How Much Do We Understand Ce L3 XANES? Ab Initio Insights into Configuration-Specific Screening at the Multiplet--Continuum Frontier

Abstract

How can local multiplet signatures, collective core-hole screening, and an extended photoelectron be reconciled in Ce $L_3$ x-ray absorption near-edge spectra? Motivated by the question raised by Kvashnina [Chem. Eur. J. 30, e202400755 (2024)], we address this challenge using XSpectruplet, which couples local multiplet dynamics to continuum photoelectron propagation in self-consistent Kohn--Sham screening potentials. For Ce${}^{4+}$ in CeO${}_2$, our heuristic search identifies primary and secondary stationary screening states whose calculated white-line maxima lie about 7.3~eV apart after including their independently calculated total-energy difference, yet both retain the same effective local spectroscopic $4f^0$ sector. Their squared overlaps with the unrelaxed sudden reference give approximate statistical weights of 63\% and 30\%, respectively, within an independent-channel description. Their contrasting screening responses arise from collective rehybridization of occupied orbitals, rather than occupation of an additional localized $4f$ spectator, and produce contributions in both the main white-line and satellite regions. Ce${}^{3+}$ in monazite CePO${}_4$ provides the contrasting case of a localized $4f^1$ spectator participating explicitly in the multiplet dynamics. Independent relaxation of neutral $4f$ and white-line states gives a CeO${}_2$ pre-edge--white-line gap of 10.51~eV, close to the experimental separation of approximately 10.7~eV. Its excess over the fixed-background spectral gap defines a net correction, which we transfer heuristically to CePO${}_4$ without changing its local multiplet structure. This gives an estimated CePO${}_4$ gap of 6.38~eV, compared with approximately 8.1~eV experimentally. Distinct spectral contributions can thus arise from collective screening without a change in the effective local configuration.