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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS2013

PowderSim: Lagrangian Discrete and Mesh-Free Continuum Simulation Code for Cohesive Soils

PowderSim is a calculation tool that combines a discrete-element method (DEM) module, including calibrated interparticle-interaction relationships, with a mesh-free, continuum, SPH (smoothed-particle hydrodynamics) based module that utilizes enhanced, calibrated, constitutive models capable of mimicking both large deformations and the flow behavior of regolith simulants and lunar regolith under conditions anticipated during in situ resource utilization (ISRU) operations. The major innovation introduced in PowderSim is to use a mesh-free method (SPH-based) with a calibrated and slightly modified critical-state soil mechanics constitutive model to extend the ability of the simulation tool to also address full-scale engineering systems in the continuum sense. The PowderSim software maintains the ability to address particle-scale problems, like size segregation, in selected regions with a traditional DEM module, which has improved contact physics and electrostatic interaction models.

Johnson, Scott↗
DOE OSTI2025

Cation selectivities in zwitterion grafted nanopores: effect of zwitterion architecture

Selective separation of monovalent cations is a critical challenge in applications such as water purification and lithium recovery from salt brines. Cross-linked zwitterionic amphiphilic copolymer (ZAC-X) membranes have gained attention for their exceptional anion permselectivity, attributed to self-assembled zwitterion-lined nanodomains that interact preferentially with anions according to their hydrated radii r hyd . However, these membranes show minimal selectivity among monovalent cations, despite significant differences in their hydration structures, motivating studies on the underlying mechanisms of cation transport and selectivity in this family of materials. In this study, we conducted molecular dynamics simulations of aqueous salt solutions within zwitterion-functionalized nanopores to elucidate the influence of dipole orientation of the zwitterionic (ZI) ligands on cation diffusivities, partitioning, and permeabilities. To this end, we examined two contrasting ZI ligand architectures: Motif A (surface–cation–anion, S–ZI + –ZI − ) and Motif B (surface–anion–cation, S–ZI − –ZI + ). Our results show that in Motif A, the sulfonate groups of the ZI ligands are localized near the pore center radially, leading to strong electrostatic interactions with small bare cations (Mg 2+ and Li + ). This configuration results in high cation partitioning but low cation diffusion, maintaining solution-diffusion tradeoff typical of functionalized membranes. In contrast, Motif B show that sulfonate groups shift radially toward the mid-region of the pore. This shift, especially for small bare cations, introduces steric constraints that weaken their interactions with the sulfonate groups, thereby enhancing hydration and lowering partitioning, while still maintaining their low self-diffusivity. These findings establish zwitterion dipole orientation as a powerful design lever for tuning cation selectivity in membrane systems and offer molecular-level insights for engineering next-generation ion separation materials.

Morishita, Kazuya [Univ. of Texas, Austin, TX (Uni↗
DOE OSTI2022

Multilayer Chitin–Chitosan–Cellulose Barrier Coatings on Poly(ethylene terephthalate)

Currently, effective barrier properties over a wide range of humidity are achieved by layering multiple plastics, resulting in structures that are nearly impossible to recycle through current systems. There is strong interest in developing barriers that are recyclable, biodegradable, or compostable. Chitin and cellulose nanomaterials are promising alternatives because of their high crystallinity, renewable sourcing, strong electrostatic interactions, and potential for biodegradation or composting. In this paper, we explore the potential to create multilayer materials with effective oxygen and water vapor barrier properties at elevated humidity by combining recyclable poly(ethylene terephthalate) (PET) films with single-layer and bilayer coatings of chitin nanowhiskers (ChNWs), chitosan (CS), and cellulose nanocrystals (CNCs). The addition of CS to the ChNW suspension improved the gas barrier properties of ChNW coatings, likely by filling voids, and short ChNWs (SChNW, 114 nm) performed better than long ChNWs (LChNW, 230 nm). At the optimal mass ratio of 1:1 SChNW/CS, the oxygen permeability (OP) of SChNW/CS-coated PET films was 5.1 cm 3 μm m –2 day –1 kPa –1 versus 15.9 cm 3 μm m –2 day –1 kPa –1 for neat PET. To take advantage of electrostatic attraction and hydrogen bonding, CNC was first coated on the PET, followed by coating with ChNW/CS, resulting in an OP as low as 3.6 cm 3 μm m –2 day –1 kPa –1 at 50% relative humidity (RH), and 6.4 cm 3 μm m –2 day –1 kPa –1 at 80% RH. Furthermore, after thermal treatment (120 °C, 2.5 h), the OP dropped to 2.2 cm 3 μm m –2 day –1 kPa –1 (50% RH) and 4.8 cm 3 μm m –2 day –1 kPa –1 (80% RH). The ChNW/CS and CNC coating can be efficiently removed with alkali treatment enabling possible recycling of the coated PET films.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

