Sub-5 fs time-resolved dynamic Franck–Condon overlaps associated with the S1 → S0 stimulated transition in oligothiophene 13-mer

The transient difference absorption spectrum of a substituted α-linked oligothiophene 13-mer was measured by sub 5-fs pump–probe spectroscopy. This molecule is the longest oligothiophene studied under time-resolved investigation. The spectrum observed in the sub-ps range exhibited a feature of the dynamic Stokes shift. A simple numerical calculation based on the Franck–Condon (FC) overlaps induced by molecular vibration reproduced the modulation on the difference absorption spectrum. These results verify the time-dependent FC overlap in this molecule.