Predicting the anomalous density of a dense fluid confined within a carbon nanotube

Abstract

The equilibrium density of fluids under nanoconfinement can differ substantially from their bulk density. Using a mean-field approach to describe the energetic landscape near the carbon nanotube (CNT) wall, we obtain analytical results describing the lengthscales associated with the layering observed at the interface of a Lennard-Jones fluid and a CNT. We also show that this approach can be extended to describe the multiple-ring structure observed in larger CNTs. When combined with molecular simulation results for fluid density in the first two rings, this approach allows us to derive a closed-form prediction for the overall equilibrium fluid density as a function of CNT radius that is in excellent agreement with molecular dynamics simulations. We also show how aspects of this theory can be extended to describe some features of water confinement within CNTs and find good agreement with results from the literature. Finally, we present evidence that this model for anomalous fluid density can also be applied to understand simple nanoscale flow phenomena.