Journal of Chemical Theory and Computation
Journal of Chemical Theory and Computation
5 years ago

Importance and Nature of Short-Range Excitonic Interactions in Light Harvesting Complexes and Organic Semiconductors

Importance and Nature of Short-Range Excitonic Interactions in Light Harvesting Complexes and Organic Semiconductors
Patrick Rowe, Rocco P. Fornari, Alessandro Troisi, Daniele Padula
The singlet excitonic coupling between many pairs of chromophores is evaluated in three different light harvesting complexes (LHCs) and two organic semiconductors (amorphous and crystalline). This large database of structures is used to assess the relative importance of short-range (exchange, overlap, orbital) and long-range (Coulombic) excitonic coupling. We find that Mulliken atomic transition charges can introduce systematic errors in the Coulombic coupling and that the dipole–dipole interaction fails to capture the true Coulombic coupling even at intermolecular distances of up to 50 Å. The non-Coulombic short-range contribution to the excitonic coupling is found to represent up to ∼70% of the total value for molecules in close contact, while, as expected, it is found to be negligible for dimers not in close contact. For the face-to-face dimers considered here, the sign of the short-range interaction is found to correlate with the sign of the Coulombic coupling, i.e. reinforcing it when it is already strong. We conclude that for molecules in van der Waals contact the inclusion of short-range effects is essential for a quantitative description of the exciton dynamics.

Publisher URL: http://dx.doi.org/10.1021/acs.jctc.7b00328

DOI: 10.1021/acs.jctc.7b00328

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