The atomic mobility in liquid pure gallium and a gallium-nickel alloy with 2 at% of nickel is studied experimentally by incoherent quasielastic neutron scattering. The integral diffusion coefficients for all-atom diffusion are derived from the experimental data at different temperatures. DFT-based ab-initio molecular dynamics (MD) is used to find numerically the diffusion coefficient of liquid gallium at different temperatures, and numerical theory results well agree with the experimental findings at temperatures below 500 K. Machine learning force fields derived from ab-initio molecular dynamics (AIMD) overestimate within a small 6% error the diffusion coefficient of pure gallium within the genuine AIMD. However, they better agree with experiment for pure gallium and enable the numerical finding of the diffusion coefficient of nickel in the considered melted alloy along with the diffusion coefficient of gallium and integral diffusion coefficient, that agrees with the corresponding experimental values within the error bars. The temperature dependence of the gallium diffusion coefficient DGa(T) follows the Arrhenius law experimentally for all studied temperatures and below 500 K also in the numerical simulations. However, DGa(T) can be well described alternatively by an Einstein-Stokes dependence with the metallic liquid viscosity following the Arrhenius law, especially for the MD simulation results at all studied temperatures. Moreover, a novel variant of the excess entropy scaling theory rationalized our findings for gallium diffusion. Obtained values of the Arrhenius activation energies are profoundly different in the competing theoretical descriptions, which is explained by different temperature-dependent prefactors in the corresponding theories. The diffusion coefficient of gallium is significantly reduced (at the same temperature) in a melted alloy with natural nickel, even at a tiny 2 at% concentration of nickel, as compared with its pure gallium value. This highly surprising behavior contradicts the existing excess entropy scaling theories and opens a venue for further research.

We report the magnetic properties of A -site spinel compound MnSc 2 Se 4 . The macroscopic magnetic measurements uncovers successive magnetic transitions at T N1 = 2.04 K, followed by two further transitions at T N2 =1.8 K and T N3 =1.6 K. Neutron powder diffraction reveals that both, T N2 < T < T N1 and T < T N3 , orders are associated with the propagation vector k =(3/4 3/4 0), while the magnetic structures are collinear amplitude modulated and helical, respectively. Using neutron powder spectroscopy we demonstrated the effect of substitution of S by Se on the magnetic exchange. The energy range of the spin-wave excitations is supressed due to the chemical pressure of the X - ion in MnSc 2 X 4 ( X =S, Se) spinels.

It is known that the organic units in hybrid halide perovskites are free to rotate, but it is not clear if this freedom is of any relevance to the structure-property relationship of these compounds. We have employed quasi-elastic neutron scattering using two different spectrometers, thus providing a wide dynamic range to investigate the cation dynamics in methylammonium lead bromide (MAPbBr3) and formamidinium lead bromide (FAPbBr3) over a large temperature range covering all known crystallographic phases of these two compounds. Our results establish a plastic crystal-like phase forming above 30 K within the orthorhombic phase of MAPbBr3 related to 3-fold rotations of MA units around the C-N axis with an activation energy, Ea, of ∼27 meV, which has no counterpart in the FA compound. MA exhibits an additional 4-fold orientational motion of the whole molecule via rotation of the C-N axis itself with an Ea of ∼68 meV common for the high-temperature tetragonal and cubic phases. In contrast, the FA compound exhibits only an isotropic orientational motion of the whole FA unit with Ea ≈ 106 meV within the orthorhombic phase and a substantially reduced common Ea of ∼62 meV for the high-temperature tetragonal and cubic phases. Our results suggest that the rotational dynamics of the organic units, crystallographic phases, and physical properties of these compounds are intimately connected.

