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Vapor-liquid critical and interfacial properties of square-well fluids in slit pores.

Vapor-liquid phase equilibria of square-well (SW) fluids of variable interaction range: lambdasigma=1.25, 1.75, 2.0, and 3.0 in hard slit pores are studied by means of grand-canonical transition-matrix Monte Carlo (GC-TMMC) simulation. Critical density under confinement shows an oscillatory behavior as slit width, H, reduced from 12sigma to 1sigma. Two linear regimes are found for the shift in the critical temperature with the inverse in the slit width. The first regime is seen for H>2.0sigma with linear increase in the slope of shift in the critical temperature against inverse slit width with increasing interaction range. Subsequent decrease in H has little consequence on the critical temperature and it remains almost constant. Vapor-liquid surface tensions of SW fluids of variable well extent in a planar slit pore of variable slit width are also reported. GC-TMMC results are compared with that from slab based canonical Monte Carlo and molecular dynamics techniques and found to be in good agreement. Although, vapor-liquid surface tension under confinement is found to be lower than the bulk surface tension, the behavior of surface tension as a function of temperature is invariant with the variable pore size. Interfacial width, xi, calculated using a hyperbolic function increases with decreasing slit width at a given temperature, which is contrary to what is being observed recently for cylindrical pores. Inverse scaled interfacial width (xi/H), however, linearly increases with increase in the scaled temperature (T(c,bulk)-T)/T(c,bulk).