Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “CATIONS”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 793 records · Page 44
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Vibrational analysis of methyl cation—Rare gas atom complexes: CH + 3 —Rg (Rg = He, Ne, Ar, Kr)

The vibrational spectra of simple CH + 3 —Rg (Rg = He, Ne, Ar, Kr) complexes have been studied by vibrational configuration interaction theory relying on multidimensional potential energy surfaces (PESs) obtained from explicitly correlated coupled cluster calculations, CCSD(T)-F12a. In agreement with experimental results, the series of rare gas atoms leads to rather unsystematic results and indicates huge zero point vibrational energy effects for the helium complex. In order to study these sensitive complexes more consistently, we also introduce configuration averaged vibrational self-consistent field theory, which is a generalization of standard vibrational self-consistent field theory to several configurations. The vibrational spectra of the complexes are compared to that of the methyl cation, for which corrections due to scalar-relativistic effects, high-order coupled-cluster terms, e.g., quadruple excitations, and core-valence correlation have explicitly been accounted for. The occurrence of tunneling splittings for the vibrational ground-state of CH + 3 —He has been investigated on the basis of semiclassical instanton theory. Furthermore these calculations and a direct comparison of the energy profiles along the intrinsic reaction coordinates with that of the hydronium cation, H 3 O + , suggest that tunneling effects for vibrationally excited states should be very small.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Photoinduced charge transfer in the Zn-methanol cation studied with selected-ion photofragment imaging

The Zn + (methanol) ion molecule complex produced by laser vaporization is studied with photofragment imaging at 280 and 266 nm. Photodissociation produces the methanol cation CH 3 OH + via excitation of a charge-transfer excited state. Surprisingly, excitation of bound excited states produces the same fragment via a curve crossing prior to separation of products. Significant kinetic energy release is detected at both wavelengths with isotropic angular distributions. Similar experiments are conducted on the perdeuterated methanol complex. The Zn + cation is a minor product channel that also exhibits significant kinetic energy release. Finally, an energetic cycle using the ionization energies of zinc and methanol together with the kinetic energy release produces an upper limit on the Zn + -methanol bond energy of 33.7 ± 4.2 kcal/mol (1.46 ± 0.18 eV).

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

Madrid-2019 force field: An extension to divalent cations Sr2+ and Ba2+

In this work, we present a parameterization of Sr2+ and Ba2+ cations, which expands the alkali earth set of cations of the Madrid-2019 force field. We have tested the model against the experimental densities of eight different salts, namely, SrCl2, SrBr2, SrI2, Sr(NO3)2, BaCl2, BaBr2, BaI2, and Ba(NO3)2. The force field is able to reproduce the experimental densities of all these salts up to their solubility limit. Furthermore, we have computed the viscosities for two selected salts, finding that the experimental values are overestimated, but the predictions are still reasonable. Finally, the structural properties for all the salts have been calculated with this model and align remarkably well with experimental observations.

Chemistry↗
DOE OSTI2015

Tuning the ion selectivity of tetrameric cation channels by changing the number of ion binding sites

Selective ion conduction across ion channel pores is central to cellular physiology. To understand the underlying principles of ion selectivity in tetrameric cation channels, we engineered a set of cation channel pores based on the nonselective NaK channel and determined their structures to high resolution. These structures showcase an ensemble of selectivity filters with a various number of contiguous ion binding sites ranging from 2 to 4, with each individual site maintaining a geometry and ligand environment virtually identical to that of equivalent sites in K{sup +} channel selectivity filters. Combined with single channel electrophysiology, we show that only the channel with four ion binding sites is K{sup +} selective, whereas those with two or three are nonselective and permeate Na{sup +} and K{sup +} equally well. These observations strongly suggest that the number of contiguous ion binding sites in a single file is the key determinant of the channel's selectivity properties and the presence of four sites in K{sup +} channels is essential for highly selective and efficient permeation of K{sup +} ions.

