Structure, Stability, Edge States, and Aromaticity of Graphene Ribbons

Abstract

We determine the stability, the geometry, the electronic, and magnetic structure of hydrogen-terminated graphene-nanoribbon edges as a function of the hydrogen content of the environment by means of density functional theory. Antiferromagnetic zigzag ribbons are stable only at extremely low ultravacuum pressures. Under more standard conditions, the most stable structures are the mono- and dihydrogenated armchair edges and a zigzag edge reconstruction with one di- and two monohydrogenated sites. At high hydrogen concentration "bulk" graphene is not stable and spontaneously breaks to form ribbons, in analogy to the spontaneous breaking of graphene into small-width nanoribbons observed experimentally in solution. The stability and the existence of exotic edge electronic states and/or magnetism is rationalized in terms of simple concepts from organic chemistry (Clar's rule).