A density functional study of actinyl containing complexes
| dc.contributor.author | Berard, Joel J. | |
| dc.contributor.examiningcommittee | Budzelaar, Peter (Chemistry)Fayek, Mostafa Fayek (Geological Science) | en |
| dc.contributor.supervisor | Schreckenbach, Georg (Chemistry) | en |
| dc.date.accessioned | 2008-05-07T17:06:16Z | |
| dc.date.available | 2008-05-07T17:06:16Z | |
| dc.date.issued | 2008-05-07T17:06:16Z | |
| dc.degree.discipline | Chemistry | en_US |
| dc.degree.level | Master of Science (M.Sc.) | en_US |
| dc.description.abstract | Density functional (DFT) methods are first used to study 22 of the most stable solution-phase UN4O12 isomers containing uranyl nitrate, UO2(NO3)2. Based on relative free energy calculations, 4 solution (a6, a5, a8, and a1) and 5 gas-phase isomers (a1, a2, a3, b1, and b2) are identified as the strongest candidates to exist and possibly predominate within their respective environments. DFT is then applied to a new form of binucleating Schiff–base polypyrrolic macrocycles containing actinyl ions [AnO2]n+ (An = U, Np, Pu; n = 1, 2) and 3d transition metals (TM): Mn, Fe, Co, and Zn. Formal bond order evidence is provided for 24 TM to actinyl–endo–oxygen partial bond formations. Special structural cases are discussed. Redox potentials for AnVIO21/AnVO21– couples closely follow the Np > Pu > U trend seen for AnO2(H2O)52+/1+. Predictions of –1.10, 0.25, and 0.01 eV are made for U, Np, and Pu redox potentials. | en |
| dc.description.note | May 2008 | en |
| dc.format.extent | 2228804 bytes | |
| dc.format.mimetype | application/pdf | |
| dc.identifier.citation | Berard, J.J., Shamov, G.A., and Schreckenbach, G., J. Phys. Chem. A, 2007. 111(42): p. 10789-10803. | en |
| dc.identifier.uri | http://hdl.handle.net/1993/3034 | |
| dc.language.iso | eng | en_US |
| dc.rights | open access | en_US |
| dc.subject | actinides | en |
| dc.subject | DFT | en |
| dc.subject | actinyls | en |
| dc.subject | UN4O12 | en |
| dc.subject | uranyl nitrate | en |
| dc.subject | polypyrrolic macrocycles | en |
| dc.title | A density functional study of actinyl containing complexes | en |
| dc.type | master thesis | en_US |