Assessing the Role of Intermolecular Interactions in a Perylene-Based Nanowire Using First-Principles Many-Body Perturbation Theory.

We present a first-principles many-body perturbation theory study of the role of intermolecular coupling in the optoelectronic properties of a one-dimensional (1D) π-stacked nanowire composed of perylene-3,4,9,10-tetracarboxylic diimide molecules on a DNA-like backbone. We determine that strong intermolecular electronic coupling results in large bandwidths and low carrier effective masses, suggesting a high-electron mobility material. Additionally, by including the role of finite-temperature phonons on optical absorption via a newly presented approach, we predict that the optical absorption spectrum  is significantly altered from that at zero temperature due to allowed indirect transitions, while the exciton delocalization and binding energy, a measure of intermolecular electronic interactions, remains constant. Overall, our studies indicate that strong intermolecular coupling can dominate the optoelectronic properties of π-conjugated 1D systems even at room temperature.