We study adsorption at periodically corrugated substrates formed by scoring rectangular grooves into a planar solid wall which interacts with the fluid via long-range (dispersion) forces. The grooves are assumed to be macroscopically long but their depth, width, and separations can all be molecularly small. We show that the entire adsorption process can be divided into three parts consisting of (i) filling the grooves by a capillary liquid; (ii) depinning of the liquid-gas interface from the wall edges; and (iii) unbinding of the interface from the top of the wall, which is accompanied by a rapid but continuous flattening of its shape. Using a nonlocal density functional theory and mesoscopic interfacial models all the regimes are discussed in some detail to reveal the complexity of the entire process and subtle aspects that affect its behavior. In particular, it is shown that the nature of the depinning phenomenon is governed by the width of the wall pillars (separating grooves), while the width of the grooves only controls the location of the depinning first-order transition, if present.

Department of Physical Chemistry University of Chemical Technology Prague Praha 6 166 28 Czech Republic and Department of Molecular and Mesoscopic Modelling ICPF of the Czech Academy Sciences Prague 165 02 Czech Republic

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