Molecular motion of a nanoscopic moonlander via translations and rotations of triphenylphosphine on graphite.

Mass transport at surfaces determines the kinetics of processes such as heterogeneous catalysis and thin-film growth, with the diffusivity being controlled by excitation across a translational barrier. Here, we use neutron spectroscopy to follow the nanoscopic motion of triphenylphosphine (P(C6H5)3 or PPh3) adsorbed on exfoliated graphite. Together with force-field molecular dynamics simulations, we show that the motion is similar to that of a molecular motor, i.e. PPh3 rolls over the surface with an almost negligible activation energy for rotations and motion of the phenyl groups and a comparably small activation energy for translation. While rotations and intramolecular motion dominate up to about 300 K, the molecules follow an additional translational jump-motion across the surface from 350-500 K. The unique behaviour of PPh3 is due to its three-point binding with the surface: Along with van der Waals corrected density functional theory calculations, we illustrate that the adsorption energy of PPh3 increases considerably compared to molecules with flat adsorption geometry, yet the effective diffusion barrier for translational motion increases only slightly. We rationalise these results in terms of molecular symmetry, structure and contact angle, illustrating that the molecular degrees of freedom in larger molecules are intimately connected with the diffusivity.

How does tuning the van der Waals bonding strength affect adsorbate structure?

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, (C4D4N2), adsorbed on the graphite (0001) basal plane surface are compared to scattering simulations and complemented by van der Waals corrected density functional theory calculations. The lattice constant of pyrazine on graphite is found to be (6.06 ± 0.02) Å. Compared to benzene (C6D6) adsorption on graphite, the pyrazine overlayer appears to be much more thermodynamically stable, up to 320 K, and continues in layer-by-layer growth. Both findings suggest a direct correlation between the intensity of van der Waals bonding and the stability of the self-assembled overlayer because the nitrogen atoms in the six-membered ring of pyrazine increase the van der Waals bonding in comparison to benzene, which only contains carbon atoms.

Microscopic Diffusion of Atomic Hydrogen and Water in HER Catalyst MoS2 Revealed by Neutron Scattering.

The design of novel and abundant catalytic materials for electrolysis is crucial for reaching carbon neutrality of the global energy system. A deliberate approach to catalyst design requires both theoretical and experimental knowledge not only of the target reactions but also of the supplementary mechanisms affecting the catalytic activity. In this study, we focus on the interplay of hydrogen mobility and reactivity in the hydrogen evolution reaction catalyst MoS2. We have studied the diffusion of atomic hydrogen and water by means of neutron and X-ray photoelectron spectroscopies combined with classical molecular dynamics simulations. The observed interaction of water with single-crystal MoS2 shows the possibility of intercalation within volume defects, where it can access edge sites of the material. Our surface studies also demonstrate that atomic hydrogen can be inserted into MoS2, where it then occupies various adsorption sites, possibly favoring defect vicinities. The motion of H atoms parallel to the layers of MoS2 is fast with D ≈ 1 × 10-9 m2/s at room temperature and exhibits Brownian diffusion behavior with little dependence on temperature, i.e., with a very low diffusion activation barrier.

Motion of water monomers reveals a kinetic barrier to ice nucleation on graphene.

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.

Neutron spectroscopy study of the diffusivity of hydrogen in MoS2.

The diffusion of hydrogen adsorbed inside layered MoS2 crystals has been studied by means of quasi-elastic neutron scattering, neutron spin-echo spectroscopy, nuclear reaction analysis, and X-ray photoelectron spectroscopy. The neutron time-of-flight and neutron spin-echo measurements demonstrate fast diffusion of hydrogen molecules parallel to the basal planes of the two dimensional crystal planes. At room temperature and above, this intra-layer diffusion is of a similar speed to the surface diffusion that has been observed in earlier studies for hydrogen atoms on Pt surfaces. A significantly slower hydrogen diffusion was observed perpendicular to the basal planes using nuclear reaction analysis.

Collective Motions and Mechanical Response of a Bulk of Single-Chain Nano-Particles Synthesized by Click-Chemistry.

