Incoherent inelastic neutron scattering from hexamethylene-tetramine and adamantane

The incoherent inelastic neutron scattering spectra of hexamethylene tetramine (HMT) and adamantane have been measured at high resolution between 200 and 1000 cm^-1. The agreement between the frequencies of the observed spectra and the optical spectra of Mecke and Spieseche (HMT) and Bailey (adamantane) is good. The observed neutron spectra are also matched very closely by the calculated one-phonon spectra, computed from a normal-coordinate analysis. There is some additional structure in the neutron spectra which appears to be due to multiphonon scattering involving lattice modes.     

Self-diffusion in liquid lithium from coherent quasielastic neutron scattering

Using the method of quasielastic coherent neutron scattering by liquid lithium, the temperature dependence of self-diffusion coefficient is investigated and compared with analogous data extracted by the incoherent scattering method.     

Hydrogen dynamics in Ce2Fe17H5: inelastic and quasielastic neutron scattering studies

The vibrational spectrum of hydrogen and the parameters of H jump motion in the rhombohedral Th(2)Zn(17)-type compound Ce(2)Fe(17)H(5) have been studied by means of inelastic and quasielastic neutron scattering. It is found that hydrogen atoms occupying interstitial Ce(2)Fe(2) sites participate in the fast localized jump motion over the hexagons formed by these tetrahedral sites. The H jump rate τ(-1) of this localized motion is found to change from 3.9 × 10(9) s(-1) at T = 140 K to 4.9 × 10(11) s(-1) at T = 350 K, and the temperature dependence of τ(-1) in the range 140-350 K is well described by the Arrhenius law with the activation energy of 103±3 meV. Our results suggest that the hydrogen jump rate in Th(2)Zn(17)-type compounds strongly increases with decreasing nearest-neighbor distance between the tetrahedral sites within the hexagons. Since each such hexagon in Ce(2)Fe(17)H(5) is populated by two hydrogen atoms, the jump motions of H atoms on the same hexagon should be correlated.     

Small-angle neutron scattering from micellar solutions

Micellar solutions are the suspension of the colloidal aggregates of the sur-factant molecules in aqueous solutions. The structure (shape and size) and the interaction of these aggregates, referred to as micelles, depend on the molecular architecture of the surfactant molecule, presence of additives and the solution conditions such as temperature, concentration etc. This paper gives the usefulness of small-angle neutron scattering to the study of micellar solutions with some of our recent results.     

Small-angle neutron scattering studies of aqueous solutions of short-chain amphiphiles

We present small angle neutron scattering measurements on binary aqueous solutions of some short-chain amphiphiles (diols, triols, glycols and diglycols) at room temperature. The spectra were analysed in terms of the Teubner-Strey phenomenological formula which allows to obtain a measure for the amphiphilicity strength of each system (amphiphilicity factor f _a). In some systems, however, other models, valid for micellar solutions, give also a good representation of the spectra. As a result, we find that, independently of the type of hydrophilic group side (oxydrilic or oxirane), these systems cover the entire accessible amphiphilicity scale ( -1 < f _a < 1). Some disordered systems ( f _a > 1) presumably are able to form micelle-like aggregates. Received 12 June 2002 Published online: 16 April 2003 RID="a" ID="a"e-mail: giovanni.darrigo@uniroma1.it     

Small-angle neutron scattering in aqueous solutions of fullerene-containing oligopropylene oxides

Propylene-oxide oligomers in heavy water (their molecular mass is ～500, and the concentration C varies from ～0.6 to 5.0 g/dL) and similar systems with C₆₀ and C₇₀ fullerenes and C₆₀(OH) _x fullerenols (x ～ 20), i.e., functionalized oligopropylene oxides, are studied via small-angle neutron scattering. The initial oligomers are found to create spherical micelles (～40 molecules) in the solution. It is ascertained that, in oligopropylene-oxide solutions, the C₆₀, C₇₀, and C₆₀(OH) _x derivatives (～1 wt % of fullerene relative to the oligomer) modify its molecular organization, acting as physical bonds whereby micelles are joined into large-scale linear, twisted, and branched chain superstructures.     

Small angle neutron scattering from micellar solutions

Small angle neutron scattering (SANS) is an ideal tool for studying structures of macromolecules and colloidal solutions. A number of micellar solutions have been studied in our laboratory using a home built SANS spectrometer. This paper gives an introduction to the technique of SANS and gives a brief survey of the results obtained at Trombay.     

