Density Functional Physicality in Electronic Coupling Estimation: Benchmarks and Error Analysis

Electronic coupling estimates from constrained density functional theory configuration interaction (CDFT-CI) depend critically on choice of density functional. In this Letter, the orbital multielectron self-interaction error (OMSIE), vertical electron affinity (VEA), and vertical ionization potential (VIP) are shown to be the key indicators inherited from the density functional that determine the accuracy of electronic coupling estimates. An error metric η is derived to connect the three properties, based on the linear proportionality between electronic coupling and overlap integral, and the hypothesis that the slope of this line is a function of VEA/VIP, η = (1/N_testset)­Σ_i^testset|−VE^Ref × OMSIE + ΔVE – ΔVE × OMSIE|_i. Based on η, BH&HLYP and LRC-ωPBEh are suggested as the best functionals for electron and hole transfer, respectively. Error metric η is therefore a useful predictor of errors in CDFT-CI electronic coupling, showing that the physical correctness of the density functional has a direct effect on the accuracy of the electronic coupling.