On the Mechanism of Bilayer Separation by Extrusion, or Why Your LUVs Are Not Really Unilamellar

Extrusion through porous filters is a widely used method for preparing biomimetic model membranes. Of primary importance in this approach is the efficient production of single bilayer (unilamellar) vesicles that eliminate the influence of interlamellar interactions and strictly define the bilayer surface area available to external reagents such as proteins. Sub-microscopic vesicles produced using extrusion are widely assumed to be unilamellar, and large deviations from this assumption would dramatically impact interpretations from many model membrane experiments. In this work, using three probe-free methods—small-angle X-ray and neutron scattering (SAXS and SANS) and cryogenic electron microscopy (cryoEM)—we report unambiguous evidence of extensive multilamellarity in extruded vesicles composed of neutral phosphatidylcholine lipids, including for the common case of neutral lipids dispersed in physiological buffer and extruded through 100 nm diameter pores. In such preparations, only ~35% of lipids are externally accessible, and this fraction is highly dependent on preparation conditions. Charged lipids promote unilamellarity, as does decreasing solvent ionic strength, indicating the importance of electrostatic interactions in determining the lamellarity of extruded vesicles. Smaller extrusion pore sizes also robustly increase the fraction of unilamellar vesicles, suggesting a role for membrane bending. Taken together, these observations suggest a mechanistic model for extrusion, wherein formation of unilamellar vesicles involves competition between bilayer bending and adhesion energies. The findings presented here have wide-ranging implications for the design and interpretation of model membrane studies, especially ensemble-averaged observations relying on the assumption of unilamellarity.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

Anions Enhance Rare Earth Adsorption at Negatively Charged Surfaces

Anions are expected to be repelled from negatively charged surfaces. At aqueous interfaces, however, ion-specific effects can dominate over direct electrostatic interactions. Using multiple in situ surface sensitive experimental techniques, we show in this study that surface affinities of SCN – anions are so strong that they can adsorb at a negatively charged floating monolayer at the air–aqueous interface. This extreme example of ion-specific effects may be very important for understanding complex processes at aqueous interfaces, such as chemical separations of rare earth metals. Adsorbed SCN – ions at the floating monolayer increase the overall negative charge density, leading to enhanced trivalent rare earth adsorption. Surface sensitive X-ray fluorescence measurements show that the surface coverage of Lu 3+ ions can be triple the apparent surface charge of the floating monolayer in the presence of SCN – . Comparison to NO 3 – samples shows that the effects are strongly dependent on the character of the anion, providing further evidence of ion-specific effects dominating over electrostatics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Modifying Specific Ion Effects: Studies of Monovalent Ion Interactions with Amines

