Equilibrium Bond Lengths from Orbital-Free Density Functional Theory

Abstract

This work presents an investigation to model chemical bonding in various dimers based on the atomic fragment approach. The atomic fragment approach is an ab-initio, parameter-free implementation of orbital-free density functional theory which is based on the bifunctional formalism, i.e., it uses both the density and the Pauli potential as two separate variables. While providing the exact Kohn-Sham Pauli kinetic energy when the orbital-based Kohn-Sham data are used, the bifunctional formalism allows for approximations of the functional derivative which are orbital-free. In its first implementation, the atomic fragment approach uses atoms in their ground state to model the Pauli potential. Here, it is tested how artificial closed-shell fragments with non-integer electron occupation perform regarding the prediction of bond lengths of diatomics. Such fragments can sometimes mimic the electronic structure of a molecule better than groundstate fragments. It is found that bond lengths may indeed be considerably improved in some of the tested diatomics, in accord with predictions based on the electronic structure.