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Title: Confinement induced binding of noble gas atoms

The stability of Ng{sub n}@B{sub 12}N{sub 12} and Ng{sub n}@B{sub 16}N{sub 16} systems is assessed through a density functional study and ab initio simulation. Although they are found to be thermodynamically unstable with respect to the dissociation of individual Ng atoms and parent cages, ab initio simulation reveals that except Ne{sub 2}@B{sub 12}N{sub 12} they are kinetically stable to retain their structures intact throughout the simulation time (500 fs) at 298 K. The Ne{sub 2}@B{sub 12}N{sub 12} cage dissociates and the Ne atoms get separated as the simulation proceeds at this temperature but at a lower temperature (77 K) it is also found to be kinetically stable. He-He unit undergoes translation, rotation and vibration inside the cavity of B{sub 12}N{sub 12} and B{sub 16}N{sub 16} cages. Electron density analysis shows that the He-He interaction in He{sub 2}@B{sub 16}N{sub 16} is of closed-shell type whereas for the same in He{sub 2}@B{sub 12}N{sub 12} there may have some degree of covalent character. In few cases, especially for the heavier Ng atoms, the Ng-N/B bonds are also found to have some degree of covalent character. But the Wiberg bond indices show zero bond order in He-He bond and very low bond order inmore » cases of Ng-N/B bonds. The energy decomposition analysis further shows that the ΔE{sub orb} term contributes 40.9% and 37.3% towards the total attraction in the He{sub 2} dimers having the same distances as in He{sub 2}@B{sub 12}N{sub 12} and He{sub 2}@B{sub 16}N{sub 16}, respectively. Therefore, confinement causes some type of orbital interaction between two He atoms, which akins to some degree of covalent character.« less
Authors:
; ;  [1]
  1. Department of Chemistry and Centre for Theoretical Studies, Indian Institute of Technology, Kharagpur 721302 (India)
Publication Date:
OSTI Identifier:
22253019
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 16; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DECOMPOSITION; DENSITY FUNCTIONAL METHOD; DISSOCIATION; ELECTRON DENSITY; HELIUM; INTERACTIONS; SIMULATION