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Advances in chemical physics

Advances in Chemical Physics

Prigogine, Ilya, Stuart A. Rice

Published Jan 1, 1996• 41 citations
Publisher

Abstract

In Resonances, Instability, and Irreversibility: The LiouvilleSpace Extension of Quantum Mechanics T. Petrosky and I. Prigogine Unstable Systems in Generalized Quantum Theory E. C. G. Sudarshan, Charles B. Chiu, and G. Bhamathi Resonances and Dilatation Analyticity in Liouville Space Erkki J. Brandas Time, Irreversibility, and Unstable Systems in QuantumPhysics E. Eisenberg and L. P. Horwitz Quantum Systems with Diagonal Singularity I. Antoniou and Z. Suchanecki Nonadiabatic Crossing of Decaying Levels V. V. and Vl. V. Kocharovsky and S. Tasaki Can We Observe Microscopic Chaos in the Laboratory? Pierre Gaspard Proton Nonlocality and Decoherence in Condensed Matter --Predictions and Experimental Results C. A. Chatzidimitriou-Dreismann "We are at a most interesting moment in the history of science.Classical science emphasized equilibrium, stability, and timereversibility. Now we see instabilities, fluctuations, evolution onall levels of observations. This change of perspective requires newtools, new concepts. This volume invites the reader not to anenumeration of final achievements of contemporary science, but toan excursion to science in the making." --from the Foreword by I.Prigogine What are the dynamical roots of irreversibility? How can past andfuture be distinguished on the fundamental level of description?Are human beings the children of time --or its progenitors? Inrecent years, a growing number of chemists and physicists haveagreed that the solution to the problem of irreversibility requiresan extension of classical and quantum mechanics. There is, however, no consensus on which direction this extension should take toinclude the dynamical description of irreversible processes. Resonances, Instability, and Irreversibility surveys recentattempts --both direct and indirect --to address the problem ofirreversibility. Internationally recognized researchers report ontheir recent studies, which run the gamut from experimental tohighly mathematical. The subject matter of these papers falls intothree categories: classical systems with emphasis on chaos anddynamical instability, resonances and unstable quantum systems, andthe general problem of irreversibility. Presenting the cutting edge of research into some of the mostcompelling questions that face contemporary chemical physics, Resonances, Instability, and Irreversibility is fascinating readingfor professionals and students in every area of the discipline.

DOI
10.1002/9780470141588

Related papers

Nonlinear, deformed and irreversible quantum systems : proceedings of the International Symposium on Mathematical Physics, Arnold Sommerfeld Institute 15-19 August 1994, Clausthat, Germany

Heinz Dietrich Doebner, V. K. Dobrev, P. Nattermann

Intrinsically irreversible representations of unstable quantum systems, I. Antoniou quantum mechanical arrows of time, A. Bohm isotropic harmonic oscillator on the quantum euclidean space, G. Fiore relevant and irrelevant nonlinear schrodinger equation, N. Gisin diffeomorphism groups and nonlinear quantum mechanics, G.A. Goldin from Hamiltonian mechanics to nonlinear Schrodinger equations, J.-D. Hennig nonlinear Schrodinger dynamics and nonlinear observables, W. Lucke nonlinear gauge transformations and the Doebner-Goldin equation, P. Nattermann chaos and the limit of classical and quantum mechanics, T. Petrosky why irreversibility? the formulation of classical and quantum mechanics for unstable dynamical systems, I. Prigogine harmonic oscillators on quantum space, S. Watamura. (Part Contents).

WORLD SCIENTIFIC eBooks•Jan 1, 1995•4 citations

WHY IRREVERSIBILITY? THE FORMULATION OF CLASSICAL AND QUANTUM MECHANICS FOR NONINTEGRABLE SYSTEMS

Ilya Prigogine

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.