Derebe, Mehabaw G.↗
DOE OSTI2024

Cation valency in water-in-salt electrolytes alters the short- and long-range structure of the electrical double layer

Highly concentrated aqueous electrolytes (termed water-in-salt electrolytes, WiSEs) at solid-liquid interfaces are ubiquitous in myriad applications including biological signaling, electrosynthesis, and energy storage. This interface, known as the electrical double layer (EDL), has a different structure in WiSEs than in dilute electrolytes. Here, we investigate how divalent salts [zinc bis(trifluoromethylsulfonyl)imide, Zn(TFSI) 2 ], as well as mixtures of mono- and divalent salts [lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) mixed with Zn(TFSI) 2 ], affect the short- and long-range structure of the EDL under confinement using a multimodal combination of scattering, spectroscopy, and surface forces measurements. Raman spectroscopy of bulk electrolytes suggests that the cation is closely associated with the anion regardless of valency. Wide-angle X-ray scattering reveals that all bulk electrolytes form ion clusters; however, the clusters are suppressed with increasing concentration of the divalent ion. To probe the EDL under confinement, we use a Surface Forces Apparatus and demonstrate that the thickness of the adsorbed layer of ions at the interface grows with increasing divalent ion concentration. Multiple interfacial layers form following this adlayer; their thicknesses appear dependent on anion size, rather than cation. Importantly, all electrolytes exhibit very long electrostatic decay lengths that are insensitive to valency. It is likely that in the WiSE regime, electrostatic screening is mediated by the formation of ion clusters rather than individual well-solvated ions. This work contributes to understanding the structure and charge-neutralization mechanism in this class of electrolytes and the interfacial behavior of mixed-electrolyte systems encountered in electrochemistry and biology.

Science & Technology - Other Topics↗
DOE OSTI2025

Strong adsorption of guanidinium cations to the air–water interface

Combining Deep-UV second harmonic generation spectroscopy with molecular simulations, we confirm and quantify the specific adsorption of guanidinium cations to the air–water interface. Using a Langmuir analysis of measurements at multiple concentrations, we extract the Gibbs free energy of adsorption, finding it larger than typical thermal energies. Molecular simulations clarify the role of polarizability in tuning the thermodynamics of adsorption, and establish the preferential parallel alignment of guanidinium at the air–water interface. As a polyatomic cation, guanidinium represents one of the few examples of a positively charged species to exhibit a propensity for the air-water interface. As such, these results expand on the growing body of work on specific ion adsorption.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Systematic approach for simultaneously correcting the band-gap and p - d separation errors of common cation III-V or II-VI binaries in density functional theory calculations within a local density approximation

We propose a systematic approach that can empirically correct three major errors typically found in a density functional theory (DFT) calculation within the local density approximation (LDA) simultaneously for a set of common cation binary semiconductors, such as III-V compounds, (Ga or In)X with X = N,P,As,Sb, and II-VI compounds, (Zn or Cd)X, with X = O,S,Se,Te. By correcting (1) the binary band gaps at high-symmetry points , L, X, (2) the separation of p-and d-orbital-derived valence bands, and (3) conduction band effective masses to experimental values and doing so simultaneously for common cation binaries, the resulting DFT-LDA-based quasi-first-principles method can be used to predict the electronic structure of complex materials involving multiple binaries with comparable accuracy but much less computational cost than a GW level theory. This approach provides an efficient way to evaluate the electronic structures and other material properties of complex systems, much needed for material discovery and design.

Wang, Jianwei↗
DOE OSTI2018

Effect of counter-ion on packing and crystal density of 5,5′-(3,3′-bi[1,2,4-oxadiazole]-5,5′-diyl)bis(1 H -tetrazol-1-olate) with five different cations

