J Chem Phys. 2012 May 14;136(18):184702. doi: 10.1063/1.4712139.

Grand canonical-like molecular dynamics simulations: application to anisotropic mass diffusion in a nanoporous medium.

The Journal of chemical physics

Hai Hoang, Guillaume Galliero

PMID: 22583304 DOI: 10.1063/1.4712139

Abstract

In this work, we describe two grand canonical-like molecular dynamics approaches to investigate mass diffusion phenomenon of a simple Lennard-Jones fluid confined between solid surfaces and in direct contact with reservoirs. In the first method, the density is used as the control variable in the reservoir whereas it is the pressure in the second method. Both methods provide consistent results, however, the constant density approach is the most efficient with respect to the computational time and implementation. Then, employing the constant density approach, we have studied the transient behavior of the diffusion process associated with the migration of one fluid into another one confined between parallel solid walls. Results have shown that the evolution of molar fraction of the invading fluid follows roughly a 1D diffusion model when the solid phase is weakly or moderately adsorbent with a characteristic time increasing when the pore width decreases. However, when the adsorption is high and the pore width small (i.e., below ten molecular sizes), the apparent mass diffusion in the adsorbed layer is reduced compared to that in the center of the slit pore. Hence, this mass diffusion process becomes a two-dimension phenomenon that must take into account an effective mass diffusion coefficient varying locally.

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• Journal Article