Electrostatic Constraints Research Articles

Boosted Li+ migration in LiPON electrolyte via introducing Ti-based bridge for solid-state thin film batteries

Lithium phosphorous oxynitride (LiPON) has become a research hotspot in the application of all solid-state thin film batteries (TFBs). Meanwhile, the electrochemical stability and Li-ion conductivity of LiPON solid electrolyte films are the critical factors for TFBs with high energy density. In this work, we demonstrate the preparation of Ti-doped LiPON electrolyte (Ti–LiPON) with the enhanced stability and ionic conductivity via a multi-target co-sputtering method. The obtained Ti–LiPON electrolyte shows a larger electrochemical stability window (>5.5 V) and a higher ionic conductivity of 4.91✕10−6 S cm−1. Moreover, the solid-state LiCoO2/Ti–LiPON/Ni film battery (TFB) has been successfully assembled and exhibits a large specific capacity (77.08 mAh g−1 at 8 μA) and good cycle performance (67.44% of capacity maintained after 50 cycles). Meanwhile, the LED indicator can be able to light up by the LiCoO2/Ti–LiPON/Ni TFB and further confirm its great potential for practical applications. Based on the different d-orbital electronic structure of Ti, the local electron density of LiPON system obtains a great change. The existence of Ti can act as a network former in LiPON electrolyte and construct multiple Li+ transport paths with the different bridge bonding forms, further promoting the migration of Li+. Moreover, the introduced Ti can also weaken the electrostatic constraint between PO3N4− and Li+ and further provide a low Li+ migration barrier center.

Collective Control of Potential-Constrained Oxygen Vacancies in Oxide Heterostructures for Gradual Resistive Switching.

Filamentary resistive switching in oxides is one of the key strategies for developing next-generation non-volatile memory devices. However, despite numerous advantages, their practical applications in neuromorphic computing are still limited due to non-uniform and indeterministic switching behavior. Given the inherent stochasticity of point defect migration, the pursuit of reliable switching likely demands an innovative approach. Herein, a collective control of oxygen vacancies is introduced in LaAlO3 /SrTiO3 (LAO/STO) heterostructures to achieve reliable and gradual resistive switching. By exploiting an electrostatic potential constraint in ultrathin LAO/STO heterostructures, the formation of conducting filaments is suppressed, but instead precisely control the concentration of oxygen vacancies. Since the conductance of the LAO/STO device is governed by the ensemble concentration of oxygen vacancies, not their individual probabilistic migrations, the resistive switching is more uniform and deterministic compared to conventional filamentary devices. It provides direct evidence for the collective control of oxygen vacancies by spectral noise analysis and modeling by Monte-Carlo simulation. As a proof of concept, the significantly-improved analog switching performance of the filament-free LAO/STO devices is demonstrated, revealing potential for neuromorphic applications. The results establish an approach to store information by point defect concentration, akin to biological ionic channels, for enhancing switching characteristics of oxide materials.

Ultrathin Non‐Ising Charged Domain Walls Confined in BiFeO3 Nanocrystals

AbstractRich functionalities have been identified for domain walls (DWs, naturally occurring interfaces in ferroics), e.g., enhanced conductance and photovoltaic effect, which specify the interest in their internal structure. The dimension/width and type are of particular interest, which is the carrier of their functionality. Recent attention has been focused on head‐to‐head or tail‐to‐tail charged DWs with greatly enhanced conductivity compared to the inner domains, which are found to be an order of magnitude thicker (tens of unit cells) than normal neutral DWs. In this study, ultrathin non‐Ising charged DWs are found, where polarization switched their direction within 2–3 unit cells in self‐assembled BiFeO3 nanocrystals. An analytical model and finite element method simulation are used to interpret the origin of this phenomenon, i.e., electrostatic constraints linked to DW configurations in a ferroelectric. This study indicates that as an intrinsic property, the width of the ferroic DWs varies with different electrostatic constraints and must be taken into consideration during its applications.