In energetic materials, the crystal density is an important parameter that affects the performance of the material. When making ionic energetic materials, the choice of counter-ion can have detrimental or beneficial effects on the packing, and therefore the density, of the resulting energetic crystal. Presented herein are a series of five ionic energetic crystals, all containing the dianion 5,5′-(3,3′-bi[1,2,4-oxadiazole]-5,5′-diyl)bis(1 H -tetrazol-1-olate), with the following cations: hydrazinium ( 1 ) (2N 2 H 5 + ·C 6 N 12 O 4 2− ), hydroxylammonium ( 2 ) 2NH 4 O + ·C 6 N 12 O 4 2− [Pagoria et al.. (2017). Chem. Heterocycl. Compd , 53 , 760–778; included for comparison], dimethylammonium ( 3 ) (2C 2 H 8 N + ·C 6 N 12 O 4 2− ), 5-amino-1 H -tetrazol-4-ium ( 4 ) (2CH 4 N 5 + ·C 6 N 12 O 4 2− ·4H 2 O), and aminoguanidinium ( 5 ) (2CH 7 N 4 + ·C 6 N 12 O 4 2− ). Both the supramolecular interactions and the sterics of the cation play a role in the density of the resulting crystals, which range from 1.544 to 1.873 Mg m −1 . In 5 , the tetrazolate ring is disordered over two positions [occupancy ratio 0.907 (5):0.093 (5)] due to a 180° rotation in the terminal tetrazole rings.

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

(NH 4 ) 2 [UO 2 Cl 4 ]·2H 2 O, a new uranyl tetrachloride with ammonium charge-balancing cations

A new uranyl tetrachloride salt with chemical formula, (NH 4 ) 2 [UO 2 Cl 4 ]·2H 2 O, namely, diammonium uranyl tetrachloride dihydrate, 1 , was prepared and crystallized via slow evaporation from a solution of 2 M hydrochloric acid. As confirmed by powder X-ray diffraction, the title compound crystallizes with an ammonium chloride impurity that formed as a result of the breakdown of a triazine precursor. The (UO 2 Cl 4 ) 2− dianion is charge balanced by ammonium cations, while an extensive hydrogen-bond network donated from structural water molecules stabilize the overall assembly. Compound 1 adds to the extensive collection of actinyl tetrachloride salts, but it represents the first without an alkali cation for purely inorganic compounds. Diffuse reflectance and luminescence spectra show typical absorption and emission behavior, respectively, of uranyl materials.

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

Femtosecond symmetry breaking and coherent relaxation of methane cations via x-ray spectroscopy

Understanding the relaxation pathways of photoexcited molecules is essential to gain atomistic-level insight into photochemistry. Here, we performed a time-resolved study of ultrafast molecular symmetry breaking through geometric relaxation (Jahn-Teller distortion) on the methane cation. Attosecond transient absorption spectroscopy with soft x-rays at the carbon K-edge revealed that the distortion occurred within 10 ± 2 femtoseconds after few-femtosecond strong-field ionization of methane. The distortion activated coherent oscillations in the asymmetric scissoring vibrational mode of the symmetry-broken cation, which were detected in the x-ray signal. These oscillations were damped within 58 ± 13 femtoseconds because vibrational coherence was lost with the energy redistributing into lower-frequency vibrational modes. This study completely reconstructs the molecular relaxation dynamics of this prototypical example and opens avenues for exploring complex systems.

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

Cation and Anion Channelrhodopsins: Sequence Motifs and Taxonomic Distribution

Cation and anion channelrhodopsins (CCRs and ACRs, respectively) primarily from two algal species, Chlamydomonas reinhardtii and Guillardia theta, have become widely used as optogenetic tools to control cell membrane potential with light. We mined algal and other protist polynucleotide sequencing projects and metagenomic samples to identify 75 channelrhodopsin homologs from four channelrhodopsin families, including one revealed in dinoflagellates in this study. We carried out electrophysiological analysis of 33 natural channelrhodopsin variants from different phylogenetic lineages and 10 metagenomic homologs in search of sequence determinants of ion selectivity, photocurrent desensitization, and spectral tuning in channelrhodopsins. Our results show that association of a reduced number of glutamates near the conductance path with anion selectivity depends on a wider protein context, because prasinophyte homologs with a glutamate pattern identical to that in cryptophyte ACRs are cation selective. Desensitization is also broadly context dependent, as in one branch of stramenopile ACRs and their metagenomic homologs, its extent roughly correlates with phylogenetic relationship of their sequences. Regarding spectral tuning, we identified two prasinophyte CCRs with red-shifted spectra to 585 nm. They exhibit a third residue pattern in their retinal-binding pockets distinctly different from those of the only two types of red-shifted channelrhodopsins known (i.e., the CCR Chrimson and RubyACRs). In cryptophyte ACRs we identified three specific residue positions in the retinal-binding pocket that define the wavelength of their spectral maxima. Lastly, we found that dinoflagellate rhodopsins with a TCP motif in the third transmembrane helix and a metagenomic homolog exhibit channel activity. Channelrhodopsins are widely used in neuroscience and cardiology as research tools and are considered prospective therapeutics, but their natural diversity and mechanisms remain poorly characterized. Genomic and metagenomic sequencing projects are producing an ever-increasing wealth of data, whereas biophysical characterization of the encoded proteins lags behind. In this study, we used manual and automated patch clamp recording of representative members of four channelrhodopsin families, including a family in dinoflagellates that we report in this study. Our results contribute to a better understanding of molecular determinants of ionic selectivity, photocurrent desensitization, and spectral tuning in channelrhodopsins.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Different Electrochemical Behavior of Cationic Dopamine from Anionic Ascorbic Acid and DOPAC at CNT Yarn Microelectrodes

