Macroscopic fluctuations, linear response theory

For systems close to equilibrium the non-equilibrium behaviour of macroscopic systems is described by linear response theory, which is based on the fluctuation-dissipation theorem. This theorem defines a relationship between rates of relaxation and absorption and the correlation of fluctuations that occur spontaneously at different times in equilibrium systems. 

Kubo s linear-response theory provides the full, quantum-mechanical relation between the response of a system to external perturbations and the spontaneous decay of fluctuations in the unperturbed system. Of course, the paper had important predecessors Nyquist s [1] paper on thermal noise in resistors and Onsager s [2] seminal paper on the relation between decay of macroscopic and microscopic fluctuations, to name but the earliest. 

P(co) is an internal field factor and A t) is a time-correlation function which represents the fluctuations of the macroscopic dipole moment of the volume V in time in the absence of an applied electric field. Equations (44) and (45) are a consequence of applying linear-response theory (Kubo-Callen-Green) to the case of dielectric relaxation, as was first described by Glarum in connexion with dipolar liquids. For the special case of flexible polymer chains of high molecular weight having intramolecular correlations between dipoles but no intermolecular correlations between dipoles of different chains we may write... 

The world surrounding us is mostly out of equihbrium, equilibrium being just an idealization that requires specific conditions to be met in the laboratory. Even today we do not have a general theory about nonequilibrium macroscopic systems as we have for equilibrium ones. Onsager theory is probably the most successful attempt, albeit its domain of validity is restricted to the linear response regime. In small systems the situation seems to be the opposite. Over the past years, a set of theoretical results that go under the name of fluctuation theorems have been unveiled. These theorems make specific predictions about energy processes in small systems that can be scrutinized in the laboratory. 

The extraction of a homogeneous process from a stationary Markov process is a familiar procedure in the theory of linear response. As an example take a sample of a paramagnetic material placed in a constant external magnetic field B. The magnetization Y in the direction of the field is a stationary stochastic process with a macroscopic average value and small fluctuations around it. For the moment we assume that it is a Markov process. The function Px (y) is given by the canonical distribution... 

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