Effect of substitution on the bonding in He dimer confined within dodecahedrane: A computational study

Abstract

The effect of substitution in the dodecahedrane (C20H20) cage on bonding in the confined He dimer is analyzed. The HeHe distances inside the halogenated dodecahedrane C20X20 (X = FBr) cages are found to be less than half of that in the free He dimer. Comparing the equilibrium structure of He2@C20H20 with He2@C20X20 at ωB97XD/def2‐TZVPP level, it is found that the He‐He distances are relatively larger in the latter cases indicating the influence of halogen groups on the interaction between the cage and the trapped He pair. The viability of the He2@C20X20 complexes is reflected in the presence of a very high activation energy barrier against the thermochemically feasible dissociation process producing free He2 and C20X20. Quantum theory of atoms in molecules (QTAIM) approach reveals a partial covalent interaction between He pair.

Substituent Effects on Electride Characteristics of Mg2(η5-C5H5)2: A Theoretical Study

“…34 The charges on Be and Mg atoms are +1 each, and an NNA has appeared in the middle point of each M−M bond. Jana et al 35 studied the effect of halogen substitution on the bonding nature in the He 2 @C 20 H 20 system and the charge transfer taking place from the He 2 moiety to the cage. Using conceptual density functional theory (CDFT), Chattaraj et al studied the substituent effect on the reactivity of oxygen and nitrogen sites of various hydroxylamine derivatives toward the soft and hard electrophiles.…”

CO2 Activation Within a Superalkali-Doped Fullerene

“…(Murata et al, 2006;Krachmalnicoff et al, 2016). In addition, a recent paper by Jana and Chattaraj (2020) describes the effects of a molecular reaction environment, dodecahedrane, on the He dimer bonding. Also, theoretical studies of a new type of endofullerenes with superalkali have been performed.…”