The UV-Vis and magnetic circular dichroism (MCD) spectra of the d1 oxomolybdenum tetrachloride ([MoOCl4]-) anion in C4v symmetry have been calculated using the ab initio complete-active-space self-consistent-field (CASSCF)/multi-reference configurational interaction (MRCI) theory. The influence of active space used in these calculations was investigated, and the use of a differential treatment of charge-transfer and ligand-field type transitions through partitioning of active space was found to be effective. Additionally, the influence of Hartree-Fock exchange on the vertical excitation energies of [MoOCl4]- has been investigated through DFT/TDDFT methods. The combined results provide a promising direction for the prediction of MCD spectroscopy in oxomolybenal complexes. The mixed-valence properties of aromatic polyferrocenyl heterocycles have received considerable attention in recent years due to their model properties for electronic intercommunication. While α, β, and α-β saturated ferrocenyl pyrroles have been synthesized and characterized, current studies of these complexes have lacked a theoretical investigation of their electronic properties. In this study, these complexes are characterized using TDDFT methods, and their mixed-valence states explored in order to provide insight to the first oxidation process of 2,3,4,5-tetraferrocenyl-pyrrole.
University of Minnesota M.S. thesis. September 2013. Major: Chemistry. Advisor: Victor V. Nemykin. 1 computer file (PDF); vii, 202 pages.
Van Stappen, Casey Michael.
Ab Initio and TDDFT investigations of the electronic spectra of [MoOCl4]- and of mixed-valency in polyferrocenyl pyrroles.
Retrieved from the University of Minnesota Digital Conservancy,
Content distributed via the University of Minnesota's Digital Conservancy may be subject to additional license and use restrictions applied by the depositor.