Modeling Singlet Fission in Rylene and Diketopyrrolopyrrole Derivatives

The Role of the Charge Transfer State in Superexchange and Excimer Formation

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24 Citations (Scopus)

Abstract

Singlet fission (SF) is being explored as a way to improve the efficiency of organic photovoltaics beyond the Shockley-Queisser limit; however, many aspects of the SF mechanism remain unresolved. The generally accepted mechanisms provide simplified models of SF that equivocate over whether a charge transfer (CT) state is involved in SF. A one-step superexchange model allows the CT state to act as a virtual state, reducing the effect of large Gibbs free energy values from SF rate calculations. Also, extending superexchange to an excimer-mediated process allows for further refinement of the triplet formation model. Application of the superexchange and excimer-mediated models to a variety of rylene and diketopyrrolopyrrole derivatives provides new insights into the role of the CT and excimer states, providing a semiquantitative description of SF that is dictated by the CT state energy.

Original languageEnglish
Pages (from-to)10345-10350
Number of pages6
JournalJournal of Physical Chemistry C
Volume121
Issue number19
DOIs
Publication statusPublished - May 18 2017

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excimers
fission
Charge transfer
charge transfer
Derivatives
Gibbs free energy
Electron energy levels

ASJC Scopus subject areas

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

Cite this

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title = "Modeling Singlet Fission in Rylene and Diketopyrrolopyrrole Derivatives: The Role of the Charge Transfer State in Superexchange and Excimer Formation",
abstract = "Singlet fission (SF) is being explored as a way to improve the efficiency of organic photovoltaics beyond the Shockley-Queisser limit; however, many aspects of the SF mechanism remain unresolved. The generally accepted mechanisms provide simplified models of SF that equivocate over whether a charge transfer (CT) state is involved in SF. A one-step superexchange model allows the CT state to act as a virtual state, reducing the effect of large Gibbs free energy values from SF rate calculations. Also, extending superexchange to an excimer-mediated process allows for further refinement of the triplet formation model. Application of the superexchange and excimer-mediated models to a variety of rylene and diketopyrrolopyrrole derivatives provides new insights into the role of the CT and excimer states, providing a semiquantitative description of SF that is dictated by the CT state energy.",
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AU - Schatz, George C

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N2 - Singlet fission (SF) is being explored as a way to improve the efficiency of organic photovoltaics beyond the Shockley-Queisser limit; however, many aspects of the SF mechanism remain unresolved. The generally accepted mechanisms provide simplified models of SF that equivocate over whether a charge transfer (CT) state is involved in SF. A one-step superexchange model allows the CT state to act as a virtual state, reducing the effect of large Gibbs free energy values from SF rate calculations. Also, extending superexchange to an excimer-mediated process allows for further refinement of the triplet formation model. Application of the superexchange and excimer-mediated models to a variety of rylene and diketopyrrolopyrrole derivatives provides new insights into the role of the CT and excimer states, providing a semiquantitative description of SF that is dictated by the CT state energy.

AB - Singlet fission (SF) is being explored as a way to improve the efficiency of organic photovoltaics beyond the Shockley-Queisser limit; however, many aspects of the SF mechanism remain unresolved. The generally accepted mechanisms provide simplified models of SF that equivocate over whether a charge transfer (CT) state is involved in SF. A one-step superexchange model allows the CT state to act as a virtual state, reducing the effect of large Gibbs free energy values from SF rate calculations. Also, extending superexchange to an excimer-mediated process allows for further refinement of the triplet formation model. Application of the superexchange and excimer-mediated models to a variety of rylene and diketopyrrolopyrrole derivatives provides new insights into the role of the CT and excimer states, providing a semiquantitative description of SF that is dictated by the CT state energy.

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