Inelastic neutron scattering from H2 on vapour deposited CO2

Inelastic neutron scattering spectra at 17 meV and 68 meV incident energies of molecular hydrogen adsorbed on vapour deposited substrates of pure CO₂, 90:10 and 50:50 CO₂:Kr are reported. The ortho-para transition is shifted from 14.7 meV in the free H₂-molecule to 9.4 meV in a presumably commensurate ortho-H₂ monolayer on the CO₂ surface. The quadrupole-quadrupole interaction of ortho-H₂ molecules with the CO₂ substrate results in a strongly anisotropic potential. In addition to rotations the dynamics of this layer comprise a local Einstein mode and phonons in resonance with the substrate, giving rise to intense multiphonon transitions. Quasielastic scattering on warmer samples is assigned to a liquidlike adsorption layer, in which the H₂ rotations are strongly perturbed. Received: 15 October 1996 / Revised: 25 August 1997 / Accepted: 24 October 1997     

Diffusional and vibrational dynamics of ZnCl2 aqueous solutions by inelastic neutron scattering

We have studied saturated solutions of ZnCl₂ (and NiCl₂) in D₂O by time-of-flight quasi-elastic and inelastic neutron scattering spectroscopy. Spectra were taken at room temperature as a function of transferred momentum. We find that ionic diffusion in these solutions is best described by a crystal vacancy diffusion model. We also find evidence of collective excitations in the region of ～ 20 meV.     

Salt-free aqueous solutions of polyelectrolytes: Small angle X-ray and neutron scattering characterization

We give an introduction to the application of small angle X-ray and neutron scattering techniques to the study of the structure of polyelectrolyte solutions. The goal is not to be exhaustive and to describe the latest progress in the field of polyelectrolytes but rather to present the potential of the technique. We aim to give an overview on the main features of the scattering curves, and discuss the structural information that can be drawn. We will first give the basics of small angle scattering and highlight the role played by neutron scattering and isotopic labeling. Thus, we will discuss the significance of the monomer and counterion partial scattering functions according to the scattering length densities of both components, and will emphasize the unique possibility to separate out the intra- and intermolecular correlations. Then, some examples will show how the dispersion state and the average conformation of macroions can be addressed. We will however focus on salt-free aqueous solutions of linear flexible hydrophilic polyelectrolytes in the semidilute regime.     

Investigating one-dimensional diffusion by quasielastic neutron scattering: a theoretical approach

Scattering functions and full widths at half maximum for quasielastic neutron scattering (QENS) are calculated for diffusion in systems of one-dimensional channels. The self-correlation function for diffusion in isotropically oriented channels is given and it is found that this function diverges at the origin. The calculations are carried out for both normal and single-file diffusion and the influence of the ballistic phase is investigated. It is found that the ballistic phase influences the scattering functions very strongly for large diffusion coefficients. QENS data from the literature are analyzed with respect to this influence. The influence of three different resolution functions (triangular, Gaussian, and Lorentzian) is considered.     

Sodium self-diffusion coefficient in sodium silicate glass by quasielastic neutron scattering

Using pulsed neutrons of 19.8 Å wavelength a quasielastic line broadening as low as 0.03 eV (FWHM) has been observed due to Na⁺ diffusion in the glass Na₂O·2SiO₂. From the linewidths a Na⁺ self-diffusion coefficient of 3.1·10^–8 cm²/s at 420°C was obtained in excellent agreement with the diffusion coefficient determined for the same sample batch using²²Na radioactive tracers. The experimental Q dependence of the quasielasic linewidths gives a hint for deviations from a purely random walk in an ionic glass.     

