Noble metal nanoparticles: Optical forces, electrochemical Ostwald ripening, and photovoltage

This thesis describes three distinct aspects of the chemical properties of noble metal nanoparticles. The first chapter introduces the surface plasmon resonance of noble metal nanoparticles.; The second chapter presents an electrodynamic model for the calculation of the attractive optical forces that arise when two dielectric particles are irradiated in a light field. These forces show resonances at dipolar plasmon wavelengths, similar to resonances in the near-field electromagnetic intensities. At MW/cm2 intensities, optical forces can be stronger than van der Waals forces.; The third chapter investigates the size dependent electrochemical properties of silver nanoparticles. These thermally evaporated silver nanoparticles spontaneously evolve in size when immersed in pure water on conducting substrates. The process is understood through an electrochemical Ostwald ripening mechanism driven by the size dependence of the work function and standard electrode potential.; The fourth and fifth chapters consider photo-induced surface reactivity of noble metal particles. First, in the fourth chapter, the light driven deposition of copper onto gold nanoparticle electrodes is presented. The photocurrent is a nonlinear function of laser intensity and increases sharply with cathodic voltage in the underpotential deposition region. The photoreduction is attributed to laser heating (caused by decay of the plasmon oscillation) of the Au nanoparticles, rather than "hot electron" processes. Secondly, in the fifth chapter, the photo-induced oxidation of citrate is studied on silver nanoparticle electrodes. Irradiation of the citrate coated particles is shown to cause the particles to charge negatively from the irreversible transfer of electrons from citrate to the particles. It is hypothesized that the particle plasmon oscillation decays into electron hole pair(s) that causes the photo-oxidation of the surface bound citrate. Both the gold and silver particle systems are simulated using the Butler-Volmer equation.