Atti della Accademia Peloritana dei Pericolanti. Classe di Scienze Fisiche, Matematiche e Naturali/Atti della Accademia Peloritana dei Pericolanti, Classe di Scienze Fisiche, Matematiche e Naturali
Quantum thermodynamics: Microscopic foundations of entropy and of entropy generation by irreversibility
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
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
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.
Entropy is a fundamental concept which emerged along with other ideas during the development of thermodynamics and statistical mechanics Landau and Lifshitz (1978); Lieb and Yngvason (1999). Entropy has developed foremost out of phenomenological thermodynamical considerations such as the second law of thermodynamics in which it plays a prominent role Wehrl (1978). With the intense interest in the investigation of the physics of matter at the atomic and subatomic quantum levels, it maywell be askedwhether this concept can emerge out of the study of systems at a more fundamental level. In fact, it may be argued that a correct definition is only possible in the framework of quantum mechanics, whereas in classical mechanics, entropy can only be introduced in a rather limited and artificial way. Entropy relates macroscopic and microscopic aspects of nature, and ultimately determines the behavior of macroscopic systems. It is the intention here to present an introduction to this subject in a readable manner from the quantum point of view. There are many reasons for undertaking this. The intense interest in irreversible thermodynamics Grossing (2008), the statistical mechanics of astrophysical objects Padmanabhan (1990); Pathria (1977), quantum gravity and entropy of black holes Peres & al. (2004), testing quantum mechanics Ballentine (1970) and applications to condensed matter and quantum optics Haroche & al. (2006); Raimond & al. (2001) are just a few areas which are directly or indirectly touched on here. Let us begin by introducing the concept of entropy from the quantummechanical perspective, realizing that the purpose is to focus on quantum mechanics in particular. Quantum mechanics makes a clear distinction between observables and states. Observables such as position and momentum are mathematically described by self-adjoint operators in a Hilbert space. States, which are generally mixed, can be described by a density matrix, which is designated by ρ throughout. This operator ρ is Hermitean, has trace one and yields the expectation value of an observable A in the state ρ through the definition
In Chapter 3 the introduction of entropy as a state function was facilitated by the realization that there exist possible and impossible processes, and by an examination of the heat and work effects occurring during these processes. From the formal statement of the Second Law of Thermodynamics, as developed from Classical Thermodynamics arguments, it is difficult to assign a physical significance or a physical quality to entropy. In this respect entropy differs from internal energy in spite of the fact that, within the scope of Classical Thermodynamics, both properties are simply mathematical functions of the state of a system. The ready acceptance of the First Law of Thermodynamics, after its enunciation, was due to the easily understood physical significance of internal energy, whereas the lack of corresponding understanding of entropy caused the acceptance of the Second Law of Thermodynamics to be slow. From the classical viewpoint the Second Law is only valid as a direct result of the fact that, to date, human ingenuity has failed to invent a perpetual motion machine. Thus, within the scope of Classical Thermodynamics, the Second Law is a “law” only because it has not yet been disproved. The physical interpretation of entropy had to await the development of quantum theory and statistical mechanics.
The law of increase of entropy is one of the most important laws in science but no exact explanation has been given to the origin of it. Statistical thermodynamics only explains it by using Boltzmann’s statistical interpretation together with not sufficiently verified assumptions. This paper shows that the increase of entropy in an isolated macroscopic system can be reasonably explained with no assumption based on quantum mechanics if we take into account that microscopic particles such as electrons and atomic nuclei not only move in space but also have the basic quality of spontaneously spreading into every possible spatial position. The present work allows us to give a plausible definition to the entropy of an isolated system by using the Hamiltonian operator and a wave function of it and provides a firm basis for thermodynamics. It also gives a new physical meaning of entropy effective for further studies of irreversible processes in nature.
The problem of time’s arrow is (roughly) to understand why macroscopic physical processes typically evolve in a specific direction (the one we call “the future”) even though the underlying laws of physics describing the individual microscopic systems are time-reversal invariant. The standard answer to this problem is given by Boltzmann’s explanation of the II law of thermodynamics: a classical system starting in a non-equilibrium state spontaneously (i.e. with a high level of probability) tends towards equilibrium, thus implementing an irreversible process. However, this explanation has two drawbacks: 1. it needs a further assumption on the entropy of the initial state of the universe (past hypothesis); 2. microscopic systems (e.g. molecules in a box) should be represented as quantum states and not classical states. In this talk, I want to propose a different hypothesis to explain the origin of time’s arrow, based on quantum mechanics, specifically on decoherence theory. Differently from isolated systems, open quantum systems described by decoherence theory showirreversible behavior, as they evolve towards decoherence and von Neumann entropy increase. Is this behavior a sign of genuine irreversibility? And, if so, can this be linked to thermodynamic irreversibility?
Thermodynamics is commonly presented as a theory of macroscopic systems in stable equilibrium, built upon assumptions of extensivity and scaling with system size. In this paper, we present a universal formulation of the elementary foundations of thermodynamics, in which entropy and energy are defined and employed beyond equilibrium and without assuming extensivity. The formulation applies to all systems -- large and small, with many or few particles -- and to all states, whether equilibrium or nonequilibrium, by relying on carefully stated operational definitions and existence principles rather than macroscopic idealizations. Key thermodynamic concepts, including adiabatic availability and available energy, are developed and illustrated using the energy-entropy diagram representation of nonequilibrium states, which provides geometric insight into irreversibility and the limits of work extraction for systems of any size. A substantial part of the paper is devoted to the analysis of entropy transfer in non-work interactions, leading to precise definitions of heat interactions and heat-and-diffusion interactions of central importance in mesoscopic continuum theories of nonequilibrium behavior in simple and complex solids and fluids. As a direct consequence of this analysis, Clausius inequalities and the Clausius statement of the second law are derived in forms explicitly extended to nonequilibrium processes. The resulting framework presents thermodynamics as a universal theory whose concepts apply uniformly to all systems, large and small, and provides a coherent foundation for both teaching and modern applications.