Silver electrodeposition from water–acetonitrile mixed solvents. Part III—an in situ investigation by optical second harmonic generation spectroscopy

In this work, we report an investigation based on silver electrodeposition from water–acetonitrile mixed solvents onto a polycrystalline Au electrode, based on in situ optical second harmonic generation (SHG) spectroscopy. This paper is the last one of a series attacking the same topic by cyclic voltammetry and potentiostatic current transients (Mele et al., J Solid State Electrochem in press, 1) and in situ surface-enhanced Raman scattering (Mele et al., J Solid State Electrochem in press, 2). SHG intensity transients following the application of potentiostatic cathodic steps have been measured in order to obtain detailed information on the formation of Ag clusters and nuclei during the electrodeposition process. Our SHG data have been rationalised in terms of a simple optical model accounting for SHG enhancement brought about by Ag cluster formation.