  Using molecular dynamics simulations with recently developed importance
sampling methods, we show that the differential capacitance of a model ionic
liquid based double-layer capacitor exhibits an anomalous dependence on the
applied electrical potential. Such behavior is qualitatively incompatible with
standard mean-field theories of the electrical double layer, but is consistent
with observations made in experiment. The anomalous response results from
structural changes induced in the interfacial region of the ionic liquid as it
develops a charge density to screen the charge induced on the electrode
surface. These structural changes are strongly influenced by the out-of-plane
layering of the electrolyte and are multifaceted, including an abrupt local
ordering of the ions adsorbed in the plane of the electrode surface,
reorientation of molecular ions, and the spontaneous exchange of ions between
different layers of the electrolyte close to the electrode surface. The local
ordering exhibits signatures of a first-order phase transition, which would
indicate a singular charge-density transition in a macroscopic limit.
