Angstrom Length Scale Research Articles

Understanding fast ion dynamics in sodiated Li4Na x Ti5O12: from interfacial to extended Li+ and Na+ dynamics in its mixed-conducting solid solutions

Climate change and energy crises require the development of new sustainable materials to realise reliable electrochemical energy storage devices. Spinel-type Li4Ti5O12 (LTO) is one of the most promising anode materials not only for Li-based batteries, but also for those relying on sodium. While Li+ ion dynamics at the early stages of lithiation has been studied already previously, almost no data on the diffusion properties of Na+ ions can be found in the literature. Here, we used nucleus-specific 7Li and 23Na nuclear magnetic resonance (NMR) spectroscopy to quantify the motional processes in mixed-conducting Li4Na x Ti5O12 with x = 0.1, 0.5 and 1.5 on the angstrom length scale. Most importantly, our results reveal a strong increase in Li+ diffusivity in the early stages of chemical sodiation that is accompanied by a sharp decrease in activation energy when x reaches 0.5. The two-component 7Li NMR spectra point to the evolution of an interfacial solid solution at very low sodiation levels (x = 0.1). At x = 0.5, these regions emerge over almost the entire crystallite area, enabling rapid 8a-16c-8a Li+ exchange (0.4 eV), which leads to facile long-range ion transport. We direct the attention of the reader towards the initial formation of solid solutions in LTO-based anode materials and their capital impact on overall ion dynamics. In contrast to macroscopic electrochemical testing, NMR is uniquely positioned to detect and to resolve these exceptionally fast ion dynamics during the initial stages of sodiation. As these processes crucially determine the fast-charging performance of LTO-type batteries, our study lays the atomistic foundations to establish a general understanding of why two-phase materials such as LTO can act as an impressive insertion host for both Li and Na ions.

Terahertz-wave decoding of femtosecond extreme-ultraviolet light pulses

In recent years, femtosecond extreme-ultraviolet (XUV) and x-ray pulses from free-electron lasers have developed into important probes to monitor processes and dynamics in matter on femtosecond-time and angstrom-length scales. With the rapid progress of versatile ultrafast x-ray spectroscopy techniques and more sophisticated data analysis tools, accurate single-pulse information on the arrival time, duration, and shape of the probing x-ray and XUV pulses becomes essential. Here, we demonstrate that XUV pulses can be converted into terahertz electromagnetic pulses using a spintronic terahertz emitter. We observe that the duration, arrival time, and energy of each individual XUV pulse is encoded in the waveform of the associated terahertz pulses, and thus can be readily deduced from single-shot terahertz time-domain detection.

Harnessing the Quantum Behavior of Spins on Surfaces.

The desire to control and measure individual quantum systems such as atoms and ions in a vacuum has led to significant scientific and engineering developments in the past decades that form the basis of today's quantum information science. Single atoms and molecules on surfaces, on the other hand, are heavily investigated by physicists, chemists, and material scientists in search of novel electronic and magnetic functionalities. These two paths crossed in 2015 when it wasfirst clearly demonstrated that individual spins on a surface can be coherently controlled and read out in an all-electrical fashion. The enabling technique is a combination of scanning tunneling microscopy (STM) and electron spin resonance, which offers unprecedented coherent controllability at the Angstrom length scale. This review aims to illustrate the essential ingredients that allow the quantum operations of single spins on surfaces. Three domains of applications of surface spins, namely quantum sensing, quantum control, and quantum simulation, are discussed with physical principles explained and examples presented. Enabled by the atomically-precise fabrication capability of STM, single spins on surfaces might one day lead to the realization of quantum nanodevices and artificial quantum materials at the atomicscale.

Regularity for nonlinear elliptic equations and systems

We study the regularity of weak solutions to the elliptic system in divergence form divA( x , D u)=0 in an open set Ω of R n , n ≥2. The vector field A( x .ξ), A: Ω×R m×n →R m×n , has a variational nature in the sense that A( x ,ξ)= D ξ f ( x ,ξ), where f :Ω×R m×n →R is a convex Caratheodory integrand ; i.e., f = f ( x ,ξ) is measurable with respect to x ∈R n and it is a convex function with respect to ξ∈R m×n . If m =1 then the system reduces to a partial differential equation . In the context m >1 of general vector-valued maps and systems , a classical assumption finalized to the everywhere regularity of the weak solutions is a modulus-dependence in the energy integrand; i.e., we require that f ( x ,ξ)= g ( x ,|ξ|), where g :Ω×[0,∞)→[0,∞) is measurable with respect to x∈ R n and it is a convex and increasing function with respect to the gradient variable t∈[0,∞).

