The ultrafast dynamics of a unique polythiophene derivative that has a degenerate ground state due to a quantum mechanical resonance was investigated using a sub-5-fs pulse laser. The method allowed us to study the electronic relaxation and vibrational dynamics in completely same conditions at the same time. The dynamics of a breather composed of a dynamic bound state of solitons generated immediately after photoexcitation was time-resolved to reveal coupling between the vibrational modes and the solitons. The C-C and C=C stretching modes were found to be modulated by the breather, whose lifetime was determined to be 30-50 fs. The results of quantum-chemical excited-state molecular dynamics simulation are consistent with experimental results. Our modeling results allow to identify related vibrational normal modes strongly coupled to the electronic degrees of freedom. Moreover, analysis of calculated trajectories of excited state shows appearance of short-lived breather excitation decaying due to intramolecular vibrational energy equilibration on a timescale of hundreds of femtoseconds, which also agrees well with the experimental results.
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Contour maps of the two-dimensional Fourier power of the vibrational components obtained by spectrogram calculation for real-time data covering 680-690 nm (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim