Optical Spectra of Open-Shell and Closed-Shell Graphene-Based Molecules

TL;DR

This study computationally investigates the optical absorption spectra of various graphene-based molecules, revealing how chemical modifications and open-shell configurations influence their spectral properties, especially the HOMO-LUMO gap and absorption shifts.

Contribution

It introduces a detailed computational analysis of absorption spectra for different graphene derivatives, highlighting the effects of edge chemistry and open-shell configurations on optical properties.

Findings

Open-shell molecules show significant red shifts in absorption spectra.

UHF-ZINDO/S method is effective for bulk molecules but less consistent for open-shell structures.

Calculated spectra align with experimental data on graphene quantum dots and oxides.

Abstract

We have computationally investigated absorption spectra of a specifically configured set of graphene-based molecules involving (1) a sp2 bare graphene sheet; (2) framed graphene sheets containing different chemical addends terminating dangling bonds of edge atoms but keeping sp2 configured basal plane; and (3) bulk sp3 graphene sheets resulted from the chemical modification occurred at not only the bare sheet circumference but at its basal plane as well. Framed molecules, open-shell by nature, present different kinds of reduced graphene oxides and present the main building blocks of graphene quantum dots. Closed-shell bulk molecules present models of nanosize graphene oxide. UHF ground states and ZINDO/S excited states of the molecules were analyzed. The UHF-ZINDO/S combination is well coherent in the case of bulk molecules for which UHF and RHF ground state results are identical. In the case of framed molecules, the incoherence of the UHF and close-shell ZINDO/S approaches is revealed in a considerable decreasing of the HOMO-LUMO energy gap, which provides unreal drastic red shift of absorption spectra of open-shell molecules into IR region. The conclusion is justified by a comparative analysis of calculated and experimental data on absorption and fluorescence spectra of graphene quantum dots and graphene oxides.