Electron-Affinity Time-Dependent Density Functional Theory: Formalism and Applications to Core-Excited States

The lack of particle–hole attraction and orbital relaxation within time-dependent density functional theory (TDDFT) lead to extreme errors in the prediction of K-edge X-ray absorption spectra (XAS). We derive a linear-response formalism that uses optimized orbitals of the n – 1-electron system as the reference, building orbital relaxation and a proper hole into the initial density. Our approach is an exact generalization of the static-exchange approximation that ameliorates the particle–hole interaction error associated with the adiabatic approximation and reduces errors in TDDFT XAS by orders of magnitude. With a statistical performance of just 0.5 eV root-mean-square error and the same computational scaling as TDDFT under the core–valence separation approximation, we anticipate that this approach will be of great utility in XAS calculations of large systems.