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Electronic Structure Study of Singlet Fission in Tetracene Derivatives
journal contribution
posted on 2014-01-14, 00:00 authored by David CasanovaA detailed theoretical study of the
singlet fission process in
tetracene and two of its derivatives, that is 5,12-diphenyltetracene
(DPT) and rubrene, is presented. This work aims to unravel the intricacies
and the differences of their singlet fission mechanism by means of
electronic structure calculations using molecular and cluster models
and a variety of computational tools. Although the electronic structure
at the molecular level is very similar for the three compounds, their
different crystal packing has important consequences in their ability
to produce two triplet states from a single exciton. The results obtained
indicate that the lowest singlet is found to delocalize at least over
seven molecules. Computed relative energies rule out the presence
of charge transfer (CT) states as intermediates in a two-step mechanism
in all cases. On the other hand, CT states do play a role as mediators,
specially in tetracene. They decisively participate in the coupling
between single and multiexcitonic states through second-order contributions.
Finally, the present study pinpoints that the transition from the
optically allowed exciton to the dark multiexciton state might be
facilitated by intramolecular motion toward the lowest excited singlet
geometry.
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DPTenergies rulesinglet geometrysinglet fission processtetraceneElectronic Structure Studycharge transferCT statestriplet statesintramolecular motionmultiexciton statemultiexcitonic statesSinglet Fissionstudy pinpointsTetracene DerivativesAsinglet fission mechanismstructure calculationscluster models
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