Quantum Statistical Mechanics

Two approaches toward the arrow of time for scattering processes have been proposed in rigged Hilbert space quantum mechanics. One, due to Arno Bohm, involves preparations and registrations in laboratory operations and results in two semigroups oriented in the forward direction of time. The other, employed by the Brussels-Austin group, is more general, involving excitations and de-excitations of systems, and apparently results in two semigroups oriented in opposite directions of time. It turns out that these two time arrows can be (...) related to each other via Wigner's extensions of the spacetime symmetry group. Furthermore, their are subtle differences in causality as well as the possibilities for the existence and creation of time-reversed states depending on which time arrow is chosen. (shrink)

Arno Bohm and Ilya Prigogine's Brussels-Austin Group have been working on the quantum mechanical arrow of time and irreversibility in rigged Hilbert space quantum mechanics. A crucial notion in Bohm's approach is the so-called preparation/registration arrow. An analysis of this arrow and its role in Bohm's theory of scattering is given. Similarly, the Brussels-Austin Group uses an excitation/de-excitation arrow for ordering events, which is also analyzed. The relationship between the two approaches is discussed focusing on their semi-group operators and time (...) arrows. Finally a possible realist interpretation of the rigged Hilbert space formulation of quantum mechanics is considered. (shrink)

The use of joint distribution functions for noncommuting observables in quantum thermodynamics is investigated in the light of L. Cohen's proof that such distributions are not determined by the quantum state. Cohen's proof is irrelevant to uses of the functions that do not depend on interpreting them as distributions. An example of this, from quantum Onsager theory, is discussed. Other uses presuppose that correlations betweenp andq values depend at least on the state. But correlations may be fixed by the state (...) even though the distribution varies from one ensemble to another represented by that state. Taking covariance as a measure of correlation, it is shown that the different commonly used joint distributions yield the same correlations for a given state. A general characterization is given for a family of distributions with this same covariance. (shrink)

Entanglement is one of the most striking features of quantum mechanics, and yet it is not specifically quantum. More specific to quantum mechanics is the connection between entanglement and thermodynamics, which leads to an identification between entropies and measures of pure state entanglement. Here we search for the roots of this connection, investigating the relation between entanglement and thermodynamics in the framework of general probabilistic theories. We first address the question whether an entangled state can be transformed into another by (...) means of local operations and classical communication. Under two operational requirements, we prove a general version of the Lo-Popescu theorem, which lies at the foundations of the theory of pure-state entanglement. We then consider a resource theory of purity where free operations are random reversible transformations, modelling the scenario where an agent has limited control over the dynamics of a closed system. Our key result is a duality between the resource theory of entanglement and the resource theory of purity, valid for every physical theory where all processes arise from pure states and reversible interactions at the fundamental level. As an application of the main result, we establish a one-to-one correspondence between entropies and measures of pure bipartite entanglement and exploit it to define entanglement measures in the general probabilistic framework. In addition, we show a duality between the task of information erasure and the task of entanglement generation, whereby the existence of entropy sinks (systems that can absorb arbitrary amounts of information) becomes equivalent to the existence of entanglement sources (correlated systems from which arbitrary amounts of entanglement can be extracted). (shrink)

In quantum theory every state can be diagonalized, i.e. decomposed as a convex combination of perfectly distinguishable pure states. This elementary structure plays an ubiquitous role in quantum mechanics, quantum information theory, and quantum statistical mechanics, where it provides the foundation for the notions of majorization and entropy. A natural question then arises: can we reconstruct these notions from purely operational axioms? We address this question in the framework of general probabilistic theories, presenting a set of axioms that guarantee that (...) every state can be diagonalized. The first axiom is Causality, which ensures that the marginal of a bipartite state is well defined. Then, Purity Preservation states that the set of pure transformations is closed under composition. The third axiom is Purification, which allows to assign a pure state to the composition of a system with its environment. Finally, we introduce the axiom of Pure Sharpness, stating that for every system there exists at least one pure effect occurring with unit probability on some state. For theories satisfying our four axioms, we show a constructive algorithm for diagonalizing every given state. The diagonalization result allows us to formulate a majorization criterion that captures the convertibility of states in the operational resource theory of purity, where random reversible transformations are regarded as free operations. (shrink)

