Bond Breaking Coupled with Translation in Rolling of Covalently Bound Molecules

The response of a ${\mathrm{C}}_{60}$ molecule to manipulation across a surface displays a long range periodicity which corresponds to a rolling motion. A period of three or four lattice constants is observed and is accompanied by complex subharmonic structure due to molecular hops through a regular, repeating sequence of adsorption states. Combining experimental data and ab initio calculations, we show that this response corresponds to a rolling motion in which two of the four $\mathrm{Si}\mathrm{\text{−}}{\mathrm{C}}_{60}$ covalent bonds act as a pivot over which the molecule rotates while moving through one lattice constant and identify a sequence of ${\mathrm{C}}_{60}$ bonding configurations that accounts for the periodic structure.