Interference effects between ion induced solvent polarisations in Liquid water

Abstract

We calculate the effective force between two oppositely charged and similarly charged ions fixed in water as a function of separation distance R. At short separations, R less than 1 nm, the effective force is vastly different from the $1/{\epsilon }_s{R}^2$ dependence advocated by the screened Coulomb force law (SCFL); ${\epsilon }_s$ being the static dielectric constant of the medium. We also find an interesting asymmetry in the force between +ve and -ve ions. This breakdown of SCFL is shown to be due to the persistent interference between the polarizations created by the two charges, in a manner similar to the vortex-antivortex pair formation in XY model Hamiltonian. The distance dependence of dielectric constants, ${\epsilon }_s$(R) extracted from our simulation exhibit interesting features and can be used in future modelling.

23 pages, 7 figures