Specific ion effects in the interactions of monovalent anions with amine groups-one of the hydrophilic moieties found in proteins-were investigated using octadecylamine monolayers floating at air–aqueous solution interfaces. Here, we find that at solution pH 5.7, larger monovalent anions induce a nonzero pressure starting at higher areas/molecules, i.e., a wider “liquid expanded” region in the monolayer isotherms. Using X-ray fluorescence at near total reflection (XFNTR), an element- and surface-specific technique, ion adsorption to the amines at pH 5.7 is confirmed to be ion-specific and to follow the conventional Hofmeister series. However, at pH 4, this ion specificity is no longer observed. We propose that at the higher pH, the amine headgroups are only partially protonated, and large polarizable ions such as iodine are better able to boost amine protonation. At the lower pH, on the other hand, the monolayer is fully protonated, and electrostatic interactions dominate over ion specificity. These results demonstrate that ion specificity can be modified by changing the experimental conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Perturbation of Hydrogen-Bonding Networks over Supported Lipid Bilayers by Poly(allylamine hydrochloride)

Water is vital to many biochemical processes and is necessary for driving fundamental interactions of cell membranes with their external environments, yet it is difficult to probe the membrane/water interface directly and without the use of external labels. Here, we employ vibrational sum frequency generation spectroscopy to understand the role of interfacial water molecules above bilayers formed from zwitterionic (phosphatidylcholine) and anionic (phosphatidylglycerol, PG, and phosphatidylserine, PS) lipids as they are exposed to the common polycation poly(allylamine hydrochloride) (PAH) in 100 mM NaCl. We show that as the concentration of PAH is increased, the interfacial water molecules are irreversibly displaced and find that it requires 10 times more PAH to displace interfacial water molecules from membranes formed from purely zwitterionic lipids when compared to membranes that contain the anionic PG and PS lipids. This outcome is likely due to the difference in (1) the energy with which water molecules are bound to the lipid headgroups, (2) the number of water molecules bound to the headgroups, which is related to the headgroup area, and (3) the electrostatic interactions between the PAH molecules and the negatively charged lipids that are favored when compared to the zwitterionic lipid headgroups. The findings presented here contribute to establishing causal relationships in nanotoxicology and to understanding, controlling, and predicting the initial steps that lead to the lysis of cells exposed to membrane-disrupting polycations or to transfection.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

A Preorganized Electric Field Leads to Minimal Geometrical Reorientation in the Catalytic Reaction of Ketosteroid Isomerase

Electrostatic interactions play a pivotal role in enzymatic catalysis and are increasingly modeled explicitly in computational enzyme design; nevertheless, they are challenging to measure experimentally. Using vibrational Stark effect (VSE) spectroscopy, we have measured electric fields inside the active site of the enzyme ketosteroid isomerase (KSI). These studies have shown that these fields can be unusually large, but it has been unclear to what extent they specifically stabilize the transition state (TS) relative to a ground state (GS). In the following, we use crystallography and computational modeling to show that KSI’s intrinsic electric field is nearly perfectly oriented to stabilize the geometry of its reaction’s TS. Moreover, we find that this electric field adjusts the orientation of its substrate in the ground state so that the substrate needs to only undergo minimal structural changes upon activation to its TS. This work provides evidence that the active site electric field in KSI is preorganized to facilitate catalysis and provides a template for how electrostatic preorganization can be measured in enzymatic systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Role of Complexation Strength on the Photophysical and Transport Properties of Semiconducting Charged Polymer Complexes

The high polymer fraction in complexes of conjugated and insulating polyelectrolytes offers unique opportunities for the fabrication of conductive thick films and bulk structures. The electrostatic interactions in these systems further provide a handle for controlling their structure and properties. The impact of charge-mediated complexation strength on the photophysical and electronic transport properties in blends of conjugated polyelectrolytes (CPEs) with oppositely charged polymeric ionic liquids (PILs) was examined. Complexes were formed with varying frequency of charged repeat units, from 50 to 100%, on an anionic polythiophene-based CPE and a complimentary cationic PIL. In highly charged complexes, the intimate mixing between the CPE and the PIL reduced the structural disorder along the CPE backbone, enhancing its intrachain conjugation and interchain stacking. In weakly charged complexes (<90%), these chain planarization effects were absent and microphase separation occurred. At all charge fractions examined, the electrical conductivity of an acid-doped complex was higher than that of the unblended constituent CPE. Further, the highest electrical conductivity, near 1 S cm –1 , was found for a charge fraction of 100%. These results demonstrate the potential for designing effective polymeric conductors using electrostatic complexation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Adsorption mechanisms of cesium at calcium-silicate-hydrate surfaces using molecular dynamics simulations

