A reduced radial potential energy function for the halogen bond and the hydrogen bond in complexes B···XY and B···HX, where X and Y are halogen atoms.
It is shown by considering 76 halogen- and hydrogen-bonded complexes BXY and BHX (where B is a Lewis base N2, CO, C2H2, C2H4, H2S, HCN, H2O, PH3 or NH3 and X, Y are F, Cl, Br or I) that the intermolecular stretching force constants kσ (determined from experimental centrifugal distortion constants via a simple model) and the intermolecular dissociation energies Dσ (calculated at the CCSD(T)(F12*)/cc-pVDZ-F12 level of theory) are related by Dσ = Cσkσ, where Cσ = 1.50(3) × 10(3) m(2) mol(-1). This suggests that one-dimensional functions implying direct proportionality of Dσ and kσ, (e.g. a Morse or Rydberg function) might serve as reduced radial potential energy functions for such complexes.
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, UK. a.c.legon@bristol.ac.uk.
Anthony C
AC
Legon
D006219:Halogens / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding
D006219:Halogens; D006859:Hydrogen