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Perovskites with Bi or Pb on the A-site host a number of interesting and yetto be understood phenomena such as negative thermal expansion in BiNiO$_3$. Weemploy hard X-ray photoemission spectroscopy of Ni 2$p$ core-level as well asvalence band to probe the electronic structure of BiNiO$_3$ and PbNiO$_3$. Theexperimental results supported by theoretical calculations using dynamicalmean-field theory reveal essentially identical electronic structure of the Ni-Osubsystem typical of Ni$^{2+}$ charge-transfer insulators. The two materialsare distinguished by filling of the Bi(Pb)-O antibonding states in the vicinityof the Fermi level, which is responsible for the Bi disproportionation inBiNiO$_3$ at ambient pressure and absence of similar behavior in PbNiO$_3$. Thepresent experiments provide evidence for this conclusion by revealing thepresence/absence of Bi/Pb $6s$ states at the top of the valence band in the twomaterials.

Mechanism of intermetallic charge transfer and bond disproportionation in BiNiO$_3$ and PbNiO$_3$ revealed by hard X-ray photoemission spectroscopy