A critical analysis of electronic density functionals for structural, energetic, dynamic, and magnetic properties of hydrogen fluoride clusters

Abstract

We present extensive computational results on density functional calculations for hydrogen fluoride species (HF)n (with 1 ≤ n ≤ 6) and compare them to results from other approaches and experiments, where available. Among the calculated properties we discuss equilibrium structural parameters, vibrational frequencies, electric dipole moments, IR intensities, dissociation energies, barriers for rearrangement by proton tunneling, NMR chemical shifts and spin couplings for 1H and 19F, and magnetic susceptibilities. It is found that density functional (particularly BLYP) and even more so hybrid approaches (particularly B3LYP) provide useful results. However, we show that due to some characteristic deficiencies, these are in general not competitive with more quantitative results from large basis set MP2 calculations. The calculated magnetic properties do not indicate any "aromaticity" connected to a hypothetical electronic ring current. © 1997 John Wiley & Sons, Inc.