Comparison of Computational Strategies for the Calculation of the Electronic Coupling in Intermolecular Energy and Electron Transport Processes

Xavier López, Aitor Sánchez-Mansilla, Carmen Sousa, Tjerk P. Straatsma, Ria Broer, Coen de Graaf*

*Corresponding author for this work

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Electronic couplings in intermolecular electron and energy transfer processes calculated by six different existing computational techniques are compared to nonorthogonal configuration interaction for fragments (NOCI-F) results. The paper addresses the calculation of the electronic coupling in diketopyrrolopyrol, tetracene, 5,5′-difluoroindigo, and benzene-Cl for hole and electron transport, as well as the local exciton and singlet fission coupling. NOCI-F provides a rigorous computational scheme to calculate these couplings, but its computational cost is rather elevated. The here-considered ab initio Frenkel-Davydov (AIFD), Dimer projection (DIPRO), transition dipole moment coupling, Michl-Smith, effective Hamiltonian, and Mulliken-Hush approaches are computationally less demanding, and the comparison with the NOCI-F results shows that the NOCI-F results in the couplings for hole and electron transport are rather accurately predicted by the more approximate schemes but that the NOCI-F exciton transfer and singlet fission couplings are more difficult to reproduce.

Original languageEnglish
Pages (from-to)10717-10731
Number of pages15
JournalJournal of Physical Chemistry A
Issue number50
Publication statusPublished - 21-Dec-2023

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