Theory of the Hydrogen Bond: Ab Initio Calculations on Hydrogen Fluoride Dimer and the Mixed Water–Hydrogen Fluoride Dimer

Abstract

High‐accuracy molecular orbital calculations have been carried out on different geometries of the hydrogen fluoride dimer and the mixed water–hydrogen fluoride dimer. A zigzag (near linear) structure is predicted for the hydrogen fluoride dimer with a dimerization energy in reasonable agreement with experiment. One geometry of the mixed water–hydrogen fluoride dimer has a very large stabilization energy (10 kcal/mole), and a microwave experiment is proposed to determine its exact structure. Changes in molecular properties and charge distribution upon dimer formation are calculated and a dimer rotational barrier determined.