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Organic molecular thin-films are employed for manufacturing a wide variety of electronic devices, including memory devices and transistors. A precise description of the atomic-scale interactions in aromatic carbon systems is of paramount importance for the design of organic thin-films and carbon-based nanomaterials. Here we investigate the binding and structure of pyrazine on graphite with neutron diffraction and spin-echo measurements. Diffraction data of the ordered phase of deuterated pyrazine, (C

Using helium-3 atom scattering, we have studied the adsorption kinetics, the structure and the diffusional dynamics of atomic hydrogen on the surface of a graphene monolayer on Ni(111). Diffraction measurements reveal a 4° rotated rectangular hydrogen overstructure. Hydrogen adsorption and desorption exhibit activation barriers of E a = ( 89 ± 7 ) meV and E d = ( 1.8 ± 0.2 ) eV, respectively. Helium-3 spin-echo measurements showed no decay of the spatial correlation function (or intermediate scattering function) within the time range of the spectrometer. Hence, we are able to set lower limits for a possible hydrogen surface diffusion rate.

Organic solar cells (OSCs) based on ADA-type (acceptor-donor-acceptor) non-fullerene acceptors (NFAs) exhibit improved power conversion efficiency (PCE) compared to the conventional fullerene-based analogues. The optoelectronic properties of OSC active layer blends are correlated to their underlying structural dynamics and therefore influence the device performance. Using synergistically different neutron spectroscopy techniques, we studied the dynamics of binary and ternary blends made of the NFAs O-IDTBR and O-IDFBR and the regioregular donor polymer P3HT. Deuteration was considered for a contrast variation purpose. In addition to shedding light on the miscibilty and alloying characters of the blends, a main outcome of this work is the evidenced similar dynamical response of the blend components. This finding is in contrast with our previous neutron spectroscopy and molecular dynamics studies of the fullerene-based blend P3HT:PCBM, where we highlighted distinct behaviors of P3HT and PCBM in terms of the vitrification/frustration of P3HT and the plasticization of PCBM by P3HT upon blending. Alike P3HT vitrification is not presently observed. The absence or the weak vitrification evidenced here is in line with recent reports and is likely related to the improved PCE exhibited by the ADA-type NFA-based OSCs.

The diffusional behaviour of H2 adsorbed in a novel mesoporous N-doped carbon material and on exfoliated graphite has been studied with quasi-elastic neutron scattering. While the activation energies for diffusion obtained for exfoliated graphite was in line with prior results, H2 in the mesoporous carbon showed an exceptionally low diffusion barrier and behaved qualitatively like liquid hydrogen. Complementary results from neutron and X-ray diffraction as well as from isothermal nitrogen sorption studies provide a full characterisation of this novel mesoporous carbon.

In this work, we present the synthesis of two analogues of a lactic acid derivative selectively deuterated on phenyl and biphenyl moieties together with a detailed investigation of their pr...

The interfacial behaviour of water remains a central question to fields as diverse as protein folding, friction and ice formation. While the properties of water at interfaces differ from those in the bulk, major gaps in our knowledge limit our understanding at the molecular level. Information concerning the microscopic motion of water comes mostly from computation and, on an atomic scale, is largely unexplored by experiment. Here, we provide a detailed insight into the behaviour of water monomers on a graphene surface. The motion displays remarkably strong signatures of cooperative behaviour due to repulsive forces between the monomers, enhancing the monomer lifetime ( ≈ 3 s at 125 K) in a free-gas phase that precedes the nucleation of ice islands and, in turn, provides the opportunity for our experiments to be performed. Our results give a molecular perspective on a kinetic barrier to ice nucleation, providing routes to understand and control the processes involved in ice formation., The dynamics of water molecules at interfaces controls natural and artificial processes, but experimental investigations have been challenging. Here the authors investigate water molecules on a graphene surface using helium spin-echo spectroscopy, and reveal a regime where freely mobile molecules undergo strong repulsive mutual interactions which inhibit ice nucleation.

In this study, we investigate the influence of the block copolymer architecture on the bending elasticity of polymer-rich lamellar phases. In detail, we study the polymer-rich system water/o-xylene/Pluronic triblock copolymer/C8TAB and change the polymer while keeping the mass ratios constant. We use neutron spin echo measurements (NSE) to determine κ. With the measurements we determine the relaxation rate Γqz,ZG of the bilayer bending mode and subsequently calculate the bilayer bending modulus κ using the Zilman-Granek approach [Zilman et al., Phys. Rev. Lett. 77, 4788–4791 (1996)]. Moreover, we have investigated the lamellar phases via small-angle X-ray scattering (SAXS) and have analysed the data with the modified Caillé theory to obtain the Caillé parameter η. Based on κ the bulk compression modulus B can be calculated. Increasing values of κ are found with increasing EO and PO block size in the range of 3.8 to 13.4 kBT. The computed values of B are in the range of 103 to 105 Pa.