Fast Li+ migration in LiPON electrolytes doped by multi-valent Fe ions

Achieving superior ionic conductivity of LiPON solid electrolyte films is critical for the solid-state thin-film batteries with high energy density. Here we describe a method of preparing LiPON with promising ionic migration capability and high work function by systematically tailoring the concentration of Fe ions doping. Fe-doped LiPON exhibits excellent ionic conductivity (1.08 × 10−5 S cm−1, nearly 10 times higher than the pristine LiPON), low ionic activation energy, and moderate equilibrium potential difference (versus LiCoO2, 0.78 V) at room temperature. The favorable ionic mobility and electrochemical stability of Fe-doped LiPON are fully confirmed. All-solid-state “Li/LiPON/LiCoO2” TFB has been successfully constructed with a large specific capacity (∼36.3 µAh cm−2 µm−1 at 10 µA cm−2) and good cycle performance (87.8 % capacity retention after 40 cycles). Fe with the unique d-orbital electronic structure changes the local electron density of LiPON system with the weakened electrostatic constraint of PO3N4− tetrahedrons to Li+. A low Li+ migration barrier center is established around the Fe–N bridge bonds.

An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

AbstractThe mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X-ray absorption near-edge structure spectroscopy (S-XANES) where S 6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms.One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel.The thermodynamics of incorporation of disulfide and bisulfide into apatite is evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S is also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS(aq)(2−n) and HnS(aq)(2−n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite, and decreases for hydroxylapatite, as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures.

Computational Investigation of Adsorptive Removal of Pb

Adsorption using metal–organic frameworks (MOFs) such as UiO-66 has shown great promise in remediating water sources contaminated with toxic heavy metals such as Pb2+, but detailed information about the adsorption process remains limited. In this article, we gained mechanistic insights into Pb2+ adsorption using both functionalised and defective UiO-66 by performing density functional theory calculations using cluster models. Our benchmarked approach led to a computational model of solvated Pb2+ (a hemidirected Pb(H2O)62+ complex) fully consistent with experimental reports. The analysis of Pb2+ adsorption using functionalised UiO-66 determined that factors such as electrostatic attraction, chelation, and limited constraints on the Pb2+ coordination geometry lead to enhanced binding affinity. For these reasons, UiO-66-COO– was identified as the most promising functionalised MOF, consistent with experimental literature. We additionally explored a novel aspect of Pb2+ adsorption by UiO-66: the role of missing linker defects that often characterise this MOF. We found that the defects expected to form in an aqueous environment can act as excellent adsorption sites for Pb2+ and the preferred adsorption geometry is again determined by electrostatic attraction, chelation, and constraints on the Pb2+ coordination geometry. Overall, we conclude that functional groups and defect sites can both contribute to Pb2+ adsorption and our study provides crucial design principles for improving the UiO-66 MOF performance in toxic Pb2+ removal from water.

Reactivity vs. Stability of Cyclopropenium Substituted Phosphonium Salts

The stability vs. reactivity of electrophilic 3‐(triphenylphosphonio)‐cyclopropenium salts towards a neutral nucleophile, such as triphenylphosphane, is reported. Depending on the nature of cyclopropenyl substituents (R), the three‐membered cyclic structure is preserved (R = Ph) or evolves by ring opening to the isomeric linear allene (R = Mes). The respective formation of 1,3‐bis(triphenylphosphonio)‐2,3‐diphenylcyclopropene and 3,3‐bis(triphenylphosphonio)‐1,1‐dimesitylallene products is rationalized on the basis of steric and electrostatic constraints.

