2,2 '-bithiophene radical cation: An experimental and computational study

Title2,2 '-bithiophene radical cation: An experimental and computational study
Publication TypeJournal Article
Year of Publication2000
AuthorsKeszthelyi, T, Grage, MML, Offersgaard, JF, Wilbrandt, R, Svendsen, C, Mortensen, OS, Pedersen, JK, Jensen, HJA
JournalJournal of Physical Chemistry A
Date Publishedmar

Electronic absorption and resonance Raman spectra of the radical cation of bithiophene are reported. The bithiophene radical cation was produced by gamma-radiolysis in a glassy matrix at 77 K, and the Raman spectrum excited in resonance with the two absorption bands at 425 and 590 nm. The electronic states relevant to the observed electronic transitions were identified and characterized by CASSCF calculations. The optical absorption and resonance Raman spectra were calculated by wave packet propagation methods using the ab initio calculated molecular parameters. The calculated spectra agree well with the experimental ones. The importance of carrying out full wave packet propagation calculations is underlined by the fact that in one case the simple Savin formula gave a completely wrong prediction of the resonance Raman spectrum.