The thermodynamic behavior is analyzed of a single classical charged particle in thermal equilibrium with classical electromagnetic thermal radiation, while electrostatically bound by a fixed charge distribution of opposite sign. A quasistatic displacement of this system in an applied electrostatic potential is investigated. Treating the system nonrelativistically, the change in internal energy, the work done, and the change in caloric entropy are all shown to be expressible in terms of averages involving the distribution of the position coordinates alone. A convenient (...) representation for the probability distribution is shown to be the ensemble average of the absolute square value of an expansion over the eigenstates of a Schrödinger-like equation, since the heat flow is shown to vanish for each hypothetical “state.” Subject to key assumptions highlighted here, the demand that the entropy be a function of state results in statistical averages in agreement with the form in quantum statistical mechanics. Examining the very low and very high temperature situations yields Planck's and Boltzmann's constants. The blackbody radiation spectrum is then deduced. From the viewpoint of the theory explored here, the method in quantum statistical mechanics of statistically counting the “states” at thermal equilibrium by using the energy eigenvalue structure, is simply a convenient counting scheme, rather than actually representing averages involving physically discrete energy states. (shrink)

Textbooks in quantum mechanics frequently claim that quantum mechanics explains the success of classical mechanics because “the mean values [of quantum mechanical observables] follow the classical equations of motion to a good approximation,” while “the dimensions of the wave packet be small with respect to the characteristic dimensions of the problem.” The equations in question are Ehrenfest’s famous equations. We examine this case for the one-dimensional motion of a particle in a box, and extend the idea deriving a special case (...) of the ideal gas law in terms of the mean value of a generalized force, which has been used in statistical mechanics to define ‘pressure’. The example may be an important test case for recent philosophical theories about the relationship between micro-theories and macro-theories in science. (shrink)

Classical mechanics is empirically successful because the probabilistic mean values of quantum mechanical observables follow the classical equations of motion to a good approximation (Messiah 1970, 215). We examine this claim for the one-dimensional motion of a particle in a box, and extend the idea by deriving a special case of the ideal gas law in terms of the mean value of a generalized force used to define "pressure." The examples illustrate the importance of probabilistic averaging as a method of (...) abstracting away from the messy details of microphenomena, not only in physics, but in other sciences as well. (shrink)

in Stochastic Processes, Physics and Geometry II, edited by S. Albeverio, U. Cattaneo, D. Merlini (World Scientific, Singapore, 1995) pp. 221-232.

In Bohmian mechanics the distribution |ψ|2 is regarded as the equilibrium distribution. We consider its uniqueness, finding that it is the unique equivariant distribution that is also a local functional of the wave function ψ.

The renewed interest in the foundations of quantum statistical mechanics in recent years has led us to study John von Neumann’s 1929 article on the quantum ergodic theorem. We have found this almost forgotten article, which until now has been available only in German, to be a treasure chest, and to be much misunderstood. In it, von Neumann studied the long-time behavior of macroscopic quantum systems. While one of the two theorems announced in his title, the one he calls the (...) “quantum H-theorem,” is actually a much weaker statement than Boltzmann’s classical H-theorem, the other theorem, which he calls the “quantum ergodic theorem,” is a beautiful and very non-trivial result. It expresses a fact we call “normal typicality” and can be summarized as follows: For a “typical” finite family of commuting macroscopic observables, every initial wave function ψ0 from a micro-canonical energy shell so evolves that for most times t in the long run, the joint probability distribution of these observables obtained from ψt is close to their micro-canonical distribution. (shrink)

