Steady-state Poiseuille flow of a simple fluid in carbon nanopores under a gravitylike force is simulated using a realistic empirical many-body potential model for carbon. Building on our previous study of slit carbon nanopores we show that fluid flow in a nanotube is also characterized by a large slip length. By analyzing temporal profiles of the velocity components of particles colliding with the wall we obtain values of the Maxwell coefficient defining the fraction of molecules thermalized by the wall and, for the first time, propose slip boundary conditions for smooth continuum surfaces such that they are equivalent in adsorption, diffusion, and fluid flow properties to fully dynamic atomistic models.

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Steady-state Poiseuille flow of a simple fluid in carbon slit pores under a gravity-like force is simulated using a realistic empirical many-body potential model for carbon. In this work we focus on the small Knudsen number regime, where the macroscopic equations are applicable, and simulate different wetting conditions by varying the strength of fluid–wall interactions. We show that fluid flow in a carbon pore is characterized by a large slip length even in the strongly wetting case, contrary to the predictions of Tolstoi’s theory. When the surface density of wall atoms is reduced to values typical of a van der Waals solid, the streaming velocity profile vanishes at the wall, in accordance with earlier findings. From the velocity profiles we have calculated the slip length and by analyzing temporal profiles of the velocity components of particles colliding with the wall we obtained values of the Maxwell coefficient defining the fraction of molecules thermalized by the wall.

Transport properties including collective and tracer diffusivities of nitrogen, modeled as a diatomic molecule, in single walled carbon nanotubes have been studied by equilibrium molecular dynamics at different temperatures and as a function of pressure. It is shown that while the asymptotic decay of the translational and rotational velocity autocorrelation function is algebraic, the collective velocity decays exponentially with the relaxation time related to the interfacial friction. The tracer diffusivity in the nanochannel, which is comparable in magnitude with diffusivity in the equilibrium bulk phase, depends only weakly on the conditions at the fluid-solid interface, whereas the collective diffusivity is a strong function of the hydrodynamic boundary conditions and is found to be three orders of magnitude higher than self-diffusivity in carbon nanotubes and for the comparatively rough surface of the rare-gas tube it is one order of magnitude greater. A relationship between the collective diffusivity and the Maxwell coefficient describing wall collisions is obtained. The transport coefficients appear to be insensitive to the long-range details of the potential function.

The hydrodynamic solutions based on Maxwell's boundary conditions include an empirical slip coefficient (SC), which depends on properties of the adsorbate and adsorbent. Existing kinetic theory derivations of the SC are usually formulated for half-space flow and do not include finite-size effects, which dominate the flow in nanopores. We present an expression for the SC applicable to flow in nanoscale pores, which has been verified by nonequilibrium molecular-dynamics simulation. Our results show that the slip coefficient depends strongly on the pore width for small pores tending to a constant value for pores of width >20 molecular diameters for our systems, in contrast to the linear scaling predicted by Maxwell's theory of slip.