title: Theoretical prediction of the hydrogen-bond basicity pK(HB).
abstract: Ab initio and DFT calculations on around 65 hydrogen bond or Lewis bases and their complexes with hydrogen fluoride have been performed, and a range of calculated properties from both free bases and complexes correlated with pK(HB), an experimental scale of hydrogen-bond basicity. For the entire range of bases, we found that the hydrogen-bond binding Gibbs free energy computed at the B3LYP/6-31+G(d,p) level of theory linearly correlated with pK(HB). Further improvements in the correlation and prediction of pK(HB) were possible with a non-linear fit by considering the hydrogen bonding Gibbs free energy of another possible stereoisomeric 1:1 complex and/or that of a linear 2:1 complex, which included a second hydrogen fluoride.
authors.affiliation: Department of Chemistry, Cardiff University, UK.
authors.forename: Olivier
authors.initials: O
authors.lastname: Lamarche
authors.forename: James A
authors.initials: JA
authors.lastname: Platts
mesh_terms: D006858:Hydrofluoric Acid / Q000737:chemistry; D006860:Hydrogen Bonding; D006863:Hydrogen-Ion Concentration; D008956:Models, Chemical; D015394:Molecular Structure; D010100:Oxygen / Q000737:chemistry; D015203:Reproducibility of Results; D012997:Solvents; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D012997:Solvents; D006858:Hydrofluoric Acid; D010100:Oxygen