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MO: Molekülphysik
MO 43: Ultrafast Processes
MO 43.1: Talk
Tuesday, March 8, 2005, 16:30–16:45, HU 2091
Electron transfer faster than inertial solvation: a vibrational mode to promote photoinduced ET in triphenylmethane lactones — •Jerzy Karpiuk1, Stefan Lochbrunner2, and Eberhard Riedle2 — 1Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland — 2LS für BioMolekulare Optik, Ludwig-Maximilians-Universität München
Investigations of the intramolecular electron transfer (ET) in condensed phase donor-acceptor (D-A) systems on a time scale shorter than diffusional solvation can provide substantial insight into the initial stages of the ET dynamics. Such ultrafast ET processes are promoted by high-frequency intramolecular vibrational modes and inertial solvation, and better understanding of the interplay between these two driving forces requires the exploration of D A systems capable of undergoing ET on a sub-100 fs time scale. A 50-fs photoinduced intramolecular ET in triarylmethane lactones (LTAMs) [1] allowed us to enter the time scale shorter than that of inertial solvation dynamics and to explore the ET coupling to vibrational modes. Using fs pump-probe spectroscopy to study the photophysics of LTAMs as a function of solvent polarity and proticity, we demonstrate a dominant role of the C-O bond in the lactonic ring in ultrafast charge separation in LTAMs.
[1] T. Bizjak, J. Karpiuk, S. Lochbrunner and E. Riedle, J. Phys. Chem. A 108, 10763 (2004).