Published online by Cambridge University Press: 13 October 2009
The object of the present chapter is small deviations from local equilibrium which are triggered by spontaneous fluctuations. In real fluids these fluctuations which temporarily disturb the system from local equilibrium are such that a fluid at global equilibrium can be viewed as a reservoir of excitations extending over a broad range of wavelengths and frequencies from the hydrodynamic scale down to the range of the intermolecular potential. Non-intrusive scattering techniques are used to probe these fluctuations at the molecular level (neutron scattering spectroscopy) and at the level of collective excitations (light scattering spectroscopy) (Boon and Yip, 1980). The quantity measured by these scattering methods is the power spectrum of density fluctuations, i.e. the dynamic structure factor S(k, ω) which is the space- and time-Fourier transform of the correlation function of the density fluctuations. The spectral function S(k, ω) is important because it provides insight into the dynamical behavior of spontaneous fluctuations (or forced fluctuations in non-equilibrium systems). Whereas the fluctuations extend continuously from the molecular level to the hydrodynamic scale, there are experimental and theoretical limitations to the ranges where they can be probed and computed. Indeed, no theory provides a fully explicit analytical description of space-time dynamics establishing the bridge between kinetic theory and hydrodynamic theory. Scattering techniques have limited ranges of wavelengths over which fluctuation correlations can be probed.
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