Ultrafast Fluorescence Depolarization in Conjugated Polymers

TL;DR

This paper uses large-scale quantum simulations to study ultrafast fluorescence depolarization in conjugated polymers, revealing how exciton-phonon interactions and torsional relaxation lead to rapid exciton localization and depolarization.

Contribution

It introduces a comprehensive simulation approach combining quantum trajectories and Lindblad operators to model exciton dynamics and depolarization in conjugated polymers.

Findings

Exciton-phonon entanglement causes decoherence.

System-bath interactions lead to exciton collapse.

Torsional relaxation results in exciton localization.

Abstract

We report on large-scale simulations of intrachain exciton dynamics in poly(para-phenylene vinylene). Our coarse-grained model describes Frenkel exciton coupling to both fast, quantized C-C bond vibrations and slow, classical torsional modes. We also incorporate system-bath interactions. The dynamics are simulated using the Time Evolution Block Decimation method, which avoids the failures of the Ehrenfest approximation to describe decoherence processes and nonadiabatic interstate conversion. System-bath interactions are modeled using quantum trajectories and Lindblad quantum jump operators. We find that following photoexcitation, the quantum mechanical entanglement of the exciton and C-C bond phonons causes exciton-site decoherence. Next, system-bath interactions cause the stochastic collapse of high-energy delocalized excitons onto chromophores. Finally, torsional relaxation causes additional exciton-density localization. We relate these dynamical processes to the predicted fluorescence depolarization and extract the timescales corresponding to them.