Inelastic Neutron Scattering Research Articles

Determining the local low-energy excitations in the Kondo semimetalCeRu4Sn6using resonant inelastic x-ray scattering

We have investigated the local low-energy excitations in CeRu$_4$Sn$_6$, a material discussed recently in the framework of strongly correlated Weyl semimetals, by means of Ce $M_5$ resonant inelastic x-ray scattering (RIXS). The availability of both $^2$F$_\frac{5}{2}$ and $^2$F$_\frac{7}{2}$ excitations of the Ce $4f^1$ configuration in the spectra allows for the determination of the crystal-electric field parameters that explain quantitatively the temperature dependence and anisotropy of the magnetic susceptibility. The absence of an azimuthal dependence in the spectra indicates that all crystal-electric field states are close to being rotational symmetric. We show further that the non-negligible impact of the $\check A_6^0$ parameter on the ground state of CeRu$_4$Sn$_6$ leads to a reduction of the magnetic moment due to multiplet intermixing. The RIXS results are consistent with inelastic neutron scattering (INS) data and are compared to the predictions from \textsl{ab-initio} based electronic structure calculations.

Dynamical Signature of Symmetry Fractionalization in Frustrated Magnets.

The nontriviality of quantum spin liquids (QSLs) typically manifests in the nonlocal observables that signify their existence; however, this fact actually casts a shadow on detecting QSLs with experimentally accessible probes. Here, we provide a solution by unbiasedly demonstrating a dynamical signature of anyonic excitations and symmetry fractionalization in QSLs. Employing large-scale quantum MonteCarlo simulation and stochastic analytic continuation, we investigate the extended XXZ model on the kagome lattice, and find out that, across the phase transitions from Z_{2} QSLs to different symmetry breaking phases, spin spectral functions can reveal the presence and condensation of emergent anyonic spinon and vison excitations, in particular, the translational symmetry fractionalization of the latter, which can be served as the dynamical signature of the seemingly ephemeral QSLs in spectroscopic techniques such as inelastic neutron or resonance (inelastic) x-ray scatterings.

Effects of Confinement and Pressure on the Vibrational Behavior of Nano-Confined Propane

Fluids confined in nanopores exhibit significant deviations in their structure and dynamics from the bulk behavior. Although phase, structural, and diffusive behaviors of confined fluids have been investigated and reported extensively, confinement effects on the vibrational properties are less understood. We study the vibrational behavior of propane confined in 1.5 nm nanopores of MCM-41-S using inelastic neutron scattering (INS) and molecular dynamics (MD) simulations. Vibrational spectra have been obtained from INS data as functions of temperature and pressure. At ambient pressure, a strong quasielastic signal observed in the INS spectrum at 80 K suggests that confined propane remains liquid below the bulk phase melting point of 85 K. The quasielastic signal is heavily suppressed when either the pressure is increased to 1 kbar or the temperature is lowered to 30 K, indicating solidification of pore-confined propane. Confinement in MCM-41-S pores results in a glass-like state of propane that exhibits a relatively featureless low-energy vibrational spectrum compared to that of the bulk crystalline propane. Increasing the pressure to 3 kbar results in hardening of the intermolecular and methyl torsional modes. The INS data are used for estimating the isochoric specific heat of confined propane, which is compared with the specific heat of bulk propane reported in literature. Data from MD simulations are used to calculate the vibrational power spectra that agree qualitatively with the experimental data. Simulation data also suggest a reduction of the structural ordering (positional, orientational, and intramolecular) of propane under confinement.

Complexity of Intercalation in MXenes: Destabilization of Urea by Two-Dimensional Titanium Carbide.

MXenes are a new class of two-dimensional materials with properties that make them important for applications that include batteries, capacitive energy storage, and electrocatalysis. These materials can be exfoliated and delaminated to create high surface areas with interlayers accessibility. Intercalation is known to be possible, and it is critical for many applications including electrochemical energy storage, water purification, and sensing. However, little is known about the nature of the intercalant and bonding interactions between the intercalant within the MXene. We have investigated urea interaction within a titanium carbide based MXene using inelastic neutron scattering (INS) to probe the state of intercalated species. By comparison with reference materials, we find that under intercalation conditions urea decomposes readily, leading to intercalation of ammonium cations observable by INS and evolving carbon dioxide detected by infrared spectroscopy. Reactive molecular dynamics calculations were conducted to provide atomistic insights about reaction pathways and their energetics. These results have implications for understanding intercalation in active layered materials.

