First principles study of the adsorption of C60 on Si(1 1 1)

The adsorption of C60 on Si(1 1 1) has been studied by means of first-principles density functional calculations. A 2×2 adatom surface reconstruction was used to simulate the terraces of the 7×7 reconstruction. The structure of several possible adsorption configurations was optimized using the ab initio atomic forces, finding good candidates for two different adsorption states observed experimentally. While the C60 molecule remains closely spherical, the silicon substrate appears quite soft, especially the adatoms, which move substantially to form extra C–Si bonds, at the expense of breaking Si–Si bonds. The structural relaxation has a much larger effect on the adsorption energies, which strongly depend on the adsorption configuration, than on the charge transfer.