  We report the statistics of electric field fluctuations produced by SPC/E
water inside a Kihara solute given as a hard-sphere core with a Lennard-Jones
layer at its surface. The statistics of electric field fluctuations, obtained
from numerical simulations, are studied as a function of the magnitude of a
point dipole placed close to the solute-water interface. The free energy
surface as a function of the electric field projected on the dipole direction
shows a cross-over with the increasing dipole magnitude. While it is a
single-well harmonic function at low dipole values, it becomes a double-well
surface at intermediate dipole moment magnitudes, transforming to a single-well
surface, with a non-zero minimum position, at still higher dipoles. A broad
intermediate region where the interfacial waters fluctuate between the two
minima is characterized by intense field fluctuations, with non-Gaussian
statistics and the variance far exceeding the linear-response expectations. The
excited state of the surface water is found to be lifted above the ground state
by the energy required to break approximately two hydrogen bonds. This state is
pulled down in energy by the external electric field of the solute dipole,
making it readily accessible to thermal excitations. The excited state is a
localized surface defect in the hydrogen-bond network creating a stress in the
nearby network, but otherwise relatively localized in the region closest to the
solute dipole.
