Insights into Direct Methods for Predictions of Ionization Potential and Electron Affinity in Density Functional Theory.

Abstract

Vertical ionization potential (IP) and electron affinity (EA) are fundamental molecular properties, while the Δ method and the direct method are the widely used approaches to compute these properties. The Δ method is calculated by taking the total energy difference of the initial and final states, whose reliability is seriously affected by the issue associated with the imbalanced treatment of these two states. The direct method based on the derivatives involving only one single-state calculation can yield a quasi-particle spectrum whose accuracy, on the other hand, is mostly affected by the levels of approximate molecular structure theories. Because of the aforementioned issues, EA prediction can be particularly problematic. Here we present, for the first time, an analytic theory on the derivation and realization of generalized Kohn-Sham (KS) eigenvalues of doubly hybrid (DH) functionals that depend on both occupied and unoccupied orbitals. The method based on the KS eigenvalues of neutral systems, termed the NKS method, is found to suffer little from the imbalance issue, while it is only the NKS method that can offer accurate EA prediction from a good functional approximation, such as the XYG3 type of DH functionals. Being less sensitive to the size of basis sets, the NKS method is of great significance for its application to large systems. The insights gained in this work are useful for the calculation of properties associated with small energy differences while emphasizing the importance of the development of generalized functionals that rely on both occupied and unoccupied orbitals.