The diffusion of hydrogen adsorbed inside layered MoS

The impact of purely intramolecular cross-linking on the properties of a polymer melt is studied by neutron diffraction and quasielastic incoherent and coherent neutron scattering on a system composed exclusively of single-chain nanoparticles. As a reference, a parallel study is presented on the melt of the linear precursor chains’ counterpart. Associated with structural heterogeneities provoked by the internal compartmentalization due to cross-links, a dramatic slowing down of the relaxation of density fluctuations is observed at intermediate length scales., We acknowledge the financial support of the Basque Government (Code No. IT-1175-19) and the Ministerio de Economía y Competitividad [Code No. PGC2018-094548-B-I00 (MCIU/AEI/FEDER, UE)]. This work was based on experiments performed at the FOCUS instrument operated by the Swiss spallation neutron source SINQ (Paul Scherrer Institute, Villigen, Switzerland) and SPHERES [Heinz–Maier–Leibnitz Zentrum (MLZ), Garching, Germany] and was supported by the European Commission under the 7th Framework Programme through the “Research Infrastructures” action of the “Capacities” Programme, NMI3-II (Grant No. 283883).

This article belongs to the Special Issue Single-Chain Polymer Nanotechnology., We investigate the effect of intra-molecular cross-links on the properties of polymer bulks. To do this, we apply a combination of thermal, rheological, diffraction, and neutron spin echo experiments covering the inter-molecular as well as the intermediate length scales to melts of single-chain nano-particles (SCNPs) obtained through ‘click’ chemistry. The comparison with the results obtained in a bulk of the corresponding linear precursor chains (prior to intra-molecular reaction) and in a bulk of SCNPs obtained through azide photodecomposition process shows that internal cross-links do not influence the average inter-molecular distances in the melt, but have a profound impact at intermediate length scales. This manifests in the structure, through the emergence of heterogeneities at nanometric scale, and also in the dynamics, leading to a more complex relaxation behavior including processes that allow relaxation of the internal domains. The influence of the nature of the internal bonds is reflected in the structural relaxation that is slowed down if bulky cross-linking agents are used. We also found that any residual amount of cross-links is critical for the rheological behavior, which can vary from an almost entanglement-free polymer bulk to a gel. The presence of such inter-molecular cross-links additionally hinders the decay of density fluctuations at intermediate length scales., This research was funded by the Basque Government, code: IT-1175-19 and the Ministerio de Economía y Competitividad code: PGC2018-094548-B-I00 (MCIU/AEI/FEDER, UE).

We present a combined experimental and theoretical study of the self-diffusion of ammonia on exfoliated graphite. Using neutron time-of-flight spectroscopy we are able to resolve the ultrafast diffusion process of adsorbed ammonia, NH3, on graphite. Together with van der Waals corrected density functional theory calculations we show that the diffusion of NH3 follows a hopping motion on a weakly corrugated potential energy surface with an activation energy of about 4 meV which is particularly low for this type of diffusive motion. The hopping motion includes further a significant number of long jumps and the diffusion constant of ammonia adsorbed on graphite is determined with D = 3.9 ⋅ 10 − 8 m 2 / s at 94 K.

International audience; Hemoglobin (Hb) is an extensively studied paradigm of proteins that alter their function in response to allosteric effectors. Models of its action have been used as prototypes for structure-function relationships in many proteins, and models for the molecular basis of its function have been deeply studied and extensively argued. Recent reports suggest that dynamics may play an important role in its function. Relatively little is known about the slow, correlated motions of hemo-globin subunits in various structural states because experimental and computational strategies for their characterization are challenging. Allosteric effectors such as inositol hexaphosphate (IHP) bind to both deoxy-Hb and HbCO, albeit at different sites, leading to a lowered oxygen affinity. The manner in which these effectors impact oxygen binding is unclear and may involve changes in structure, dynamics or both. Here we use neutron spin echo measurements accompanied by wide-angle X-ray scattering to show that binding of IHP to HbCO results in an increase in the rate of coordinated motions of Hb subunits relative to one another with little if any change in large scale structure. This increase of large-scale dynamics seems to be coupled with a decrease in the average magnitude of higher frequency modes of individual residues. These observations indicate that enhanced dynamic motions contribute to the functional changes induced by IHP and suggest that they may be responsible for the lowered oxygen affinity triggered by these effectors.

The diffusion of hydrogen molecules adsorbed in a highly porous carbon aerogel has been studied with quasi-elastic neutron scattering. Hydrogen diffusion in this carbon substrate followed an activated jump process with a single activation barrier. The temperature dependence of the diffusion rate agrees well with previous results from activated carbons and other highly porous carbons. The carbon aerogel sample showed a strongly enhanced conversion between the ortho- and para-hydrogen spin states. The ortho-para conversion process, however, was inhibited for a fraction of the hydrogen molecules. This inhibition process is attributed to a rotational confinement of the hydrogen molecules at the nanometre scale.

