Electron-correlated study of excited states and absorption spectra of some low-symmetry graphene quantum dots

We have computed the linear optical absorption spectra of three graphene quantum dots (GQDs), saturated by hydrogens on the edges, using both first-principles time-dependent density-functional theory (TDDFT) and the Pariser-Parr-Pople (PPP) model coupled with the configuration-interaction (CI) approach. To understand the influence of electron-correlation effects, we have also calculated the singlet-triplet energy gap (spin gap) of the three GQDs. Because of the presence of edge hydrogens, these GQDs are effectively polycyclic aromatic hydrocarbons (PAHs) dibenzo[bc,ef]coronene (also known as benzo(1,14)bisanthene, C₃₀H₁₄), and two isomeric compounds, dinaphtho[8,1,2abc;2,1,8klm]coronene and dinaphtho[8,1,2abc;2,1,8jkl]coronene with the chemical formula C₃₆H₁₆. The two isomers have different point group symmetries, C₂ᵥ, and C₂ₕ, therefore, this study will also help us understand the influence of symmetry on optical properties. A common feature of the absorption spectra of the three GQDs is that the first peak representing the optical gap is of low to moderate intensity, while the intense peaks appear at higher energies. For each GQD, PPP model calculations performed with the screened parameters agree well with the experimental results of the corresponding PAH, and also with the TDDFT calculations.