DFT + U Simulation of the X-ray Absorption Near-edge Structure of Bulk UO2 and PuO2

Jiali Chen, Peter Blaha, Nikolas Kaltsoyannis

Research output: Contribution to journalArticlepeer-review

Abstract

Hubbard U corrected density functional theory within the periodic boundary condition model in the WIEN2k code is used to simulate the actinide LIII and O K edge X-ray absorption near-edge structure (XANES) for UO2 and PuO2. Spin-orbit coupling effects are included, as are possible excitonic effects using supercells with a core-hole on one of the atoms. Our calculations yield spectra in excellent agreement with previous experiments, and superior to previous simulations. Density of states analysis reveals the mechanism behind the XANES peaks: the main contribution to the U/Pu LIII edges comes from the U/Pu d states hybridized with O p states, while as expected the O p states primarily determine the O K edges of both UO2 and PuO2. The O K edges also feature O p hybridizing with U/Pu d and f states in the low energy region, and with U/Pu s and p states for the higher energy peaks.
Original languageEnglish
Pages (from-to)17994-18000
JournalJournal of Physical Chemistry
Volume127
Publication statusPublished - 5 Sept 2023

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