motion that is delimited by but more general than the Schroedinger equation, and that accounts for both reversible and irreversible evolutions of the state of the system in time. Both the more general quantum probabilities, and the equation of motion have been defined, and the three laws of thermodynamics are shown to be theorems of this equation.
The nonlinear equation of motion that accomplishes a self-consistent unification of quantum mechanics (QM) and thermodynamics conceptually different from the (von Neumann) foundations of quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but which reduces to the same mathematics for the thermodynamic equilibrium (TE) states, and contains standard QM in that it reduces to the time-dependent Schrodinger equation for zero entropy states is discussed in full mathematical detail. By restricting the discussion to a strictly isolated system (noninteracting, disentangled and uncorrelated), we show how the theory departs from the conventional QSM/QIT rationalization of the second law of thermodynamics, which instead emerges in QT (quantum thermodynamics) as a theorem of existence and uniqueness of a stable equilibrium state for each set of mean values of the energy and the number of constituent particles. To achieve this, the theory assumes Trρ lnρ B −k for the physical entropy and is designed to implement two fundamental ansatzs: (1) that in addition to the standard QM states described by idempotent density operators (zero entropy), a strictly isolated and uncorrelated system admits also states that must be described by non-idempotent density operators (nonzero entropy); (2) that for such additional states the law of causal evolution is determined by the simultaneous action of a Schrodinger-von Neumann-type Hamiltonian generator and a nonlinear dissipative generator which conserves the mean values of the energy and the number of constituent particles, and in forward time drives the density operator in the 'direction' of steepest entropy ascent (maximal entropy generation). The resulting dynamics is well defined for all non-equilibrium states, no matter how far from TE. Existence and uniqueness of solutions of the Cauchy initial value problem for all density operators implies that the equation of motion can be solved not only in forward time, to describe relaxation towards TE, but also in backward time, to reconstruct the 'ancestral' or primordial lowest entropy state or limit cycle from which the system originates. Zero entropy states as well as a well defined family of non-dissipative states evolve unitarily according to pure Hamiltonian dynamics and can be viewed as unstable limit cycles of the general nonlinear dynamics.
The author presents his experience in teaching at a graduate level the quantal exposition of a new non-statistically based paradigm of physics and thermodynamics. This paradigm, called the Unified Quantum Theory of Mechanics and Thermodynamics, applies to all systems large or small (including one particle systems) either in a state of thermodynamic (i.e. stable) equilibrium or not in a state of thermodynamic equilibrium. It uses as its primitives inertial mass, force, and time and introduces the laws of thermodynamics in the most unambiguous and general formulations found in the literature. Starting with a precise definition of system and of state followed by statements and corollaries of the laws of thermodynamics, the thermodynamic formalism is developed without circularity and ambiguity. In this quantal exposition of the new paradigm, a brief review of the formalism of thermodynamics as a general science not limited to stable equilibrium and large (macroscopic) systems as well as a very brief summary of the three prevalent formalisms in classical physics are presented followed by a presentation and development of solutions for a number of elementary problems in quantum physics (e.g., a particle in a box, a harmonic oscillator, a rigid rotor, etc.). These solutions and the maximum entropy principle are then used in a constrained optimization to develop the canonical and grand canonical distributions for Fermi-Dirac and Bose-Einstein types of particles, i.e. for fermions and bosons. This is done without the use of analogies between statistical and thermodynamic results and without additional hypotheses such as the ergodic hypothesis of statistical mechanics. These distributions are then employed under various assumptions (i.e. the Boltzmann, constant-potential, point-particle, and continuous eigenvalue-spectrum approximations) to derive the corresponding thermodynamic property expressions for perfect, semi-perfect (ideal), and Sommerfeld gases as well as for mixtures of ionized and dissociated gases. In a similar fashion but with a change from a single- to a multi-particle partition function and with the addition of various inter-particle potentials for two-particle interactions (e.g., the Lennard-Jones potential, the square-well potential, etc.), expressions for the thermodynamic properties of dense gases are developed and presented.An initial version of this paper was published inJuly of 2006 in the proceedings of ECOS’06, AghiaPelagia, Crete, Greece.
