Valence State of Pb in Transition Metal Perovskites PbTMO3 (TM= Ti, Ni) Determined From X-Ray Absorption Near-Edge Spectroscopy

We present a combined experimental and theoretical Pb‐L3 X‐ray absorption near‐edge spectroscopy (XANES) to investigate the chemical state of Pb in transition metal perovskites PbTMO3 (TM= Ti, Ni). A pre‐edge feature originated from the excitation of a 2p core electron to the 6s orbital is only observed in PbNiO3, from which the valence of Pb is determined to be Pb4+ with two 6s holes. However, no such 2p–6s related excitation was observed in PbTiO3, indicating the formation of Pb2+ with fully occupied 6s2 state in this materials. Our results demonstrate that this pre‐edge peak from dipole allowed 2p–6s transition is a sensitive finger‐print of the Pb valence state in solid state materials.