HOMO–LUMO Gaps and Molecular Structures of Polycyclic Aromatic Hydrocarbons in Soot Formation

A large number of PAH molecules is collected from recent literature. The HOMO-LUMO gap value of PAHs was computed at the level of B3LYP/6-311+G (d,p). The gap values lie in the range of 0.64–6.59 eV. It is found that the gap values of all PAH molecules exhibit a size dependency to some extent. However, the gap values may show a big variation even at the same size due to the complexity in the molecular structure. All collected PAHs are further classified into seven groups according to features in the structures, including the types of functional groups and the molecular planarity. The impact of functional groups, including –OH, –CHO, –COOH, =O, –O– and –C<jats:sub>n</jats:sub>H<jats:sub>m</jats:sub> on the bandgap is discussed in detail. The substitution of ketone group has the greatest reduction on the HOMO-LUMO gap of PAH molecules. Besides functional groups, we found that both local structure and the position of five-member rings make critical impacts on the bandgap <jats:italic>via</jats:italic> a detailed analysis of featured PAHs with unexpected low and high gap values. Among all these factors, the five-member rings forming nonplanar PAHs impact the gap most. Furthermore, we developed a machine learning model to predict the HOMO-LUMO gaps of PAHs, and the average absolute error is only 0.19 eV compared with the DFT calculations. The excellent performance of the machine learning model provides us an accurate and efficient way to explore the band information of PAHs in soot formation.