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Quantum statistical mechanics, extended

William C. Schieve, Lawrence Paul Horwitz

Intrinsic theory of irreversibility In connection with the previous chapter on Wigner–Weisskopf, quantum irreversibility, Gamov states and the Lax–Phillips theory of decay, we shall examine the recent program in statistical mechanics carried forward by Ilya Prigogine and his colleagues since his early book in 1962 (Prigogine, 1962). This discussion is somewhat out of the focus of the present book, since the work to be discussed has principally been devoted to isolated quantum systems, not those in interaction with “reservoirs.” In addition, Prigogine's work is very classical in its content. We shall not attempt the task of reviewing the many changes that have taken place between 1962 and the present. Fine texts describing some of this work are those of Balescu (1963, 1975). A recent critical overview of the “modern view” is in the unpublished thesis of B. C. Bishop of the University of Texas Philosophy Department (Bishop, 1999). In many ways this is related to the use of Gel'fand triplets (Gel'fand and Vilenkin, 1968), mentioned in Chapter 17.6, to describe irreversible quantum states, i.e. Gamov states. See Chapter 17, the book of Bohm and Gadella (1989) and also the more recent review article by Bohm and colleagues (Bohm et al. , 1997). The object in statistical mechanics is to extend the range of the Liouville operator (classical and quantum) such that its eigenvalues are complex and intrinsically irreversible. Statistical mechanics has always been focused on many particle systems and the appearance of a continuum spectrum in the thermodynamic limit, already used in many places in this book. In the classical case Antoniou and Tasaki carried out the adaptation of the Gel'fand triplet approach to the Liouville operator, but this is, apparently, not possible quantum mechanically (Antoniou and Tasaki, 1993). Thus, another route must be taken in what Prigogine has termed, for emphasis, “large Poincaré systems” which have a continuum spectrum (Prigogine, 1997).

Cambridge University Press eBooks•Apr 16, 2009•0 citations

Why irreversibility? The formulation of classical and quantum mechanics for nonintegrable systems

Ilya Prigogine

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.

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Karl E. Gustafson, William P. Reinhardt

Total Cross Sections in Non-Relativistic Scattering Theory.- Classical-Quantum Correspondence in Non-Linear Systems.- Real Axis Asymptotics and Estimates of Hamiltonian Resolvent Kernels.- Statistical Inference in Quantum Mechanics.- Schrodinger Operators with Oscillating Potentials.- Time Delay and Resonance in Simple Scattering.- A Study of the Helmholtz Operator.- Invariant Manifolds and Bifurcations in the Taylor Problem.- On the Dimension of a Finite Difference Approximation to Divergence-Free Vectors.- Intramolecular Dynamics in the Quasiperiodic and Stochastic Regimes.- Problems in the Semiclassical Quantization of Integrable and Nonintegrable Classical Dynamical Systems.- Nonselfadjoint Operators in Diffraction and Scattering.- One-Dimensional Crystals in an External Field.- Dynamics of Forced Coupled Oscillators: Classical Phenomenology of Infrared Multiphoton Absorption.- Irreversibility and Stochasticity of Chemical Processes.- On the Representations of the Local Current Algebra and the Group of Diffeomorphisms (I).- Regular and Chaotic Regimes in Quantum Mechanics.- Barrier Penetration and Exponential Decay in the Stark Effect.- A Nonlinear Schrodinger Equation Yielding the Shape of Molecules by Spontaneous Symmetry Breaking.- Classical Limit of the Number of Quantum States.- Formal Integrals for a Nonintegrable Dynamical System: Preliminary Report.- On a Generalized Weyl-Von Neumann Converse Theorem.- Scattering Theory in Many-Body Quantum Systems. Analyticity of the Scattered Matrix.- Existence, Uniqueness, Stability and Calculation of the Stationary Regimes in Some Nonlinear Systems.- Weighted Trigonometric Approximations in L2(Rn).- The Phenomenon of Magnetic Pairing and Exactly Soluble Models of Magnetic Resonances.- Dyons Solutions to Yang-Mills Equations.- Asymptotic Resonance Properties of the Finite-Dimensional Friedrichs Model.- Self-Consistent Field Methods for Metastable Electronic States: A Promising Extension of the Complex Coordinate Technique.- Timestep Control for the Numerical Solutions of Initial-Boundary-Value Problems.- Quantum Mechanical Angular Distributions and Group Representations on Banach Spaces.- Tensor Product Decomposition of Holomorphically Induced Representations and Clebsch-Gordan Coefficients.- Orthogonal Laurent Polynomials and Gaussian Quadrature.- Measurement Theory with Instruments Treated Partially Quantum Mechanically.- Transition Maps and Locality.- The Feynman-Kac Formula for Boson Wiener Processes.- On Nonunitary Equivalence Between Unitary Group of Dynamics and Contraction Semigroups of Markov Processes.

