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We define the dielectric constant (susceptibility) that should enter theMaxwell boundary value problem when applied to microscopic dielectricinterfaces. The dielectric constant (susceptibility) of the interface isdefined by exact linear-response equations involving correlations ofstatistically fluctuating interface polarization and the Coulomb interactionenergy of external charges with the dielectric. The theory is applied to theinterface between water and spherical solutes of altering size studied bymolecular dynamics (MD) simulations. The effective dielectric constant ofinterfacial water is found to be significantly lower than its bulk value, andit also depends on the solute size. For TIP3P water used in MD simulations theinterface dielectric constant changes from 9 to 4 when the effective soluteradius is increased from ~5 to 18 A.

Dielectric constant of water in the interface