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Spherical confinement can alter the properties of a dipolar fluid in severaldifferent ways. In an atomistic molecular dynamics simulation study of twodifferent dipolar liquids (SPC/E water and a model Stockmayer fluid) confinedto nanocavities of different radii ranging from Rc=1nm to 4nm, we find that theKirkwood correlation factor remains surprisingly small in water, but not so inmodel Stockmayer liquid. This gives rise to an anomalous ultrafast relaxationof the total dipole moment time correlation function (DMTCF). The staticdielectric constant of water under nanoconfinement (computed by employingClausius-Mossotti equation, the only exact relation) exhibits a strongdependence on the size of the nanocavity with a remarkably slow convergence tothe bulk value. Interestingly, the value of the volume becomes ambiguous inthis nanoworld. It is determined by the liquid-surface interaction potentialand is to be treated with care because of the sensitivity of theClausius-Mossotti equation to the volume of the nanosphere. We discover thatthe DMTCF for confined water exhibit a bimodal 1/f noise power spectrum. Wealso comment on the applicability of certain theoretical formalisms that becomedubious in the nanoworld.

Altered Dielectric Behaviour, Structure and Dynamics of Nanoconfined Dipolar Liquids: Signatures of Enhanced Cooperativity