Computing the Fukui function from ab initio quantum chemistry: approaches based on the extended Koopmans’ theorem

The extended Koopmans’ theorem is related to Fukui function, which measures the change in electron density that accompanies electron attachment and removal. Two approaches are used, one based on the extended Koopmans’ theorem differential equation and the other based directly on the expression of the ionized wave function from the extended Koopmans’ theorem. It is observed that the Fukui function for electron removal can be modeled as the square of the first Dyson orbital, plus corrections. The possibility of useful generalizations to the extended Koopmans’ theorem is considered; some of these extensions give approximations, or even exact expressions, for the Fukui function for electron attachment.