Issue 16, 2023

The impact of stacking and phonon environment on energy transfer in organic chromophores: computational insights

Abstract

Energy transfer in organic materials is extensively studied due to many applications in optoelectronics. The electronic and vibrational relaxations within molecular assemblies can be influenced by stacking arrangements or additions of a backbone that unites them. Here, we present the computational study of the photoexcitation dynamics of a perylene diimide monomer, and face-to-face stacked dimer and trimer. By using non-adiabatic excited-state molecular dynamics simulations, we show that the non-radiative relaxation is accelerated with the number of stacked molecules. This effect is explained by differences in the energy splitting between states that impacts their corresponding nonadiabatic couplings. Additionally, our analysis of the vibronic dynamics reveals that the passage through the different conical intersections that participate in the relaxation of the stacked systems, activate a positive feedback mechanism. This effect involves a narrow set of vibrational normal modes that accelerate the process by increasing the efficiency of its vibronic dynamics. In contrast, an addition of a biologically inspired backbone slows down the relaxation rate due to its participation in the vibronic dynamics of the molecular stacking arrangements. Our results suggest the stacking arrangements and common backbones as strategies to modulate the efficiency of electronic and vibrational relaxation of diimide-based systems and other molecular aggregates.

Graphical abstract: The impact of stacking and phonon environment on energy transfer in organic chromophores: computational insights

  • This article is part of the themed collection: #MyFirstJMCC

Supplementary files

Article information

Article type
Paper
Submitted
10 Feb 2023
Accepted
22 Mar 2023
First published
27 Mar 2023

J. Mater. Chem. C, 2023,11, 5297-5306

Author version available

The impact of stacking and phonon environment on energy transfer in organic chromophores: computational insights

A. Mukazhanova, H. Negrin-Yuvero, V. M. Freixas, S. Tretiak, S. Fernandez-Alberti and S. Sharifzadeh, J. Mater. Chem. C, 2023, 11, 5297 DOI: 10.1039/D3TC00479A

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