Interfacial fluctuations in the cohesive (van der Waals) interaction energy of spherical oil-drops with water provide evidence of a length scale dependent transition from linear to non-linear response behavior. For sub-nanometer oil-drop sizes, energy fluctuations are found to be independent of van der Waals coupling strength, while nanometer (and larger) size oil drops experience highly non-linear energy fluctuations. The latter behavior is linked to enhanced hydrophobic density fluctuations and the emergence of entropic contributions to oil-water cohesive interaction free energies.

Length scale dependent oil-water energy fluctuations

243rd National Meeting (2012)

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