Some optical and catalytic properties of metallic nanoparticles

Nanomaterials have been the focus of many previous publications and studies. This fact is due to the wealth of new and tunable properties that exist when a material is confined in size. This thesis discusses some of those properties pertaining to metallic nanoparticles. The primarily focus is on the plasmonic properties of gold nanoparticles with a final chapter discussing nanocatalysis and the nature of nanocatalytic reactions.;The strong electromagnetic field that is induced at the surface of a plasmonic nanoparticle can be utilized for many important applications, including spectroscopic enhancements for molecular sensors and electromagnetic waveguides for sub-wavelength light manipulation. For many of these applications, it is necessary to use two or more nanoparticles in close proximity with overlapping plasmonic fields. Knowledge of how these overlapping fields are affected by the particle orientation, size, and shape is critically important, not only in understanding the fundamental properties of plasmons but also in designing future architectures that employ plasmonic particles.;The field of metallic nanoparticles is introduced from its beginning, with artistic use as early as the 4th century AD through current applications and understanding. The broad spectrum of current methodologies for fabricating nanoparticles is discussed, from top down methods using lithography and from bottom up methods using metal salt reduction in solution. There are several methods used in this thesis, all of which are discussed in great detail, with some details pertaining to the specific instrumentation used here.;The first study is on the transfer of surface supported gold nanoprisms from a substrate into solution using photo-thermal heating with a femtosecond pulse coincident with the plasmon resonance frequency of the nanoprisms. The mechanism of transfer is discovered to be due to super heating of solvent molecules dissolved at the particle-substrate interface. This process is studied as a function of irradiance fluence and solvent. The stability of the unprotected nanoprisms in solution is discussed. This technique has applications for creating a colloidal suspension of nanoparticle without a surfactant layer covering the surface. The particles can be chemically functionalized with any desired moiety for specific solution phase applications.;The second study is on the fundamentals of plasmonic near-field coupling between two plasmonic nanoparticles as a function of the nanoparticle size, shape, and orientation. Experimental results using electron beam lithography fabricated samples are used to better understand the plasmonic coupling between dimers. Previously, the coupling between plasmonic fields around nanoparticles has been described as a near-exponential decay dependence on interparticle separation. This decay was proposed to be consistent among all sizes and shapes of nanoparticles, which was quantitatively measured using the best-fit decay length in units of the nanoparticle size. Experimental proof is presented of the shape dependence of this decay length, which is roughly 50% greater for nanoprisms than for nanodiscs, nanospheres, and nanoellipses. This was shown using simulated and experimental data. Using simulated results, the coupling decay length was shown to be independent of size for all nanoparticle shapes examined.;Additionally, the effect of particle orientation on the coupling of the induced nearfields of the plasmonic particles is intensely investigated. Systematic studies using a combination of experimental samples and computer simulations are presented that examine the role of one particle's orientation to another within a plasmonic dimer system. This dependence is compared to the mathematically derived dependence and shown to be in excellent agreement. The plasmon hybridization method is given as a straightforward method to understand and predict the effect of plasmon near-field coupling on orientation. Previous methods used to understand the effect of separation on the plasmon coupling are incorporated into this method.;As an extension, the coupling between plasmonic nanoparticles is shown in a common application, namely surface enhanced Raman scattering. This phenomenon is studied using colloidally prepared silver nanocubes deposited on a substrate using the Langmuir-Blodgett technique. Using various surface pressures during deposition, the surface density of the deposited nanocubes can be controlled, and thus the degree of plasmonic coupling. By controlling the plasmonic coupling, the enhancement of the Raman scattering from the PVP capping layer was altered and a correlation between the enhancement and the plasmon field intensity is reported.;The final study investigates the nature of nanocatalysis for several reactions using metal nanoparticles. Arguably, the largest unanswered question currently in nanocatalysis is the nature of the catalytic reaction, namely homogeneous catalysis or heterogeneous catalysis. This question has been very difficult to answer because of the lack of current techniques to completely restrict one form of catalysis. The issue is reviewed in this thesis with new insights discussed while using experiments that show evidence of both sides of the issues, homogeneous and heterogeneous.