Inelastic Neutron-scattering Measurements Research Articles

Inelastic Neutron Scattering Measurement of the Ground State Tunneling Gap in Tb and Ho Analogues of a Dy Field-Induced Single-Molecule Magnet.

Recent advances in single-molecule magnet (SMM) research have placed great value on interpretation of inelastic neutron scattering (INS) data for rare earth (RE)-containing SMMs. Here, we present the synthesis of several rare earth complexes where combined magnetic and INS studies have been performed, supported by ab initio calculations. The reaction of rare earth nitrate salts with 2,2'-bipyridine (2,2'-bpy) and tetrahalocatecholate (X4Cat2-, X = Br, Cl) ligands in methanol (MeOH) afforded two new families of compounds [RE(2,2'-bpy)2(X4Cat)(X4CatH)(MeOH)] (X = Br and RE = Y, Eu, Gd, Tb, Dy, Ho, Yb for 1-RE; X = Cl and RE = Y, Tb, Dy, Ho, and Yb for 2-RE). Addition of triethylamine (Et3N) to the reaction mixture delivered Et3NH[RE(2,2'-bpy)2(Br4Cat)2] (3-RE, RE = Er and Yb). Interestingly, cerium behaves differently to the rest of the series, generating (2,2'-bpyH)2[Ce(Br4Cat)3(2,2'-bpy)] (4-Ce) with tetravalent Ce(IV) in contrast to the trivalent metal ions in 1-3. The static magnetic properties of 1-RE (RE = Gd, Tb, Dy and Ho) were investigated in conjunction with INS measurements on 1-Y, 1-Tb, and 1-Ho to probe their ground state properties and any crystal field excitations. To facilitate interpretation of the INS spectra and provide insight into the magnetic behavior, ab initio calculations were performed using the single-crystal X-ray diffraction structural data of 1-RE (RE = Tb, Dy and Ho). The ab initio calculations indicate ground doublets dominated by the maximal angular momentum projection states of Kramers type for 1-Dy and Ising type for 1-Tb and 1-Ho. Dynamic magnetic susceptibility measurements indicate that 1-Dy exhibits slow magnetic relaxation in the presence of a small applied magnetic field mainly through Raman pathways. Inelastic neutron scattering spectra exhibit distinct transitions corresponding to crystal field-induced tunneling gaps between the pseudo-doublet ground state components for 1-Tb and 1-Ho, which is one of the first direct experimental measurements with INS of such tunneling transitions in a molecular nanomagnet. The power of high-resolution INS is demonstrated with evidence of two distinct tunneling gaps measurable for the two crystallographically unique Tb coordination environments observed in the single crystal X-ray structure.

Bond ordering and molecular spin-orbital fluctuations in the cluster Mott insulator GaTa4Se8

For materials where spin-orbit coupling is competitive with electronic correlations, the spatially anisotropic spin-orbital wave functions can stabilize degenerate states that lead to many and diverse quantum phases of matter. Here we find evidence for a dynamical spin-orbital state preceding a ${T}^{*}$ = 50 K order-disorder spin-orbital ordering transition in the $j=3/2$ lacunar spinel ${\mathrm{GaTa}}_{4}{\mathrm{Se}}_{8}$. Above ${T}^{*}, {\mathrm{GaTa}}_{4}{\mathrm{Se}}_{8}$ has an average cubic crystal structure, but total scattering measurements indicate local noncubic distortions of ${\mathrm{Ta}}_{4}$ tetrahedral clusters for all measured temperatures $2<T<300$ K. Inelastic neutron-scattering measurements reveal the dynamic nature of these local distortions through symmetry forbidden optical phonon modes that modulate $j=3/2$ molecular orbital occupation as well as intercluster Ta-Se bonds. Spin-orbital ordering at ${T}^{*}$ cannot be attributed to a classic Jahn-Teller mechanism and, based on our findings, we propose that intercluster interactions acting on the scale of ${T}^{*}$ act to break global symmetry. The resulting staggered intercluster dimerization pattern doubles the unit cell, reflecting a spin-orbital valence bond ground state.