The presence of spin-fluctuations deep within the ordered state of ferromagnetic [Formula: see text] alloy [Formula: see text] has long been suspected but seldom directly observed. Inhomogeneities of one type or another have been cited as important in stabilizing [Formula: see text] behaviour-either longitudinal spin-fluctuations associated with the [Formula: see text]-state (local environment) model or transverse magnetisation arising from non-collinear spin structures. In this study we employ small-angle neutron scattering with neutron polarization analysis to distinguish between the two possibilities. Surprisingly we in fact find evidence of dominant but uncorrelated longitudinal spin-fluctuations coexisting with transverse magnetisation which exists in short-range clusters of size ~[Formula: see text]. This finding supports recent first principles calculations of [Formula: see text] in which both longitudinal spin-fluctuations and magnetic short-range order are identified as important ingredients in reproducing the equilibrium [Formula: see text] lattice.

Excitations in a spin ice behave as magnetic monopoles, and their population and mobility control the dynamics of a spin ice at low temperature. CdEr_{2}Se_{4} is reported to have the Pauling entropy characteristic of a spin ice, but its dynamics are three orders of magnitude faster than the canonical spin ice Dy_{2}Ti_{2}O_{7}. In this Letter we use diffuse neutron scattering to show that both CdEr_{2}Se_{4} and CdEr_{2}S_{4} support a dipolar spin ice state-the host phase for a Coulomb gas of emergent magnetic monopoles. These Coulomb gases have similar parameters to those in Dy_{2}Ti_{2}O_{7}, i.e., dilute and uncorrelated, and so cannot provide three orders faster dynamics through a larger monopole population alone. We investigate the monopole dynamics using ac susceptometry and neutron spin echo spectroscopy, and verify the crystal electric field Hamiltonian of the Er^{3+} ions using inelastic neutron scattering. A quantitative calculation of the monopole hopping rate using our Coulomb gas and crystal electric field parameters shows that the fast dynamics in CdEr_{2}X_{4} (X=Se, S) are primarily due to much faster monopole hopping. Our work suggests that CdEr_{2}X_{4} offer the possibility to study alternative spin ice ground states and dynamics, with equilibration possible at much lower temperatures than the rare earth pyrochlore examples.

The dynamic properties of heavy water (D2O) and light water (H2O) confined in porous silica SBA-16 were studied over a temperature range of 210-290 K by neutron spin echo measurements. SBA-16 has predominant spherical pores (7.1 nm in pore size), channels interconnecting the spherical pores, and micropores (corona). The coherent intermediate scattering function on D2O filled SBA-16 showed the rotational dynamics of confined water without significant translational motion over the temperature range measured. This finding is due probably to collective entities of water due to cooperativity of hydrogen-bonds among water molecules in SBA-16 pores. The relaxation time of the collective entities followed the Vogel-Fulcher-Tammann relation at temperatures down to the freezing temperature of 235 K, suggesting a behavior of fragile water in the spherical pore. A comparison with previous NSE measurements of D2O in MCM-41 showed that the collective entities of water in the SBA-16 spherical pores have higher rotational mobility than those in the MCM-41 cylindrical pores. On the other hand, the incoherent intermediate scattering function on H2O filled SBA-16 revealed the translational motion of individual water molecules in the collective entities. It has been found that water in micropores is not frozen and is mobile down to 210 K from data of both D2O and H2O in SBA-16. Phase changes of various water confined in SBA-16 with decreasing and increasing temperatures are discussed based on the obtained dynamic properties.

International audience; When probed at the macroscopic scale, Ionic Liquids (ILs) behave as highly dissociated (i.e. strong) electrolytes while, at the molecular scale, they show clear characteristics of weak ionic solutions. The multi-scale analysis we report in this paper reconciles these apparently at odds behaviors. We investigate by quasi-elastic neutron scattering (QENS) and neutron spin-echo (NSE), the nanometer/nanosecond dynamics of OMIM-BF4, an imidazolium-based IL showing strong nanostructuration. We also probe the same IL on the microscopic (μm and ms) scale by pulsed field gradient NMR. To interpret the neutron data, we introduce a new physical model to account for the dynamics of the side-chains and for the diffusion of the whole molecule. This model describes the observables over the whole and unprecedented investigated spatial ([0.15–1.65] Å−1) and time ([0.5–2000] ps) ranges. We arrive at a coherent and unified structural/dynamical description of the local cation dynamics: a localized motion within the IL nanometric domains is combined with a genuine long-range translational motion. The QENS, NSE and NMR experiments describe the same long-range translational process, but probed at different scales. The associated diffusion coefficients are more than one order of magnitude different. We show how this apparent discrepancy is a manifestation of the IL nanostructuration.