DFT Simulations of the Vibrational Spectrum and Hydrogen Bonds of Ice XIV

It is always a difficult task to assign the peaks recorded from a vibrational spectrum. Herein, we explored a new pathway of density functional theory (DFT) simulation to present three kinds of spectra of ice XIV that can be referenced as inelastic neutron scattering (INS), infrared (IR), and Raman experimental spectrum. The INS spectrum is proportional to the phonon density of states (PDOS) while the photon scattering signals reflect the normal vibration frequencies near the Brillouin zone (BZ) center. Based on good agreements with the experimental data, we identified the relative frequency and made scientific assignments through normal vibration modes analysis. The two hydrogen bond (H-bond) peaks among the ice phases from INS were discussed and the dynamic process of the H-bond vibrations was found to be classified into two basic modes. We deduced that two H-bond modes are a general rule among the ice family and more studies are ongoing to investigate this subject.

A first principle study of the perovskite lanthanum aluminate

A self-consistent first-principles calculation with a precise hybrid PBEsol functional, Density Functional Theory (DFT) have been used to investigate the stability, elastic, mechanical, electronic, acoustic and thermodynamic properties of the cubic perovskite Lithium Aluminate (LaAlO3). An investigation of the stability showed that the computed lattice parameter LaAlO3 is stable, results also show that the lattice of LaAlO3 becomes more distorted and deviates from the hydrostatic behavior as pressure is increased up to 11 GPa, after this limit, the structure encounter a phase shift, which is seen from the nature of the thermal properties of heat capacity. LaAlO3 is thermos conversion-efficient cubic perovskite with its strong phonon scattering interactions resides mostly unclear. The energy band structure appears to display an indirect band gap insulator, with Γ−R separating the valence and conduction bands. Pressure dependence of cubic elastic Moduli, elastic wave velocities, Debye temperature and the density of states of LaAlO3 were calculated, our results appear to converge with available experimental data. The elastic constants reveal the fact that the crystal is stable and show nature of crispness. The thermal characteristics were computed within the hybrid functional PBEsol using the Debye-Waller model and response functions. Lattice dynamics investigation of the perovskite thermoelectric LaAlO3 are investigated with the single-crystal first-principles simulations and compared against inelastic neutron scattering (INS) at 100 K. Our ab-initio calculations of LaAlO3 show a free asymmetry in the first nearest-neighbor peak. In addition, our first principles calculations data reveal stiffer bonding at the anion sites, which is in good agreement with the partial phonon densities of states from INS. The 4-dimensional phonon-dispersion surfaces of LaAlO3, have been mapped and it is found that the origins of the ionic potential an-harmonicity being responsible for the unique behavior and phonon properties of LaAlO3. The latter results provide clear evidence for the anharmonicity phonon distribution associated with the resonant bonding leading to a ferroelectric nature.

Inelastic and deep inelastic neutron spectroscopy of water molecules under ultra-confinement

Water confined within sub-nanometer channels of silicate minerals presents an extreme case of confinement, where the restricted molecules are situated in channels whose diameter is not much larger than the water molecule itself. Recently, we discovered a new quantum tunneling state of the water molecule confined in 5 Å channels in the mineral beryl, characterized by extended proton and electron delocalization. Several peaks were observed in the inelastic neutron scattering (INS) spectra which were uniquely assigned to water quantum tunnelling. In addition, the water proton momentum distribution measured with deep inelastic neutron scattering (DINS) at 4.3 K directly showed coherent delocalization of the water protons in the ground state. The obtained average kinetic energy (EK) of the water protons was found to be ~30% less than it is in bulk liquid water and ice phases. In the current work we present INS and DINS study of water in single crystal beryl in wider temperature range, T=5–260 K, where we observed significant increase of EK of the confined water protons with temperature increase. The obtained INS data also indicate that with increasing temperature water molecules are progressively involved in hydrogen bonding (HB) with the beryl cage, while HB is almost absent at low temperatures.

