Quantifying Delocalization and Static Correlation Errors by Imposing (Spin)Population Redistributions through Constraints on Atomic Domains.

Abstract

The failure of many density functional approximations can be traced to their behavior under fractional (spin)population redistributions in the asymptotic limit toward infinite bonding distances, which should obey the flat-plane conditions. However, such errors can only be characterized sufficiently in terms of those redistributions if exact energies are available for many possible (spin)population redistributions at different bonding distances. In this study, we propose to model such redistributions by imposing (spin)populations on atomic domains by constraining full configuration interaction wave functions. The resulting N-representable descriptions of small hydrogen chains at different bonding distances allow us to computationally illustrate the effects of the flat-plane conditions in the limit to infinite bond distances, leading to more chemical insight into those flat-plane conditions. As the proposed methodology is able to capture the effects of the flat plane conditions, it could be used to generate the reference data that is required to measure the extent to which approximate methods violate the requirements of the exact functional, leading to a quantification of the delocalization and static correlation error of such methods.