The effects of atomic multipole moments obtained by the potential‐derived method on hydrogen bonding

Abstract A potential‐derived atomic multipole method called the cumulative potential‐derived atomic multipole method is developed, with which electrostatic atomic multipole moments are derived by fitting the molecular electric potential in a cumulative way. It is applied to the hydrides of N, O, F, S, Cl, and methanol and the hydrogen‐bonded dimers formed between them. The relationship between atomic multipole moments and molecular charge distributions is found. The structures calculated with Buckingham's electrostatic model are in good agreement with experiments. The phenomena of nonlinear structures of most H‐bonded complexes—the deviations of symmetry axes of electron donors from H bonds—and correct distinguishing between two alternative structures are attributed to atomic dipole and quadrupole moments. Compared with other methods, this method has a quantitative and qualitative advantage and simple algorithm. The main conclusion is that the atomic multipole moments play a substantial role, although a potential‐derived charge model was deemed sufficient previously. © 1993 John Wiley & Sons, Inc.