International audience; Hydrated samples of the two proton conducting perovskites BaZr 0.9 M 0.1 O 2.95 (M = Y and Sc) were investigated using neutron spin−echo spectroscopy together with thermal gravimetric measurements, polarized neutron diffraction, and infrared spectroscopy, with the aim to determine how the atomic-scale proton dynamics depend on temperature, and type of dopant atom, M. The results show the presence of pronounced localized proton motions for temperatures above ca. 300 K, characterized by relaxation times on the order of picoseconds to nanoseconds and governed by a wide distribution of activation energies due to a heterogeneous distribution of proton sites present, with no strong dependence on the type of dopant atom.

Membrane pores can significantly alter not only the permeation dynamics of biological membranes but also their elasticity. Large membrane pores able to transport macromolecular contents represent an interesting model to test theoretical predictions that assign active-like (non-equilibrium) behavior to the permeability contributions to the enhanced membrane fluctuations existing in permeable membranes [Maneville et al. Phys. Rev. Lett. 82, 4356 (1999)]. Such high-amplitude active contributions arise from the forced transport of solvent and solutes through the open pores, which becomes even dominant at large permeability. In this paper, we present a detailed experimental analysis of the active shape fluctuations that appear in highly permeable lipid vesicles with large macromolecular pores inserted in the lipid membrane, which are a consequence of transport permeability events occurred in an osmotic gradient. The experimental results are found in quantitative agreement with theory, showing a remarkable dependence with the density of membrane pores and giving account of mechanical compliances and permeability rates that are compatible with the large size of the membrane pore considered. The presence of individual permeation events has been detected in the fluctuation time-series, from which a stochastic distribution of the permeation events compatible with a shot-noise has been deduced. The non-equilibrium character of the membrane fluctuations in a permeation field, even if the membrane pores are mere passive transporters, is clearly demonstrated. Finally, a bio-nano-technology outlook of the proposed synthetic concept is given on the context of prospective uses as active membrane DNA-pores exploitable in gen-delivery applications based on lipid vesicles.

9 pags.; 5 figs.; 1 tab.; 2 apps., © 2014 Elsevier Ltd. All rights reserved. New insight into the nature of diffusion and the origin of friction of a prototype system for weak physisorption-benzene molecules, C6H6, adsorbed on the basal plane (0001) of graphite-has been obtained with quasi-elastic neutron scattering (QENS). Spectra were measured at relative adsorbate coverages between 0.1 and 1.0 monolayers (ML) and at sample temperatures between 60 K and 140 K. Our experimental observations require a substantial modification of the model of interaction between benzene molecules and graphite surfaces: in contrast to recent studies we find only weak kinetic surface friction, but a substantial dissipative interaction during inter-molecular collisions. At coverages of up to 0.5 ML the molecular dynamics are successfully modeled by a rough hard disk model, which we derive from a three-dimensional rough hard sphere model. At the full monolayer, three body and higher order collisions are dominant and the rough hard disk model breaks down, as expected.

An exact description of the interactions in aromatic carbon systems is a key condition for the design of carbon based nanomaterials. In this paper we investigate the binding and adsorbate structure of the simplest prototype system in this class – the single aromatic ring molecule benzene on graphite. We have collected neutron diffraction data of the ordered phase of deuterated benzene, C6D6, adsorbed on the graphite (0001) basal plane surface. We examined relative coverages from 0.15 up to 1.3 monolayers (ML) in a temperature range of 80 to 250 K. The results confirm the flat lying commensurate (√7 x √7) R19.1° monolayer with lattice constants a = b = 6.5 Å at coverages of less than 1 ML. For this structure we observe a progressive melting well below the desorption temperature. At higher coverages we do neither observe an ordered second layer nor a densification of the structure by upright tilting of first layer molecules, as generally assumed up to now. Instead, we see the formation of clusters with a bulk crystalline structure for coverages only weakly exceeding 1 ML.

