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We present a systematic study on the effect of water on the microscopic dynamics of 1-butyl-3-methylimidazolium tetrafluoroborate by means of quasielastic neutron scattering. By mixing the ionic liquid with either heavy or light water, the different contributions to the quasielastic broadening could be identified and treated separately. This study was performed at room temperature, which is more than 15 °C above the demixing line. Our results show that even small amounts of water accelerate the diffusion mechanisms considerably. While samples with small water percentage reveal a diffusion process confined within ionic liquid nanodomains, an admixture of more than 15 wt. % water relieves the confinement. Furthermore, the presence of two water species was identified: one behaving as free water, whereas the other was interpreted as a component bound to the ionic liquid motion. Based on the fact that water preferentially binds to the BF 4 anion, which itself has a negligible contribution to the scattered intensity, our experiments reveal unprecedented information about the microscopic anion dynamics.

Temperature-dependent dynamic structure factors S(Q, ω) for liquid water have been calculated using a composite model, which is based on the decoupling approximation of the mean square displacement of the water molecules into diffusion and solid-like vibrational parts. The solid-like vibrational part S vib (Q, ω) is calculated with the phonon expansion method established in the framework of the incoherent Gaussian approximation. The diffusion part S diff (Q, ω) relies on the Egelstaff-Schofield translational diffusion model corrected for jump diffusions and rotational diffusions with the Singwi-Sjölander random model and Sears expansion, respectively. Systematics of the model parameters as a function of temperature were deduced from quasi-elastic neutron scattering data analysis reported in the literature and from molecular dynamics (MD) simulations relying on the TIP4P/2005f model. The resulting S(Q, ω) values are confronted by means of Monte Carlo simulations to inelastic neutron scattering data measured with IN4, IN5, and IN6 time-of-flight spectrometers of the Institut Laue-Langevin (ILL) (Grenoble, France). A modest range of temperatures (283-494 K) has been investigated with neutron wavelengths corresponding to incident neutron energies ranging from 0.57 to 67.6 meV. The neutron-weighted multiphonon spectra deduced from the ILL data indicate a slight overestimation by the MD simulations of the frequency shift and broadening of the librational band. The descriptive power of the composite model was suited for improving the comparison to experiments via Bayesian updating of prior model parameters inferred from MD simulations. The reported posterior temperature-dependent densities of state of hydrogen in H 2 O would represent valuable insights for studying the collective coupling interactions in the water molecule between the inter- and intramolecular degrees of freedom.

We have investigated the dynamics of liquid water confined in mesostructured porous silica (MCM-41) and periodic mesoporous organosilicas (PMOs) by incoherent quasielastic neutron scattering experiments. The effect of tuning the water/surface interaction from hydrophilic to more hydrophobic on the water mobility, while keeping the pore size in the range 3.5 nm-4.1 nm, was assessed from the comparative study of three PMOs comprising different organic bridging units and the purely siliceous MCM-41 case. An extended dynamical range was achieved by combining time-of-flight (IN5B) and backscattering (IN16B) quasielastic neutron spectrometers providing complementary energy resolutions. Liquid water was studied at regularly spaced temperatures ranging from 300 K to 243 K. In all systems, the molecular dynamics could be described consistently by the combination of two independent motions resulting from fast local motion around the average molecule position and the confined translational jump diffusion of its center of mass. All the molecules performed local relaxations, whereas the translational motion of a fraction of molecules was frozen on the experimental timescale. This study provides a comprehensive microscopic view on the dynamics of liquid water confined in mesopores, with distinct surface chemistries, in terms of non-mobile/mobile fraction, self-diffusion coefficient, residence time, confining radius, local relaxation time, and their temperature dependence. Importantly, it demonstrates that the strength of the water/surface interaction determines the long-time tail of the dynamics, which we attributed to the translational diffusion of interfacial molecules, while the water dynamics in the pore center is barely affected by the interface hydrophilicity.

Large-scale domain motions in alcohol dehydrogenase (ADH) have been observed previously by neutron spin-echo spectroscopy (NSE). We have extended the investigation on the dynamics of ADH in solution by using high-resolution neutron time-of-flight (TOF) and neutron backscattering (BS) spectroscopy in the incoherent scattering range. The observed hydrogen dynamics were interpreted in terms of three mobility classes, which allowed a simultaneous description of the measured TOF and BS spectra. In addition to the slow global protein diffusion and domain motions observed by NSE, a fast internal process could be identified. Around one third of the protons in ADH participate in the fast localized diffusive motion. The diffusion coefficient of the fast internal motions is around two third of the value of the surrounding D2O solvent. It is tempting to associate the fast internal process with solvent exposed amino acid residues with dangling side chains.

We investigated molecular motions in the 0.3-350 ps time range of D2O-hydrated bilayers of 1-palmitoyl-oleoyl-sn-glycero-phosphocholine and 1,2-dimyristoyl-sn-glycero-phosphocholine in the liquid phase by quasielastic neutron scattering. Model analysis of sets of spectra covering scale lengths from 4.8 to 30 Å revealed the presence of three types of motion taking place on well-separated time scales: (i) slow diffusion of the whole phospholipid molecules in a confined cylindrical region; (ii) conformational motion of the phospholipid chains; and (iii) fast uniaxial rotation of the hydrogen atoms around their carbon atoms. Based on theoretical models for the hydrogen dynamics in phospholipids, the spatial extent of these motions was analysed in detail and the results were compared with existing literature data. The complex dynamics of protons was described in terms of elemental dynamical processes involving different parts of the phospholipid chain on whose motions the hydrogen atoms ride.

Elastic and quasielastic neutron scattering experiments are used to investigate the dynamics of side chains in proteins, using hydrophobic peptides, from dry and hydrated powders up to solutions, as models. The changes of the internal dynamics of a prototypical hydrophobic amino acid, N-acetyl-leucine-methylamide, and alanine amino acids are investigated as a function of water/peptide molecular ratio. While previous results have shown that, in concentrated solution, when the hydrophobic side chains are hydrated by a single hydration water layer, the only allowed motions are confined and can be attributed to librational/rotational movements associated with the methyl groups. In the present work we observe a dynamical evolution from dry to highly hydrated powder. We also observe rotational and diffusive motions and a dynamical transition at approximately 250 K for long side chain peptides while for peptides with short side chains, there is no dynamical transition but only rotational motions. With a local measurement of the influence of hydration water dynamics on the amino acid side chains dynamics, we provide unique experimental evidence that the structural and dynamical properties of interfacial water strongly influence the side chain dynamics and the activation of diffusive motions. We also emphasize that the side chain length has a role on the onset of dynamical transition.