Localised and Delocalised Charge Distribution in a Diamine Cation and Rydberg Excited State: A Challenging Test for Density Functionals

Abstract

The balance between localised and delocalised electron distribution in the N,N'-dimethylpiperazine (DMP) molecule in the 3s Rydberg excited state and in the fully ionised DMP$^+$ provides a valuable test of density functionals, in particular the weight of Fock exchange (FE) in hybrid functionals and the scaling of explicit orbital-based self-interaction correction (SIC) applied to less elaborate functionals. We present results of calculations using density functionals of all rungs of Jacob's ladder, ranging from LDA to the DM21 machine learned local hybrid as well as double hybrids. For DMP$^+$, the commonly used hybrid functionals, such as PBE0(.25) with FE weight of 0.25, as well as PBE0(.32) with a weight of 0.32 only produce the more delocalised charge. The latter mimics the DM21 energy surface well. However, hybrid functionals with stronger FE, such as BHLYP and PBE0(.50) as well as some double hybrid functionals, also produce local energy minima corresponding to localised charge. When full SIC is applied to the PBE functional, an energy surface analogous to hybrid functionals with FE weight of 0.50 is obtained, while the scaling of SIC by 0.50, which has previously been shown to give improved atomisation energy and band gap of solids, only produces the more delocalised charge. For the 3s Rydberg excited state of DMP, two types of configurations with a localised hole are obtained in calculations using the PBE0(.32) functional, in addition to the delocalised hole, but only the latter is found with the PBE functional, showing that a significant reduction of the self-interaction error is needed in order to obtain agreement between density functional calculations and experimental measurements of the Rydberg state