Describing Molecular Polarizability by a Bond Capacity Model.

ABSTRACT

We propose a bond capacity model for describing molecular polarization in force field energy functions at the charge-only level. Atomic charges are calculated by allowing charge to flow between atom pairs according to a bond capacity and a difference in electrostatic potential. The bond capacity is closely related to the bond order and decays to zero as the bond distance is increased. The electrostatic potential is composed of an intrinsic potential, identified as the electronegativity, and a screened Coulomb potential from all other charges. The bond capacity model leads to integer fragment charges upon bond dissociation and displays linear scaling of the polarizability with system size. Bond capacity parameters can be derived from reference molecular polarizabilities, while electronegativity parameters can be derived from reference atomic charges or a reference molecular electrostatic potential. Out-of-plane polarization for planar systems is modeled by off-nuclei charge sites. The model is shown to be able to reproduce anisotropic reference molecular polarizabilities with an accuracy of ∼10% using a limited set of bond capacity parameters and can describe both inter- and intramolecular polarization.