Two methods to study inelastic neutron-scattering measurements based on ω n (q) versus S(q, ω) applied to the magnetic open honeycomb lattice Tb2Ir3Ga9

This work describes two methods to fit the inelastic neutron-scattering spectrum S(q, ω) with wavevector q and frequency ω. The common and well-established method extracts the experimental spin-wave branches ω n (q) from the measured spectra S(q, ω) and then minimizes the difference between the observed and predicted frequencies. When n branches of frequencies are predicted but the measured frequencies overlap to produce only m < n branches, the weighted average of the predicted frequencies must be compared to the observed frequencies. A penalty is then exacted when the width of the predicted frequencies exceeds the width of the observed frequencies. The second method directly compares the measured and predicted intensities S(q, ω) over a grid {q i , ω j } in wavevector and frequency space. After subtracting background noise from the observed intensities, the theoretical intensities are scaled by a simple wavevector-dependent function that reflects the instrumental resolution. The advantages and disadvantages of each approach are demonstrated by studying the open honeycomb material Tb2Ir3Ga9.

Panther — the new thermal neutron time-of-flight spectrometer at the ILL

Panther is a new high-flux medium-resolution direct-geometry thermal-neutron time-of-flight spectrometer at the Institut Laue-Langevin (ILL). It is designed for inelastic neutron-scattering measurements of excitations in condensed matter using single crystals, polycrystalline samples, and liquids. Panther uses double focusing graphite or Cu monochromators, a Fermi chopper, and position-sensitive 3He detectors covering 2 steradians of solid angle. A system of disc choppers and an optional sapphire filter are used to reduce the epithermal neutron background. Thermal neutron background is reduced by a radial oscillating collimator, a beam dump, and an elaborate set of Cd shielding inside the evacuated detector tank. The outside of the tank is covered by a 0.3 m thick layer of borated high-density polyethylene to reduce ambient and cosmic background. The design and performance of the instrument in its current status are described, as well as planned developments.

Suppressed-moment 2-k order in the canonical frustrated antiferromagnet Gd2Ti2O7

In partially ordered magnets, order and disorder coexist in the same magnetic phase, distinct from both spin liquids and spin solids. Here, we determine the nature of partial magnetic ordering in the canonical frustrated antiferromagnet Gd2Ti2O7, in which Gd3+ spins occupy a pyrochlore lattice. Using single-crystal neutron-diffraction measurements in applied magnetic field, magnetic symmetry analysis, inelastic neutron-scattering measurements, and spin-wave modeling, we show that its low-temperature magnetic structure involves two propagation vectors (2-k structure) with suppressed ordered magnetic moments and enhanced spin-wave fluctuations. Our experimental results are consistent with theoretical predictions of thermal fluctuation-driven order in Gd2Ti2O7, and reveal that inelastic neutron-scattering measurements on powder samples can solve the longstanding problem of distinguishing single-k and multi-k magnetic structures.

Mechanical and Thermal Properties for Uranium and U–6Nb Alloy from First-Principles Theory

Elasticity, lattice dynamics, and thermal expansion for uranium and U–6Nb alloy (elastic moduli) are calculated from density functional theory that is extended to include orbital polarization (DFT+OP). Introducing 12.5 at.% of niobium, substitutionally, in uranium softens all the cii elastic moduli, resulting in a significantly softer shear modulus (G). Combined with a nearly invariant bulk modulus (B), the quotient B/G increases dramatically for U–6Nb, suggesting a more ductile material. Lattice dynamics from a harmonic model coupled with a DFT+OP electronic structure is applied for α uranium, and the obtained phonon density of states compares well with inelastic neutron-scattering measurements. The Debye temperature associated with the lattice dynamics falls within the range of experimentally observed Debye temperatures and it also validates our quasi-harmonic (QH) phonon model. The QH Debye–Grüneisen phonon method is combined with a DFT+OP electronic structure and used to explore the anisotropic thermal expansion in α uranium. The anomalous negative thermal expansion (contraction) of the b lattice parameter of the α-phase orthorhombic cell is relatively well reproduced from a free-energy model consisting of QH-phonon and DFT+OP electronic structure contributions.