We report understanding the mechanisms of interactions and immobilization of radionuclides in cement systems at the molecular level is key to developing safe and novel solutions for the long-term storage of nuclear wastes. The molecular level adsorption mechanisms of cesium (Cs + ) ions onto tobermorite 9 Å, tobermorite 14 Å, and jennite – three crystalline structural analogues for calcium-silicate-hydrates, the main components in cement-based materials, were investigated using molecular dynamics (MD) simulations. Convergence monitoring of the simulations, using the root mean square displacement with average correlation analysis, indicated that MD trajectories of 10–15 ns were needed given the size of the selected computational cell to properly capture the dynamic process of adsorption. Cs + ions adsorbed as inner-sphere complexes at the tobermorite surfaces, while they showed lower affinity for jennite. The charge and structure of the surface layer strongly influenced the adsorption mechanisms of Cs + ions. Strong association with the hexagonal cavities of the silica sites were seen at the tetrahedral SiO 4 surface of the tobermorite structures. Cs + ion adsorption was attributed to co-ion adsorption at the octahedral CaO 6 surface of tobermorite 9 Å, cation exchange at that of tobermorite 14 Å, and electrostatic interaction with the surface hydroxyl groups for jennite. Distribution coefficients of Cs + ions onto cement pastes derived from molecular dynamics by taking the surface structure and dynamics of Cs + ions directly into account showed a range of overlap with experimental results.

42 ENGINEERING↗
DOE OSTI2019

Adsorption Study of Al 3+ , Cr 3+ , and Mn 2+ onto Quartz and Corundum using Flow Microcalorimetry, Quartz Crystal Microbalance, and Density Functional Theory

The adsorption of aqueous ions onto natural mineral surfaces controls numerous mineral–water interactions and is governed by, among other numerous factors, ion dehydration and hydrolysis. This work explored the extent to which dehydration and hydrolysis affect the adsorption of three metal cations, Al 3+ , Cr 3+ , and Mn 2+ , onto quartz (SiO2) and corundum (Al 2 O 3 ) surfaces at pH 3.8 through the integration of flow microcalorimetry (FMC), quartz crystal microbalance with dissipation (QCM-D) measurements and density functional theory (DFT) calculations. At pH 3.8, negligible amounts of Mn 2+ and Al 3+ are hydrolyzed, while 78% of Cr 3+ exist in hydrolyzed species. QCM-D and FMC measurements showed that Al 3+ and Cr 3+ adsorb to both surfaces, while Mn 2+ adsorbed only to Al 2 O 3 . DFT bond energy calculations confirmed the favorable bonding between the mineral surfaces and Al 3+ and Cr 3+ , and that Mn 2+ adsorption onto SiO 2 was unfavorable. Furthermore, FMC showed that on both surfaces, the adsorption of Al 3+ was endothermic and reversible, while that of Cr 3+ was exothermic and partially irreversible. Through the integration of experimental and computational methods, this work suggested that the reversible adsorption of unhydrolyzed cations (Mn 2+ and Al 3+ ) occurred through weak electrostatic interactions. The large energy cost required to dehydrate unhydrolyzed cations resulted in an endothermic adsorption process. Meanwhile, hydrolyzed Cr 3+ species can adsorb on quartz and corundum through covalent-bond formation, and thus, their adsorption was partially irreversible. Furthermore, the hydrolysis of Cr 3+ lowered the dehydration energy during adsorption, resulting in an exothermic adsorption. By using bond energies as a guide to indicate the possibility of thermodynamically favored adsorption, there was a strong agreement between the DFT and experimental techniques. The findings presented here contribute to understanding and predicting various mineral–water interfacial processes in the natural environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