•Nov 1, 2011•50 citations
In Resonances, Instability, and Irreversibility: The LiouvilleSpace Extension of Quantum Mechanics T. Petrosky and I. Prigogine Unstable Systems in Generalized Quantum Theory E. C. G. Sudarshan, Charles B. Chiu, and G. Bhamathi Resonances and Dilatation Analyticity in Liouville Space Erkki J. Brandas Time, Irreversibility, and Unstable Systems in QuantumPhysics E. Eisenberg and L. P. Horwitz Quantum Systems with Diagonal Singularity I. Antoniou and Z. Suchanecki Nonadiabatic Crossing of Decaying Levels V. V. and Vl. V. Kocharovsky and S. Tasaki Can We Observe Microscopic Chaos in the Laboratory? Pierre Gaspard Proton Nonlocality and Decoherence in Condensed Matter --Predictions and Experimental Results C. A. Chatzidimitriou-Dreismann "We are at a most interesting moment in the history of science.Classical science emphasized equilibrium, stability, and timereversibility. Now we see instabilities, fluctuations, evolution onall levels of observations. This change of perspective requires newtools, new concepts. This volume invites the reader not to anenumeration of final achievements of contemporary science, but toan excursion to science in the making." --from the Foreword by I.Prigogine What are the dynamical roots of irreversibility? How can past andfuture be distinguished on the fundamental level of description?Are human beings the children of time --or its progenitors? Inrecent years, a growing number of chemists and physicists haveagreed that the solution to the problem of irreversibility requiresan extension of classical and quantum mechanics. There is, however, no consensus on which direction this extension should take toinclude the dynamical description of irreversible processes. Resonances, Instability, and Irreversibility surveys recentattempts --both direct and indirect --to address the problem ofirreversibility. Internationally recognized researchers report ontheir recent studies, which run the gamut from experimental tohighly mathematical. The subject matter of these papers falls intothree categories: classical systems with emphasis on chaos anddynamical instability, resonances and unstable quantum systems, andthe general problem of irreversibility. Presenting the cutting edge of research into some of the mostcompelling questions that face contemporary chemical physics, Resonances, Instability, and Irreversibility is fascinating readingfor professionals and students in every area of the discipline.
Intrinsically irreversible representations of unstable quantum systems, I. Antoniou quantum mechanical arrows of time, A. Bohm isotropic harmonic oscillator on the quantum euclidean space, G. Fiore relevant and irrelevant nonlinear schrodinger equation, N. Gisin diffeomorphism groups and nonlinear quantum mechanics, G.A. Goldin from Hamiltonian mechanics to nonlinear Schrodinger equations, J.-D. Hennig nonlinear Schrodinger dynamics and nonlinear observables, W. Lucke nonlinear gauge transformations and the Doebner-Goldin equation, P. Nattermann chaos and the limit of classical and quantum mechanics, T. Petrosky why irreversibility? the formulation of classical and quantum mechanics for unstable dynamical systems, I. Prigogine harmonic oscillators on quantum space, S. Watamura. (Part Contents).
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.
Examines the intersection of quantum information and chemical physics The Advances in Chemical Physics series is dedicated to reviewing new and emerging topics as well as the latest developments in traditional areas of study in the field of chemical physics. Each volume features detailed comprehensive analyses coupled with individual points of view that integrate the many disciplines of science that are needed for a full understanding of chemical physics. This volume of the series explores the latest research findings, applications, and new research paths from the quantum information science community. It examines topics in quantum computation and quantum information that are related to or intersect with key topics in chemical physics. The reviews address both what chemistry can contribute to quantum information and what quantum information can contribute to the study of chemical systems, surveying both theoretical and experimental quantum information research within the field of chemical physics. With contributions from an international team of leading experts, Volume 154 offers seventeen detailed reviews, including: Introduction to quantum information and computation for chemistry Quantum computing approach to non-relativistic and relativistic molecular energy calculations Quantum algorithms for continuous problems and their applications Photonic toolbox for quantum simulation Vibrational energy and information transfer through molecular chains Tensor networks for entanglement evolution Reviews published in Advances in Chemical Physics are typically longer than those published in journals, providing the space needed for readers to fully grasp the topic: the fundamentals as well as the latest discoveries, applications, and emerging avenues of research. Extensive cross-referencing enables readers to explore the primary research studies underlying each topic.