Spin waves in the collinear antiferromagnetic phase of Mn5Si3

By combining two independent approaches, inelastic neutron-scattering measurements and density-functional-theory calculations, we study the spin waves in the collinear antiferromagnetic phase (AFM2) of ${\mathrm{Mn}}_{5}{\mathrm{Si}}_{3}$. We obtain its magnetic ground-state properties and electronic structure. This study allowed us to determine the dominant magnetic exchange interactions and magnetocrystalline anisotropy in the AFM2 phase of ${\mathrm{Mn}}_{5}{\mathrm{Si}}_{3}$. Moreover, the evolution of the spin excitation spectrum is investigated under the influence of an external magnetic field perpendicular to the anisotropy easy axis. The low-energy magnon modes show a different magnetic field dependence, which is a direct consequence of their different precessional nature. Finally, possible effects related to the Dzyaloshinskii-Moriya interaction are also considered.

Electron correlation effects on exchange interactions and spin excitations in 2D van der Waals materials

Despite serious effort, the nature of the magnetic interactions and the role of electron-correlation effects in magnetic two-dimensional (2D) van der Waals materials remains elusive. Using CrI3 as a model system, we show that the calculated electronic structure including nonlocal electron correlations yields spin excitations consistent with inelastic neutron-scattering measurements. Remarkably, this approach identifies an unreported correlation-enhanced interlayer super-superexchange, which rotates the magnon Dirac lines off, and introduces a gap along the high-symmetry Γ-K-M path. This discovery provides a different perspective on the gap-opening mechanism observed in CrI3, which was previously associated with spin–orbit coupling through the Dzyaloshinskii–Moriya interaction or Kitaev interaction. Our observation elucidates the critical role of electron correlations on the spin ordering and spin dynamics in magnetic van der Waals materials and demonstrates the necessity of explicit treatment of electron correlations in the broad family of 2D magnetic materials.

Unfolding the complexity of phonon quasi-particle physics in disordered materials

The concept of quasi-particles forms the theoretical basis of our microscopic understanding of emergent phenomena associated with quantum-mechanical many-body interactions. However, the quasi-particle theory in disordered materials has proven difficult, resulting in the predominance of mean-field solutions. Here, we report first-principles phonon calculations and inelastic X-ray and neutron-scattering measurements on equiatomic alloys (NiCo, NiFe, AgPd, and NiFeCo) with force-constant dominant disorder—confronting a key 50-year-old assumption in the Hamiltonian of all mean-field quasi-particle solutions for off-diagonal disorder. Our results have revealed the presence of a large, and heretofore unrecognized, impact of local chemical environments on the distribution of the species-pair-resolved force-constant disorder that can dominate phonon scattering. This discovery not only identifies a critical analysis issue that has broad implications for other elementary excitations, such as magnons and skyrmions in magnetic alloys, but also provides an important tool for the design of materials with ultralow thermal conductivities.

Determination of the scattering cross section of calcium using the VESUVIO spectrometer

Abstract With the aim to study the bound-atom neutron scattering cross section of natural calcium we measured the total cross sections of calcium carbonate and calcium oxide for the energy range between 10−3 and 100 eV, at the VESUVIO spectrometer (Rutherford Appleton Laboratory, UK), where we carried out simultaneous transmission and Deep Inelastic Neutron Scattering measurements. We present a method that allows us to determine in situ the amount of water present in the samples, which are both of hygroscopic nature. By employing it, we were able to subtract the contribution of hydrogen from the total cross section, as well as that of the other atoms present in the sample whose amount was known by their stoichiometry, what allowed us to determine the calcium contribution. The process of quantifying the amount of water involves the analysis of the scattered neutrons and multiple scattering corrections. In order to perform this last correction, we made a prior study of the dynamics of the system by means of the Density Functional Theory technique, along with measurements of the vibrational spectra at the TOSCA spectrometer (Rutherford Appleton Laboratory, UK). The value determined for the bound-atom scattering cross section of calcium was 4.27 ± 0.04 barns.

