Solid state effects on exciton states and optical properties of PPV

TL;DR

This study uses ab initio calculations to explore how crystalline packing influences exciton states and optical properties of PPV, revealing complex exciton structures and non-radiative decay channels relevant for optoelectronic applications.

Contribution

It provides detailed insights into the impact of solid-state effects on exciton behavior in PPV using explicit electron-hole interaction modeling.

Findings

Crystalline arrangement significantly alters exciton structure.

Solid-state effects introduce non-radiative decay channels.

Optical properties are highly sensitive to packing details.

Abstract

We perform ab initio calculations of optical properties for a typical semiconductor conjugated polymer, poly-para-phenylenevinylene, in both isolated chain and crystalline packing. In order to obtain results for excitonic energies and real-space wavefunctions we explicitly include electron-hole interaction within the density-matrix formalism. We find that the details of crystalline arrangement crucially affect the optical properties, leading to a richer exciton structure and opening non-radiative decay channels. This has implications for the optical activity and optoelectronic applications of polymer films.