Molecular reorientations were studied in amorphous, partially and fully recrystallized felodipine (calcium channel blocker, a drug from the family of 1',4-dihydropyridine) using a set of experimental methods: high-resolution solid-state nuclear magnetic resonance (NMR), relaxometry NMR and quasielastic neutron scattering (QENS). The results were compared with molecular dynamics in crystalline felodipine previously investigated [A. Pajzderska, K. Drużbicki, M. A. Gonzalez, J. Jenczyk, J. Mielcarek, J. Wąsicki, Diversity of Methyl Group Dynamics in Felodipine: a DFT Supported NMR and Neutron Scattering Study, CrystEngComm, 2018, 20, 7371-7385]. The kinetics of the recrystallization was also studied. The most stable sample was the sample stored in a closed ampoule (at room temperature, in 0% RH) and its complete recrystallization lasted 105 days. In the fully recrystallized sample, the same molecular reorientation identified in the crystalline form was detected, so reorientations of all methyl groups and the ethyl ester fragment. In the partially recrystallized sample, static disorder caused by the two positions of both side chains was revealed. In the amorphous sample the reorientation of all methyl groups was analyzed and the distribution of correlation times and energy barriers connected with the loss of long-range ordering and disorder of side chains were analyzed. Additionally, inhibition of reorientation in the ethyl ester fragment was observed.

Recent experiments on proton conducting ionic liquids point to half-neutralized diamine-triflate salts as promising candidates for applications in power generation and energy conversion electrochemical devices. Structural and dynamical properties of the simplest among these compounds are investigated by a combination of density functional theory (DFT) and molecular dynamics (MD) simulations based on an empirical force field. Three different cations have been considered, consisting of a pair of amine-ammonium terminations joined by a short aliphatic segment -(CH2) n- with n = 2, 3, and 4. First, the ground state structure, vibrational eigenstates, and hydrogen-bonding properties of single ions, neutral ion pairs, small neutral aggregates of up to eight ions, and molecularly thin hydrogen bonded wires have been investigated by DFT computations. Second, structural and dynamical properties of homogeneous liquid and amorphous phases are investigated by MD simulations over the temperature range of 200 ≤ T ≤ 440 K. Structure factors, radial distribution functions, diffusion coefficient, and electrical conductivity are computed and discussed, highlighting the inherent structural heterogeneity of these compounds. The core investigation, however, is the characterization of connected paths consisting of cation chains that could support proton transport via a Grotthuss-type mechanism. Since simulations are carried out using a force field of fixed bonding topology, this analysis is based on the equilibrium structure only, using geometrical criteria to identify potential paths for proton conduction. Paths of connected cations can reach a length of 80 cations and 30 Å, provided that bridging oxygen atoms from triflate anions are taken into account. The effects of water contamination at 1% weight concentration on the structure, dynamics, and paths for proton transport are discussed.

Systematic molecular dynamics simulations based on an empirical force field have been carried out for samples of triethylammonium trifluoromethanesulfonate (triethylammonium triflate, [TEA][Tf]), covering a wide temperature range 200 K ≤ T ≤ 400 K and analyzing a broad set of properties, from self-diffusion and electrical conductivity to rotational relaxation and hydrogen-bond dynamics. The study is motivated by recent quasi-elastic neutron scattering and differential scanning calorimetry measurements on the same system, revealing two successive first order transitions at T ≈ 230 and 310 K (on heating), as well as an intriguing and partly unexplained variety of subdiffusive motions of the acidic proton. Simulations show a weakly discontinuous transition at T = 310 K and highlight an anomaly at T = 260 K in the rotational relaxation of ions that we identify with the simulation analogue of the experimental transition at T = 230 K. Thus, simulations help identifying the nature of the experimental transitions, confirming that the highest temperature one corresponds to melting, while the one taking place at lower T is a transition from the crystal, stable at T ≤ 260 K, to a plastic phase (260 ≤ T ≤ 310 K), in which molecules are able to rotate without diffusing. Rotations, in particular, account for the subdiffusive motion seen at intermediate T both in the experiments and in the simulation. The structure, distribution, and strength of hydrogen bonds are investigated by molecular dynamics and by density functional computations. Clustering of ions of the same sign and the effect of contamination by water at 1% wgt concentration are discussed as well.

