Raman spectroscopy of the charge- and orbital-ordered state in La0.5Ca0.5MnO3 -: art. no. 144429

Polarized Raman spectra from microcrystals of La0.5Ca0.5MnO3 were studied as a function of temperature, excitation photon energy, and scattering configuration. At temperatures below the transition from ferromagnetic metallic phase to antiferromagnetic insulating charge- and orbital-ordered (COO) phase, several lines appear in Raman spectra excited with photon energies (h) over bar omega (L)<2.5 eV. We argue that their appearance signals ordering and freezing of the Jahn-Teller distortions at this transition temperature into a superstructure with a doubled elementary cell. We suggest a simplified structural model based on an analysis of the normal phonon modes in the COO phase, neglecting the octahedral tilts and containing ordered Mn4+O6 (undistorted) and Mn3+O6 (Jahn-Teller distorted) octahedra. The symmetries of the experimentally observed Raman lines are determined by comparing their relative intensities to those predicted by the polarization selection rules for a finely twinned quasicubic crystal. The most intensive Raman lines are assigned to definite normal modes in close comparison with corresponding modes in COO layered manganites and undoped RMnO3 (R=La, Y).