The Role of Surface Hydrophobicity on the Structure and Dynamics of CO2 and CH4 Confined in Silica Nanopores

Advancing a portfolio of technologies that range from the storage of excess renewable natural gas for distributed use to the capture and storage of CO 2 in geological formation are essential for meeting our energy needs while responding to challenges associated with climate change. Delineating the surface interactions and the organization of these gases in nanoporous environments is one of the less explored approaches to ground advances in novel materials for gas storage or predict the fate of stored gases in subsurface environments. To this end, the molecular scale interactions underlying the organization and transport behavior of CO 2 and CH 4 molecules in silica nanopores need to be investigated. To probe the influence of hydrophobic surfaces, a series of classical molecular dynamics (MD) simulations are performed to investigate the structure and dynamics of CO 2 and CH 4 confined in OH-terminated and CH 3 -terminated silica pores with diameters of 2, 4, 6, 8, and 10 nm at 298 K and 10 MPa. Higher adsorption extents of CO 2 compared to CH 4 are noted on OH-terminated and CH 3 -terminated pores. The adsorbed extents increase with the pore diameter. Further, the interfacial CO 2 and CH 4 molecules reside closer to the surface of OH-terminated pores compared to CH 3 -terminated pores. The lower adsorption extents of CH 4 on OH-terminated and CH 3 -terminated pores result in higher diffusion coefficients compared to CO 2 molecules. The diffusivities of both gases in OH-terminated and CH 3 -terminated pores increase systematically with the pore diameter. The higher adsorption extents of CO 2 on OH-terminated and CH 3 -terminated pores are driven by higher van der Waals and electrostatic interactions with the pore surfaces, while CH 4 adsorption is mainly due to van der Waals interactions with the pore walls. These findings provide the interfacial chemical basis underlying the organization and transport behavior of pressurized CO 2 and CH 4 gases in confinement.

Mohammed, Sohaib↗
DOE OSTI2019

Effect of Cysteine Substitutions on the Structural and Magnetic Properties of Fe{sub 3}O{sub 4}–Cysteine/RGO and Fe{sub 3}O{sub 4}/RGO–Cysteine Nanocomposites

We synthesized by electrostatic self-assembly route in basic solution Fe{sub 3}O{sub 4}–cysteine/RGO and Fe{sub 3}O{sub 4}/RGO–cysteine nanocomposites. In this method, electrostatic interaction was created via negatively charged surface of the reduced graphene oxide and reduced graphene oxide–cysteine sheets and positively charged surface of the Fe{sub 3}O{sub 4} and Fe{sub 3}O{sub 4}–Cys nanoparticles in aqueous solution. The structural and magnetic properties of the prepared samples were analyzed by x-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy, transmission electron microscopy (TEM), and vibrating sample magnetometer (VSM), respectively. The dependences of magnetization as a function of applied field using a vibrating sample magnetometer exhibit S-like curves, indicating a magnetic hysteresis behavior for all samples. It clearly showed that, the nanocomposites showed a reduction of saturation magnetization to the Fe{sub 3}O{sub 4} nanoparticles.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2025

Charge regulation effects on colloidal mixture nanoparticles

Changes in pH within a system containing dissociable sites affect the protonation and deprotonation of these groups, thereby influencing their physical properties. In response, the system modifies their surface charge, affecting electrostatic interactions, aggregation, stability, and structural behavior. Although the pH can be tuned in experiments, it is difficult to model this phenomenon using simulations or theoretical approaches. Here, we perform hybrid Monte Carlo-molecular dynamics simulations to model charge regulation effects in an equimolar colloidal charged system. We compare charge regulation effects with those of a system in which the charges of colloidal nanoparticles are not dissociable. The comparison between the two cases modifies the phase diagram, and it changes the volume fraction where a percolation network of nanoparticles is found. Charge regulation is found to destroy network formation, as the charge in the nanoparticles is modified because of the cooperativity dependency of the degree of charge dissociation sites among the nanoparticles favoring cluster formation. Furthermore, our work suggests that the ionic and/or electronic conductivity in functionalized nanoparticles can be modified by changing pH values. It also guides the experimental design of oppositely charged nanoparticles as inks for 3D printing processes.

