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  1. Individual water molecules or small clusters of water molecules contained within microporous minerals present an extreme case of confinement where the local structure of hydrogen bond networks are dramatically altered from bulk water. In the zinc silicate hemimorphite, the water molecules form a two-dimensional hydrogen bond network with hydroxyl groups in the crystal framework. Here in this paper, we present a combined experimental and theoretical study of the structure and dynamics of water molecules within this network. The water molecules undergo a continuous phase transition in their orientational configuration analogous to a two-dimensional Ising model. The incoherent dynamic structure factormore » reveals two thermally activated relaxation processes, one on a subpicosecond timescale and another on a 10–100 ps timescale, between 70 and 130 K. The slow process is an in-plane reorientation of the water molecule involving the breaking of hydrogen bonds with a framework that, despite the low temperatures involved, is analogous to rotational diffusion of water molecules in the bulk liquid. The fast process is a localized motion of the water molecule with no apparent analogs among known bulk or confined phases of water.« less
  2. Well-tailored mixtures of distinct ionic liquids can act as optimal electrolytes that extend the operating electrochemical window and improve charge storage density in supercapacitors. Here, we explore two room-temperature ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EmimTFSI) and 1-ethyl-3-methylimidazolium tetrafluoroborate (EmimBF 4). We study their electric double-layer behavior in the neat state and as binary mixtures on the external surfaces of onion-like carbon electrodes using quasielastic neutron scattering (QENS) and classical density functional theory techniques. Computational results reveal that a mixture with 4:1 EmimTFSI/EmimBF 4 volume ratio displaces the larger [TFSI ] anions with smaller [BF 4 ] ions, leading to an excessmore » adsorption of [Emim +] cations near the electrode surface. These findings are corroborated by the manifestation of nonuniform ion diffusivity change, complementing the description of structural modifications with changing composition, from QENS measurements. In conclusion, molecular-level understanding of ion packing near electrodes provides insight for design of ionic liquid formulations that enhance the performance of electrochemical energy storage devices.« less
  3. Living planarian flatworms were probed using quasielastic neutron scattering to measure, on the pico-to-nanosecond time scale and nanometer length scale, microscopic diffusion of water and cell constituents in the planarians. Measurable microscopic diffusivities were surprisingly well defined in such a complex system as living animals. The overall variation in the microscopic diffusivity of cell constituents was found to be far lower than the variation in the microscopic diffusivity of water in planarians in a temperature range of 284.5 to 304.1K.
  4. Two-dimensional carbides and nitrides of early transition metals (MXenes) combine high conductivity with hydrophilic surfaces, which make them promising for energy storage, electrocatalysis, and water desalination. Effects of intercalated metal ions on the vibrational states of water confined in Ti 3C 2T x MXenes have been explored using inelastic neutron scattering (INS) and molecular dynamics simulations to better understand the mechanisms that control MXenes’ behavior in aqueous electrolytes, water purification and other important applications. Here, we observe INS signal from water in all samples, pristine and with lithium, sodium or potassium ions intercalated between the 2D Ti 3C 2T xmore » layers. However, only a small amount of water is found to reside in Ti 3C 2T x intercalated with metal ions. Water in pristine Ti 3C 2T x is more disordered, with bulk-like characteristics, in contrast to intercalated Ti 3C 2T x, where water is more ordered, irrespective of the metal ions used for intercalation. The ordering of the confined water increases with the ion size. Lastly, this finding is further confirmed from molecular dynamics simulation which showed an increase in interference of water molecules with increasing ion size resulting in a concomitant decrease in water mobility, therefore, providing a guidance to tailor MXene properties for energy and environmental applications.« less
  5. The modification of polymer dynamics in the presence of strongly interacting nanoparticles has been shown to significantly change themacroscopic properties above the glass transition temperature of polymer nanocomposites (PNCs). However, much less attention has been paid to changes in the dynamics of glassy PNCs. Analysis of neutron and light scattering data presented herein reveals a surprising enhancement of local dynamics, e.g., fast picosecond and secondary relaxations, in glassy PNCs accompanied with a strengthening of mechanical modulus. Here we ascribe this counter-intuitive behavior to the complex interplay between chain packing and stretching within the interfacial layer formed at the polymer-nanoparticle interface.