We discuss the content and significance of John von Neumann’s quantum ergodic theorem (QET) of 1929, a strong result arising from the mere mathematical structure of quantum mechanics. The QET is a precise formulation of what we call normal typicality, i.e., the statement that, for typical large systems, every initial wave function ψ0 from an energy shell is “normal”: it evolves in such a way that |ψt ψt| is, for most t, macroscopically equivalent to the micro-canonical density matrix. The QET (...) has been mostly forgotten after it was criticized as a dynamically vacuous statement in several papers in the 1950s. However, we point out that this criticism does not apply to the actual QET, a correct statement of which does not appear in these papers, but to a different (indeed weaker) statement. Furthermore, we formulate a stronger statement of normal typicality, based on the observation that the bound on the deviations from the average specified by von Neumann is unnecessarily coarse and a much tighter (and more relevant) bound actually follows from his proof. (shrink)

We consider an isolated, macroscopic quantum system. Let H be a microcanonical “energy shell,” i.e., a subspace of the system’s Hilbert space spanned by the (finitely) many energy eigenstates with energies between E and E + δE. The thermal equilibrium macro-state at energy E corresponds to a subspace Heq of H such that dim Heq/ dim H is close to 1. We say that a system with state vector ψ H is in thermal equilibrium if ψ is “close” to Heq. (...) We show that for “typical” Hamiltonians with given eigenvalues, all initial state vectors ψ0 evolve in such a way that ψt is in thermal equilibrium for most times t. This result is closely related to von Neumann’s quantum ergodic theorem of 1929. (shrink)

The renewed interest in the foundations of quantum statistical mechanics in recent years has led us to study John von Neumann’s 1929 article on the quantum ergodic theorem. We have found this almost forgotten article, which until now has been available only in German, to be a treasure chest, and to be much misunderstood. In it, von Neumann studied the long-time behavior of macroscopic quantum systems. While one of the two theorems announced in his title, the one he calls the (...) “quantum H-theorem,” is actually a much weaker statement than Boltzmann’s classical H-theorem, the other theorem, which he calls the “quantum ergodic theorem,” is a beautiful and very non-trivial result. It expresses a fact we call “normal typicality” and can be summarized as follows: For a “typical” finite family of commuting macroscopic observables, every initial wave function ψ0 from a micro-canonical energy shell so evolves that for most times t in the long run, the joint probability distribution of these observables obtained from ψ is close to.. (shrink)

In an earlier paper by one of us [K.-E. Hellwig (1981)], elements of discrete quantum stochastic processes which arise when the classical probability space is replaced by quantum theory have been considered. In the present paper a general formulation is given and its properties are compared with those of classical stochastic processes. Especially, it is asked whether such processes can be Markovian. An example is given and similarities to methods in quantum statistical thermodynamics are pointed out.

In 1916, Einstein rederived the blackbody radiation law of Planck that originated the idea of quantized energy one hundred years ago. For this purpose, Einstein introduced the concept of transition probability, which had a profound influence on the development of quantum theory. In this article, we adopt Einstein's assumptions with two exceptions and seek the statistical condition for the thermal equilibrium of matter without referring to the inner details of either statistical thermodynamics or quantum theory. It is shown that the (...) conditions of thermodynamic equilibrium of electromagnetic radiation and the energy balance of thermal radiation by the matter, between any of its two energy-states, not only result in Planck's radiation law and the Bohr frequency condition, but they remarkably yield the law of the statistical thermal equilibrium of matter: the Maxwell–Boltzmann distribution. Since the transition probabilities of the modern quantum theory of radiation coincide with their definition in Einstein's theory of blackbody radiation, the presented deduction of the Maxwell–Boltzmann distribution is equally valid within the bounds of modern quantum theory. Consequently, within the framework of the fundamental assumptions, the Maxwell–Boltzmann distribution of energy-states is not only a sufficient, but a necessary condition for thermal equilibrium between the matter and radiation. (shrink)

I discuss the question: Is it possible to prepare, by purely thermodynamic means, an ensemble described by a quantum state having a definite phase relation between two component states which have never been in direct contact? Resolution of this question requires us to take explicit account of the nature of the correlations between the system and its thermal environment.