Water mobility through porous rock has a role to play in many systems, such as contaminant remediation, CO2 storage, and oil recovery. We used inelastic and quasielastic neutron scattering to describe water dynamics in two different chalk samples that have similar pore volume (ranging from tens of micrometers to a few nanometers) but different water uptake properties. We observed distinct water populations, where the analysis of the quasielastic data shows that after the hydration process most of the water behaves as bulk water. However, the lack of quasielastic signal, together with the observation of a translational mode at 10 meV, imply that in chalk samples that take up less water confinement occurs mostly in the pore volume that is accessible with nitrogen adsorption measurements.

The structural phase transitions occurring in a series of perovskite-type complex hydrides based on the tetrahydroborate anion BH4(-) are investigated by means of in situ synchrotron x-ray powder diffraction, vibrational spectroscopy, thermal methods and ab initio calculations in the solid state. Structural dynamics of the BH4 anion are followed with quasi-elastic neutron scattering. We show that unexpected temperature-induced lattice instabilities in perovskite-type ACa(BH4)3 (A = K, Rb, Cs) have their origin in close hydridic di-hydrogen contacts. The rich lattice dynamics lead to coupling between internal B-H vibrations and phonons, resulting in distortions in the high-temperature polymorph that are identical in symmetry to well-known instabilities in oxide perovskites, generally condensing at lower temperatures. It is found that anion-substitution BH4(-) <-> (X = Halide) can relax distortions in ACa(BH4)3 by eliminating coulomb repulsive H(-)···H(-) effects. The interesting nature of phase transition in ACa(BH4)3 enters an unexplored field of weak interactions in ceramic-like host lattices and is the principal motivation for this study. Close di-hydrogen contacts suggest new concepts to tailor crystal symmetries in complex hydride perovskites in the future.

YbNi4P2 is one of the very few heavy-fermion systems which allow the study of ferromagnetic quantum criticality. The Curie temperature TC=0.17 K can be suppressed by substituting arsenic on the phosphorus site, without changing the ferromagnetic nature of the ordered state. The ordered moment, even of the unsubstituted compound, is only around 0.05 μB, which hinders elastic neutron scattering experiments. To gain microscopic insight into the nature of the interactions, we have studied the magnetic excitations of polycrystalline YbNi4P2 by time-of-flight neutron spectroscopy. For momentum transfers larger than about 0.6 Å−1 we find a quasi-elastic response whose width at low temperatures is limited by the Kondo effect. In contrast, the low-energy magnetic response is distinctly different for Q approaching zero: At low temperatures, but still in the paramagnetic phase, susceptibility and lifetime of the spin fluctuations are strongly enhanced, indicating the proximity of ferromagnetism.

Inelastic neutron scattering was employed to study the crystal-field interaction in the strontium-doped rare-earth compounds R(x)Sr(1-x)CoO(3-z) (R=Pr, Nd, Ho, and Er). Particular emphasis is laid on the effect of oxygen deficiencies which naturally occur in the synthesis of these compounds. The observed energy spectra are found to be the result of a superposition of crystal fields with different nearest-neighbor oxygen coordination at the R sites. The experimental data are interpreted in terms of crystal-field parameters which behave in a consistent manner through the rare-earth series, thereby allowing a reliable extrapolation for rare-earth ions not considered in the present work.

Defects intentionally introduced into magnetic materials often have a profound effect on the physical properties. Specifically tailored neutron spectroscopic experiments can provide detailed information on both the local exchange interactions and the local distances between themagnetic atoms around the defects. This is demonstrated for manganese dimer excitations observed for the magnetically diluted three- and two-dimensional compounds KMnx Zn1-x F-3 andK(2)Mn(x) Zn1-x F-4, respectively. The resulting local exchange interactions deviate up to 10% from the average, and the local Mn-Mn distances are found to vary stepwise with increasing internal pressure due to the Mn/Zn substitution. Our analysis qualitatively supports the theoretically predicted decay of atomic displacements according to 1/r2, 1/r, and constant (for three-, two-, and one-dimensional compounds, respectively) where r denotes the distance of the displaced atoms from the defect.

