Title: Monolayer protected noble metal nanocrystals
Description: This research focuses on the production and characterization of monolayer protected silver and gold nanocrystals with novel optical and electronic properties. The nanoparticles manifest optical and electronic qualities that differ from the bulk noble metal, depending on their size, surface properties, and morphology. The work is divided into three parts. The main part is dedicated to the synthesis and characterization of small (1.3 nm) Ag nanoclusters (clusters), protected by a ligand shell of arylthiolates, referred to as Intense Broadly Absorbing Nanoclusters (IBANs). The IBANs were produced in a novel modification of the proto-typical Brust synthesis to overcome the kinetic bottle neck that usually prevents small silver clusters from forming; due to the exceptional stability of the thiol:Ag polymer complex, an intermediate in the cluster synthesis. The IBANs were synthesized monodispersely, without the need for further steps to narrow the size distribution. The synthesis method was shown to work on a wide variety of arylthiol ligands. The IBANs possess unique optical properties, compared to larger nanocrystals. They have eight molecular-like transition bands in their UV-Visible linear absorption spectra. The composition and size distribution of the IBAN's were determined using a unique method that is described in the dissertation for the first time. The technique is based on the solvent-density variation method in sedimentation velocity analytical ultracentrifiigation (SV-AUC), but is modified further to allow SV-AUC measurements to determine the mass and dimension of the core and the monolayer in the ligand shell.

This technique was used to ascertain that IBANs are a unique thiolated Ag cluster with a tentative molecular formula of Ag 74±2 (SR) 40±1 . The described SV-AUC technique has accuracy comparable to that of mass spectroscopy, but has the advantage of being compatible with even the most delicate clusters. The IBANs represent the first report of a stable, monodispersely synthesized thiolated Ag cluster to be reliably assigned a molecular formula. The last part of the dissertation deals with the synthesis and optical properties of gold nanourchins. These are large (∼40-50nm) gold nanoparticles (NPs) that have multiple branches and possess a morphology similar to sea urchins. The particles are protected with a monolayer of thiols. Finite-difference time domain (FDTD) modeling suggests that these particles have large local field enhancements in the vicinity of their branches. These enhancements are found to increase the optical limiting performance of nanourchins, in comparison to spherical particles of the same dimensions.