Overlap properties of chemical bonds in generic systems including unusual bonding situations

• Published in: Journal of molecular modeling 2020-11, Vol.26 (11), p.301-301, Article 301
• Main Authors: Moura, Renaldo T., Carneiro Neto, Albano N., Malta, Oscar L., Longo, Ricardo L.
• Format: Article
• Language: English
• Subjects: Characterization and Evaluation of Materials; Chemical bonds; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Correlation analysis; Electronegativity; Hydrogen peroxide; Molecular Medicine; Molecular orbitals; Original Paper; Properties (attributes); Theoretical and Computational Chemistry; XX-Brazilian Symposium of Theoretical Chemistry (SBQT2019)
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-020-04535-w

Chemical bond is a ubiquitous and fundamental concept in chemistry, in which the overlap plays a defining role. By using a new approach based on localized molecular orbitals, the overlap properties, e.g., polarizability α ¯ OP , population p OP , intra J OP intra , and inter J OP inter repulsions, and density ρ OP , of polyatomic systems were calculated, analyzed, and correlated. Several trends are shown for these properties, which are rationalized by the balance of some well-known effects, such as, electron donor/withdrawing character and electronegativity. The overlap properties of unusual bonds are also analyzed, revealing an OZn 4 (OOCH) 6 structure with four equivalent Zn–O chemical bonds with overlap properties like the O–O bond in H 2 O 2 , while in protonated methane C H 5 + , it is observed that a CH 3 ⋯ H 2 + bond pattern at the equilibrium structure changes to a C H 3 + ⋯H 2 pattern upon dissociation. Charge-shift resonance energies, atom-in-molecule properties, and the lone-pair-bond-weakening effects are related to the overlap properties, which can provide alternative views and insights into chemical bonds. Graphical abstract A chemical bond analysis approach based on its overlap properties is presented for the first time. The model was applied directly to 25 diatomics and for 28 bonds in polytomics employing localized molecular orbitals. Correlations of the overlap properties with the charge-shift resonance energies and with atom-in-molecule (AIM) properties were uncovered. In addition, it provided insights into the Zn–O bonds in the unusual OZn 4 (OOCH) 6 system as well as in the bonding patterns of C H 5 + at equilibrium and upon dissociation.