Coherent collective dynamics in phospholipid membranes: where are we now?

We review the main achievements accomplished in the study of the coherent collective dynamics of phospholipid membranes, i.e. , the collective vibrational excitations active on the sub-picoseconds to picoseconds time scale and terahertz frequencies, over a length scale comparable to the angstrom length scale. The first descriptions of the terahertz collective spectrum, mainly assigned to a single longitudinal acoustic-like mode similarly to simple liquids, have been progressively replaced by a complex scenario, with longitudinal and transverse acoustic-like and optic-like inelastic excitations. Complex phenomena (avoided crossing mechanisms between modes, a phonon gap introduced by the disorder and a slow- to fast-sound transition) have been highlighted in the dispersion curves of lipid bilayers. Systematic and comprehensive studies along the lines of the investigations reviewed here contribute to understand the role of the collective (coherent) chain dynamics in the passive transport across bilayers, in the formation of water wires inside dynamic defects in lipid bilayers and in other biological functions of biomembranes.

Backbone Hydrogen Bond Energies in Membrane Proteins Are Insensitive to Large Changes in Local Water Concentration.

A hallmark feature of biological lipid bilayer structure is a depth-dependent polarity gradient largely resulting from the change in water concentration over the angstrom length scale. This gradient is particularly steep as it crosses the membrane interfacial regions where the water concentration drops at least a million-fold along the direction of the bilayer normal. Although local water content is often assumed to be a major determinant of membrane protein stability, the effect of the water-induced polarity gradient upon backbone hydrogen bond strength has not been systematically investigated. We addressed this question by measuring the free energy change for a number of backbone hydrogen bonds in the transmembrane protein OmpW. These values were obtained at 33 backbone amides from hydrogen/deuterium fractionation factors by nuclear magnetic resonance spectroscopy. We surprisingly found that OmpW backbone hydrogen bond energies do not vary over a wide range of water concentrations that are characteristic of the solvation environment in the bilayer interfacial region. We validated the interpretation of our results by determining the hydrodynamic and solvation properties of our OmpW-micelle complex using analytical ultracentrifugation and molecular dynamics simulations. The magnitudes of the backbone hydrogen bond free energy changes in our study are comparable to those observed in water-soluble proteins, the H-segment of the leader peptidase helix used in the von Heijne and White biological scale experiments, and several interfacial peptides. Our results agree with those reported for the transmembrane α-helical portion of the amyloid precursor protein after the latter values were adjusted for kinetic isotope effects. Overall, our work suggests that backbone hydrogen bonds provide modest thermodynamic stability to membrane protein structures and that many amides are unaffected by dehydration within the bilayer.

Self-diffusion and ionic exchange in mechanosynthesized, nanocrystalline solid solutions of PbF2 and CaF2[sbnd]19F 2D NMR visualizes the flourine hopping preferences

Ionic conductors based on PbF2, being one of the archetypes to study ion dynamics, serve as excellent model substances to study the elementary steps of translational anion dynamics in the solid state. Here, high-energy ball milling was employed to prepare a structurally disordered, metastable solid solution by mixing PbF2 with CaF2. The cation-mixed lattice in cubic Ca0.4Pb0.6F2 provides a range of magnetically distinct fluorine sites. We used 2D 19F magic angle spinning nuclear magnetic resonance (NMR) exchange spectroscopy to reveal the site preference of the F anions when hopping through the lattice. It turned out that the F anions located in sites coordinated by Pb cations are more mobile than those residing near or in Ca-rich environments. Conductivity measurements and variable-temperature 19F NMR spin-lattice relaxation experiments provide activation energies (0.24 eV, 0.40 eV) from which we deduce that in cation-mixed Ca0.4Pb0.6F2 anion diffusivity, on the angstrom length-scale, is mainly determined by vacant F− sites. Macroscopic ion transport has to be characterized by an activation energy of 0.55 eV suggesting that the F anions also use interstitial sites for long-range ionic transport.

