  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
phase transformation from the Pbnm and R3-c phase at a chemical composition of
x=0.625. Correlation of octahedral distortion and phase transition 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 phase transition. 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 phase transformation. 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 a in-depth analysis of the
structure correlated phase transition of the LFO-LMO solid solution.
