Intramolecular Singlet Fission: Insights from Quantum Dynamical Simulations

Pedro B. Coto

Friedrich-Alexander Universität Erlangen-Nürnberg, Institut für Theoretische Physik und Interdisziplinäres Zentrum für Molekulare Materialien (ICMM), Staudtstraße 7/B2, Erlangen, 91058, Germany

Email: pedro.brana-coto@physik.uni-erlange.de

Singlet fission (SF) is a spin-allowed process by which two triplet excitons are generated from a singlet exciton.1 It has received great attention recently as a feasible way to overcome the Shockley-Queisser limit,2 which could enable the development of more efficient solar cells. In this contribution, we discuss the dynamics of intramolecular SF (iSF) in a series of modified pentacene dimers covalently bonded to a phenylene spacer in ortho-, meta-, and paraconformations employing multireference perturbation theory and quantum dynamical methods.3-6 The results provide insight into the different contributions of the direct and mediated mechanisms to the global iSF process, disentangling the key roles that molecular vibrations and the conformation of the chromophores have in the process.

 

References

1. M. B. Smith, J. Michl, Chem. Rev. 2010, 110, 6891-6936.

2. W. Shockley, H. J. Queisser, J. Appl. Phys. 1961, 32, 510-519.

3. J. Zirzlmeier, D. Lehnherr, P. B. Coto, E. T. Chernick, R. Casillas, B. Basel, M. Thoss, R. R. Tykwinski, D. M. Guldi, Proc. Natl. Acad. Sci. (USA) 2015, 112, 5325-5330.

4. J. Zirzlmeier, R. Casillas, S. R. Reddy, P. B. Coto, D. Lehnherr, E. T. Chernick, I. Papadopoulos, M. Thoss, R. R. Tykwinski, D. M. Guldi, Nanoscale 2016, 8, 10113-10123.

5. B. S. Basel, J. Zirzlmeier, C. Hetzer, B. T. Phelan, M. D. Krzyaniak, S. R. Reddy, P. B. Coto, N. E. Horwitz, R. M. Young, F. White, F. Hampel, T. Clark, M. Thoss, R. R. Tykwinski, M. R. Wasielewski, D. M. Guldi, Nat. Comm., DOI: 10.1038/ncomms15171.

6. R. Reddy, D. M. Guldi, P. B. Coto, M. Thoss, J. Phys. Chem. Lett., submitted.