The manuscript combines rational density functional theory simulations and experimental data to investigate the electrical properties of eight polycyclic aromatic hydrocarbons (PAHs). The optimized geometries reveal a preference for one-row, two-row and three-row ring distributions. Band structure plots demonstrate an inverse correlation between the number of aromatic rings and band gap size, with a specific order observed across the PAHs. Gas phase simulations support these findings, though differences in values are noted compared to the literature. Introducing a two-row ring distribution concept resolves discrepancies, particularly in azulene. The B3LYP function successfully bridges theoretical and experimental gaps, particularly in large PAHs. The manuscript highlights the potential for designing electronic devices based on different-sized PAHs, emphasizing a multi-ring distribution approach and opening new avenues for practical applications.