Electron-phonon interaction and surface effects on the optoelectronic properties of diamondoids: A comparative study

TL;DR

This study investigates how electron-phonon interactions and surface chemistry influence the optoelectronic properties of diamondoids, resolving discrepancies between experimental results and theoretical predictions using advanced computational methods.

Contribution

It combines TD-DFT and Franck-Condon approximation to analyze surface effects and electron-phonon interactions on optical gaps in diamondoids, providing explanations for previous overestimations.

Findings

Electron-phonon interactions modify the optical gap predictions.

Surface chemistry significantly affects optical properties.

The study explains overestimations by previous quantum Monte-Carlo methods.

Abstract

Unusual optoelectronic properties of diamondoids produce some discrepancies between experiments and the outstanding many-body calculation outputs. Therefore, many theoretical efforts are attracted to resolve these inconsistencies. Here first, by combining time-dependent density functional theory (TD-DFT) and Franck-Condon (FC) approximation, the effect of electron-phonon (e-ph) interaction on the optical gap (OG) of the smallest diamondoids and one of its derivatives is studied. Then, the surface effects on the e-ph coupling and the optical properties of these structures in a comparative manner are considered. We show that the collective motion of carbons modifies the previous OG of adamantane predicted by TD-DFT technique. The introduction of this effect can also fully explain the overestimated gap predicted by the diffusion quantum Monte-Carlo (DMC) method. In addition, we show that the chemistry of the surface is another noticeable effect that can influence the OG renormalization and the spectral lineshape of the system.