Abstract:
The photochemical and spectral properties of fac-[Re(X)(CO)3(bpy)]ⁿ⁺ (X=NCS, Cl, pyridine), (n=0,1) were studied by experimental and theoretical approaches. The ground state electronic structures were calculated by density functional theory (DFT) method. The spectral transitions and charge density redistribution in the course of electronic excitations were calculated by the time-dependent DFT (TD-DFT) method. The lowest lying triplet and singlet excited states of these complexes were optimized at TD-DFT level or unrestricted Kohn-Sham calculations. The electrostatic solvent influence on spectra was modeled using polarizable continuum model (PCM) or conductor - like screening model (COSMO). The interpretation of ground and excited state IR spectra was based on the vibration analysis at optimized structures. Simulated ground and excited-state IR spectra correspond to the experimental spectra measured by ps-time-resolved IR spectroscopy. At the second part of the presentation, the DFT modeling of the interaction of organic molecules with gold and platinum clusters will be presented. There is a need to develop electrocatalytic materials for oxygen insertion to double bonds. Specific reactivity could be achieved using metal nanostructured electrodes. The current understanding is, at present, rather limited. The DFT method was used for the study of possible mechanism of the ethylene oxidation or electro-oxidation at metal interfaces. The understanding of catalytic properties of surfaces requires the proper modeling the interface. In this study, a cluster approach was used for the modeling of electrocatalytical ethylene epoxidation at metal interface. Pt and Au clusters were modeled as an interface simplification or as a part of real experimental system.