Kohn-Sham Density Functional Theory: Application to Metal Clusters and Nanoparticles

Abstract

Metal clusters and nanoparticles are important in chemistry and materials science because of their unique properties that are different from those of bulk materials. The most widely used theoretical method for studying metal clusters and nanoparticles is Kohn–Sham density functional theory. This method would be exact if the exact exchange-correlation (xc) functional were known and were used; however, the exact xc functional is unknown and probably unknowable, therefore one must use approximate xc functionals. The continued development of xc functionals enables us to apply the theory to the more and more chemistry problems, and it also leads to questions: Which of the xc functionals are reliable for metal clusters? Which ingredient in the xc functionals is necessary for accurately predicting the properties of metals clusters? This thesis provides high-level benchmarking calculations, as well as validation of various xc functionals for silver and magnesium clusters and nanoparticles. This thesis also shows the new charge model for silver clusters and its application in CO adsorption.