Core Excitations with Excited State Mean Field and Perturbation Theory

Abstract

We test the efficacy of excited state mean field theory and its excited-state-specific perturbation theory on the prediction of K-edge positions and X-ray peak separations. We find that the mean field theory is surprisingly accurate, even though it contains no accounting of differential electron correlation effects. In the perturbation theory, we test multiple core-valence separation schemes and find that, with the mean field theory already so accurate, electron-counting biases in one popular separation scheme become a dominant error when predicting K-edges. Happily, these appear to be relatively easy to correct for, leading to a perturbation theory for K-edge positions that is lower scaling and more accurate than coupled cluster theory and competitive in accuracy with recent high-accuracy results from restricted open-shell Kohn Sham theory. For peak separations, our preliminary data show excited state mean field theory to be exceptionally accurate, but more extensive testing will be needed to see how it and its perturbation theory compare to coupled cluster peak separations more broadly.

arXiv comment7 pages, 2 figures, 3 tables

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• A benchmark study of core-excited states of organic molecules computed with the generalized active space driven similarity renormalization group
• MP2-based composite extrapolation schemes can predict core-ionization energies for first-row elements with coupled-cluster level accuracy
• Leveraging configuration interaction singles for qualitative descriptions of ground and excited states: state-averaging, linear-response, and spin-projection