Efficient construction of exchange and correlation potentials by inverting the Kohn-Sham equations

Given a set of canonical Kohn-Sham orbitals, orbital energies, and an external potential for a many-electron system, one can invert the Kohn-Sham equations in a single step to obtain the corresponding exchange-correlation potential, upsilon(XC)(r). For orbitals and orbital energies that are solutions of the Kohn-Sham equations with a multiplicative upsilon(XC)(r) this procedure recovers upsilon(XC)(r) (in the basis set limit), but for eigenfunctions of a non-multiplicative one-electron operator it produces an orbital-averaged potential. In particular, substitution of Hartree-Fock orbitals and eigen-values into the Kohn-Sham inversion formula is a fast way to compute the Slater potential. In the same way, we efficiently construct orbital-averaged exchange and correlation potentials for hybrid and kinetic-energy-density-dependent functionals. We also show how the Kohn-Sham inversion approach can be used to compute functional derivatives of explicit density functionals and to approximate functional derivatives of orbital-dependent functionals. (C) 2013 AIP Publishing LLC.