Polycyclic Aromatic Hydrocarbons: Trends for Bonding Hydrogen

Hydrogenation of carbonaceous materials is important within carbon-based electronics, hydrogen storage, and the catalytic formation of molecular hydrogen in space. This study presents a systematic investigation at the density functional theory level of the hydrogenation of all small closed-shell polycyclic aromatic hydrocarbons comprising up to four carbon hexagons plus pentacene, hexacene, and heptacene. Binding energies span from 0.43 to 2.70 eV. Two-fold coordinated carbon atoms are preferred as binding sites with binding energies from 1.06 to 2.70 eV. Analyzing the binding sites yields three different motifs each with a clear structural and electronic fingerprint explaining the ordering of the binding sites.