Procedure for the determination of effective temperatures employing VESUVIO spectrometer

We describe the procedure to determine effective temperatures employing the data collected by the detectors of the VESUVIO spectrometer (ISIS pulsed neutron source), employing the Deep Inelastic Neutron Scattering technique. A scheme to group the detectors is proposed, based on their positions and angular ranges, in order to add their spectra and improve the statistics. We show the details of all the corrections that must be made on the raw experimental data to reach the spectra on which the desired effective temperatures can be fitted. Most of the correction stages require ad-hoc auxiliary simulations by the Monte Carlo method, that were deviced and described in previous papers. The corrections, that involve background subtraction, empty cell subtraction, and multiple scattering corrections, are described in detail. The efficiencies of the defined detector groups are determined, and employed in the expressions used in data fitting. Data treatment steps performed in hydrogenated and deuterated alcohols, are shown as examples of application of this procedure.

Effect of electron correlations on spin excitation bandwidth in Ba0.75K0.25Fe2As2 as seen via time-of-flight inelastic neutron scattering

We use inelastic neutron scattering (INS) to investigate the effect of electron correlations on spin dynamics in the iron-based superconductor Ba$_{0.75}$K$_{0.25}$Fe$_{2}$As$_{2}$. Our INS data show a spin-wave-like dispersive feature, with a zone boundary energy of 200 meV. A first principles analysis of dynamical spin susceptibility, incorporating the mass renormalization factor of 3, as determined by angle-resolved photoemission spectroscopy, provides a reasonable description of the observed spin excitations. This analysis shows that electron correlations in the Fe-3$d$ bands yield enhanced effective electron masses, and consequently, induce substantial narrowing of the spin excitation bandwidth. Our results highlight the importance of electron correlations in an itinerant description of the spin excitations in iron-based superconductors.

Rigid versus Flexible Protein Matrix: Light-Harvesting Complex II Exhibits a Temperature-Dependent Phonon Spectral Density.

Dynamics-function correlations are usually inferred when molecular mobility and protein function are simultaneously impaired at characteristic temperatures or hydration levels. In this sense, excitation energy transfer in the photosynthetic light-harvesting complex II (LHC II) is an untypical example because it remains fully functional even at cryogenic temperatures relying mainly on interactions of electronic states with protein vibrations. Here, we study the vibrational and conformational protein dynamics of monomeric and trimeric LHC II from spinach using inelastic neutron scattering (INS) in the temperature range of 20-305 K. INS spectra of trimeric LHC II reveal a distinct vibrational peak at ∼2.4 meV. At temperatures above ∼160 K, however, the inelastic peak shifts toward lower energies, which is attributed to vibrational anharmonicity. A more drastic shift is observed at about 240 K, which is interpreted in terms of a "softening" of the protein matrix along with the dynamical transition. Monomeric LHC II exhibits a higher degree of conformational mobility at physiological temperatures, which can be attributed to a higher number of solvent-exposed side chains at the protein surface. The effects of the changes in protein dynamics on the spectroscopic properties of LHC II are considered in comparative model calculations. The absorption line shapes of a pigment molecule embedded into LHC II are simulated for the cases of (i) a rigid protein matrix, (ii) a protein matrix with temperature-dependent spectral density of protein vibrations, and (iii) temperature-dependent electron-phonon coupling strength. Our findings indicate that vibrational and conformational protein dynamics affect the spectroscopic (absorption) properties of LHC II at physiological temperatures.

Zero-Field Ambient-Pressure Quantum Criticality in the Stoichiometric Non-Fermi Liquid System CeRhBi

The strange electronic state of a class of materials which violates the predictions of conventional Fermi-liquid theory of metals remains enigmatic. Proximity to a quantum critical point is a possible origin of this non-Fermi liquid (NFL) behavior, which is usually accomplished by tuning the ground state with non-thermal control parameters such as chemical composition, magnetic field or pressure. We present the spin dynamics study of a stoichiometric NFL system CeRhBi, using low-energy inelastic neutron scattering (INS) and muon spin relaxation (muSR) measurements. It shows evidence for an energy-temperature (E/T) scaling in the INS dynamic response and a time-field scaling of the muSR asymmetry function indicating a quantum critical behavior in this compound. The E/T scaling reveals a local character of quantum criticality consistent with the power-law divergence of the magnetic susceptibility, logarithmic divergence of the magnetic heat capacity and T-linear resistivity at low temperature. The NFL behavior and local criticality occur over a very wide dynamical range at zero field and ambient pressure without any tuning in this stoichiometric heavy fermion compound is striking, making CeRhBi an exemplary model system amenable to in-depth studies for quantum criticality.