6 págs.; 3 figs.; 2 tabs., This work presents an experimental picture of molecular ballistic diffusion on a surface, a process that is difficult to pinpoint because it generally occurs on very short length scales. By combining neutron time-of-flight data with molecular dynamics simulations and density functional theory calculations, we provide a complete description of the ballistic translations and rotations of a polyaromatic hydrocarbon (PAH) adsorbed on the basal plane of graphite. Pyrene, CH, adsorbed on graphite is a unique system, where at relative surface coverages of about 10-20% its mean free path matches the experimentally accessible time/space scale of neutron time-of-flight spectroscopy (IN6 at the Institut Laue-Langevin). The comparison between the diffusive behavior of large and small PAHs such as pyrene and benzene adsorbed on graphite brings a strong experimental indication that the interaction between molecules is the dominating mechanism in the surface diffusion of polyaromatic hydrocarbons adsorbed on graphite. © 2016 American Chemical Society, I.C.-A. is grateful to the Ramón Areces foundation for the funding of her postdoctoral research position. M.S. thanks the U.K.’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202); this work used the ARCHER U.K. National Supercomputing Service. E.B. acknowledges financial support by the graduate college of the Université de Grenoble (France) and A.T. thanks the FWF (Austrian Science Fund) for financial support within the project J3479-N20. S.M.-A. acknowledges the funding from the project FIS2014-52172- C2-1-P, from Ministerio de Economia y Competitividad (Spain).

We investigate the collective dynamics of comblike polymers displaying nanosegregation in side groups and main-chain rich domains, where side groups and backbones are dynamically equivalent. Neutron spin-echo experiments on poly(alkylene oxide)s with increasing side-group length have been focused on the decay of inter- and intradomain correlations and are complemented with molecular dynamics simulations on a coarse-grained model. In general, a good qualitative agreement between simulation and experiment is found. The collective times at inter- and intradomain levels converge with decreasing temperature, implying a common glass transition, and separate at high temperatures, revealing an increasing role of connectivity. The features of collective relaxations—regarding stretching, characteristic time, and temperature dependence—are independent of branching. The standard stretching for side-group motions and the closeness of collective and self-motions show that the anomalies exhibited by dynamically asymmetric comblike macromolecules disappear., The authors acknowledge financial support from the projects MAT2015-63704-P (Spanish-MINECO and EU) and IT-654-13 (Basque Government). This work is partially based on experiments performed at JCNS-instrument J-NSE (Heinz Maier-Leibnitz Zentrum (MLZ), Garching, Germany) and has been supported by the European Commission under the seventh Framework Programme through the “Research Infrastructures” action of the “Capacities” Programme, NMI3-II Grant 283883, and through the grant agreement for the Integrated Infrastructure Initiative N. 262348 European Soft Matter Infrastructure (ESMI).

This paper describes the optimization of an entire neutron guide system, from the moderator to the sample position for several instruments simultaneously, using no more than a desktop computer and a few days of CPU time. This is made possible by merging two relatively advanced computational techniques. Neutron acceptance diagram shading is a fast new method for modelling neutron beams, using an approach based on polygons similar to those featuring in computer games. Optimization algorithms based on swarm intelligence are efficient and reliable ways to maximize numerically calculable figures of merit with many strongly coupled geometry parameters. Recent developments in these methods are described, as well as their combination to optimize the geometry of the H5 beamlines at the Institut Laue–Langevin. The optimization was such that all instruments simultaneously gain as much on-sample flux as possible by taking unused phase space from their neighbours, whilst no instrument suffers any losses in its useful flux.

The presence of spin-fluctuations deep within the ordered state of ferromagnetic [Formula: see text] alloy [Formula: see text] has long been suspected but seldom directly observed. Inhomogeneities of one type or another have been cited as important in stabilizing [Formula: see text] behaviour-either longitudinal spin-fluctuations associated with the [Formula: see text]-state (local environment) model or transverse magnetisation arising from non-collinear spin structures. In this study we employ small-angle neutron scattering with neutron polarization analysis to distinguish between the two possibilities. Surprisingly we in fact find evidence of dominant but uncorrelated longitudinal spin-fluctuations coexisting with transverse magnetisation which exists in short-range clusters of size ~[Formula: see text]. This finding supports recent first principles calculations of [Formula: see text] in which both longitudinal spin-fluctuations and magnetic short-range order are identified as important ingredients in reproducing the equilibrium [Formula: see text] lattice.

Neutron spin-echo spectroscopy was used to study structural fluctuations that occur in hemoglobin (Hb) and myoglobin (Mb) in solution. Using neutron spin-echo data up to a very high momentum transfer q ( approximately 0.62 A(-)(1)), we characterized the internal dynamics of these proteins at the levels of dynamic pair correlation function and self-correlation function in the time range of several picoseconds to a few nanoseconds. In the same protein solution, data transition from pair correlation motion to self-correlation motion as the momentum transfer q increases. At low q, coherent scattering dominates; at high q, observations are largely due to incoherent scattering. The low q data were interpreted in terms of an effective diffusion coefficient; on the other hand, the high q data were interpreted in terms of mean square displacements. Comparison of data from the two homologous proteins collected at different temperatures and protein concentrations was used to assess the contributions made by translational and rotational diffusion and internal modes of motion to the data. The temperature dependence of decay times can be attributed to changes in the viscosity and temperature of the solvent, as predicted by the Stokes-Einstein relationship. This is true for contributions from both diffusive and internal modes of motion, indicating an intimate relationship between the internal dynamics of the proteins and the viscosity of the solvent. Viscosity change associated with protein concentration can account for changes in diffusion observed at different concentrations, but is apparently not the only factor involved in the changes in internal dynamics observed with change in protein concentration. Data collected at high q indicate that internal modes in Mb are generally faster than those in Hb, perhaps due to the greater surface-to-volume ratio of Mb and the fact that surface groups tend to exhibit faster motion than buried groups. Comparison of data from Hb and data from Mb at low q indicates an unexpectedly rapid motion of Hb alphabeta dimers relative to one another. Dynamic motion of subunits is increasingly perceived as important to the allosteric behavior of Hb. Our data demonstrate that this motion is highly sensitive to protein concentration, temperature, and solvent viscosity, indicating that great care needs to be exercised in interpreting its effect on protein function.

