Extending Conceptual Density Functional Theory toward First-Order Reduced Density Matrices: An Open Subsystems Viewpoint on the Fukui Matrix.

Abstract

As a matrix extension of the Fukui function, a reactivity descriptor grounded within Conceptual Density Functional Theory, the Fukui matrix extends Frontier Molecular Orbital Theory to correlated regimes with its eigendecomposition in Fukui occupations and Fukui naturals. Despite successful applications, the questions remain as to whether replacing a quantity derived from a purely density-based framework by its matrix extension is theoretically well-founded and what chemical information is contained in the corresponding eigendecomposition. In this study, we show that the matrix extension of the Fukui function is only well-defined if one also generalizes the external potential to become nonlocal, leading to the introduction of Conceptual First-Order Reduced Density Matrix Functional Theory. By interpreting the Anderson impurity model from an interacting open subsystem perspective, we show how Fukui occupations and Fukui naturals reflect the influence of an increasing (static) correlation and which characteristic patterns we should expect within a molecular context. This study represents a step in generalizing Conceptual Density Functional Theory beyond its density-based perspective.