Raman scattering study of charge ordering in beta-Ca0.33V2O5
2003
Polarized Raman spectra of the calcium vanadium oxide bronze beta-Ca0.33V2O5 are measured in the temperature range between 300 K and 20 K. The charge ordering phase transition at about 150 K is characterized by the appearance of the new Raman-active modes in the spectra, and by anomalies in the electronic background scattering. The high temperature Raman scattering spectra of beta-Ca0.33V2O5 are in apparent resemblance with those of alpha'-NaV2O5, which suggests that there is a similar charge-phonon dynamics in both compounds. The study of dynamical properties and the symmetry analysis of the Raman modes show that in the mixed valence state of beta-Ca0.33V2O5 the electrons are delocalized into V1-O5-V3 orbitals. We propose that in the charge ordered state below 150 K the d-electrons localize within V1-V3 ladders, either in "zig-zag" fashion like in alpha'-NaV2O5 or in the forms of the double chains like in gamma-LiV2O5.
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