| Plasmonic nanoparticles support surface plasmon resonances that are sensitive to the environment. Factors contributing to the refractive index sensitivity are explored systematically through simulation, theory, and experiment. Particles small with respect to the wavelength of light and with size parameters much less than 1 have optical properties accurately predicted by quasi-electrostatic theory while particles with larger size parameters necessitate electrodynamics. A theory is developed that captures the effects of geometry on the refractive index sensitivity with a single factor, plasmon band location, and, although based on electrostatic theory, well predicts the sensitivity of particles whose properties are beyond the electrostatic limit. This theory is validated by high quality simulations for compact particles with shape parameters approaching 1 and, therefore, electrodynamic in nature, as well as higher aspect ratio particles that are electrostatic. Experimentally observed optical spectra for nanorods immobilized on glass and subjected to changes in n of the medium are used to calculate the sensitivity of the particles, found to be well matched by a variation on the homogeneous plasmon band theory. The separate electrostatic and electrodynamic components of plasmon band width, are explored and the overall width is found to affect the observability of the aforementioned sensitivity similarly within each particle class. The extent of the sensing volume around a spherical particle is explored and found to vary with particle size for small particles. Through simulation of oriented dielectric layers, it is shown particles are most sensitive to material located in regions of highest field enhancement. Variations on seed-mediated growth of gold nanorods results in spectra exhibiting a middle peak, intermediate to the generally accepted longitudinal and transverse modes. Simulated optical properties and calculated field enhancement illustrates the correlation between geometry and optical properties and allows for identification of the middle peak. |