It is shown that in the quantum theory of systems with a finite number of degrees of freedom which employs a set of algebraic states, a statistical element introduced by averaging the mean values of operators over the distribution of continuous quantities (a spectrum point of a canonical operator and time) is conserved for the limiting transition to the δ distribution. On that basis, quantum statistical dynamics, i.e., a theory in which dynamics (time evolution) includes a statistical element, is advanced. (...) The theory is equivalent to orthodox quantum mechanics as regards the orthodox states, but is essentially different with respect to the coherence properties in a continuous spectrum. The measurement-process theory, including the statistical interpretation of quantum mechanics, and the irreversibility theory are constructed, and the law of increasing chaos, which is a strengthening of the law of entropy increase, is obtained. In our theory, mechanics and statistics are organically connected, whereby the fundamental nature of probabilities in quantum physics manifests itself. (shrink)

A universal, unified theory of transformations of physical systems based on the propositions of probabilistic physics is developed. This is applied to the treatment of decay processes and intramolecular rearrangements. Some general features of decay processes are elucidated. A critical analysis of the conventional quantum theories of decay and of Slater's quantum theory of intramolecular rearrangements is given. It is explained why, despite the incorrectness of the decay theories in principle, they can give correct estimations of decay rate constants. The (...) reasons for the validity of the Arrhenius formula for the temperature dependence of an intramolecular rearrangement rate constant are discussed. A criterion for the possibility of a proper intramolecular rearrangement is given. The issue of causality in quantum physics is settled. (shrink)

The aim of the present paper is to show that the formalism of equilibrium quantum statistical mechanics can fully be incorporated into Ludwig's embedding scheme for classical theories in many-body quantum mechanics. A construction procedure based on a recently developed reconstruction procedure for the so-called macro-observable is presented which leads to the explicit determination of the set of classical ensembles compatible with the embedding scheme.

It is shown that the traditional formalism of equilibrium quantum statistical mechanics may fully be incorporated into a general macro-observable approach to quantum statistical mechanics recently proposed by the same author. (1,2) In particular, the partition functions which in the traditional approach are assumed to connect nonnormalized density operators with thermodynamic functions are reinterpreted as functions connecting so-called quantum mechanical effect operators with state parameters. It is argued that these functions although only part of a much richer internal structure of (...) the macro-observable are sufficient to cope with all problems one usually encounters in equilibrium quantum statistical mechanics. p]Denn eigentlich unternehmen wir umsonst, das Wesen eines Dinges auszudrücken. Wirkungen werden wir gewahr, und eine vollständige Geschichte dieser Wirkungen umfaßte wohl allenfalls das Wesen jenes Dinges.Johann W. v. Goethe Farbenlehre. (shrink)

The aim of this paper is to reconcile the two modes of description of macrosystems, i.e., to remove certain inconsistencies between the classical phenomenological and the quantum-theoretical descriptions of a macrosystem. Starting from Ludwig's formulation of a general framework for classical theories and his ansatz for a compatibility condition between the quantum theoretical and the classical mode of description for a macrosystem, we try to make clear what the “classical content” of many-body quantum theory really is. It is shown that (...) this classical content may be described by a certain “observable,” i.e., an operator-valued measure over the Borel sets of the classical trajectory space. There exists a reduced time evolution within this classical content which has the structure of a true semigroup in case of an irreversible classical time evolution. (shrink)

A major part of Einstein’s 1905 light quantum paper is devoted to arguing that high frequency heat radiation bears the characteristic signature of a microscopic energy distribution of independent, spatially localized components. The content of his light quantum proposal was precarious in that it contradicted the great achievement of nineteenth century physics, the wave theory of light and its accommodation in electrodynamics. However the methods used to arrive at it were both secure and familiar to Einstein in 1905. A mainstay (...) of Einstein’s research in statistical physics, extending to his earliest publications of 1901 and 1902, had been the inferring of the microscopic constitution of systems from their macroscopic properties. In his statistical work of 1905, Einstein dealt with several thermal systems consisting of many, independent, spatially localized components. They were the dilute sugar solutions of his doctoral dissertation and suspended particles of his Brownian motion paper. (shrink)