Theory of Electron Spin Resonance in Ferromagnetically Correlated Heavy Fermion Compounds

We studied the electron spin resonance (ESR) line width for localized moments within the framework of the Kondo lattice model. Only for a sufficiently small Kondo temperature can an ESR signal be observed for a Kondo impurity. On the other hand, for a Kondo lattice representing a heavy fermion compound, short-range ferromagnetic correlations (FM) between the localized moments are crucial to observe a signal. The spin relaxation rate (line width) and the static magnetic susceptibility are inversely proportional to each other. The FM enhance the susceptibility and hence reduce the line width. For most of the heavy fermion systems displaying an ESR signal, the FM order arises in the ab-plane from the strong lattice anisotropy. CeB6 is a heavy fermion compound with cubic symmetry having a Γ8 ground-quartet. Four transitions are expected for individual Ce ions with a Γ8 ground-multiplet, but only one has been observed. Antiferro-quadrupolar order (AFQ) arises below 4 K due to the orbital content of the Γ8-quartet. We addressed the effects of the interplay of AFQ and FM on the ESR line width and the phase diagram. It is usually difficult to distinguish among ESR resonances due to localized moments and conducting heavy electron spins, especially for anisotropic Ce and Yb compounds. However, for CeB6, an itinerant picture within the AFQ phase is necessary to explain the electron spin resonances. The longitudinal magnetic susceptibility has a quasi-elastic central peak of line width 1/T1 and inelastic peaks for the absorption/emission of excitations. The latter are measured via inelastic neutron scattering (INS) and provide insights into the magnetic order. We briefly summarize some of the INS results for CeB6 in the context of the picture that emerged from the ESR experiments.

Ferromagnetic Cluster Spin Wave Theory: Concepts and Applications to Magnetic Molecules

Ferromagnetic cluster spin wave theory (FCSWT) provides an exact and concise description of the low-energy excitations from the ferromagnetic ground state in finite magnetic systems, such as bounded magnetic molecules. In particular, this theory is applicable to the description of experimental inelastic neutron scattering (INS) spectra at low temperatures. We provide a detailed conceptual overview of the FCSWT. Additionally, we introduce a pictorial representation of calculated wavefunctions, similar to the usual depiction of vibrational normal modes in molecules. We argue that this representation leads to a better intuitive understanding of the excitations, their symmetry properties, and has links to the energy and wavevector dependence of intensity in the neutron scattering experiments. We apply FCSWT and illustrate the results on a series of examples with available low-temperature INS data, ranging from the Mn10 supertetrahedron, the Mn7 disk to the Mn6 single molecule magnet.

Understanding the magnetism in noncentrosymmetric CeIrGe3 : Muon spin relaxation and neutron scattering studies

The magnetic properties of a pressure induced noncentrosymmetric heavy-fermion superconductor CeIrGe$_3$ have been investigated by muon spin relaxation ($\mu$SR), powder neutron diffraction (ND) and inelastic neutron scattering (INS) techniques at ambient pressure. For completeness we have also measured the ac magnetic susceptibility $\chi_{\rm ac}(T)$, dc magnetic susceptibility $\chi(T)$, dc isothermal magnetization $M(H)$ and heat capacity $C_{\rm p}(T,H)$ down to 2 K. CeIrGe$_{3}$ is known to exhibit pressure induced superconductivity ($T_{\rm c}\approx 1.5$ K) at a pressure of 20 GPa and antiferromagnetic ordering at 8.7 K, 4.7 K and 0.7 K at ambient pressure. Our $\chi_{\rm ac}(T)$ and $\chi(T)$ data show an additional anomaly near 6.2 K which is also captured in $C_{\rm p}(T)$ data. From $\chi_{\rm ac}(T)$, $\chi(T)$ and $C_{\rm p}(T)$ measurements we infer three antiferromagnetic transitions above 2 K at $T_{\rm N1}= 8.5$ K, $T_{\rm N2}= 6.0$ K and $T_{\rm N3}= 4.6$ K. Our $\mu$SR study also confirms the presence of three transitions through the observation of one frequency for $T_{\rm N2} < T\leq T_{\rm N1}$, two frequencies for $T_{\rm N3} < T\leq T_{\rm N2}$ and three frequencies for $T\leq T_{\rm N3}$ in the oscillatory asymmetry. The ND data reveal an incommensurate nature of the magnetic ordering at $T=7$ K with the propagation vector k = (0,0,0.688(3)), and a commensurate magnetic structure at $T=1.5$ K with the propagation vector locked to the value k = (0,0,2/3) and magnetic moments oriented along the $c$ axis. The commensurate structure couples a macroscopic ferromagnetic component, resulting in a strong dependence of the lock-in transition temperature on external magnetic field. The INS data show two well defined crystal electric field (CEF) excitations arising from the CEF-split Kramers doublet ground state of Ce$^{3+}$.