The shape of the photon transfer curve of CCD sensors

The photon transfer curve (PTC) of a CCD depicts the variance of uniform images as a function of their average. It is now well established that the variance is not proportional to the average, as Poisson statistics would indicate, but rather flattens out at high flux. This “variance deficit”, related to the brighter-fatter effect, feeds correlations between nearby pixels that increase with flux, and decay with distance. We propose an analytical expression for the PTC shape, and for the dependence of correlations with intensity, and relate both to some more basic quantities related to the electrostatics of the sensor, which are commonly used to correct science images for the brighter-fatter effect. We derive electrostatic constraints from a large set of flat field images acquired with a CCD e2v 250, and eventually question the generally-admitted assumption that boundaries of CCD pixels shift by amounts proportional to the source charges. Our results show that the departure of flat field statistics from the Poisson law is entirely compatible with charge redistribution during the drift in the sensor.

Improvement of energy conversion effectiveness and maximum output power of electrostatic induction-type MEMS energy harvesters by using symmetric comb-electrode structures

We introduce symmetric comb-electrode structures for the electrostatic vibrational MEMS energy harvester to lower the electrostatic constraint force attributed to the built-in electret potential, thereby allowing the harvester device to operate in a small acceleration range of 0.05 g or lower (1 g = 9.8 m s−2). Given the same device structure, two different potentials for the electret are tested to experimentally confirm that the output induction current is enhanced 4.2 times by increasing the electret potential from −60 V to −250 V. At the same time, the harvester effectiveness has been improved to as high as 93%. The device is used to swiftly charge a 470 µF storage capacitor to 3.3 V in 120 s from small sinusoidal vibrations of 0.6 g at 124 Hz.

Electrostatic Constraints Assessed by 1H MAS NMR Illuminate Differences in Crystalline Polymorphs.

Atomically resolved crystal structures not only suffer from the inherent uncertainty in accurately locating H atoms but also are incapable of fully revealing the underlying forces enabling the formation of final structures. Therefore, the development and application of novel techniques to illuminate intermolecular forces in crystalline solids are highly relevant to understand the role of hydrogen atoms in structure adoption. Novel developments in 1H NMR MAS methodology can now achieve robust measurements of 1H chemical shift anisotropy (CSA) tensors which are highly sensitive to electrostatics. Herein, we use 1H CSA tensors, measured by MAS experiments and characterized using DFT calculations, to reveal the structure-driving factors between the two polymorphic forms of acetaminophen (aka Tylenol or paracetamol) including differences in hydrogen bonding and the role of aromatic interactions. We demonstrate how the 1H CSAs can provide additional insights into the static picture provided by diffraction to elucidate rigid molecules.

A Palladium(II) Complex of a C4 Chelating Bis(NHC) Diphosphonium Bis(ylide) Ligand

The preparation and the structure of a palladium(II) complex bearing an extremely electron rich C4 chelating bis(NHC) diphosphonium bis(ylide) ligand are described. This Pd complex is obtained as a single diastereoisomer via a four-step synthesis from the bis(imidazol-1-yl)methane in 43% overall yield. It results from two fully selective processes: the deprotonation of two imidazolium moieties in the presence of phosphonium centers and the coordination of two phosphonium ylides at the metal center. Steric and electrostatic constraints between the triphenylphosphonio substituents at the C-ylidic positions are proposed to explain the diastereoselectivity of the C2 coordination in favor of the dl form (RR/SS).

Framework Structures for Mg Battery Cathodes

Rechargeable Mg batteries have received intensive attention as affordable rechargeable batteries with high electromotive force, high energy density, and high safety. Mg possesses two valence electrons and has the lowest standard electrode potential (ca. -2.36 V vs. SHE) among the air-stable metals. There is another advantage that Mg metal can be used as an active material because Mg metal hardly forms dendrites. However, the slow diffusion of Mg ions in solid crystals prevents the realization of active materials for Mg rechargeable batteries at room temperature. Although some complex oxides have been reported to work as active materials at higher temperatures, Chevrel compounds are still the gold standards, which work at room temperature. However, the working voltage of the Mg battery using a Chevrel compound for the cathode is only ca. 1.2 V, which is far below that of Li-ion batteries (3-5 V). Nevertheless, Chevrel compounds have the significant advantage that a relatively large space exists in the crystal structure, which allows for fast Mg ion diffusion. In the present study, we investigated some materials with framework structures as cathodes for Mg batteries, which can alleviate the electrostatic constraint between Mg ions and cathode constituents. Specifically, we investigated the redox behavior of the thin films of Prussian blue and Prussian blue analogues in electrolytes containing an Mg salt using electrochemical quartz crystal microbalance and X-ray absorption spectroscopy. In addition, we discuss the electrochemical insertion/extraction behavior of Mg ions and their solvation structures.

