Transient grating (TG) signals in β -carotene homologues, by using sub-20-fs excitation pulses, were measured in order to investigate the dependence of the vibrational coherence dynamics on the π -conjugation length of these carotenoids. The experimental TG traces can be well reproduced by computational simulations based on a Brownian oscillator model using the spectral density determined from their respective resonance Raman spectra and their previously reported excited-state population-relaxation times. The total dephasing times of the ground-state vibrational modes of the homologues were determined by applying a wavelet transformation of their coherent oscillations, which were observed in the experimental TG traces. The total dephasing time decreases as the number of conjugated C=C double bonds increases. The decoherence of the ground-state vibrational modes in the homologues is mainly caused by system-bath interactions. The dephasing time of the C-C stretching modes strongly depends on the conjugation length, whereas that of the C=C stretching does not. This trend clearly shows that shorter-chain carotenoids have a specific major channel of energy dissipation to the environment (the C=C stretching), whereas the longer-chain carotenoids do not.
|Journal||Physical Review B - Condensed Matter and Materials Physics|
|Publication status||Published - May 21 2008|
ASJC Scopus subject areas
- Electronic, Optical and Magnetic Materials
- Condensed Matter Physics