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Vibrationally resolved fluorescence spectra of four angular [N]phenylenes were recorded with laser excited Shpol’skii spectroscopy (LESS) in an n-octane matrix at 10 K. In general, the same vibrational frequencies were observed in the fluorescence excitation and emission spectra, indicating that the geometries of ground and electronically excited state are very similar. Because of intensity borrowing from the S2 state, vibrations of two different symmetries were observed in the fluorescence excitation spectra of angular [3]phenylene and zig-zag[5]phenylene. This finding allowed the location of the S2 state for these compounds. DFT calculations(RB3LYP/6-31G*) of the ground state vibrational frequencies were made. The calculated vibrational modes were in reasonably good agreement with the experimental data. A new very low-frequency vibration of approximately 100 cm-1 was predicted and experimentally confirmed for all [N]phenylenes investigated. This vibration seems to be unique for [N]phenylenes and is attributed to an in-plane movement of the carbon backbone.
Deuteration effects on the vibronic structure of the emission and excitation spectra of triangular [ 4] phenylene (D-3h [4]phenylene) were studied using laser-excited Shpol'skii spectroscopy (LESS) in an octane matrix at 4.2 K. For correct assignment of the vibrational modes, the experimental results were compared with calculated frequencies (B3LYP/6-31G*). CH vibrations were identified by their characteristic isotopic shifts in the spectra of deuterated triangular [4]phenylenes. Two CC stretching modes, at 100 cm(-1) and 1176 cm(-1), suitable as probes for bond strength changes in the excited state, were identified. The isotope effect on the internal conversion rates of triangular [4] phenylene was evaluated from measurements of temperature dependent lifetime. Isotope dependency and the magnitude of the internal conversion rates indicate that internal conversion in triangular [4] phenylene is most likely induced by CH vibrations. The results obtained by LESS and lifetime measurements were compared with PM3 PECI calculations of the excited state structure. The theoretical results and the relation between ground and excited state vibration energies of the 1176 cm(-1) probe vibration indicate a reduction of bond alternation of the central cyclohexatriene ring in the excited state
Deuteration effects on the vibronic structure of the emission and excitation spectra of triangular [4]phenylene (D3h[4]phenylene) were studied using laser-excited Shpolskii spectroscopy (LESS) in an octane matrix at 4.2 K. For correct assignment of the vibrational modes, the experimental results were compared with calculated frequencies (B3LYP/6-31G*). CH vibrations were identified by their characteristic isotopic shifts in the spectra of deuterated triangular [4]phenylenes. Two CC stretching modes, at 100 cm–1 and 1176 cm–1, suitable as probes for bond strength changes in the excited state, were identified. The isotope effect on the internal conversion rates of triangular [4]phenylene was evaluated from measurements of temperature dependent lifetime. Isotope dependency and the magnitude of the internal conversion rates indicate that internal conversion in triangular [4]phenylene is most likely induced by CH vibrations. The results obtained by LESS and lifetime measurements were compared with PM3 PECI calculations of the excited state structure. The theoretical results and the relation between ground and excited state vibration energies of the 1176 cm–1 probe vibration indicate a reduction of bond alternation of the central cyclohexatriene ring in the excited state.
Tectonic and climatic control on evolution of rift lakes in the Central Kenya Rift, East Africa
(2009)
The long-term histories of the neighboring Nakuru-Elmenteita and Naivasha lake basins in the Central Kenya Rift illustrate the relative importance of tectonic versus climatic effects on rift-lake evolution and the formation of disparate sedimentary environments. Although modem climate conditions in the Central Kenya Rift are very similar for these basins, hydrology and hydrochemistry of present-day lakes Nakuru, Elmenteita and Naivasha contrast dramatically due to tectonically controlled differences in basin geometries, catchment size, and fluvial processes. In this study, we use eighteen C-14 and Ar-40/Ar-39 dated fluvio-lacustrine sedimentary sections to unravel the spatiotemporal evolution of the lake basins in response to tectonic and climatic influences. We reconstruct paleoclimatic and ecological trends recorded in these basins based on fossil diatom assemblages and geologic field mapping. Our study shows a tendency towards increasing alkalinity and shrinkage of water bodies in both lake basins during the last million years. Ongoing volcano-tectonic segmentation of the lake basins, as well as reorganization of upstream drainage networks have led to contrasting hydrologic regimes with adjacent alkaline and freshwater conditions. During extreme wet periods in the past, such as during the early Holocene climate optimum, lake levels were high and all basins evolved toward freshwater systems. During drier periods some of these lakes revert back to alkaline conditions, while others maintain freshwater characteristics. Our results have important implications for the use and interpretation of lake sediment as climate archives in tectonically active regions and emphasize the need to deconvolve lacustrine records with respect to tectonics versus climatic forcing mechanisms.