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• W2002255645 abstract "A combination of transient absorption (TAS) and femtosecond stimulated Raman (FSRS) spectroscopies were used to interrogate the photo-induced nuclear relaxation dynamics of poly(3-cyclohexyl,4-methylthiophene) (PCMT). The large difference in inter-ring dihedral angles of ground and excited-state PCMT make it an ideal candidate for studying large-amplitude vibrational relaxation associated with exciton trapping. Spectral shifting in the S1 TA spectra on sub-ps timescales (110 ± 20 and 800 ± 100 fs) is similar to spectroscopic signatures of excited-state relaxation observed with related photoexcited conjugated polymers and which have been attributed to exciton localization and a combination of resonant energy transfer and torsional relaxation, respectively. Measurements made with both techniques reveal fast PCMT S1 decay and triplet formation (τS1 = 25–32 ps), which is similar to the excited-state dynamics of short oligothiophenes and highly twisted polyconjugated molecules. On ultrafast timescales FSRS of S1 PCMT offers a new perspective on the nuclear dynamics that underlie localization of excitons in photoexcited conjugated polymers: Spectral dynamics in the C=C stretching region (1400–1600 cm−1) include a red-shift of the in-phase C=C stretching frequency, as well as a change in the relative intensity of in-phase and out-of-phase stretch intensities on a timescale of ∼100 fs. Both changes indicate an ultrafast vibrational distortion that increases the conjugation length in the region of the localized excitation and are consistent with exciton self-localization or trapping. Wavelength-dependent excited-state FSRS measurements further demonstrate that the C=C stretching frequency provides a useful spectroscopic handle for interrogating the degree of delocalization in excited conjugated polymers given the selectivity achieved via resonance enhancement." @default.
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• W2002255645 date "2014-07-28" @default.
• W2002255645 modified "2023-09-23" @default.
• W2002255645 title "Ultrafast photo-induced nuclear relaxation of a conformationally disordered conjugated polymer probed with transient absorption and femtosecond stimulated Raman spectroscopies" @default.
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• W2002255645 doi "https://doi.org/10.1063/1.4890326" @default.
• W2002255645 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/25084903" @default.
• W2002255645 hasPublicationYear "2014" @default.
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