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arXiv:1311.4995

Toward a new foundation of statistical mechanics

J. P. Badiali

Published Nov 20, 2013• 0 citations
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Abstract

We propose a new approach concerning the introduction of time-irreversibility in statistical mechanics. It is based on a transition function defined in terms of path integral and verifying a time-irreversible equation. We show first how dynamic processes may enter in the description of equilibrium states. In order to do that a characteristic time is associated with closed paths. For large isolated systems at equilibrium or for systems in contact with a thermostat our results are identical with those obtained with the Gibbs ensemble methods. For a model used in the microscopic approaches of the brownian motion no new basic assumption is required to predict a transition from a quantum state to a classical one exhibiting a time-irreversible behavior. This demonstration is sufficient to show that very well accepted approximations can lead to time-irreversible behaviors for a large class of systems. The difference between our work and the system+reservoir approaches is underlined. Here equilibrium states and irreversible processes are described on the same footing representing a progress in the question of time-irreversibility in statistical physics. The transition function is also used for describing a small system for which there is no thermodynamics. By adding to the transition function a second one characterizing the reverse motion we may describe time-reversible systems. In a simple case we replace two real valued transition functions by a complex function verifying a Schrodinger like equation. From this we see how to break the time-reversibility of this equation and how to investigate the connection quantum mechanics-thermodynamics from a very fundamental point of view.

