Electronic excitations and the Becke-Johnson potential : The need for and the problem of transforming model potentials to functional derivatives

摘要

Constructing approximations for the exchange-correlation (xc) potential in density functional theory instead of the energy appears attractive because it may provide for a way of easily incorporating desirable features such as a particle number discontinuity into xc functionals. However, xc potentials that are constructed directly are problematic: An xc potential that is not a priori derived as a functional derivative of some xc energy functional is most likely not a functional derivative of any density functional at all. This severely limits the usefulness of directly constructed xc potentials, e.g., for calculating electronic excitations. For the explicit example of the Becke-Johnson (BJ) potential we discuss defining corresponding energy expressions by density path integrals. We show that taking the functional derivative of these energies does not lead back to potentials that are close to the BJ one, and the new potentials do not share the attractive features of the original BJ expression. With further examples we demonstrate that this is a general finding and not specific to the BJ potential form.