Driving Force and Nonequilibrium Vibronic Dynamics in Charge Separation of Strongly Bound Electron-Hole Pairs

TL;DR

This paper develops a non-perturbative simulation method to study how vibrational dynamics influence charge separation in organic photovoltaics, revealing conditions that optimize long-range electron-hole dissociation.

Contribution

It extends simulation techniques to multi-dimensional vibronic systems, enabling detailed analysis of vibrational effects on charge separation mechanisms.

Findings

Underdamped vibrational modes induce efficient charge separation.

Electronic and vibronic mechanisms are distinguishable across different forces.

Entropic effects are significant in large vibronic systems.

Abstract

Electron-hole pairs in organic photovoltaics dissociate efficiently despite their Coulomb-binding energy exceeding thermal energy at room temperature. The electronic states involved in charge separation couple to structured vibrational environments containing multiple underdamped modes. The non-perturbative simulations of such large, spatially extended electronic-vibrational (vibronic) systems remains an outstanding challenge. Current methods bypass this difficulty by considering effective one-dimensional Coulomb potentials or unstructured environments. Here we extend and apply a recently developed method for the non-perturbative simulation of open quantum systems to the dynamics of charge separation in one, two and three-dimensional donor-acceptor networks. This allows us to identify the precise conditions in which underdamped vibrational motion induces efficient long-range charge separation. Our analysis provides a comprehensive picture of ultrafast charge separation by showing how different mechanisms driven either by electronic or vibronic couplings are well differentiated for a wide range of driving forces and how entropic effects become apparent in large vibronic systems. These results allow us to quantify the relative importance of electronic and vibronic contributions in organic photovoltaics and provide a toolbox for the design of efficient charge separation pathways in artificial nanostructures.