Ultrafast intramolecular electron transfer studied by Picosecond and stationary Raman spectroscopy

Wolfgang Werncke, Sebastian Wachsmann-Hogiu, Jens Dreyer, Alexander Ivanovich Vodchits, Thomas Elsaesser

Research output: Contribution to journalArticlepeer-review

5 Scopus citations


Ultrafast photoinduced intramolecular electron transfer (ET) of betaine-30 (B-30) is studied in different solvents by resonance Raman spectroscopy. We apply stationary and picosecond time-resolved Raman techniques combined with ab initio Hartree-Fock calculations. Picosecond Raman spectroscopy of the first excited singlet state allows to monitor changes of vibrational frequencies due to ET. From the intense Raman lines of the stationary resonance Raman spectra we predict relevant geometric changes of B-30 due to ET which are confirmed by calculations of geometrical changes between the ground and excited electronic states of B-30. The torsional motion between the phenolate and the pyridinium rings as well as nitrogen pyramidalization play an essential role in electron transfer. Vibrational modes accepting the bulk of excess energy after back-electron transfer are identified by time-resolved anti-Stokes resonance Raman spectroscopy. In particular, the highest-frequency mode of the resonance Raman spectrum exhibiting a large Franck-Condon factor is most effective in accepting energy. Mode specific excitation of B-30 after back-electron transfer results in nonequilibrium vibrational populations within the first few picoseconds and subsequent quasi-equilibrium populations of hot Raman active modes. The observed vibrational kinetics can be qualitatively understood by a solvent dependent interplay of direct vibrational excitation and intramolecular vibrational energy redistribution.

Original languageEnglish (US)
Pages (from-to)1049-1055
Number of pages7
JournalBulletin of the Chemical Society of Japan
Issue number5
StatePublished - May 2002
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)


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