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Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies

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Abstract

The group-theoretical study of the structural phase transition to incommensurate state of MgSiF6·6H2O crystals, revealed by the electron paramagnetic resonance (EPR) method, as well as analysis of the EPR results, are presented. The consideration of temperature dependences of Mn2+ admixture ion EPR spectrum symmetry and parameters leads to the conclusion that at T i1 = 370 ± 0.3 K they undergo second-order structural phase transition to incommensurately modulated state, the order parameter of this transition may be the angle of [Mg(H2O)6]2+ octahedra rotation around crystal C 3 axis. At temperature decreasing below T i1 the gradual transformation of plane-wave modulation of lattice displacements into soliton mode occurs, which is interrupted by the first-order phase transition at T i2 = 343 ± 0.3 K accompanied by abrupt decrease in modulation amplitude. At T c = 298.5 ± 0.3 K the first-order improper ferroelastic phase transition into monoclinic phase occurs. The group-theoretical analysis of the phase transition at T i1 in the investigated crystals, carried out for the first time, has shown that the existence of the incommensurately modulated phase is conditioned by the fundamental reasons (presence of Lifshitz invariant). The conclusions of this analysis on the nature of order parameter, the structural motifs of incommensurate phase and the possible character of temperature evolution of the structure are in agreement with the EPR investigation data.

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Acknowledgments

We thank Prof. R.L. Davidovich and Dr. T.F. Antohina for providing us with the MgSiF6·6H2O:Mn2+ crystals and Dr. V.G. Kuryavyi for help in the EPR experiments.

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  1. Institute of Chemistry of the Far Eastern Branch of the Russian Academy of Sciences, 159, Prospekt 100-letiya, 690022, Vladivostok, Russia

    Peter G. Skrylnik & Albert M. Ziatdinov

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  1. Peter G. Skrylnik
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  2. Albert M. Ziatdinov
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Correspondence to Albert M. Ziatdinov.

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Skrylnik, P.G., Ziatdinov, A.M. Incommensurate Phases of the MgSiF6·6H2O Crystals: EPR and Group-Theoretical Studies. Appl Magn Reson 45, 623–640 (2014). https://doi.org/10.1007/s00723-014-0542-6

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  • DOI: https://doi.org/10.1007/s00723-014-0542-6

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