Structure and Picosecond Excited-States Dynamics in Isolated, Supercooled 4-(N,N-Dimethylamino)benzonitrile

F. Perez Salgado, Jurek Herbich, A.G.M. Kunst, R.P.H. Rettschnick

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The first experimental evidence is presented for a strong coupling between electronic states in isolated, supercooled 4-(N,N-dimethylamino)benzonitrile, DMABN. In the fluorescence excitation spectrum, measured under isolated supercooled conditions, two types of transitions were found (B-type and C-type). Rotational contour analysis of the B-type bands (ππ* character) shows that there is hardly any difference between the geometries of the ground and excited states; the molecule retains its planar conformation. In the out-of-plane transition (C-type band) the equilibrium position of the dimethylamino group twists 90° with respect to the benzonitrile part. The broadening of the rotational lines indicates that the fluorescence is preceded by a fast radiationless intramolecular process (internal conversion) on a picosecond time scale. For the B-type bands it was found that the broadening increases with the vibrational energy.
Original languageEnglish
Pages (from-to)3184–3192
Number of pages9
JournalJournal of Physical Chemistry A
Issue number17
Publication statusPublished - 9 Apr 1999
Externally publishedYes


  • Physics
  • supercooled molecules
  • transformation
  • dynamics
  • lasers
  • energy transitions
  • solar energy conversion
  • solar energy storage


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