It is known from experiments that the dielectric constant of a solvent might decrease in regions where there is a strong electric field, for example, near a highly charged ion in an infinitely dilute solution. In such a case the dielectric constant of the liquid might be described as function of the distance from the ion (considering a monoatomic ion, so that we can approximate the dielectric function by a spherically symmetric one), and this description is supposed to capture all the effects of the strong electric field on the dielectric medium. What I am trying to understand here and cannot actually find a good theoretical discussion of is why the dielectric constant would be reduced in regions where the electric field is strong, i.e., what is the molecular mechanism of dielectric saturation.
Magnetic saturation usually happens when the external magnetic field is strong enough so that all the magnets are oriented in a manner which will maximize the interactions between the field and the particles. One cannot help to imagine that in dielectric saturation the dielectric medium will polarize itself in a "maximal" way, in order to maximize the interactions with the strong electric field. It is also not hard to imagine that at some saturation point (a certain electric field), the relaxation/reorientation/etc of the solvent in response to the electric field would increase its energy instead of decreasing it, and hence, it becomes unfavorable for the liquid to polarize itself. The most favorable configuration of this system (strong electric field at a small region of a dielectric liquid) would then be attainable by some other kind of reorganization of the solvent which would reduce its effective polarity, thus effectively decreasing its dielectric constant function. If the argument here given is true, then I would be interested in this molecular reorganization that follows the dielectric saturation, although I can imagine it is probably specific to the actual molecules that make up this dielectric medium.
Any insights on this issue will be greatly appreciated.
In order to clarify the origin of the term:
Dielectric saturation is a popular term in solvation chemistry and materials science. It is known to arise at regions in a dielectric medium where there is a strong field, and the liquid/material responds nonlinearly. Effectively, i.e., what experiments find, is that a reduction in the dielectric constant of the system arises at the region where the field is strong. You can find this term easily in continuum solvent models literature, such as in the 1st chapter ("Modern Theories of Continuum Models") of the recent book "Continuum Solvation Models in Chemical Physics", by Mennucci and Cammi, which is available here http://onlinelibrary.wiley.com/doi/10.1002/9780470515235.ch1/summary provided one has access to it.
