Can near-edge structure of the Bi L₃ edge determine the formal valence states of Bi?

We analyse the manner in which local atomic structure affects the identification of Bi valence states in the x-ray absorption near-edge structure (XANES) of the BiL₃ edge, by comparing simulations of the BiL ₃ edges in various polymorphs of Bi₂O₃, NaBiO₃ and Ag₂₅Bi₃O₁₈. We find that while the XANES is certainly sensitive to the ionicity of Bi, it is better described in terms of its sensitivity to the local bond lengths and coordination associated with the valence states of Bi.