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•Jan 1, 2005•3 citations
We propose a new approach concerning the introduction of time-irreversibility in statistical mechanics. It is based on a transition function defined in terms of path integral and verifying a time-irreversible equation. We show first how dynamic processes may enter in the description of equilibrium states. In order to do that a characteristic time is associated with closed paths. For large isolated systems at equilibrium or for systems in contact with a thermostat our results are identical with those obtained with the Gibbs ensemble methods. For a model used in the microscopic approaches of the brownian motion no new basic assumption is required to predict a transition from a quantum state to a classical one exhibiting a time-irreversible behavior. This demonstration is sufficient to show that very well accepted approximations can lead to time-irreversible behaviors for a large class of systems. The difference between our work and the system+reservoir approaches is underlined. Here equilibrium states and irreversible processes are described on the same footing representing a progress in the question of time-irreversibility in statistical physics. The transition function is also used for describing a small system for which there is no thermodynamics. By adding to the transition function a second one characterizing the reverse motion we may describe time-reversible systems. In a simple case we replace two real valued transition functions by a complex function verifying a Schrodinger like equation. From this we see how to break the time-reversibility of this equation and how to investigate the connection quantum mechanics-thermodynamics from a very fundamental point of view.
We establish a rather deep relation between statistical mechanics and quantum mechanics at an imaginary time. For the quantum field theory, this implies a relation between finite temperature quantum field theory in Minkowski space and quantum field theory in Euclidean space with one compact Euclidean time direction. The quantum mechanical language being a proper formulation of statistical physics as a molecular theory is basically the study of quantum equilibrium as well as non-equilibrium systems. A quantum system found in a thermodynamic equilibrium state with an external classical system (thermostat or thermal reservoir) may be characterized by fixed values of thermodynamic parameters of the system, say, for example, temperature T , volume V and number of particles N . In this way the total energy of the thermostat is assumed to be much greater than the energy of the system. The behavior of the quantum system may be assumed to be independent of the nature of the thermostat. The most convenient object of the quantum theory to describe such non-isolated systems is the density matrix since the partition function does not determine any local thermodynamic quantities. It is for this reason that we introduced quantum mechanical and quantum statistical density matrices which are necessary to do the investigation via path integration. This enables us to make a transition to the quasi-classical approximation of quantum statistical mechanics, which, in turn, enables us to evaluate the first quantum correction to the classical Boltzmann distribution function.
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.
Abstract Nonintegrable Poincaré systems with a continuous spectrum (so‐called large Poincaré systems, LPS) lead to the appearance of diffusive terms in the frame of classical or quantum dynamics. These terms break time symmetry. They lead, therefore, to limitations to classical trajectory theory and of wave‐function formalism (Schrödinger's equation). These diffusive terms correspond to well‐defined classes of dynamical processes (i.e., so‐called vacuum‐vacuum transitions). The diffusive effects are amplified in situations corresponding to persistent interactions. As a result, we have to include, already, in the fundamental dynamical description the two basic aspects, probability and irreversibility, which are so conspicuous on the macroscopic level. We have to formulate both classical and quantum mechanics on the Liouville level of probability distributions (or density matrices). For integrable systems, we recover the usual formulation of classical or quantum mechanics. Instead of being primitive concepts, which cannot be further analyzed, trajectories and wave functions appear as special solutions of the Liouville–von Neumann equations. This extension of classical and quantum dynamics permits us to unify the two concepts of nature that we inherited from the nineteenth century, based, on the one hand, on dynamical time‐reversible laws and, on the other, on an evolutionary view associated to entropy. It leads also to a unified formulation of quantum theory, avoiding the conventional dual structure based on Schrödinger's equation, on the one hand, and on the “collapse” of the wave function, on the other. A dynamical interpretation is given to processes such as decoherence or approach to equilibrium without any appeal to extra dynamic considerations (such as many‐world theory, coarse graining, or averaging over the environment). There is a striking parallelism between classical and quantum theory. For large Poincaré systems (LPS), we have, in general, both a “collapse” of trajectories and of wave functions. In both cases, we need a generalized formulation of dynamics in terms of probability distributions or density matrices. Since the beginning of this century, we have known that classical mechanics had to be generalized to take into account the existence of universal constants. We now see that classical as well as quantum mechanics also have to be extended to include unstable dynamical systems such as LPS. As a result, we achieve a new formulation of “laws of physics” dealing no more with certitudes but with probabilities. This formulation is appropriate to describe an open, evolving universe. © 1995 John Wiley & Sons, Inc.
The purpose of this work is to discuss recent progress in deriving the fundamental laws of thermodynamics (0th, 1st and 2nd-law) from nonequilibrium quantum statistical mechanics. Basic thermodynamic notions are clarified and different reversible and irreversible thermodynamic processes are studied from the point of view of quantum statistical mechanics. Special emphasis is put on new adiabatic theorems for steady states close to and far from equilibrium, and on investigating cyclic thermodynamic processes using an extension of Floquet theory.
We suggest a new approach for describing quantum dissipation in a small systems for which the system-plus-reservoir approach is not relevant. We first analyze the fact that equilibrium thermodynamics may reveal the existence of an underlying dynamics. This is true in the algebraic approach of quantum mechanics via the Tomita-Takesaki theorem. A similar result is obtained if we start from the path integral expression of the partition function, an equation of motion is introduced. In both cases a parameter has to be identified with the physical time. Several arguments are presented showing that it is so. By investigating the dynamics for short times we introduce an equilibrium condition from which a natural unit of time appears. The equation of motion is extended to non equilibrium situations for which a H-theorem can be derived. The equation of motion can be transformed into a quantum Smoluchovski equation, its solution is a probability having a clear physical meaning. The relaxation of this probability towards its equilibrium value requires a time during which a thermodynamic description is possible or not. A standard bistable model is investigated and the chemical rate k(t)k(t)k(t) is calculated as a function of time, it appears to be a non monotonic function of time. In some conditions the stationary value of k(t)k(t)k(t) can be identified with the Kramers result. Finally we compare our approach which is naturally irreversible with an analysis based on the Schrödinger equation which is reversible. From all these results it appears that our equation of motion or its Smoluchovski version appear as a realistic starting point for describing quantum dissipation in small systems.
The purpose of this work is to discuss recent progress in deriving the fundamental laws of thermodynamics (0 th, 1 st and 2 nd-law) from nonequilibrium quantum statistical mechanics. Basic thermodynamic notions are clarified and different reversible and irreversible thermodynamic processes are studied from the point of view of quantum statistical mechanics. Special emphasis is put on new adiabatic theorems for steady states close to and far from equilibrium, and on investigating cyclic thermodynamic processes using an extension of Floquet theory. This work is based on the author’s doctoral thesis, ETH-Diss 16187.