Excitonic transverse and amplitude fluctuations in the noncollinear and charge-ordered RbFe2+^{2+}Fe3+^{3+}F6_{6}

RbFe$^{2+}$Fe$^{3+}$F$_{6}$ is an example of an antiferromagnet with charge ordering of the octahedrally coordinated Fe$^{2+}$ and Fe$^{3+}$ ions. As well as different spin values, Fe$^{2+}$ ($S=2$) and Fe$^{3+}$ ($S={5\over2}$) possess differing orbital ground states with Fe$^{2+}$ having an orbital degeneracy with an effective orbital angular momentum of $l=1$. The resulting low temperature magnetic structure is non collinear with the spins aligned perpendicular to nearest neighbors (S. W. Kim \textit{et al.} Chem. Sci. {\bf{3}}, 741 (2012)). The combination of an orbital degeneracy and non collinear spin arrangements introduces the possibility for unusual types of excitations such as amplitude modes of the order parameter. In this paper we investigate this by applying a multi-level analysis to model neutron spectroscopy data (M. Songvilay \textit{et al.} Phys. Rev. Lett. {\bf{121}}, 087201 (2018)). In particular, we discuss the possible origins of the momentum and energy broadened continuum scattering observed in terms of amplitude fluctuations allowed through the presence of an orbital degree of freedom on the Fe$^{2+}$ site. We extend previous spin-orbit exciton models based on a collinear spin structure to understand the measured low-energy excitations and also to predict and discuss possible amplitude mode scattering in RbFe$^{2+}$Fe$^{3+}$F$_{6}$.Comment: 17 pages and 7 figure

Broadband critical dynamics in disordered lead-based perovskites*

Materials based on the cubic perovskite unit cell continue to provide the basis for technologically important materials with two notable recent examples being lead-based relaxor piezoelectrics and lead-based organic-inorganic halide photovoltaics. These materials carry considerable disorder, arising from site substitution in relaxors and molecular vibrations in the organic-inorganics, yet much of our understanding of these systems derives from the initial classic work of Prof. Roger A. Cowley, who applied both theory and neutron scattering methods while at Chalk River Laboratories to the study of lattice vibrations in SrTiO$_{3}$. Neutron scattering continues to play a vital role in characterizing lattice vibrations in perovskites owing to the simple cross section and the wide range of energy resolutions achievable with current neutron instrumentation. We discuss the dynamics that drive the phase transitions in the relaxors and organic-inorganic lead-halides in terms of neutron scattering and compare them to those in phase transitions associated with a ``central peak" and also a soft mode. We review some of the past experimental work on these materials and present new data from high-resolution time-of-flight backscattering spectroscopy taken on organic-inorganic perovskites. We will show that the structural transitions in disordered lead-based perovskites are driven by a broad frequency band of excitations.Comment: 23 pages, 9 figures, submitted as part of a special issue of JPCM on X-ray and Neutron Scattering and dedicated to the memory of Prof. R. A. Cowle

Magnetic properties of the honeycomb oxide Na2_2Co2_2TeO6_6

We have studied the magnetic properties of Na$_2$Co$_2$TeO$_6$, which features a honeycomb lattice of magnetic Co$^{2+}$ ions, through macroscopic characterization and neutron diffraction on a powder sample. We have shown that this material orders in a zig-zag antiferromagnetic structure. In addition to allowing a linear magnetoelectric coupling, this magnetic arrangement displays very peculiar spatial magnetic correlations, larger in the honeycomb planes than between the planes, which do not evolve with the temperature. We have investigated this behavior by Monte Carlo calculations using the $J_1$-$J_2$-$J_3$ model on a honeycomb lattice with a small interplane interaction. Our model reproduces the experimental neutron structure factor, although its absence of temperature evolution must be due to additional ingredients, such as chemical disorder or quantum fluctuations enhanced by the proximity to a phase boundary.Comment: 9 pages, 13 figure

Decoupled molecular and inorganic framework dynamics in CH3NH3PbCl3

The organic-inorganic lead halide perovskites are composed of organic molecules imbedded in an inorganic framework. The compounds with general formula CH$_{3}$NH$_{3}$PbX$_{3}$ (MAPbX$_{2}$) display large photovoltaic efficiencies for halogens $X$=Cl, Br, and I in a wide variety of sample geometries and preparation methods. The organic cation and inorganic framework are bound by hydrogen bonds that tether the molecules to the halide anions, and this has been suggested to be important to the optoelectronic properties. We have studied the effects of this bonding using time-of-flight neutron spectroscopy to measure the molecular dynamics in CH$_3$NH$_3$PbCl$_3$ (MAPbCl$_3$). Low-energy/high-resolution neutron backscattering reveals thermally-activated molecular dynamics with a characteristic temperature of $\sim$ 95\,K. At this same temperature, higher-energy neutron spectroscopy indicates the presence of an anomalous broadening in energy (reduced lifetime) associated with the molecular vibrations. By contrast, neutron powder diffraction shows that a spatially long-range structural phase transitions occurs at 178\,K (cubic $\rightarrow$ tetragonal) and 173\,K (tetragonal $\rightarrow$ orthorhombic). The large difference between these two temperature scales suggests that the molecular and inorganic lattice dynamics in MAPbCl$_3$ are actually decoupled. With the assumption that underlying physical mechanisms do not change with differing halogens in the organic-inorganic perovskites, we speculate that the energy scale most relevant to the photovoltaic properties of the lead-halogen perovskites is set by the lead-halide bond, not by the hydrogen bond.Comment: (10 pages, 5 figures, to be published in Physical Review Materials

