Insights into adsorptions of SHMe, SMe ₂ , and thiophene on Ni-decorated Mg ₄ O ₄ nanoclusters: a quantum chemical investigation

In this work, adsorptions of SHMe, SMe2, and thiophene molecules on the Mg4O4 cluster and Ni-decorated Mg4O4 nanoclusters was examined at the LC-ωPBE/6-311G(d,p) level of theory. Effect of Ni-decorated Mg4O4 nanocluster on the adsorption of these molecules was compared to Mg4O4 nanocluster. Energetic and thermodynamics aspects of adsorption process were illustrated. Computed adsorption energy values exposed pronounced adsorption between pollutant molecules with Ni-decorated Mg4O4 respect to Mg4O4. Also, molecular orbital analysis of the studied systems was reported. Smaller HOMO-LUMO gap and hardness values were found in the presence of Ni-decorated Mg4O4 nano-cluster than Mg4O4 nano-cluster. The interactions between two fragments was explored with energy decomposition analysis (EDA), charge decomposition analysis (CDA), and electron localization function (ELF) investigations. CDA results were adopted with our chemical insight for the reason that conferring to classical theory, the electrons of coordinate bonds are virtuously donated from ligands. Difference map of electron density and ELF of these systems were provided. The stability of the studied systems was proved by atom centered density matrix propagation (ADMP) molecular dynamics molecular dynamics analyses, where these complexes revealed small changes in their total energy.