Acrylonitrile (AN)–Cu₉(100) interfaces: Electron distribution and nature of bonded interactions

Abstract

There is a fundamental interest in the investigation of the interfacial interactions and charge migration processes between organic molecules and metallic surfaces from a theoretical standpoint. Quantum mechanical (QM) concepts of bonding are contrasted, and the vital importance of using combined QM methods to explore the nature of the interfacial interactions is established. At the one-electron level, the charge distribution and nature of bonded interactions at the AN–Cu9(100) (neutral and charged (–1)) interfaces are investigated by both the Becke (B) – Vosko (V) – Wilk (W) – Nusair (N)/DZVP density functional theory (DFT) method and the MP2/6–31+G* strategy within the conceptual framework provided by natural bond orbital (NBO) – natural atomic orbital (NAO) population analysis and Atoms-In-Molecules (AIM) theory. By this approach, the interfacial interactions are given physical definitions free of any assumptions and are visualized by using the topological features of the total electron density. A natural link between the electron density on the one side and the shapes (not energies) of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) on the other side is clarified. The question of whether the spatial extents of the HOMO and LUMO resemble the corresponding spatial maps of the negative (charge locally concentrated) and positive (charge locally depleted) Laplacian of the total electron density in [AN–Cu9(100)]–1 is addressed.Key words: AN–Cu9(100) interfaces, NBO–NAO population, electron distribution, AIM, bonded interactions.

Substituent effect in para substituted Cr(CO)5–pyridine complexes

“…This can be explained by the presence of the pyridine ligand, which, as a lower field ligand than the CO one, weakens the cis-placed Cr-CO bonds. It has been proved, that the AIM-based analysis of electron density can provide valuable information on many physical and chemical properties of the molecular systems [39][40][41][42][43]. (It is fair to mention here some criticism of AIM Quantum Theory.…”

Solvent Effect on the Structural, Electronic, Spectra Properties and First Hyperpolarizability of W(co)5l, L=(4-Pyridylmethylene)malononitrile

“…It has been proved that the AIM-based analysis of electron density can provide valuable information on many physical and chemical properties of molecular systems [62][63][64][65][66]. Table 11 indicates that ∇ 2 ρ values of W-C cis , W-C trans , and W-N bonds at corresponding BCPs are positive, as it was found for closed-shell interactions.…”

Bonding in β-diketiminate boron and its analogues

“…It was proved that the AIM-based analysis of electron density could provide valuable information on many physical and chemical properties of the molecular systems [31][32][33][34][35]. (It is fair to mention here some criticism of AIM Quantum Theory.…”