Two-dimensional ferromagnetic spin-orbital excitations in honeycomb VI3

VI$_{3}$ is a ferromagnet with planar honeycomb sheets of bonded V$^{3+}$ ions held together by van der Waals forces. We apply neutron spectroscopy to measure the two dimensional ($J/J_{c} \approx 17$) magnetic excitations in the ferromagnetic phase, finding two energetically gapped ($\Delta \approx k_{B} T_{c} \approx$ 55 K) and dispersive excitations. We apply a multi-level spin wave formalism to describe the spectra in terms of two coexisting domains hosting differing V$^{3+}$ orbital ground states built from contrasting distorted octahedral environments. This analysis fits a common nearest neighbor in-plane exchange coupling ($J$=-8.6 $\pm$ 0.3 meV) between V$^{3+}$ sites. The distorted local crystalline electric field combined with spin-orbit coupling provides the needed magnetic anisotropy for spatially long-ranged two-dimensional ferromagnetism in VI$_{3}$.Comment: (main text - 7 pages, 4 figures; supplementary information - 13 pages, 9 figures, to be published in Phys. Rev. B

Magnetic surface reconstruction in the van der Waals antiferromagnet Fe1+xTe

We acknowledge financial support from the EPSRC (EP/R031924/1 and EP/R032130/1) and NIST Center for Neutron Research. C.H. acknowledges support by the Austrian Science Fund (FWF) Project No. P32144-N36 and the VSC4 of the Vienna University of TechnologyFe1+xTe is a two-dimensional van der Waals antiferromagnet that becomes superconducting on anion substitution on the Te site. The properties of the parent phase of Fe1+xTe are sensitive to the amount of interstitial iron situated between the iron-tellurium layers. Fe1+xTe displays collinear magnetic order coexisting with low-temperature metallic resistivity for small concentrations of interstitial iron x and helical magnetic order for large values of x. While this phase diagram has been established through scattering [see, for example, E. E. Rodriguez et al., Phys. Rev. B 84, 064403 (2011); S. Rossler et al., ibid. 84, 174506 (2011)], recent scanning tunneling microscopy measurements [C. Trainer et al., Sci. Adv. 5, eaav3478 (2019)] have observed a different magnetic structure for small interstitial iron concentrations x with a significant canting of the magnetic moments along the crystallographic c axis of θ = 28° ± 3°. In this paper, we revisit themagnetic structure of Fe1.09Te using spherical neutron polarimetry and scanning tunneling microscopy to search for this canting in the bulk phase, and we compare surface and bulk magnetism. The results show that the bulk magnetic structure of Fe1.09Te is consistent with collinear in-plane order (θ= 0 with an error of ∼ 5°). Comparison with scanning tunneling microscopy on a series of Fe1+xTe samples reveals that the surface exhibits a magnetic surface reconstruction with a canting angle of the spins of θ = 29.8°. We suggest that this is a consequence of structural relaxation of the surface layer resulting in an out-of-plane magnetocrystalline anisotropy. The magnetism in Fe1+xTe displays different properties at the surface when the symmetry constraints of the bulk are removed.Publisher PDFPeer reviewe

From one- to two-magnon excitations in the S=3/2 magnet β-CaCr2O4

We apply neutron spectroscopy to measure the magnetic dynamics in the S=3/2 magnet $\beta$-CaCr$_2$O$_4$ (T$_N$=21 K). The low-energy fluctuations, in the ordered state, resemble large-S linear spin-waves from the incommensurate ground state. However, at higher energy transfers, these semi-classical and harmonic dynamics are replaced by an energy and momentum broadened continuum of excitations. Applying kinematic constraints required for energy and momentum conservation, sum rules of neutron scattering, and comparison against exact diagonalization calculations, we show that the dynamics at high-energy transfers resemble low-S one-dimensional quantum fluctuations. $\beta$-CaCr$_2$O$_4$ represents an example of a magnet at the border between classical N\'eel and quantum phases, displaying dual characteristics

Kitaev interactions in the Co honeycomb antiferromagnets Na3Co2SbO6 and Na2Co2TeO6

Co$^{2+}$ ions in an octahedral crystal field, stabilise a j$_{eff}$ = 1/2 ground state with an orbital degree of freedom and have been recently put forward for realising Kitaev interactions, a prediction we have tested by investigating spin dynamics in two cobalt honeycomb lattice compounds, Na$_2$Co$_2$TeO$_6$ and Na$_3$Co$_2$SbO$_6$, using inelastic neutron scattering. We used linear spin wave theory to show that the magnetic spectra can be reproduced with a spin Hamiltonian including a dominant Kitaev nearest-neighbour interaction, weaker Heisenberg interactions up to the third neighbour and bond-dependent off-diagonal exchange interactions. Beyond the Kitaev interaction that alone would induce a quantum spin liquid state, the presence of these additional couplings is responsible for the zigzag-type long-range magnetic ordering observed at low temperature in both compounds. These results provide evidence for the realization of Kitaev-type coupling in cobalt-based materials, despite hosting a weaker spin-orbit coupling than their 4d and 5d counterparts