Is Vibrational Coherence a Byproduct of Singlet Exciton Fission?

摘要： A phenomenological wavefunction-based model of vibrationally coherent absorption modulation is proposed and applied to reproduce the triplet-triplet absorption spectra of bis-triisopropylsilylethynyl (TIPS)-pentacene, with the objective of testing whether the singlet fission process in that system spontaneously generates coherent vibrational packets, as recently suggested for TIPS-tetracene. The model is parametrized by a complete set of Franck-Condon parameters obtained from methodologically consistent DFT calculations for all relevant normal modes in all relevant electronic states. The results strongly depend on inhomogeneous broadening of absorption bands, which is explicitly included. They very well agree with the recently published experimental coherence spectra of the pertinent system, validating our underlying principal assumption that the singlet fission process, which generates the observed triplet states, is neutral with respect to vibrational coherences. Experimental confirmation of this interpretational posit demonstrates that in the pentacene derivative, apparently in contrast to the case of its tetracene analogue, fission is not a source of vibrational coherence. Our finding suggests that although the singlet fission process may possibly in individual cases induce vibrational coherence, this feature is not a constitutive characteristic of the fission phenomenon.