Solvation of Carbon Nanoparticles in Water/Alcohol Mixtures: Using Molecular Simulation To Probe Energetics, Structure, and Dynamics.

Molecular dynamics simulations were used to examine the solvation behavior of buckminsterfullerene and single-walled carbon nanotubes (SWCNT) in a range of water/alcohol solvent compositions at 1 atm and 300 K. Results indicate that the alcohols assume the role of pseudosurfactants by shielding the nanotube from the more unfavorable interactions with polar water molecules. This is evident in both the free energies of transfer (ΔΔGwater→xOH = -68.1 kJ/mol and -86.5 kJ/mol for C60 in methanol and ethanol; ΔΔGwater→xOH = -345.6 kJ/mol and -421.2 kJ/mol for the (6,5)-SWCNT in methanol and ethanol) and the composition of the solvation shell at intermediate alcohol concentrations. Additionally, we have observed the retardation of both the translational and rotational dynamics of molecules near the nanoparticle surface through use of time correlation functions. A 3-fold increase in the residence times of the alcohol molecules within the solvation shells at low concentrations further reveals their surfactant-like behavior. Such interactions are important when considering the complex molecular environment present in many schemes used for nanoparticle purification techniques.