CONTACT ANGLE OF A NANO-DROP ON A HETEROGENEOUS SURFACE By John Andre Ritchie, Master of Science A thesis submitted in partial fulfillment of the requirements for the degree of Master of Science at Virginia Commonwealth University Virginia Commonwealth University, 2010 Major Director: Dr. Alenka Luzar, Professor of Chemistry We examine the relation between contact angle of a nanodrop of water and the location of surface-water interaction energy at the perimeter and beneath the drop. Young’s equations gives the relationship between surface tension, at the three phase solid liquid vapor interface, and contact angle on a homogeneous surface. Cassie and Baxter generalized this equation to heterogeneous surfaces implying that contact angle corresponds to the average properties of the surface under the drop. McCarthy and coworkers pointed out it is the nature of the substrate at droplet perimeter that controls contact angle. And more recently, McHale in his theoretical derivation applies the Cassie-Baxter equation to the area at the drop’s perimeter. For a nanodrop, the situation is further complicated by the finite range of water-substrate interactions making the definition of the perimeter region somewhat arbitrary. We simulate nanodroplets of water on graphene-like surfaces having hydrophobic and hydrophilic interaction energy at the perimeter and beneath the drop using molecular dynamics. The microscopic analogue of the contact angle was extracted from simulation trajectory data. We confirm the contact angle is exclusively related to the surface interaction energy in the region of the drop’s perimeter. We test the role of finite range of substrate-water interaction when the area of a circular hydrophilic patch beneath the drop’s core is incrementally expanded until the contact angle is equivalent to that on the pure hydrophilic surface. We identify a range of interaction corresponding to a considerable drop in θ when plotting contact angle as a function of patch size. We show the observed contact angle dependence on the size of the patch can be predicted by the Cassie-Baxter mixing relation when limited to the area within the interaction range from the drop’s perimeter.