Structural change from Pbnm to R3̅c phase with varying Fe/Mn content in (1-x) LaFeO₃.xLaMnO₃ solid solution leading to modifications in octahedral tilt and valence states

A theoretically supported experimental study of the (1-x)LaFeO₃.xLaMnO₃ (LFO-LMO) solid solution is being reported for the first time which reveals a structural change from the Pbnm and R3̅c phase at a chemical composition of x = 0.625. Correlation of octahedral distortion and structural change was extensively investigated using x-ray photoelectron spectroscopy (XPS), Raman and x-ray diffraction (XRD) measurements and density functional theory (DFT) calculation. A detailed study of the structural lattice parameters, bond lengths, bond angles have been done, supported by valence state and electronic properties studies. All the above parameters show a correlated modification to the structural change. The distortion and tilting of the BO₆ octahedra has been studied as a function of different Fe:Mn content and expressed by Glazer representation from the refined Crystallographic Information Files (CIF). The angle of tilting from the central non-tilted position also shows a correlated modification with the structural change. The valence state and size of cations influences the octahedral tilting. Octahedral volume is reduced as the entire perovskite structure is relatively flattened with increasing Mn-content implying a flattening of both the BO₆ octahedra and the La₈O₆ cage. The vibrational properties were studied experimentally and supported by DFT phonon calculations, detailing the displacement pattern (eigen vectors) revealing considerable insight into the lattice dynamics of the compounds. The optoelectronic modifications in the band properties were studied experimentally and supported with theory. Hence, this manuscript is an in-depth analysis of the structure-correlated structural change of the LFO-LMO solid solution.