We report a systematic study for metal-on-metal surface migration in the weak corrugation regime, i.e., with migration barriers falling below ഠ100 meV. The migration characteristics are elucidated by variable-temperature scanning tunneling microscopy observations in the 50 -200 K temperature range, which are analyzed by means of nucleation theory. The results demonstrate that, upon entering the weak corrugation regime, the dynamics of the systems are characterized by increasingly reduced effective preexponential factors, while Arrhenius behavior prevails. PACS numbers: 68.35.Fx, 61.16.Ch, 68.35.Ja, The thermal migration of adsorbed atoms on the periodic lattice of a surface offers an ideal test case to systematically investigate the energetics and dynamics of a rate phenomenon in chemical physics. Surface migration requires the overcoming of an energy barrier E m separating two identical states, a process usually obeying an Arrhenius law [1][2][3]. In particular, the mobility of atoms on metal surfaces has been extensively studied due to its importance for a variety of processes in science and technology, such as heterogeneous catalysis or epitaxial growth [4][5][6]. The phenomenology is simple: Atoms or small molecules are preferentially adsorbed at specific highsymmetry sites of the surface periodic atomic lattice, which are separated by energy barriers being generally a mere fraction of the adsorption energy. The lateral mobility of the adspecies is driven by the substrate heat bath providing stochastic excitations whose characteristic energy is given by the Debye temperature (ϳ25 meV for metals). When the density is low, a two-dimensional random motion of isolated adspecies or tracer diffusion [5] is operational; i.e., adsorbates hop from energy minima to neighboring energy minima. This process can be adequately described in terms of transition state theory (TST) [7], when the thermal energies are much smaller than the migration barrier, i.e., k B T ø E m , and when the coupling of the adspecies to the substrate is sufficiently effective to ensure equilibration between the individual jumps. These conditions normally hold for metallic adsorbates on metal surfaces, and the corresponding tracer diffusion coefficient D ء is given by [5]where b 1͞k B T, a is the periodicity of the surface lattice, and n 0 is the attempt frequency, frequently associated with the lateral vibrational mode of the adatom; D 0 is the preexponential factor.The situation becomes more intricate when the thermal energy increases such that k B T ϳ E m and it is anticipated that TST breaks down, until for k B T ¿ E m a free twodimensional Brownian motion of the adatoms is expected, where the diffusivity is directly proportional to the temperature [8]. Another complication may arise when the coupling of the adatom to the substrate is weak or strong. The resulting effect is twofold: On the one hand, a decrease of the attempt frequency is expected, which lowers the mobility [9][10][11]. On the other hand, for the case of weak coupling, adspec...