title: Experimental and theoretical comparison of the O K-edge nonresonant inelastic X-ray scattering and X-ray absorption spectra of NaReO4.
abstract: Accurate X-ray absorption spectra (XAS) of first row atoms, e.g., O, are notoriously difficult to obtain due to the extreme sensitivity of the measurement to surface contamination, self-absorption, and saturation affects. Herein, we describe a comprehensive approach for determining reliable O K-edge XAS data for ReO(4)(1-) and provide methodology for obtaining trustworthy and quantitative data on nonconducting molecular systems, even in the presence of surface contamination. This involves comparing spectra measured by nonresonant inelastic X-ray scattering (NRIXS), a bulk-sensitive technique that is not prone to X-ray self-absorption and provides exact peak intensities, with XAS spectra obtained by three different detection modes, namely total electron yield (TEY), fluorescence yield (FY), and scanning transmission X-ray microscopy (STXM). For ReO(4)(1-), TEY measurements were heavily influenced by surface contamination, while the FY and STXM data agree well with the bulk NRIXS analysis. These spectra all showed two intense pre-edge features indicative of the covalent interaction between the Re 5d and O 2p orbitals. Density functional theory calculations were used to assign these two peaks as O 1s excitations to the e and t(2) molecular orbitals that result from Re 5d and O 2p covalent mixing in T(d) symmetry. Electronic structure calculations were used to determine the amount of O 2p character (%) in these molecular orbitals. Time dependent-density functional theory (TD-DFT) was also used to calculate the energies and intensities of the pre-edge transitions. Overall, under these experimental conditions, this analysis suggests that NRIXS, STXM, and FY operate cooperatively, providing a sound basis for validation of bulk-like excitation spectra and, in combination with electronic structure calculations, suggest that NaReO(4) may serve as a well-defined O K-edge energy and intensity standard for future O K-edge XAS studies.
authors.affiliation: Los Alamos National Laboratory, Los Alamos, New Mexico 87545, USA.
authors.forename: Joseph A
authors.initials: JA
authors.lastname: Bradley
authors.forename: Ping
authors.initials: P
authors.lastname: Yang
authors.forename: Enrique R
authors.initials: ER
authors.lastname: Batista
authors.forename: Kevin S
authors.initials: KS
authors.lastname: Boland
authors.forename: Carol J
authors.initials: CJ
authors.lastname: Burns
authors.forename: David L
authors.initials: DL
authors.lastname: Clark
authors.forename: Steven D
authors.initials: SD
authors.lastname: Conradson
authors.forename: Stosh A
authors.initials: SA
authors.lastname: Kozimor
authors.forename: Richard L
authors.initials: RL
authors.lastname: Martin
authors.forename: Gerald T
authors.initials: GT
authors.lastname: Seidler
authors.forename: Brian L
authors.initials: BL
authors.lastname: Scott
authors.forename: David K
authors.initials: DK
authors.lastname: Shuh
authors.forename: Tolek
authors.initials: T
authors.lastname: Tyliszczak
authors.forename: Marianne P
authors.initials: MP
authors.lastname: Wilkerson
authors.forename: Laura E
authors.initials: LE
authors.lastname: Wolfsberg