Fast Na ion transport triggered by rapid ion exchange on local length scales

The realization of green and economically friendly energy storage systems needs materials with outstanding properties. Future batteries based on Na as an abundant element take advantage of non-flammable ceramic electrolytes with very high conductivities. Na3Zr2(SiO4)2PO4-type superionic conductors are expected to pave the way for inherently safe and sustainable all-solid-state batteries. So far, only little information has been extracted from spectroscopic measurements to clarify the origins of fast ionic hopping on the atomic length scale. Here we combined broadband conductivity spectroscopy and nuclear magnetic resonance (NMR) relaxation to study Na ion dynamics from the µm to the angstrom length scale. Spin-lattice relaxation NMR revealed a very fast Na ion exchange process in Na3.4Sc0.4Zr1.6(SiO4)2PO4 that is characterized by an unprecedentedly high self-diffusion coefficient of 9 × 10−12 m2s−1 at −10 °C. Thus, well below ambient temperature the Na ions have access to elementary diffusion processes with a mean residence time τNMR of only 2 ns. The underlying asymmetric diffusion-induced NMR rate peak and the corresponding conductivity isotherms measured in the MHz range reveal correlated ionic motion. Obviously, local but extremely rapid Na+ jumps, involving especially the transition sites in Sc-NZSP, trigger long-range ion transport and push ionic conductivity up to 2 mS/cm at room temperature.

Fast Na Ion Transport Triggered By Rapid Ion Exchange on Local Length Scales

The realization of green and economically friendly energy storage systems needs materials with outstanding properties. Future batteries based on Na as an abundant element take advantage of nonflammable ceramic electrolytes with very high conductivities. Na3Zr2(SiO4)2PO4-type superionic conductors are expected to pave the way for inherently safe and sustainable all-solid-state batteries. So far, only little information has been extracted from spectroscopic measurements to clarify the origins of fast ionic hopping on the atomic length scale. Here we combined broadband conductivity spectroscopy and nuclear magnetic resonance (NMR) relaxation to study Na ion dynamics from the μm to the angstrom length scale. Spin-lattice relaxation NMR revealed a very fast Na ion exchange process in Na3.4Sc0.4Zr1.6(SiO4)2PO4 that is characterized by an unprecedentedly high self-diffusion coefficient of 9 ' 10−12 m2s−1 at –10 °C. Thus, well below ambient temperature the Na ions have access to elementary diffusion processes with a mean residence time τNMR of only 2 ns. The underlying asymmetric diffusion- induced NMR rate peak and the corresponding conductivity isotherms measured in the MHz range reveal correlated ionic motion. Obviously, local but extremely fast Na jumps, involving especially the transition sites in Sc-NZSP, trigger long-range ion transport and push ionic conductivity up to 2 mS/cm at room temperature.

Small Angle X-ray Scattering for Nanoparticle Research.

X-ray scattering is a structural characterization tool that has impacted diverse fields of study. It is unique in its ability to examine materials in real time and under realistic sample environments, enabling researchers to understand morphology at nanometer and angstrom length scales using complementary small and wide angle X-ray scattering (SAXS, WAXS), respectively. Herein, we focus on the use of SAXS to examine nanoscale particulate systems. We provide a theoretical foundation for X-ray scattering, considering both form factor and structure factor, as well as the use of correlation functions, which may be used to determine a particle's size, size distribution, shape, and organization into hierarchical structures. The theory is expanded upon with contemporary use cases. Both transmission and reflection (grazing incidence) geometries are addressed, as well as the combination of SAXS with other X-ray and non-X-ray characterization tools. We conclude with an examination of several key areas of research where X-ray scattering has played a pivotal role, including in situ nanoparticle synthesis, nanoparticle assembly, and operando studies of catalysts and energy storage materials. Throughout this review we highlight the unique capabilities of X-ray scattering for structural characterization of materials in their native environment.

