A detailed theoretical and spectroscopic study on the electronically excited states of a trinuclear palladium complex is presented both in the gas phase and solution. The application of DFT and TDDFT methods as well as a variety of spectroscopic methods to the chosen complex [Pd3{Si(mt(Me))3}2] (1, mt(Me) = methimazole) leads to the first detailed analysis of the photophysics of a symmetric trinuclear complex. In combination with the calculations, energies, structures and lifetimes of the excited electronic states (with an (3)A1 state as the lowest one) are characterized by applying the resonant-2-photon-ionization method in a molecular beam experiment as well as luminescence, time-correlated single photon counting and excited state femtosecond absorption spectroscopy in solution. These investigations are of fundamental interest to analyze photophysical properties of metal containing complexes on a molecular level.
The structural identification of small nickel clusters with ethanol can help to understand fundamental steps for heterogenous catalysis. We investigate the rows [Ni x (EtOH) 1 ] + with x = 1-4, and [Ni 2 (EtOH) y ] + with y = 1-3 via IR photodissociation spectroscopy in a molecular beam experiment. Analyzing the CH-and OH-stretching frequencies and comparing these experimental results with density functional theory (DFT) calculations on the PW91/6-311 + G(d,p) level leads to the identification of intact motifs for all clusters and hints for CÀ O cleavage of the ethanol in two particular cases. Furthermore, we analyze the effects of frequency shifts with the increasing clusters sizes using the results of natural bond orbitals (NBO) analyses and an energy decomposition method.
We present a combined theoretical and experimental study of the infrared (IR) and electronic absorption spectra in a molecular beam experiment as well as an analysis of spin dynamics in the clusters Co + 3 (EtOH) and Co + 3 (EtOH,H 2 O). The calculated IR and ground-state absorption spectra show very good agreement with experiment. By using high-level quantum chemistry methods, laser-induced ultrafast spin-flip scenarios in these structures are predicted. For the spin flip in Co + 3 (EtOH), our investigation indicates a 5 meV tolerance with respect to the laser detuning and a 6.5 meV tolerance with respect to the pulse spectral broadening, which are quite acceptable for the experimental implementation. In addition, we find that with the increase of the laser detuning the fitness of the processes gradually decays to zero on both sides but with different origins. This joint study of the homotrinuclear clusters provides insight into the experimentally observed spectra and optical properties, and steps towards the optical control of molecular magnetism for future spintronics application.
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