Abstract
The quantum mechanical modeling of noble metal nanoclusters is critical for unlocking the structure-property relationships that govern their optical properties. The two main considerations in the selection of an appropriate computational method for modeling noble metal nanoclusters are accuracy and computational expense. The level of theory for a computational method is determined by the combination of method and the set of functions used to describe molecular orbitals, termed the basis set. One class of methods with lower computational expense than ab initio methods is semi-empirical quantum mechanical methods. The accuracy of semi-empirical methods depends on the quality of their parameters, which can be tuned to reproduce the results of high accuracy reference data. In this work, we generate ab initio gold nanocluster reference data and select an appropriate level of theory for silver nanocluster reference data in chapters 2 and 3. A second class of methods with lower computational expense than ab initio methods is density functional theory. The accuracy of different basis sets for silver nanoclusters is verified by comparing the electron delocalization of molecular orbitals computed with density functional theory in chapter 4. Considered together, these projects demonstrate progress towards more accurate and efficient approximate modeling of silver and gold nanoclusters.