Carbon nanotube yarn microelectrodes (CNTYMEs) have micron-scale surface crevices that momentarily trap molecules. CNTYMEs improve selectivity among cationic catecholamines because secondary reactions are enhanced, but no anions have been studied. Here, we compared fast-scan cyclic voltammetry (FSCV) of dopamine and anionic interferents 3,4 dihydroxyphenylacetic acid (DOPAC) and L-ascorbic acid (AA) at CNTYMEs and carbon fiber microelectrodes (CFMEs). At CFMEs, dopamine current decreases with increasing FSCV repetition frequency at pH 7.4, whereas DOPAC and AA have increasing currents with increasing frequency, because of less repulsion at the negative holding potential. Both DOPAC and AA have side reactions after being oxidized, which are enhanced by trapping. At pH 4, the current increases for DOPAC and AA because they are not repelled. In addition, AA has a different oxidation pathway at pH 4, and an extra peak in the CV is enhanced by trapping effects at CNTYMEs. At pH 8.5, co-detection of dopamine in the presence of DOPAC and AA is enhanced at 100 Hz frequency because of differences in secondary peaks. Thus, the trapping effects at CNTYMEs affects anions differently than cations and secondary peaks can be used to identify dopamine in mixture of AA and DOPAC with FSCV.

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

Performance Losses and Current-Driven Recovery from Cation Contaminants in PEM Water Electrolysis

Water contaminants are a common cause of failure for polymer electrolyte membrane (PEM) electrolyzers in the field as well as a confounding factor in research on cell performance and durability. In this study, we investigated the performance impacts of feed water containing representative tap water cations at concentrations ranging from 0.5–500 μ M, with conductivities spanning from ASTM Type II to tap-water levels. We present multiple diagnostic signatures to help identify the presence of contaminants in PEM electrolysis cells. Through analysis of polarization curves and impedance spectroscopy to understand the origins of performance losses, we found that a switch from the acidic to alkaline hydrogen evolution mechanism is a key factor in contaminated cell behavior. Finally, we demonstrated that this mechanism switching can be harnessed to remove cation contaminants and recover cell performance without the use of an acid wash. We demonstrated near-complete recovery of cells contaminated with sodium and calcium, and partial recovery of a cell contaminated with iron, which was further investigated by post-mortem microscopy. The improved understanding of contaminant impacts from this work can inform development of strategies to mitigate or recover performance losses as well as improve the consistency and rigor of electrolysis research.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2018

Role of Cation-Anion Organic Ligands for Optical Properties of Fully Inorganic Perovskite Quantum Dots

ABSTRACT Application of lead-halide perovskite nanostructures for photovoltaic and light emitting applications depends on fashion of the surface termination. The reasonable choice of surface ligands for perovskite nanostructures prevent formation of trap states and contribute to chemical stability, wide opening of the bandgap, and intensity of absorption and photoluminescence of perovskite nanostructures. This work provides atomistic arguments for dual ligand protocol of surface passivation of fully inorganic perovskite quantum dots with fully organic ligands being a mix of cations (ethyl-ammonium) and anions (acetic) in nearly equal proportions. Computed binding energies of either individual ligands or anion-cation pairs demonstrate high stability in comparison to thermal energy and are concluded to be favourable choice in synthesis of colloidal perovskite quantum dots for light emitting applications.

