Related Experiment Video
Updated: Mar 13, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Biphasic aggregation of a perylene bisimide dye identified by exciton-vibrational spectra
P-A Plötz1, S P Polyutov2, S D Ivanov1
1Institut für Physik, Universität Rostock, Albert-Einstein-Str. 23-24, 18059 Rostock, Germany. oliver.kuehn@uni-rostock.de.
Abstract:
The quantum efficiency of light emission is a crucial parameter of supramolecular aggregates that can be tuned by the molecular design of the monomeric species. Here, we report on a strong variation of the fluorescence quantum yield due to different phases of aggregation for the case of a perylene bisimide dye. In particular, a change of the dominant aggregation character from H- to J-type within the first aggregation steps is found, explaining the observed dramatic change in quantum yield. This behaviour is rationalised by means of a systematic study of the intermolecular potential energy surfaces using the time-dependent density functional based tight-binding (TD-DFTB) method. This provides a correlation between structural changes and a coupling strength and supports the notion of H-type stacked dimers and J-type stack-slipped dimers. The exciton-vibrational level structure is modelled by means of an excitonic dimer model including two effective vibrational modes per monomer. Calculated absorption and fluorescence spectra are found to be in reasonable agreement with experimental ones, thus supporting the conclusion on the aggregation behaviour.
More Related Videos
Related Concept Videos
¹H NMR: Complex Splitting
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied...
¹³C NMR: Distortionless Enhancement by Polarization Transfer (DEPT)
¹H NMR: Interpreting Distorted and Overlapping Signals
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
UV–Vis Spectroscopy of Conjugated Systems
One of the factors influencing λmax is the extent of conjugation in...
¹H NMR: Pople Notation
A proton...
Double Resonance Techniques: Overview
Spin decoupling is usually achieved by...