Elastic and quasielastic neutron scattering studies in KBr:KCN mixed crystals

Neutron scattering studies in (KBr)_1–x(KCN)_x mixed crystals are presented utilizing powder diffraction, single crystal diffraction and time-of-flight techniques. Forx>0.6 (KBr)_1–x(KCN)_x crystals exhibit ferroelastic and ferroelectric low-temperature phases. Crystals withx<0.6 undergo transitions into an orientational glass state. Here we present a detailed phase diagram including new results for x=0.85 and x=0.65. For the latter system a stable rhombohedral low-temperature phase has been detected where the orientational disorder of the plastic phase is only partly removed and quadrupolar relaxations between three body diagonals are still possible. From the powder diffraction experiments we determined further the concentration dependence of the static Debye-Waller factors which can be explained by an interplay of the rotation-translation and the rotation-random strain coupling. With single crystal diffraction techniques we studied the diffuse scattered intensities which are directly related to the order parameter of the glass state. The temperature dependence of the quasielastic intensities near the critical concentration shows a strong increase forT<110K indicative for a freezing-in of shear fluctuations which is a characteristic feature of a non-ergodic instability. This phenomenon appears for ordering (x=0.65) and for non-ordering, glassy compounds. A further anomaly in (KBr)_0.43(KCN)_0.57 at 75 K is interpreted in terms of a residual elastic ordering process. With high-resolution time-of-flight techniques we analysed the dynamic structure factor for x=0.57. We demonstrate that the central peak consists of a static and a dynamic component. The results are compared with mode coupling theories which describe the glass transition in supercooled liquids.     

Incoherent neutron scattering by the phonon-libron system in solid ortho-hydrogen

The incoherent scattering cross section of slow neutrons by ortho hydrogen atT=0 K has been calculated for the case where only one excitation (phonon, libron resp. a mixed mode quantum) is created. The results are compared with the experiment of Stein, Stiller and Stockmeyer and prove that only the coupling of phonons and librons can produce the measured cross section.     

The diffusive motion of silver ions in α-AgI: Results from quasielastic neutron scattering

The diffusive motion of silver ions in σ-AgI at 250°C has been studied by quasielastic cold neutron scattering. Spectra were taken in the range of wavevector transfer 0.5 < Q < 2.2Å^?1 for elastic scattering. The quasielastic line shapes contain a narrow and a broad component. They are compared to model calculations allowing for the superposition of two kinds of motion on two different time scales, a local random motion and a translational motion of the jump-diffusion type. The model closely fits the data. The local random motion takes place on a time scale of the order of 10^?12 s, with amplitudes of the order of 1 Å. It is probably caused by rapid fluctuations of the local potentials due to the diffusive motion of the other cations. The translational motion results in a mean displacement of the silver ion over a distance of the order of a lattice constant (5 Å) with a correlation time of the order of 10^?11s. This correlation time is composed of a residence time and a time-of-flight, which are both of comparable magnitude.     

Sodium diffusion in cryolite at elevated temperatures studied by quasielastic neutron scattering

Quasielastic neutron scattering (QENS) has been applied to study the sodium mobility on nanosecond time scales in the perovskite fluoride cryolite, Na₃AlF₆, at high temperatures. Up to T = 1153 K the diffusion of Na ions is well described by a diffusion process of jumps between six and eight-fold coordinated sites. Above this temperature, where a step-like increase in the electrical conductivity occurs, the jump length increases, which indicates additional jumps over larger distances. The electrical conductivity derived from the self-diffusion coefficient via the Nernst–Einstein relation and the corresponding activation energy are in excellent agreement with the previous conductivity measurements. We conclude that the jump diffusion of sodium ions is the dominant mechanism for the electrical conductivity in cryolite at high temperatures up to T = 1153 K.     

Low energy elastic differential electron scattering from H2O

Normalized differential cross sections for elastic (rotationally averaged) electron scattering from gaseous water (H2O) are obtained using the relative flow method against helium with a thin aperture collimating source of gas instead of a tube. This method obviates the use of gas kinetic molecular diameters for helium or water. Our measurements are found to be largely in quantitative disagreement with past differential elastic electron scattering measurements and suggest that present recommended electron scattering total cross sections for water be revised.     

Hydration of the chloride ion in concentrated aqueous solutions using neutron scattering and molecular dynamics

Neutron scattering experiments were performed on 6 m LiCl solutions in order to obtain the solvation structure around the chloride ion. Molecular dynamics simulations on systems mirroring the concentrated electrolyte conditions of the experiment were carried out with a variety of chloride force-fields. In each case the simulations were run with both full ionic charges and employing the electronic continuum correction (implemented through charge scaling) to account effectively for electronic polarisation. The experimental data were then used to assess the successes and shortcomings of the investigated force-fields. We found that due to the very good signal-to-noise ratio in the experimental data, they provide a very narrow window for the position of the first hydration shell of the chloride ion. This allowed us to establish the importance of effectively accounting for electronic polarisation, as well as adjusting the ionic size, for obtaining a force-field which compares quantitatively to the experimental data. The present results emphasise the utility of performing neutron diffraction with isotopic substitution as a powerful tool in gaining insight and examining the validity of force-fields in concentrated electrolyte solutions.