Forde, Aaron↗
DOE OSTI2022

Simulation and characterization of cation disorder in ZnGeP 2

New optoelectronic materials are needed for improving the efficiency and reliability of devices such as solar cells. Cation ordering presents one means of controlling optoelectronic properties while introducing potential to also diversify the mineral constituents of electronic devices; however, the mechanisms of ordering are not yet well understood. To better understand cation ordering in a system integratable with current devices, we assess short- and long-range order parameters of ZnGeP 2 , a material closely lattice matched to Si. Structures are simulated using cluster-based Monte Carlo and first-principles calculations to compare structural distortions, periodicity, and local coordination environments in ZnGeP 2 to experimental data both from the literature and presented here. Comparing order parameters, we relate the transition in order parameters of ZnGeP 2 to that of ZnGeP 2 , discuss the reduction of band gaps with disorder, and show that traditional structural characterization alone is insufficient for understanding order in ZnGeP 2 .

14 SOLAR ENERGY↗
DOE OSTI2015

Colloid-Facilitated Transport of Cations in an Unsaturated Fractured Soil Under Transient Conditions

Rainfall experiments were conducted using intact soil cores and an instrumented soil pedon to examine the effect of physical heterogeneity and rainfall characteristics on the mobilization of colloids, organic matter, cesium, and strontium in a fractured soil. To measure the spatial variability of infiltration of colloids and contaminants, samples were collected through a 19-port grid placed below the soil core in laboratory study and in 27 samplers at multiple depths in the soil pedon in the field study. Cesium and strontium were applied to the soil cores and the soil pedon prior to mobilization experiments. Rainwater solutions of multiple ionic strengths and organic matter concentrations were applied to the soil cores and soil pedon to mobilize in situ colloids, cesium, and strontium. The mobilization of colloids and metal cations occurred through preferential flow paths in the soil cores. Compared to steady rainfall, greater amounts of colloids were mobilized during rainfall interrupted by pauses, which indicates that the supply of colloids to be mobilized was replenished during the pauses. A maximum in the amount of mobilized colloids were mobilized during a rainfall following a pause of 2.5 d. Pauses of shorter or longer duration resulted in less colloid mobilization. Freeze-thaw cycles, a transient condition in winter, enhanced colloid mobilization and colloid-facilitated transport of cesium and strontium in the soil cores. The exchange of solutes between the soil matrix and macropores caused a hysteretic mobilization of colloids, cesium, and strontium during changes in ionic strength. Colloid-facilitated mobilization of cesium and strontium was important at low ionic strength in fractures where slow flow allowed greater exchange of flow between the fractures and the surrounding matrix. The release of cesium and strontium by cation exchange occurred at high ionic strength in fractures where there is a little exchange of pore water with the surrounding matrix. The results of the field experiment suggested that ion exchange, and not organic matter- or colloid-facilitated transport, was the dominant mechanism for mobilization of cesium and strontium through the macropores of the fractured soil.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2018

Field Demonstration of the Combined Use of Thermally-Degrading and Cation-Exchanging Tracers to Predict Thermal Drawdown in a Geothermal Reservoir

This paper presents the results and interpretation of a reactive tracer test in a geothermal reservoir involving a cation-exchanging tracer to interrogate flow pathway surface area to volume ratios and a thermally-degrading tracer to interrogate average flow pathway temperatures. The test interpretations, which are based on comparing the reactive tracer responses to that of a nonreactive tracer, are used to predict when thermal drawdown will occur at the production well due to injecting cooler, spent geothermal water into an injection well. It is shown that the cation- exchanging tracer provides constraints on the timing of thermal drawdown, and the thermally-degrading tracer provides constraints on the magnitude of thermal drawdown. Thus, the combined use of the two reactive tracers provides a better prediction of thermal drawdown than either one alone. Uncertainties associated with the method, including assumptions made about flow pathway geometry, are discussed. It is also shown that interrogating average temperatures along flow pathways using a thermally-degrading tracer at different times can be translated into an estimate of when thermal drawdown will occur without direct knowledge of flow pathway geometry.

15 GEOTHERMAL ENERGY↗