Quantum dynamic simulation of triplet formation in an effective model of Y6 (BTP-4F)

Abstract

We construct a five-state model for photoexcitation in Y6 (BTP-4F) dimers, and then solve the non-adiabtic dynamics using the Hierarchical Equations of Motion (HEOM) method. We find that triplets are populated mainly via a transiently excited \textit{intermolecular} charge-transfer singlet to triplet Frenkel exciton route; this route is not available to the monomer. Analysis of one-particle transition density matrices suggests that the charge-transfer states are spatially distinct to the Frenkel exciton states, indicating that the large spin-orbit-coupling for this transition is due to it being permitted by an associated change in orbital character. Aggregation in Y6 therefore directly enables fast and high-yield intersystem crossing. We selenise our model dimers, significantly enhancing spin-orbit-coupling, which then accelerates this charge-transfer mediated route. Looking forwards to simulations on larger aggregates, we show that, though Marcus theory gives qualitatively correct dynamics, the long-time yields are incorrect due to it missing quantum recurrences. Instead, we show that the recently developed memory-kernel projector\cite{Gestsson2025-ez} method can produce semi-classical rates directly from the HEOM equations which lead to quantitatively correct dynamics and yields.