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DOE OSTI · 3015471

Kβ X-ray Emission Spectra Analysis Using Bayesian Optimization

Ranjan, Rishabh [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0009000803974579)·Di, Zichao Wendy [Argonne National Laboratory (ANL), Argonne, IL (United States)]·Wolfman, Mark [Argonne National Laboratory (ANL), Argonne, IL (United States)]·Kelly, Shelly D. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:000000018996628X)·Hwang, In-Hui [Pohang Accelerator Lab. (PAL) (Korea, Republic of)]·Sun, Chengjun [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000191588337)
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Abstract

The Kβ X-ray emission spectrum of 3 d transition metals is rich with electronic and structural information due to strong exchange interactions with the valence shell of the metal, and has become crucial for understanding their spin and oxidation states. The spectrum is commonly treated using crystal-field multiplet theory, a semi-empirical theory that uses tunable parameters to control the strength of the effects present in X-ray emission spectroscopy (XES). However, determining the experimental values of these parameters remains a challenge. We present a methodology that applies Bayesian optimization to crystal-field multiplet theory to determine parameter values. The algorithm is tested on the X-ray emission spectra of a collection of Mn, Co, and Ni oxides. We are able to find optimal values for the four most impactful parameters: Slater−Condon reduction factors F dd , F pd , and G pd , and crystal field splitting 10 Dq . The algorithm produces significantly improved accuracy compared to current analysis methods, and probes interparameter dependencies by modeling the error landscape. This advancement enhances XES analysis by offering an approach of obtaining quantitative electronic structural information on 3 d transition metal valence shells, facilitating applications across various scientific fields.

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Bayesian optimizationXEScrystal field multiplet theorymetal oxidesslater-condon parameters

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Ranjan, Rishabh [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0009000803974579), Di, Zichao Wendy [Argonne National Laboratory (ANL), Argonne, IL (United States)], Wolfman, Mark [Argonne National Laboratory (ANL), Argonne, IL (United States)], Kelly, Shelly D. [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:000000018996628X), Hwang, In-Hui [Pohang Accelerator Lab. (PAL) (Korea, Republic of)], Sun, Chengjun [Argonne National Laboratory (ANL), Argonne, IL (United States)] (ORCID:0000000191588337). 2025-10-22. Kβ X-ray Emission Spectra Analysis Using Bayesian Optimization. https://doi.org/10.1021/photonsci.5c00007

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