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 language | English (US) |
|---|---|
| Pages (from-to) | 8-16 |
| Number of pages | 9 |
| Journal | Chemical Physics Letters |
| Volume | 287 |
| Issue number | 1-2 |
| State | Published - Apr 24 1998 |
| Externally published | Yes |
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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 journal › Article
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TY - JOUR
T1 - Picosecond time-resolved CARS spectroscopy of a mixed excited singlet state of diphenylhexatriene
AU - Wachsmann-Hogiu, Sebastian
AU - Werncke, W.
AU - Pfeiffer, M.
AU - Lau, A.
AU - Steinke, T.
PY - 1998/4/24
Y1 - 1998/4/24
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=0032562328&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0032562328&partnerID=8YFLogxK
M3 - Article
AN - SCOPUS:0032562328
VL - 287
SP - 8
EP - 16
JO - Chemical Physics Letters
JF - Chemical Physics Letters
SN - 0009-2614
IS - 1-2
ER -