An interactive graphical user interface (GUI) for the CATGIXRF program – for microstructural evaluation of thin film and impurity doped surfaces

This paper is a continuation and extension of our earlier work (X‐ray Spectrom. 2010, 39, 127–134, DOI:10.1002/xrs.1215) on the development of a software platform CATGIXRF, as a solution to provide non‐destructive evaluation of nanostructured materials. Here, we describe an interactive graphical user interface (GUI) for the CATGIXRF program. The newly developed GUI interface facilitates determination of microstructural parameters on angstrom length scale for the nanostructured thin layered materials using synchrotron as well as laboratory X‐ray sources. It allows combined analysis capabilities for both the X‐ray reflectivity and grazing incidence X‐ray fluorescence (GIXRF) data simultaneously, thus enabling us a greater sensitivity for the determination of microstructural parameters such as thickness, interface mixing, and roughness of a thin film medium with improved accuracies. The utility and various newly added salient features of the GUI‐CATGIXRF program are described by providing example calculations as well as by analyzing experimentally a few thin film structures with different surface‐interface properties. Copyright © 2016 John Wiley & Sons, Ltd.

POSS-Containing Jacketed Polymer: Hybrid Inclusion Complex with Hierarchically Ordered Structures at Sub-10 nm and Angstrom Length Scales

A series of organic–inorganic hybrid polymers, PnPOSS (n = 6, 10, which is the number of carbon atoms in the flexible alkyl spacers), containing a mesogen-jacketed liquid crystalline polymer (MJLCP) as the main chain and a crystalline nanobuilding block, polyhedral oligomeric silsesquioxane (POSS), in the side chains were designed and synthesized for constructing a hybrid inclusion complex. The phase structures and phase transitions of PnPOSS were investigated by differential scanning calorimetry, polarized light microscopy, wide-angle X-ray diffraction, small-angle X-ray scattering, and high-resolution transmission electron microscopy. With the competitive self-assemblies of the two covalently connected building blocks, namely MJLCP and POSS moieties, PnPOSS shows various phase structures including a sub-10 nm hexagonal columnar (Colh) or columnar nematic liquid crystalline phase, an angstrom rhombohedral crystalline (KR) phase, and a hierarchically ordered phase with Colh and KR coexisting. This work provides a new approach for the design and synthesis of hybrid inclusion materials.

Atomic Layer Deposition in Bio-Nanotechnology: A Brief Overview

Atomic layer deposition (ALD) is a technique increasingly used in nanotechnology and ultrathin film deposition; it is ideal for films in the nanometer and Angstrom length scales. ALD can effectively be used to modify the surface chemistry and functionalization of engineering-related and biologically important surfaces. It can also be used to alter the mechanical, electrical, chemical, and other properties of materials that are increasingly used in biomedical engineering and biological sciences. ALD is a relatively new technique for optimizing materials for use in bio-nanotechnology. Here, after a brief review of the more widely used modes of ALD and a few of its applications in biotechnology, selected results that show the potential of ALD in bio-nanotechnology are presented. ALD seems to be a promising means for tuning the hydrophilicity/hydrophobicity characteristics of biomedical surfaces, forming conformal ultrathin coatings with desirable properties on biomedical substrates with a high aspect ratio, tuning the antibacterial properties of substrate surfaces of interest, and yielding multifunctional biomaterials for medical implants and other devices.

Nanometer-sized dynamic entities in an aqueous system.

Using neutron spin-echo and backscattering spectroscopy, we have found that at low temperatures water molecules in an aqueous solution engage in center-of-mass dynamics that are different from both the main structural relaxations and the well-known localized motions in the transient cages of the nearest neighbor molecules. While the latter localized motions are known to take place on the picosecond time scale and Angstrom length scale, the slower motions that we have observed are found on the nanosecond time scale and nanometer length scale. They are associated with the slow secondary relaxations, or excess wing dynamics, in glass-forming liquids. Our approach, therefore, can be applied to probe the characteristic length scale of the dynamic entities associated with slow dynamics in glass-forming liquids, which presently cannot be studied by other experimental techniques.

