A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers.
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.
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Eric G
EG
Fuemmeler
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Samuel N
SN
Sanders
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Andrew B
AB
Pun
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Elango
E
Kumarasamy
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Tao
T
Zeng
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Kiyoshi
K
Miyata
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Michael L
ML
Steigerwald
Department of Chemistry, Columbia University , New York, New York 10027, United States.
X-Y
XY
Zhu
Center for Functional Nanomaterials, Brookhaven National Laboratory , Upton, New York 11973, United States.
Matthew Y
MY
Sfeir
Department of Chemistry, Columbia University , New York, New York 10027, United States.
Luis M
LM
Campos
Department of Chemistry and Chemical Biology, Cornell University , Ithaca, New York 14853, United States.
Nandini
N
Ananth