Low-temperature dynamics of (S)-4-(1-methylheptyloxy)-4ʹ-cyanobiphenyl (8*OCB) and (S)-4-(2-methylbutyl)-4ʹ-cyanobiphenyl (5*CB) in disordered crystalline and glassy phases

ABSTRACTThe inelastic neutron scattering (INS) spectra were measured for two materials of chiral molecules: (S)-4-(1-methylheptyloxy)-4ʹ-cyanobiphenyl (8*OCB) and (S)-4-(2-methylbutyl)-4ʹ-cyanobiphenyl (5*CB), revealing solid state polymorphism with two partially disordered crystalline phases I and II and glassy state of liquid and of crystalline phase in each substance. The experiments were performed in the energy range up to 30 µeV in the temperature range from 4 to 35 K. For 8*OCB the elastic scans were measured as well up to 300 K illustrating well the phase diagram. For all solid phases of both substances in the µeV range of INS spectra, the existence of the excess density of vibrational states over that typical for fully ordered crystalline phases was evidenced. Contribution of this so-called boson peak occurred to be much larger in glass of isotropic phase than in the phase II and glass of phase I of 8*OCB, while for 5*CB it was larger in the phase I and glass of phase II than in glass of cholesteric phase. The quasi-elastic broadening of elastic peak corresponding to stochastic reorientations in the ns time scale was detected for both substances. Comparison of the results obtained for glassy and crystalline phases of 8*OCB and 5*CB compounds have been given and confronted with those obtained previously in meV energy range.

Dependence of Tc on the q−ω structure of the spin-fluctuation spectrum

A phenomenological spin-fluctuation analysis (Ref. 1), based upon inelastic neutron scattering (INS) and angular resolved photoemission spectroscopy (ARPES) data for ${\rm YBCO}_{6.6}(T_c=61K)$, is used to calculate the functional derivative of the d-wave eigenvalue $\lambda_d$ of the linearized gap equation with respect to the imaginary part of the spin susceptibility $\chi''(q,\omega)$ at 70K. For temperatures near $T_c$, the variation of $T_c$ with respect to $\chi''(q,\omega)$ is proportional to this functional derivative. Based on this, we discuss how different parts of the $q$ and $\omega$ dependent spin-fluctuation spectrum of YBCO$_{6.6}$ contribute to $T_c$.

Inelastic Neutron Scattering Study of the Aluminum and Brønsted Site Location in Aluminosilicate LTA Zeolites

Inelastic neutron scattering (INS) has been employed to determine the location of aluminum and Bronsted acid sites in an LTA-5 sample (Si/Al = 5) with few defects of connectivity. A large number of Al and Bronsted distributions were computationally generated, and a selection of nine distributions were found to be in agreement with the 29Si NMR spectrum of the LTA sample. From the nine subsequent periodic density functional theory calculations, one of the models shows a good agreement with the INS spectrum. The suggested distribution shows Al atoms to be homogeneously distributed in the framework and protons distributed relatively far from each other. A CIF file containing the LTA-5 distribution of Al and H matching the experiments is given as the result.

