Articles you may be interested inA DFT study of the NO dissociation on gold surfaces doped with transition metals J. Chem. Phys. 138, 074701 (2013); 10.1063/1.4790602 Trends in C-O and C-N bond formations over transition metal surfaces: An insight into kinetic sensitivity in catalytic reactionsRecent low energy electron diffraction experiments have shown that partial dissociation of benzene at the Ir͕100͖ surface yields an ordered overlayer of ortho-benzyne radicals (C 6 H 4 ) with ring-planes inclined at 47.2°to the normal. The primary molecule-surface interaction may be attributed to bonds between radical C and surface Ir atoms, but this characteristic alone does not uniquely constrain the adsorbate to the observed orientation. Through first-principles density functional theory which gives good agreement with the experimental structure, we now demonstrate that the molecular tilt arises due to interaction of the aromatic orbitals with the surface d orbitals, and not because of any dispersive intermolecular forces.