Carbon nanotubes in benzene: internal and external solvation

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The structure and dynamics of benzene inside and outside of single-walled carbon nanotubes (SWNTs) in the (n,n) armchair configuration are studied via molecular dynamics computer simulations. Irrespective of the nanotube diameter, benzene molecules form cylindrical solvation shell structures on the outside of the nanotubes. Their molecular planes near the SWNTs in the first external solvation shell are oriented parallel to the nanotube surface, forming a π-stacked structure between the two. By contrast, the benzene distributions in the interior of the SWNTs are found to vary markedly with the nanotube diameter. In the case of the (7,7) and (8,8) nanotubes, internal benzene forms a single-file distribution, either in a vertex-to-vertex (n = 7) or face-to-face (n = 8) orientation between two neighboring molecules. Inside a slightly wider (9,9) nanotube channel, however, a cylindrical single-shell distribution of benzene arises. A secondary solvation structure, which begins to appear inside (10,10), develops into a full structure separate from the first internal solvation shell in (12,12). The ring orientation of internal benzene is generally parallel to the nanotube wall for n = 9-12, while it becomes either slanted with respect to (n = 7), or perpendicular to (n = 8), the nanotube axis. The confinement inside the small nanotube pores exerts a strong influence on the dynamics of benzene. Both translational and rotational dynamics inside SWNTs are slower and more anisotropic than in liquid benzene. It is also found that reorientational dynamics of internal benzene deviate dramatically from the rotational diffusion regime and change substantially with the nanotube diameter.