Quantum simulations of charge-separation at a model donor-acceptor interface: role of delocalization and local packing

TL;DR

This study uses quantum simulations to explore how molecular arrangement and delocalization influence charge separation dynamics at a model donor-acceptor interface in organic photovoltaics, revealing rapid mixing and decay into charge-separated states.

Contribution

It introduces a mixed MM/QM approach to connect energy fluctuations with electronic couplings, providing new insights into ultrafast charge separation mechanisms.

Findings

Electronic states rapidly mix at the interface.

Charge transfer occurs on sub-100 fs timescales.

Interfacial states decay into charge-separated states.

Abstract

We investigate the electronic dynamics of a model organic photovoltaic (OPV) system consisting of polyphenylene vinylene (PPV) oligomers and a [6,6]-phenyl C61-butyric acid methylester (PCBM) blend using a mixed molecular mechanics/quantum mechanics (MM/QM) approach. Using a heuristic model that connects energy gap fluctuations to the average electronic couplings and decoherence times, we provide and estimate of the state-to-state internal conversion rates within the manifold of the lowest few electronic excitations. We show that the electronic dynamics of the OPV are dramatically altered by varying the positions of the molecules simulated at the interface. The lowest few excited states of the model interface rapidly mix allowing low frequency C-C out of plain torsions to modulate the potential energy surface such that the system can sample both intermolecular charge-transfer and charge-separated electronic configurations on sub 100 fs time scales. Our simulations support an emerging picture of carrier generation in OPV systems in which interfacial electronic states can rapidly decay into charge-separated and current producing states via coupling to vibronic degrees of freedom.