Ryderfors Linus, Mukhtar Emad, Johansson Lennart B-A
Department of Photochemistry and Molecular Science, Uppsala University, P. O. Box 523, S-751 20 Uppsala, Sweden.
J Phys Chem A. 2007 Nov 15;111(45):11531-9. doi: 10.1021/jp074506g. Epub 2007 Oct 18.
A new experimental and theoretical approach is presented for the quantitative determination and assignment of the two-photon absorption tensor of fluorophores dissolved in liquid solutions. Two linearly independent time-resolved fluorescence anisotropies and the two-photon polarization ratio were determined from experiments based on using the time-correlated single photon counting technique. The data were analyzed in a global manner under the assumption of prevailing diffusive molecular reorientations and when accounting for the influence of rapid unresolved reorientations. The method has been applied in fluorescence studies of perylene, two-photon excited at 800 nm. The analysis suggests that the two-photon transition is mediated via vibronic coupling including at least two vibrations of different symmetry, and also that the first singlet excited electronic state acts as a dominating intermediate state.
