The sigma-Hole Coulombic Interpretation of Trihalide Anion Formation

Journal article

Publication Details

Author(s): Clark T, Murray JS, Politzer P
Journal: Chemphyschem
Publication year: 2018
Volume: 19
Journal issue: 22
Pages range: 3044-3049
ISSN: 1439-4235


It is shown that the interactions of dihalogen molecules XY with halide anions Z(-) to form trihalide anions (XYZ)(-) can be satisfactorily described as Coulombic, involving the sigma-holes on the atoms Y, but only if polarization is taken into account. We have approximated the polarizing effect of the halide anion Z(-) by means of a unit negative point charge. The CCSD/aug-cc-pVTZ computed interaction energies Delta E correlate well with the most positive electrostatic potentials associated with the induced sigma-holes over a Delta E range of -12 to -63 kcal mol(-1). The (XYZ)(-) anions are more stable when the central atom is the largest, as has been observed, because the central atom is then the most polarizable, making the electrostatic potential associated with its sigma-hole more positive.

FAU Authors / FAU Editors

Clark, Timothy apl. Prof. Dr.

External institutions with authors

University of New Orleans

How to cite

Clark, T., Murray, J.S., & Politzer, P. (2018). The sigma-Hole Coulombic Interpretation of Trihalide Anion Formation. Chemphyschem, 19(22), 3044-3049.

Clark, Timothy, Jane S. Murray, and Peter Politzer. "The sigma-Hole Coulombic Interpretation of Trihalide Anion Formation." Chemphyschem 19.22 (2018): 3044-3049.


Last updated on 2018-18-12 at 08:38