We report on TmMnO3 far infrared emissivity and reflectivity spectra from 1910 K to 4 K. At the highest temperature the number of infrared bands is lower than that predicted for centrosymmetric P63/mmc (D6h4) (Z=2) space group due high temperature an
harmonicity and possible defect induced bitetrahedra misalignments. On cooling, at ~1600 K TmMnO3 goes from non-polar to an antiferroelectric-ferroelectric polar phase reaching the ferroelectric onset at the ~700 K. The 300 K reflectivity is fitted using 19 oscillators and this number of phonons is maintained down to 4 K. A weak phonon anomaly in the band profile at 217 cm-1 (4 K) suggests subtle Rare Earth magnetoelectric couplings at ~TN and below. A low energy collective excitation is identified as a THz instability associated with room temperature eg electrons in a d-orbital fluctuating environment. It condenses into two modes that emerge pinned to the E-type antiferromagmetic order hardening simultaneously down to 4 K. They obey power laws with TN as the critical temperature and match known zone center magnons. The one peaking at 26 cm-1, with critical exponent b{eta}=0.42 as for antiferromagnetic order in a hexagonal lattice, is dependent on the Rare Earth. The band at ~50 cm-1, with b{eta}=0.25, splits at ~TN into two peaks. The weaker band of the two is assimilated to the upper branch of gap opening in the transverse acoustical (TA) phonon branch crossing the magnetic dispersion found in YMnO3. (Petit et al, 2007 PRL 99, 266604). The stronger second at ~36 cm-1 corresponds to the lower branch of the TA gap. We assign both excitations as zone center magnetoelectric hybrid quasiparticles concluding that in NdMnO3 perovskite the equivalent picture corresponds to an instability which may be driven by an external field to transform NdMnO3 into a multiferroic compound by perturbation enhancing the TA phonon-magnetic correlation.
We report on near normal far- and mid-infrared emission and reflectivity of NdMnO3 perovskite from room temperature to sample decomposition above 1800 K. At 300 K the number infrared active phonons is in close agreement with the 25 calculated for the
orthorhombic D2h16-Pbnm (Z=4) space group. Their number gradually decreases as we approach the temperature of orbital disorder at ~1023 K where the orthorhombic O lower temperature cooperative phase coexists with the cubic orthorhombic O. At above ~1200 K, the three infrared active phonons coincide with the expected for cubic Pm-3m (Z=1) in the high temperature insulating regime. Heating samples in dry air triggers double exchange conductivity by Mn3+ and Mn4+ ions and a small polaron mid-infrared band. Fits to the optical conductivity single out the octahedral antisymmetric and symmetric vibrational modes as main phonons in the electron-phonon interactions at 875 K. For 1745 K, it is enough to consider the symmetric stretching internal mode. An overdamped defect induced Drude component is clearly outlined at the highest temperatures. We conclude that Rare Earth manganites eg electrons are prone to spin, charge, orbital, and lattice couplings in an intrinsic orbital distorted perovskite lattice favoring embryonic low energy collective excitations.
We report on far- and mid-infrared reflectivity of NdMnO3 from 4 K to 300K. Two main features are distinguished in the infrared spectra: active phonons in agreement with the expected for orthorhombic D2h 16-Pbnm (Z=4) space group remaining constant d
own to 4 K and a well-defined collective excitation in the THz region due to eg electrons in a d-orbital fluctuating environment. We trace its origin to the NdMnO3 high temperature orbital disordered intermediate phase not being totally dynamically quenched at lower temperatures. This results in minute orbital misalignments that translate in randomize non-static eg electrons within orbitals yielding a room temperature collective excitation. Below TN~78 K, electrons gradually localize inducing long-range magnetic order as the THz band condenses into two modes that emerge pinned to the A-type antiferromagmetic order. They harden simultaneously down to 4 K obeying power laws with TN as the critical temperature and exponents {beta}~0.25 and {beta}~0.53, as for a tri-critical point and Landau magnetic ordering, respectively. At 4K they match known zone center spin wave modes. The power law dependence is concomitant with a second order transition in which spin modes modulate orbital instabilities in a magnetoelectric hybridized orbital/charge/spin/lattice scenario. We also found that phonon profiles also undergo strong changes at TN~78 K due to magnetoelasticity.
We report on the lattice evolution of BiFeO3 as function of temperature using far infrared emissivity, reflectivity, and X-ray absorption local structure. A power law fit to the lowest frequency soft phonon in the magnetic ordered phase yields an exp
onent {beta}=0.25 as for a tricritical point. At about 200 K below TN~640 K it ceases softening as consequence of BiFeO3 metastability. We identified this temperature as corresponding to a crossover transition to an order-disorder regime. Above ~700 K strong band overlapping, merging, and smearing of modes are consequence of thermal fluctuations and chemical disorder. Vibrational modes show band splits in the ferroelectric phase as emerging from triple degenerated species as from a paraelectric cubic phase above TC~1090 K. Temperature dependent X-ray absorption near edge structure (XANES) at the Fe K-edge shows that lower temperature Fe3+ turns into Fe2+. While this matches the FeO wustite XANES profile, the Bi LIII-edge downshift suggests a high temperature very complex bond configuration at the distorted A perovskite site. Overall, our local structural measurements reveal high temperature defect-induced irreversible lattice changes, below, and above the ferroelectric transition, in an environment lacking of long-range coherence. We did not find an insulator to metal transition prior to melting.
