Stojanovic, Ljiljana; Giannini, Samuele; Blumberger, Jochen; (2024) Exciton Transport in the Nonfullerene Acceptor O-IDTBR from Nonadiabatic Molecular Dynamics. Journal of Chemical Theory and Computation , 20 (14) pp. 6241-6252. 10.1021/acs.jctc.4c00605.

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Abstract

Theory, computation, and experiment have given strong evidence that charge carriers in organic molecular crystals form partially delocalized quantum objects that diffuse very efficiently via a mechanism termed transient delocalization. It is currently unclear how prevalent this mechanism is for exciton transport. Here we carry out simulation of singlet Frenkel excitons (FE) in a molecular organic semiconductor that belongs to the class of nonfullerene acceptors, O-IDTBR, using the recently introduced FE surface hopping nonadiabatic molecular dynamics method. We find that FE are, on average, localized on a single molecule in the crystal due to sizable reorganization energy and moderate excitonic couplings. Yet, our simulations suggest that the diffusion mechanism is more complex than simple local hopping; in addition to hopping, we observe frequent transient delocalization events where the exciton wave function expands over 10 or more molecules for a short period of time in response to thermal excitations within the excitonic band, followed by de-excitation and contraction onto a single molecule. The transient delocalization events lead to an increase in the diffusion constant by a factor of 3-4, depending on the crystallographic direction as compared to the situation where only local hopping events are considered. Intriguingly, O-IDTBR appears to be a moderately anisotropic 3D “conductor” for excitons but a highly anisotropic 2D conductor for electrons. Taken together with previous simulation results, two trends seem to emerge for molecular organic crystals: excitons tend to be more localized and slower than charge carriers due to higher internal reorganization energy, while exciton transport tends to be more isotropic than charge transport due to the weaker distance dependence of excitonic versus electronic coupling.

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