Optical Signatures of the Coupling between Excitons and Charge Transfer States in Linear Molecular Aggregates

TL;DR

This paper presents a scattering matrix approach to analyze how charge transfer states influence the optical absorption spectra of linear molecular aggregates, effectively bridging theoretical gaps across coupling regimes.

Contribution

It introduces a versatile scattering matrix method capable of handling large systems and both strong and weak exciton-CT state mixing, advancing spectral analysis techniques.

Findings

Homogeneous linewidth often obscures individual transitions in experimental spectra.

The high-frequency peak skewness correlates with exciton-CT coupling strength.

The method accurately models absorption spectra across different coupling regimes.

Abstract

Charge Transfer (CT) has enjoyed continuous interest due to increasing experimental control over molecular structure leading to applications in, for example, photovoltaics and hydrogen production. In this paper, we investigate the effect of CT states on the absorption spectrum of linear molecular aggregates using a scattering matrix technique that allows us to deal with arbitrarily large systems. The presented theory performs well for both strong and weak mixing of exciton and CT states, bridging the gap between previously employed methods which are applicable in only one of these limits. In experimental spectra the homogeneous linewidth is often too large to resolve all optically allowed transitions individually, resulting in a characteristic two-peak absorption spectrum in both the weak- and strong-coupling regime. Using the scattering matrix technique we examine the contributions of free and bound states in detail. We conclude that the skewness of the high-frequency peak may be used as a new way to identify the exciton-CT-state coupling strength.