Local atomic and electronic structure in LaMnO_3 across the orbital ordering transition

TL;DR

This study investigates the local atomic and electronic changes in LaMnO_3 across its orbital ordering transition using x-ray absorption spectroscopy, revealing persistent Jahn-Teller distortions and subtle electronic structure modifications.

Contribution

It provides detailed insights into the local structural and electronic behavior of LaMnO_3 during the orbital ordering transition, highlighting the coexistence of local distortions with increased thermal disorder.

Findings

Mn-O bond lengths remain split across the transition

Disorder in super-exchange angles decreases at the transition

Electronic structure shows increased covalence at transition

Abstract

The local atomic disorder and the electronic structure in the environment of manganese atoms in LaMnO_3 has been studied by x-ray absorption spectroscopy, over a temperature range (300K to 870K) covering the orbital ordering transition (710K). The Mn-O distances splitting into short and long bonds (1.95 and 2.15A) is kept across the transition temperature, so that the MnO_6 octahedra remain locally Jahn-Teller distorted. Discontinuities in the Mn local structure are identified in the extended x-ray fine structure spectra at this temperature, associated to a reduction of the disorder in the super-exchange angle and to the removal of the anisotropy in the radial disorder within the coordination shell. Subtle changes in the electronic local structure also take place at the Mn site at the transition temperature. The near edge spectra show a small drop of the Mn 4p hole count and a small enhancement in the pre-edge structures at the transition temperature. These features are associated to an increase of the covalence of the Mn-O bonds. Our results shed light on the local electronic and structural phenomena in a model of order-disorder transition, where the cooperative distortion is overcome by the thermal disorder.