Classical statistical mechanics↗
DOE OSTI2021

Gaseous cyclodextrin- closo -dodecaborate complexes χCD·B 12 X 12 2– (χ = α, β, and γ; X = F, Cl, Br, and I): electronic structures and intramolecular interactions

A fundamental understanding of cyclodextrin- closo -dodecaborate inclusion complexes is of great interest in supramolecular chemistry. Herein, we report a systematic investigation on the electronic structures and intramolecular interactions of perhalogenated closo -dodecaborate dianions B 12 X 12 2– (X = F, Cl, Br and I) binding to α-, β-, and γ-cyclodextrins (CDs) in the gas phase using combined negative ion photoelectron spectroscopy (NIPES) and density functional theory (DFT) calculations. The vertical detachment energy (VDE) of each complex and electronic stabilization of each dianion due to the CD binding (ΔVDE, relative to the corresponding isolated B 12 X 12 2– ) are determined from the experiments along α-, β- and γ-CD in the form of VDE (ΔVDE): 4.00 (2.10), 4.33 (2.43), and 4.30 (2.40) eV in X = F; 4.09 (1.14), 4.64 (1.69), and 4.69 (1.74) eV in X = Cl; 4.11 (0.91), 4.58 (1.38), and 4.70 (1.50) eV in X = Br; and 3.54 (0.74), 3.88 (1.08), and 4.05 (1.25) eV in X = I, respectively. All complexes have significantly higher VDEs than the corresponding isolated dodecaborate dianions with ΔVDE spanning from 0.74 eV at (α, I) to 2.43 eV at (β, F), sensitive to both host CD size and guest substituent X. DFT-optimized complex structures indicate that all B 12 X 12 2– prefer binding to the wide openings of CDs with the insertion depth and binding motif strongly dependent on the CD size and halogen X. Dodecaborate anions with heavy halogens, i.e. , X = Cl, Br, and I, are found outside of α-CD, while B 12 F 12 2– is completely wrapped by γ-CD. Partial embedment of B 12 X 12 2– into CDs is observed for the other complexes via multipronged B–X … H–O/C interlocking patterns. The simulated spectra based on the density of states agree well with those of the experiments and the calculated VDEs well reproduce the experimental trends. Molecular orbital analyses suggest that the spectral features at low binding energies originated from electrons detached from the dodecaborate dianion, while those at higher binding energies are derived from electron detachment from CDs. Energy decomposition analyses reveal that the electrostatic interaction plays a dominating role in contributing to the host–guest interactions for the X = F series partially due to the formation of a O/C–H … X–B hydrogen bonding network, and the dispersion forces gradually become important with the increase of halogen size.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Evolution of the Crystal and Electronic Structures of the RBa{sub 2}Cu{sub 3}O{sub 6 + δ} Cuprates in Annealing

