High Temperature Far Infrared Dynamics of Orthorhombic NdMnO3: Emissivity and Reflectivity

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.Comment: 32 pages with 5 figure

Phonons and Hybrid Modes in the High and Low Temperature Far Infrared Dynamics of Hexagonal TmMnO3

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 anharmonicity 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.Comment: 39 pages, 9 Figure

Phonon activity and intermediate glassy phase of YVO₃

We show that in YVO₃ additional hard phonons gradually become zone center infrared active below ∼210 K, verifying that a lattice phase transition takes place at about that temperature. Their gradual increment in intensity between ∼210 and ∼77 K is associated with a "glassy" behavior found in the temperature-dependent V K edge pseudoradial distribution. This translates into an increase in the Debye-Waller factors ascribed to the appearance of V local structural disorder below ∼150 K. Conflicts between various ordering mechanisms in YVO₃ bring up similarities of the intermediate phase to known results in dielectric incommensurate systems, suggesting the formation of commensurate domains below 116 K, the onset temperature of G-type antiferromagnetism. We propose that ∼210 and ∼77 K be understood as the temperatures where the commensurate-incommensurate and incommensurate-commensurate "lock-in" phase transitions take place. We found support for this interpretation in the inverted λ shapes of the measured heat capacity and in the overall temperature dependence of the hard phonons.Facultad de Ciencias ExactasCentro de Química Inorgánic

High temperature far-infrared dynamics of orthorhombic NdMnO₃: emissivity and reflectivity

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 D¹⁶2h-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.Facultad de Ciencias ExactasCentro de Química Inorgánic

Paramagnetic collective electronic mode and low temperature hybrid modes in the far infrared dynamics of orthorhombic NdMnO₃

We report on the far- and mid-infrared reflectivity of NdMnO₃ from 4 to 300 K. Two main features are distinguished in the infrared spectra: active phonons in agreement with expectations for the orthorhombic D¹⁶2h-Pbnm (Z = 4) space group remaining constant down 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 into randomized 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 antiferromagnetic order. They harden simultaneously down to 4 K, obeying power laws with TN as the critical temperature and exponents β ∼ 0.25 and β ∼ 0.53, as for a tri-critical point and Landau magnetic ordering, respectively. At 4 K 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.Facultad de Ciencias ExactasCentro de Química Inorgánic

Possible common ground for the metal-insulator phase transition in the rare-earth nickelates <i>R</i>NiO₃ (R = Eu, Ho, Y)

We report on the infrared spectra of RNiO₃ (R = E, Ho, Y). They provide evidence of phonon and insulating gap behavior and point to the monoclinic distortion at the metal-insulator (MI) transition as a feature for all RNiO₃ (R ≠ La). We hypothesize that the intermediate paramagnetic phase (above TN and below TMI in RNiO₃ (R = Sm, Eu, Ho, Y) might be consequence of a self-doping effect, gradually triggering a phase segregation in electron-rich and electron-poor regions. This picture is concomitant to the temperature-dependent effect of octahedral tilting and distortion and self-trapped electrons in a polaronic medium.Facultad de Ciencias ExactasCentro de Química Inorgánic

Phonons and hybrid modes in the high and low temperature far infrared dynamics of hexagonal TmMnO<SUB>3</SUB>

We report on temperature dependent 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 (Z = 2) space group due to high temperature anharmonicity and possible defect induced bitetrahedra misalignments. On cooling, at ~1600 ± 40 K, TmMnO3 goes from non-polar to an antiferroelectric–ferroelectric polar phase reaching the ferroelectric onset at ~700 K.Room temperature 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 magneto-electric 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 antiferromagnetic 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 β=0.42 as for antiferromagnetic order in a hexagonal lattice, is dependent on the Rare Earth ion. The higher frequency companion at ~50 cm−1, with β=0.25, splits at ~TN into two peaks. The weaker band of the two is assimilated to the upper branch of the gap opening in the transverse acoustical (TA) phonon branch crossing the magnetic dispersion found in YMnO3. (Petit et al 2007 Phys. Rev. Lett. 99 266604). The stronger second band at ~36 cm−1 corresponds to the lower branch of the TA gap. We assign both excitations as zone center magneto-electric 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.Centro de Química Inorgánic

Short-range charge order in RNiO₃ perovskites (R = Pr, Nd, Eu, Y) probed by x-ray-absorption spectroscopy

The short-range organization around Ni atoms in orthorhombic RNiO₃ (R = Pr, Nd, Eu) perovskites has been studied over a wide temperature range by Ni K-edge x-ray absorption spectroscopy. Our results demonstrate that two different Ni sites, with different average Ni-O bond lengths, coexist in those orthorhombic compounds and that important modifications in the Ni nearest neighbors environment take place across the metal-insulator transition. We report evidences for the existence of short-range charge-order in the insulating state, as found in the monoclinic compounds. Moreover, our results suggest that the two different Ni sites coexists even in the metallic state. The coexistence of two different Ni sites, independently on the R ion, provides a common ground to describe these compounds and shed new light in the understanding of the phonon-assisted conduction mechanism and unusual antiferromagnetism present in all RNiO₃ compounds.Facultad de Ciencias ExactasCentro de Química Inorgánic

Spin-orbit-induced mixed-spin ground state in RNiO₃ perovskites probed by x-ray absorption spectroscopy: Insight into the metal-to-insulator transition

We report on a Ni L2,3 edge x-ray absorption spectroscopy study in RNiO₃ perovskites. These compounds exhibit a metal-to-insulator (MI) transition as temperature decreases. The L₃ edge presents a clear splitting in the insulating state, associated to a less hybridized ground state. Using charge transfer multiplet calculations, we establish the importance of the crystal field and 3d spin-orbit coupling to create a mixed-spin ground state. We explain the MI transition in RNiO₃ perovskites in terms of modifications in the Ni³⁺ crystal field splitting that induces a spin transition from an essentially low-spin to a mixed-spin state.Facultad de Ciencias ExactasCentro de Química Inorgánic

Collective Phase-like Mode and the Role of Lattice Distortions at TN~TC in RMn2O5 (R= Pr, Sm, Gd, Tb, Bi)

We report on electronic collective excitations in RMn2O5 (R= Pr, Sm, Gd, Tb) showing condensation starting at and below TN\simTC\sim40-50 K. Its origin is understood as partial delocalized eg electron orbitals in the Jahn-Teller distortion of the pyramids dimmer with strong hybridized Mn3+-O bonds. Our local probes, Raman, infrared, and X-ray absorption, back the conclusion by which there is no structural phase transition at TN\simTC. Ferroelectricity is magnetically assisted by electron localization triggering lattice polarizability by unscreening. We have also found phonon hardening as the rare earth is sequentially replaced. This is understood as consequence of lanthanide contraction. It is suggested that partially f-electron screened Rare Earth nuclei might be introducing a perturbation to eg electrons prone to delocalize as the superexchange interaction takes place.Centro de Química Inorgánic