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- W10808549 abstract "Vibrational energy flows within and between polyatomic molecules drives chemistry and governs their reactivity. In the past decade, intramolecular vibrational energy redistribution (IVR) in isolated molecules has been investigated with good success. Much less, however, is known about IVR in solution where the intramolecular energy redistribution process is influenced by the surrounding solvent. The reason for this lack of knowledge is that IVR for a particular molecule could not yet be measured in the gas phase and in solution with the same technique. Consequently, it was nearly impossible to correlate timescales of isolated and solvated molecules and to obtain a quantitative understanding of IVR and its underlying mechanisms in solution. In addition, the impact of chemical substitution on IVR remained largely unclear in solution. The initially excited non-stationary “states” in the two quanta region of the C-H stretch vibration are Franck-Condon (FC) inactive, but as energy redistributes in the molecule, the population of isoenergetic (zeroth order) combination vibrations having quanta in the FC active modes causes an increase in the absorption on the long wavelength wing of the electronic absorption spectrum. The limited number of FC-active modes of the molecules can be identified by the resonance Raman and the dispersed fluorescence experiments. Subsequent intermolecular vibrational energy transfer (VET) to the surrounding solvent decreases the absorption again." @default.
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- W10808549 date "2004-01-01" @default.
- W10808549 modified "2023-09-26" @default.
- W10808549 title "The impact of different molecular environments and chemical substitution on timescales of intramolecular vibrational energy redistribution in aromatic molecules" @default.
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- W10808549 doi "https://doi.org/10.1016/b978-044451656-5/50055-4" @default.
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