Send to

Choose Destination
See comment in PubMed Commons below
J Chem Phys. 2012 Dec 28;137(24):244505. doi: 10.1063/1.4769971.

Femtosecond Raman spectra of cis-stilbene and trans-stilbene with isotopomers in solution.

Author information

Department of Chemistry, Humboldt-Universit├Ąt zu Berlin, Brook-Taylor-Str. 2, D-12489 Berlin, Germany.


Femtosecond stimulated Raman spectra of trans-stilbene (D0), its isotopomers D2, D10, D12, (13)C2 and of cis-stilbene in hexane are measured in the ground (S(0)) and excited (S(1)) electronic states. The ground (13)C2 and excited D12 spectra are presented for the first time; the excited cis-spectra differ substantially from previously published ones. S(1) Raman bands of trans-stilbene are 20 cm(-1) wide corresponding to ~1 ps vibrational dephasing. For cis-stilbene the bands are broadened to 40 cm(-1) reflecting a short excited-state lifetime of 0.3 ps, in agreement with transient absorption data. From a dynamic shift of the 1569 cm(-1) band, pump-induced intramolecular cooling is estimated to be less than 20 K. Many S(1) Raman lines are detected for the first time. Vibrational spectra are calculated at MP2/cc-pVTZ (for S(0)) and XMCQDPT2/cc-pVTZ (for S(1)) levels of theory. Experimental and computational results can be used for a re-evalution of Rice-Ramsberger-Kassel-Marcus (RRKM) predictions for this famous photoisomeration reaction.

PubMed Commons home

PubMed Commons

How to join PubMed Commons

    Supplemental Content

    Full text links

    Icon for American Institute of Physics
    Loading ...
    Support Center