A Direct Mechanism of Ultrafast Intramolecular Singlet Fission in Pentacene Dimers
Abstract
Interest in materials that undergo singlet fission (SF) has been catalyzed by the potential to exceed the ShockleyQueisser 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.
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 24, 2016
- Accession Number
- AD1010921
Entities
People
- Andrew B Pun
- Elango Kumarasamy
- Eric G. Fuemmeler
- Kiyoshi Miyata
- Luis M Campos
- Matthew Y. Sfeir
- Michael L Steigerwald
- Nandini Ananth
- Samuel N Sanders
- Tao Zeng
- Xiaoyang Zhu
Organizations
- Cornell University