ESTUDO COMPUTACIONAL DA INFLUÊNCIA DE CO2 NO EMPILHAMENTO-π DE MONÔMEROS DE CORONENO SUBSTITUÍDOS COM ENXOFRE

COMPUTATIONAL STUDY OF THE INFLUENCE OF CO₂ ON THE π-STACKING OF SULFUR-SUBSTITUTED CORONENE MONOMERS

Asphaltenes are complex molecules with a tendency to aggregate. This property can be an issue for the oil industry due to CO₂ reinjection into reservoirs to mitigate these gas emissions. The present theoretical study aimed to study the CO₂ interaction with no-substitute and substituted coronene as an asphaltene model compound at CAM-B3LYP-D3/6-311G(d,p) level. The electronic properties were evaluated using harmonic oscillator model of aromaticity (HOMA), quantum theory of atoms in molecules (QTAIM), and reduced density gradient (RDG) methods. The results showed that the coronene’s functionalization by a sulfur atom changes the coronene’s electronic structure. However, functionalization does not change the type of interactions between the monomers, as they remain predominantly van der Waals interactions. CO₂ interaction with substituted coronene barely changed due to the presence of sulfur atoms. However, in dimers, the position of the heteroatom directly influences the interaction with CO₂, although it is insufficient to change the interaction’s magnitude. For this reason, our results indicate that the sulfur heteroatom in asphaltenes should be addressed. However, new studies must be conducted by increasing the number of substituents, CO₂ numbers, and the model size.