Jump to main content
Jump to site search

Issue 10, 2016
Previous Article Next Article

Halogen bonding. The role of the polarizability of the electron-pair donor

Author affiliations

Abstract

The nature of F–Br⋯X–R interactions (with X = F, Cl, Br, I and R = –H, –F) has been investigated through theoretical calculation of molecular potential electrostatic (MEP), molecular polarizability, atoms in molecules (AIM) analysis and energetic decomposition analysis (EDA). A detailed analysis of the MEPs reveals that considering only the static electrostatic interactions is not sufficient to explain the nature of these interactions. The molecular polarizabilities of X–R molecules suggest that the deformation capacity of the electronic cloud of the lone pairs of the X atom plays an important role in the stability of these complexes. The topological analysis of the L(r) = −¼∇2ρ(r) function and the detailed analysis of the atomic quadrupole moments reveal that the Br⋯X interactions are electrostatic in nature. The electron acceptor Br atom causes a polarization of the electronic cloud (electronic induction) on the valence shell of the X atom. Finally, the electrostatic forces and charge transfer play an important role not only in the stabilization of the complex, but also in the determination of the molecular geometry of equilibrium. The dispersive and polarization forces do not influence the equilibrium molecular geometry.

Graphical abstract: Halogen bonding. The role of the polarizability of the electron-pair donor

Back to tab navigation

Supplementary files

Publication details

The article was received on 23 Dec 2015, accepted on 12 Feb 2016 and first published on 12 Feb 2016


Article type: Paper
DOI: 10.1039/C5CP07941A
Citation: Phys. Chem. Chem. Phys., 2016,18, 7300-7309
  •   Request permissions

    Halogen bonding. The role of the polarizability of the electron-pair donor

    D. J. R. Duarte, G. L. Sosa, N. M. Peruchena and I. Alkorta, Phys. Chem. Chem. Phys., 2016, 18, 7300
    DOI: 10.1039/C5CP07941A

Search articles by author

Spotlight

Advertisements