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.

Transverse and longitudinal spin-fluctuations in INVAR Fe0.65Ni0.35.

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.

Ionic Liquids: evidence of the viscosity scale-dependence.

Ionic Liquids (ILs) are a specific class of molecular electrolytes characterized by the total absence of co-solvent. Due to their remarkable chemical and electrochemical stability, they are prime candidates for the development of safe and sustainable energy storage systems. The competition between electrostatic and van der Waals interactions leads to a property original for pure liquids: they self-organize in fluctuating nanometric aggregates. So far, this transient structuration has escaped to direct clear-cut experimental assessment. Here, we focus on a imidazolium based IL and use particle-probe rheology to (i) catch this phenomenon and (ii) highlight an unexpected consequence: the self-diffusion coefficient of the cation shows a one order of magnitude difference depending whether it is inferred at the nanometric or at the microscopic scale. As this quantity partly drives the ionic conductivity, such a peculiar property represents a strong limiting factor to the performances of ILs-based batteries.

A neutron spin echo study of low-temperature water confined in the spherical silica pores of SBA-16.

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.

Nanostructuration of ionic liquids: impact on the cation mobility. A multi-scale study.

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.

Modulation of hemoglobin dynamics by an allosteric effector.

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 hemoglobin 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.

Ballistic Diffusion in Polyaromatic Hydrocarbons on Graphite.

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, C16H10, 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.

Graphene on Ni(111): Electronic Corrugation and Dynamics from Helium Atom Scattering.

Using helium atom scattering, we have studied the structure and dynamics of a graphene layer prepared in situ on a Ni(111) surface. Graphene/Ni(111) exhibits a helium reflectivity of ∼20% for a thermal helium atom beam and a particularly small surface electron density corrugation ((0.06 ± 0.02) Å peak to peak height). The Debye-Waller attenuation of the elastic diffraction peaks of graphene/Ni(111) and Ni(111) was measured at surface temperatures between 150 and 740 K. A surface Debye temperature of θD = (784 ± 14) K is determined for the graphene/Ni(111) system and θD = (388 ± 7) K for Ni(111), suggesting that the interlayer interaction between graphene and the Ni substrate is intermediary between those for strongly interacting systems like graphene/Ru(0001) and weakly interacting systems like graphene/Pt(111). In addition we present measurements of low frequency surface phonon modes on graphene/Ni(111) where the phonon modes of the Ni(111) substrate can be clearly observed. The similarity of these findings with the graphene/Ru(0001) system indicates that the bonding of graphene to a metal substrate alters the dynamic properties of the graphene surface strongly and is responsible for the high helium reflectivity of these systems.

Fluctuation dynamics of bilayer vesicles with intermonolayer sliding: experiment and theory.

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 curvature 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 [Rodríguez-García, R., Arriaga, L.R., Mell, M., Moleiro, L.H., López-Montero, I., Monroy, F., 2009. Phys. Rev. Lett. 102, 128201.]. 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.

The structure of deuterated benzene films adsorbed on the graphite (0001) basal plane: what happens below and above the monolayer coverage?

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 × âˆš7)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.

Bending stiffness of biological membranes: what can be measured by neutron spin echo?

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.

Neutron spin-echo studies of hemoglobin and myoglobin: multiscale internal dynamics.

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.

Questions arising for future surface diffusion studies using scattering techniques--the case of benzene diffusion on graphite basal plane surfaces.

This paper gives a review of recent work on benzene diffusion on graphitic carbon surfaces using neutron and helium scattering spectroscopy as well as computational modelling. Recent spin-echo spectroscopy measurements have demonstrated that benzene/graphite displays almost perfect Brownian diffusion and that it can be used as a tool to study dynamic friction. Incoherent neutron backscattering measurements, on the other hand, reveal a jump diffusion behaviour, related to the molecular rotational modes of the benzene rings. Molecular dynamics (MD) simulations have delivered a very detailed picture of the adsorbate dynamics. We use this review to illustrate the open questions and possible future directions of this research field.

Protein diffusion in crowded electrolyte solutions.

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.