The crystal structure and the magnetic properties of the HTSC cuprates YBa{sub 2}Cu{sub 3}O{sub 6 + δ}, Y{sub 1 ‒} {sub x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub 6 + δ}, and Nd{sub 1 +x}Ba{sub 2 –x}Cu{sub 3}O{sub 6 + δ} (x = 0.2) with the structure of a layered perovskite are studied. The well-known aging effect detected in these HTSC materials during storage under standard conditions, namely, an increase in their critical temperature T{sub c} and a decrease in lattice parameter c in time, is investigated. Using YBa{sub 2}Cu{sub 3}O{sub 6 + δ} as an example, we show that the dependence of c on the oxygen content undergoes the following changes in time: (1) the negative slope of the dependence with respect to axis δ increases and (2) nonlinearity appears and grows in time according to a quadratic law. The first type of changes is explained by an increase in the valence of copper ions, which is accompanied by a decrease in their radius. The second type is explained by the electrostatic interaction of structural CuO{sub 2} planes due to the accumulation of electron holes, which come from CuO{sub δ} planes, in them. The calculation of the second type of changes in parameter c in the YBa{sub 2}Cu{sub 3}O{sub 6 + δ} cuprate exhibits good quantitative agreement with the experimental data. The second-type changes in the Y{sub 1 –x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub 6 + δ} compound (hole doping of CuO{sub 2} planes) turn out to be identical to those in YBa{sub 2}Cu{sub 3}O{sub 6 + δ}. However, the differently directed (in time) changes in lattice parameter c in Nd{sub 1 +x}Ba{sub 2 –x}Cu{sub 3}O{sub 6 + δ} indicate that the CuO{sub 2} planes in the neodymium cuprate are doped by electrons at the initial stage of aging. However, when these planes are saturated with holes in time, the type of doping changes from n to p without a noticeable change in the crystal structure, which has been considered to be impossible for layered cuprates to date.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Ligation Kinetics as a Probe for Non-Covalent Electrostatic Bonding and Electron Solvation of Alkali and Alkaline Earth Cations with Ammonia

Mono-ligation kinetics were measured for ammonia reacting with atomic cations in the first two groups of the periodic table (K{sup +}, Rb{sup +}, Cs{sup +} and Ca{sup +}, Sr{sup +}, Ba{sup +}). Also, mono-ligation energies were computed using density functional theory (DFT) in an attempt to assess the role of non-covalent electrostatic interactions in these chemical reactions. The measurements were performed at room temperature in helium bath gas at 0.35 Torr using an inductively coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometer. Rate coefficients are reported for ammonia addition, the only reaction channel that was observed with all these cations. A systematic decrease in the rate of addition of NH{sub 3} was observed for both group 1 and 2 cations going down the periodic table. The computational studies predict a decrease in the adduct binding energy and an increase in the bond separation going down groups 1 and 2 of the periodic table and provide some insight into the role of the extra selectron in the group 2 radical cations in ligand bonding. A correlation is seen between the efficiency of ligation and the binding energy of the adduct ion and attributed to the lifetime of the intermediate encounter complex against back dissociation which is dependent on its well depth. Higher-order additions of ammonia were also observed. Remarkable differences in the extent and kinetics were seen between the group 1 and 2 cations, and these were attributed to the occurrence of ammonia solvation of the extra s electron in the higher-order adducts of the alkaline earth cations. .

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Predicting molecular dipole moments by combining atomic partial charges and atomic dipoles

The molecular dipole moment ( μ ) is a central quantity in chemistry. It is essential in predicting infrared and sum-frequency generation spectra as well as induction and long-range electrostatic interactions. Furthermore, it can be extracted directly—via the ground state electron density—from high-level quantum mechanical calculations, making it an ideal target for machine learning (ML). Here, we choose to represent this quantity with a physically inspired ML model that captures two distinct physical effects: local atomic polarization is captured within the symmetry-adapted Gaussian process regression framework which assigns a (vector) dipole moment to each atom, while the movement of charge across the entire molecule is captured by assigning a partial (scalar) charge to each atom. The resulting “MuML” models are fitted together to reproduce molecular μ computed using high-level coupled-cluster theory and density functional theory (DFT) on the QM7b dataset, achieving more accurate results due to the physics-based combination of these complementary terms. The combined model shows excellent transferability when applied to a showcase dataset of larger and more complex molecules, approaching the accuracy of DFT at a small fraction of the computational cost. We also demonstrate that the uncertainty in the predictions can be estimated reliably using a calibrated committee model. The ultimate performance of the models—and the optimal weighting of their combination—depends, however, on the details of the system at hand, with the scalar model being clearly superior when describing large molecules whose dipole is almost entirely generated by charge separation. These observations point to the importance of simultaneously accounting for the local and non-local effects that contribute to μ ; furthermore, they define a challenging task to benchmark future models, particularly those aimed at the description of condensed phases.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