Thermodynamic Stability and Electronic Properties of Graphene Nanoflakes

We conducted a large set of ab initio density functional theory computations to model a variety of hammer-terminated graphene nanoflakes-finite counterparts of armchair graphene nanoribbons. We focused on the relationships among the length and width of the nanoflakes, the stoichiometry and the conformation of the hydrogen saturation of the caps, and the resulting electronic structure. The energetics and the thermodynamic stability of the nanoflakes were investigated as well. Based on this study, we provide a recipe for determining the most stable saturation of the dangling bonds at the caps, which is generally disregarded in theoretical studies, and we prove that this step is crucial for a reliable description of the electronic structure of these systems. Data analysis proved that flakes far from the most stable C-H pattern exhibited electronic properties that were typical of an unsaturated bonding structure. Based on thermodynamics, we also proved that, for any given flake, there was a well-defined hydrogen content and a conformation of H atoms at the caps, which were favored across a wide range of environmental conditions.