We investigate proton self-dynamics in the acceptor-doped and hydrated proton-conducting perovskite-type oxides BaInxZr1-xO3-x/2 (x = 0.10 and 0.50) on a microscopic length scale for temperatures in the range 470-525 K, using neutron spin-echo spectroscopy. For the highly doped material (x = 0.50), we observe a wide range of translational diffusional rates of the protons in the Structure, oil the nanosecond time scale and with in effective activation energy of about 0.75 eV. The wide distribution of diffusional rates is related to the In-doping, which creates local structural distortions or the average Cubic Structure and thus many structurally different Configurations of the protons, each with slightly different energy barriers for the protonic motion. For the weakly doped material (x = 0.10), which has a more ordered local Structure, the results show proton dynamics oil a Much more well-defined time scale, similar to 60 ps at 500 K, but also Suggest that a significant part of the protons ill the Structure are "immobile" within the experimental neutron spin-echo time window (similar to 5 ps to 1.3 ns). Furthermore, the results indicate that the dopant atoms affect the proton diffusion ill a nonlocalized manner and not as well-localized trapping centers.

We review recent advances in neutron and helium spin-echo spectroscopy, applied to the diffusion of atoms and simple molecules adsorbed on surfaces. A comparative introduction to the techniques is given, including advances in theory and simulation techniques, followed by a summary of several recent sets of experimental results.

We report on a combined cold neutron backscattering and spin-echo study of the short-range and long-range nanosecond diffusion of the model globular protein bovine serum albumin (BSA) in aqueous solution as a function of protein concentration and NaCl salt concentration. Complementary small angle X-ray scattering data are used to obtain information on the correlations of the proteins in solution. Particular emphasis is put on the effect of crowding, i.e. conditions under which the proteins cannot be considered as objects independent of each other. We thus address the question at which concentration this crowding starts to influence the static and in particular also the dynamical behaviour. We also briefly discuss qualitatively which charge effects, i.e. effects due to the interplay of charged molecules in an electrolyte solution, may be anticipated. Both the issue of crowding as well as that of charge effects are particularly relevant for proteins and their function under physiological conditions, where the protein volume fraction can be up to approximately 40% and salt ions are ubiquitous. The interpretation of the data is put in the context of existing studies on related systems and of existing theoretical models.

A classical molecular dynamics study of the diffusive motion of benzene molecules on graphite basal planes has been performed in the sub-monolayer coverage regime. Atomistic calculations were performed using the second generation forcefield COMPASS as well as the general purpose forcefields Dreiding and Universal. The COMPASS based calculations show evidence for a Brownian nature of the diffusion with a very small diffusion activation barrier of 11 ± 2 meV in agreement with recent helium and neutron spin-echo spectroscopy data [Fouquet P, Hedgeland H, Jardine AP, Alexandrowicz G, Allison W, Ellis J. Measurements of molecule diffusion on surfaces using neutron and helium spin echo. Physica B 2006;385–386:269-71]. Reasonable agreement is also found for the general purpose forcefields if screened charges are used in the description of the Coulombic non-bond interaction. The less computationally intensive Dreiding forcefield was shown to give a good qualitative description of the diffusion validating its applicability for future large scale calculation, i.e., for long times or enlarged systems. A potential energy surface (PES) has been established for the translational and rotational diffusive motion. The PES shows a peculiar dependence of the lateral diffusion barriers on the rotation angle of the benzene molecule which leads to a preferential selection of certain rotational states in the MD trajectories.

This paper describes design and optimization for the wide angle spin-echo spectrometer (WASP) presently being planned at the ILL. The spectrometer will be a replacement for the high intensity spectrometer IN11 and will enhance its signal by more than one order of magnitude while maintaining the resolution of the present spectrometer. The paper outlines the magnetic field calculations and the considerations about possible limitations. The projected performance has been verified carefully by Monte Carlo raytracing and Biot–Savart magnetic field calculations. The maximum momentum transfer of the new spectrometer is to be extended to 4 A− 1.