Obtaining solid-state electrolytes with good electrochemical performances remain challenging. Ionogels, i. e. solid host network confining an ionic liquid, are promising as they keep the macroscopic properties of the confined liquid. However, confinement of an ionic liquid can imply important changes in its molecular dynamics, depending on the route of synthesis and on the confining network. We studied this effect on an imidazolium based ionic liquid with its Lithium salt confined in a biopolymersilica matrix. Dynamics of bulk and confined solution was probed by quasi-elastic neutron scattering (QENS). The scattering function was modeled successfully with two Lorentzian functions in both cases and revealed a weakly slowed dynamics of imidazoliumbased ionic liquid inside the polymer-silica host network.

Saponite clay belongs to the phyllosilicate family and is comprised of layers of Si(IV) tetrahedra and Al(III) or Mg(II) octahedra with definite interlayer spacing. In these systems, the trivalent ion substitutions in the tetrahedral layers lead to negative charge on the layers. Here we report the dynamics of water contained in [Si(6.97)Al(1.03)][Ni(6.00)]O(20)(OH)(4)[Na(1.03)]·28H(2)O (SAP-1) and [Si(7.13)Fe(0.86)][Ni(6.00)]O(20)(OH)(4)[Na(0.86)]·14H(2)O (SAP-2) saponite clays in the temperature range 200-310 K as studied by quasielastic neutron scattering technique. Particularly the effect of the ion substitution towards the dynamics of water is addressed here. Data analysis is carried out using the relaxing cage model. The existence of distribution in relaxation times indicated that the water molecules in saponite clay have a different local environment which leads to complex diffusion behavior. It is found that water exists in a supercooled state in the temperature range up to 235 K. However, some of the water molecules are found to be immobile in the temperature range 240-285 K. The fraction of immobile water decreases with increase in temperature. At higher temperatures, some of the water molecules in the hydration shells or those near the surface start participating in the diffusion process and at 293 K, almost all water molecules contribute to the dynamics. Diffusivity of water in both SAP-1 and SAP-2 are found to be lower in comparison to the bulk, and within the two samples of saponite clay diffusivity in SAP-1 is found to be lower compared to SAP-2; this has been explained on the basis of the charge on the tetrahedral layers and the charge balancing cations in the interlayer spacing.

Dynamics of water contained in interlamellar space in synthetic saponite clay, [Si-6.343 Al-1.657] [Mg-6.000]O-20(OH)(4)[Na1.465Mg0.096]center dot 34H(2)O is studied in the temperature range of the 220-310 K using quasielastic neutron scattering (QENS) technique. Saponite clay belongs to the phyllosilicate family comprising the layers of Si(IV) tetrahedra and Fe(III) or Mg(II) octahedra with definite interlayer spacing. It is known that structure and dynamical properties of water confined in clay systems change due to the interactions with the clay surface. Relaxing Cage Model (RCM) is used in the data analysis as it takes into account the effects arising from the clay-water interaction and gives the best physical description to the dynamical behaviour of the confined water. Data analysis showed that water confined in the interlamellar spacing undergoes partial freezing at T similar to 285 K. Translational diffusivity of the confined water is hindered compared to the bulk water indicating that the bond formation between water and clay surface as well as charge balancing cations alters the dynamical behaviour of the water.

We investigate the dynamics of water absorbed in amorphous and semicrystalline aromatic polyamide copolymers. The combination of dielectric spectroscopy and quasi-elastic neutron scattering experiments allows us to characterize the water dynamics over a wide range of temperatures (dielectric spectroscopy) and at microscopic length scales (neutron scattering). The dielectric investigation evidences two relaxations associated with water motions: a fast process corresponding to motions of loosely bonded water molecules and a slower process corresponding to motions of amide-water complexes. While the slower process presents the characteristic Arrhenius temperature dependence of a secondary local relaxation over the whole temperature range, the fast process shows a crossover from Arrhenius to Vogel-Fulcher-Tamman (VFT) behavior at T approximate to 225 K, characteristic of confined water dynamics. The microscopic investigation by neutron scattering shows than in the VFT regime of the fast process the dynamics present a diffusive nature similar to bulk water. A large distribution of diffusion coefficients indicates possible differences in the connectivity of the hydrogen bond network. Diffusive heterogeneous dynamics can arise from a nonuniform distribution of water. The confinement effect of the polymer matrix is detected as a considerable reduction of the diffusion coefficient of water with respect to bulk. The presence of a crystalline phase results in a slowing down of both the fast and slow processes involving water motions. This could give a hint to the presence of a rigid amorphous phase in the semicrystalline material.

