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

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

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 journal › Article › peer-review

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 1A_g-1B_u 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 1B_u and 2A_g 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

ASJC Scopus subject areas

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

Cite this

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title = "Picosecond time-resolved CARS spectroscopy of a mixed excited singlet state of diphenylhexatriene",

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.",

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year = "1998",

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journal = "Chemical Physics Letters",

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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.

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

Abstract

ASJC Scopus subject areas

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