Investigation on foundational aspects of quantum statistical mechanics recently entered a renaissance period due to novel intuitions from quantum information theory and to increasing attention on the dynamical aspects of single quantum systems. In the present contribution a simple but effective theoretical framework is introduced to clarify the connections between a purely mechanical description and the thermodynamic characterization of the equilibrium state of an isolated quantum system. A salient feature of our approach is the very transparent distinction between the statistical aspects and the dynamical aspects in the description of isolated quantum systems. Like in the classical statistical mechanics, the equilibrium distribution of any property is identified on the basis of the time evolution of the considered system. As a consequence equilibrium properties of quantum system appear to depend on the details of the initial state due to the abundance of constants of the motion in the Schrodinger dynamics. On the other hand the study of the probability distributions of some functions, such as the entropy or the equilibrium state of a subsystem, in statistical ensembles of pure states reveals the crucial role of typicality as the bridge between macroscopic thermodynamics and microscopic quantum dynamics. We shall consider two particular ensembles: the random pure state ensemble and the fixed expectation energy ensemble. The relation between the introduced ensembles, the properties of a given isolated system, and the standard quantum statistical description are discussed throughout the presentation. Finally we point out the conditions which should be satisfied by an ensemble in order to get meaningful thermodynamical characterization of an isolated quantum system.
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? The bulk of the physics community accepts and teaches that all these fundamental questions are rationalized within statistical mechanics. Indeed, for everyday laboratory physics, the mathematical formalism of statistical mechanics (canonical and grandcanonica1, Boltzmann, Bose-Einstein and Fermi-Dirac distributions) allows a successful description of the thermodynamic equilibrium properties of matter, including entropy values. But an ever growing handful of physicists (Schrodinger among the first) have realized that, even in its explanation of the meaning of entropy, statistical mechanics is impaired by ambiguities and logical inconsistencies. They have started to search for a better theory to eliminate these stumbling blocks while maintaining the mathematical formalism that has been so successful in so many applications. This handful of upstreamers must not be confused with the many schools of physicists that have thrived on the more renowned incompleteness of statistical mechanics, namely, the lack of a quantitative (and the weakness of the qualitative) explanation of the origin of irreversibility. In these studies the thrust is provided by the discovery that the macroscopic dynamics of certain complex systems may be modeled using a few-degrees-of-freedom nonlinear Hamiltonian with singularities that give rise to bifurcations and chaotic behavior. These results have generated successful ways to describe irreversible behavior, but their link to the origin of irreversibility is still only heuristic (what is the connection between the nonlinear model Hamiltonian and the true full Hamiitonian?) and does not provide yet a rigorous resolution of the century-old paradox of the conflict between the irreversibiiity of macroscopic behavior, and the reversibility of the laws of mechanics. To resolve both the problem of the meaning of entropy and that of the origin of irreversibility we have built entropy and irreversibility into the laws of mechanics. The result is a theory that we call quantum thermodynamics that has all the necessary properties to combine mechanics and thermodynamics uniting all the successful results of both theories, eliminating the logical inconsistencies of statistical mechanics and the paradox on irreversibiiity, and providing an entirely new perspective on the microscopic origin of irreversibility, nonlinearity and therefore chaotic behavior. The mathematical formalism of quantum thermodynamics differs from that of statistical mechanics mainly in the equation of motion which is nonlinear but has solutions identical to those of the Schrodinger equation for all the states for which statistical mechanics reduces to quantum mechanics. The physical meaning of the formalism of quantum thermodynamics differs more drastically from that of statistical mechanics. The significance of the state operator of quantum thermodynamics is entirely different from that of the density operator of statistical mechanics, even though the two are mathematically equivalent. Indeed they obey different equations of motion. In particular, quantum thermodynamics is concerned only with those systems for which quantum mechanics would describe the states with vectors in Hilbert space or, equivalently, projection operators. Using a well known jargon, we can say that quantum thermodynamics like quantum mechanics is concerned only with pure quantum states. However, it postulates that the set of pure quantum states of a system is much broader than contemplated by quantum mechanics. Pure quantum states must be described by operators defined by all the features of projection operators except the condition of idempotence. As a result, an operator that within statistical mechanics would describe a mixed quantum state (that is, the average state of a statistical mixture of identical systems in different pure quantum states) in quantum thermodynamics describes a pure quantum state, a state that neither quantum mechanics non statistical mechanics would contemplate. Conceptually, the increased richness of pure quantum states is a new revolutionary postulate of quantum physics. But from the point of view of the statistical mechanics practitioners the new theory is not as traumatic as it seems. Whenever one uses a nonidempotent density operator to describe a thermodynamic equilibrium state one simply has to reinterpret it as one of the new pure quantum states. One even saves the usual ad hoc arguments on thermal baths and reservoirs that are usually required in statistical mechanics to justify the use of a nonidempotent density operator to describe the state of a system. In this paper we discuss the background and formalism of quantum thermodynamics including its nonlinear equation of motion and the main general results. Our objective is to show in a not-too-technical manner that this theory provides indeed a complete and coherent resolution of the century-old dilemma on the meaning of entropy and the origin of irreversibility. As a byproduct, we discuss a long set of criteria that a theory should meet in order to afford the same claim.
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.