Chemical applications of density functional theory as an analytical tool

UnrestrictedThis body of work uses density functional theory (DFT) to calculate chemical properties. DFT is a powerful theoretical method that allows chemists to obtain valuable information at reasonable levels of computational time. Here, DFT is specifically used to calculate chiroptical properties and help deduce mechanistic information for the methanol-to-olefins reaction.; The recently-available time-dependent DFT (TDDFT) methods for calculating optical rotation (OR) and electronic circular dichroism (CD) are critiqued. Calculations of OR and CD are performed for many molecules, and the results are compared to experimentally available sources. The accuracies of these two chiroptical methods are developed based on the comparisons.; DFT is also used to study the methanol-to-olefins reaction, where intramolecular isomerizations of polymethylated benzenium cations are performed to investigate the plausibility of carbon atom scrambling and simultaneous olefin production. Initial gas-phase studies are performed for polymethylated benzenium cations and, based on these results, an additional study with the influence of a zeolite cluster is performed. A polymethylated benzenium cation is produced from a neutral aromatic using a complete supramolecular zeolite cluster model. This polymethylated benzenium cation is further subjected to intramolecular isomerizations, leading to carbon scrambling and the production of an olefin, in the presence of the zeolite cluster model