Electronic and Structural Elucidation of ZnO-ZnS–Aniline Nanocomposite Interactions via DFT and Microscopy Techniques
نویسندگان
1 Department of Pharmaceutics, College of Pharmacy, University of Al-Ameed, Iraq
2 Department of Chemistry, College of Science for Women, University of Babylon, Iraq
3 Department of Medical Laboratories Technology, AL-Nisour University College, Baghdad, Iraq
4 Al-Hadi University College, Baghdad, 10011, Iraq
5 Department of Sciences, Al-Manara College For Medical Sciences, Maysan, Iraq
6 Department of Chemistry, College of Science for Women, University of Babylon, Iraq
doi
10.22052/JNS.2025.03.019چکیده
Nanostructured surfaces are notable for diverse applications like molecular adsorption. Here, we utilize density functional theory (DFT) to explore the adsorption characteristics of aniline on a hybrid ZnO/ZnS cluster. To clarify the interaction’s nature, we performed a comprehensive analysis using Quantum Theory of Atoms in Molecules (QTAIM), Electrostatic Potential (ESP), Electron Localization Function (ELF), Non-Covalent Interaction (NCI) analysis via Reduced Density Gradient (RDG) and sign(λ₂)•ρ plots, along with Frontier Molecular Orbital (FMO) analysis. The QTAIM analysis revealed the presence of a bond critical point (BCP) between aniline’s nitrogen atom and a zinc atom on the surface. The electron density (ρ) at this point was measured to be 0.075341 a.u., with a Laplacian (∇²ρ) of +0.278076 a.u., suggesting a non-covalent, closed-shell interaction. ESP mapping revealed a distinct electrostatic complementarity between the nitrogen atom of aniline, with high electron density, and the electron-poor zinc sites on the surface. ELF analysis indicated a partial delocalization of the nitrogen lone pair upon adsorption, which implies a redistribution of electron density. NCI analysis primarily identified van der Waals interactions. RDG isosurfaces highlighted areas of weak attractive forces, which were supported by sign(λ₂)•ρ values. FMO analysis showed a decrease in the HOMO–LUMO gap from 5.44 eV for isolated aniline to 2.74 eV for the composite sample, indicating a greater electronic interaction and the possibility of charge transfer.
