The polarized Raman spectra of orthorhombic RMnO3 series (R=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho,Y) were studied at room temperature.The variation of phonon frequencies with R ionic radius rR as a whole confirms the commonly accepted Raman line assignments with two noticeable exceptions: (1) with decreasing rR the stretching Ag(1) and bending Ag(3) modes strongly mix for R=Sm to Tb, while for further decrease or rR (R=Dy,Ho,Y) the Ag(3) mode is observed at higher frequency than Ag(1) mode; (2) similar distortion-dependent mode mixing takes place for the rotational Ag(2) and O1(x) [Ag( 7)] modes. The mode mixing is particularly strong for the RMnO3 compounds with rR values close to the transition from A-type to incommensurate sinusoidal antiferromagnetic ordering at low temperatures. The frequency of rotational Ag(2) and Ag(4) modes scales to the angles of MnO6 [101] and [010] rotations, respectively, and could be used as a measure of their value.
The field-induced re-entrant phase in multiferroic hexagonal HoMnO 3 is investigated to lower temperatures by dc magnetization, ac susceptibility, and specific heat measurements at various magnetic fields. Two new phases have been unambiguously identified below the Néel transition temperature, T N = 76 K, for magnetic fields up to 50 kOe. The existence of an intermediate phase between the P6 គ 3 c គm and P6 គ 3 cm គ magnetic structures ͑previously predicted from dielectric measurements͒ was confirmed and the magnetic properties of this phase have been investigated. At low temperatures ͑T Ͻ 5 K͒ a dome shaped phase boundary characterized by a magnetization jump and a narrow heat capacity peak was detected between the magnetic fields of 5 kOe and 18 kOe. The transition across this phase boundary is of first order and the magnetization and entropy jumps obey the magnetic analogue of the Clausius-Clapeyron relation. Four of the five low-temperature phases coexist at a tetracritical point at 2 K and 18 kOe. The complex magnetic phase diagram so derived provides an informative basis for unraveling the underlying driving forces for the occurrence of the various phases and the coupling between the different orders.
A reentrant novel phase is observed in the hexagonal ferroelectric HoMnO3 in the presence of magnetic fields in the temperature range defined by a plateau of the dielectric constant anomaly. The plateau evolves with fields from a narrow dielectric peak at the Mn-spin rotation transition at 32.8 K in zero field. The anomaly appears both as a function of temperature and as a function of magnetic field without detectable hysteresis. This is attributed to the indirect coupling between the ferroelectric (FE) and antiferromagnetic (AFM) orders, arising from an FE-AFM domain wall effect.
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