Quantum Mechanical / Molecular Mechanical Study of Electronically Excited 
States and Assessment of Methods for Calculating Vertical Excitation Energies

da Silva Junior, Mario Ramos

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Quantum Mechanical / Molecular Mechanical Study of Electronically Excited States and Assessment of Methods for Calculating Vertical Excitation Energies

da Silva Junior, M. R. (2011). Quantum Mechanical / Molecular Mechanical Study of Electronically Excited States and Assessment of Methods for Calculating Vertical Excitation Energies. PhD Thesis, Heinrich-Heine-Universität Düsseldorf, Düsseldorf.

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Datensatz-Permalink: https://hdl.handle.net/11858/00-001M-0000-0014-C914-F Versions-Permalink: https://hdl.handle.net/21.11116/0000-000D-708B-8

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Urheber:
da Silva Junior, Mario Ramos¹, Autor

Affiliations:
1Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590

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Zusammenfassung: A systematic and extensive benchmark of theoretical methods for computing electronically excited states is presented in the first part of the dissertation. The chosen reference set comprised 28 organic molecules and diverse types of singlet
and triplet valence excited states. Using the same ground-state geometries and the medium-sized TZVP basis set, MS-CASPT2 and coupled-cluster CC3 calculations were carried out and compared with high-level theoretical work in the literature. On the basis of these own calculation and high-level literature results, a set of theoretical best estimates (TBE) for vertical excitation energies was derived and used as reference data for evaluating the performance of methods based on density functional theory (DFT) and of semiempirical methods.
In the second part of the dissertation, the photoinduced processes in a blue-light
photoreceptor with artificial chromophores were studied using combined quantum mechanics / molecular mechanics (QM/MM) methods. This work was motivated by experimental findings that the insertion of the chromophores 1- and 5-deaza flavin mononucleotide (1DFMN and 5DFMN) into the binding pocket of the LOV domain of the YtvA protein leads to unexpected and different behavior: 1DFMN-YtvA does not undergo any photoinduced reactions, whereas 5DFMN-YtvA forms a photoadduct in a triplet reaction (similar to the parent FMN chromophore) followed by photochemical dark state recovery.