Validity of Macroscopic Concepts for Fluids on a Microscopic Scale

By Fourier decomposition of the appropriate fluctuation it is possible within the regime of linear response to extend the concept of both thermo‐dynamic quantities and transport coefficients to their dependence on both wavelength and frequency. Experimentally these generalized macroscopic properties are accessible through neutron diffraction and, as examples, the dependence of the sound speed on wavelength and the diffusion coefficient on time are discussed. Through the molecular dynamics computer method the dependence of the viscosity on wavelength is calculated and applied with spectacular success to predict the dependence of the friction coefficient on the size of a Brownian particle all the way to atomic dimensions. On the other hand, the dielectric constant continuum concept, as applied to a charge or dipole in a cavity, generally fails to predict even the correct field at large distance from the charge. Avoiding the introduction of a cavity cures that problem, but the generalized dielectric constant fails badly in predicting the field at shorter distances from the charge.