DFT and Model Hamiltonian Study of Optoelectronic Properties of Some Low-Symmetry Graphene Quantum Dots

We have studied the electronic and optical properties of three low-symmetry graphene quantum dots (GQDs), with point-group symmetries <i>C</i>_2<i>v</i> and <i>C</i>_2<i>h</i>. For the calculations of linear optical absorption spectra, we employed both first-principles time-dependent density-functional theory (TDDFT) and the electron-correlated Pariser-Parr-Pople (PPP) model coupled with the configuration-interaction (CI) approach. In the PPP-CI approach, calculations were performed using both screened and standard parameters, along with efficiently incorporating electron correlation effects using multireference singles-doubles CI for both ground and excited states. We assume that the GQDs are saturated by hydrogen atoms at the edges, making them effectively polycyclic aromatic hydrocarbons (PAHs) dibenzo[<i>bc</i>,<i>ef</i>]coronene (also known as benzo(1,14)bisanthene, C₃₀H₁₄) and two isomeric compounds, dinaphtho[8,1,2<i>abc</i>;2',1',8'<i>klm</i>]coronene and dinaphtho[8,1,2<i>abc</i>;2',1',8'<i>jkl</i>]coronene with the chemical formula C₃₆H₁₆. The two isomers have different point group symmetries; therefore, this study will also help us understand the influence of symmetry on the 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. To further quantify the influence of electron-correlation effects, we also computed the singlet-triplet gap (spin gap) of the three GQDs, and we found them to be significant.