Toward a Physically Motivated Force Field: Hydrogen Bond Directionality from a Symmetry-Adapted Perturbation Theory...

It is argued here that the functional forms adopted in almost all popular force fields are too restrictive to allow for accurate and physics-based parametrization. Some important modifications are suggested based on symmetry-adapted intermolecular perturbation theory, which directly separates the intermolecular interaction energy into four physically interpretable components: electrostatics, exchange-repulsion, dispersion, and induction. The exact electrostatic energy is approximated as a sum of the short-range contribution (due to charge density penetration effects), included explicitly, and the long-range part (via distributed atomic multipoles), whereas the induction energy is evaluated by means of the distributed induced damped point dipole model. The dispersion energy is fitted to a simple analytical function and the exchange-repulsion contribution is approximated by the overlap of the valence-only electron charge densities of monomers. The water dimer is used to illustrate the approach and to discuss its potential and possible improvements. Analysis of the four main contributions to the binding energy allows for a deeper understanding of the hydrogen bond directionality. It is found that a notorious geometrical preference in the water dimer results mainly from large polarization contributions, including induction and dispersion.