Analysis of multi-configuration Kohn-Sham methods

Abstract

We consider the extension of the standard single-determinant Kohn-Sham method to the case of a multiconfiguration trial wavefunction. By applying the rigorous Kohn-Sham method to this case, we construct the proper interacting and non-interacting energy functionals. Following the Hohenberg-Kohn theorem for both energy functionals, we derive the corre-sponding multiconfiguration Kohn-Sham equations. At the end of the analysis we show that, at the ground state, the multiconfiguration wavefunction must collapse into a single-determinant wavefunction, equal to the regular KS wavefunction. We also discuss the non-collapse of the wavefunction in other multiconfiguration density functional theory methods where the auxiliary system is partially interacting.