HFI and DFT study of the bonding in complexes of halogen and interhalogen diatomics with Lewis base

O. Kh Poleshchuk, V. Branchadell, B. Brycki, A. V. Fateev, A. C. Legon

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We have analyzed by means of DFT calculations with use of the pseudo-potential the nuclear quadrupole coupling constants of a range of XY⋯B complexes (n aσ type in Mulliken notation) formed between diatomic interhalogen molecules XY and Lewis bases B. The geometrical parameters, rotational and halogen nuclear quadrupole coupling constants obtained by these calculations substantially corresponded to the data of microwave spectroscopy in the gas phase. An analysis of the quality of the calculations that employ the pseudo-potential and the expanded basis set for the halogen compounds was carried out. The ZORA model is shown to be a viable alternative to the computationally demanding BH and HLYP model for the calculation of halogen and nitrogen coupling constants in molecules. In addition, the ZORA model, in contrast to the pseudo-potential model, leads to realistic values of iodine nuclear quadrupole coupling constants. From electron partitioning analyses and Klopman's approach it follows that for the ICl⋯B complexes the electrostatic bonding is predominant relative to covalent bonding. © 2006 Elsevier B.V. All rights reserved.
Original languageEnglish
Pages (from-to)175-182
JournalJournal of Molecular Structure: THEOCHEM
Issue number1-3
Publication statusPublished - 28 Feb 2006


  • Bond energies
  • DFT calculations
  • Interhalogen complexes
  • Quadrupole coupling constants
  • ZORA model


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