We introduce a novel method for local structure determination with a spatial resolution of the order of 0.01 Å. It can be applied to materials containing clusters of exchange-coupled magnetic atoms. We use neutron spectroscopy to probe the energies of the cluster excitations which are determined by the interatomic coupling strength J. Since for most materials J is related to the interatomic distance R through a linear relation dJ/dR=α (for dR/R≪1), we can directly derive the local distance R from the observed excitation energies. This is exemplified for the mixed one-dimensional paramagnetic compound CsMn(x)Mg(1-x)Br3 (x=0.05,0.10) containing manganese dimers oriented along the hexagonal c axis. Surprisingly, the resulting Mn-Mn distances R do not vary continuously with increasing internal pressure but lock in at some discrete values.

We studied the aggregation of magnetic particles into chain-like structures in a cobalt-based magnetic fluid, exposed to external magnetic fields. The length of chain segments in very strong magnetic fields of up to 2 Tesla was measured in situ using small angle neutron scattering. Arrangement of the magnetic particles was studied with the scattering vector (Q) over right arrow aligned parallel to the magnetic field lines, and at angles of 30 degrees and 60 degrees with respect to (B) over right arrow. Although chains several hundred particles in length were predicted, we observe a maximum correlation length of similar to 65 nm equivalent to 3-4 particles up to highest fields. We speculate that the interaction between chains, i.e., the interplay between the entropy and energy of the system combined with the particular properties of the magnetic dipole-dipole interaction ultimately decide the length of the particle chains.

We present a quasielastic neutron scattering (QENS) investigation of the component dynamics in an aqueous Poly(vinyl methyl ether) (PVME) solution (30% water content in weight). In the glassy state, an important shift in the Boson peak of PVME is found upon hydration. At higher temperatures, the diffusive-like motions of the components take place with very different characteristic times, revealing a strong dynamic asymmetry that increases with decreasing T. For both components, we observe stretching of the scattering functions with respect to those in the bulk and non-Gaussian behavior in the whole momentum transfer range investigated. To explain these observations we invoke a distribution of mobilities for both components, probably originated from structural heterogeneities. The diffusive-like motion of PVME in solution takes place faster and apparently in a more continuous way than in bulk. We find that the T-dependence of the characteristic relaxation time of water changes at T ≲ 225 K, near the temperature where a crossover from a low temperature Arrhenius to a high temperature cooperative behavior has been observed by broadband dielectric spectroscopy (BDS) [S. Cerveny, J. Colmenero and A. Alegría, Macromolecules, 38, 7056 (2005)]. This observation might be a signature of the onset of confined dynamics of water due to the freezing of the PVME dynamics, that has been selectively followed by these QENS experiments. On the other hand, revisiting the BDS results on this system we could identify an additional "fast" process that can be attributed to water motions coupled with PVME local relaxations that could strongly affect the QENS results. Both kinds of interpretations, confinement effects due to the increasing dynamic asymmetry and influence of localized motions, could provide alternative scenarios to the invoked "strong-to-fragile" transition.

Inelastic neutron scattering was employed to study the magnetic excitations of Mn${}^{3+}$ dimers in LaMn${}_{0.1}$Ga${}_{0.9}$O${}_{3}$. The nearest-neighbor interaction of Mn${}^{3+}$ ions is ferromagnetic in the basal (a-b) plane, but antiferromagnetic along the $c$ direction; thus two different types of dimer excitations are simultaneously present in the experiments. From the observed energy spectra we derive Heisenberg-type exchange interactions ${J}_{\mathit{ab}}$ $=$ 0.210(4) meV and ${J}_{c}$ $=$ --0.285(5) meV as well as an axial anisotropy parameter $D$ $=$ 0.036(6) meV. These parameters differ considerably from those derived for the isostructural parent compound LaMnO${}_{3}$ due to structural effects.