Theory of singlet fission in polyenes, acene crystals, and covalently linked acene dimers

Karan Aryanpour, Alok Shukla, Sumitendra Mazumdar

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

We report quadruple configuration interaction calculations within the extended Pariser Parr Pople Hamiltonian on the excited states of aggregates of polyenes, crystalline acenes, and covalently linked dimers of acene molecules. We determine the precise energy orderings and analyze the cluster wave functions in order to arrive at a comprehensive physical understanding of singlet fission in these diverse families of materials. Our computational approach allows us to retain a very large number of basis states and thereby obtain the correct relative energy orderings of one electron one hole Frenkel and charge transfer excitons versus intra and intermolecular two electron two hole triplet triplet excited states. We show that from the energy orderings it is possible to understand the occurrence of singlet fission in polyene and acene crystals, as well as its near total absence in the covalently linked acene dimers. As in the acene crystals, singlet fission in the polyenes is a multichromophoric phenomenon, with the well known 21Ag playing no direct role. Intermolecular charge transfer is essential for singlet fission in both acenes and polyenes, but because of subtle differences in the natures and orderings of the aggregate excited states, the mechanisms of singlet fission are slightly different in the two classes. We are thus able to give qualitative physical reasoning for the slower singlet fission in the polyenes, relative to that in crystalline pentacene. Our work also gives new insight into the complex exciton dynamics in tetracene crystals, which has been difficult to understand theoretically. Our large scale many body calculations provide us with the ability to understand the qualitative differences in the singlet fission yields and rates between different classes of π conjugated materials.

Original languageEnglish (US)
Pages (from-to)6966-6979
Number of pages14
JournalJournal of Physical Chemistry C
Volume119
Issue number13
DOIs
StatePublished - Apr 2 2015

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Polyenes
Dimers
fission
dimers
Crystals
Excited states
crystals
Excitons
Charge transfer
Crystalline materials
Hamiltonians
Electrons
charge transfer
excitons
Wave functions
excitation
configuration interaction
energy
Molecules
electrons

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Electronic, Optical and Magnetic Materials
  • Surfaces, Coatings and Films
  • Energy(all)

Cite this

Theory of singlet fission in polyenes, acene crystals, and covalently linked acene dimers. / Aryanpour, Karan; Shukla, Alok; Mazumdar, Sumitendra.

In: Journal of Physical Chemistry C, Vol. 119, No. 13, 02.04.2015, p. 6966-6979.

Research output: Contribution to journalArticle

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