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Theoretical prediction on the structures and stability of the noble-gas containing anions FNgCC- (Ng=He, Ar, Kr, and Xe)

Abstract

We have made high-level theoretical study on a new type of noble-gas (Ng) containing anions FNgCC-. The calculated short Ng-CC bond lengths of 1.13, 1.77, 1.89, and 2.04 Å for Ng=He, Ar, Kr, and Xe, respectively, and the electron density distributions indicated strong covalent interactions between the Ng and CC induced by the polarizing fluoride ion. Except for FHeCC-, the structures of all other FNgCC- were predicted to be linear. The intrinsic stability of the FNgCC- was studied by calculating the energies of the three-body dissociation reaction: FNgCC- → F- + Ng + CC and by calculating the energy barriers of the two-body dissociation reaction: FNgCC- → Ng + FCC-. The results showed that FNgCC- (Ng=Ar, Kr, Xe) could be kinetically stable in the gas phase with the three-body dissociation energies of 17, 37, and 64 kcal/mol and two body-dissociation barriers of 22, 31, and 42 kcal/mol, respectively, at the coupled-cluster single double (triple)/aug-cc-pVQZ level of theory. The structures and the stability were also confirmed using the multi-reference CASPT2 calculation. Future experimental identification of the FNgCC- anions is expected under cryogenic conditions.


Publication:
Journal of Chemical Physics
Pub Date:
November 2012
DOI:

10.1063/1.4766326

Bibcode:
2012JChPh.137s4303P
Keywords:
  • atom-molecule collisions;
  • atom-molecule reactions;
  • bond lengths;
  • coupled cluster calculations;
  • dissociation;
  • dissociation energies;
  • electron density;
  • molecular configurations;
  • negative ions;
  • organic compounds;
  • polarisation;
  • 31.15.bw;
  • 33.15.Bh;
  • 33.15.Dj;
  • 33.15.Fm;
  • 82.30.Lp;
  • Clusters: electronic properties equilibrium geometries coupled-cluster theory;
  • General molecular conformation and symmetry;
  • stereochemistry;
  • Interatomic distances and angles;
  • Bond strengths dissociation energies;
  • Decomposition reactions
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