New routes towards even shorter attosecond soft X‐ray pulses

New routes towards even shorter attosecond soft X‐ray pulses

X-ray standing wave induced Compton and elastic scattering from thin periodic multilayer structures

We report determination of structural parameters on angstrom length scale of nanostructured periodic multilayers using x-ray standing wave (XSW) enhanced elastic and Compton scattering. We show that the elastic scattered x-ray intensities emitted from the thin periodic multilayer structures, under strong XSW condition, are largely sensitive to the structural parameters of high-$z$ layers, whereas the Compton scattered intensities are sensitive to the parameters of low-$z$ layers. The utility of the methodology is demonstrated by analyzing two repetitive W/B${}_{4}$C multilayer structures with different surface-interface properties. The results are compared with those obtained using x-ray reflectivity and conventional x-ray standing wave fluorescence techniques. It is further shown that the Bragg angle can be derived with high accuracy (\ensuremath{\sim}0.002${}^{\ensuremath{\circ}}$) from the ratio of the scattering intensities, which in turn improves the accuracy of the derived multilayer periodicity. The method presents an opportunity to probe structures on angstrom length scale of any periodic multilayer structure comprising of low atomic number layers. Unlike the conventional XSW fluorescence measurements, the present method has an advantage that it permits the determination of structural parameters of both the high- and the low-$z$ layers independently.

Classification of Protein Binding in Hydroxyapatite Chromatography: Synergistic Interactions on the Molecular Scale

A protein library exhibiting a range of properties was employed to study protein binding behavior in hydroxyapatite systems. Chromatographic retention on ceramic hydroxyapatite (CHT) chromatography was determined using a sodium chloride gradient in the presence of different phosphate concentrations. Results from the column experiments were then analyzed using various quantitative structure property relationship (QSPR) based modeling approaches. Using the experimental data set in concert with new molecular descriptors, QSPR classification models were generated to provide improved understanding of protein binding in CHT systems. In addition, nonlinear SVM QSPR prediction models were generated and employed as a predictive tool for protein affinity in CHT. Interestingly, a class of descriptors which describe synergistic binding with both metal chelation and cation exchange interactions on the angstrom length scale was found to play a vital role for protein binding in all of the models developed for CHT. The importance of this descriptor suggests the importance of synergistic binding in CHT, which has not been previously described in the literature. This study provides a deeper understanding into the mechanisms and selectivity of protein adsorption in CHT and will help to create predictive models which could be used for methods development in bioseparation processes.

Atomic Dynamics in Extreme Environments via Inelastic X-Ray Scattering at SPring-8

Atomic motions and, especially, correlations in atomic motion over angstrom length scales are a sensitive probe of material properties: phonons in single crystals respond to the detailed interactions between atoms, including both short- and long-range forces, and screening thereof, while the atomic dynamics of liquids is intimately connected with nearly all aspects of liquid behavior. Scientific questions associated with measuring dynamics include the detailed nature of phase transitions, correlations of atomic motions with electronic or magnetic properties (superconductivity, ferro-electric behavior, magnetoelastic coupling, etc.), and also very practical issues, such as investigating elasticity. Not surprisingly, both from the point of view of basic science and for applications such as geology, there is strong desire to extend studies of atomic dynamics throughout material phase diagrams, into extreme conditions.

A versatile high resolution scanning tunneling potentiometry implementation

We have developed a new scanning tunneling potentiometry technique which can-with only minor changes of the electronic setup-be easily added to any standard scanning tunneling microscope (STM). This extension can be combined with common STM techniques such as constant current imaging or scanning tunneling spectroscopy. It is capable of performing measurements of the electrochemical potential with microvolt resolution. Two examples demonstrate the versatile application. First of all, we have determined local variations of the electrochemical potential due to charge transport of biased samples down to angstrom length scales. Second, with tip and sample at different temperatures we investigated the locally varying thermovoltage occurring at the tunneling junction. Aside from its use in determining the chemical identity of substances at the sample surface our method provides a controlled way to eliminate the influence of laterally varying thermovoltages on low-bias constant current topographies.

Hydration Dynamics at Femtosecond Time Scales and Angstrom Length Scales from Inelastic X-Ray Scattering

We use high resolution dynamical structure factor S(q,omega) data measured with inelastic x-ray scattering to reconstruct the Green's function of water, which describes its density response to a point charge, and provides a fundamental comparative model for solvation behavior at molecular time scales and length scales. Good agreement is found with simulations, scattering and spectroscopic experiments. These results suggest that a moving point charge will modify its hydration structure, evolving from a spherical closed shell to a steady-state cylindrical hydration "sleeve".