Journal
CHEMPHYSCHEM
Volume 16, Issue 18, Pages 3824-3835Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/cphc.201500586
Keywords
kinetics; photophysics; time-resolved spectroscopy
Funding
- Deutsche Forschungsgemeinschaft [ER 154/10-2]
- ERC [259432]
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beta-Carotene in n-hexane was examined by femtosecond transient absorption and stimulated Raman spectroscopy. Electronic change is separated from vibrational relaxation with the help of band integrals. Overlaid on the decay of S-1 excited-state absorption, a picosecond process is found that is absent when the C-9-methyl group is replaced by ethyl or isopropyl. It is attributed to reorganization on the S-1 potential energy surface, involving dihedral angles between C-6 and C-9. In Raman studies, electronic states S-2 or S-1 were selected through resonance conditions. We observe a broad vibrational band at 1770cm(-1) in S-2 already. With 200fs it decays and transforms into the well-known S-1 Raman line for an asymmetric C=C stretching mode. Low-frequency activity (<800cm(-1)) in S-2 and S-1 is also seen. A dependence of solvent lines on solute dynamics implies intermolecular coupling between -carotene and nearby n-hexane molecules.
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