Outstanding improvement in removing the delocalization error by global natural orbital functional.

Abstract

This work assesses the performance of the recently proposed global natural orbital functional (GNOF) against the charge delocalization error. GNOF provides a good balance between static and dynamic electronic correlations leading to accurate total energies while preserving spin, even for systems with a highly multi-configurational character. Several analyses were applied to the functional, namely, (i) how the charge is distributed in super-systems of two fragments, (ii) the stability of ionization potentials while increasing the system size, and (iii) potential energy curves of a neutral and charged diatomic system. GNOF was found to practically eliminate the charge delocalization error in many of the studied systems or greatly improve the results obtained previously with PNOF7.