Premium
Effect of substitution on the bonding in He dimer confined within dodecahedrane: A computational study
Author(s) -
Jana Gourhari,
Chattaraj Pratim K.
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26403
Subject(s) - dimer , halogen , dissociation (chemistry) , cage , chemistry , covalent bond , molecule , crystallography , atoms in molecules , computational chemistry , organic chemistry , alkyl , mathematics , combinatorics
The effect of substitution in the dodecahedrane (C 20 H 20 ) cage on bonding in the confined He dimer is analyzed. The HeHe distances inside the halogenated dodecahedrane C 20 X 20 (X = FBr) cages are found to be less than half of that in the free He dimer. Comparing the equilibrium structure of He 2 @C 20 H 20 with He 2 @C 20 X 20 at ω B97XD/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 He 2 @C 20 X 20 complexes is reflected in the presence of a very high activation energy barrier against the thermochemically feasible dissociation process producing free He 2 and C 20 X 20 . Quantum theory of atoms in molecules (QTAIM) approach reveals a partial covalent interaction between He pair.