Step fluctuations on metals in contact with an electrolyte: a new access to dynamical processes at the solid/liquid interface

Comparative STM studies on island equilibrium shapes, shape fluctuations and island coalescence on Au(001) electrodes in chloric and sulfuric acid solutions

“…In principle, one cannot a priori assume that the coalescence kinetics is independent of the electrode potential. On the contrary, one should expect the mass transport on the surface to depend on the electrode potential as has been shown in studies on equilibrium step fluctuations on metal electrodes [3,16]. Then, if τ is a function of the area A as well as of the potential φ, the coalescence relaxation exponent δ (Eq.…”

“…Quantitative studies on atomic motion on metal surfaces in electrolyte cover investigations on equilibrium fluctuations of isolated steps [3,[16][17][18][19][20], the decay of clusters on metal electrodes [5,6,[13][14][15][21][22][23], island shape and shape fluctuation analyses [20,22,[24][25][26] and single-atom diffusion studies [4,11,12]. In all these studies, relevant surface migration processes were identified and the respective activation barriers were 0013 measured.…”

The Role of Hydrophobic Chains in Self-Assembly at Electrified Interfaces: Observation of Potential-Induced Transformations of Two-Dimensional Crystals of Hexadecane by In-situ Scanning Tunneling Microscopy

“…32 Closer inspection of the images reveals that the island edges are fuzzy, suggesting that the islands are in the process of dynamic evolution. 39 Atoms are continuously attaching, detaching, or diffusing along the island edges. Clearly the presence of the hexadecane molecules affects the structures and dynamics of the gold islands.…”

Migration of point defects at charged Cu, Ag, and Au (100) surfaces

“…These energies play also an important role in the structuring of charged solid-electrolyte interfaces, including processes like electrochemical annealing, [1][2][3][4][5][6][7] and in equilibrium fluctuations of monoatomic steps. [8][9][10] Since the initial and final states of surface transport processes are both on the surface, the driving force of these processes is given by the temperature of the system and is not directly affected by the electrode potential. However, in a recent presentation, Giesen et al showed that for solid electrodes held in an electrolyte at a constant potential, all defect formation and activation energies become renormalized by the electrostatic energy of the defect dipoles.…”

“…Since in typical electrochemical systems the electrostatic dipole energy is of the same order of magnitude as the formation and activation energies of the point defects, this potential dependence is experimentally readily observable. [1][2][3][4][5][6][7][8][9][10][11] Therefore, in order to properly describe the mass transport along charged solid-electrolyte interfaces we not only need information about formation and activation energies of the surface defects leading to surface mass transport, but also a detailed knowledge of their electrical properties. In this paper we present ab initio results for the formation and activation energies for migration, as well as for the electrical dipole moments of adatoms and vacancies at the Cu, Ag and Au ͑100͒ surfaces, and we discuss the role played by the electrostatic dipole energy in the mass transport by point defects at charged metal-electrolyte interfaces as a function of the applied potential.…”