Accurate frozen-density embedding potentials as a first step towards a subsystem description of covalent bonds

Abstract

The frozen-density embedding (FDE) scheme [Wesolowski and Warshel, J. Phys. Chem. 97, 8050 (1993)] relies on the use of approximations for the kinetic-energy component vT [ρ 1, ρ 2] of the embedding potential. While with approximations derived from generalized-gradient approximation kinetic-energy density functional weak interactions between subsystems such as hydrogen bonds can be described rather accurately, these approximations break down for bonds with a covalent character. Thus, to be able to directly apply the FDE scheme to subsystems connected by covalent bonds, improved approximations to vT are needed. As a first step toward this goal, we have implemented a method for the numerical calculation of accurate references for vT. We present accurate embedding potentials for a selected set of model systems, in which the subsystems are connected by hydrogen bonds of various strength (water dimer and F-H- F-), a coordination bond (ammonia borane), and a prototypical covalent bond (ethane). These accurate potentials are analyzed and compared to those obtained from popular kinetic-energy density functionals. © 2010 American Institute of Physics.