  6. Direct experimental insights into the structural and dynamical mechanisms for ferroelectric β to paraelectric α phase transition in a poled PVDF-TrFE copolymer is obtained from in situ x-ray diffraction and quasielastic neutron scattering measurements at high temperatures. It is observed that the β-to-α phase transition proceeds through two energetically distinct processes, which are identified here as the nucleation and growth of an intermediate γ phase with random skew linkages followed by a γ-to-α transition. The two energetically distinct microscopic processes can explain the stages of evolution for β-to-α phase transition observed from heat flow measurements.
  7. We have studied microscopic diffusion of water in fully hydrated encysted eggs of brine shrimp (Artemia). We utilized quasielastic neutron scattering. Dry eggs of brine shrimp were rehydrated using (1) water without additives, (2) eutectic mixture of water and dimethyl sulfoxide, and (3) a concentrated aqueous solution of lithium chloride. Despite the complexity of the hydrated multicellular organism, measurable microscopic diffusivity of water is rather well defined. Pure hydration water in eggs exhibits freezing temperature depression, whereas hydration water in eggs mixed with dimethyl sulfoxide or lithium chloride does not crystallize at all. The characteristic size of the voids occupiedmore » by water or aqueous solvents in hydrated brine shrimp eggs is between 2 and 10 nm. Those voids are accessible to co-solvents such as dimethyl sulfoxide and lithium chloride. There is no evidence of intracellular water in the hydrated eggs. The lack of intracellular water in the fully hydrated (but still under arrested development) state must be linked to the unique resilience against adverse environmental factors documented not only for the anhydrous, but also hydrated encysted eggs of brine shrimp.« less
  8. Here, the calorimetric glass-transition temperature of water is 136 K, but extrapolation of thermodynamic and relaxation properties of water from ambient temperature to below its homogeneous nucleation temperature T H = 235 K predicts divergence at T S = 228 K. The “no-man’s land” between the T H and glassy water crystallization temperature of 150 K, which is encountered on warming up from the vitrified state, precludes a straightforward reconciliation of the two incompatible temperature dependences of water properties, above 235 K and below 150 K. The addition of lithium chloride to water allows bypassing both T H and Tmore » S on cooling, resulting in the dynamics with no features except the calorimetric glass transition, still at 136 K. We show that lithium chloride prevents hydrogen-bonding network completion in water on cooling, as manifested, in particular, in changing microscopic diffusion mechanism of the water molecules. Thus thermodynamic and relaxation peculiarities exhibited by pure water on cooling to its glass transition, such as the existence of the T H and T S, must be associated specifically with the hydrogen-bonding network.« less
  9. Selectively labeled GroEL protein was produced in living deuterated bacterial cells to enhance its neutron scattering signal above that of the intracellular milieu. Quasi-elastic neutron scattering shows that the in-cell diffusion coefficient of GroEL was (4.7 ± 0.3) × 10 –12 m 2/s, a factor of 4 slower than its diffusion coefficient in buffer solution. Furthermore, for internal protein dynamics we see a relaxation time of (65 ± 6) ps, a factor of 2 slower compared to the protein in solution. Comparison to the literature suggests that the effective diffusivity of proteins depends on the length and time scale beingmore » probed. Retardation of in-cell diffusion compared to the buffer becomes more significant with the increasing probe length scale, suggesting that intracellular diffusion of biomolecules is nonuniform over the cellular volume. This approach outlined here enables investigation of protein dynamics within living cells to open up new lines of research using “in-cell neutron scattering” to study the dynamics of complex biomolecular systems.« less
  10. Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo 132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton ofmore » the internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.« less

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