A one-dimensional quantum gas with \ensuremath{\delta}-function interaction is known to be integrable for any finite number of particles. We show that in the thermodynamic limit invariants of motion are destroyed in conjunction with a class of singular density matrices that appear commonly in both equilibrium and nonequilibrium statistical mechanics. The system becomes nonintegrable, due to Poincar\'e resonances. However, the eigenvalue problem of the Liouville--von Neumann operator ${L}_{H}$ may be solved in an extended functional space that contains the singular density matrices. We may in this way describe the approach to equilibrium. This is a simple example of the Liouville space extension of quantum mechanics, due to Prigogine and his co-workers. The fundamental quantity in this formulation is the probability (and not the wave function). We obtain indeed an irreducible complex spectral representation of ${L}_{H}.$ Irreducible means that the eigenstates of ${L}_{H}$ cannot be implemented by wave functions, and complex means that the eigenvalues are complex numbers, whose imaginary parts determine relaxation times of the system. The dynamical evolution is described by a semigroup. Due to dissipative effects the real part of the eigenvalues is no more a difference of energy levels, as is the case in standard quantum mechanics.
A one-dimensional quantum gas with \ensuremath{\delta}-function interaction is known to be integrable for any finite number of particles. We show that in the thermodynamic limit invariants of motion are destroyed in conjunction with a class of singular density matrices that appear commonly in both equilibrium and nonequilibrium statistical mechanics. The system becomes nonintegrable, due to Poincar'e resonances. However, the eigenvalue problem of the Liouville--von Neumann operator LH may be solved in an extended functional space that contains the singular density matrices. We may in this way describe the approach to equilibrium. This is a simple example of the Liouville space extension of quantum mechanics, due to Prigogine and his co-workers. The fundamental quantity in this formulation is the probability (and not the wave function). We obtain indeed an irreducible complex spectral representation of LH. Irreducible means that the eigenstates of LH cannot be implemented by wave functions, and complex means that the eigenvalues are complex numbers, whose imaginary parts determine relaxation times of the system. The dynamical evolution is described by a semigroup. Due to dissipative effects the real part of the eigenvalues is no more a difference of energy levels, as is the case in standard quantum mechanics.
Nonintegrable Poincaré systems with continuous spectrum (so-called Large Poincaré Systems, LPS) lead to the appearance of diffusive terms in the framework of dynamics. These terms break time symmetry. They lead, therefore, to limitations to classical trajectory dynamics and of wave functions. 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 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 formulations of classical or quantum mechanics. Instead of being irreducible 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 we inherited from the 19th 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 the many-world theory, coarse graining or averaging over the environment). There is a striking parallelism between classical and quantum theory. For LPS we have, in general, both a “collapse” of trajectories and of wave functions for LPS. 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 know 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. The formulation is appropriate to describe an open, evolving universe.
Abstract We discuss the spectral property of unstable dynamical systems in both classical and quantum mechanics. An important class of unstable dynamical systems corresponds to the Large Poincare Systems (LPS). Conventional perturbation technique leads then to divergences. We introduce methods for the elimination of Poincare divergences to obtain a solution of the spectral problem analytic in the coupling constant. To do so, we have to enlarge the class of permissible transformations, to include non-unitary transformations as well as to extend the Hilbert space. A simple example refers to the Friedrichs model, which was studied independently by George Sudarshan and his co-workers. However, our main interest is the irreducible representations in the Liouville space. In these representations the central quantity is the density matrix, and the eigenfunctions of the Liouville operator cannot be expressed in terms of the wave functions. We suggest that this situation corresponds to quantum chaos. Indeed, classical chaos does not mean that Newton's equation becomes "wrong" but that trajectories loose their operational meaning. Similarly, whenever we have an irreducible representation in the Liouville space this means that the wave function description looses its operational meaning. Additional statistical features appear. A simple example corresponds to persistent interactions in the scattering problem which cannot be treated in the frame of usual S-matrix theory.
Kinetic theory in nonequilibrium statistical physics is discussed in terms of the complex spectral representation of the Liouvillian for quantum systems. We show that the collision operator appearing in the kinetic equation is the “self-energy part” of the Liouvillian. Solving the dispersion equation associated to the “self-energy part”, one can construct the resonance states of the Liouvillian which have complex eigenvalues. The imaginary part of the eigenvalue gives a decay rate in irreversible process in nonequilibrium statistical physics. As illustrations of the resonance states of the Liouvillian we consider two examples; one is a one-dimensional system in which a polaron is weakly interacting with a thermal reservoir consisting of an acoustic phonon field, and the other is a molecular chain that is described by the Davydov Hamiltonian, which has been introduced as a simple model that describes a protein chain. We show that the imaginary part of the spectrum of the Liouvillian in these systems has rich structures showing band structure, an accumulation point, and a fractal structure reminiscent of Hofstadter's butterfly.
The starting point of the classical description of motion is the Newton equations that yield a phase space trajectory (rN (t), pN (t)) for a given initial condition (rN (0), pN (0)). Alternatively one may describe classical motion in the framework of the Liouville equation (Section (1.2.2)) that describes the time evolution of the phase space probability density f (rN , pN ; t). For a closed system fully described in terms of a well specified initial condition, the two descriptions are completely equivalent. Probabilistic treatment becomes essential in reduced descriptions that focus on parts of an overall system, as was demonstrated in Sections 5.1–5.3 for equilibrium systems, and in Chapters 7 and 8 that focus on the time evolution of classical systems that interact with their thermal environments. This chapter deals with the analogous quantum mechanical problem. Within the limitations imposed by its nature as expressed, for example, by Heisenbergtype uncertainty principles, the Schrödinger equation is deterministic. Obviously it describes a deterministic evolution of the quantum mechanical wavefunction. The analog of the phase space probability density f (rN , pN ; t) is now the quantum mechanical density operator (often referred to as the “density matrix”), whose time evolution is determined by the quantum Liouville equation. Again, when the system is fully described in terms of a well specified initial wavefunction, the two descriptions are equivalent. The density operator formalism can, however, be carried over to situations where the initial state of the system is not well characterized and/or a reduced description of part of the overall system is desired. Such situations are considered later in this chapter.
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.