Continuous condensation in nanogrooves.

We consider condensation in a capillary groove of width L and depth D, formed by walls that are completely wet (contact angle θ=0), which is in a contact with a gas reservoir of the chemical potential μ. On a mesoscopic level, the condensation process can be described in terms of the midpoint height ℓ of a meniscus formed at the liquid-gas interface. For macroscopically deep grooves (D→∞), and in the presence of long-range (dispersion) forces, the condensation corresponds to a second-order phase transition, such that ℓ∼(μ_{cc}-μ)^{-1/4} as μ→μ_{cc}^{-} where μ_{cc} is the chemical potential pertinent to capillary condensation in a slit pore of width L. For finite values of D, the transition becomes rounded and the groove becomes filled with liquid at a chemical potential higher than μ_{cc} with a difference of the order of D^{-3}. For sufficiently deep grooves, the meniscus growth initially follows the power law ℓ∼(μ_{cc}-μ)^{-1/4}, but this behavior eventually crosses over to ℓ∼D-(μ-μ_{cc})^{-1/3} above μ_{cc}, with a gap between the two regimes shown to be δ[over ¯]μ∼D^{-3}. Right at μ=μ_{cc}, when the groove is only partially filled with liquid, the height of the meniscus scales as ℓ^{*}∼(D^{3}L)^{1/4}. Moreover, the chemical potential (or pressure) at which the groove is half-filled with liquid exhibits a nonmonotonic dependence on D with a maximum at D≈3L/2 and coincides with μ_{cc} when L≈D. Finally, we show that condensation in finite grooves can be mapped on the condensation in capillary slits formed by two asymmetric (competing) walls a distance D apart with potential strengths depending on L. All these predictions, based on mesoscopic arguments, are confirmed by fully microscopic Rosenfeld's density functional theory with a reasonable agreement down to surprisingly small values of both L and D.