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Title: Electronic structures and geometries of the XF{sub 3} (X = Cl, Br, I, At) fluorides

The potential energy surfaces of the group 17 XF{sub 3} (X = Cl, Br, I, At) fluorides have been investigated for the first time with multiconfigurational wave function theory approaches. In agreement with experiment, bent T-shaped C{sub 2v} structures are computed for ClF{sub 3}, BrF{sub 3}, and IF{sub 3}, while we predict that an average D{sub 3h} structure would be experimentally observed for AtF{sub 3}. Electron correlation and scalar relativistic effects strongly reduce the energy difference between the D{sub 3h} geometry and the C{sub 2v} one, along the XF{sub 3} series, and in the X = At case, spin-orbit coupling also slightly reduces this energy difference. AtF{sub 3} is a borderline system where the D{sub 3h} structure becomes a minimum, i.e., the pseudo-Jahn-Teller effect is inhibited since electron correlation and scalar-relativistic effects create small energy barriers leading to the global C{sub 2v} minima, although both types of effects interfere.
Authors:
 [1] ;  [2] ; ;  [3] ;  [2] ;  [4] ;  [1]
  1. SUBATECH, UMR CNRS 6457, IN2P3/EMN Nantes/Université de Nantes, 4 Rue A. Kastler, BP 20722, 44307 Nantes Cedex 3 (France)
  2. (France)
  3. Sorbonne Universités, UPMC Univ Paris 06, UMR 7616, Laboratoire de Chimie Théorique, Case Courier 137, 4 Place Jussieu, 75252 Paris Cedex 05 (France)
  4. CEISAM, UMR CNRS 6230, Université de Nantes, 2 Rue de la Houssinière, BP 92208, 44322 Nantes Cedex 3 (France)
Publication Date:
OSTI Identifier:
22489605
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 11; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHLORINE FLUORIDES; ELECTRON CORRELATION; ELECTRONIC STRUCTURE; JAHN-TELLER EFFECT; L-S COUPLING; POTENTIAL ENERGY; RELATIVISTIC RANGE