Picosecond time-resolved CARS spectroscopy of a mixed excited singlet state of diphenylhexatriene

Sebastian Wachsmann-Hogiu, W. Werncke, M. Pfeiffer, A. Lau, T. Steinke

Research output: Contribution to journalArticle

16 Citations (Scopus)

Abstract

Time-resolved coherent antistokes Raman spectroscopy (CARS) spectra from an excited singlet state of diphenylhexatriene (DPH) are reported. As determined from the CARS measurements, the excited-state population increases on a sub-picosecond time scale after excitation in the 1Ag-1Bu absorption band. We observe two strongly upshifted and anomalously broadened resonances in the double-bond stretching region. According to our semi-empirical calculations of vibrational frequencies, they can be assigned to polyenic p-chain modes of the 1Bu and 2Ag states, respectively. Frequency shifts as well as broadenings are extremely solvent-dependent, indicating a strong influence on the excited-state conformations. Our time-resolved measurements support a mixed excited singlet state with drastically different geometries of the local minima.

Original languageEnglish (US)
Pages (from-to)8-16
Number of pages9
JournalChemical Physics Letters
Volume287
Issue number1-2
StatePublished - Apr 24 1998
Externally publishedYes

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Diphenylhexatriene
Excited states
Raman spectroscopy
Spectroscopy
spectroscopy
excitation
Vibrational spectra
Time measurement
Stretching
Conformations
Absorption spectra
frequency shift
time measurement
Geometry
absorption spectra
geometry

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Spectroscopy
  • Atomic and Molecular Physics, and Optics

Cite this

Picosecond time-resolved CARS spectroscopy of a mixed excited singlet state of diphenylhexatriene. / Wachsmann-Hogiu, Sebastian; Werncke, W.; Pfeiffer, M.; Lau, A.; Steinke, T.

In: Chemical Physics Letters, Vol. 287, No. 1-2, 24.04.1998, p. 8-16.

Research output: Contribution to journalArticle

Wachsmann-Hogiu, Sebastian ; Werncke, W. ; Pfeiffer, M. ; Lau, A. ; Steinke, T. / Picosecond time-resolved CARS spectroscopy of a mixed excited singlet state of diphenylhexatriene. In: Chemical Physics Letters. 1998 ; Vol. 287, No. 1-2. pp. 8-16.
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