The calculation of rate coefficients is a discipline of nonlinear science of importance to much of physics, chemistry, engineering, and biology. Fifty years after Kramers' seminal paper on thermally activated barrier crossing, the authors report, extend, and interpret much of our current understanding relating to theories of noise-activated escape, for which many of the notable contributions are originating from the communities both of physics and of physical chemistry. Theoretical as well as numerical approaches are discussed for single- and many-dimensional metastable systems (including fields) in gases and condensed phases. The role of many-dimensional transition-state theory is contrasted with Kramers' reaction-rate theory for moderate-to-strong friction; the authors emphasize the physical situation and the close connection between unimolecular rate theory and Kramers' work for weakly damped systems. The rate theory accounting for memory friction is presented, together with a unifying theoretical approach which covers the whole regime of weak-to-moderate-to-strong friction on the same basis (turnover theory). The peculiarities of noise-activated escape in a variety of physically different metastable potential configurations is elucidated in terms of the mean-first-passage-time technique. Moreover, the role and the complexity of escape in driven systems exhibiting possibly multiple, metastable stationary nonequilibrium states is identified. At lower temperatures, quantum tunneling effects start to dominate the rate mechanism. The early quantum approaches as well as the latest quantum versions of Kramers' theory are discussed, thereby providing a description of dissipative escape events at all temperatures. In addition, an attempt is made to discuss prominent experimental work as it relates to Kramers' reaction-rate theory and to indicate the most important areas for future research in theory and experiment.

Reaction-rate theory: fifty years after Kramers

N G van Kampen 1981 Amsterdam: North-Holland xiv + 419 pp price Dfl 180 This is a book which, at a lower price, could be expected to become an essential part of the library of every physical scientist concerned with problems involving fluctuations and stochastic processes, as well as those who just enjoy a beautifully written book. It provides an extensive graduate-level introduction which is clear, cautious, interesting and readable.

https://iopscience.iop.org/article/10.1088/0031-9112/34/4/040/pdf

Stochastic Processes in Physics and Chemistry

as quantum engineering. In the past two decades it has become increasingly clear that many (perhaps all) of the symptoms of classicality can be induced in quantum systems by their environments. Thus decoherence is caused by the interaction in which the environment in effect monitors certain observables of the system, destroying coherence between the pointer states corresponding to their eigenvalues. This leads to environment-induced superselection or einselection, a quantum process associated with selective loss of information. Einselected pointer states are stable. They can retain correlations with the rest of the universe in spite of the environment. Einselection enforces classicality by imposing an effective ban on the vast majority of the Hilbert space, eliminating especially the flagrantly nonlocal ''Schrodinger-cat states.'' The classical structure of phase space emerges from the quantum Hilbert space in the appropriate macroscopic limit. Combination of einselection with dynamics leads to the idealizations of a point and of a classical trajectory. In measurements, einselection replaces quantum entanglement between the apparatus and the measured system with the classical correlation. Only the preferred pointer observable of the apparatus can store information that has predictive power. When the measured quantum system is microscopic and isolated, this restriction on the predictive utility of its correlations with the macroscopic apparatus results in the effective ''collapse of the wave packet.'' The existential interpretation implied by einselection regards observers as open quantum systems, distinguished only by their ability to acquire, store, and process information. Spreading of the correlations with the effectively classical pointer states throughout the environment allows one to understand ''classical reality'' as a property based on the relatively objective existence of the einselected states. Effectively classical pointer states can be ''found out'' without being re-prepared, e.g, by intercepting the information already present in the environment. The redundancy of the records of pointer states in the environment (which can be thought of as their ''fitness'' in the Darwinian sense) is a measure of their classicality. A new symmetry appears in this setting. Environment-assisted invariance or envariance sheds new light on the nature of ignorance of the state of the system due to quantum correlations with the environment and leads to Born's rules and to reduced density matrices, ultimately justifying basic principles of the program of decoherence and einselection.

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Decoherence, einselection, and the quantum origins of the classical

Quantum tunnelling in a dissipative system

We apply the influence-functional method of Feynman and Vernon to the study of Brownian motion at arbitrary temperature. By choosing a specific model for the dissipative interaction of the system of interest with its environment, we are able to evaluate the influence functional in closed form and express it in terms of a few parameters such as the phenomenological viscosity coefficient. We show that in the limit h→0 the results obtained from the influence functional formalism reduce to the classical Fokker-Planck equation. In the case of a simple harmonic oscillator with arbitrarily strong damping and at arbitrary temperature, we obtain an explicit expression for the time evolution of the complete density matrix ϱ(x, x′, t) when the system starts in a particular kind of pure state. We compare our results with those of other approaches to the problem of dissipation in quantum mechanics.

Path integral approach to quantum Brownian motion

Classical and quantum mechanics of the damped harmonic oscillator

A previously developed novel theory for the formal canonical quantization of classically dissipating systems will be the starting point for a detailed discussion of the quantum statistical aspects of the simple linearly damped harmonic oscillator. The formalism essentially involves complex classical canonical coordinates and momenta, and thus quite naturally leads to the possibility of creation and annihilation operators. Furthermore, the occurrence of quantal noise operators appears to be of principal importance for the conservation of the fundamental commutator in the course of time, as will be expressed in a simple fluctuation-dissipation relation. Making a canonical transformation back to the real, Cartesian Hermitian position and momentum an "effective" Hermitian Hamiltonian will be derived, with which a transformation is made from the Heisenberg frame to the Schr\"odinger frame where the density operator equation will be computed. This will make it obvious that no proper Schr\"odinger equation exists for the dissipative subsystem on its own, thus reflecting an incomplete knowledge. The master equation will then be translated into its Wigner representation. The intimate connection between the diffusion coefficients in the resulting Fokker-Planck equation and the uncertainty relation will be demonstrated in a clear fashion.

Quantization of the linearly damped harmonic oscillator

A very simple yet novel derivation is presented of the dynamics of the dissipative two-state system in the ``noninteracting-blip approximation.''

Noninteracting-blip approximation for a two-level system coupled to a heat bath

Suppose one knows the classical equation of motion for a certain dissipating system. Of course, the dissipation arises from the system's quantum mechanical interaction with its damping reservoirs. However, the question can be raised how much information one is able to obtain about the quantum mechanical features of the system without having any detailed knowledge concerning the quantum nature of these underlying interactions. In this paper the quantization of dissipative systems is considered in the Lagrange-Hamilton formalism. Making use of complex variables it is possible to formulate a classical Lagrange-Hamilton theory where the Hamiltonian is non-Hermitian. The real part of the Hamiltonian can be quantized in the usual manner. For the imaginary part a procedure is presented, which results in a self-consistent quantum mechanical formulation. It will be seen that the quantum information that can be obtained about the classical dissipation may be expressed in terms of an anti-commutator. In the appendix a dissipation-fluctuation theorem is given which in the case of a simple damped harmonic oscillator yields a well-known expression.

H. Dekker

Papers

Classical and quantum mechanics of the damped harmonic oscillator

Quantization of the linearly damped harmonic oscillator

Noninteracting-blip approximation for a two-level system coupled to a heat bath

On the Quantization of Dissipative Systems in the Lagrange-Hamilton Formalism

A fundamental constraint on quantum mechanical diffusion coefficients