Flat-structural Motives in Small Alumino-Carbon Clusters C(n)Al(m) (n = 2-3, m = 2-8)

Small clusters consisting of a carbon diatom or triatom and several aluminum atoms are investigated ab initio, at an MP2 level of theory. The mainly ionic character of C-Al bonding predominantly leads to structures different from corresponding hydrocarbons (also if starting from analogous initial geometries), while still producing closed-shell ground states. It is found that in many cases stable geometries correspond to flat CAl(3) units. These include unique metal-framed dicarbon and tricarbon all-flat species with unusual planar tetra-coordination. Another frequent feature is a hyper-coordination of carbon atoms, supported by their high negative charges and critically examined via atom-in-molecule calculations. Also characterized are anionic states, electronic excitation and ionization, electron attachment and detachment, and charge distributions.