Effective model with strong Kitaev interactions for α−RuCl3

We use an exact numerical diagonalization method to calculate the dynamical spin structure factors (DSFs) of three ab-initio models and one ab-initio-guided model for a honeycomb-lattice magnet $\alpha$-RuCl$_3$. We also use thermal pure quantum states to calculate the temperature dependence of the heat capacity, the nearest-neighbor (NN) spin-spin correlation function, and the static spin structure factor. From the results obtained from these four effective models, we find that, even when the magnetic order is stabilized at low temperature, the intensity at the $\Gamma$ point in the DSFs increases with increasing NN spin correlation. In addition, we find that the four models fail to explain heat-capacity measurements whereas two of the four models succeed in explaining inelastic-neutron-scattering (INS) experiments. In the four models, when temperature decreases, the heat capacity shows a prominent peak at a high temperature where the NN spin-spin correlation function increases. However, the peak temperature in heat capacity is too low in comparison with that observed experimentally. To address these discrepancies, we propose an effective model that includes strong ferromagnetic Kitaev coupling, and we show that this model quantitatively reproduces both INS experiments and heat-capacity measurements. To further examine the adequacy of the proposed model, we calculate the field dependence of the polarized terahertz spectra, which reproduces the experimental results: the spin-gapped excitation survives up to an onset field where the magnetic order disappears and the response in the high-field region is almost linear. Based on these numerical results, we argue that the low-energy magnetic excitation in $\alpha$-RuCl$_3$ is mainly characterized by interactions such as off-diagonal interactions and weak Heisenberg interactions between NN pairs, rather than by the strong Kitaev interactions.

Novel platinum-based anticancer drug: a complete vibrational study.

The introduction of cisplatin to oncology, in the 1970s, marked the onset of the search for novel and improved metal-based anticancer drugs. Polynuclear PtII and PdII complexes with linear alkylamines as bridging ligands are a class of potential antineoplastic agents that have shown promising cytotoxicity against low-prognosis human cancers, such as metastatic breast adenocarcinoma and osteosarcoma. The present study reports an analysis of [μ-N,N'-bis(3-aminopropyl)butane-1,4-diamine-κ4N,N':N'',N''']bis[dichloridoplatinum(II)], [Pt2Cl4(C10H26N4)], denoted Pt2Spm (Spm is spermine), by vibrational spectroscopy coupled to theoretical calculations. Within the latter, the Density Functional Theory (DFT - mPW1PW/6-31G*) and Effective Core Potential (ECP - LANL2DZ) approaches were used, in order to ensure the most accurate representation of the molecule and achieve a maximum agreement with the experimental data. The solid-state geometry of Pt2Spm corresponds to Ci symmetry, displaying 132 vibrational modes. A complete assignment of the experimental vibrational profile of the system was attained through the combined application of complementary Raman, FT-IR and Inelastic Neutron Scattering (INS) techniques. INS allowed an unequivocal identification of the CH2 and NH2 rocking modes, not clearly detected by the optical techniques, while Raman measurements led to a clear discrimination of the Pt-N stretching frequencies from the two distinct Pt-N moieties within the chelate. The metal-to-metal distances calculated for the molecule under study were found to allow the establishment of effective inter- and intrastrand crosslinks with DNA. These results will hopefully help to clarify the mode of action of the compound, at the molecular level, contributing to the development of improved cisplatin-like chemotherapeutic drugs having a higher efficacy and specificity coupled to lower acquired resistance and deleterious side effects.

Electron–Phonon Coupling in Luminescent Europium-Doped Hydride Perovskites Studied by Luminescence Spectroscopy, Inelastic Neutron Scattering, and First-Principles Calculations

We present a case study on the vibrational coupling of lattice phonons to the electronic 4f7 (8S7/2)–4f65d1 (eg) transition of divalent europium in the hydrides and deuterides LiMH3 and LiMD3 (M = Sr and Ba). For low doping concentrations, these compounds show extraordinarily well-resolved vibronic fine structures at low temperatures. Besides luminescence emission spectroscopy of the europium-doped compounds, we carried out inelastic neutron scattering (INS) experiments of the europium-free compounds. The phonons coupling to the electronic transition are identified, and a good agreement between the vibronic and the INS data is found. The frequencies of the low-energy acoustic modes do not significantly change upon replacing hydride by deuteride, whereas a decrease by a factor of approximately 2 can be observed for the higher energy optic modes. Furthermore, we compare these experimental results to density functional calculations performed with the Vienna Ab initio Simulation Package. Knowledge of the phon...