On the Choice of Reference Orbitals for Linear-Response Calculations of Solution-Phase K-Edge X-Ray Absorption Spectra

The simplest procedures for computing vertical excitation spectra in condensed-phase are configuration interaction with single excitations (CIS) and linear-response time-dependent density functional theory (TDDFT) within the Tamm-Dancoff approximation. In applications to X-ray absorption spectroscopy (XAS), methods like CIS and TDDFT that codify only single excitations into the wave function are prone to catastrophic errors in main-edge and post-edge features whose shapes act as a crucial fingerprint in structural analyses of liquids. We show that these errors manifest primarily due to a lack of orbital relaxation in conventional linear-response theories and that core-ionized (n-1-electron) references, like those of electron-affinity TDDFT, can eliminate the errors in the spectral profile, even in the highest-energy parts of the post-edge. Crucially, we find that single excitations atop core-ionized references are sufficient to elucidate liquid-phase XAS spectra with semi-quantitative accuracy, opening the door for methods like electron-affinity CIS/TDDFT to be used as efficient alternatives to higher-order wave function approaches.