The curious case of cuprous chloride: Giant thermal resistance and anharmonic quasiparticle spectra driven by dispersion nesting

Strongly anharmonic phonon properties of CuCl are investigated with inelastic neutron-scattering measurements and first-principles simulations. An unusual quasiparticle spectral peak emerges in the phonon density of states with increasing temperature, in both simulations and measurements, emanating from exceptionally strong coupling between conventional phonon modes. Associated with this strong anharmonicity, the lattice thermal conductivity of CuCl is extremely low and exhibits anomalous, nonmonotonic pressure dependence. We show how this behavior arises from the structure of the phonon dispersions augmenting the phase space available for anharmonic three-phonon scattering processes, and contrast this mechanism with common arguments based on negative Gr\"uneisen parameters. These results demonstrate the importance of considering intrinsic phonon-dispersion structure toward understanding scattering processes and designing new ultralow thermal conductivity materials.

Spin-wave excitations in the spin-density wave state of doped iron pnictides

We investigate spin-wave excitations in the spin-density wave state of doped iron pnictides within a five-orbital model. We find that the excitations along () → () are very sensitive to dopings whereas they do not exhibit a similar sensitivity along () → (). Secondly, the ellipticity of the elliptical ring-like excitations around () is also very much dependent on doping. Thirdly, the spin-wave spectral weight shifts towards the low-energy region as it moves away from zero doping. We find several features to be in qualitative agreement with the inelastic neutron-scattering measurements for the doped pnictides.

Quantum skyrmions in two-dimensional chiral magnets

We study the quantum mechanics of magnetic skyrmions in the vicinity of the skyrmion-crystal to ferromagnet phase boundary in two-dimensional magnets. We show that the skyrmion excitation has an energy dispersion that splits into multiple bands due to the combination of magnus force and the underlying lattice. Condensation of the skyrmions can give rise to an intermediate phase between the skyrmion crystal and ferromagnet: a quantum liquid, in which skyrmions are not spatially localized. We show that the critical behavior depends on the spin size $S$ and the topological number of the skyrmion. Experimental signatures of quantum skyrmions in inelastic neutron-scattering measurements are also discussed.

Application of Geant4 simulation for analysis of soil carbon inelastic neutron scattering measurements

Inelastic neutron scattering (INS) was applied to determine soil carbon content. Due to non-uniform soil carbon depth distribution, the correlation between INS signals with some soil carbon content parameter is not obvious; however, a proportionality between INS signals and average carbon weight percent in ~10cm layer for any carbon depth profile is demonstrated using Monte-Carlo simulation (Geant4). Comparison of INS and dry combustion measurements confirms this conclusion. Thus, INS measurements give the value of this soil carbon parameter.

Magnetic moments induce strong phonon renormalization in FeSi.

The interactions of electronic, spin and lattice degrees of freedom in solids result in complex phase diagrams, new emergent phenomena and technical applications. While electron–phonon coupling is well understood, and interactions between spin and electronic excitations are intensely investigated, only little is known about the dynamic interactions between spin and lattice excitations. Noncentrosymmetric FeSi is known to undergo with increasing temperature a crossover from insulating to metallic behaviour with concomitant magnetic fluctuations, and exhibits strongly temperature-dependent phonon energies. Here we show by detailed inelastic neutron-scattering measurements and ab initio calculations that the phonon renormalization in FeSi is linked to its unconventional magnetic properties. Electronic states mediating conventional electron–phonon coupling are only activated in the presence of strong magnetic fluctuations. Furthermore, phonons entailing strongly varying Fe–Fe distances are damped via dynamic coupling to the temperature-induced magnetic moments, highlighting FeSi as a material with direct spin–phonon coupling and multiple interaction paths.

Influence of interstitial Mn on magnetism in the room-temperature ferromagnetMn1+δSb

We report elastic and inelastic neutron-scattering measurements of the high-${T}_{\mathrm{C}}$ ferromagnet ${\mathrm{Mn}}_{1+\ensuremath{\delta}}\mathrm{Sb}$. Measurements were performed on a large, ${T}_{\mathrm{C}}=434$ K, single crystal with an interstitial Mn content of $\ensuremath{\delta}\ensuremath{\approx}0.13$. The neutron-diffraction results reveal that the interstitial Mn has a magnetic moment, and that it is aligned antiparallel to the main Mn moment. We perform density functional theory calculations including the interstitial Mn and find the interstitial to be magnetic, in agreement with the diffraction data. The inelastic neutron-scattering measurements reveal two features in the magnetic dynamics: (i) a spin-wave-like dispersion emanating from ferromagnetic Bragg positions $(\mathrm{H}\phantom{\rule{4pt}{0ex}}\mathrm{K}\phantom{\rule{0.16em}{0ex}}2n)$, and (ii) a broad, nondispersive signal centered at forbidden Bragg positions $(\mathrm{H}\phantom{\rule{4pt}{0ex}}\mathrm{K}\phantom{\rule{0.16em}{0ex}}2n+1)$. The inelastic spectrum cannot be modeled by simple linear spin-wave-theory calculations and appears to be significantly altered by the presence of the interstitial Mn ions. The results show that the influence of the interstitial Mn on the magnetic state in this system is more important than previously understood.