Structural Studies of Supramolecular G-Quadruplexes Formed from 8-Aryl-2'-deoxyguanosine Derivatives.

Self-assembly is a powerful tool for the construction of complex nanostructures. Despite advances in the field, the development of precise self-assembled structures remains a challenge. We have shown that, in the presence of suitably sized cations like K(+), 8-aryl-2'-deoxyguanosine (8ArG) derivatives self-assemble into sets of coaxially stacked planar tetramers, which we term supramolecular G-quadruplexes (SGQs). Previously, we reported that, when the 8-aryl group is a phenyl ring with a meta-carbonyl group, the resulting supramolecule is a hexadecamer, which is remarkably robust as illustrated by its isostructural assembly in both organic and aqueous environments. We report here a detailed three-dimensional structure of the SGQs formed by lipophilic, and hydrophilic, 8ArG derivatives with either 8-(meta-acetylphenyl), 8-(para-acetylphenyl), or 8-(meta-ethoxycarbonylphenyl) groups. The chirality and close contacts between the subunits impose different levels of steric and electrostatic constraints on opposite sides of the tetrads, which determine their preferred relative orientation. The balance between attractive noncovalent interactions juxtaposed with repulsive steric and electrostatic interactions explains the high cooperativity, fidelity, and stability of these SGQs. These structural studies, together with titration experiments and molecular dynamics simulations, provide insight into the mechanism of formation of these SGQs.

Deciphering Thylakoid Sub-compartments using a Mass Spectrometry-based Approach

Photosynthesis has shaped atmospheric and ocean chemistries and probably changed the climate as well, as oxygen is released from water as part of the photosynthetic process. In photosynthetic eukaryotes, this process occurs in the chloroplast, an organelle containing the most abundant biological membrane, the thylakoids. The thylakoids of plants and some green algae are structurally inhomogeneous, consisting of two main domains: the grana, which are piles of membranes gathered by stacking forces, and the stroma-lamellae, which are unstacked thylakoids connecting the grana. The major photosynthetic complexes are unevenly distributed within these compartments because of steric and electrostatic constraints. Although proteomic analysis of thylakoids has been instrumental to define its protein components, no extensive proteomic study of subthylakoid localization of proteins in the BBY (grana) and the stroma-lamellae fractions has been achieved so far. To fill this gap, we performed a complete survey of the protein composition of these thylakoid subcompartments using thylakoid membrane fractionations. We employed semiquantitative proteomics coupled with a data analysis pipeline and manual annotation to differentiate genuine BBY and stroma-lamellae proteins from possible contaminants. About 300 thylakoid (or potentially thylakoid) proteins were shown to be enriched in either the BBY or the stroma-lamellae fractions. Overall, present findings corroborate previous observations obtained for photosynthetic proteins that used nonproteomic approaches. The originality of the present proteomic relies in the identification of photosynthetic proteins whose differential distribution in the thylakoid subcompartments might explain already observed phenomenon such as LHCII docking. Besides, from the present localization results we can suggest new molecular actors for photosynthesis-linked activities. For instance, most PsbP-like subunits being differently localized in stroma-lamellae, these proteins could be linked to the PSI-NDH complex in the context of cyclic electron flow around PSI. In addition, we could identify about a hundred new likely minor thylakoid (or chloroplast) proteins, some of them being potential regulators of the chloroplast physiology.