The presence of coupled modes of membrane motion in closed shells is extensively predicted by theory. The bilayer structure inherent to lipid vesicles is suitable to support hybrid modes of ctirvature motion coupling membrane bending with the local reorganization of the bilayer material through relaxation of the dilatational stresses. Previous experiments evidenced the existence of such hybrid modes facilitating membrane bending at high curvatures in lipid vesicles [Rodriguez-Garcia, R., Arriaga, L.R., Mell, M., Moleiro, L.H., Lopez-Montero, I., Monroy, F., 2009. Phys. Rev. Lett. 102, 1282011. For lipid bilayers that are able to undergo intermonolayer sliding, the experimental fluctuation spectra are found compatible with a bimodal schema. The usual tension/bending fluctuations couple with the hybrid modes in a mechanical interplay, which becomes progressively efficient with increasing vesicle radius, to saturate at infinity radius into the behavior expected for a flat membrane. Grounded on the theory of closed shells, we propose an approximated expression of the bimodal spectrum, which predicts the observed dependencies on the vesicle radius. The dynamical features obtained from the autocorrelation functions of the vesicle fluctuations are found in quantitative agreement with the proposed theory. (C) 2014 Elsevier Ireland Ltd. All rights reserved.

Highly polarizable metastable He* ($\mathrm{2^3S}$) and Ne* ($\mathrm{2^3P}$) atoms have been diffracted from a 100 nm period silicon nitride transmission grating and the van der Waals coefficients $C_3$ for the interaction of the excited atoms with the silicon nitride surface have been determined from the diffraction intensities out to the 10th order. The results agree with calculations based on the non-retarded Lifshitz formula., 7 pages, 2 figures, accepted for publication in Europhysics Letters

Liquid monohydroxy alcohols exhibit unusual dynamics related to their hydrogen bonding induced structures. The connection between structure and dynamics is studied for liquid 1-propanol using quasi-elastic neutron scattering, combining time-of-flight and neutron spin-echo techniques, with a focus on the dynamics at length scales corresponding to the main peak and the pre-peak of the structure factor. At the main peak, the structural relaxation times are probed. These correspond well to mechanical relaxation times calculated from literature data. At the pre-peak, corresponding to length scales related to H-bonded structures, the relaxation times are almost an order of magnitude longer. According to previous work [C. Gainaru, R. Meier, S. Schildmann, C. Lederle, W. Hiller, E. Rössler, and R. Böhmer, Phys. Rev. Lett. 105, 258303 (2010)] this time scale difference is connected to the average size of H-bonded clusters. The relation between the relaxation times from neutron scattering and those determined from dielectric spectroscopy is discussed on the basis of broad-band permittivity data of 1-propanol. Moreover, in 1-propanol the dielectric relaxation strength as well as the near-infrared absorbance reveal anomalous behavior below ambient temperature. A corresponding feature could not be found in the polyalcohols propylene glycol and glycerol.

Microgels are generally synthesised above the lower critical solution temperature (LCST) of the used polymer (poly(N-isopropyl-acrylamide)(PNIPAM) in the present case) and there is evidence that, due to the “bad” solvent conditions and due to the differences in reactivity between the monomers and the crosslinker, an inhomogeneous crosslinker distribution in the network is created. In contrast, macrogels are statistically crosslinked, because they are polymerised below the LCST (good solvent conditions). With the neutron spin-echo (NSE) technique, the diffusion of the polymer network on a local length scale can be studied. Due to essentially different crosslinker distributions in the micro- and macrogels, a difference in the collective diffusion of the network could be expected. However, the measured intermediate scattering functions of the studied micro- and macrogel are similar and can both be described by a single exponential decay without a q-dependent baseline. Hence, both systems behave pseudo-ergodically on the length scale available in the NSE experiment. A determination of the diffusion coefficient of the breathing mode D G of the gel network and the dynamic correlation length ξ leads to comparable values for the homologous micro- and macrogels. The studied microgels contain butenoic acid as comonomer and also the pH dependence of the network dynamics is investigated.

We present design and construction details for a novel high field, small bore permanent hexapole magnet. The design is intended for focusing atomic beams of 3He at thermal energies. The magnet uses an optimized polepiece design which includes vacuum gaps to enable its use with high intensity atomic and molecular beams. The 0.3 m long, 1 mm internal radius magnet achieves a polepiece tip field of 1.1 T using NdFeB permanent magnets and Permendur 49 polepieces. The polepiece shanks are designed to saturate so that the hexapole properties are determined predominantly by the shape of the polepiece tip. The performance of the hexapole assembly is demonstrated with an 8 meV 3He beam in the beam source of the Cambridge spin echo spectrometer and the measured focused beam results show excellent agreement with theoretical predictions and negligible beam attenuation.

