Overlap-Driven Splitting of Triplet Pairs in Singlet Fission

Elliot J. Taffet, David Beljonne, Gregory D. Scholes

Research output: Contribution to journalArticlepeer-review

2 Scopus citations

Abstract

We analyze correlated-triplet-pair (TT) singlet-fission intermediates toward two-triplet separation (T⋯T) using spin-state-averaged density matrix renormalization group electronic-structure calculations. Specifically, we compare the triplet-triplet exchange (J) for tetracene dimers, bipentacene, a subunit of the benzodithiophene-thiophene dioxide polymer, and a carotenoid (neurosporene). Exchange-split energy gaps of J and 3J separate a singlet from a triplet and a singlet from a quintet, respectively. We draw two new insights: (a) the canonical tetracene singlet-fission unit cell supports precisely three low-lying TT intermediates with order-of-magnitude differences in J, and (b) the separable TT intermediate in carotenoids emanates from a pair of excitations to the second triplet state. Therefore, unlike with tetracenes, carotenoid fission requires above-gap excitations. In all cases, the distinguishability of the molecular triplets - that is, the extent of orbital overlap - determines the splitting within the spin manifold of TT states. Consequently, J represents a spectroscopic observable that distnguishes the resemblance between TT intermediates and the T⋯T product.

Original languageEnglish (US)
Pages (from-to)20040-20047
Number of pages8
JournalJournal of the American Chemical Society
Volume142
Issue number47
DOIs
StatePublished - Nov 25 2020

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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