Electrostatic model of radial pn junction nanowires

Poisson's equation is solved for a radial pn junction nanowire (NW) with surface depletion. This resulted in a model capable of giving radial energy band and electric field profiles for any arbitrary core/shell doping density, core/shell dimensions, and surface state density. Specific cases were analyzed to extract pertinent underlying physics, while the relationship between NW specifications and the depletion of the NW were examined to optimize the built-in potential across the junction. Additionally, the model results were compared with experimental results in literature to good agreement. Finally, an optimum device design is proposed to satisfy material, optical, and electrostatic constraints in high efficiency NW solar cells.

A Measure of the Broad Substrate Specificity of Enzymes Based on ‘Duplicate’ Catalytic Residues

The ability of an enzyme to select and act upon a specific class of compounds with unerring precision and efficiency is an essential feature of life. Simultaneously, these enzymes often catalyze the reaction of a range of similar substrates of the same class, and also have promiscuous activities on unrelated substrates. Previously, we have established a methodology to quantify promiscuous activities in a wide range of proteins. In the current work, we quantitatively characterize the active site for the ability to catalyze distinct, yet related, substrates (BRASS). A protein with known structure and active site residues provides the framework for computing ‘duplicate’ residues, each of which results in slightly modified replicas of the active site scaffold. Such spatial congruence is supplemented by Finite difference Poisson Boltzmann analysis which filters out electrostatically unfavorable configurations. The congruent configurations are used to compute an index (BrassIndex), which reflects the broad substrate profile of the active site. We identify an acetylhydrolase and a methyltransferase as having the lowest and highest BrassIndex, respectively, from a set of non-homologous proteins extracted from the Catalytic Site Atlas. The acetylhydrolase, a regulatory enzyme, is known to be highly specific for platelet-activating factor. In the methyltransferase (PDB: 1QAM), various combinations of glycine (Gly38/40/42), asparagine (Asn101/11) and glutamic acid (Glu59/36) residues having similar spatial and electrostatic profiles with the specified scaffold (Gly38, Asn101 and Glu59) exemplifies the broad substrate profile such an active site may provide. ‘Duplicate’ residues identified by relaxing the spatial and/or electrostatic constraints can be the target of directed evolution methodologies, like saturation mutagenesis, for modulating the substrate specificity of proteins.

Electrostatic field management and electrodynamic modeling of switched quarter-wave oscillators

Quarter-wave switched oscillators (SWOs), sometimes referred to as MATRIX oscillators, are an important technology for the generation of high-power, moderate bandwidth (mesoband) waveforms. The use of SWOs in high power microwave sources has been discussed for the past 10 years but a detailed discussion of the design of this type of oscillators for particular waveforms has been lacking. In this work a design methodology for a realization of SWOs is developed. A key element in the design of SWOs is the self-breakdown switch, which is created by a large electric field. In order for the switch to close as expected from the design, it is essential to manage the electrostatic field distribution inside the oscillator during the charging time. This enforces geometric constraints on the shape of the conductors inside the oscillator. At the same time, the electrodynamic operation of the system is dependent on the geometry of the structure. In order to generate a geometry that satisfies both the electrostatic and electrodynamic constraints, a new approach is developed to generate this geometry using iterative solutions to the 2-D static Laplace equation, subject to a particular set of boundary conditions. These boundary conditions are manipulated to generate equipotential lines with specific dimensions that satisfy the electrodynamic constraints. Meanwhile, these equipotential lines naturally support an electrostatic field distribution that meets the requirements for the field enhancement. To study the electrodynamic aspects of SWOs, three different (but inter-related) numerical models are built. Depending on the assumptions made in each model, different information about the electrodynamic properties of the designed SWO are obtained. In addition, the agreement and consistency between the different models, validate and give confidence in the calculated results.

