Maximizing singlet fission by intermolecular packing

Linjun Wang, Yoann Olivier, Oleg V. Prezhdo, David Beljonne

Research output: Contribution to journalArticlepeer-review


A novel nonadiabatic molecular dynamics scheme is applied to study the singlet fission (SF) process in pentacene dimers as a function of longitudinal and lateral displacements of the molecular backbones. Detailed two-dimensional mappings of both instantaneous and long-term triplet yields are obtained, characterizing the advantageous and unfavorable stacking arrangements, which can be achieved by chemical substitutions to the bare pentacene molecule. We show that the SF rate can be increased by more than an order of magnitude through tuning the intermolecular packing, most notably when going from cofacial to the slipped stacked arrangements encountered in some pentacene derivatives. The simulations indicate that the SF process is driven by thermal electron-phonon fluctuations at ambient and high temperatures, expected in solar cell applications. Although charge-transfer states are key to construct continuous channels for SF, a large charge-transfer character of the photoexcited state is found to be not essential for efficient SF. The reported time domain study mimics directly numerous laser experiments and provides novel guidelines for designing efficient photovoltaic systems exploiting the SF process with optimum intermolecular packing.

Original languageEnglish
Pages (from-to)3345-3353
Number of pages9
JournalJournal of Physical Chemistry Letters
Issue number19
Publication statusPublished - 2 Oct 2014
Externally publishedYes


  • charge-transfer character
  • nonadiabatic molecular dynamics
  • pentacene derivatives
  • singlet fission


Dive into the research topics of 'Maximizing singlet fission by intermolecular packing'. Together they form a unique fingerprint.

Cite this