Correlation of femtosecond wave packets and fluorescence interference in a conjugated polymer: Towards the measurement of site homogeneous dephasing

Franz Milota, Jaroslaw Sperling, Vojtech Szöcs, Andreas Tortschanoff, Harald Kauffmann

Veröffentlichungen: Beitrag in FachzeitschriftArtikelPeer Reviewed


Probing electronic femtosecond (fs) coherence among segmental sites that are congested by static and dynamic site disorder and subject to structural relaxation is a big, experimental challenge in the study of photophysics of poly(p-phenylenevinylene). In this work, fs-wave-packet fluorescenceinterferometry experiments are presented that measure macroscopic coherent kernels and their phase-relaxation in the low-temperature, bottom-state regime of the density-of-states below the migrational threshold energy where downhill site-to-site transfer is marginal. By using freely propagating and tunable 70 fs excitation/probing pulses and employing narrow-band spectral filtering of wave packets, fluorescence interferograms with strongly damped beatings can be observed. The coherences formally follow the in-phase superpositions of two site-optical free-induction-decays and originate from distinct pairs of coherent doorway-states, different in energy and space, each of them being targeted, by two discrete quantum-arrival-states 1α and 1β, via independent, isoenergetic 0→1 fluorescence transitions. The coherent transients are explained as site-to-site polarization beatings, caused by the interference of two fluorescencecorrelation signals. The numerical analysis of the damping regime, based upon second-order perturbational solutions, reveals the lower limit value of homogeneous dephasing in the range from T2≃100 fs to T2≃200 fs depending on the site-excitation energy of the bottom-states. The experiments enable to look into the formation of the relaxed state as a special molecular process of electron–phonon coupling and hence open-up a quite new perspective in the puzzle of multichromophore optical dynamics and structural relaxation in conjugated polymers. © 2004 American Institute of Physics
Seiten (von - bis)9870-9885
FachzeitschriftJournal of Chemical Physics
PublikationsstatusVeröffentlicht - 2004

ÖFOS 2012

  • 104017 Physikalische Chemie