On the nature of inter-anion coinage bonds

Abstract

To explore the binding energy profiles and elucidate the bonding nature in counter-intuitive anion‧‧‧anion coinage bonds (CiBs), thirty-one complexes were constructed, and the inter-anion CiBs were studied theoretically. The metastability...

Anion⋯anion self-assembly under the control of σ- and π-hole bonds

“…Similar computational results were obtained for the anion⋯anion interactions between Au(CN) 4 − and several different mono- and polyatomic anions. 167 For instance, the dimers with fluoride, chloride, cyanide, and hypochlorite anions are metastable species characterized by potential wells. The electron withdrawing ability of the CN − residues in Au(CN) 4 − units and the small size of the anion approaching the gold atom seem to be two critical aspects for the existence of these metastable dianions.…”

Quantum chemical analysis of noncovalent bonds within crystals. Concepts and concerns

“…66 There is now a good deal of evidence that anions can in general interact with one another so as to form a metastable minimum, so long as there is a surrounding polarizable continuum to mitigate the ion-ion coulombic repulsion. [67][68][69][70][71][72][73][74][75][76][77] Even when this complex is less stable than the pair of separated anions, the AIM parameters indicate the presence of a legitimate noncovalent bond, 78 bringing to the fore the question as to whether a metastable equilibrium, higher in energy than the two isolated subunits, ought to be categorized as a stabilizing interaction. In a broader sense, it is possible to find exothermic binding between pairs of anions, but only under certain conditions.…”

Conformational Preference of Lithium Polysulfide Clusters Li2Sx (x = 4–8) in Lithium–Sulfur Batteries

“…In this regard, the ab initio valence bond (VB) theory stands out as an ideal option. It offers a chemically intuitive solution for a molecular wave function, which is a linear combination of Lewis structures constructed from strictly localized and fully optimized orbitals. , As the simplest ab initio VB method, the block-localized wave function (BLW) retains the localized orbitals but simplifies the multireference wave function to a single determinant, making it computationally efficient. − Its associated energy decomposition (BLW-ED in short) approach can decompose the binding energy into physically meaningful energy components − and has provided a multitude of new insights into the conventional and unconventional interactions. − Moreover, the BLW method has the capabilities of geometrical optimization and spectral calculation for the strictly electron-localized state.…”

“… 71 − 74 Its associated energy decomposition (BLW-ED in short) approach can decompose the binding energy into physically meaningful energy components 75 − 77 and has provided a multitude of new insights into the conventional and unconventional interactions. 78 − 82 Moreover, the BLW method has the capabilities of geometrical optimization and spectral calculation for the strictly electron-localized state.…”