Atomic-Level Insights into the Adsorption of Methyl-Substituted Quinoxalinones on Fe(110): A Dispersion-Corrected DFT Analysis

Corrosion of metallic equipment is a critical issue across various industries, necessitating the development of advanced protective strategies. This study utilized dispersion-corrected density functional theory (DFT) with Becke–Johnson D3(BJ) to examine the atomic-level adsorption of quinoxalinones on Fe(110) surfaces, focusing on optimizing substitution strategies to enhance corrosion inhibition. Three quinoxalinones, quinoxalin-2(1H)-one (QNO), 3-methylquinoxalin-2(1H)-one (QNOM), and 3,7-dimethylquinoxalin-2(1H)-one (QNO2M), were investigated in various configurations and protonation states. Protonated quinoxalinones demonstrated a stronger surface affinity, primarily interacting through oxygen atoms and conjugated systems, with greater energetic stability compared to neutral molecules, driven by enhanced electrostatic interactions and charge transfer mechanisms. The parallel adsorption configuration was more stable than the perpendicular mode, which in some adsorption systems did not form bonds with the iron surface. Notably, the presence of methyl substitutions did not significantly enhance adsorption strength; QNO exhibited higher energetic stability due to reduced steric interference, which maintained its planarity. Projected density of states (PDOS), electron density difference (EDD), and electron localization function (ELF) analyses confirmed the importance of charge transfer between quinoxalinone active sites and the 3d orbitals of iron in stabilizing the adsorption of molecules. These findings underscore the importance of judicious quinoxalinone functionalization to preserve their efficacy as corrosion inhibitors.