A novel general modeling of the viscoelastic properties of fluids: application to mechanical relaxation and low frequency oscillation measurements of liquid water

Abstract: The aim of this paper is to calculate the time dependence of the mean position (and orientation) of a fluid particle when a fluid system at thermodynamic equilibrium is submitted to a mechanical action. The starting point of this novel theoretical approach is the introduction of a mechanical energy functional. Then using the notions of inertial modes and action temperature, and assuming a mechanical energy equipartition principle per mode, the model predict the existence of a dynamic phase transition where the rheological behavior of the medium evolves from a solid-like to a liquid-like regime when the mechanical action is increased. The well-known Newtonian behavior is recovered as limiting case. The present modeling is applied to the analysis of recent liquid water viscoelastic data pointing out a prevalent elastic behavior in confined geometry. It is demonstrated that the model makes it possible to understand these data in a coherent and unified way with the transport properties (viscosity and self-diffusion coefficient). It is concluded that any finite volume of fluid at rest possesses a static shear elasticity and should therefore be considered as a solid-like medium.