In the sixth section of his light quantum paper of 1905, Einstein presented the miraculous argument, as I shall call it. Pointing out an analogy with ideal gases and dilute solutions, he showed that the macroscopic, thermodynamic properties of high frequency heat radiation carry a distinctive signature of finitely many, spatially localized, independent components and so inferred that it consists of quanta. I describe how Einstein’s other statistical papers of 1905 had already developed and exploited the idea that the ideal (...) gas law is another macroscopic signature of finitely many, spatially localized, independent components and that these papers in turn drew on his first two, “worthless” papers of 1901 and 1902 on intermolecular forces. However, while the ideal gas law was a secure signature of independence, it was harder to use as an indicator that there are finitely many components and that they are spatially localized. Further, since his analysis of the ideal gas law depended on the assumption that the number of components was fixed, its use was precluded for heat radiation, whose component quanta vary in number in most processes. So Einstein needed and found another, more powerful signature of discreteness applicable to heat radiation and which indicated all these properties. It used one of the few processes, volume fluctuation, in which heat radiation does not alter the number of quanta. (shrink)

There have been attempts to derive anti-haeccetistic conclusions from the fact that quantum mechanics (QM) appeals to non-standard statistics. Since in fact QM acknowledges two kinds of such statistics, Bose-Einstein and Fermi-Dirac, I argue that we could in the same vein derive the sharper anti-haeccetistic conclusion that bosons are bundles of tropes and fermions are bundles of universals. Moreover, since standard statistics is still appropriate at the macrolevel, we could also venture to say that no anti-haecceitistic conclusion is warranted for (...) ordinary objects, which could then tentatively be identified with substrates. In contrast to this, however, there has been so far no acknowledgement of the possibility of inclusivism, according to which ontological accounts of particulars as widely different as those can possibly coexist in one world picture. The success of the different statistics in physics at least calls for a revision in this respect. (shrink)

Using linear invariant operators in a constructive way we find the most general thermal density operator and Wigner function for time-dependent generalized oscillators. The general Wigner function has five free parameters and describes the thermal Wigner function about a classical trajectory in phase space. The contour of the Wigner function depicts an elliptical orbit with a constant area moving about the classical trajectory, whose eccentricity determines the squeezing of the initial vacuum.

The Jarzynski equality equates the mean of the exponential of the negative of the work (per fixed temperature) done by a changing Hamiltonian on a system, initially in thermal equilibrium at that temperature, to the ratio of the final to the initial equilibrium partition functions of the system at that fixed temperature. It thus relates two thermal equilibrium quantum states.

Using Schrödinger's generalized probability relations of quantum mechanics, it is possible to generate a canonical ensemble, the ensemble normally associated with thermodynamic equilibrium, by at least two methods, statistical mixing and subensemble selection, that do not involve thermodynamic equilibration. Thus the question arises as to whether an observer making measurements upon systems from a canonical ensemble can determine whether the systems were prepared by mixing, equilibration, or selection. Investigation of this issue exposes antinomies in quantum statistical thermodynamics. It is conjectured (...) that resolution of these paradoxes may involve a new law of motion in quantum dynamics. (shrink)

If the ordinary quantal Liouville equation ℒρ= $\dot \rho $ is generalized by discarding the customary stricture that ℒ be of the standard Hamiltonian commutator form, the new quantum dynamics that emerges has sufficient theoretical fertility to permit description even of a thermodynamically irreversible process in an isolated system, i.e., a motion ρ(t) in which entropy increases but energy is conserved. For a two-level quantum system, the complete family of time-independent linear superoperators ℒ that generate such motions is derived; and (...) a physically interesting example is presented in detail. (shrink)

