Probing Sulfur Chemical And Electronic Structure With Experimental Observation And Quantitative Theoretical Prediction Of K Alpha And Valence-To-Core K Beta X-Ray Emission Spectroscopy

An extensive experimental and theoretical study of the K alpha and K beta high-resolution X-ray emission spectroscopy (XES) of sulfur-bearing systems is presented. This study encompasses a wide range of organic and inorganic compounds, including numerous experimental spectra from both prior published work and new measurements. Employing a linear-response time-dependent density functional theory (LR-TDDFT) approach, strong quantitative agreement is found in the calculation of energy shifts of the coreto-core K alpha as well as the full range of spectral features in the valence-to-core K beta spectrum. The ability to accurately calculate the sulfur K alpha energy shift supports the use of sulfur K alpha XES as a bulk-sensitive tool for assessing sulfur speciation. The fine structure of the sulfur K beta spectrum, in conjunction with the theoretical results, is shown to be sensitive to the local electronic structure including effects of symmetry, ligand type and number, and, in the case of organosulfur compounds, to the nature of the bonded organic moiety. This agreement between theory and experiment, augmented by the potential for high-access XES measurements with the latest generation of laboratory-based spectrometers, demonstrates the possibility of broad analytical use of XES for sulfur and nearby third-row elements. The effective solution of the forward problem, i.e., successful prediction of detailed spectra from known molecular structure, also suggests future use of supervised machine learning approaches to experimental inference, as has seen recent interest for interpretation of X-ray absorption near-edge structure (XANES).