Local distortion of MnO$_6$ octahedron in La$_{1-x}$Sr$_x$MnO$_{3+\delta}$ (x = 0.1 to 0.9): an EXAFS study

TL;DR

This study uses EXAFS to reveal local distortions in MnO$_6$ octahedra of La$_{1-x}$Sr$_x$MnO$_{3+\delta}$, showing a transition from Jahn-Teller to breathing distortions around x=0.4.

Contribution

It provides detailed local structural insights into MnO$_6$ distortions across different compositions, highlighting a transition in distortion type.

Findings

Local Mn site structure differs from global structure, especially for x ≤ 0.4.

Maximum distortion occurs at x=0.1 with distinct bond lengths.

Transition from Jahn-Teller to breathing distortion at x=0.4.

Abstract

Room temperature Mn K-edge extended x-ray absorption fine structure (EXAFS) studies were carried out on La$_{1-x}$Sr$_x$MnO$_{3+\delta}$ (x = 0.1 to 0.9) compounds. It is found from the detailed EXAFS analysis that the local structure around Mn sites is different from the global structure inferred from x-ray diffraction, especially for x <= 0.4, indicating presence of local distortions in MnO$_6$ octahedra. For the rhombohedral compounds, x = 0.1 to 0.3 the distortion is maximum for x = 0.1 and two bond lengths are seen- short one in basal plane and long one in apical plane. For compounds with x = 0.4 to 0.8 two short bonds in basal plane and four long bonds- two in the basal plane and remaining two in the apical plane are seen. For the compounds up to x = 0.3 compositions long bond length decreases and short bond length increases with increase in x whereas for the compounds 0.4 <= x <= 0.8 both types of bond lengths decrease. Such behaviour of bond lengths is an indication of the changed nature of distortion from Jahn-Teller type to breathing type at x = 0.4 composition.