This communication is part I of a series of papers which explore the theoretical possibility of generalizing quantum dynamics in such a way that the predicted motions of an isolated system would include the irreversible (entropy-increasing) state evolutions that seem essential if the second law of thermodynamics is ever to become a theorem of mechanics. In this first paper, the general mathematical framework for describing linear but not necessarily Hamiltonian mappings of the statistical operator is reviewed, with particular attention to (...) detailed representations of the Kossakowski conditions for the case of a two-level system. (shrink)

In previous publications we have criticized the usual application of information theory to quantal situations and proposed a new version of information-theoretic quantum statistics. This paper is the first in a two-part series in which our new approach is applied to the fundamental problem of thermodynamic equilibrium. Part I deals in particular with informational definitions of equilibrium and the identification of thermodynamic analogs in our modified quantum statistics formalism.

Quasi-probability distribution functions fj WW, fj MM for quantum spin-j systems are derived based on the Wigner-Weyl, Margenau-Hill approaches. A probability distribution fj sph which is nonzero only on the surface of the sphere of radius √j(j+1) is obtained by expressing the characteristic function in terms of the spherical moments. It is shown that the Wigner-Weyl distribution function turns out to be a distribution over the sphere in the classical limit.

If a classical system has infinitely many degrees of freedom, its Hamiltonian quantization need not be unique up to unitary equivalence. I sketch different approaches (Hilbert space and algebraic) to understanding the content of quantum theories in light of this non‐uniqueness, and suggest that neither approach suffices to support explanatory aspirations encountered in the thermodynamic limit of quantum statistical mechanics.

In this paper the quantum covariant relativistic dynamics of many bodies is reconsidered. It is emphasized that this is an event dynamics. The events are quantum statistically correlated by the global parameter τ. The derivation of an event Boltzmann equation emphasizes this. It is shown that this Boltzmann equation may be viewed as exact in a dilute event limit ignoring three event correlations. A quantum entropy principle is obtained for the marginal Wigner distribution function. By means of event linking (concatenations) (...) particle properties such as the equation of state may be obtained. We further reconsider the generalized quantum equilibrium ensemble theory and the free event case of the Fermi-Dirac and Bose-Einstein distributions, and some consequences. The ultra-relativistic limit differs from the non-covariant theory and is a test of this point of view. (shrink)

Various formalisms for recasting quantum mechanics in the framework of classical mechanics on phase space are reviewed and compared. Recent results in stochastic quantum mechanics are shown to avoid the difficulties encountered by the earlier approach of Wigner, as well as to avoid the well-known incompatibilities of relativity and ordinary quantum theory. Specific mappings among the various formalisms are given.

In quantum mechanics, the expression for entropy is usually taken to be -kTr(ln), where is the density matrix. The convention first appears in Von Neumann's Mathematical Foundations of Quantum Mechanics. The argument given there to justify this convention is the only one hitherto offered. All the arguments in the field refer to it at one point or another. Here this argument is shown to be invalid. Moreover, it is shown that, if entropy is -kTr(ln), then perpetual motion machines are possible. (...) This and other considerations support the conclusion that this expression is not the quantum-mechanical correlate of thermodynamic entropy. Its usefulness in quantum-statistical mechanics can be explained by its being a convenient quantification of information, but information and entropy are not synonymous. As the present paper shows, one can change while the other is conserved. (shrink)

The recent renewed interest in the foundation of quantum statistical mechanics and in the dynamics of isolated quantum systems has led to a revival of the old approach by von Neumann to investigate the problem of thermalization only in terms of quantum dynamics in an isolated system [1, 2]. It has been demonstrated in some general or concrete settings that a pure initial state evolving under quantum dynamics indeed approaches an equilibrium state [3–9]. The underlying idea that a single pure (...) quantum state can fully describe thermal equilibrium has also become much more concrete [10–12]. (shrink)