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dc.contributor.advisor Mata, Ricardo Prof. Dr.
dc.contributor.author Andrejić, Milica
dc.date.accessioned 2015-06-08T08:22:28Z
dc.date.available 2015-06-08T08:22:28Z
dc.date.issued 2015-06-08
dc.identifier.uri http://hdl.handle.net/11858/00-1735-0000-0022-6011-C
dc.language.iso eng de
dc.publisher Niedersächsische Staats- und Universitätsbibliothek Göttingen de
dc.rights.uri http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subject.ddc 540 de
dc.title Development of Hybrid QM/QM Local Correlation Methods for the Study of Metal Sites in Biomolecular Catalysis de
dc.type doctoralThesis de
dc.contributor.referee Mata, Ricardo Prof. Dr.
dc.date.examination 2015-03-27
dc.description.abstracteng Metal-containing systems present a challenge for both theoretical and experimental chemists. Joint efforts are required to fully understand their complex electronic structure and their role in catalysis. On the side of theory, accuracy is essential but the cost of wave function methods is deterrent to this goal. The emphasis of this work is on the development of a QM/QM method for biomolecules which can reach wavefunction accuracy. To properly describe the electron correlation in transition metals inclusion of higher-order excitations is required. However, some of these effects are relatively local in nature (regularly connected with the metal center) and hybrid or embedding approaches offer a cost-effective alternative for their computation. In the proposed QM/QM scheme, localized orbitals are used to split the system into different groups. This allows for high accuracy in regions where bond breaking/formation takes place, while the remaining environment is described at a low level. Coupled cluster and MP2 approaches can be combined in a single calculation, without resource to model systems. In the present thesis, this QM/QM method will be applied for the first time in the treatment of closed-shell metal systems and for open-shell systems in general. The application on different complexes containing a wide variety of metals will be presented. It will be shown that this method provides valuable insights into the aurophilic interaction. On the example of molybdenum enzymes, it will be shown that high accuracy for the calculation of reaction pathways can be obtained with significantly reduced computational costs. On the example of nitrite reductase, it will also be shown that properties, such as electron affinities, can be reliably calculated. de
dc.contributor.coReferee Ryde, Ulf Prof. Dr.
dc.contributor.thirdReferee Clever, Guido Prof. Dr.
dc.subject.eng Local correlation methods de
dc.subject.eng QM/QM method de
dc.subject.eng Aurophilicity de
dc.subject.eng Open shell systems de
dc.subject.eng Molybdenum enzymes de
dc.subject.eng Copper nitrite reductase de
dc.identifier.urn urn:nbn:de:gbv:7-11858/00-1735-0000-0022-6011-C-5
dc.affiliation.institute Fakultät für Chemie de
dc.subject.gokfull Chemie  (PPN62138352X) de
dc.identifier.ppn 826982697

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