Intrinsic theory of irreversibility In connection with the previous chapter on Wigner–Weisskopf, quantum irreversibility, Gamov states and the Lax–Phillips theory of decay, we shall examine the recent program in statistical mechanics carried forward by Ilya Prigogine and his colleagues since his early book in 1962 (Prigogine, 1962). This discussion is somewhat out of the focus of the present book, since the work to be discussed has principally been devoted to isolated quantum systems, not those in interaction with “reservoirs.” In addition, Prigogine's work is very classical in its content. We shall not attempt the task of reviewing the many changes that have taken place between 1962 and the present. Fine texts describing some of this work are those of Balescu (1963, 1975). A recent critical overview of the “modern view” is in the unpublished thesis of B. C. Bishop of the University of Texas Philosophy Department (Bishop, 1999). In many ways this is related to the use of Gel'fand triplets (Gel'fand and Vilenkin, 1968), mentioned in Chapter 17.6, to describe irreversible quantum states, i.e. Gamov states. See Chapter 17, the book of Bohm and Gadella (1989) and also the more recent review article by Bohm and colleagues (Bohm et al. , 1997). The object in statistical mechanics is to extend the range of the Liouville operator (classical and quantum) such that its eigenvalues are complex and intrinsically irreversible. Statistical mechanics has always been focused on many particle systems and the appearance of a continuum spectrum in the thermodynamic limit, already used in many places in this book. In the classical case Antoniou and Tasaki carried out the adaptation of the Gel'fand triplet approach to the Liouville operator, but this is, apparently, not possible quantum mechanically (Antoniou and Tasaki, 1993). Thus, another route must be taken in what Prigogine has termed, for emphasis, “large Poincaré systems” which have a continuum spectrum (Prigogine, 1997).
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.
Total Cross Sections in Non-Relativistic Scattering Theory.- Classical-Quantum Correspondence in Non-Linear Systems.- Real Axis Asymptotics and Estimates of Hamiltonian Resolvent Kernels.- Statistical Inference in Quantum Mechanics.- Schrodinger Operators with Oscillating Potentials.- Time Delay and Resonance in Simple Scattering.- A Study of the Helmholtz Operator.- Invariant Manifolds and Bifurcations in the Taylor Problem.- On the Dimension of a Finite Difference Approximation to Divergence-Free Vectors.- Intramolecular Dynamics in the Quasiperiodic and Stochastic Regimes.- Problems in the Semiclassical Quantization of Integrable and Nonintegrable Classical Dynamical Systems.- Nonselfadjoint Operators in Diffraction and Scattering.- One-Dimensional Crystals in an External Field.- Dynamics of Forced Coupled Oscillators: Classical Phenomenology of Infrared Multiphoton Absorption.- Irreversibility and Stochasticity of Chemical Processes.- On the Representations of the Local Current Algebra and the Group of Diffeomorphisms (I).- Regular and Chaotic Regimes in Quantum Mechanics.- Barrier Penetration and Exponential Decay in the Stark Effect.- A Nonlinear Schrodinger Equation Yielding the Shape of Molecules by Spontaneous Symmetry Breaking.- Classical Limit of the Number of Quantum States.- Formal Integrals for a Nonintegrable Dynamical System: Preliminary Report.- On a Generalized Weyl-Von Neumann Converse Theorem.- Scattering Theory in Many-Body Quantum Systems. Analyticity of the Scattered Matrix.- Existence, Uniqueness, Stability and Calculation of the Stationary Regimes in Some Nonlinear Systems.- Weighted Trigonometric Approximations in L2(Rn).- The Phenomenon of Magnetic Pairing and Exactly Soluble Models of Magnetic Resonances.- Dyons Solutions to Yang-Mills Equations.- Asymptotic Resonance Properties of the Finite-Dimensional Friedrichs Model.- Self-Consistent Field Methods for Metastable Electronic States: A Promising Extension of the Complex Coordinate Technique.- Timestep Control for the Numerical Solutions of Initial-Boundary-Value Problems.- Quantum Mechanical Angular Distributions and Group Representations on Banach Spaces.- Tensor Product Decomposition of Holomorphically Induced Representations and Clebsch-Gordan Coefficients.- Orthogonal Laurent Polynomials and Gaussian Quadrature.- Measurement Theory with Instruments Treated Partially Quantum Mechanically.- Transition Maps and Locality.- The Feynman-Kac Formula for Boson Wiener Processes.- On Nonunitary Equivalence Between Unitary Group of Dynamics and Contraction Semigroups of Markov Processes.