New spectroscopic and diffraction data to solve the vanadium-doped zircon pigment conundrum

Electronic structure of ZrSiO₄ with interstitially doped V

“…Recently, Ardit et al performed Rietveld structural analysis, electronic absorption spectroscopy, and electronic paramagnetic resonance measurements on V-doped ZrSiO 4 and discussed the V 3d position in the bandgap of ZrSiO 4 . 20) Their structural results support the position of V 4+ at the interstitial 16g site (local symmetry C 2 ), as reported by Niesert et al 11) Using the angular overlap model (AOM) method, they also concluded that the ground, first, and third excited states consist of linear combinations of d z 2 , d xy , and d x 2 ¹y 2 , respectively, while the second and fourth excited states are pure d xz and d yz . The AOM method is a qualitative method used for complex molecules and cannot be simply compared with first-principles calculations on solid crystals.…”