Contribution of the Multiplicity Fluctuation in the Temperature Dependence of Phonon Spectra of Rare-Earth Cobaltites

Orlov, Yuri S.; Sokolov, Alexey E.; Dudnikov, Vyacheslav A.; Shulga, Karina V.; Volochaev, Mikhail N.; et al. Molecules.

We have studied, both experimentally and theoretically, the unusual temperature dependence of the phonon spectra in NdCoO3, SmCoO3 and GdCoO3, where the Co3+ ion is in the low-spin (LS) ground state, and at the finite temperature, the high-spin (HS) term has a nonzero concentration nHS due to multiplicity fluctuations. We measured the absorption spectra in polycrystalline and nanostructured samples in the temperature range 3–550 K and found a quite strong breathing mode softening that cannot be explained by standard lattice anharmonicity. We showed that the anharmonicity in the electron–phonon interaction is responsible for this red shift proportional to the nHS concentration.