Contact angles of nanodrops on chemically rough surfaces

The experimental observations of Gao and McCarthy [Gao, L.; McCarthy, T. Langmuir, 2007, 23, 3762] that only the interfacial area near the leading edges of the drop on physically smooth but chemically rough solid surfaces affects the contact angle and that most of the contact area has no effect is checked for nanodrops on the basis of a density functional theory. The contact angle was calculated for three cases: (i) the leading edges of the drops are located on much higher or (ii) much lower hydrophobic surfaces than the remaining surface beneath the drop; (iii) the surface is composed of a periodic array of two kinds of stripelike solid plates. In the first two cases, if the distance between the leading edges and the region which has higher or lower hydrophobicity is sufficiently large, there is agreement with the experiments mentioned. However, when those distances are sufficiently small, the internal part affects the value of the angle. In the third case, we found that the internal part always affects the wetting angle. All these peculiarities, as well as the contact angle hysteresis, can be explained by accounting for the local conditions in the vicinity of the leading edges of the drop.