Prediction of the structures of hydrogen-bonded complexes using the laplacian of the charge density

Abstract

The laplacian of the charge density is used to predict the structures and geometries of hydrogen-bonded gas-phase complexes of the type BASE-HF. The bases used are N₂, OC, SC, OCO, SCO, HCN, N₂O, HCP, H₂O, H₂S, H₃N, H₃P, O₃, OSO, H₂CO, HF, HCl, N₂S and H₂CS. Many of the weaker complexes have not been characterized experimentally, and so, results of full 6–31 G** geometry optimizations are presented. The laplacian of the charge density, ∇²ρ, determines where charge is locally concentrated and depleted. The point where ∇²ρ attains its maximum magnitude in a region of charge concentration in the base defines the site of electrophilic attack by the acidic H of HF. The angle of electrophilic attack predicted in this manner is compared with the ab initio equilibrium angle that the hydrogen of HF makes with the base. In general, the angles predicted using the laplacian are in good agreement with the ab initio and experimental results. The present results are also compared with those obtained from electrostatic models.