The nature of the chemical bond

H., Dunning, Jr., Thom; Gordon, Mark S.; Xantheas, Sotiris S.

doi:10.1063/5.0148500

Cited by 2 publications

(1 citation statement)

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“…For an overview of the physical nature of chemical bonding, including the latest computational approaches, we refer the reader to a very recent collection of articles. [3] Among others, the Energy Decomposition Analysis (EDA), [4,5] also known as the Extended Transition State method (ETS), combined with the density partitioning Natural Orbitals for the Chemical Valence (NOCV) method, [6,7] represents a very powerful approach that allows a conceptually simple interpretation of the nature of chemical bonding. This method, known as EDA-NOCV (or ETS-NOCV), has become today an important tool, able to deliver both qualitative and quantitative insights into the chemical bond.…”

Section: Introductionmentioning

confidence: 99%

The Chemical Bond at the Bottom of the Periodic Table: The Case of the Heavy Astatine and the Super‐Heavy Tennessine

Gamboni,

Belpassi,

Belanzoni

2024

ChemPhysChem

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In this work, we study the chemical bond in molecules containing heavy and super‐heavy elements according to the current state‐of‐the‐art bonding models. An Energy Decomposition Analysis in combination with Natural Orbital for Chemical Valence (EDA‐NOCV) within the relativistic four‐component Dirac‐Kohn‐Sham (DKS) framework is employed, which allows to successfully include the spin‐orbit coupling (SOC) effects on the chemical bond description.Simple halogen‐bonded adducts ClXL (X=At, Ts; L= NH3, Br‐, H2O, CO) of astatine and tennessine have been selected to assess a trend on descending along a group, while modulating the ClXL bond features through the different electronic nature of the ligand L. Interesting effects caused by SOC have been revealed: i) a huge increase of the ClTs dipole moment (which is almost twice as that of Cl At), ii) a lowering of the ClX…L bonding energy arising from different contributions to the ClX…L interaction energy strongly depending on the nature of L, iii) a quenching of one of the π back‐donation components to the bond. In the ClTs(CO) adduct, the back‐donation from ClTs to CO becomes the most important component. The analysis of the electronic structure of the ClX dimers allows for a clear interpretation of the SOC effects in these systems.

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