Continuing challenges in the parametrization of intermolecular force fields. Towards an accurate description of electrostatic and induction terms

Abstract

The improvement in the description of molecular liquids by statistical mechanics simulations, going beyond the limitations of the pairwise additive approximation, has triggered the development of novel approaches for the design of tractable and reliable sets of electrostatic and induction parameters. Progress made in this direction over the past years is reviewed with an emphasis on the underlying theory of the formalism utilized. Generation of the models of distributed multipoles and polarizabilities relies upon the knowledge of the electrostatic potential and the induction energy mapped on a grid of points around the molecule. Exploitation of the symmetry and the transferability properties of the latter is achieved by means of local atomic frames of reference, which allow the distributed components to be expressed in a simple and compact form. Investigation of the prototypical cases of benzene and naphthalene illustrates the robustness of the methodology for the reproduction of electrostatic and induction interaction energies.