Theoretical Investigations of Surface-Adsorbate Interfaces

Density functional calculations were performed in order to elucidate properties of surface-adsorbate interfaces. These studies are primarily concerned with the electronic structure and charge transfer between the surface and the adsorbate molecule. Molecular orbital interactions at the surface adsorbate interface are discussed in Chapter 3. A review the basics of density functional theory (DFT), empirically corrected DFT, and non-local DFT is included in Chapter 4. The results of our computational studies of benzene and substituted benzenes adsorbed on the Cu(111) surfaces are given in Chapter 5. The influence of increasing the surface coverage on the electronic states of a quinoid zwitterion on the Au(111) surface is given in Chapter 6. In Chapter 7, we present findings involving the previously mentioned quinoid zwitterion adsorbed to the Cu(111) surface in which pi back-donation is predicted to strengthen a bond.;In Chapter 8 we provide the results of studies which have arisen out of collaborations with experimental groups. This includes: Section 8.2, tetraphenyl porphyrin adsorbed on the Cu(111) and Ag(111) surfaces; Section 8.3, p-benzoquinonemonoimine zwitterion adsorbed to the Cu(111), and Ag(111) surfaces; 8.4, 4-fluorostyrene adsorbed on the Cu(111) and Au(111) surfaces.;In Chapter 9, we revisit our studies on the formation of 2 dimensional H-bonded networks: Section 9.1, croconic acid adsorbed to the Ag(111) surface; Section 9.2, Rhodizonic acid formation of a metal organic framework (MOF) on the Cu(111) surface; Section 9.3, the formation of chiral networks of 3-Hydroxyphenalenone (HPLN) on Ag(111). Chapter 10 is a comment on the future prospects of this research.