The structure and the electronic valence state occupation of ultrathin K, Rb, and Cs films grown on a GaAs(1 0 0)-(4×2) surface have been studied by means of metastable He atom scattering (MHAS), He atom scattering (HAS), and low-energy electron diffraction (LEED) at temperatures ranging from 150 to 400 K. From the survival probability of the scattered He ∗ atoms, detailed information on the coverage-dependent filling of the alkali metal valence states and their emptying upon subsequent exposure to oxygen were derived. These data reveal for K and Rb a nearly linear band filling with increasing coverage starting at about 0.5 ML whereas a more rapid filling is observed for Cs which is almost completed at about 0.7 ML. Subsequent oxygen adsorption causes a demetallization of the metallic alkali metal monolayers. In case of Cs, a distinct minimum of the He ∗ signal appears at an oxygen exposure of about 0.8 L, presumably indicating the onset of subsurface oxidation.

We have studied the 3D Heisenberg ferromagnetic model system CdCr2xIn2−2xS4 in the ferromagnetic and reentrant phases as a function of temperature and momentum transfer using neutron spin echo (NSE) spectroscopy. The results from the pure sample CdCr2S4 are in excellent agreement with the predictions of the renormalization group theory. In the presence of disorder, we see the evolution from a simple critical ferromagnetic scattering with single fast relaxation times to a more complex slow dynamics characteristic of spin glasses.

A thermally activated magnetic relaxation is observed using neutron spin-echo in the pyrochlore slab (kagome bilayer) compound SrCr 9 x Ga 12 - 9 x O 19 ( x = 0.95 ) in a restricted temperature range, 4 K T 7 K , above a cross-over to a low temperature relaxation regime with a weaker temperature dependence. The activation energy of the thermally activated relaxation, of the order of 7 meV, coincides with the energy of a phonon mode observed with neutron and Raman spectroscopy, indicating a phonon-assisted regime. The experimental observation of phonon-assisted process gives additional insight to the importance of spin–phonon coupling in frustrated magnets with regard to the models mostly based on purely magnetic interactions.

We present a new approach to gain detailed surface-molecule potential information by combining neutron and helium atom scattering. First results are presented for a prototype study of benzene molecule diffusion on graphite surfaces. The measurements show good agreement and confirm the transferability of the results between the two methods. Future instrumental improvements are described that will improve the sensitivity of NSE by a factor of 50 for studies of molecules adsorbed on surfaces and mesoporous substrates.

Large vesicles obtained by the extrusion method represent adequate membrane models to probe membrane dynamics with neutron radiation. Particularly, the shape fluctuations around the spherical average topology can be recorded by neutron spin echo (NSE). In this paper we report on the applicable theories describing the scattering contributions from bending-dominated shape fluctuations in diluted vesicle dispersions, with a focus on the relative relevance of the master translational mode with respect to the internal fluctuations. Different vesicle systems, including bilayer and non-bilayer membranes, have been scrutinized. We describe the practical ranges where the exact theory of bending fluctuations is applicable to obtain the values of the bending modulus from experiments, and we discuss about the possible internal modes that could be alternatively contributing to shape fluctuations.

The magnetic properties of Ho(2)Sn(2)O(7) have been investigated and compared to other spin ice compounds. Although the lattice has expanded by 3% relative to the better studied Ho(2)Ti(2)O(7) spin ice, no significant changes were observed in the high temperature properties, T is more or approximately equal to 20 K. As the temperature is lowered and correlations develop, Ho(2)Sn(2)O(7) enters its quantum phase at a slightly higher temperature than Ho(2)Ti(2)O(7) and is more antiferromagnetic in character. Below 80 K a weak inelastic mode associated with the holmium nuclear spin system has been measured. The hyperfine field at the holmium nucleus was found to be ≈700 T.

A complete analytical model for the rotational and translational diffusion of molecules with a six-fold point symmetry on a hexagonal lattice is presented. It can be applied, in particular, to the diffusion of benzene molecules adsorbed flat on the basal plane of graphite in the case of incoherent scattering. Under the weak hindered approximation, the classical mechanics framework and making use of the van Hove formalism of correlation functions, the intermediate scattering function and its Fourier transform, the scattering law, are both obtained. They can be expressed as sums of exponential decays or Lorentzian functions, respectively, containing the contribution of each of the dynamical processes taking place. In the case of benzene lying flat on the substrate we expect translational diffusion, continuous rotations of isolated molecules and hindered rotations of molecules within clusters. Each particular diffusive mechanism can be recognized owing to its particular signature in the dependence of the quasi-elastic broadening on the momentum transfer. © 2012 IOP Publishing Ltd., Support from the Ministerio de Ciencia e Innovacion (Spain) under project FIS2010-18132 is acknowledged