Unraveling the temperature-responsive charge-disproportionation in BaBiO$_3$

TL;DR

This paper investigates how temperature affects charge disproportionation in BaBiO$_3$, revealing a transition from covalent to more ionic character and changes in electronic structure as temperature decreases.

Contribution

It provides detailed experimental evidence of temperature-induced modifications in charge distribution and hybridization in BaBiO$_3$, highlighting the dynamic nature of charge disproportionation.

Findings

Charge disproportionation decreases at lower temperatures.

Bi-O hybridization reduces with decreasing temperature.

O 2$p$ hole density diminishes as temperature drops.

Abstract

This study shows that the charge disproportionation at the Bi site in BaBiO$_3$ alters as a function of temperature. Decreasing the temperature from 300K down to 160K leads to a significant modification of the density of states corresponding to the Bi-O hybridized band near the Fermi level (E$_\text{F}$). This modification indicates reduction of Bi 6$sp$ - O 2$p$ hybridization and O 2$p$ spectral weight near E$_\text{F}$. The strong decrement of covalency at lower temperatures is accompanied by a decrement in O 2$p$ hole density due to possible charge transfer from Bi 6$s$ to the O 2$p$ band. Bi-charge state analysis from Bi-4$f$ core-level spectra showed that at 300K, $\delta$ (charge difference between alternate Bi sites) value in 4$\pm\delta$ is much less than at 160K, which reveals the transition towards the ionic nature of CD or static CD in BBO at low temperature. On the other hand, O 1$s$ core-level spectra displayed an asymmetric shape, and temperature-dependent modifications of the asymmetric shape and intensity have been observed. This highlights the significant influence of the O 2$p$ band hole on the dynamical CD at the Bi site.