PNNL

Abstract

Understanding fundamental nanoassembly processes on intermediate scales beween the molecular and the continuum requires an in-depth analysis of the coupling between particle interactions and molecular detail. This is because the discrete nature of the solvent becomes comparable to the characteristic length scales of assembly molecular fluctuations. Utilizing the spatial density resonse of a solvent to a surface in conjunction with the Clausius-Mossotti equation, we present a simple theory relating the discrete nature of solvent to dispersion interactions. Our study reveals that dispersion interactions are indeed sensitive to the spatial variation of solvent density, manifesting in dramatic deviations in van der Waals forces from the conventional formulation (e.g. with uniform solvent density). This study provides the first steps toward incorporating molecular scale principles that underlie hydration forces where the detailed nature of solvent responses play a significant role.