Resistance Profiles of Novel Electrostatically Constrained HIV-1 Fusion Inhibitors

Human immunodeficiency virus (HIV) gp41 plays a key role in viral fusion; the N- and C-terminal heptad repeats (N-HR and C-HR) of gp41 form a stable 6-helical conformation for fusion. Therefore, HR-derived peptides, such as enfuvirtide (T-20), inhibit HIV-1 fusion by acting as decoys, and have been used for the treatment of HIV-1 infection. However, the efficacy of T-20 is attenuated by resistance mutations in gp41, including V38A and N43D. To suppress the resistant variants, we previously developed electrostatically constrained peptides, SC34 and SC34EK, and showed that both exhibited potent anti-HIV-1 activity against wild-type and T-20-resistant variants. In this study, to clarify the resistance mechanism to this next generation of fusion inhibitors, we selected variants with resistance to SC34 and SC34EK in vitro. The resistant variants had multiple mutations in gp41. All of these mutations individually caused less than 6-fold resistance to SC34 and SC34EK, indicating that there is a significant genetic barrier for high-level resistance. Cross-resistance to SC34 and SC34EK was reduced by a simple difference in the polarity of two intramolecular electrostatic pairs. Furthermore, the selected mutations enhanced the physicochemical interactions with N-HR variants and restored activities of the parental peptide, C34, even to resistant variants. These results demonstrate that our approach of designing gp41-binding inhibitors using electrostatic constraints and information derived from resistance studies produces inhibitors with enhanced activity, high genetic barrier, and distinct resistance profile from T-20 and other inhibitors. Hence, this is a promising approach for the design of future generation peptide fusion inhibitors.

Towards the stability limit of cyclic diphosphonium bis-ylides

A typology of molecules containing two phosphonium ylide groups (bis-ylides) is proposed, versus the bridge length (fused, ω- and α-bisylides) and their relative topographical orientations (head-to-head, tail-to-tail or head-to-tail). The formal electrostatic constraint occurring in the head-to-head series is systematically addressed for cyclic representatives based on the o-bis(diphenylphosphonio)benzene framework. After a survey of previously reported results in the fused and β-bis-ylide series, emphasis is given to the cyclic α-bis-ylides. The non-substituted, non-stabilized version escaped isolation through spontaneous fragmentation to bis(diphenylphosphino)benzene and acetylene. Inspired by this result, the reverse process was employed for the generation of stabilized representatives with ethoxycarbonyl and benzoyl substituents at the ylidic carbon atoms. The stability and stereochemistry of the obtained head-to-head α-bis-ylides was investigated by NMR techniques and reproduced and analyzed by DFT calculations. The role of electrostatics in determining structural and reactivity features of cyclically constrained species is here illustrated.

Linking the Diffusion of Water in Compacted Clays at Two Different Time Scales: Tracer Through-Diffusion and Quasielastic Neutron Scattering

Diffusion of water and solutes through compacted clays or claystones is important when assessing the barrier function of engineered or geological barriers in waste disposal. The shape and the connectivity of the pore network as well as electrostatic interactions between the diffusant and the charged clay surfaces or cations compensating negative surface charges affect the resistance of the porous medium to diffusion. Comparing diffusion measurements performed at different spatial or time scales allows identification and extraction of the different factors. We quantified the electrostatic constraint q for five different highly compacted clays (rhob = 1.85 +/- 0.05 g/cm3) using quasielastic neutron scattering (QENS) data. We then compared the QENS data with macroscopic diffusion data for the same clays and could derive the true geometric tortuosities G of the samples. Knowing the geometric and electrostatic factors for the different clays is essential when trying to predict diffusion coefficients for other conditions. We furthermore compared the activation energies Ea for diffusion at the two measurement scales. Because Ea is mostly influenced by the local, pore scale surroundings of the water, we expected the results to be similar at both scales. This was indeed the case for the nonswelling clays kaolinite and illite, which had Ea values lower than that of bulk water, but not for montmorillonite, which had values lower than that in bulk water at the microscopic scale, but larger at the macroscopic scale. The differences could be connected to the strongly temperature dependent mobility of the cations in the clays, which may act as local barriers in the narrow pores at low temperatures.