Abstract
We use temperature-dependent inelastic light scattering to study the origin of the strong multiphonon scattering of a local oxygen breathing mode present in the mixed -site orthorhombic (space group ) perovskite but absent in isostructural and . It is seen that the multiphonon scattering is critically sensitive to the presence of both Fe and Cr ions on the site. These results support our interpretation that the multiphonon scattering is activated by local electron-phonon interactions according to the Franck-Condon picture following an Fe-Cr charge transfer. Further, substitution is performed on the , 0.04, and 0.5 compounds and clearly shows that all modes appearing above the first-order phonon-scattering region in these compounds originate from higher-order oxygen stretching vibrations. In particular this is the case for the strong second-order scattering dominating the scattering response in . Accordingly we propose that these modes are generated by infrared-active longitudinal optical (IR LO) two-phonon and combination scattering activated by Fröhlich interaction. For and 0.04 the characteristic IR LO two-phonon and Franck-Condon multiphonon-scattering profiles mix. We also study the influence of isovalent cation substitution and Sr doping in (, Nd, and Gd) and (, 0.16, and 0.5) on the strong electron-phonon coupling present in . The Franck-Condon effect in , is not significantly affected by isovalent -site substitution, despite the increasing orthorhombic distortion associated with decreasing -site ionic radii. On the contrary, aliovalent Sr doping causes a rapid decrease in the Franck-Condon scattering. This shows that the strong electron-phonon coupling in these compounds is highly sensitive to local lattice and electronic decoherence but insensitive to global lattice distortions. Finally, a preliminary assignment of the and phonon modes in (, Nd, and Gd) is made based on the present observations and published results for and . The modes associated with oxygen octahedral tilt and bending vibrations are heavily influenced by the magnitude of the orthorhombic distortion.
7 More- Received 31 January 2008
DOI:https://doi.org/10.1103/PhysRevB.78.235103
©2008 American Physical Society