Understanding n-Octane Behavior near Graphene with Scaled Solvent-Solute Attractions

We employ molecular dynamics simulations of n-octane near a layered graphene surface to study the related phenomena of solvation, density fluctuations, wettability, and structure and dynamics of n-octane molecules in the inhomogeneous interfacial environment. That solvation in bulk n-octane displays a lengthscale-dependent crossover similar to that of hydrophobic solvation in water is known. Here we show that, near an extended graphene interface having attractive interactions with n-octane, lengthscale-dependent solvation is similar to that in the bulk and displays a small to large crossover. However, as the n-octane–graphene interactions are reduced to make the surface increasingly solvophobic, the crossover behavior is modulated and essentially absent near the most solvophobic surfaces, similar to that in water near hydrophobic interfaces. We show that the macroscopic measure of wettability, namely, the contact angle, characterizes n-octane–graphene coupling over a limited range of attractions. In contrast, molecular measures such as the free energy of cavity formation or the local compressibility in the interfacial region provide an effective measure of this coupling over a broader range of attractions. Finally, as n-octane–graphene attractions are increased, the n-octane liquid displays a wetting transition and corresponding change from sigmoidal to layered density profile. Analysis of the local structure shows that n-octane molecules prefer approximately linear conformations and surface-parallel orientations near the graphene surface, and their translational dynamics slow down with increasing n-octane–graphene attractions. Our study highlights molecular scale behavior of n-octane molecules that is relevant to understanding nanoparticle–solvent coupling in composite materials with enhanced mechanical or thermal properties.

@article{wu2016understanding,
  title   = {Understanding n-Octant Behavior near Graphene with Scaled Solvent-Solute Attractions},
  author  = {Wu, Eugene and Garde, Shekhar},
  journal = {J. Phys. Chem. B},
  volume  = {120},
  number  = {8},
  pages   = {2033--2042},
  year    = {2016},
  doi     = {10.1021/acs.jpcb.5b10262}
}