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Chemical Pressure, Structural Instability, and IR-Active Phonons in a Series of Rare-Earth Analogues of Francisite Cu3RE(SeO3)2O2Cl

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Abstract

ATR and transmission spectra of a series of rare-earth francisite-like phases Cu3RE(SeO3)2O2Cl (RE is a rare earth element, RE = Nd, Sm, Eu, Gd, Dy, Ho, Tm, Yb) were studied. The frequencies of the IR-active phonons of the crystals under study were determined. In the dependences of phonon frequencies on the ionic radius in a series of isostructural compounds, two tendencies are observed: a hardening of frequencies due to an increase in chemical pressure and a softening of the vibration frequencies, in which rare-earth ions are involved, due to an increase in the mass of a specific rare-earth ion. In the Cu3Dy(SeO3)2O2Cl crystal, an anomalous softening of low-frequency phonons at low temperatures was observed, which was apparently associated with the structural instability of the compound.

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Funding

The work of N.N.N., VA.Ya. and S.A.K. (spectroscopic studies) was carried out at ISAS and supported by the Russian Foundation for Basic Research under the grant no. 1902-00251, the work of E.S.K. (synthesis of compounds) was carried out at Lomonosov Moscow State University and supported by the Russian Foundation for Basic Research under the grant no. 19-33-60093 “Perspektiva.”

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Authors and Affiliations

  1. Institute of Spectroscopy, Russian Academy of Sciences, Moscow, Troitsk, Russia

    N. N. Novikova, V. A. Yakovlev & S. A. Klimin

  2. Chemical Faculty, Lomonosov Moscow State University, 119991, Moscow, Russia

    E. S. Kuznetsova & P. S. Berdonosov

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  1. N. N. Novikova
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  2. V. A. Yakovlev
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  3. E. S. Kuznetsova
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Correspondence to S. A. Klimin.

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Novikova, N.N., Yakovlev, V.A., Kuznetsova, E.S. et al. Chemical Pressure, Structural Instability, and IR-Active Phonons in a Series of Rare-Earth Analogues of Francisite Cu3RE(SeO3)2O2Cl. Opt. Spectrosc. 131, 870–880 (2023). https://doi.org/10.1134/S0030400X23070123

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