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The Journal of Chemical Physics

On the generalized Langevin equation: Classical and quantum mechanicala)

Emilio Cortés, Bruce J. West, Katja Lindenberg

Published Mar 15, 1985• 215 citations
Publisher

Abstract

The generalized Langevin equation and its attendant fluctuation–dissipation relation (FDR) for both classical and quantum systems is explictly derived for a large class of system-bath interaction potentials. We demonstrate for this class of potentials that the classical FDR involving only the temperature of the bath is satisfied, and that in general the decay times of the dissipative processes and of the system are temperature dependent. We also demonstrate that the quantum FDR depends in detail on the nature of the bath and on the specific system-bath interaction. Thus we conclude that while the classical Langevin equation is phenomenologically useful, its quantum counterpart is much more limited.

DOI
10.1063/1.448268

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The generalized Langevin equation and its attendant fluctuation–dissipation relation (FDR) for both classical and quantum systems is explictly derived for a large class of system-bath interaction potentials. We demonstrate for this class of potentials that the classical FDR involving only the temperature of the bath is satisfied, and that in general the decay times of the dissipative processes and of the system are temperature dependent. We also demonstrate that the quantum FDR depends in detail on the nature of the bath and on the specific system-bath interaction. Thus we conclude that while the classical Langevin equation is phenomenologically useful, its quantum counterpart is much more limited.
Quantum diffusion equations featuring explicitly time-dependent transport coefficients are derived from generalized non-Markovian Langevin equations. Generalized fluctuation-dissipation relations and analytic expressions for calculating the friction and diffusion coefficients in nuclear processes are obtained. The asymptotic behavior of the transport coefficients and correlation functions for a damped harmonic oscillator that is linearly coupled in momentum to a heat bath is studied. The coupling to a heat bath in momentum is responsible for the appearance of the diffusion coefficient in coordinate. The problem of regression of correlations in quantum dissipative systems is analyzed.
Abstract This review provides a brief and quick introduction to the quantum Langevin equation for an oscillator, while focusing on the steady-state thermodynamic aspects. A derivation of the quantum Langevin equation is carefully outlined based on the microscopic model of the heat bath as a collection of a large number of independent quantum oscillators, the so-called independent-oscillator model. This is followed by a discussion on the relevant ‘weak-coupling’ limit. In the steady state, we analyze the quantum counterpart of energy equipartition theorem which has generated a considerable amount of interest in recent literature. The free energy, entropy, specific heat, and third law of thermodynamics are discussed for one-dimensional quantum Brownian motion in a harmonic well. Following this, we explore some aspects of dissipative diamagnetism in the context of quantum Brownian oscillators, emphasizing upon the role of confining potentials and also upon the environment-induced classical-quantum crossover. We discuss situations where the system-bath coupling is via the momentum variables by focusing on a gauge-invariant model of momentum-momentum coupling in the presence of a vector potential; for this problem, we derive the quantum Langevin equation and discuss quantum thermodynamic functions. Finally, the topic of fluctuation theorems is discussed (albeit, briefly) in the context of classical and quantum cyclotron motion of a particle coupled to a heat bath.
A temperature-dependent Schrödinger equation is proposed for the study of quantum dynamics in systems which interact with an external bath. The derivation is based on a time-dependent self consistent field (TDSCF) approximation for a system-bath wave function. As previously shown by Miller, this approximation leads to a quantum mechanical analog to the classical generalized Langevin equation. By replacing the time-evolution of the quantum mechanical bath observables with the corresponding classical trajectories, the fluctuating force and the nonlinear friction kernel in the Langevin-Schrödinger equation become temperature-dependent where the fluctuations intensity is proportional to T. Application of the new equation to the spin-boson model shows agreement with numerically exact path integral calculations for T>0. We relate the success of the TDSCF approximation in this case to the bath-induced noise which diminishes the importance of quantum mechanical system-bath correlations.
The fluctuation-dissipation relations (FDR) in physical systems are studied at all levels of the statistical description. The most general FDR are the relations for the fluctuations of many-body distribution functions. It is pointed out the problem of formulation of FDR is related to the problem of deriving irreversible equations based on the reversible equations of classical and quantum mechanics. The FDR are divided into two classes: 1) FDR for fluctuations with infinite correlation times (collisionless approximation), which correspond to infinitely narrow resonances, and 2) FDR for fluctuations with finite correlation times (collisional approximation). The corresponding spectral densities have finite widths, determined by the collision integrals. The fundamental questions about which different viewpoints have been published in the literature are critically analyzed: 1) the limits of applicability of the Callen-Welton formula and 2) the quantum generalization of Nyquist's formula for the intensity of a Langevin source of oscillatory systems. It is shown that the traditional form of the quantum Nyquist formula, is not well-founded and leads to unphysical consequences. A different expression, used in the literature, for the quantum Nyquist formula is examined. It is not universal, but holds in many important cases. Its region of applicability is determined by the corresponding quantum kinetic equations. The consequences of the two forms of the quantum Nyquist formula, which can be checked experimentally, are studied. The question of the formulation of the quantum Nyquist formula is studied as a part of the general problem of determining the intensity of a Langevin source and the corresponding diffusion coefficient in quantum systems. It arises, in particular, also in quantum electrodynamics in the calculation of the Lamb shift (Sec. 12). In this connection two derivations of Bethe's formula for the Lamb shift are analyzed. It is established that the subtraction formalism of quantum electrodynamics corresponds to the nontraditional form of the quantum Nyquist formula. The exposition is illustrated with many specific examples.
A wide variety of dissipative and fluctuation problems involving a quantum system in a heat bath can be described by the independent-oscillator (IO) model Hamiltonian. Using Heisenberg equations of motion, this leads to a generalized quantum Langevin equation (QLE) for the quantum system involving two quantities which encapsulate the properties of the heat bath. Applications include: atomic energy shifts in a blackbody radiation heat bath; solution of the problem of runaway solutions in QED; electrical circuits (resistively shunted Josephson barrier, microscopic tunnel junction, etc.); conductivity calculations (since the QLE gives a natural separation between dissipative and fluctuation forces); dissipative quantum tunneling; noise effects in gravitational wave detectors; anomalous diffusion; strongly driven quantum systems; decoherence phenomena; analysis of Unruh radiation and entropy for a dissipative system.