Competition between the inter- and intra-sublattice interactions inYb2V2O7

We studied the magnetic properties of single-crystal ${\mathrm{Yb}}_{2}{\mathrm{V}}_{2}{\mathrm{O}}_{7}$ using dc and ac susceptibility measurements, elastic and inelastic neutron-scattering measurements, and linear spin-wave theory. The experimental data show a ferromagnetic ordering of ${\mathrm{V}}^{4+}$ ions at 70 K, a short-range ordering of ${\mathrm{Yb}}^{3+}$ ions below 40 K, and finally a long-range noncollinear ordering of ${\mathrm{Yb}}^{3+}$ ions below 15 K. With external magnetic field oriented along the [111] axis, the Yb sublattice experiences a spin flop transition related to the ``three-in one-out'' spin structure. By modeling the spin-wave excitations, we extract the Hamiltonian parameters. Our results confirm that although the extra inter-sublattice Yb-V interactions dramatically increase the Yb ordering temperature to 15 K, the intra-sublattice Yb-Yb interactions, based on the pyrochlore lattice, still stabilize the Yb ions' noncollinear spin structure and spin flop transition.

Transport and Thermodynamic Studies of Stripe and Checkerboard Ordering in Layered Nickel Oxides R2−xSrxNiO4 (R = La and Nd)

We have investigated the Sr-doped layered nickelates Nd2−xSrxNiO4 and La2−xSrxNiO4 to elucidate qualitative differences between the stripe-type and checkerboard (CB)-type charge/spin ordered phases. From electrical resistivity, specific heat, magnetic susceptibility and inelastic neutron-scattering measurements, we construct a revised phase diagram around the border of the stripe and CB phases in Nd2−xSrxNiO4, and show the marked difference in the hole-concentration dependence of physical properties between two phases. These results strongly indicate that the CB order is not a simple structural limit of the stripe order.

Nd-ion Substitution Effect on f-electron Multipole Order of PrRu4P12

We studied the effect of magnetic Nd-ion substitution on the metal-nonmetal transition at a transition temperature of 63 K of PrRu4P12, which is characterized by antiferro-type electric multipole ordering of Pr-ion 4f electrons. The transition temperature of Pr1-xNdxRu4P12 depends weakly on the Nd concentration x as compared to Laand Ce-substituted compounds. Inelastic neutron-scattering measurements revealed that the energies and widths of crystalline field excitation peaks of Pr 4f2 in Pr0.85Nd0.15Ru4P12 are very similar to those of PrRu4P12. These experimental results indicate that the ordered state is robust against the substitution of magnetic Nd ions as compared to the La and Ce substitutions. Magnetic interactions between the Pr ions and the Nd ions in Pr1-xNdxRu4P12 help stabilize the magnetic triplet ground state of the Pr ions that appears in the antiferro-type multipole ordered phase. Therefore, the nonmagnetic multipole ordered phase of PrRu4P12 is compatible with the magnetic perturbation.

Sample environment issues relevant to the acquisition of inelastic neutron scattering measurements of heterogeneous catalyst samples

Refinements to established sample handling issues connected with the acquisition of inelastic neutron scattering (INS) spectra of heterogeneous catalyst samples are described. This involves modification of a reactor and improvements to gas handling apparatus. The latter includes provision of laboratory space and ventilation facilities that are suited to the increasingly wide range of catalytic samples being examined. INS measurements for CO hydrogenation over an iron-based Fischer-Tropsch catalyst recorded using the MARI spectrometer are presented to illustrate the applicability of the new arrangements.