Interplay of point multipole moments and charge penetration for intermolecular electrostatic interaction energies from the University at Buffalo pseudoatom databank model of electron density

Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials

4 years ago

Interplay of point multipole moments and charge penetration for intermolecular electrostatic interaction energies from the University at Buffalo pseudoatom databank model of electron density

Paulina M. Dominiak, Prashant Kumar, Sławomir A. Bojarowski

The strength of the University at Buffalo DataBank (UBDB) in Ees estimation is mainly due to charge overlap effects because the UBDB offers continuous representation of charge density which allows for a direct account of charge penetration in the derivation of electrostatic energies. In the UBDB model, these effects begin to play an important role at distances below twice the equilibrium distance and significantly increase as distances decrease. At equilibrium distances they are responsible for 30–50% of Ees for polar molecules and around 90% of Ees for nonpolar molecules. When the energy estimation from the UBDB is reduced to point multipoles, the results are comparable to point charges fitted to electrostatic potentials. On the other hand, particular components of energy from point multipole moments from the UBDB model are sensitive to the type of interaction and might be helpful in the characterization of interactions.University at Buffalo DataBank (UBDB)-derived electrostatic energies () closely approach those computed using quantum mechanics mainly because the UBDB allows for a direct account of charge penetration effects. For interactions between polar molecules, penetration constitutes up to 50% of Ees, but for nonpolar molecules, it may reach 100% of Ees at the equilibrium distance.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1107/S2052520617005510