Influence of chemical effects on the Li (i = 1–3) subshell X-ray spectra for 79Au compounds

Highlights: • Influences of chemical environment on L X-ray spectra of ₇₉Au compounds have been investigated. • L X-ray emission spectra of ₇₉Au compounds were taken using WDXRF and EDXRF techniques. • Measurements reports significant variation in intensity ratios of different L X-ray components. • Energy shifts of ∼1–7 eV has been notice in Ll and Lγ₁ X-ray emission spectra of ₇₉Au compounds. • Observed chemical effects are attributed to core-valence exchange interactions and crystal effects. The influence of chemical effects on intensity ratios i.e. I_Li/I_Lα (i = l, β₁, β_15,2,3 and β_5/2), I_Lα2/I_Lα1, I_Lj/I_Lβ1 (j = η, γ₁ and γ₅), I_Lk/I_Lγ4 (k = β_6,4, β_10,9/1 and γ_2,3,6) and I_Lβ1/I_Lγ1 and chemical shift of Ll and Lγ₁ X-ray emission peaks for ₇₉Au compound has been investigated using polychromatic high resolution wavelength dispersive X-ray fluorescence (WDXRF). The measured intensity ratios of L X-ray emission spectra were corrected for spectrometers detector efficiencies and self-absorption correction factors. The experimental values of intensity ratios have been compared with the theoretical values evaluated using different set of available fractional emission rates, fluorescence and Coster-Kronig yields. The measurements also report significant energy shift (∼1–7 eV) in Ll and Lγ₁ X-ray peaks of ₇₉Au compounds relative to pure elemental form. The discrepancies in measured intensity ratios and shift in L X-ray emission spectra of ₇₉Au compounds from the theoretical predicated values can be attributed to chemical effects due to core-valence exchange interactions and crystal effects of different ligands attached to central ₇₉Au atom.