A direct mechanism of ultrafast intramolecular singlet fission in pentacene dimers

Eric G. Fuemmeler, Samuel N. Sanders, Andrew B. Pun, Elango Kumarasamy, Tao Zeng, Kiyoshi Miyata, Michael L. Steigerwald, X. Y. Zhu, Matthew Y. Sfeir, Luis M. Campos, Nandini Ananth

Research output: Contribution to journalArticlepeer-review

140 Citations (Scopus)


Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the Shockley-Queisser limit of solar power conversion efficiency. In conventional materials, the mechanism of SF is an intermolecular process (xSF), which is mediated by charge transfer (CT) states and depends sensitively on crystal packing or molecular collisions. In contrast, recently reported covalently coupled pentacenes yield ∼2 triplets per photon absorbed in individual molecules: the hallmark of intramolecular singlet fission (iSF). However, the mechanism of iSF is unclear. Here, using multireference electronic structure calculations and transient absorption spectroscopy, we establish that iSF can occur via a direct coupling mechanism that is independent of CT states. We show that a near-degeneracy in electronic state energies induced by vibronic coupling to intramolecular modes of the covalent dimer allows for strong mixing between the correlated triplet pair state and the local excitonic state, despite weak direct coupling.

Original languageEnglish
Pages (from-to)316-324
Number of pages9
JournalACS Central Science
Issue number5
Publication statusPublished - May 25 2016
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)


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