  The motion of molecules on solid surfaces is of interest for technological
applications such as catalysis and lubrication, but it is also a theoretical
challenge at a more fundamental level. The concept of activation barriers is
very convenient for the interpretation of experiments and as input for Monte
Carlo simulations but may become inadequate when mismatch with the substrate
and molecular vibrations are considered. We study the simplest objects
diffusing on a substrate at finite temperature $T$, namely an adatom and a
diatomic molecule (dimer), using the Langevin approach. In the driven case, we
analyse the characteristic curves, comparing the motion for different values of
the intramolecular spacing, both for T=0 and $T\ne 0$. The mobility of the
dimer is higher than that of the monomer when the drift velocity is less than
the natural stretching frequency. The role of intramolecular excitations is
crucial in this respect. In the undriven case, the diffusive dynamics is
considered as a function of temperature. Contrary to atomic diffusion, for the
dimer it is not possible to define a single, temperature independent,
activation barrier. Our results suggest that vibrations can account for drastic
variations of the activation barrier. This reveals a complex behaviour
determined by the interplay between vibrations and a temperature dependent
intramolecular equilibrium length.
