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  • Title: Excited stilbene: intramolecular vibrational redistribution and solvation studied by femtosecond stimulated Raman spectroscopy.
    Author: Weigel A, Ernsting NP.
    Journal: J Phys Chem B; 2010 Jun 17; 114(23):7879-93. PubMed ID: 20481560.
    Abstract:
    Excited-state relaxation of cis- and trans-stilbene is traced with femtosecond stimulated Raman spectroscopy, exploiting S(n) <-- S(1) resonance conditions. For both isomers, decay in Raman intensity, shift of spectral positions, and broadening of the bands indicate intramolecular vibrational redistribution (IVR). In n-hexane this process effectively takes 0.5-0.7 ps. Analysis of the intensity decay allows us to further distinguish two phases for trans-stilbene: fast IVR within a subset of modes (approximately 0.3 ps) followed by slower equilibration over the full vibrational manifold (approximately 0.9 ps). In acetonitrile IVR completes with 0.15 ps; this acceleration may originate from symmetry breakage induced by the polar solvent. Another process, dynamic solvation by acetonitrile, is seen as spectral narrowing and characteristic band shifts of the C=C stretch and phenyl bending modes with 0.69 ps. Wavepacket motion is observed in both isomers as oscillation of low-frequency bands with their pertinent mode frequency (90 or 195 cm(-1) in trans-stilbene; 250 cm(-1) in cis-stilbene). Anharmonic coupling shows up as a modulation of high-frequency peak positions by phenyl/ethylene torsion modes of 57 and 90 cm(-1). Decay and shift of the 90 cm(-1) inverse Raman band within the first 0.3 ps suggests a gradual involvement of phenyl/ethylene torsion in relaxation. In cis- and trans-stilbene, low-frequency spectral changes are found within 0.15 ps, indicating an additional ultrafast process.
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